Polymer User Guide

SimSci®
®
352,, .
3RO\PHUV8VHU*XLGH
May 2014
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Contents
Contents 1
Chapter P1
Introduction to Polymers
Polymer Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P1-1
Addition or Chain Polymerization . . . . . . . . . . . . . . . . . . . . . . . P1-1
Condensation or Step Growth Polymerization . . . . . . . . . . . . . P1-2
Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P1-3
Chapter P2
Using the Polymer Module with PRO/II
Steps for Using Polymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P2-1
Selecting the Units of Measure . . . . . . . . . . . . . . . . . . . . . . . . . P2-1
Entering Polymer Segment and Component Data . . . . . . . . . . . P2-3
Calculating Molecular Weight Distributions . . . . . . . . . . . . . . . P2-4
Choosing Thermodynamic Methods . . . . . . . . . . . . . . . . . . . . . P2-6
Building the Flowsheet and Selecting Polymer Reactors . . . . . P2-8
Chapter P3
Estimating Polymer Properties
van Krevelen Group Contribution Method . . . . . . . . . . . . . . . . P3-1

Keyword Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P3-1
van Krevelen Structural Groups. . . . . . . . . . . . . . . . . . . . . . . . . P3-3
Entering Polymer Segment and Component Data . . . . . . . . . . P3-10
Chapter P4
Supplying Polymer Pure
Component Property Data
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P4-3
Entering Molecular Weight Distributions . . . . . . . . . . . . . . . . P4-10
Chapter P5
Supplying Polymer Stream Data
PRO/II Polymers User Guide Contents-1

Entering Stream Polymer Data . . . . . . . . . . . . . . . . . . . . . . . . .P5-10
Chapter P6
Stream Output Report Options
Keyword Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P6-1
Entering PWRATE and PCONV . . . . . . . . . . . . . . . . . . . . . . . . .P6-2
Chapter P7
Specifying the Thermodynamic Method
Advanced Lattice Model (ALM). . . . . . . . . . . . . . . . . . . . . . . . .P7-2
UNIFAC Free Volume K-Value Method . . . . . . . . . . . . . . . . . . .P7-8
Flory-Huggins Liquid Activity Method . . . . . . . . . . . . . . . . . .P7-11
SAFT and PHSC Equations of State . . . . . . . . . . . . . . . . . . . . .P7-17
Selecting Polymer Thermodynamic Methods . . . . . . . . . . . . . .P7-27
Chapter P8
User-Added Polymer Reactor
Kinetic Rate Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P8-2
CSTR Mass and Energy Operating Equations . . . . . . . . . . . . . .P8-3
PFR Mass and Energy Operating Equations . . . . . . . . . . . . . . . .P8-4
Heat Transfer Coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P8-5
Population Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P8-6
Moment Expansions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P8-7
Chapter P9
User-Added Free Radical
Polymerization Model
Polymerization via Free-Radical Kinetics. . . . . . . . . . . . . . . . . .P9-2
Free-Radical Kinetics Mechanisms . . . . . . . . . . . . . . . . . . . . . . .P9-2
Required Data for the Polymer Reactor Unit . . . . . . . . . . . . . .P9-12
User-Added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P9-13
Chapter P10
User-Added Coordination Complex Polymerization Model
Polymerization via Coordination Complex Kinetics. . . . . . . . .P10-2
Required Data for the Polymer Reactor Unit . . . . . . . . . . . . .P10-10
User-Added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P10-11
Contents -2
Chapter P11
User-Added Step Growth
Polymerization Reactor Model
Polymerization via Step-wise Kinetics . . . . . . . . . . . . . . . . . . .P11-2
Required Data for the Polymer Reactor Unit. . . . . . . . . . . . . . .P11-8
User-Added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .P11-9
Chapter P12
Interpreting Polymer Output
Description of Polymer Report . . . . . . . . . . . . . . . . . . . . . . . . P12-1
Polymer Characterization via Moments. . . . . . . . . . . . . . . . . . P12-3
Chapter P13
Wiped Film Evaporator
WFE Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P13-1
PRO/II Wiped Film Evaporator Model . . . . . . . . . . . . . . . . . . P13-2
Using the Wiped Film Evaporator to Model Systems . . . . . . . P13-9
General Information. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . P13-10
Appendix A
van Krevelen Structural Groups
Index 1
PRO/II Polymers User Guide Contents-3

Contents -4
Chapter P1
Introduction to Polymers
Polymer Overview
Polymers form the basis of many useful, synthetic materials com-
mon today. A polymer is a large molecule that has been constructed
from atoms linked together by covalent bonds. This large molecule
is formed by systematically joining together groups of simpler mol-
ecules or monomers. The result is a high molecular weight, long-
chain component made up of various combinations of monomer
POLYMERS
units having a recurring chemical structure. The monomer unit
itself has a fixed molecular weight. Monomers may be combined to
produce a polymer by either of two basic mechanisms−addition or
chain polymerization or condensation or step polymerization.
Addition or Chain Polymerization

In this polymerization mechanism, a highly reactive center is cre-
ated, and the monomer is then incorporated into the live chain only
at this center. In the synthesis phase, the reactive center must be
maintained during monomer addition until a polymer of acceptable
molecular weight is generated. The monomer addition process con-
tinues rapidly until the reactive center is transferred away from the
growing chain or deactivated by a termination process. The transfer
or deactivation of the reactive center turns the live or growing poly-
mer chain radical into an inactive or dead polymer chain. Free radi-
cal, ionic, group transfer, metallocene or Ziegler-Natta
polymerization are special types of addition polymerization.
The recurring unit of the polymer structure that results from addi-
tion polymerization is identical to that of the monomer. Most poly-
mers formed by addition polymerization are thermoplastic; i.e., the
polymer softens or hardens by the addition or removal of heat. Typ-
ical polymers formed by this process include:
 Polyethylene—used in packaging, pipes, and containers
 Polystyrene—used in insulation, pipes, and car panels
 Poly(vinylchloride) or PVC—used in pipes, adhesives, and
shoes.
PRO/II Polymers User Guide P1-1

Condensation or Step Growth Polymerization
In this polymerization mechanism, monomers react with one
BATCH
another to form larger monomers or macromolecules. These large

molecules essentially assume the role of macromonomers and con-
tinue to react with residual monomer and other macromonomers to
form progressively larger macromonomers. The terms monomer
and macromonomer will be used interchangeably unless some dis-
tinction between the two structures is required. Eventually, the
resulting molecules are of sufficient size that the term polymer is
applicable. This is the step growth polymerization method. In the
course of the polymerization reaction, a low molecular weight com-
ponent (such as H2O or HCl) is usually expelled, and therefore the
term condensation polymerization is common.
In this procedure, the recurring unit of the resulting polymer is not
POLYMERS
identical to that of the monomer. Many polymers formed by con-

densation polymerization are thermosetting; i.e., the polymer
becomes rigid and insoluble when heat processed. In addition, poly-
mers created by condensation polymerization techniques may be
cross-linked; i.e., sections of the long-chain polymer react with
each other, resulting in an enhancement of their strength properties
(e.g., hardness or toughness). Typical polymers formed by conden-
sation polymerization include:
 Polyesters (e.g., Mylar)—used in valves, pumps, and coatings
 Polyurethane—used in foam linings, adhesives, and insulation
 Polyamides (e.g., Nylon and Kevlar)—used in gears, bottles,
and appliances.
Polymerization reactions are exothermic in nature and require
sophisticated heat controls. The molecular structure and the bulk
polymer morphology are highly temperature dependent.
Polymers also occur naturally as derivatives of animal and plant
products, e.g., cellulose resins, proteins (soybean, casein), and lig-
nin. Both synthetic and natural polymer products may be spun and
stretched to form a wide variety of fibers. These fibers can then be
modified (e.g., by adding water repellents or flame retardants),
dyed, and woven to produce natural and synthetic fabrics and yarns.
P1-2 - May 2014 Introduction to Polymers

Terminology
Descriptions of common polymer terms are provided below.
Polymer chain A high molecular weight structure made up of a large

number of polymer segments. In a typical polymer, the
polymer chains may be of varying lengths, and their
distribution can, under certain polymerization condi-
tions, be represented by a Gaussian curve. The poly-
mer properties (e.g., molecular weight) are determined
by a statistical average of a sampling of the polymer
chains.
Polymer A representative section of the polymer chain that con-
POLYMERS
segment tains a recurring chemical structural unit.
Cross-linking A process in which polymer chains react with each

other and increase the hardness of the polymer.
Monomer A building block unit of a polymer. Monomer units

can be combined by addition polymerization or con-
densation polymerization to form a polymer.
Homopolymer A polymer formed by a single type of monomer unit.
Copolymer A polymer formed by two types of monomer units.
Thermosetting A polymer that remains rigid and insoluble when

polymer heated.
Thermoplastic A polymer that softens or hardens by the addition or

polymer removal of heat.
Polymer blend A non-homogeneous mixture of polymers that results

in desired polymer properties. Special compatibilizers
are used to make the separate polymer components
adhere to each other while still maintaining distinct
phases.
Condensation or A process in which monomer units are combined by

step growth eliminating small molecules (e.g., HCl, or H2O).
polymerization

Chain or free A process in which monomer units are combined to
radical form polymers with recurring structures identical to
BATCH
polymerization those of the monomer.
Bulk A process in which monomer units are combined in

polymerization bulk in the vapor or liquid phase or on a solid surface.
Solution A process in which monomer units are combined in the

polymerization presence of a solvent to control and slow the polymer-
ization reaction. This process is often used for highly
exothermic reactions and produces polymers of low to
medium molecular weights.
Suspension A process in which monomer units are combined in the

polymerization presence of water and stabilizers to prevent the result-
POLYMERS
ing polymer globules from aggregating to each other.
Emulsion A process in which monomer units are combined in the

polymerization presence of water and emulsifiers to create aggregates
or micelles of polymer particles. This process can cre-
ate high molecular weight polymers.
P1-4 - May 2014 Introduction to Polymers

Chapter P2
Using the Polymer Module
with PRO/II
Steps for Using Polymers
To create a simulation for a polymer system using PRO/II, follow
these six steps:
1. Select the input units of measure to be SI.
POLYMERS
2. Enter the segment data and select the polymer components
(required).
3. Enter the polymer molecular weight distribution and moments
of distributions (optional).
4. Select the polymer thermodynamic method.
5. Create the flowsheet by selecting the desired polymer reac-
tor(s) and other pre- and/or post-processing units (such as flash,
mixer, wiped film evaporator) and completing the stream con-
nections between each unit.
6. Solve the flowsheet and generate the output to view the results
of the simulation.
This chapter includes a brief overview of the first five steps. The
following chapters give a more detailed descriptions.
Selecting the Units of Measure

The current version of the polymers module in PRO/II requires the
units of measure basis for input data to be SI. To set the input units
basis to be SI, do the following:
Click the Units of Measure button on the toolbar (or select Input/
Units of Measure from the menu bar) to display the Default Units of
Measure for Problem Data Input dialog box.

Figure P2-1: Default Units of Measure for Problem Data Input Dialog Box
BATCH
POLYMERS
 Click Initialize from UOM Library... to display the Initialize Units

of Measure from UOM Library dialog box (Figure P2-2).
Figure P2-2: Initialize Units of Measure from UOM Library
 Select SI-SET1 from the drop-down list, and click OK. The
units of measure for all properties will now be in SI units; e.g.,
temperature in degrees Kelvin, pressure in kilopascals, etc.
P2-2 - May 2014 Using the Polymer Module with PRO/II

Entering Polymer Segment and Component Data
First, enter the information regarding the segments that make up the
polymers, and then enter the polymer components based on the
selected segments.
To enter the segment and polymer component data:
 Click the Component Selection button on the toolbar (or select
Input/Component Selection from the menu bar) to display the
Component Selection dialog box.
 Click Polymer... to display the Definition of Polymer Compo-
nents dialog box (Figure P2-3).
Figure P2-3: Definition of Polymer Components Dialog Box
POLYMERS
 Complete all the segment data by entering the segment names

and their van Krevelen structures (required entry) and the
UNIFAC structures (optional entry).
 After defining the segment data, enter the polymer components
by providing their names, average molecular weights, and the

segment compositions that make up each of the polymer com-
ponents.
BATCH
All the polymer components selected in this dialog box will be dis-
played in the List of Selected Components in the Component Selec-
tion dialog box after you click OK.
To delete a polymer component:
 Select the desired component from the List of Selected Compo-
nents in the Component Selection dialog box and click Delete.
A segment can be deleted by selecting the desired row in the Poly-
mer Segments section of the Definition of Polymer Components dia-
log box and clicking Cut.
Calculating Molecular Weight Distributions

POLYMERS
To calculate or input the molecular weight distributions, first enter

the molecular weight of the pseudocomponents that make up the
distribution. This can be achieved by entering the discrete molecu-
lar weight range values for each of the polymer components. Also,
you can specify the number of moments of the molecular weight
distribution that need to be considered during calculations. Each
moment can be assigned a name, or a default name will be used.
To enter data for the molecular weight distribution:
 Click the Component Properties button on the toolbar, or select
Input/Component Properties from the menu bar, to display the
Component Properties dialog box.
 Click Distribution Functions... under Polymer Properties to dis-
play the Distribution Functions for Components dialog box
(Figure P2-4). All the polymer components selected earlier
under the Component Selection dialog box will be available in
the drop-down lists.

Figure P2-4: Distribution Function for Components Dialog Box
POLYMERS
To enter the distribution data for a polymer component:
 Select the desired polymer component from the drop-down list.
 Select the appropriate kinetic type for the polymer (Free Radi-
cal, Ziegler-Natta, or Step Growth).
 Click Enter Data... to display the Distribution Function Data
dialog box for the selected component (Figure P2-5).
Figure P2-5: Distribution Function Data Dialog Box
 Select the desired distribution names from the list boxes in the
first column. If you select Discrete Mol. Wt. Cuts, enter the
molecular weight ranges by clicking Enter Data.... For the vari-
ous moments, specify the number of moments and optionally
enter the names of the moments by clicking Enter Data.... The

moment names default to M0, M1, M2, etc., and up to five
moments can be selected (M0 through M4).
BATCH
Choosing Thermodynamic Methods

PRO/II currently supports five polymer thermodynamic methods
[Advanced Lattice Model (ALM), Flory-Huggins Model (Flory),
Unifac Free Volume Model (UNFV), Statistical Associating Fluid
Theory (SAFT), and Perturbed Hard-Sphere-Chain Theory
(PHSC)].
To select the method to be used in the simulation:
 Click the Thermodynamic Data button on the toolbar, or select
Input/Thermodynamic Data from the menu bar, to display the
Thermodynamic Data dialog box (Figure P2-6).
POLYMERS
Figure P2-6: Thermodynamic Data Dialog Box
 From the Category list, select Polymers. All five polymer ther-
modynamic methods are displayed in the Primary Method list.
 Select the desired method, and click Add > to include that
method in the simulation.
 To change the thermodynamic method to be used for calculat-
ing various properties, click Modify.... The Modification dialog
box appears (Figure P2-7).

Figure P2-7: Modification Dialog Box
POLYMERS
 To enter the following, click Enter Data.... Detailed information
on entering these data can be found in Chapter 7, Specifying the
Thermodynamic Method.
 Pure species parameters
 Binary interaction parameters between two non-polymer
components
 Binary interaction parameters between two segments
 Binary interaction parameters between a non-polymer com-
ponent and a segment.

Building the Flowsheet and Selecting Polymer Reactors
Select the desired unit operations and the polymer reactors to be
BATCH
used in the flowsheet from the unit operation palette by clicking on

the appropriate icons and placing them on the PFD.
To add a polymer reactor to the flowsheet:
 Select the Polymer Reactors icon and click on the PFD. The
Polymer Reactors dialog box (Figure P2-8) appears.
 Select the desired polymer reactor type from the drop-down list
box. PRO/II supports seven types of CSTRs and seven types of
PFRs.
Figure P2-8: Polymer Reactors Dialog Box
POLYMERS
 Double-click on the polymer reactor icon on the PFD to display

the dialog box for the selected calculation model. Figure P2-9
shows the CSTR for Free Radical Homopolymerization dialog
box.

Figure P2-9: CSTR for Free Radical Homopolymerization Dialog Box
POLYMERS
 Enter reactor operating and kinetic data in the Real Data for
Unit (RPARM), Integer Data for Unit (IPARM), and Supple-
mental Data for Unit (SUPPLE) sections. See Chapter 8, Incor-
porating User-Added Polymer Reactor Models, for more
information on the data requirements for the polymer reactor.

BATCH
POLYMERS

Chapter P3
Estimating Polymer Properties
van Krevelen Group Contribution Method

PRO/II provides a segment approach to simulate polymer systems.
It requires you to input the van Krevelen structural groups for
defined segments. The segment approach is applicable to both
POLYMERS
homopolymers and copolymers. The van Krevelen group contribu-
tion method is used to predict the properties of the segments that
make up the polymers on the basis of structural groups. This
method, based on the additivity principle, calculates the property of
a segment as the sum of the contribution of structural groups that
make up the segment. You provide information on the structure of
the segments in the form of group identifiers and counts. This
allows you to simulate processes that involve polymers for which
no experimental data are available, or for which no experimental
data are limited. The structure of a given segment is defined using a
unified set of groups. This unified set is a superset of a number of
group sets developed by van Krevelen for the prediction of various
properties of polymers.
Keyword Summary
Segment Definition (required)
SEGMENT DATA
SEGMENT α, name/…, &
FILL= VANKREVELEN
STRUCTURE(VANKRE) α, igroup(n)/…
Component Definition (required)
COMPONENT DATA
POLYMER i, name/…
PCOMPOSITION(M or W) i, Xα,(α), Xβ(β), …/…
MWAVG i, value/…
PHASE VLS or LS or S = i, j…

Input Description
SEGMENT DATA
BATCH
SEGMENT α, name/…, FILL= VANKREVELEN

STRUCTURE(VANKRE) α, igroup(n)/…
All segments must be defined under SEGMENT DATA.
a Segment type letter.
name Name of segment α.
FILL This keyword is used to activate the van Krevelen

group contribution method.
The STRUCTURE statement with a VANKRE qualifier is required for

POLYMERS
the van Krevelen group contribution method. The default VANKRE

qualifier distinguishes this statement from the UNIFAC structural
group statement (STRUCTURE(UNIFAC)).
a Segment type letter.
igroup(n) The seven-digit identifier for an individual structural

group contained in the segment α with n being used to
define the number of such groups.
COMPONENT DATA
POLYMER i, name/…
MWAVG i, value/…
All polymer components must be defined as POLYMER components.
i Component number.
name Name of component i (polymer).
MWAVG The molecular weight of each polymer component

must be supplied.
iComponent number.
value Molecular weight of component i.
P3-2 - May 2014 Estimating Polymer Properties

PCOMPOSITION The segment compositions in the polymer must be
supplied.
MMole units.
WWeight units.
Xα(α)Composition of segment in the polymer.
PHASE The polymer phase type can be defined as VLS or

LS or S; default VLS.
i, j Component numbers continuously from

i to j.
POLYMERS
In van Krevelen’s original work, different group sets are used for
each individual property. Numerous auxiliary rules are used to
account for the location of a group within a main chain or a side
chain and to describe the proximity effects between a number of
groups. Thus, the logical structure of the van Krevelen group sets is
much more complex than the structure of the UNIFAC group sets; a
set of structural groups of over 700 is identified and used to predict
properties of segments that make up polymers in the van Krevelen
method (see Appendix A, van Krevelen Structural Groups).
The van Krevelen structural group codes are constructed through
three subcodes, CC, SS, and GGG, combined into an integer with a
maximum of seven digits, CCSSGGG. The subcodes have the follow-
ing meanings:
CC An optional number of methylene (CH2) groups in a side chain;

this number can be entered only when the main chain unit con-
tains a methyl (CH3) group.
SS An optional code of the group system; it can equal 00 or 01. If

SS=00, the structure has to be constructed from only main chain
groups, which are marked by a plus (+) sign in the van Krevelen
Structural Groups Table. If SS=01, the structure can be con-
structed from any combination of the van Krevelen structural
groups.
GGG A code from the van Krevelen Structural Groups Table; it is

required.

It is best to use the group system SS=00. This is due to the fact that
the van Krevelen group contributions have been developed primar-
ily for groups that can serve as main chain segments in a polymer. It
BATCH
is anticipated that this group system will be used for the vast major-
ity of polymer segments of interest. However, it is possible that cer-
tain polymer segments cannot be constructed from the main chain
groups given in the van Krevelen Groups Table because of their
chemical complexity. For such cases, the SS=01 group system is
needed; it allows you to calculate the properties of polymer seg-
ments that are composed of any combination from the van Krevelen
Structural Groups Table.
When choosing the group codes GGG, it is recommended to start
with the most complex groups to construct the structural units of
polymer segments of interest. Select more elementary groups only
POLYMERS
when an appropriate complex group is not found. While this is not

mandatory, it will maximize accuracy.
Example P3-1: Segment Structures

The segment structure of polystyrene is constructed using the
SS=00 system (the leading zeros are dropped):
SEGMENT DATA
SEGMENT A, STYRENE1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)
COMPONENT DATA
POLYMER 1, POLYSTRENE
PCOMPOSITION 1, 1(A)

The segment structure of poly(1-pentene) (PP) is constructed using
the SS=00 system. The number of methylene groups in the side
chain (which is equal to 2) is specified using the CC subcode:
SEGMENT DATA
SEGMENT A, PENTENE1, FILL=VANKREVELEN
COMPONENT DATA
POLYMER 1, PP

The segment structure of poly(phenyl methacrylate) (PPMA) can-
not be constructed using the SS=00 system. Therefore, the SS=01
system is used:
SEGMENT DATA
SEGMENT A, PPMA1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 01004(1), &
01001(1), 01012(1), 01110(1), &
01238(1), 01710(2), 01708(2)
COMPONENT DATA
POLYMER 1, PPMA
POLYMERS
The segment structure of poly(p-phenylene terephthalamide)
(Kevlar) is best defined by just one group (522), even though the
repeat unit of Kevlar is composed of two phenyl rings, two C=O
groups, and two N-H groups.
SEGMENT DATA
SEGMENT A, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 522(1)
COMPONENT DATA
POLYMER 1, KEVLAR
The van Krevelen group technique can be used to predict polymer
segment properties if structural information is available for the
polymer segments of interest. In PRO/II, over 700 structural groups
have been identified and may be used to define the polymer seg-
ments.

Table P3-1 shows the fixed and temperature-dependent properties
of polymer segments that are predicted by the van Krevelen group
method.
BATCH
Table P3-1: van Krevelen Properties of Polymers

Fixed Temperature-Dependent
Molecular weight Liquid density
Average segment number Liquid enthalpy
van der Waals volume Surface tension
Normal melting point (NMP) Solid density
Glass transition temperature Solid enthalpy
Specific gravity of liquid at 60 F
Enthalpy of fusion at NMP
POLYMERS
Standard enthalpy of formation at 298.15 K

Standard Gibb’s energy of formation at
298.15 K
Solubility parameter
Liquid thermal conductivity at 298.15 K
Reference
[1] D.W. van Krevelen, 1990, Properties of Polymers. Their Correlation with
Chemical Structure; Their Numerical Estimation and Prediction from Additive
Group Contributions, 3rd edition, Elsevier. Amsterdam.

Example P3-5: Segment Property Prediction
This example uses the van Krevelen group contribution method to
predict properties of segments for polystyrene (PS),
poly(1-pentene) (PP), poly(phenyl methacrylate) (PPMA), and
poly(p-phenylene terephthalamide) (Kevlar). The polymer proper-
ties are generated from the calculated segment properties by the van
Krevelen method. Segment compositions are provided in the input.
TITLE PROB=HOMOPOLYMER
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, STYRENE1/B, PENTENE1/C,PPMA1/&
POLYMERS
D, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) &
A, 144(1), 4(1)/ &
B, 200015(1), 4(1)/ &
C, 01004(1), 01001(1), 01012(1),&
01110(1), 01238(1), 01710(2), 01708(2)/&
D, 522(1)
COMPONENT DATA
POLYMER 1, PS/ 2, PP/ 3, PPMA/ 4, KEVLAR
PCOMPOSITION 1,1(A)/ 2,1(B)/ 3,1(C)/ 4,1(D)
PHASE VLS = 1,4
MWAVG 1,10000/ 2,10000/ 3,10000/ 4,10000
$
LIBRARY 5, HEXANE
$
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
PROP STRM=F1L, TEMP=300, PRES=10, COMP=1,1
PROP STRM=F1S, TEMP=200, PRES=10,
SOLID STREAM=F1S, COMP=1,1
$
$
$
$
UNIT OPERATION

HCUR UID=HC1L
ISO STREAM=F1L, TEMP=200, 400, PRES=10, POIN=20
PROP THERMO
BATCH
HCUR UID=HC1S
ISO STREAM=F1S, TEMP=200, 300, PRES=10, POIN=20
PROP THERMO
$
HCUR UID=HC2L
PROP THERMO
HCUR UID=HC2S
PROP THERMO
$
HCUR UID=HC3L
PROP THERMO
HCUR UID=HC3S
POLYMERS

PROP THERMO
$
HCUR UID=HC4L
ISO STREAM=F4L, TEMP=200, 400, PRES=10, &POIN=20
PROP THERMO
HCUR UID=HC4S
PROP THERMO

Example P3-6: Segment Property Prediction
This example uses the van Krevelen group contribution method to
predict properties of segments for the copolymer poly(methyl meth-
acrylate-co-vinyl acetate) (PMMACcoVAC), which has 25% vinyl
acetate. The copolymer properties are generated using calculated
segment properties by the van Krevelen method. Segment composi-
tions are provided in the input.
TITLE PROB=COPOLYMER
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, MMAC1/B, VAC1, FILL=VANKREVELEN
POLYMERS
STRUCTURE(VANKRE) A, 5(1),252(1),9(1)/ &
B, 5(1),250(1),9(1)
$
COMPONENT DATA
POLYMER 1, PMMACcoVAC
PCOMPOSITION 1, 0.75(A),0.25(B)
PHASE VLS = 1
MWAVG 1,10000
$
LIBRARY 2, HEXANE
$
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
$
UNIT OPERATION
HCUR UID=HC1L
ISO STREAM=F1L, TEMP=200, 400, PRES=10, &
POIN=20
PROP THERMO
HCUR UID=HC1S
ISO STREAM=F1S, TEMP=200, 300, PRES=10, &
POIN=20
PROP THERMO
$

Entering Polymer Segment and Component Data
To enter the segment and polymer component information:
BATCH
 Click the Component Selection button on the tool bar, or select

Input/Component Selection from the menu bar, to display the
Component Selection dialog box (Figure P3-1).
Figure P3-1: Component Selection Dialog Box
POLYMERS
 Click Polymer... to display the Definition of Polymer Compo-

nents dialog box (Figure P3-2).

Figure P3-2: Definition of Polymer Components Dialog Box
POLYMERS
 Enter the names of the desired segments, and click Enter Data...
for each segment to display the Define van Krevelen Structures
dialog box (Figure P3-3).

Figure P3-3: Define van Krevelen Structures Dialog Box
BATCH
POLYMERS
 Enter the van Krevelen structure groups and counts by either

selecting from the lists at the top of the dialog box or by enter-
ing the group number directly into the table.

 You can also enter the UNIFAC structures for the segments by
clicking Enter Data... under UNIFAC Structures. The Define
UNIFAC Structures dialog box appears (Figure P3-4). UNI-
FAC structures are required if the selected polymer thermody-
namic method is UNIFAC Free Volume.
Figure P3-4: Define UNIFAC Structures Dialog Box
POLYMERS
 After the segment information is complete, enter the compo-
nent names in the Polymer Components table. Supply an aver-
age molecular weight for each component.

 To specify the segment composition for each component (in
either the mole or mass basis), click Enter Data... under Segment
Composition… to display the Segment Composition Data dia-
BATCH
log box (Figure P3-5).

Figure P3-5: Segment Composition Data Dialog Box
POLYMERS

Chapter P4
Supplying Polymer Pure
Component Property Data
In PRO/II, component property data can be supplied for homo-

polymers and copolymers. You can provide polymer segment com-
positions, polymer phase types, and polymer molecular weights.
You can also provide the molecular weight distribution (MWD),
moments of the molecular weight distribution (MMWD), and other
POLYMERS
moment distributions. You also supply values for a number of
invariant properties (e.g., heat of fusion, crystallinity, and tacticity)
and temperature-dependent properties (e.g., density, enthalpy, vis-
cosity, and thermal conductivity).
Keyword Summary
Polymer Definition (required)
POLYMER i, name/…
MWAVG i, value/…
Polymer Attributes (conditional)

ATTRIBUTE COMPONENT = i,j, &
KINETICS = FR or ZN or SG, &
MWD = mw1, mw2, …, &
{MMWD = M0, M1, M2, M3, M4}, &
{MBCL = M0, M1, M2, M3, M4}, &
{MTTB = M0, M1, M2, M3, M4}, &
{MDSD(unit)= s0, s1, s2, …}, &
{PSD(unit) = s0, s1, s0, …}, &
GENERAL = 10, &
{GNAME = text1, text2, text3, …}
Polymer Invariant Properties (optional)

NMP(utemp) i, value
TGLASS(utemp) i, value
HFUSION(unit) i, value
SOLUPARA(unit)i, value

Polymer Temperature-Dependent Properties (optional)
DENSITY(L or S, propunit, tunit, WT or M) &
BATCH
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
ENTHALPY(L or S, propunit, tunit, WT or M) &
CORRELATION=icorr,
or
TABULAR= t1, t2, … /i, p1, p2, … /…
SURFACE(L, propunit, tunit, WT or M) &
CORRELATION=icorr,
or
POLYMERS
TABULAR= t1, t2, … /i, p1, p2, … /…

CONDUCTIVITY(L or S, propuom, utemp, WT or M) &
CORRELATION=icorr,
or
TABULAR= t1, t2, … /i, p1, p2, …/…
VISCOSITY(L, propunit, tunit, WT or M)&
CORRELATION=icorr,
or
TABULAR= t1, t2, … /i, p1, p2, … /…
P4-2 - May 2014 Supplying Polymer Pure Component Property

Input Description
Polymer Definition (required)
POLYMER i, name/…
PCOMPOSITION(W or M) i, Xα(α), Xβ(β),…/…
MWAVG i, value/…
POLYMER Defines the polymer component.
PCOMPOSITION Provides the composition (e.g. Xα, Xβ, …) for each

segment in the polymer. The composition of seg-
ments can be given in weight or mole units and will
POLYMERS
be normalized before calculation.
MWAVG Supplies the polymer molecular weight.
PHASE Provides the phase assignments for the polymer

components as well as for the regular components.
Because most polymers at normal processing con-
ditions can exist only in L and/or S phases, phase
designations of VLS, LS, or S are appropriate for
polymer components.
Note: Polymer components by definition are non-library compo-

nents and will not have any data stored in the component
library. All polymer properties must be either input or cal-
culated from properties of the constituent segments pre-
dicted by the van Krevelen method, known structure-
property relationships, and the input segment composi-
tions.
Polymer Attributes (required for unit US21)
ATTRIBUTE COMPONENT = i,j, &
KINETICS = FR or ZN or SG, &
MWD = mw1, mw2, …, &
{MMWD = M0, M1, M2, M3, M4}, &
{MBCL = M0, M1, M2, M3, M4}, &
{MTTB = M0, M1, M2, M3, M4}, &
{MDSD(unit)= s0, s1, s2, …}, &
{PSD(unit) = s0, s1, s0, …}, &
GENERAL = 10, &
{GNAME = text1, text2, text3, …}

Polymer component attributes consist of required defined attributes
(MWD) and optional defined attributes. General attributes may be
used by certain users for properties of interest to them, such as acid
BATCH
number or special end-use properties. A PSD attribute must be

defined for modeling the particle size distribution of crystalline
polymer solids. The defined attributes are:
KINETICS Specifies the kinetics type of polymerization as Free

Radical (FR) Polymerization, Ziegler-Natta (ZN)
Polymerization, or Step Growth (SG) Polymerization.
MWD Specifies the molecular weight distribution (MWD) to

be used in the polymerization processes. If the poly-
mer component can be modeled as a distribution of
discrete pseudo-components, then mw1 is the average
POLYMERS
molecular weight of the first pseudocomponent, mw2

is the average molecular weight of the second pseudo-
component, and so on.
Note: The MWD must be supplied for the polymer components if

the polymer reactor unit US21 is used.
MMWD Specifies the molecular weight distribution (MWD) that
will be used in the polymerization processes. M0 is the
zeroth order moment, M1 is the first order moment, M2
is the second order moment, and so on.
MBCL Specifies the moments with respect to the branch chain

length, measured as the numbers of average monomer
units in the branches. It is called Moments of
Branching Length.
MTTB Specifies the moments with respect to the number of

tri-functional and tetra-functional branches. It is called
Moments of Branching Density.
MDSD Specifies the distribution of monomer droplets in

emulsion and suspension polymerization. Monomer
droplets are dispersed in the liquid phase and may be
uniform in size (emulsion polymerization) or may fol-
low a size distribution (suspension polymerization).
The first range has particles with diameters ranging
from s0 to s1; the second range has particles from s1
to s2, and so on. The last range is sn-1 to sn, where
n is the size given for the component. It is called Drop-
let Size Distribution.

PSD Specifies Particle Size Distribution, defaulting to
problem fine length units. The first range has particles
with diameters ranging from s0 to s1; the second
range has particles from s1 to s2, and so on. The last
range is
sn-1 to sn, where n is the number of size given for
the component.
GENERAL Specifies the number of user-defined solid attributes.

The default is 10. The range extends to 100.
GNAME Specifies the user-defined names for each of the

GENERAL attributes. A maximum of four alphanu-
meric characters are allowed. If the number of GNAME
POLYMERS
arguments is less than the GENERAL integer value,
PRO/II fills in the remaining names. The default
assigned names are AT01, AT02, etc.
Polymer Invariant Properties (optional)

NMP(unit) i, value
TGLASS(unit) i, value
HFUSION(unit) i, value
SOLUPARA(unit) i, value
Property Unit Description

NMP Temperature Normal melting point
TGLASS Temperature Glass temperature
HFUSION Energy/Mole (default) or Heat of fusion
Energy/Mass
SOLUPARA Fixed, (cal/cc)1/2 Solubility parameter

Polymer Temperature-Dependent Properties (optional)
DENSITY(L or S, uprop, tunit, WT or M) &
BATCH
CORRELATION=icorr, &
or
TABULAR= t1, t2, … /i, p1, p2, … /…
ENTHALPY(L or S, uprop, tunit, WT or M) &
or
TABULAR= t1, t2, … /i, p1, p2, … /…
SURFACE(L, uprop, tunit, WT or M) &
or
TABULAR= t1, t2, …/i, p1, p2, … /…
CONDUCTIVITY(L or S, uprop, utemp, WT or M) &
POLYMERS
or
TABULAR= t1, t2, … /i, p1, p2, … /…
VISCOSITY(L, propunit, tunit, WT or M) &
CORRELATION=icorr,
or
TABULAR= t1, t2, … /i, p1, p2, … /…
The defined attributes include:
allowable phase I-Ideal gas, V-Vapor, L-Liquid, S-Solid phase.
tunit Temperature units used in correlation or tabular data:

F, R, C, K. Defaults to problem units.
propunit Specific to each property. See Table 1.8-4 of the PRO/

II Thermodynamic Data Input Manual.
allowable basis M-Mole, WT-Weight
CORRELATION The correlation form for equation-based data. See

Table 1.8-5 of the PRO/II Component Data Input
Manual for the available equation forms for each
property.

DATA Data entry for equation-based correlations:
iComponent number.
tmax, tminTemperature limits for the data. Required
for Chebychev equations, optional for others.
C1, … ,C8Equation coefficients.
or
TABULAR Data entry for tabular based data.
t1,… Temperatures at which tabular data are entered.
Correspond to data points p1,….
A minimum of two points must be given.
IComponent number
p1,… Data values at temperatures t1,.... A minimum
POLYMERS
of one value must be given. It is not necessary to
provide a value for every temperature point. A
place-holding comma must be supplied for every
value skipped. For vapor pressures and viscosities,
ln(p) vs. 1/t, where t is absolute temperature, is used
for interpolation. For all others, linear pres vs. temp
is used.
PRO/II also predicts the (pseudo) critical properties of polymers

based on the molecular weight only. This method is an extension of
a correlation originally developed by Tsonopoulos and Tan1 for nor-
mal alkanes (from methane to polyethylene).
Reference
[1] C. Tsonopoulos and Z. Tan, 1993, The Critical Constants of
Normal Alkanes from Methane to Polyethylene II. Application of
the Flory Theory, Fluid Phase Equilibria, 83:127-138.

Example P4-1: WFE with Pseudocomponent Distribution
This example tests the wiped film evaporator (WFE) model with a
BATCH
polymer pseudocomponent distribution. The WFE unit operation

model requires the transport properties.
TITLE PROJECT=WFE, PROBLEM=PS, USER=SIMSCI, DATE=Jan-07
DESC Test WFE with POLYMER PSEUDOCOMPONENT DISTRIBUTION
PRINT STREAM=ALL, RATE=WT, FRACTION=WT
DIMENSION SI
SEQUENCE PROCESS
SEGMENT DATA
SEGMENT A, STYR1, FILL=VANKREVLEN
STRUCTURE(VANKRE) A,144(1),4(1)
COMPONENT DATA
LIBID 2, STYRENE/3,EBZN/4,BOBZ, BANK=SIMSCI
POLYMERS
POLY 1, PSTYR
PCOMPOSITION 1,1(A)
PHASE VLS=1
MWAVG 1,31000
ATTRIBUTE COMP=1, KINETICS=FR,&

MWD= 1000, 3000, 5000, 7000, 10000, &
30000, 40000, 60000, 80000, 100000, &
120000,150000,200000, 300000,400000, &
500000,600000, &
MMWD=MU0,MU1,MU2
VISCOSITY(V,K,PAS) TABULAR= 300, 500/ &
1,0.001,0.001
VISCOSITY(L,C,PAS) TABULAR= 30,100,500/ &
1,500,450,300
CONDUCTIVITY(V,K,W/MK) TABULAR=300,500/1,1,1
THERMODYNAMIC DATA
METHOD SYSTEM=ALM, TRANSPORT=PURE, &
DIFFUSIVITY=DATA, KVAL(VLE)
ALME 3,A, 0.022,11.02
ALMC A,1.338
DIFFUSIVITY(L)
DIFDATA(K) 1,2,1E-8
DIFDATA(K) 1,3,5E-8
DIFDATA(K) 1,4,1E-9
STREAM DATA
PROPERTY STREAM=F1, TEMPERATURE=343, &
PRESSURE=1013.3, &
COMPOSITION(WT,KG/M)=2,10.4188/4,0.15
UNIT OPERATIONS
PCSTR UID=REACTOR_1, NAME=1st PS REACTOR
FEED F1
PRODUCT P1

IPARM =1,1,1,0,79,0,1,1,1,3,1,2,0,3,4,0,0,0,0,0,0
RPARM=69900,200,0,0,0,355,0,0.5,0,0,0,0,1, &
0,0,0,0,0
SUPPLEMENTAL = 1,1.58E15/128870/0/0/1.05E7/&
29540/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/1.05E7/29540/0/0/0/0/0/0/0/0/0/0/0/0/ &
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/1.26E9/7030/0/0/0/&
POLYMERS
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0
FLASH UID=F2
FEED P1
PRODUCT V=V2, L=L2
ISO TEMPERATURE=400, PRESSURE=0.666
CONTROLLER UID=CN1
SPEC STREAM=L2,FRACTION(WT), COMP=2,4, VALUE=0.02
VARY FLASH=F2, TEMP
CPARAMETER IPRINT, NOSTOP
WFEV UID=WFE1
FEED L2
PRODUCT L3,V3
IPARM =1,,,1,,2,4
RPARM =3,0.75,0.2,,,,,,,, &
500,,,,,,,,,0.0001,1E-5,400
END

Entering Molecular Weight Distributions
To enter the molecular weight distribution:
BATCH
 Click the Component Properties button on the tool bar, or

select Input/Component Properties from the menu bar, to dis-
play the Component Properties dialog box (Figure P4-1).
Figure P4-1: Component Properties Dialog Box
POLYMERS

 Click Distribution Functions... in the Polymer Properties section
to display the Distribution Functions for Components dialog
box (Figure P4-2). All the polymer components selected earlier
under the Component Selection dialog box will be available in
the drop-down lists.
Figure P4-2: Distribution Functions for Components Dialog Box
POLYMERS
To enter the distribution data for a polymer component:
 Select the desired component from the drop-down list.
 Select the kinetic type of the component (Free Radical, Ziegler-
Natta, or Step Growth).
 Click Enter Data... to display the Distribution Function Data
dialog box for the selected component (Figure P4-3).
Figure P4-3: Distribution Function Data Dialog Box

 Select the desired distribution names from the list boxes in the
first column.
BATCH
 For Discrete Mol. Wt. Cuts, enter the molecular weight ranges
by clicking Enter Data.... The Molecular Weight Distribution
dialog box appears (Figure P4-4).
Figure P4-4: Molecular Weight Distribution Data Dialog Box
POLYMERS
 For the moments of various distributions, specify the number of

moments, and enter the names of the moments by selecting
them from the drop-down list box (optional task). The moment
names default to M0, M1, M2, etc., and up to five moments can
be selected (M0 through M4).

Chapter P5
Supplying Polymer Stream Data
In addition to the composition of the polymer components, defined

streams containing polymers will also require input of MWD mole
fraction or weight fraction values to be interpreted in terms of
moments that might be submitted to a polymer reactor or other unit
operation process. You can also supply values of various moments,
size distributions, and general attributes that are defined in the poly-
mer component attributes. PRO/II will calculate the SCHULZ-
POLYMERS
FLORY distribution from bulk moments generated from a polymer
reactor model or input by the user. PRO/II will also calculate the
number average molecular weight, weight average molecular
weight, and polydispersity index from the moments for various
chain types (e.g., live, dead, and bulk).
PRO/II provides the polymer characterization conversion utility to
establish a useful translation between the molecular weight distribu-
tion and the moments of the molecular weight distribution. You can
supply a molecular weight distribution to be interpreted in terms of
moments, or you can supply moments of a molecular weight distri-
bution to be converted to amounts of pseudocomponents that define
the molecular weight distribution.
Values of moments of distributions with respect to other parameters
of interest may also be input in the stream data section; e.g. moment
attributes for branch chain length for a branched polymer. Moments
or properties defined as general attributes in the component data
section will also have their values entered here. Mole fraction and
weight fraction attributes for the different types of polymer chains
as fractions of the total chains can also be input for the polymer in
the stream. If there are polymer solids in the stream and PSD attri-
butes have been defined for the solid components, then PSD weight
fractions can be input for the solid polymers.

Keyword Summary
Stream Polymers (optional)
BATCH
MWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC

or PBC or DA or DB or DAA or DBB,
L or S, M or WT),
COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
MMWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC

or PBC or DA or DB or DAA or DBB,
L or S, unit),
COMPONENT = i, j,
PCFRAC(L or S, M or WT) COMPONENT = i, j, &

POLYMERS
DATA = value1, value2, value3, value4, &

value5, value6, value7, value8, &
value9, value10, value11, value12, &
value13, {STREAM = sid}
MBCL(P or D, L or S, unit) COMPONENT = i, j, &

MTTB(P or D, L or S, unit) COMPONENT = i, j, &

MDSD COMPONENT = i, j, &

PSD COMPONENT = i, j, &

GENERAL COMPONENT = i, j,
Polymer-specific data in the stream data section include composi-
tions of polymer components in the streams. This input is the same
as that for the regular components. Polymer solids in streams are
also specified using the same input as regular or low molecular
weight solids, i.e., using the SOLID and PSD statements.
Values of moments of distributions of polymer components with
respect to various parameters can be input as attributes. The
moments are defined in Chapter 4. For distributions that are func-
tions of the topology of the polymer, moments of live chains P and
dead chains D can be input for polymer components in the liquid (L)
and solid (S) phase in the stream.
P5-2 Supplying Polymer Stream Data

You can provide data for either the molecular weight distribution
through the MWD statement or for the moments of the molecular
weight distribution through the MMWD statement. Data input is not
allowed simultaneously for both of the MWD and MMWD statements.
The polymer characterization conversion utility will convert one
characterization into another. For instance, if mole or weight frac-
tion values are input for the MWD attributes, PRO/II will convert the
MWD attributes into the MMWD attributes (e.g., zero order, first
order, and second order). Conversely, if the moments are input for
the MMWD attributes, the MWD attribute values will be calculated and
then will be converted into the amounts of pseudocomponents that
define the molecular weight distribution.
The PCFRAC attribute refers to the mole or weight fraction compo-
POLYMERS
sitions of the polymer chain types. These attributes can be input for
polymer components in the liquid (L) and solid phase (S) in the
stream. The PCFRAC attribute input is required for the MMWD
attributes and will be calculated for the MWD attributes.
For monomer emulsion/suspension in the stream, the distribution of
the monomer droplet size must be specified. Finally, values of gen-
eral attributes can also be entered here.
The moments or attributes of the polymer component in the stream
can be accessed and modified by the polymerization reactors and
unit operations in the flowsheet, although the type of the distribu-
tion function will continue to remain the same (or undefined)
throughout the flowsheet.
All data entered from POLYMER STREAM ATTRIBUTES affect all
components in sequence from component i through j. If j is not
given, only component i is activated. Separate statements are
allowed for each component having these attributes declared in
COMPONENT DATA. These attributes are listed below.

MWD or MMWD Attributes for Free Radical (FR) Polymerization
(Monomers are up to two, A and B)
BATCH
PA refers to live chains terminating in single type A bond

PB refers to live chains terminating in single type B bond
PC not used for FR
PAA refers to live chains terminating in double type A bonds
PBB refers to live chains terminating in double type B bonds
PCC not used for FR
PAB not used for FR
PAC not used for FR
PBC not used for FR
POLYMERS
DA refers to dead chains terminating in single type A bond

DB refers to dead chains terminating in single type B bond
DAA refers to dead chains terminating in double type A bonds
DBB refers to dead chains terminating in double type B bonds
MWD or MMWD Attributes for Coordination Complex (ZN) Polymerization

(Monomers are up to two, A and B)
PA refers to live polymer chain bounded by monomer A at site 1
PB refers to live polymer chain bounded by monomer A at site 1
PC refers to dead polymer chain generated from site 1
PAA refers to live polymer chain bounded by monomer A at site 2
PBB refers to live polymer chain bounded by monomer A at site 2
PCC refers to dead polymer chain generated from site 2
PAB refers to live polymer chain bounded by monomer A at site 3
PAC refers to live polymer chain bounded by monomer A at site 3
PBC refers to dead polymer chain generated from site 3
DA refers to live polymer chain bounded by monomer A at site 4
DB refers to live polymer chain bounded by monomer A at site 4
DAA refers to dead polymer chain generated from site 4
DBB not used for ZN

MWD or MMWD Attributes for Step Growth (SG) Polymerization
(Monomers are up to three, A, B, and, C)
PA refers to monofunctional live chains terminating in A
PB refers to monofunctional live chains terminating in B
PC refers to monofunctional live chains terminating in C
PAA refers to bifunctional live chains terminating in A and A
PBB refers to bifunctional live chains terminating in B and B
PCC refers to bifunctional live chains terminating in C and C
PAB refers to bifunctional live chains terminating in A and B
PAC refers to bifunctional live chains terminating in A and C
POLYMERS
PBC refers to bifunctional live chains terminating in B and C
DA refers to dead chains
DB not used for SG
DAA not used for SG
DBB not used for SG
PCFRAC Attributes for Free Radical (FR) Polymerization

(Monomers A and B)
value1 fraction of live chains terminating in single type A bond
value2 fraction of live chains terminating in single type B bond
value3 zero, not used for FR
value4 fraction of live chains terminating in double type A bonds
value5 fraction of live chains terminating in double type B bonds
value10 fraction of dead chains terminating in single type A bond
value11 fraction of dead chains terminating in single type B bond
value12 fraction of live chains terminating in double type A bonds
value13 fraction of live chains terminating in double type B bonds

PCFRAC Attributes for Coordination Complex (ZN) Polymerization
(Monomers A and B)
BATCH
value1 fraction of live polymer chain bounded by monomer A at site 1

value2 fraction of live polymer chain bounded by monomer B at site 1
value3 fraction of dead polymer chain generated from site 1
POLYMERS

value13 not used for ZN
(PCFRAC Attributes for Step Growth (SG) Polymerization

(Monomers A, B, and C)
value1 fraction of monofunctional live chains terminating in A
value2 fraction of monofunctional live chains terminating in B
value3 fraction of monofunctional live chains terminating in C
value4 fraction of bifunctional live chains terminating in A and A
value5 fraction of bifunctional live chains terminating in B and B
value6 fraction of bifunctional live chains terminating in C and C
value7 fraction of bifunctional live chains terminating in A and B
value8 fraction of bifunctional live chains terminating in A and C
value9 fraction of bifunctional live chains terminating in B and C
value10 fraction of dead chains
value11 zero, not used for SG

Example P5-1: Component and Stream Attribute Input
This example illustrates the input of the polymer component attri-
butes and the polymer stream attributes. This sequence converts the
input MWD attributes into the MMWD attributes for the kinetics of free
radical polymerization. The PCFRAC attributes will be calculated.
TITLE PROJ=MWD, PROB=TEST, USER=SIMSCI, DATE=1997
DIME METRIC
PRINT RATE=WT, INPUT=ALL
SEGMENT DATA
SEGMENT A, STY1/B, MMAC, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/B, 5(1), 252(1), 9(1)
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
POLYMERS
MWAVG 1, 8578.6
$ POLYMER COMPONENT ATTRIBUTES
ATTRIBUTE COMPONENT = 1, KINETICS = FR, &
MWD = 1000, 2000, 5000, 7000, 10000, 15000, 20000, &
MMWD = MU0, MU1, MU2, MU3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM
KVALUE
ALMC A, 1.338/B, 1.441
ALME 2,A, 0.022,11.02/2,B, 0.010, 16.36
STREAM DATA
PROP STRM=FEED, TEMP(K)=298.15, PRES(ATM)=1, &
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES
$ COMPONENT 1 (TWO SEGMENTS A AND B)
MWD(PA,L) COMP= 1, DATA = 25,10, 5,30,50,20,40, NORM, STREAM = FEED

MWD(PB,L) COMP= 1, DATA = 5,30,15,25,50,20,10, NORM, STREAM = FEED
MWD(PAA,L) COMP= 1, DATA = 35, 5,20,30,40,15,25, NORM, STREAM = FEED
MWD(PBB,L) COMP= 1, DATA = 15,40,30,20,10, 5,25, NORM, STREAM = FEED
MWD(DA,L) COMP= 1, DATA = 25,35,45,20,15,50,30, NORM, STREAM = FEED
MWD(DB,L) COMP= 1, DATA = 15,25,35,10, 5,40,20, NORM, STREAM = FEED
MWD(DAA,L) COMP= 1, DATA = 5,45,55,25,20,10,30, NORM, STREAM = FEED
MWD(DBB,L) COMP= 1, DATA = 25,30,20,40,10,50,15, NORM, STREAM = FEED
MBCL(P,L) COMP = 1, DATA = 1, 1000, 100000, STREAM=FEED

MTTB(P,L) COMP = 1, DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1, DATA = 5, 5000, 500000, STREAM=FEED

MTTB(D,L) COMP = 1, DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1, DATA = 30, 30, 40, STREAM=FEED

PSD COMP = 1, DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1, DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=298.15, PRES(ATM)=1
END

Example P5-2: Component and Stream Attribute Input
This example shows the input of the polymer component attributes
BATCH
and the polymer stream attributes. This sequence converts the input
MMWD attributes into the amounts of the pseudocomponents that
define the molecular weight distribution. The input PCFRAC attri-
butes are required for the conversion.
TITLE PROJ=MMWD, PROB=TEST, USER=SIMSCI, DATE=1997
DIME METRIC
PRINT RATE=WT, INPUT=ALL
SEGMENT DATA
SEGMENT A, STY1/B, MMAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/ &
B, 5(1), 252(1), 9(1)
POLYMERS
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
MWAVG 1, 11276
$ POLYMER COMPONENT ATTRIBUTES
ATTRIBUTE COMPONENT = 1, KINETICS = FR, &

MWD = 1000,2000, 5000, 6000,8000,10000,&
12000,15000,20000,50000,70000,100000,&
MMWD = MU0, MU1, MU2, MU3
MBCL = BCL0, BCL1, BCL2, &
MTTB = TTB0, RHO1, RHO2, &
MDSD = 10, 100, 1000, &
PSD = 20, 200, 2000, &
GENERAL = 3, &
GNAME = ATT1, ATT2, ATT3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM

KVALUE
ALMC A, 1.338/ B, 1.441
ALME 2, A, 0.022, 11.02/ &
2, B, 0.010, 16.36
STREAM DATA
PROP STRM=FEED, TEMP(K)=300, PRES(ATM)=1, &
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES

$ COMPONENT 1 (TWO SEGMENTS A AND B)
MMWD(PA,L) COMP = 1, &
DATA = 0.1,10,2500,1000000, STREAM = FEED
MMWD(PB,L) COMP = 1, &
DATA = 0.2,20,3500,2000000, STREAM = FEED
MMWD(PAA,L) COMP = 1, &
DATA = 0.3,30,4500,3000000, STREAM = FEED
MMWD(PBB,L) COMP = 1, &
DATA = 0.4,40,5500,4000000, STREAM = FEED
MMWD(DA,L) COMP = 1, &
DATA = 0.5,50,6500,5000000, STREAM = FEED
MMWD(DB,L) COMP = 1, &
DATA = 0.6,60,7500,6000000, STREAM = FEED
MMWD(DAA,L) COMP = 1, &
DATA = 0.7,70,8500,7000000, STREAM = FEED
POLYMERS
MMWD(DBB,L) COMP = 1, &
DATA = 0.8,80,9500,8000000, STREAM = FEED
PCFRAC(L,WT)COMP=1, &
DATA= 0.1, 0.2, 0.0, 0.05, 0.05, &
0.0, 0.0, 0.0, 0.0, 0.1, &
0.1, 0.1, 0.1, NORM, STREAM=FEED
BCL(P,L) COMP = 1, &
DATA = 1, 1000, 100000, STREAM=FEED
MTTB(P,L) COMP = 1, &
DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1, &
MTTB(D,L) COMP = 1, &
DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1, &
PSD COMP = 1, &
DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1 &
DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=300, PRES(ATM)=1
END

Entering Stream Polymer Data
Stream data for the polymer components can be supplied for the
BATCH
various distributions that were selected previously in the Compo-

nent Property section of Chapter P4, Supplying Polymer Pure Compo-
nent Property Data.
 Double-click on the desired stream to display the Stream Data

dialog box (Figure P5-1).
Figure P5-1: Stream Data Dialog Box
POLYMERS
 Click Stream Polymer Data... to display the Polymer Distributions

dialog box (Figure P5-2). The distribution data must be sup-
plied on a component-by-component basis. Only those compo-
nents with distributions that were specified in the Component
Properties section in Chapter P4 will be available in the drop-
down lists.

Figure P5-2: Polymer Distributions Dialog Box
POLYMERS
 Select the desired component, and click Enter Data... under MW/
Moment Distributions to display the Polymer Component
Distributions dialog box (Figure P5-3), in which the various
distribution types can be selected. Only those distributions that
were selected for the current component in the Component
Properties section in Chapter 4 will be displayed in this dialog
box.
Figure P5-3: Polymer Component Distributions Dialog Box

Also, data for only one of Molecular Weight Distribution or
Moments of Molecular Weight Distribution can be supplied. If one
is selected, the other will not be available.
BATCH
 After selecting the distributions, click Enter Data... under

Additional Data to supply data for various chain types of the
polymer component in the Polymer Distribution Data dialog
box (Figure P5-4). Note that the chain type available will
depend on the polymer type (homopolymer or copolymer) and
the selected kinetic type (free radical, Ziegler-Natta, or step
growth).
Figure P5-4: Polymer Distribution Data Dialog Box
POLYMERS
 Click Enter Data... under Additional Data to supply the data for
that chain type.
If Discrete Mol. Wt. Cuts (MWD) is selected, supply the molecular
weight fractions (Figure P5-5).

Figure P5-5: Discrete Mol. Wt. Cuts Dialog Box
POLYMERS
 If Moments of Mol. Wt. Distribution (MMWD) is selected, sup-
ply the values for the moments for the selected chain type and
the chain type fraction (PCFRAC) (Figure 5-6). Data can be sup-
plied for liquid and/or solid phase.

Figure P5-6: Moments of Mol. Wt. Distribution Dialog Box
BATCH
POLYMERS

Chapter P6
Stream Output Report Options
By default, the weight rates of the individual polymer pseudo-com-
ponents (which result from the MWD attributes given for the poly-
mer) are printed in the Stream Weight Component Rates section of
the Stream Summary output. By using the optional PWRATE key-
word on the PRINT statement in the General Data category of input,
the weight rate of the TOTAL polymer is printed instead.
Also by default, the polymer characterization conversion utility is
activated for a simulated system containing polymers, and the con-
POLYMERS
verted results either for the MWD attributes or for the MMWD attributes
will be printed out in the stream output. By using the optional
PCONV keyword on the PRINT statement in the General Data cate-
gory of input, the polymer characterization conversion utility is dis-
abled.
Keyword Summary
PRINT …, PWRATE, PCONV
PWRATE This optional keyword specifies that the rate (on a weight
basis) of the total polymer component be printed in the
Stream Component Rates section of the output report.
PCONV This optional keyword disables the polymer characterization

conversion utility that converts one characterization (e.g. the
MWD attributes or the MMWD attributes) into another.
Typical Usage
TITLE
DIME METRIC
PRINT RATE=WT, INPUT=ALL, PWRATE, PCONV …

Entering PWRATE and PCONV
To enter PWRATE:
BATCH
 Select Output/Report Format from the menu bar, and then

select Stream Properties to display the Stream Property Report
Options dialog box (Figure P6-1). By default, the Include Poly-
mer Pseudocomponent Flowrates option is checked, indicating
that the output report includes pseudocomponent flow rates.
Uncheck this box to obtain the total polymer component rate
(on a weight basis) in the Stream Component Rates section of
the output report.
Figure P6-1: Stream Property Report Options Dialog Box
POLYMERS
To toggle PCONV, the polymer characterization conversion:
P6-2 Stream Output Report Options

 Select Input/Miscellaneous Data from the menu bar to display
the Input Miscellaneous Data dialog box (Figure P6-2). By
default, the Polymer Consistency Check option is set to Yes. To
turn off the polymer characterization conversion utility, select
No in the drop-down list.
Figure P6-2: Input Miscellaneous Data Dialog Box
POLYMERS

BATCH
POLYMERS
P6-4 Stream Output Report Options

Chapter P7
Specifying the Thermodynamic
Method
In addition to the van Krevelen group contribution method for pre-

dicting thermophysical properties of polymers from structures of
segments, PRO/II also provides a set of superior polymer-specific
thermodynamic methods for phase equilibrium calculations for the
system containing polymers. These methods include the classical
POLYMERS
Flory-Huggins model (FLORY), the popular UNIFAC-Free Volume
model (UNFV), the Advanced Lattice Model (ALM) developed by
SIMSCI, and the two state-of-the-art polymer equations of state,
i.e., the Statistical Associating Fluid Theory (SAFT) and the
Perturbed Hard-Sphere-Chain (PHSC) Theory.
All these methods have been implemented in PRO/II using the seg-
ment approach. For the pure component parameters, data may be
input for non-polymer components (solvents) and for segments that
make up the polymers. The polymer component parameters will be
generated from the segment properties predicted by the van
Krevelen method and segment compositions through input. For the
binary parameters, data can be input for non-polymer component
pairs (solvent-solvent), solvent-segment pairs, and segment-
segment pairs.
PRO/II automatically uses a new polymer flash algorithm devel-
oped by SIMSCI when a polymer-specific method is specified in
the input.

Advanced Lattice Model (ALM)
The advanced lattice model (ALM) is used to predict VLE and
BATCH
VLLE phase behavior for mixtures containing polymers. ALM is a

segment-based activity coefficient model and is especially useful
for polymer solutions and polymer blends. It gives much more
accurate VLE and LLE correlations than the commonly used Flory-
Huggins model.
Typical Usage
…
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
COMPONENT DATA
LIBID 1,BENZENE
POLYMERS
POLYMER 2, PIB
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=ALM
…
Properties predicted by ALM methods K-values

Required pure component properties* Molecular weight
Liquid molar volume
Two liquid phase behavior VLLE Supported
* Automatically supplied by PRO/II for library and petroleum
components. Must be supplied or estimated using the van Krevelen
group contributions method for polymer components.
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=ALM, &
PHI=IDEAL, {HENRY},…
or
METHOD KVALUE(VLE and/or LLE or VLLE)=ALM, &
SYSTEM Selects a combination of consistent thermodynamic

property generators. When SYSTEM=ALM is chosen,
ALM K-values, IDEAL enthalpies, IDEAL liquid den-
sities, and IDEAL vapor densities are the defaults.
P7-2 Specifying the Thermodynamic Method

KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available with
the ALM method. The VLLE option automatically
selects both. See Section 2.1.7 of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual
(CTDIM) for more details on liquid-liquid equilibrium
calculations.
PHI Selects the option used to calculate pure component

and mixture vapor phase fugacity coefficients (φi). A
vapor fugacity method should generally be selected for
high pressure applications. The options are the equa-
tions of state methods SRK, PR, SRKM, PRM, SRKH,
PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and UNI-
POLYMERS
WAAL (see Section 2.4 of the SIMSCI CTDIM and
HOCV (the Hayden-O’Connell method), TVIRIAL
(the Truncated Virial method), and the IDIMER
method. See sections 2.5.12, 2.5.13, and 2.5.14,
Hayden-O’Connell, Vapor Fugacity, Truncated Virial
Vapor Fugacity, and IDIMER Vapor Fugacity, of the
SIMSCI CTDIM for details on these last three options.
The default is PHI=IDEAL.
HENRY Selects Henry’s Law data (either user-supplied or from

databanks) to model dissolved gases in a liquid solu-
tion. See Section 2.5.11, Henry’s Law for Non-
condensable Components, of the SIMSCI CTDIM for
details.
Note: A heat of mixing option, HMIX, is available for the

enthalpy method selected. See Section 2.5.15, Redlich-Kister,
Gamma Heat of Mixing, of the SIMSCI CTDIM for details on the
use of this option.

K-Value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON
BATCH
ALME a, b, e1, e2, e3/…

ALMC a, c/…
POYNTING Selects whether to apply the Poynting correction to

fugacities of components in the liquid phase. The
default is OFF unless a PHI method is selected, in
which case the default is ON.
ALME Used to introduce binary energetic parameters. The

default values are zero. The temperature-dependent
energy parameter is calculated as:
e
ε r = e 1 + ----2 + e 3 ln T
T
POLYMERS
ALMC Used to introduce the size correction factor c. The

default value is 1.
α or β Non-polymer component (solvent) number or segment

type letter.
Table P7-1 lists values of c for ALMC, and e1, and e2 for ALME
(e3 = 0) for homopolymer segment-solvent component pairs.
Table P7-1: Parameters for AML Methods

Segment Name Homopolymer Solvent ALM
Symbol
c e1 e2
Butadiene PBD Benzene 1.370 0.017 11.12
Carbon tetrachloride 2.506 0.081
Chloroform 1.117 0.008
Cyclohexane 1.479 0.031 4.851
Dichloromethane 2.528 0.140
Ethylbenzene 0.710 -0.180 67.10
n-Hexane 1.663 0.058
n-Nonane 0.310 -0.258 88.54
Ethylene LDPE n-Butane 1.119 -0.488 192.7
1-Butene 0.554 -0.613 214.6
n-Heptane 1.837 0.007 41.82
n-Hexane 0.856 -0.210 90.55

Symbol
c e1 e2
Isobutane 0.942 -0.302 127.2
Isobutylene 0.744 -0.575 209.2
n-Pentane 0.894 -0.103 68.69
Dimethylsiloxane PDMS Benzene 0.971 -0.039 30.21
Chloroform 1.086 0.078
Dichloromethane 0.986 0.113
n-Heptane 0.956 -0.041 86.27
POLYMERS
n-Hexane 1.032 -0.015 13.29
n-Nonane 0.726 -0.011 8.890
n-Octane 2.022 -0.056 24.92
n-Pentane 1.119 0.035
Toluene 1.022 -0.037 24.52
2,2,4- 1.986 0.048 -8.317
Trimethylpentane
Isobutylene PIB Benzene 1.019 -0.116 56.28
Cyclohexane 0.903 0.032
n-Pentane 1.223 0.033 11.04
Methyl PMMA Toluene 1.559 0.066
Methacrylate
i-Propylene i-PP Dichloromethane 0.229 0.160
Decene-1 PD Toluene 1.263 0.054
Dodecene-1 PDD Toluene 0.544 0.005
Heptene-1 PH Toluene 1.165 0.052
Octadecene-1 POD Toluene 0.387 0.006
p-Bromostyrene PpBrS Toluene 0.943 0.062
p-Chlorostyrene PpClS Toluene 1.172 0.065
p-Methylstyrene PpMS Toluene 1.187 0.050
Styrene PS Acetone 0.677 -0.001 27.48
Benzene 1.338 0.022 11.02
n-Butyl acetate 1.044 0.061
Carbon disulfide 0.990 -0.340 153.6

BATCH
Symbol
c e1 e2
Carbon tetrachloride 1.053 -0.647 200.6
Chloroform 2.182 0.156 -22.52
Cyclohexane 0.711 0.141 -28.75
1,4-Dioxane 0.463 0.395 -120.9
Ethylbenzene 0.701 -0.062 26.38
Nitromethane 1.103 0.218
n-Nonane 0.760 -0.061 40.00
n-Propyl acetate 1.124 0.006 16.24
POLYMERS
di-n-Propyl ether 0.816 0.053

Toluene 0.770 -0.135 45.70
1,2,4- 0.809 -0.211 94.74
Trimethylbenzene
m-Xylene 2.272 0.071 -0.807
Tetrahydrofuran PTHF 1,4-Dioxane 1.283 0.052
Vinyl Acetate PVAC Benzene 1.441 0.010 16.36
Vinyl acetate 1.861 0.071
Vinyl Chloride PVC 1,4-Dioxane 1.769 0.096
di-n-Propyl ether 2.231 0.088
Tetrahydrofuran 2.072 0.070
Toluene 2.648 0.095

Example P7-1: ALM with Polyvinylacetate and Benzene
This example uses the ALM model to calculate the flash and BVLE
for a binary mixture containing benzene and polyvinylacetate
(PVAC). The van Krevelen group contribution method (VANKRE)
is used to predict the properties of the polymer segment, and the
properties of the polymer are calculated from the segment proper-
ties and the segment composition.
TITLE PROB=ALM
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1), 9(1)
POLYMERS
$
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PHASE VLS=2
MWAVG 2, 48200
$
THERMODYNAMIC DATA
METHOD SYSTEM = ALM
KVALUE
ALME 1,A, 0.010,16.36
ALMC A, 1.441
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 298.15, PRES =10.0, &
COMP = 1, 0.93166/2, 0.06834
$
UNIT OPERATION
FLASH UID=FL1
FEED F1
PRODUCT V=V1, L=L1
BUBBLE TEMP=298.15
BVLE UID=BVLE1
EVAL COMP=1,2, TEMP(K)=298.15, &
XVALUES=0.95,1.0, POINTS=51, PLOT=GAMMA
END

UNIFAC Free Volume K-Value Method
The UNFV free volume data method is designed to model both
BATCH
VLE and VLLE for polymer solutions. It should not be used for
non-polymer systems.
Typical Usage
…
SEGMENT DATA
STRUCTURE(VANKRE) A, 16(1),4(1)
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MWAVG 2, 10000
POLYMERS
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
…
Note: When using the UNFV method for polymer systems, UNI-
FAC structural groups must be defined for the polymer segments
via a STRUCTURE(UNIFAC) statement under SEGMENT DATA.
For more information on non-polymer components, see Section
1.9, UNIFAC Structural Groups, of the SIMSCI Component and
Thermodynamic Data Input Manual.
Properties predicted by UNFV K-values

Required pure component Molecular weight
properties* Liquid molar volume
van der Waals volume
Suggested application ranges Pressure up to 10 atm
Temperature 70 - 300 F
Two liquid phase behavior Freewater decant not supported
VLLE supported
group contributions method for polymer components.
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=UNFV, PHI=IDEAL, &
{HENRY},…
or

METHOD KVALUE(VLE and/or LLE or VLLE)=UNFV, &
SYSTEM Selects a combination of compatible thermodynamic

property generators. The available option is:
UNFV When SYSTEM=UNFV is chosen, UNFV
K-values, IDEAL vapor enthalpies, IDEAL liquid
enthalpies, IDEAL liquid densities, and IDEAL vapor
densities are the defaults.
KVALUE Selects the method for K-value calculations. Both

VLE and LLE K-value calculations are available with
the UNFV method. The VLLE option automatically
selects both. See Section 2.1.7, Vapor Liquid-Liquid
POLYMERS
Equilibrium Considerations, of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual for more
details on liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component

and mixture vapor phase fugacity coefficients (fi). A
vapor fugacity method should generally be selected for
high pressure applications. The options are the equa-
tions of state methods SRK, PR, SRKM, PRM, SRKH,
PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and UNI-
WAAL (see Section 2.4 of the SIMSCI Component and
Thermodynamic Data Input Manual) and HOCV (the
Hayden-O’Connell method), TVIRIAL (the Trun-
cated Virial method), and the IDIMER method. See
Sections 2.5.12, 2.5.13, and 2.5.14, Hayden-O’Connell
Vapor Fugacity, Truncated Virial Vapor Fugacity, and
IDIMER Vapor Fugacity, of the SIMSCI Thermody-
namic Data Input Manual for details on the last three
options. The default is PHI=IDEAL.
HENRY This option selects Henry’s Law data (either user-sup-

plied or from databanks) to model dissolved gases in a
liquid solution. See Section 2.5.11, Henry’s Law for
Non-condensable Components, of the SIMSCI Ther-
modynamic Data Input Manual for further details.
A heat of mixing option, HMIX, is available for the enthalpy method

selected. See Section 2.5.15, Redlich-Kister, Gamma Heat of Mixing,
of the SIMSCI Thermodynamic Data Input Manual for further
information on using this option.

Example P7-2: UNIFAC with Polyisobutylene and Benzene
This example uses the UNIFAC free volume method to perform a
BATCH
VLE flash calculation for a binary mixture containing benzene and

polyisobutylene. The van Krevelen group contribution method
(VANKRE) is used to predict properties of the polymer segment,
and the UNIFAC-FV model (UNFV) is used as the thermodynamic
method for calculating activity coefficients of mixtures. You need
to provide information only on polymer molecular weight and seg-
ment structures for both the van Krevelen and UNIFAC group con-
tribution. The two methods are distinguished by different identifiers
VANKRE and UNIFAC, respectively, in the STRUCTURE statement.
TITLE PROB=UNFV
DIMENSION SI
PRINT INPUT=FULL, RATE=WT, FRACTION=WT
POLYMERS
$
SEGMENT DATA

STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 400, PRES =10, &
COMP = 1, 0.9/2, 0.1
$
UNIT OPERATION
FLASH UID=FL1, NAME=FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 400, PRES = 10
$
END

Flory-Huggins Liquid Activity Method
The Flory-Huggins liquid activity method is used to predict VLE
and VLLE phase behavior. This method does not support free water
decant.
The Flory-Huggins liquid activity method is generally useful for
mixtures of components that differ vastly in size, e.g., polymer
solutions. This method should be used only for modeling polymer
systems. See the PRO/II Reference Manual for additional informa-
tion.
Typical Usage
…
POLYMERS
SEGMENT DATA
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=FLORY
Properties predicted by FLORY methods K-values

Required pure component properties* Molecular weight
Liquid molar volume
Solubility parameter
Two liquid phase behavior Freewater decant not
supported
VLLE supported
group contribution method for polymer components.

METHOD Statement
METHOD SYSTEM(VLE or VLLE)=FLORY,
BATCH
PHI=IDEAL,{HENRY},…
or
METHOD KVALUE(VLE and/or LLE or VLLE)=FLORY,
SYSTEM Selects a combination of compatible thermodynamic property

generators. When SYSTEM=FLORY is chosen, FLORY K-values,
IDEAL vapor enthalpies, IDEAL vapor densities, IDEAL liquid
densities, and IDEAL liquid enthalpies are the defaults.
KVALUE Selects the method for K-value calculations. Both VLE and LLE
K-value calculations are available with the Margules method.
The VLLE option automatically selects both. See Section 2.1.7,
Vapor-Liquid-Liquid Equilibrium Considerations, of the SIMSCI
POLYMERS
Thermodynamic Data Input Manual for more details on liquid-

liquid equilibrium calculations.
PHI Selects the option used to calculate pure component and mixture
vapor phase fugacity coefficients (φi). A vapor fugacity method
should generally be selected for high pressure applications. The
options are the equations of state methods SRK, PR, SRKM,
PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and
UNIWAAL (see Section 2.4 of the SIMSCI Thermodynamic Data
Input Manual) and HOCV (the Hayden-O’Connell method),
TVIRIAL (the Truncated Virial method), and the IDIMER
method.
See Sections 2.5.12, 2.5.13, and 2.5.14, Hayden-O’Connell Vapor Fugacity,

Truncated Virial Vapor Fugacity, and IDIMER Vapor Fugacity, of the SIMSCI
Thermodynamic Data Input Manual for details on these last three options. The
default is PHI=IDEAL.
HENRY This option selects Henry’s Law data (either user-supplied or

from databanks) to model dissolved gases in a liquid solution.
See Section 2.5.11, Henry’s Law for Non-condensable Compo-
nents, of the SIMSCI Component and Thermodynamic Data Input
Manual for further details.
Note: A heat of mixing option, HMIX, is available for the enthalpy method
selected. See Section 2.5.15, Redlich-Kister, Gamma Heat of Mixing, of the SIM-
SCI Thermodynamic Data Input Manual for further information on the use of
this option.

K-Value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON
CHI or FLORY α, β, a1, a2/…
POYNTING Selects whether to apply the Poynting correction to

fugacities of components in the liquid phase. The
default is OFF unless a PHI method is selected, in
which case the default is ON.
CHI or FLORY Allows entry of the binary temperature-dependent χ

parameters for the Flory-Huggins liquid activity coef-
ficient method.
The χ parameter is calculated as:
POLYMERS
a
χ = a 1 + ----2-
T
Missing χ parameters are estimated from solubility
parameters.
The χ binary parameters for polymer segment-solvent systems are

given in Table P7-2.
Table P7-2: Parameters for Flory-Huggins Methods
a1 a2
Butadiene PBD Benzene -0.115 124.3

Carbon 0.101
Tetrachloride
Chloroform -0.004
Cyclohexane 0.109 41.23
Dichloromethane 0.295
Ethylbenzene -1.865 819.6
n-Hexane 0.419
n-Nonane -2.309 1124
Ethylene LDPE Butane -4.684 1892
1-Butene -4.609 1844
n-Heptane 0.087 507.4
n-Hexane -1.057 784.5
Isobutane -2.433 1168

a1 a2
BATCH
Isobutylene -4.639 1849

n-Pentane -0.410 626.9
Dimethylsilox PDMS Benzene 0.151 143.5
ane
Chloroform 0.646
Dichloromethane 0.878
n-Heptane -0.891 229.6
n-Hexane 0.345 13.57
n-Nonane 0.269 53.49
POLYMERS
n-Octane -2.301 654.3

n-Pentane 0.356
Toluene -0.197 210.1
2,2,4- 0.535 -238.1
Trimethylpentane
Isobutylene PIB Benzene -0.884 474.1
Cyclohexane 0.456
n-Pentane 0.683 30.58
Methyl PMMA Toluene 0.465
Methacrylate
i -Propylene i -PP Dichloromethane 2.182
Decene-1 PD Toluene 0.451
Dodecene-1 PDD Toluene 0.579
Heptene-1 PH Toluene 0.497
Octadecene-1 POD Toluene 0.802
p- PpBrS Toluene 0.724
Bromostyrene
p- PpClS Toluene 0.649
Chlorostyrene
p- PpMS Toluene 0.463
Methylstyrene
Styrene PS Acetone 0.729 65.14
Benzene 0.187 52.13
n-Butyl acetate 0.820

a1 a2
Carbon disulfide 2.444 1134

Carbon -6.331 1960
tetrachloride
Chloroform 1.792 -506.8
Cyclohexane 1.355 -185.9
1,4-Dioxane 3.120 -757.4
Ethylbenzene -0.185 223.8
Nitromethane 1.670
POLYMERS
n-Nonane -0.166 476.7
n-Propyl acetate 0.274 118.9
Di-n-Propyl ether 0.869
Toluene 0.418
1,2,4- 0.323
Trimethylbenzene
m-Xylene 0.385 -26.35
Tetrahydrofura PTHF 1,4-Dioxane 0.333
n
Vinyl Acetate PVAC Benzene 0.346 4.916
Vinyl acetate 0.261
Vinyl Chloride PVC 1,4-Dioxane 0.563
Di-n-Propyl ether 0.759
Tetrahydrofuran 0.074
Toluene 0.390
Any χ parameters for homopolymer segment-solvent interactions

not given in Table P7-2 may be derived from Brandrup, J. and
Immergut, E.H., 1989. Polymer Handbook, 3rd Ed., Wiley-Inter-
science, New York.

Example P7-3: Flory-Huggins with Polystyrene and Ace-
tone
BATCH
This example uses the Flory-Huggins method to perform polymer

VLE flash calculations for a binary mixture containing acetone and
polystyrene. The van Krevelen group contribution method
(VANKRE) is used to predict properties of the polymer component.
TITLE PROJ=FLORY-HUGGINS METHOD
DIMENSION SI
PRINT INPUT = FULL, RATE=WT, FRACTION=WT
$
SEGMENT DATA
COMPONENT DATA
LIBID 1, ACETONE
POLYMERS
POLYMER 2, POLYSTYRENE
PHASE LS = 2
MWAVG 2, 20000
$
THERMODYNAMIC DATA
METHOD SYSTEM = FLORY
KVALUE
CHI 1,A, 0.729, 65.14
$
STREAM DATA
PROPERTY STRM= F1, TEMP= 400, PRES= 10.,&
COMP(W) = 1, 0.9 / 2, 0.1
$
UNIT OP
FLASH UID = FL1, NAME = FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP=400., PRES=10
END

SAFT and PHSC Equations of State
The statistical associating fluid theory equation of state (SAFT) and
the perturbed hard-sphere-chain equation of state (PHSC) are used
to predict VLE and VLLE phase behavior for mixtures containing
polymers. They predict K-values, enthalpies, entropies, and densi-
ties. Compared to commonly-used cubic equations of state, both of
the SAFT and PHSC equations of state are applicable to a wider
variety of systems, including small and medium molecules, as well
as large substances like polymers, and a wider range of fluid condi-
tions including vapor, liquids, and supercritical regions.
The SAFT and PHSC equations of state are especially useful for
polymer solutions and polymer blends. They are also uniquely
POLYMERS
applicable to high-pressure polymer-supercritical solvent systems.
They are characterized by a much higher accuracy of VLE and LLE
correlation than any of the existing thermodynamic models for
polymer systems.
Typical Usage
…
SEGMENT DATA
STRUCTURE(VANKRE)A, 16(1), 4(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=SAFT or PHSC
Properties predicted by SAFT and K-values, enthalpies,

PHSC EOS entropies, vapor and liquid
densities
Required pure component properties* Segment size, energy, and
chain length parameters
Non-polymer component size,
energy, and chain length
parameters
Two liquid phase behavior VLLE Supported
* All required pure parameters must be supplied.

METHOD Statement
METHOD SYSTEM(VLE or VLLE)=SAFT or PHSC
BATCH
or
METHOD KVALUE(VLE and/or LLE or VLLE)=SAFT
or PHSC
SYSTEM When SYSTEM=SAFT or PHSC is chosen, K-values,

enthalpies, entropies, liquid densities, and vapor densi-
ties are assumed.
K-Value Data (required)

KVALUE (VLE or LLE or VLLE)
EPSILONα, value / …
SIGMA α, value / …
RMW α, value / …
POLYMERS
KIJ α,β, value / …
EPSILON Introduces the pure energy parameter ε.
SIGMA Introduces the pure size parameter σ.
RMW Introduces the pure chain length parameter. For non-

polymer components, it is the chain length r. For poly-
mer segments, it is the ratio of the chain length to the
molecular weight r/M.
KIJ Introduces the interaction binary parameters for seg-

ment-segment pairs, segment-solvent pairs, and non-
polymer component pairs. The default value is 0.
α or β Non-polymer component (solvent) number or segment

type letter.

Table P7-3 lists values of the SAFT and PHSC EOS parameters for
common solvents. Table P7-4 lists values of the SAFT and PHSC
EOS parameters for some homopolymer segments. Table P7-5 lists
values of the SAFT EOS binary parameter for some homopolymer
segment-solvent pairs.
.
Table P7-3: SAFT and PHSC Parameters for Common Solvents
SAFT PHSC
Name ε σ(Å) r ε σ(Å) r

kB(K) size chain kB(K) size chain
Argon 150.9 3.370 1 143.2 3.757 1
POLYMERS
Oxygen 126.7 3.480 1.235
Nitrogen 123.5 3.575 1 97.9 3.613 1.340
Carbon dioxide 216.1 3.171 1.417 153.7 2.774 2.859
Normal Alkanes
Methane 190.3 3.700 1 182.1 4.126 1
Ethane 191.4 3.238 1.941 206.3 3.916 1.694
Propane 193.0 3.162 2.696 219.0 3.998 2.129
Butane 195.1 3.093 3.458 231.3 4.085 2.496
Pentane 200.0 3.088 4.091 226.0 3.995 3.149
Hexane 202.7 3.083 4.724 235.6 4.084 3.446
Heptane 204.6 3.067 5.391 225.9 3.947 4.255
Octane 206.0 3.063 6.045 219.6 3.850 5.055
Nonane 203.6 3.063 6.883 217.3 3.804 5.748
Decane 205.5 3.020 7.527 212.7 3.723 6.616
Undecane 215.4 3.754 7.057
Dodecane 205.9 3.032 8.921 214.8 3.733 7.712
Tridecane 218.3 3.794 7.986
Tetradecane 209.4 3.076 9.978 213.7 3.682 9.023
Pentadecane 211.3 3.662 9.851
Hexadecane 210.7 3.068 11.209 214.2 3.703 10.168
Heptadecane 213.7 3.680 10.834
Octadecane 216.5 3.698 11.110
Nonadecane 216.1 3.718 11.659

SAFT PHSC
BATCH

Eicosane 211.3 3.043 13.940 212.1 3.633 12.925
Branched and Cyclic Alkanes
Isobutane 226.2 4.155 2.397
Isopentane 236.7 4.182 2.777
Neopentane 233.7 4.351 2.526
2,2-Dimethylbutane 247.7 4.368 2.849
2,3-Dimethylbutane 247.1 4.278 2.998
Cyclopentane 226.7 3.082 3.670 277.3 4.090 2.509
POLYMERS
Methylcyclopentane 223.3 3.141 4.142 267.2 4.153 2.902

Ethylcyclopentane 229.0 3.186 4.578 269.4 4.181 3.277
Propylcyclopentane 232.2 3.223 5.037 262.7 4.130 3.823
Cyclohexane 236.4 3.165 3.970 286.7 4.215 2.723
Methylcyclohexane 248.4 3.325 3.954 283.7 4.336 2.968
Ethylcyclohexane 243.2 3.314 4.656 282.4 4.306 3.392
Propylcyclohexane 238.5 3.281 5.326 272.3 4.230 3.969
Butylcyclohexane 234.3 3.238 6.060 264.5 4.151 4.580
Alkenes
Ethylene 212.1 3.494 1.464 196.8 3.839 1.609
Propylene 213.9 3.325 2.223 221.9 3.951 2.029
1-Butene 202.5 3.138 3.162 218.3 3.882 2.677
trans-2-Butene 233.9 3.984 2.504
cis-2-Butene 235.7 3.941 2.530
1-Pentene 237.1 4.087 2.828
1-Hexene 204.7 3.125 4.508 234.5 4.042 3.395
trans-Decaline 333.8 4.657 3.160
Aromatics
Benzene 250.2 2.993 3.749 291.6 3.958 2.727
Toluene 245.3 3.025 4.373 287.0 4.019 3.138
Ethylbenzene 248.8 3.100 4.719 279.4 4.018 3.607
Propylbenzene 238.7 3.078 5.521 270.6 4.007 4.137

SAFT PHSC

o-Xylene 285.4 3.998 3.620
m-Xylene 276.4 3.977 3.721
p-Xylene 287.9 4.104 3.455
Chlorobenzene 305.3 3.975 3.144
Fluorobenzene 276.9 3.883 3.012
Styrene 304.3 4.083 3.291
Acetates
POLYMERS
Methyl acetate 224.8 3.338 3.804
Ethyl acetate 213.5 3.369 4.509
n-Propyl acetate 213.9 3.440 4.989
i-Propyl acetate 210.6 3.484 4.779
n-Butyl acetate 216.3 3.514 5.413
i-Butyl acetate 207.4 3.461 5.574
t-Butyl acetate 220.2 3.743 4.485
n-Pentyl acetate 206.6 3.403 6.547
i-Pentyl acetate 220.5 3.628 5.568
n-Hexyl acetate 212.9 3.514 6.720
Vinyl acetate 218.2 3.371 4.259
Ethers
Dimethyl ether 207.8 3.003 2.799 216.6 3.553 2.519
Diethyl ether 191.9 2.885 4.430 237.9 3.780 2.985
Ethylene oxide 277.5 3.390 2.242
1,3-Propylene oxide 295.4 3.729 2.381
Tetrahydrofuran 279.5 3.811 2.758
Ketones
Acetone 210.9 2.632 4.504 250.9 3.510 3.164
Methyl ethyl ketone 230.0 3.032 4.193 255.8 3.694 3.344
Diethyl ketone 230.4 3.014 4.644 245.4 3.684 3.931
2-Pentanone 241.2 3.661 4.041
2-Hexanone 224.5 3.506 5.151

SAFT PHSC
BATCH

Chlorinated Hydrocarbons
Methyl chloride 238.4 2.935 2.377 256.7 3.591 2.018
Dichloromethane 253.0 2.896 3.114 268.1 3.541 2.669
Carbon tetrachloride 301.7 4.187 2.507
Chloroform 268.1 3.726 2.878
Vinyl chloride 249.7 3.773 2.175
1,2-Dichlorethane 280.9 3.691 2.994
POLYMERS
Table P7-4: SAFT and PHSC Parameters for Homopolymer Segments

Segment Name Homopolymer SAFT PHSC
Name
ε σ(Å) r ε σ(Å) r
Ethylene HDPE 216.2 3.043 0.0510 324.1 3.825 0.04938
Ethylene LDPE 306.0 3.603 0.05854
i-Propylene i-PP 392.1 4.705 0.02831
i-1-Butene i-PB 353.2 4.120 0.04024
4-Methyl-1-pentene PMP 381.7 4.685 0.02890
Styrene PS 206.9 3.043 0.0389 385.4 3.899 0.03834
o-Methyl styrene PoMS 393.5 3.893 0.03925
Vinyl chloride PVC 365.1 3.590 0.03672
Ethylene glycol PEG 316.6 3.532 0.04778
Vinyl acetate PVAC 275.1 3.043 0.0394 292.6 3.346 0.05166
Methyl methacrylate PMMA 373.5 3.608 0.04222
i-Methyl methacrylate i-PMMA 347.6 3.367 0.05071
Butyl methacrylate PBMA 323.4 3.604 0.04764
Cyclohexyl PCHMA 379.3 3.856 0.03742
methacrylate
Ethylene terephthalate PETP 363.5 3.320 0.04777
Carbonate PC 393.0 3.707 0.03885

Table P7-4: SAFT and PHSC Parameters for Homopolymer Segments
Segment Name Homopolymer SAFT PHSC
Name
ε σ(Å) r ε σ(Å) r
Ether ether ketone PEEK 375.0 3.429 0.04424
Sulphone PSF 425.7 3.721 0.03720
Tetrafluoroethylene PTFE 215.9 3.244 0.02705
Isobutylene PIB 220.6 3.043 0.0484
Propylene PP 110.9 3.043 0.0361
Tetrahydrofuran PTHF 327.6 3.833 0.04277
POLYMERS
Table P7-5: SAFT and PHSC Parameters for Homopolymer
Segment-Solvent Pairs
Segment Name Homopolymer Solvent SAFT kij
Symbol
Styrene PS Ethyl benzene 0.0259
Benzene 0.024
Cyclohexane 0.0447
Ethylene PE C6H14 0.0119
C7H16 0.0121
C8H18 0.0112
Isobutylene PIB C6H5CH3 0.0292
C6H14 0.0199
C6H12 0.0282
Propane 0.0324
Butane 0.0239
Pentane 0.0168
Propylene PP Diethyl ketone -0.0474
Hexane -0.0259
Vinyl acetate PVAC Benzene 0.0108

References
[1] S. H. Huang and M. Radosz, 1990, Equation of State for Small, Large,
BATCH
Polydisperse, and Associating Molecules, Ind. Eng. Chem. Res.,

29:2284-2294.
[2] Y. Song, T. Hino, S. M. Lambert, and J. M. Prausnitz, 1996, Liquid-
Liquid Equilibria for Polymer Solutions and Blends, Including Copoly-
mers, Fluid Phase Equilibria, 117:69-76.
[3] C. S. Wu and Y. P. Chen, 1994, Calculation of Vapor-Liquid Equilibria
of Polymer Solution Using the SAFT Equation of State, Fluid Phase
Equilibria, 100:103-119.
POLYMERS

Example P7-4: SAFT EOS with PVAC and Benzene
This example uses the SAFT equation of state to perform a vapor-
liquid flash calculation. The system is a binary mixture of PVAC
and benzene.
TITLE=SAFT
DIMENSION SI
PRINT INPUT = ALL
$
SEGMENT DATA
SEGMENT A, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1),9(1)
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
POLYMERS
PCOMPOSITION 2, 1.0(A)
MWAVG 2, 12000
PHASE VLS=2
THERMODYNAMIC DATA
METHOD SYSTEM = SAFT
KVALUE
EPSI 1, 250.2/A, 275.1
SIGM 1, 2.993/A, 3.043
RMW 1, 3.749/A, 0.0394
KIJ 1, A, 0.0108
STREAM DATA
PROPERTY STRM = F1, TEMP = 500, PRES = 300, *
COMP = 1, 0.95 /2, 0.05
UNIT OP
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 500, PRES = 300
END

Example P7-5: PHSC EOS with PVAC and Benzene
This example uses the PHSC equation of state to perform a liquid-
BATCH
liquid equilibrium calculation. The system is a binary mixture of

PVAC and benzene. The binary parameter kij is set to zero.
TITLE PROJ=PHSC
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, VAC, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1), 9(1)
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PHASE VLS = 2
MWAVG 2, 48000
POLYMERS
THERMODYNAMIC DATA
METHOD SYSTEM (VLLE) = PHSC
KVALUE
EPSI 1, 291.6/A, 292.6
SIGM 1, 3.958/A, 3.346
RMW 1, 2.727/A, 0.05166
STREAM DATA
PROPERTY STRM = F1, TEMP = 298.15, PRES = 100., &
COMP = 1, 0.9996 / 2,0.0004
UNIT OP
FEED F1
PRODUCT V=V1, L=L1, W=W1
ISOT TEMP=298.15, PRES=100.
END

Selecting Polymer Thermodynamic Methods
To select the method and supply its parameters:
 Click the Thermodynamic Data button, or select Input/Thermo-
dynamic Data from the menu bar, to display the Thermody-
namic Data dialog box (Figure P7-1).
Figure P7-1: Thermodynamic Data Dialog Box
POLYMERS
 Select Polymers in the Category list to display the five polymer
thermodynamic methods currently available in PRO/II. Select
the desired polymer method, and click Add > or double click on
the entry) to include the method in the simulation.
To modify data and to enter method parameters:
 Highlight the entry in the Defined Systems list, and click
Modify... to display the Modification dialog box (Figure P7-2).
The method to calculate various properties can be changed in this

dialog box. Also, to enter the parameter data for the selected meth-
ods, click Enter Data... corresponding to the desired property. Nor-
mally, for the polymer methods, parameters are required only for
the K-value (VLE) method. The data supplied for this property are
used for all other properties that can be predicted for the selected
thermodynamic method.

Figure P7-2: Modification Dialog Box
BATCH
POLYMERS
The parameters are entered through a dialog box similar to that

shown in Figure P7-3. The available parameters will depend on the
property and the thermodynamic method category (equation of
state, liquid activity, etc.).

Figure P7-3: VLE K-Values Dialog Box
POLYMERS
To supply pure species parameters:
 Click Enter Data... corresponding to the row. The Pure Species
Parameter dialog box (Figure P7-4) will contain the parame-
ters applicable to the thermodynamic method.
Figure P7-4: Pure Species Parameters Dialog Box

For some thermodynamic methods (Flory, ALM, UNIFAC), PRO/II
supplies the default values; for others (PHSC, SAFT), the pure spe-
cies parameters are required information. Pure species parameters
BATCH
can be supplied for non-polymer components and for segments.

Three types of binary interaction parameters can be supplied: (Non-
Polymer Component - Non-Polymer Component, Non-Polymer
Component - Segment, and Segment - Segment). To supply data for
the desired type:
 Click Enter Data... to display the Binary Interaction Parameters
dialog box (Figure P7-5). Depending on the thermodynamic
method selected, the number of parameters will vary.
Figure P7-5: Binary Interaction Parameters Dialog Box
POLYMERS

Chapter P8
User-Added Polymer Reactor
The PRO/II features for handling polymers (e.g., van Krevelen

property prediction method, polymer moment attributes, polymer-
specific thermodynamic methods, and polymer flash) offer you the
ability to develop individual models for a wide variety of polymer
systems.
As outlined in previous chapters, polymers are formed through two
distinct atomistic mechanisms − chain (or addition) polymerization
POLYMERS
and step growth (or condensation) polymerization. However,
PRO/II also contains built-in CSTR and PFR units with the capabil-
ity of modeling a polymerization kinetics reactor operating under
the following, more specific conditions:
 Free-radical homopolymerization to produce a linear homopol-
ymer
 Free-radical copolymerization to produce a linear copolymer
 Multi-site coordination complex polymerization to produce a
linear homopolymer
linear copolymer
 Type I, Type II and Type III stepwise polymerization
 Ideal CSTR (steady-state, well mixed, constant volume reactor)
 Ideal PFR (steady-state, plug flow, constant diameter reactor)
 Single-phase kinetic reaction environment (effects of heat and
flow fields on the mass transport are not considered)
 Bulk or solution polymerization.
This reactor unit has been modeled in PRO/II as user-added subrou-
tine US21 and is included as part of this release.

Kinetic Rate Constants
The free-radical kinetic rate constants follow the Arrhenius form
BATCH
given as:
 E a – ΔV ( P – P o ) 
k = A exp  – ----------------------------------------- 
 RT 
where A is the preexponential factor, Ea is the activation energy, ΔV

is the volume coefficient, and Po is the reference pressure. These
four parameters are given sequentially as SUPPLE(i), SUP-
POLYMERS
PLE(i+1), SUPPLE(i+2), and SUPPLE(i+3) in the SUPPLE data

for reaction step i.
The stepwise kinetic rate constants follow the form given as:
+
k = ko + kc [ H ]
where ko is the intrinsic kinetic rate constant given by:

Ea
o
k o = A o exp – ---------
RT
and kc is the acid catalyzed kinetic rate constant given by:
Ea
c
k c = A c exp – ---------
RT
Figure 0-1: and the equilibrium rate constant is defined as:
ΔH – TΔS
K = – -------------------------
RT
and where Ao is the preexponential factor for the intrinsic reaction
rate, Eao is the activation energy for the intrinsic reaction rate, Ac is
the preexponential factor for the catalytic reaction rate, Eac is the
activation energy for the catalytic reaction rate, ΔH is the enthalpy
change, and ΔS is the entropy change. These six parameters are
given sequentially as SUPPLE(i), SUPPLE(i+1), SUPPLE(i+2),
SUPPLE(i+3), SUPPLE(i+4), and SUPPLE(i+5) in the SUPPLE
data for reaction step i.
P8-2 User-Added Polymer Reactor

CSTR Mass and Energy Operating Equations
The ideal CSTR model is used to calculate steady state reactor per-
formance. The ideal CSTR assumption states that there are no tem-
perature or concentration gradients in the reactor. Therefore, the
CSTR is operated at a single temperature with a uniform composi-
tion. Also, the reactor is characterized with a single residence time.
The CSTR mass and energy balances are written for a general
copolymerization reaction scheme below. Consequently, the gov-
erning mass and energy equations for the homopolymerization case
are a subset of the copolymerization case. Symbol definitions can
be found in the nomenclature. A general energy balance equation
for the copolymerization polymerization is given as:
POLYMERS
dT dV
Vρc ------ = Q f ρ f c p T f – Qρc p T – UA j ( T – T j ) – ρc p T -------
dt f dt
* *
+ ( ΔH aa )Vk paa [ A ]P + ( ΔH ba V )k pba [ A ]Q
+
* *
+ ( ΔH ab )Vk pab [ A ]P + ( ΔH bb )Vk pbb [ A ]Q
The CSTR is operated at steady state; therefore, the time-dependent

temperature and volume derivatives in this equation are zero. These
same derivatives are zero in the mass and moment equations that
follow. The heat of polymerization is generated from the polymer-
ization mechanisms such as those given in Steps (22), (23), (24),
and (25) of Table 9-1. The energy balance becomes:
0 = Q f ρ f c p T f – Qρc p T – UA j ( T – T j )
f
* *
+
* *
Mole balances are written for each chemical species according to

the general equation given by:
d[W]
V -------------- = Q f [ W f ] – Q [ W ] – VR W
dt
where [W] represents the concentration of each small molecule
chemical species present, [W] = {[A], [B], [S],…}, and RW is the
molar rate of production for species [W].
Moments are introduced below. The moment equations follow this
same hierarchy, and the moment balances describing moments of
identical order are written as:

BATCH
d [ Λ n, m ]
V --------------------- = Q f [ Λ n, m, f ] – Q [ Λ n, m ] – VR Λ
dt n, m
where [Λn,m] represents the moment of order n,m for the distribution
in question, and RΛn,m is the molar rate of production for moment
[Λn,m]. For example, these moments could describe the variance in
length of the live or growing polymer chains.
PFR Mass and Energy Operating Equations

POLYMERS
The ideal PFR model is used to calculate steady state reactor perfor-
mance. The ideal PFR assumption states that there are no tempera-
ture or concentration gradients along the reactor radius. Therefore,
the PFR is characterized with gradients along the axial dimension
only.
The PFR mass and energy balances are written for a general copoly-
merization reaction scheme below. Consequently, the governing
mass and energy equations for the homopolymerization case are a
subset of the copolymerization case. Symbol definitions can be
found in the nomenclature. A general energy balance equation for
the copolymerization polymerization is given as:
dT U
ρc ------ = 4 ----- ( T – T j )
dz Di
* *
+
* *
The PFR is operated at steady state; therefore, temperature, pres-

sure, and composition along the reactor length do not vary with
time. The heat of polymerization is generated from the polymeriza-
tion mechanisms such as those given in Steps (22), (23), (24), and
(25) of Table 9-1.
Mole balances are written for each chemical species according to
the general equation given by:
d[W]
u -------------- = – QR W
dz

where [W] represents the concentration of each small molecule
chemical species present, [W] = {[A], [B], [S],…}, and RW is the
molar rate of production for species [W].
Moments are introduced below. The moment equations follow this
same hierarchy. The moment balances associated with moments of
the same order are written as:
d [ Λ n, m ]
u --------------------- = – QR Λ
dz n, m
where [Λn,m] represents the moment of order n,m for the distribution
in question, and RΛn,m is the molar rate of production for moment
[Λn,m]. For example, these moments could describe the variance in
length of the live or growing polymer chains.
POLYMERS
Heat Transfer Coefficient
In some reaction processes, the heat transfer coefficient is a critical
parameter in the operation. The reaction temperature, reaction pres-
sure, and polymer concentration will affect the heat transfer coeffi-
cient, perhaps to the point that polymer production is by the heat
transfer capabilities of the rector. The functional form used for the
overall heat transfer coefficient is:
1
U i = -------------------------------------------------------------
( o /r i )
A ln r Ai 1
1 i
---- + ---------------------------- + ------- ------
hi 2 π kL Ao ho
The overall heat transfer coefficient is specified in RPARM(5). Heat

transfer is then calculated from:
Qxfer = UATfm
Reactor Pressure Effects

In some cases, the kinetic reaction mechanisms are different in dif-
ferent pressure ranges. A change in pressure can change the reac-
tion mechanism, leading to a broadening in the molecular weight
distribution. The polymer broadening of the MWD function or dis-
persity is determined by the relative rates of the competing termina-
tion mechanisms. The termination mechanisms here are then
greatly influenced by the operating pressure. PRO/II supports pres-
sure coefficients for the intrinsic free-radical kinetic rate constants.
Reactor pressure may be a critical design variable.
For the CSTR, the pressure drop across the reactor is given in
RPARM(7). For the PFR, the pressure drop is calculated from a

mechanical energy balance parameterized with a Fanning friction
factor specified in RPARM(18). The mechanical energy balance
takes the form:
BATCH
2
dP μ
------- = – 4fρ ---------
dz 2D i
Population Balance
The rationale for introducing the population balance into polymer-
ization kinetics is that there exist an essentially infinite number of
molecules of different length in a polymer sample. An essentially
infinite set of pseudocomponent balance equations must be solved
to obtain the individual polymer species concentration. To decrease
the computation time required to solve this large set of equations,
POLYMERS
the method of moments is introduced to reduce the size of the equa-

tion set. For example, in reaction Step 22 of Table 9-1, the variable
n refers to the number of monomer units incorporated into the poly-
mer or degree of polymerization. The value of n can take on values
from 1 to very large numbers.
The population balance is very similar to the mass balance equa-
tions given above. From the kinetic mechanisms presented in
Table 9-1, a balance equation is written for the production and con-
sumption rates of a polymer molecule of length n. Samples of the
population balance can be seen in the review paper presented by
Ray (1972). An example population balance for the molar rate of
*
production of polymer species Pn, m, b, 1 is:
 * * 
R * = R δ + k paa [ A ]  P n – 1, m, b, l – P n, m, b, l 
P n – ( 1, m, b, l )  
 *   * 
– k pab [ B ]  P n, m, b, l  + k pba [ A ]  Q n – 1, m, b, l 
   
k * 
*  tpaa P ( n + m )D n, m, b, l 
– ( A′ 1, s + A′ 0, s )P n, m, b, l +  
* k Q ( n + m )D n, m, b, l 
 tpba 

Reference
1. Ray, W. H. (1972), “On the Mathematical Modeling of Polym-
erization Reactors”, J. Macromol. Sci. – Revs. Macromol.
Chem., C(8):1 – 56.
Moment Expansions
Once the population balances have been generated, it remains to
solve these equations to predict the size and shape of the polymer
molecule. Rather than attempting to solve a very large set of cou-
pled population balance equations for individual polymer molecules
of length n, the method of moments is used to make the population
balance solution tractable. An example moment equation for the
POLYMERS
molar rate of production of polymer moment ψk,l is:
k
k
Rψ k, i = R Aδ δ ( 1 ) + k paa [ A ]  i
Ψ i , l – ψ k, l
i
k
k
– k paa [ A ] [ Ψ k, l ] + k pba [ A ]  i
χ i, l
i
l
l
–  A′ 1, s + A′ 0, s [ Ψ k, l ] + Ω l  j
μ k + l, j
j

BATCH
POLYMERS

Chapter P9
User-Added Free Radical

systems.
POLYMERS
 Free-radical homopolymerization to produce a linear homo-
polymer
linear homopolymer
linear copolymer

Polymerization via Free-Radical Kinetics
Chain polymerization can be accomplished via a number of chemis-
BATCH
tries that include free-radical, ionic, and coordination catalysis.

Common to all these chemistries is the reactive center, which is at
the core of the chain polymerization process. The reactive center
can be identified as a free-radical center, an anionic or cationic spe-
cies, or the active center of a coordination catalyst. The reactions
associated with these polymerizations are very active and rapid.
In free-radical polymerization, the monomer is a small molecular
weight molecule (100 g/mol) that contains a double bond. When a
thermally active initiator molecule is added to the system, the initia-
tor fragments via thermal degradation into free-radical(s), and the
monomer double bond is then attacked by the free-radical. A bond
is created between the monomer and the initiator free-radical frag-
POLYMERS
ment. This new radical is called the primary polymer radical. Poly-
mer is formed as more monomer is added to the primary polymer
radical. This process continues rapidly (0.1 second) until the poly-
mer radical is deactivated by a transfer or termination step. The
kinetic mechanisms are described later. Olefins are the most com-
mon monomers reacted through free-radical chemistry. Examples
are polyethylene, polypropylene, polyvinyl chloride, polybutadiene,
and polystyrene.
Free-Radical Kinetics Mechanisms

A free-radical bulk or solution polymerization process can be ade-
quately modeled by the kinetic mechanisms presented in Table
P9-1. Symbols A, I, P, etc., within the table indicate low molecular
weight species that include monomer(s), a solvent, an initiator(s), a
transfer agent, and an inhibitor, live or growing polymer chain radi-
cals that contain the reactive center, and inactive or dead polymer
chains in which the reactive center is no longer present.
P9-2 User-Added Free Radical Polymerization Model

Table P9-1: Summary of Polymer Reactions
Decomposition and Initiation Reactions
* * f k
a da *
1 Decomposition of initiator A to form I a I a ———>2I a
* k *
* iaa
2 Initiation of monomer A by I a I a + A——> P1, 0, 0, 1
* k *
* iab
3 Initiation of monomer B by I a I a + B——> Q 0, 1, 0, 1
* * f k
b db *
4 Decomposition of initiator B to form I b I b ———> 2I b
* k *
* iba
5 Initiation of monomer A by I b I b + A——> P1, 0, 0, 1
POLYMERS
* k *
* ibb
6 Initiation of monomer B by I b I b + B——> Q 0, 1, 0, 1
* * f k
c dc *
7 Decomposition of initiator C to form I c I c ———>2I c
* k *
* ica
8 Initiation of monomer A by I c I c + A——> P1, 0, 0, 1
* k *
* icb
9 Initiation of monomer B by I c I c + B——> Q 0, 1, 0, 1
k *
spa
10 Spontaneous initiation of A to form A
* γ ra A——>γ pa A (see note a at end of table) a
k *
spb
11 Spontaneous initiation of B to form B
* γ rb B——>γ pb B (see note a at end of table)
k *
tha
12 Thermal decomposition of A to form R a
* η pa A——>η pa R a (see note a at end of table)
k *
thb
13 Thermal decomposition of B to form R b
* η pb B——>η pb R b (see note a at end of table)
k *
* dOa
14 Initiation of monomer A by O2 to form R a O 2 + A——>2R a
k *
* dOb
15 Initiation of monomer B by O2 to form R b O 2 + B——>2R b
k *
* dpa
16 Peroxide decomposition to form R a RO 2 + A——>2R a
k *
* dpb
17 Peroxide decomposition to form R b RO 2 + B——>2R b
* k
* ra
18 Peroxide production by R a R a + O 2 ——>RO 2 + inert products
* k
* rb
19 Peroxide production by R b R b + O 2 ——>RO 2 + inert products

* k *
* raa
20 Reinitiation of monomer A by R a R a + A——> P1, 0, 0, 1
BATCH
* k *
* rbb
21 Reinitiation of monomer B by R b R b + B——> Q 0, 1, 0, 1
Propagation Reactions
* k *
* paa
22 Monomer A added to P P n, m, b, t + A——> P n + 1, m, b, t
* k *
* pba
23 Monomer A added to Q Q n, m, b, t + A——> P n + 1, m, b, t
* k *
* pab
24 Monomer B added to P P n, m, b, t + B——> Q n, m + 1, b, t
* k *
* pbb
25 Monomer B added to Q Q n, m, b, t + B——> Q n, m + 1, b, t
POLYMERS
Chain Transfer and Reinitiation Reactions
* k *
* *
26 Transfer from P to solvent to form S
tsa
P n, m, b, t + S——> D n, m, b, t + S
* k *
* *
27 Transfer from Q to solvent to form S
tsb
Q n, m, b, t + S——> D n, m, b, t + S
* k *
* rsa
28 Reinitiation of monomer A by S S + A——> P1, 0, 0, 1
* k *
* rsb
29 Reinitiation of monomer B by S S + B——> Q 0, 1, 0, 1
* k *
* *
30 Transfer from P to modifier to form T
txa
P n, m, b, t + T x ——> D n, m, b, t + T x
* k *
* *
31 Transfer from Q to solvent to form T
txb
Q n, m, b, t + T x ——> D n, m, b, t + T x
* k *
* rta
32 Reinitiation of monomer A by T T x + A——> P1, 0, 0, 1
* k *
* rtb
33 Reinitiation of monomer B by T T x + B——> Q 0, 1, 0, 1
* k *
* *
34 Transfer from P to initiator A to form I a
tiaa
P n, m, b, t + I a ——> D n, m, b, t + I a
* k *
* *
35 Transfer from Q to initiator A to form I a
tiba
Q n, m, b, t + I a ——> D n, m, b, t + I a
* k *
* riaa
36 Reinitiation of monomer A by I a I a + A——> P1, 0, 0, 1
* k *
* riab
37 Reinitiation of monomer B by I a I a + B——> Q 0, 1, 0, 1

* k *
* *
38 Transfer from P to initiator B to form I b
tiab
P n, m, b, t + I b ——> D n, m, b, t + I b
* k *
* *
39 Transfer from Q to initiator B to form I b
tibb
Q n, m, b, t + I b ——> D n, m, b, t + I b
* k *
* riba
40 Reinitiation of monomer A by I b I b + A——> P1, 0, 0, 1
* k *
* ribb
41 Reinitiation of monomer B by I b I b + B——> Q 0, 1, 0, 1
* k *
* *
42 Transfer from P to initiator C to form I c
tiac
P n, m, b, t + I c ——> D n, m, b, t + I c
* k *
* *
43 Transfer from Q to initiator C to form I c
tibc
Q n, m, b, t + I c ——> D n, m, b, t + I c
POLYMERS
* k *
* rica
44 Reinitiation of monomer A by I c I c + A——> P1, 0, 0, 1
* k *
* ricb
45 Reinitiation of monomer B by I c I c + B——> Q 0, 1, 0, 1
* k *
* *
46 Transfer from P to monomer A to form A
maa
P n, m, b, t + A———> D n, m, b, t + A
* k *
* *
47 Transfer from Q to monomer A to form A
mba
Q n, m, b, t + A———> D n, m, b, t + A
* k *
* rmaa
48 Reinitiation of monomer A by A A + A———> P1, 0, 0, 2
* k *
* rmab
49 Reinitiation of monomer B by A A + B———> Q 0, 1, 0, 2
* k *
* *
50 Transfer from P to monomer B to form B
mab
P n, m, b, t + B———> D n, m, b, t + B
* k *
* *
51 Transfer from Q to monomer B to form B
mbb
Q n, m, b, t + B———> D n, m, b, t + B
* k *
* rmba
52 Reinitiation of monomer A by B B + A———> P1, 0, 0, 2
* k *
* rmbb
53 Reinitiation of monomer B by B B + B———> Q 0, 1, 0, 2
* k *
* *
54 Transfer from polymer P to form P
tpaa
P n, m, b, t + D r, q, x, t ———> D n, m, b, t + P r, q, x + 1, t
with rate constant ktpaa
* k *
* *
tpba
Q n, m, b, t + D r, q, x, t ———> D n, m, b, t + P r, q, x + 1, t
with rate constant ktpba

* k *
* *
tpab
P n, m, b, t + D r, q, x, t ———> D n, m, b, t + Q r, q, x + 1, t
BATCH
with rate constant ktpab
* k *
* *
tpbb
Q n, m, b, t + D r, q, x, t ———> D n, m, b, t + Q r, q, x + 1, t
with rate constant ktpbb
Termination Reactions
* * k
* * caa
58 Combination of P and P P n, m, b, s + P r, q, x, t ———> D n + r, m + q, b + x, max ( s, t )
* * k
* * cba
59 Combination of Q and P Q n, m, b, s + P r, q, x, t ———> D n + r, m + q, b + x, max ( s, t )
* * k
* * cab
60 Combination of P and Q P n, m, b, s + Q r, q, x, t ———> D n + r, m + q, b + x, max ( s, t )
POLYMERS
* * k
* * cbb
61 Combination of Q and Q Q n, m, b, s + Q r, q, x, t ———> D n + r, m + q, b + x, max ( s, t )
* * * * k
daa D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
62 Disproportionation of P and P P n, m, b, s + P r, q, x, t ——> ------------------
- + ------------------- + ----------------- + -----------------
2 2 2 2
* * * * k
dba D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
63 Disproportionation of Q and P Q n, m, b, s + P r, q, x, t ——> ------------------
- + ------------------- + ----------------- + -----------------
2 2 2 2
* * * * k
dab D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
64 Disproportionation of P and Q P n, m, b, s + Q r, q, x, t ——> ------------------
- + ------------------- + ----------------- + -----------------
2 2 2 2
* * * * k
dbb D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
65 Disproportionation of Q and Q Q n, m, b, s + Q r, q, x, t ——> ------------------
- + ------------------- + ----------------- + -----------------
2 2 2 2
* k
*
66 Termination of P by inhibitor
za
P n, m, b, t + I n ——> D n, m, b, t + Y
* k
*
67 Termination of Q by inhibitor
zb
Q n, m, b, t + I n ——> D n, m, b, t + Y
* k
*
68 Beta-scission of P to form R
* P n, m, b, 1 ——>D
bta
n, m, b, t
+ R*
* k
*
69 Beta-scission of Q to form R
* Q n, m, b, 1 ——>D
btb
n, m, b, t
+ R*
* k *
* rra
70 Reinitiation of monomer A by R R + A——> P 1, 0, 0, 1
* k *
* rrb
71 Reinitiation of monomer B by R R + B——> Q 0, 1, 0, 1
Side Reactions

* k
*
72 Thermal degradation of P to form H
* P n, m, b, t ——>D
tta
n, m, b, t
+ H*
* k
*
73 Thermal degradation of Q to form H
* Q n, m, b, t ——>D
ttb
n, m, b, t
+ H*
* k *
* kha
74 Reinitiation of monomer A by H H + A——> P 1, 0, 1, 0
* k *
* khb
75 Reinitiation of monomer B by H H + B——> Q 0, 1, 0, 1
* k *
* * bnaa
76 Terminal double bond from P and P P n, m, b, s + D r, q, x, 2 ———> P n + r, m + q, b + x + 1, 2
with rate constant kbnaa
POLYMERS
* * * bnba *
with rate constant kbnba
* k *
* * bnab
with rate constant kbnab
* k *
* * bnbb
with rate constant kbnbb
a. Values for γ and η are currently fixed internally at 2.0 and 1.1, respectively. In future releases, γ
and η will accept user-specified values.
Free-Radical Initiation
Some organic molecules contain unstable double bonds that can be
induced to undergo thermal disassociation to form free-radicals.
The radical center is an atom possessing an unpaired electron, and it
is this unpaired electron that attacks the double bond present in the
monomer. Because the parent organic initiator molecule is con-
sumed by the reaction, the term initiator rather than catalyst is
appropriate. Up to three initiators may be used in the free-radical
simulation. Each initiator is characterized by its molecular weight,
its decomposition kinetic rate data, and its recombination effi-
ciency. The activity of each initiator is set through its preexponen-
tial factor and activation energy kinetic constants. The initiator
radical recombination efficiency is also set through input. The
mechanism for initiator decomposition is given in Table 9-1
through the following reactions.

REACTION STEP(1): DECOMPOSITION OF INITIATOR A TO FORM IA* KDA
REACTION STEP(2): INITIATION OF MONOMER A BY IA*KIAA
REACTION STEP(3): INITIATION OF MONOMER B BY IA* KIAB
BATCH
REACTION STEP(4): DECOMPOSITION OF INITIATOR B TO FORM IB* KDB

REACTION STEP(5): INITIATION OF MONOMER A BY IB*KIBA
REACTION STEP(6): INITIATION OF MONOMER B BY IB* KIBB
REACTION STEP(7): DECOMPOSITION OF INITIATOR C TO FORM IC*KDC
REACTION STEP(8): INITIATION OF MONOMER A BY IC*KICA
REACTION STEP(9): INITIATION OF MONOMER B BY IC*KICB
REACTION STEP(10): SPONTANEOUS INITIATION OF A TO FORM A*KSPA
REACTION STEP(11): SPONTANEOUS INITIATION OF B TO FORM B*KSPB
REACTION STEP(12): THERMAL DECOMPOSITION OF A TO FORM RA*KTHA
REACTION STEP(13): THERMAL DECOMPOSITION OF B TO FORM RB*KTHB
REACTION STEP(14): INITIATION OF MONOMER A BY O2 TO FORM RA*KDOA
REACTION STEP(15): INITIATION OF MONOMER B BY O2 TO FORM RB*KDOB
REACTION STEP(16): RO2 DECOMPOSITION TO FORM RA* KDPA
REACTION STEP(17): RO2 DECOMPOSITION TO FORM RB* KDPB
REACTION STEP(18): PEROXIDE PRODUCTION BY RA* KRA
REACTION STEP(19): PEROXIDE PRODUCTION BY RB*KRB
POLYMERS
Chain Propagation
The reactive center continues to add monomer to the growing or
live chain, thereby increasing the molecular weight of the polymer
molecule. The mechanisms are given in the following steps:
REACTION STEP(22): PROPAGATION OF P* WITH MONOMER AKPAA
REACTION STEP(23): PROPAGATION OF Q* WITH MONOMER AKPBA
REACTION STEP(24): PROPAGATION OF P* WITH MONOMERKPAB
REACTION STEP(25): PROPAGATION OF Q* WITH MONOMER BKPBB
Chain Transfer
The reactive center is very active and, as such, can react with other
chemical species in the reaction mixture. The reactive center can be
transferred to other polymer, monomer, or solvent molecules. The
original live polymer chain is now inactive or dead, but the reactive
site remains active on some other molecule.
RNX STEP(26): TRANSFER FROM P* TO SOLVENT TO FORM S*KTSA
RNX STEP(27): TRANSFER FROM Q* TO SOLVENT TO FORM S*KTSB
RNX STEP(30): TRANSFER FROM P* TO XFER AGENT TO FORM T*KTXA
RXN STEP(31): TRANSFER FROM Q* TO XFER AGENT TO FORM T*KTXB
RXN STEP(34): TRANSFER FROM P* TO INITIATOR A TO FORM IA**KTIAA
RXN STEP(35): TRANSFER FROM Q* TO INITIATOR A TO FORM IA**KTIBA
RXN STEP(38): TRANSFER FROM P* TO INITIATOR B TO FORM IB**KTIAB
RXN STEP(39): TRANSFER FROM Q* TO INITIATOR B TO FORM IB**KTIBB
RXN STEP(42): TRANSFER FROM P* TO INITIATOR C TO FORM IC**KTIAC
RXN STEP(43): TRANSFER FROM Q* TO INITIATOR C TO FORM IC**KTIBC
RXN STEP(46): TRANSFER FROM P* TO MONOMER A TO FORM A*KMAA
RXN STEP(47): TRANSFER FROM Q* TO MONOMER A TO FORM A*KMBA
RXN STEP(50): TRANSFER FROM P* TO MONOMER B TO FORM B*KMAB
RXN STEP(51): TRANSFER FROM Q* TO MONOMER B TO FORM B*KMBB
RXN STEP(54): TRANSFER FROM POLYMER P* TO FORM P*KTPAA
RXN STEP(55): TRANSFER FROM POLYMER Q* TO FORM P*KTPBA
RXN STEP(56): TRANSFER FROM POLYMER P* TO FORM Q*KTPAB

RXN STEP(57): TRANSFER FROM POLYMER Q* TO FORM Q*KTPBB
Free-Radical Recombination
These radicals recombine with the monomer to form new primary
polymer radicals, which then generate a new polymer. Some kinetic
models assume that the active radical recombines instantaneously
so that it is the radical formation step that is rate limiting. This
assumption is not made here. Kinetic data for each free-radical
resulting from a transfer reaction must be input in the order in
which the radical participates in the polymerization.
The following recombination steps are present in the kinetic
scheme:
POLYMERS
RXN STEP(20): REINITIATION OF MONOMER A BY RA*KRAA
RXN STEP(21): REINITIATION OF MONOMER B BY RB*KRBB
RXN STEP(28): REINITIATION OF MONOMER A BY S*KRSA
RXN STEP(29): REINITIATION OF MONOMER B BY S*KRSB
RXN STEP(32): REINITIATION OF MONOMER A BY T*KRTA
RXN STEP(33): REINITIATION OF MONOMER B BY T*KRTB
RXN STEP(36): REINITIATION OF MONOMER A BY IA**KRIAA
RXN STEP(37): REINITIATION OF MONOMER B BY IA**KRIAB
RXN STEP(40): REINITIATION OF MONOMER A BY IB**KRIBA
RXN STEP(41): REINITIATION OF MONOMER B BY IB**KRIBB
RXN STEP(44): REINITIATION OF MONOMER A BY IC**KRICA
RXN STEP(45): REINITIATION OF MONOMER B BY IC**KRICB
RXN STEP(48): REINITIATION OF MONOMER A BY A*KRMAA
RXN STEP(49): REINITIATION OF MONOMER B BY A*KRMAB
RXN STEP(52): REINITIATION OF MONOMER A BY B*KRMBA
RXN STEP(53): REINITIATION OF MONOMER B BY B*KRMBB
RXN STEP(70): REINITIATION OF MONOMER A BY R*KRRA
RXN STEP(71): REINITIATION OF MONOMER B BY R*KRRB
RXN STEP(74): REINITIATION OF MONOMER A BY H*KRHA
RXN STEP(75): REINITIATION OF MONOMER B BY H*KRHB
Chain Termination
An obvious termination method, whereby the polymerization pro-
cess is stopped, is for two kinetic chain ends to combine and pro-
duce a dead chain. This process is called combination. A less
apparent termination mechanism is for one live chain to abstract an
alpha hydrogen with respect to the reactive center on a second live
chain. This process is called disproportionation and results in two
stable chains. Inhibitors are organic molecules that are added to
chemically react with the reactive center and to terminate the
growth mechanism, thereby lowering the polymer molecular
weight.
RXN STEP(58): TERMINATION BY COMBINATION OF P* AND P*KCAA
RXN STEP(59): TERMINATION BY COMBINATION OF Q* AND P*KCBA
RXN STEP(60): TERMINATION BY COMBINATION OF P* AND Q*KCAB

RXN STEP(61): TERMINATION BY COMBINATION OF Q* AND Q*KCBB
RXN STEP(62): TERMINATION BY DISPROPORTIONATION P* & P*KDAA
RXN STEP(63): TERMINATION BY DISPROPORTIONATION Q* & P*KDBA
BATCH
RXN STEP(64): TERMINATION BY DISPROPORTIONATION P* & Q*KDAB

RXN STEP(65): TERMINATION BY DISPROPORTIONATION Q* & Q*KDBB
RXN STEP(66): TERMINATION OF P* BY INHIBITORKZA
RXN STEP(67): TERMINATION OF Q* BY INHIBITORKZB
RXN STEP(68): BETA-SCISSION OF P* CHAIN TO FORM R*KBTA
RXN STEP(69): BETA-SCISSION OF Q* CHAIN TO FORM R*KBTB
RXN STEP(72): THERMAL DEGRADATION OF P* TO FORM H*KTTA
RXN STEP(73): THERMAL DEGRADATION OF Q* TO FORM H*KTTB
RXN STEP(76): TERMINAL DOUBLE BOND FROM P* TO P*KBNAA
RXN STEP(77): TERMINAL DOUBLE BOND FROM Q* TO P*KBNBA
RXN STEP(78): TERMINAL DOUBLE BOND FROM P* TO Q*KBNAB
RXN STEP(79): TERMINAL DOUBLE BOND FROM Q* TO Q*KBNBB
Gel and Glass Effects

As the polymerization reactions proceed, the concentration of poly-
mer and size of the average polymer molecule increases. Accompa-
POLYMERS
nying this increased monomer conversion is a substantial increase

in the viscosity of the reacting mixture. The increased viscosity
introduces adverse effects of diffusion on the propagation and ter-
mination kinetic rate constants. The gel and glass effects have been
implemented for free-radical homopolymerization only.
The polymer product composition consists of mostly dead polymer
chains accompanied by a few live or kinetic chains; however, both
dead polymer and kinetic chains contribute to the viscosity of the
reacting solution. Increased solution viscosity leads to a substantial
decrease in the diffusion of kinetic chains such that the bimolecular
chain termination reactions presented in Reaction Steps (58)
through (65) of Table 9-1 are effectively stopped. At this point, the
reacting solution undergoes autoacceleration. This is the gel effect.
At low monomer conversion, intrinsic values of the propagation
and termination kinetic rate constants are used. As conversion
increases and solution viscosity increases (which is typical of the
gel effect), modified or hindered termination rate constants are
obtained from empirical or experimentally obtained functions. For
the polymer propagation step to continue, unreacted monomer must
be transported to the reactive center. Eventually, the solution viscos-
ity increases acceptably to hinder the transport of the small mole-
cule monomer, and hence the propagation reactions listed in
Reaction Steps (22) through (25) of Table 9-1 is decreased. The
polymerization rate decreases and the glass effect is encountered.
The modification of the propagation and termination kinetic rate
constants to account for gel and glass effects is accomplished

through the use of empirical and semi-empirical correlation func-
tions. These correlation functions are important because they are
used to curtail the polymerization reaction at medium to high mono-
mer conversions.
In the input file for the user-added polymer CSTR, IPARM(10) is
used to specify the correlation for gel effect and glass effect. The
options shown in Table P9-2 are available.
Table P9-2: Gel Effect and Glass Effect Input Code
Numbers
Input Value of Gel Effect and Glass Effect
IPARM(10) Correlation
0 No Gel Effect or Glass Effect
POLYMERS
1 Reference 1 for PMMA
3 Reference 3 for PS, PMMA
4 Reference 4 for PVA, PMMA
References
1. Kumar, V.R. and S.K. Gupta, “Optimal Parameter Estimation for Methyl
Methacrylate Polymerization,” Polymer, 32:3233-3243 (1991).
2. Baillagou, P.E. and D.S. Soong, “Molecular Weight Distribution of Products
of Free-Radical Nonisothermal Polymerization with Gel Effect Simulation
for Polymerization of Poly(Methyl Methacrylate,” Chem. Eng. Sci., 40:87-
104 (1985).
3. Jaisinghani, J. and W.H. Ray, “On the Dynamic Behavior of a Class of Homo-
geneous Continuous Stirred Tank Polymerization Reactors,” Chem. Eng. Sci.,
32:811-825 (1977).
4. Hamer, J.W., T.A. Akramov, and W.H. Ray, “The Dynamic Behaviour of
Continuous Polymerization Reactors - II,” Chem. Eng. Sci., 36:1897-1914
(1981).
5. Schmidt, A.D. and W.H. Ray, “The Dynamic Behaviour of Continuous
Polymerization Reactors - I,” Chem. Eng. Sci., 36:1401-1410 (1981).

Required Data for the Polymer Reactor Unit
The polymer reactor unit requires the following data:
BATCH
 Component data
 Components – Monomer(s), polymer, solvent, initiator
(required), transfer agent (optional), inhibitor (optional)
 van Krevelen structural group data (required)
 Average MW and MW distribution of polymer
 Names of “moments” (will be calculated by US21)
 Thermodynamics data (required)
 ALM (recommended), Flory-Huggins, UNIFAC Free Volume,
SAFT, or PHSC
 Unit data (US21)
POLYMERS
 Heat of polymerization (required)

 CSTR volume or PFR diameter and length (required)
 Temperature (required for isothermal reactor) or temperature
estimate (for non-isothermal reactor)
 Jacket temperature and heat transfer area (for non-isothermal
reactor)
 Overall heat transfer coefficient (for non-isothermal reactor)
 CSTR pressure drop or PFR friction factor
 Free-radical kinetic data
 Free-radical initiator efficiency factor
 Required free-radical reactions (initiation, propagation, termi-
nation)
 Optional reactions.

User-Added Subroutines
An outline of the keyword input syntax for user-added unit opera-
tions such as the polymer reactor unit US21 is given below. IPARM
and RPARM arrays are used to pass information on the component
and reactor configuration from the keyword file to the user-added
subroutine. The SUPPLE array is used to supply kinetics data.
Note: Details of user-added subroutines may be found in the

PRO/II Data Transfer System and User-Added Subroutines User’s
Guide.
Communicating with PRO/II for Free-Radical Kinetics

The keyword headers that contain the descriptions of IPARM,
POLYMERS
RPARM, and SUPPLE are quite lengthy. These headers are given here
and do not appear in the example problems:
US21 UID=uid {NAME=text}
IPARM integer,… (up to 21 values)
RPARM real no,… (up to 18 values)
SUPPLEMENTAL i,Ri/Ri+1/…/j,Rj/Rj+1… (up to 316 values)
Integer IPARM Data:

$ IPARM( 1) = REACTOR Type REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE REQ
$ = 1 FOR FREE RADICAL HOMOPOLYMERIZATION
$ = 2 FOR FREE RADICAL COPOLYMERIZATION
$ = 3 FOR TYPE I STEP GROWTH POLYMERIZATION
$ = 4 FOR TYPE II STEP GROWTH POLYMERIZATION
$ = 5 FOR TYPE III STEP GROWTH POLYMERIZATION
$ IPARM( 4) = NO. REVERSIBLE POLYMERIZATION RXN STEPS N/A
$ IPARM( 5) = NO. IRREVERSIBLE POLYMERIZATION RXN STEPS REQ
$ IPARM( 6) = NUMBER OF RINGS N/A
$ IPARM( 7) = BASIS FOR KINETIC RATE CONSTANTS REQ
$ = 1 FOR VOLUME BASIS
$ = 2 FOR WEIGHT BASIS
$ IPARM( 8) = REVERSIBLE KINETICS FLAG N/A
$ = 1 FORWARD KINETIC RATE CONSTANTS ONLY
$ = 2 INCLUDE REVERSE KINETIC RATE CONSTANTS
$ IPARM( 9) = HIGH PRESSURE KINETIC RATE CONSTANTS FLAG REQ
$ = 0 NO COEFFICIENTS
$ = 1 INCLUDE COEFFICIENTS
$ IPARM(10) = FLAG FOR TYPE OF GEL AND GLASS EFFECT OPT
$ CORRELATION ( DEFAULT = 0 )
$ IPARM(11) = POLYMER COMPONENT
$ IPARM(12) = MONOMER A COMPONENT
$ IPARM(13) = MONOMER B COMPONENT (OR 0)

$ IPARM(14) = SOLVENT COMPONENT (OR 0)
$ IPARM(15) = INITIATOR A COMPONENT
$ IPARM(16) = INITIATOR B COMPONENT (OR 0)
BATCH
$ IPARM(17) = INITIATOR C COMPONENT (OR 0)

$ IPARM(18) = TRANSFER AGENT COMPONENT (OR 0)
$ IPARM(19) = INHIBITOR COMPONENT (OR 0)
$ IPARM(20) = O2 COMPONENT (OR 0)
$ IPARM(21) = PEROXIDE COMPONENT (OR 0)
$——————————————————————————————————————————————————————————
Real RPARM Data:

$ RPARM( 1)
= HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2)
= CSTR REACTOR VOLUME, LITER
$ RPARM( 3)
= JACKET TEMPERATURE, K, FOR NONISOTHERMAL REACTOR
$ RPARM( 4)
= JACKET AREA, M2, FOR NONISOTHERMAL REACTOR
$ RPARM( 5)
= OVERALL HTC, J/SEC/M2/K, FOR NONISO REACTOR
$ RPARM( 6)
= REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE FOR ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
POLYMERS
$ RPARM( 7) = CSTR REACTOR PRESSURE DROP (kPa) ; DEFAULT=0.0

$ RPARM( 8) = DECOMPOSITION EFFIC FACTOR FOR 1ST INITIATOR
$ RPARM( 9) = DECOMPOSITION EFFIC FACTOR FOR 2ND INITIATOR
(OR 0)
$ RPARM(10) = DECOMPOSITION EFFIC FACTOR FOR 3RD INITIATOR
(OR 0)
$ RPARM(11) = PFR LENGTH, M
$ RPARM(12) = PFR DIAMETER, CM
$ RPARM(13) = FEED STREAM LIVE CHAIN A FRACTION
$ RPARM(14) = FEED STREAM LIVE CHAIN B FRACTION
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba) , J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab) , J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb) , J/GMOL
$ RPARM(18) = PFR FANNING FRICTION FACTOR
$
Real SUPPLE Data:

REACTION STEP( 1): DECOMPOSITION OF INITIATOR A TO FORM IA*KDA
$ SUPPLE( 1) = PREEXPONENTIAL FACTOR (SEC-1)
$ SUPPLE( 2) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE( 3) = VOLUME COEFFICIENT (J/GMOL/ATM)
$ SUPPLE( 4) = REFERENCE PRESSURE (ATM)
$
REACTION STEP( 2): INITIATION OF MONOMER A BY IA*KIAA
$ SUPPLE( 5) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$
REACTION STEP( 3): INITIATION OF MONOMER B BY IA*KIAB
$
REACTION STEP( 4): DECOMPOSITION OF INITIATOR B TO FORMB*KDB

$
REACTION STEP( 5): INITIATION OF MONOMER A BY IB*KIBA
$
REACTION STEP( 6): INITIATION OF MONOMER B BY IB*KIBB
$
REACTION STEP( 7): DECOMPOSITION OF INITIATOR C TO FORM IC*KDC
POLYMERS
$
REACTION STEP( 8): INITIATION OF MONOMER A BY IC*KICA
$
REACTION STEP( 9): INITIATION OF MONOMER B BY IC*KICB
$
REACTION STEP(10): SPONTANEOUS INITIATION OF A TO FORM A*KSPA
$
REACTION STEP(11): SPONTANEOUS INITIATION OF B TO FORM B*KSPB
$
REACTION STEP(12): THERMAL DECOMPOSITION OF A TO FORM RA*KTHA
$
REACTION STEP(13): THERMAL DECOMPOSITION OF B TO FORM RB*KTHB
$
REACTION STEP(14): INITIATION MONOMER A BY O2 TO FORM RA*KDOA

BATCH

$
REACTION STEP(15): INITIATION MONOMER B BY O2 TO FORM RB*KDOB
$
REACTION STEP(16): RO2 DECOMPOSITION TO FORM RA*KDPA
$
REACTION STEP(17): RO2 DECOMPOSITION TO FORM RB*KDPB
POLYMERS

$
REACTION STEP(18): PEROXIDE PRODUCTION BY RA* KRA
$
REACTION STEP(19): PEROXIDE PRODUCTION BY RB*KRB
$
REACTION STEP(20): REINITIATION OF MONOMER A BY RA*KRAA
$
REACTION STEP(21): REINITIATION OF MONOMER B BY RB*
$
REACTION STEP(22): PROPAGATION OF P* WITH MONOMER A KPAA
$
REACTION STEP(23): PROPAGATION OF Q* WITH MONOMER A KPBA

$
REACTION STEP(24): PROPAGATION OF P* WITH MONOMER B KPAB
$
REACTION STEP(25): PROPAGATION OF Q* WITH MONOMER B KPBB
$ SUPPLE(100) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(26): TRANSFER FROM P* TO SOLVENT TO FORM S*KTSA
$ SUPPLE(101) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(102) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(103) = VOLUME COEFFICIENT (J/GMOL/ATM)
POLYMERS
$
REACTION STEP(27): TRANSFER FROM Q* TO SOLVENT TO FORM S*KTSB
$
REACTION STEP(28): REINITIATION OF MONOMER A BY S*KRSA
$
REACTION STEP(29): REINITIATION OF MONOMER B BY S* KRSB
$
REACTION STEP(30): TRANSFER FROM P* TO XFER AGENT,FORM T*KTXA
$
REACTION STEP(31): TRANSFER FROM Q* TO XFER AGENT,FORM T*KTXB
$
REACTION STEP(32): REINITIATION OF MONOMER A BY T*KRTA
$
REACTION STEP(33): REINITIATION OF MONOMER B BY T*KRTB

$
BATCH
REACTION STEP(34): TRANSFER FROM P* TO INITIATOR A TO FORM

IA** KTIAA
$
REACTION STEP(35): TRANSFER FROM Q* TO INITIATOR A TO FORM
IA** KTIBA
$
REACTION STEP(36): REINITIATION OF MONOMER A BY IA**KRIAA
POLYMERS

$
REACTION STEP(37): REINITIATION OF MONOMER B BY IA**KRIAB
$
REACTION STEP(38): TRANSFER FROM P* TO INITIATOR B TO FORM
IB** KTIAB
$
REACTION STEP(39): TRANSFER FROM Q* TO INITIATOR B TO FORM
IB** KTIBB
$
REACTION STEP(40): REINITIATION OF MONOMER A BY IB** KRIBA
$
REACTION STEP(41): REINITIATION OF MONOMER B BY IB**KRIBB
$
REACTION STEP(42): TRANSFER FROM P* TO INITIATOR C TO FORM
IC**KTIAC

$
REACTION STEP(43): TRANSFER FROM Q* TO INITIATOR C,FORM
IC**KTIBC
$
REACTION STEP(44): REINITIATION OF MONOMER A BY IC** KRICA
$
REACTION STEP(45): REINITIATION OF MONOMER B BY IC** KRICB
POLYMERS
$
REACTION STEP(46): TRANSFER FROM P* TO MONOMER A, FORM A*KMAA
$
REACTION STEP(47): TRANSFER FROM Q* TO MONOMER A, FORM A*KMBA
$
REACTION STEP(48): REINITIATION OF MONOMER A BY A*KRMAA
$
REACTION STEP(49): REINITIATION OF MONOMER B BY A* KRMAB
$
REACTION STEP(50): TRANSFER FROM P* TO MONOMER B, FORM B*KMAB
$
REACTION STEP(51): TRANSFER FROM Q* TO MONOMER B, FORM B*KMBB

$
REACTION STEP(52): REINITIATION OF MONOMER A BY B* KRMBA
BATCH

$
REACTION STEP(53): REINITIATION OF MONOMER B BY B*KRMBB
$
REACTION STEP(54): TRANSFER FROM POLYMER P* TO FORM P*KTPAA
$
POLYMERS
REACTION STEP(55): TRANSFER FROM POLYMER Q* TO FORM P*KTPBA

$
REACTION STEP(56): TRANSFER FROM POLYMER P* TO FORM Q*KTPAB
$
REACTION STEP(57): TRANSFER FROM POLYMER Q* TO FORM Q* KTPBB
$
REACTION STEP(58): TERMINATION BY COMBINATION OF P* AND P*KCAA
$
REACTION STEP(59): TERMINATION BY COMBINATION OF Q* AND P*KCBA
$
REACTION STEP(60): TERMINATION BY COMBINATION OF P* AND Q*KCAB
$
REACTION STEP(61): TERMINATION BY COMBINATION OF Q* AND Q*KCBB

$
REACTION STEP(62): TERMINATION BY DISPROPORTIONATION P* AND P*
KDAA
$
REACTION STEP(63): TERMINATION BY DISPROPORTIONATION Q* AND P*
KDBA
$
REACTION STEP(64): TERMINATION BY DISPROPORTIONATION P* AND Q*
POLYMERS
KDAB
$
REACTION STEP(65): TERMINATION BY DISPROPORTIONATION Q* AND Q*
KDBB
$
REACTION STEP(66): TERMINATION OF P* BY INHIBITOR KZA
$
REACTION STEP(67): TERMINATION OF Q* BY INHIBITOR KZB
$
REACTION STEP(68): BETA-SCISSION OF P* CHAIN TO FORM R* KBTA
$ SUPPLE(269) = PREEXPONENTIAL FACTOR (SEC-1)
$
REACTION STEP(69): BETA-SCISSION OF Q* CHAIN TO FORM R* KBTB
$
REACTION STEP(70): REINITIATION OF MONOMER A BY R* KRRA

$
BATCH
REACTION STEP(71): REINITIATION OF MONOMER B BY R* KRRB

$
REACTION STEP(72): THERMAL DEGRADATION OF P* TO FORM H* KTTA
$
REACTION STEP(73): THERMAL DEGRADATION OF Q* TO FORM H* KTTB
POLYMERS

$
REACTION STEP(74): REINITIATION OF MONOMER A BY H*KRHA
$
REACTION STEP(75): REINITIATION OF MONOMER B BY H*KRHB
$
REACTION STEP(76): TERMINAL DOUBLE BOND FROM P* TO P*KBNAA
$
REACTION STEP(77): TERMINAL DOUBLE BOND FROM Q* TO P*KBNBA
$
REACTION STEP(78): TERMINAL DOUBLE BOND FROM P* TO Q*KBNAB
$
REACTION STEP(79): TERMINAL DOUBLE BOND FROM Q* TO Q* KBNBB
$

Using Reactor Unit US21 to Model Free-Radical Systems
Polymer systems that may be modeled with unit US21 are solution
and bulk polymerizations:
 Homopolymer: Polystyrene (PS), Polymethymethacrylate
(PMMA)
 Copolymer: Polymethymethacrylate –Polyvinylacetate
(PMMA-PVAC), HDPE , LDPE.
Example P9-1: Free-Radical Homopolymerization in a CSTR

In this example problem, the built-in polymer CSTR unit US21 is
used to model the bulk polymerization of styrene to polystyrene
with n-butyl benzoate as the initiator. If solution polymerization is
POLYMERS
of interest, this problem can be modified easily to add the input
component ethylbenzene to the reactor feed for use as a solvent. It
is important to note:
1. Van Krevelen structural groups (from Appendix A) are given
for the polymer polystyrene. The FILL=VANKREVELEN key-
word is used to specify that van Krevelen prediction methods
be used for polymer properties.
2. Advanced Lattice Model (ALM) binary interaction parameters
for the ethyl benzene-polystyrene pair are taken from Table 7-2
and are provided with the ALME and ALMC statements.
3. The kinetics type and the molecular weight distribution are pro-
vided on the ATTRIBUTE statement. The distribution given will
result in the creation of 19 polymer pseudocomponents
(1MW500 through 1MW500000).
4. Names are defined for the first three moments of molecular
weight distribution (MMWD) on the ATTRIBUTE statement.
These moments will be calculated by the US21 unit, but will be
printed in the stream report output only if the names are given
on this statement.
5. The polymer CSTR is modeled as two US21 units in series.
6. Data on the reaction component types involved in the reaction
and the isothermal reactor operating conditions are provided on
the IPARM and RPARM statements.
7. Data for the free-radical kinetics for the polymerization reac-
tion are taken from Table P9-1 and are provided in the US21
units via the SUPPLE data statement.

8. The product from the second reactor unit is flashed isother-
mally in unit FLASHDEV to remove volatiles.
BATCH
9. A stream calculator, WFE, is used to model a wiped film evap-

orator. This unit removes the polymer component as product
stream POLYMER. Reaction kinetics data for this example are
summarized in Table P9-3.
Table P9-3: Reaction Kinetics Used in Example p9-1
Reaction Rate Constant Activation
Step Energy (J/
ko Prefactor Prefactor Units
gmol)
1 KDA 1.5800e15 1/sec 128870
2 KIAA 1.0500e7 m3/kmol/sec 29540
22 KPAA 1.0500e7 m3/kmol/sec 29540
POLYMERS
58 KCAA 1.2600e7 m3/kmol/sec 7030

Note: The heat of polymerization (-ΔHaa) for styrene is 69900 joule/gmol,
and the initiator efficiency is 0.7.
Polystyrene CSTR Input File

TITLE PROJ=POLYSTYRENE, PROB=PSTYR, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, STYR, FILL=VANKREVELEN
STRUCTURE A, 144(1), 4(1)
COMPONENT DATA
LIBID 2,STYRENE/3,EBZN/4,BOBZ , BANK=SIMSCI
POLYMER 1,PSTYR
MWAVG 1, 25000
PHASE VLS=1
ATTRIBUTE COMP=1, *
KINETICS=FR, MWD= 500, 1000, 3000, 5000, 7000,*
10000, 15000, 20000, 25000, 30000,*
50000, 60000, 70000, 80000,100000,*
200000,300000,400000,500000, *
MMWD= MU0, MU1, MU2
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,3, -.062, 26.38
ALMC A, 0.701
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=363, PRES(ATM)=1.0, *
COMP(WT, KG/MIN)=0.0/10.4188/0.0/4,0.150
UNIT OPERATION
MIXER UID=MIXER_1

FEED FEED_0,RECYCLE
PRODUCT M=FEED_1
OPERATION PRES(ATM)=1.75
US21 UID=REACTOR_1, NAME=1st PS REACTOR
FEED FEED_1
PROD PROD_1
$------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
POLYMERS
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = HIGH PRESSURE KINETIC RATE CONSTANT REQ
$ = 0 NO PRESSURE COEFFICIENTS
$ = 1 INCLUDE PRESSURE COEFFICIENTS
$ IPARM(10) = GEL AND GLASS EFFECT CORRELATION OPT
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 1,1,1,0,0, 0,1,0,1,3, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
$ RPARM( 8) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 1ST INITIATOR
$ FOR 2ND INITIATOR (OR 0)
$ RPARM(10) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 3RD INITIATOR (OR 0)

BATCH

$------------------------------------------------------------
RPARM 69900., 200.0, 0.0, 0.0, 0.0, 350.0, 0.0, &
0.7, 0.0, 0.0, 0.0, 0.0, 1.0, 0.0, &
0.0, 0.0, 0.0, 0.0
$------------------------------------------------------------
SUPPLE 1,1.580E15/128870/0.0/0.0/1.050E07/ 29540/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/
POLYMERS
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&

0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 1.050E07/ 29540/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 1.26E09/ 7030/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0
$-----------------------------------------------------------
US21 UID=REACTOR_2, NAME=2nd PS REACTOR
FEED PROD_1
PROD PROD_2
$------------------------------------------------------------

$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
POLYMERS
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 1,1,1,0,0, 0,1,0,1,3, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------
$ FOR 1ST INITIATOR

$------------------------------------------------------------
RPARM 69900., 250.0, 0.0, 0.0, 0.0, 350.0, 0.0, &
BATCH
0.5, 0.0, 0.0, 0.0, 0.0, 1.0, 0.0, &

0.0, 0.0, 0.0, 0.0
$------------------------------------------------------------
SUPPLE 1,1.580E15/ 128870/0.0/0.0/ 1.050E07/ 29540/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 1.050E07/ 29540/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
POLYMERS
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &

0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 1.26E09/ 7030/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/ 0.0
$ FIRST STAGE - FLASH DEVOLATILIZER
FLASH UID=FLASHDEV
FEED PROD_2
PRODUCT V=MON_RECYCLE, L=POLYMER_MELT
ISOT TEMP(K)=440, PRES(ATM)=1
$ SECOND STAGE - SPLITTER
SPLITTER UID=SPLITTER_1
FEED MON_RECYCLE
PRODUCT L=RECYCLE, V=WASTE
SPEC STREAM=RECYCLE, RATE, RATIO, &
STREAM=MON_RECYCLE, RATE, VALUE=0.40
$ THIRD STAGE - WIPED FILM EVAPORATOR

STCALC UID=WFE
FEED POLYMER_MELT
OVHD V=OFF-GAS, TEMP(K)=440, PRES(ATM)=1
FOVHD 1,4,1.0
BTMS M=POLYMER, TEMP(K)=440, PRES(ATM)=1
FBTMS 5,24,1.0
$
Example P9-2: Free-Radical Homopolymerization in a PFR

In this example problem, the built-in polymer PFR unit US21 is
used to model the solution polymerization of ethylene to polyethyl-
ene with benzoyl peroxide as the initiator. If bulk polymerization is
of interest, this problem can be modified easily to remove the input
solvent component ethyl acetate from the reactor feed. It is impor-
tant to note:
POLYMERS
for the polymer polystyrene, and the FILL=VANKREVELEN
keyword is used to specify that van Krevelen prediction meth-
ods be used for polymer properties.
(1MW10 through 1MW500000).
on this statement.
4. The polymer PFR is initially heated by the reactor jacket up to
an initiation temperature, after which the PFR is cooled by the
reactor jacket.
and the nonisothermal reactor operating conditions are pro-
vided on the IPARM and RPARM statements.
7. The product from the reactor unit is flashed isothermally in unit
PRODUCT to remove volatiles.

Table P9-4: Reaction Kinetics Used in Example P9-2
BATCH
Step Rate Prefactor Prefactor Units Activation Volume Reference

Constant ko Energy Coefficient Pressure
(J/gmol) (J/gmol/atm) (atm)
1 KDA 2.5000e14 1/sec 125520 0.6276 1.0
2 KIAA 2.5000e14 m3/kmol/sec 125520 0.6276 1.0
4 KDB 5.9300e18 1/sec 195210 - -
5 KIBA 5.9300e18 m3/kmol/sec 195210 - -
22 KPAA 1.2500e8 m3/kmol/sec 31045 -2.0920 1301.
26 KTSA 2.7500e7 m3/kmol/sec 43390 -2.1171 0.0
28 KRSA 2.7500e7 m3/kmol/sec 43390 -2.1171 0.0
POLYMERS
46 KMAA 1.2500e5 m3/kmol/sec 45355 - -

48 KRMAA 1.2500e5 m3/kmol/sec 45355 - -
54 KTPAA 1.2400e6 m3/kmol/sec 30335 - -

58 KCAA 2.5000e9 m3/kmol/sec 4184 - -
62 KDAA 2.5000e9 m3/kmol/sec 4184 - -
68 KBTA 6.0700e7 m3/kmol/sec 45185 - -
Note: The heat of polymerization (-ΔHaa) for ethylene is 89540 joule/gmol, and the initiator
efficiency is 0.98.
Polyethylene PFR Input File

TITLE PROJ=POLYMER, PROB=HDPE, USER=RAS, DATE=12/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, PE1, FILL=VANKREVELEN
STRUCTURE A, 4(2)
COMPONENT DATA
LIBID 2,ETHYLENE/3,EOAC/4,BZPOX
POLYMER 1,HDPE
MWAVG 1, 16000
PHASE VLS = 1
ENTHALPY(L,K,J/G,WT) CORRELATION= 1, DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
DENSITY(L,K,G/LIT,WT) CORRELATION=1,DATA=1,400,200,524/*
2,400,200,524/*
3,400,200,524/*

4,400,200,524
ATTRIBUTE COMP=1, KINE = FR, MWD = 10,50,100,300,500,1000,*
2000,3000,5000,7000,8000,9000,*
10000,15000,20000,30000,50000,70000,*
100000,300000,500000*
MMWD = psi0, psi1, psi2
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,3 ,0.5
STREAM DATA
PROP STRM=Feed_1, TEMP(K)=363.15, PRES(ATM)=2400.0, *
COMP(WT,KG/MIN)=0.0/1244.7/12.45/1.12
UNIT OPERATION
US21 UID=REACTOR_1, NAME=HDPE PFReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
POLYMERS
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 2,0,1,0,0, 0,1,0,1,0, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------

BATCH

$ FOR 1ST INITIATOR
POLYMERS
$-------------------------------------------------------------
RPARM 89540., 0.0, 393.15, 1.0, 1255.2, 363.15, 0.0, &
0.98, 0.0, 0.0, 097.28, 5.25018, 1.0, 0.0, &
0.0, 0.0, 0.0, 0.015
$-------------------------------------------------------------
$ SUPPLE( ) KINETIC DATA
$-------------------------------------------------------------
SUPPLE 1,2.50E14/125520/0.6276/1.0/2.50E14/125520/0.6276/1.0/&
0.0/ 0.0/ 0.0/0.0/ 5.93E18/195210/ 0.0/ 0.0/&
5.93E18/195210/ 0.0/0.0/ 0.0/ .0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.25E08/ 31045/-2.0920/1301.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.75E07/ 43390/-2.1171/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.75E07/ 43390/-2.1171/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.25E06/ 45355/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.25E06/ 45355/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.24E06/ 30335/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.50E09/ 4184/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.50E09/ 4184/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &

0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 6.07E07/ 45185/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
PRODUCT V=VAPOR, L=POLYMER_MELT
Example P9-3: Free-Radical Copolymerization in a CSTR

used to model the solution copolymerization of methyl methacry-
POLYMERS
late (MMAC) and vinyl acetate (VAC) with n-butyl benzoate as the
initiator. If bulk polymerization is of interest, this problem can be
modified easily to remove the input solvent component benzene
from the reactor feed. It is important to note:
for the polymer polystyrene, and the FILL=VANK keyword is
used to specify that van Krevelen prediction methods be used
for polymer properties.
(1MW500 through 1MW1000000).
3. The solution density and heat capacity have been set with the
ENTHALPY and DENSITY CORRELATION statements.
on this statement.
tion are summarized in Table P9-5 and are provided in the

US21 units via the SUPPLE data statement.The product is
flashed isothermally in unit PRODUCT to remove volatiles.
BATCH

Step Rate Prefactor ko Prefactor Activation
Constant Units Energy (J/gmol)
1 KDA 4.5000e14 1/sec 125000
2 KIAA 4.5000e14 m3/kmol/sec 125000
3 KIAB 4.5000e14 m3/kmol/sec 125000
22 KPAA 3.2070e6 m3/kmol/sec 24200
23 KPBA 2.1030e8 m3/kmol/sec 18000
24 KPAB 1.2330e5 m3/kmol/sec 24200
25 KPBB 6.3080e6 m3/kmol/sec 24200
POLYMERS
26 KTSA 8.6600e1 m3/kmol/sec 24200

27 KTSB 1.5140e3 m3/kmol/sec 18000
28 KRSA 8.6600e1 m3/kmol/sec 24200
29 KRSB 1.5140e3 m3/kmol/sec 18000
30 KTXA 2.0850e3 m3/kmol/sec 24200
31 KTXB 4.1630e5 m3/kmol/sec 24200
32 KRTA 2.0850e3 m3/kmol/sec 24200
33 KRTB 4.1630e5 m3/kmol/sec 24200
46 KMAA 3.2080e1 m3/kmol/sec 24200
47 KMBA 5.2570e4 m3/kmol/sec 18000
48 KRMAA 3.2080e1 m3/kmol/sec 24200
50 KRMAB 1.2340e0 m3/kmol/sec 24200
51 KMAB 1.2340e0 m3/kmol/sec 24200
52 KMBB 1.5770e3 m3/kmol/sec 18000
53 KRMBA 5.2570e4 m3/kmol/sec 18000
54 KRMBB 1.5770e3 m3/kmol/sec 18000
58 KCAA 4.2090e14 m3/kmol/sec 26900
Note: The heats of polymerization for this system (- ΔHaa), (-ΔHba), (-ΔHab),
and (-ΔHbb) are 54000, 54000, 86000, and 86000 joule/gmol, respectively; the
initiator efficiency is 1.0.

Step Rate Prefactor ko Prefactor Activation
61 KCBB 1.6100e9 m3/kmol/sec 4000
66 KZA 2.2000e0 m3/kmol/sec 0
67 KKZB 1.1300e5 m3/kmol/sec 0
Note: The heats of polymerization for this system (- ΔHaa), (-ΔHba), (-ΔHab),
and (-ΔHbb) are 54000, 54000, 86000, and 86000 joule/gmol, respectively; the
initiator efficiency is 1.0.
Polymethylmethacrylate - Polyvinylacetate CSTR Input File
POLYMERS
TITLE PROJ=COPOLYMER, PROB=PMMAC-VAC, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
STRUCTURE A, 252(1),4(1)/B, 250(1),4(1)
COMPONENT DATA
LIBID 2,MMAC/3,VACT/4,BNZN/5,BOBZ, BANK=SIMSCI
POLYMER 1,PMMAC-VAC
MWAVG 1, 54300
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION=1, DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676/*
5,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, DATA= *
1, 400, 200, 1000/*
2, 400, 200, 1000/*
3, 400, 200, 1000/*
4, 400, 200, 1000/*
5, 400, 200, 1000
ATTRIBUTE COMP=1,KINE = FR, *
MWD = 500,700,1000,3000,5000,7000,10000,*
30000,40000,50000,60000,80000,*
100000,300000,500000,700000,*
1000000,*
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4, 0.5/ B,4, 0.5
STREAM DATA
PROP STRM=S1, TEMP(K)=333.13, PRES(ATM)=5.0, *
COMP(WT,KG/MIN)=0.0/0.30/1.5/0.60/0.003
UNIT OPERATION
US21 UID=REACTOR, NAME=1st PMMAC-VAC CSTReactor
FEED S1

PROD S2
$-----------------------------------------------------------
-
BATCH

$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
POLYMERS
$ ( DEFAULT = 0 )
$-----------------------------------------------------------
-
IPARM 1,1,2,0,0, 0,1,0,1,0, 1,2,3,4,5, 0,0,0,0,0,0
$-----------------------------------------------------------
-
$-----------------------------------------------------------
-
$ FOR 1ST INITIATOR

$-----------------------------------------------------------
-
RPARM 54000., 1000.0, 333.15, 4.6, 60., 333.15, 405.3, &
1.0, 0.0, 0.0, 0.0, 0.0, 1.0, 1.0, &
54000., 86000., 86000.
$-----------------------------------------------------------
-
$-----------------------------------------------------------
-
SUPPLE 1,4.500E14/125000/0.0/0.0/4.500E14/ 125000/0.0/0.0/&
POLYMERS
4.500E14/ 125000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.207E06/ 24200/ 0.0/ 0.0/ &
2.103E08/ 18000/ 0.0/ 0.0/ 1.233E05/ 24200/ 0.0/ 0.0/ &
6.308E06/ 24200/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
4.163E05/ 24200/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
4.163E05/ 24200/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
5.257E04/ 18000/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
1.234E00/ 24200/ 0.0/ 0.0/ 1.234E00/ 24200/ 0.0/ 0.0/&
1.577E03/ 18000/ 0.0/ 0.0/ 5.257E04/18000/ 0.0/ 0.0/ &
1.577E03/ 18000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 4.209E11/26900/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
1.610E09/ 4000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 2.2/ 0.0/ 0.0/ 0.0/ &
1.130E05/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0

FLASH UID=PRODUCT
FEED S2
BATCH
Example P9-4: Free-Radical Copolymerization in a PFR

used to model the solution copolymerization of methyl methacry-
late and vinyl acetate with n-butyl benzoate as the initiator. If bulk
polymerization is of interest, this problem can be modified easily to
remove the input solvent component benzene from the reactor feed.
It is important to note:
POLYMERS
(1MW500 through 1MW1000000).
on this statement.
7. The product is flashed isothermally in unit PRODUCT to remove
volatiles.

Polymethylmethacrylate - Polyvinylacetate PFR Input File
TITLE PROJ=COPOLYMER, PROB=PMMAC-VAC, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
STRUCTURE A, 5(1),252(1),9(1)/B, 5(1),252(1),9(1)
COMPONENT DATA
LIBID 2,MMAC/3,VACT/4,BNZN/5,BOBZ, BANK=SIMSCI
POLYMER 1,PMMAC-VAC
MWAVG 1, 63950
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION=1, DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
POLYMERS
4,400,200,-457.7994,1.676/*
5,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, DATA= *
1, 400, 200, 1000/*
2, 400, 200, 1000/*
3, 400, 200, 1000/*
4, 400, 200, 1000/*
5, 400, 200, 1000
ATTRIBUTE COMP=1,KINE = FR, *
MWD = 500,1000,2000,3000,5000,7000,*
10000,30000,50000,60000,70000,*
80000,100000,300000,500000,*
700000,1000000,*
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4, 0.5/ B,4, 0.5
STREAM DATA
PROP STRM=S1, TEMP(K)=358.15, PRES(ATM)=5.0, *
COMP(WT,KG/MIN)=0.0/0.60/1.5/0.60/0.010
UNIT OPERATION
US21 UID=REACTOR, NAME=1st PMMAC-VAC PFReactor
FEED S1
PROD S2
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A

$ IPARM( 8) = N/A
BATCH
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 2,0,2,0,0, 0,1,0,1,0, 1,2,3,4,5, 0,0,0,0,0,0
$------------------------------------------------------------
POLYMERS

$------------------------------------------------------------
$ FOR 1ST INITIATOR
$------------------------------------------------------------
RPARM 54000., 0.0, 358.15, 0.0, 60., 0.0, 0.0, &
1.0, 0.0, 0.0, 500.0, 5.0, 1.0, 1.0, &
54000., 86000., 86000., 0.0045
$------------------------------------------------------------
$------------------------------------------------------------
SUPPLE 1,4.500E14/ 125000/0.0/0.0/4.500E14/125000/0.0/0.0/ &
4.500E14/ 125000/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/&
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &

0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.207E06/ 24200/ 0.0/ 0.0/&
2.103E08/ 18000/ 0.0/ 0.0/ 1.233E05/ 24200/ 0.0/ 0.0/ &
6.308E06/ 24200/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
4.163E05/ 24200/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
4.163E05/ 24200/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
5.257E04/ 18000/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
POLYMERS
1.234E00/ 24200/ 0.0/ 0.0/ 1.234E00/ 24200/ 0.0/ 0.0/ &
1.577E03/ 18000/ 0.0/ 0.0/ 5.257E04/ 18000/ 0.0/ 0.0/ &
1.577E03/ 18000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 4.209E11/ 26900/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
1.610E09/ 4000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 2.2/ 0.0/ 0.0/ 0.0/ &
1.130E05/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0
FLASH UID=PRODUCT
FEED S2

BATCH
POLYMERS

Chapter P10
User-Added Coordination Complex
systems.
POLYMERS
polymer
linear homopolymer
linear copolymer

Polymerization via Coordination Complex Kinetics
A large percentage of commercial olefin and diene polymerization
BATCH
reactions fit in the category of stereo specific, coordination com-

plex, or coordination polymerization. Here, active polymerization
centers (sites) are generated from a special initiator called a cata-
lyst. The catalyst may be a single compound or a system of com-
pounds whose synergistic effects lead to the creation of robust and
highly selective active polymerization centers.
There are two distinct paths to generate polymer with a given
molecular architecture. The first path is to use cascade reactor tech-
nology where polymer of a given characteristic is produced in an
upstream reactor. Polymerization with a different catalyst is then
performed in a downstream reactor to produce the desired charac-
teristics of the polymer product. It is now becoming possible to
POLYMERS
combine two or more catalysts in a single reactor to obtain similar

results. The multi-site catalyst has been engineered to perform both
polymerizations in a single reactor.
Ultimately, bulk physiochemical properties, and consequently, the
final application of the product, are determined by the polymer
microstructure formed by the catalyst complex during the polymer-
ization process. Distributions such as the molecular weight distribu-
tion, MWD, the chemical composition distribution (CCD), and the
long chain branching distribution (LCB) determine mechanical and
rheological properties. These properties must meet a wide range of
performance and processing criteria, and it is then desirable to tai-
lor-make more molecularly homogeneous homopolymers and copo-
lymers.
The catalyst performs two major functions in coordination polymer-
ization reactions, the first function is to provide a more accessible
energetic pathway from monomer reactant(s) to polymer product,
and secondly, the catalyst complex controls molecular architecture
via molecular selectivity. Selectivity here includes chemo-selectiv-
ity, regioselectivity, and stereo selectivity. Of primary importance in
olefin polymerization is stereo selectivity where the head to tail
bonding facilitated by the catalyst structure influences the tacticity,
and hence, the bulk properties of the polymer product. The degree
of stereo regulation is controlled by the degree of exposure of the
active site, the more exposure to the reacting medium, the less ste-
reo specific the reaction that will occur.
P10-2 User-Added Coordination Complex Polymerization Model

Numerous catalysts and catalyst systems have been developed that
promote highly reactive and specific polymerization. The catalysts
available to facilitate a coordination polymerization include organic
catalysts, the newly developed metallocene catalysts, and the classi-
cal Ziegler-Natta catalysts. Although soluble (homogeneous)
Ziegler-Natta catalysts are used in industry, currently the most
widely used coordination polymerization is via a supported (hete-
reogeneous) Ziegler-Natta catalyst polymerization. The Ziegler-
Natta catalyst consists of a mixture of a
 transition metal compound (normally a halide) from groups IV
to VIII of the periodic table, and
 an organometallic compound (hydrides, alkyls, or aryls) of a
metal from groups I to III of the periodic table.
POLYMERS
By convention the transition metal compound is labeled the catalyst
and includes compounds such as TiCl3, TiCl4, TiCl2, Ti(OR)4,
TiI4, (C2H5)2,TiCl2, VCl4, VoCl3, vacetyl-acetonate, ZrCl4, Zr
tetrabenzyl, and (C2H5)2ZrCl2. The organometallic compound is
labeled the cocatalyst and includes compounds such as Al(C2H5)3,
Al(i-C4H9)3, Al(n-C6H13)3, Al(C2H5)2Cl, Al(i-C4H9)2Cl,
Al(C2H5)Cl2, and Al2(C2H5)3Cl.
Traditional Ziegler-Natta catalysts consist of multiple active cata-
lytic sites, all of which are chemically related, but each site can
have its own reactivity ratio for monomer and/or comonomer. This
type of catalyst can lead to a broad and unacceptable MWD func-
tion.
A well-known example is the coordination polymerization of poly-
propylene that is carried out in the presence of a stereo selective cat-
alyst. This Ziegler-Natta catalyst-cocatalyst system is a mixture of
TiCl3 and AlEt3 supported on an inert silica substrate. It is possible
for propylene to form in various ways leading to either atactic, syn-
diotactic, or isotactic configurations.
The single site metallocene or constrained geometry catalyst (CGC)
is a relatively new system to tailor make polymer molecules. The
ligand environment around the central metal atom is optimized to
generate polymer with certain characteristics. The selectivity of the
catalyst is given by the steric hindrance of the substituted ligands
with respect to bulk monomer. An added feature of the CGC is the
large area for reinsertion of polymer moieties into a polymer chain.
This allows for the addition of branches. The advantages of the
metallocene catalyst system are:

 a variety of comonomer choices,
 a narrow to broad MWD,
 an ability to control crystallinity,
BATCH
 incorporation of long chain branching, and

 a clean reaction environment with high catalyst efficiency.
Coordination Complex Kinetic Mechanisms

A homogeneous coordination complex (Ziegler-Natta) bulk or solu-
tion polymerization process can be adequately modeled by the
kinetic mechanisms presented in Table P10-1. Symbols A, B, S, C,
Z, H, P, etc., within the table indicates low molecular weight species
that include monomer(s), a solvent, catalyst(s), cocatalyst(s), a
transfer agent, live or growing polymer chains that contain the
active center, and inactive or dead polymer chains in which the
POLYMERS
active center is no longer present.

Table P10-1: Multi-site Homogeneous Coordination Complex Polymerization
Scheme
Activation and Initiation Reactions
1 activation of site j on
catalyst
2 monomer A initiation at
site j on catalyst
3 monomer B initiation at
site j on catalyst
Propagation Reactions
4 monomer A propagation at
site j on catalyst

Scheme
5 monomer B propagation at
site j on catalyst
6 monomer A propagation at
site j on catalyst
7 monomer B propagation at
POLYMERS
site j on catalyst
Chain Transfer Reactions

8 transfer to monomer A at
site j on catalyst
9 transfer to monomer B at
site j on catalyst
10 transfer to monomer A at
site j on catalyst
11 transfer to monomer B at
site j on catalyst
12 transfer to solvent at site j

on catalyst

Scheme
13 transfer to solvent at site j
BATCH
on catalyst
14 transfer to modifier at site j

on catalyst
15 transfer to modifier at site j

on catalyst
POLYMERS
16 transfer to cocatalyst at
site j on catalyst
17 transfer to cocatalyst at
site j on catalyst
18 spontaneous transfer at site

j on catalyst
19 spontaneous transfer at site

j on catalyst
Termination Reactions
20 spontaneous termination
of site j on catalyst
21 termination of activated
site j on catalyst

Scheme
22 termination of activated
site j on catalyst
Catalyst Initiation
Mechanisms 1, 2, and 3 from Table 10-1 describe the catalyst initia-
tion steps, the catalyst being activated by the cocatalyst, required to
produce active polymerization sites. If from a practical standpoint,
the catalyst is preactivated before entering the reactor, then set the
pre-exponential factors of these mechanism to a large value, such as
five orders of magnitude greater than the polymerization steps 4
POLYMERS
through 7.
RXN STEP (1): CATALYST SITE ACTIVATION BY
COCATALYSTKACT
RXN STEP (2): INITIATION OF MONOMER A BY C*
KICA
RXN STEP (3): INITIATION OF MONOMER B BY C*
KICB
Chain Propagation at Catalyst Site

The insertion reaction at the active center continues to add mono-
mer to the growing or live chain, thereby increasing the molecular
weight of the polymer molecule. The insertion mechanisms are
modeled with the following steps:
RXN STEP (4): PROPAGATION OF P* WITH MONOMER AKPAA
RXN STEP (5): PROPAGATION OF Q* WITH MONOMER AKPBA
RXN STEP (6): PROPAGATION OF P* WITH MONOMER BKPAB
RXN STEP (7): PROPAGATION OF Q* WITH MONOMER BKPBB
Chain Transfer at Catalyst Site

The active center is very reactive and, as such, can react with other
chemical species in the reaction mixture. The reactive center can be
transferred to monomer, solvent, or modifier molecules. The origi-
nal live polymer chain is now inactive or dead, but the reactive site
remains active on a different molecule.
RXN STEP (8): TRANSFER FROM P* TO MONOMER A TO FORM RP*KPAB
RXN STEP (9): TRANSFER FROM Q* TO MONOMER A TO FORM RP*KPBA
RXN STEP (10): TRANSFER FROM P* TO MONOMER B TO FORM RQ*KMAB
RXN STEP (11): TRANSFER FROM Q* TO MONOMER B TO FORM RQ*KMBB
RXN STEP (12): TRANSFER FROM P* TO SOLVENT TO FORM RP*KTSA
RXN STEP (13): TRANSFER FROM Q* TO SOLVENT TO FORM RQ*KTSB

RXN STEP (14): TRANSFER FROM P* TO SOLVENT TO FORM RP*KTHA
RXN STEP (15): TRANSFER FROM Q* TO SOLVENT TO FORM RQ*KTHB
RXN STEP (16): TRANSFER FROM P* TO COCATALYST TO FORM C*KTAC
BATCH
RXN STEP (17): TRANSFER FROM Q* TO COCATALYST TO FORM C*KTBC
Chain Termination
The current model presented in Table 10-1 provides for spontane-
ous and thermal termination of the active site. Once a site has been
market dead through these reactions, the mechanism does not allow
the site to be regenerated, rather that site is carried around as dead
catalyst.
RXN STEP (18): SPONTANEOUS TERMINATION OF P* TO FORM C*KZA
RXN STEP (19): SPONTANEOUS TERMINATION OF Q* TO FORM C*KZB
POLYMERS
RXN STEP (20): SPONTANEOUS TERMINATION OF C* TO FORM D*KSPT

RXN STEP (21): THERMAL DEGRADATION OF P* TO FORM D*KTDA
RXN STEP (22): THERMAL DEGRADATION OF Q* TO FORM D*KTDB
The coordination complex polymerization scheme given in Table

10-1 is presented in pictorial form in Figure P10-1. Reaction path-
ways are represented with arrows and rate constants are indicated.
Inactive, active, and dead catalyst at site (j) are given by C(j), C*(j),
and D(j), respectively. Live polymer is represented by P(n,m) and
Q(n,m). Product polymer is represented by D(n,m). A sample poly-
mer reaction scheme occurring at site (j) is indicated with the dotted
arrows in this figure. Inactive catalyst, C(j), is converted to active
catalyst C*(j) at a rate given by the rate constant Kact. Monomer A
is inserted at the site at a rate given by the rate constant Kica after
which the propagation reaction given by the rate constant Kpaa pro-
ceeds. A termination reaction given by Ktda produces polymer
product, D(n,m) and dead catalyst, D(j).

Figure P10-1: Pictorial Representation of Coordination Complex Polymerization
Scheme
POLYMERS

BATCH
 Component data
 Components – Monomer(s), polymer, solvent, catalyst(s)
(required), cocatalyst(s) (optional), transfer agent (optional),
inhibitor (optional)
SAFT, or PHSC
POLYMERS

reactor)
 Coordination Complex kinetic data
 Required Coordination Complex reactions (initiation, propaga-
tion)
P10-10 User-Added Coordination Complex Polymerization


Guide.
Communicating with PRO/II for Coordination Complex

Kinetics
POLYMERS
The keyword headers that contain the descriptions of IPARM,
RPARM, and SUPPLE are quite lengthy. These headers are given on
the next page and do not appear in the example problems.
The homogeneous multi-site catalyst model developed here allows
for a maximum of four (N=4) distinct reaction sites generated from
a maximum of 2 catalysts or 2 catalyst-cocatalyst pairs. Each type
of reaction site is assumed to be unique kinetically; therefore, each
type of site has a unique set of kinetic rate parameters assigned to it
through the SUPPLE data vector.
The catalyst(s) or catalyst-cocatalyst pair(s) flow rate is set in the
STREAM DATA section. The first catalyst contains N types of
sites, and the second catalyst (if present) contains up to 4 – N types
of sites. The relative amount and state of each type of reaction site
is described by a set of 3 numbers given sequentially in the RPARM
vector.
The site fraction gives the relative portion of that type of site to all
of the types of sites present on that particular catalyst. Since the
possible states for each type of site can be activated, inactive, or
dead, the second and third entries convey what portion of the type
of site is activated and inactive, respectively. The fraction of dead
sites is then calculated internally by difference.
From a processing standpoint, it is preferable to have a single cata-
lyst exhibiting polymerization characteristics of a single type of cat-
alyst site throughout the reaction process. In this case IPARM(4)
and IPARM(5) would be set to 1 and 0, respectively. The site frac-
tion defined in RPARM(22) would then be set to 1.0, there is only

one type of site. Now if the catalyst was pre-activated upstream of
the reactor inlet such that 95% of the available sites were reactive,
RPARM(23) and RPARM(24) would be 0.05 and 0.95, respectively.
BATCH
Additional types of reaction sites can be introduced in the simula-

tion as needed. Figure P10-2 represents two catalysts, the 1st cata-
lyst with 3 types of sites, and the 2nd catalyst with one type of site.
Figure P10-2: An example of two catalysts with four types of sites.
Type I Sites
- inactive
- activated
- dead Type II Sites
- inactive Type IVSites
- activated - inactive
POLYMERS
Type III Sites

- inactive - dead - activated
- activated - dead
dead
In this case IPARM(4) and IPARM(5) would be set to 3 and 1,

respectively.
Assuming that the concentrations of types of sites on the 1st catalyst
are equal in value, RPARM(22), RPARM(25), and RPARM(28) are
set close to 1/3 (site fractions will be normalized internally).
Assuming the catalyst has not been pre-activated upstream of the
reactor, the inactive fractions RPARM(23), RPARM(26), and
RPARM(29) are set to 1.0’s and the activated fractions
RPARM(24), RPARM(27), and RPARM(30) are set to 0.0’s,
respectively.
For the 2nd catalyst, the site fraction for the 4th type of site is 1.0,
there is only one type of site on the 2nd catalyst and RPARM(31) is
set to 1.0.
Assuming the Type IV sites have not been activated, RPARM(32)
and RPARM(33) are 1.0 and 0.0, respectively.
IPARM integer,…. (up to 21 values)
RPARM real no,…. (up to 18 values)
SUPPLEMENTAL i,Ri/Ri+1/…/j,Rj/Rj+1… (up to 86 values)

Integer IPARM Data:
$
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ = 6 FOR HOMOGENEOUS ZN HOMOPOLYMERIZATION
$ = 7 FOR HOMOGENEOUS ZN COPOLYMERIZATION
$ IPARM( 4) = SITES ( 4 MAX ) ON 1ST CATALYST (=n)
REQ
$ IPARM( 5) = SITES (4-n MAX) ON 2ND CATALYST (=m OR 0)
POLYMERS
$
$ IPARM( 6) -> IPARM(10) N/A
$
$ IPARM(11) = POLYMER COMPONENT REQ
$
$ IPARM(12) = MONOMER A COMPONENT REQ
$ IPARM(15) = MODIFIER COMPONENT (OR 0)
$
$ IPARM(16) = 1ST CATALYST COMPONENT REQ
$ IPARM(17) = 1ST COCATALYST COMPONENT (OR 0)
$
$ IPARM(18) = 2ND CATALYST COMPONENT (OR 0)
$ IPARM(19) = 2ND COCATALYST COMPONENT (OR 0)
$
$————————————————————————————————

Real RPARM Data:
$
BATCH

$ RPARM( 2) = CSTR REACTOR VOLUME, LITER
$ RPARM( 3) = JACKET TEMPERATURE, K, FOR NONISOTHERMAL
$ REACTOR
$ RPARM( 4) = JACKET AREA, M2, FOR NONISOTHERMAL REACTOR
$ RPARM( 5) = OVERALL HTC, J/SEC/M2/K, FOR NONISOTHERMAL
$ REACTOR
$ = OPERATING TEMPERATURE FOR ISOTHERMAL CSTR/PFR
$ RPARM( 7) = CSTR REACTOR PRESSURE DROP (kPa); DEFAULT=0.0
$
$ RPARM( 8) -> RPARM(10) N/A
$
POLYMERS

$ RPARM(14) = FEED STREAM LIVE CHAIN B FRACTION (COPOLYMER)
$ RPARM(19) = N/A
$
$ RPARM(20) = INTERACTION ORDER FOR TRANSFER AGENT TO P*
$ RPARM(21) = INTERACTION ORDER FOR TRANSFER AGENT TO Q*
$
$ RPARM(22) = TYPE I SITE FRACTION
$ RPARM(23) = FRACTION OF TYPE I SITES WHICH ARE INACTIVE
$ RPARM(24) = FRACTION OF TYPE I SITES WHICH ARE ACTIVE
$
$ RPARM(25) = TYPE II SITE FRACTION
$ RPARM(26) = FRACTION OF TYPE II SITES WHICH ARE INACTIVE
$ RPARM(27) = FRACTION OF TYPE II SITES WHICH ARE ACTIVE
$
$ RPARM(28) = TYPE III SITE FRACTION
$ RPARM(29) = FRACTION OF TYPE III SITES WHICH ARE INACTIVE
$ RPARM(30) = FRACTION OF TYPE III SITES WHICH ARE ACTIVE
$
$ RPARM(31) = TYPE IV SITE FRACTION
$ RPARM(32) = FRACTION OF TYPE IV SITES WHICH ARE INACTIVE
$ RPARM(33) = FRACTION OF TYPE IV SITES WHICH ARE ACTIVE
$————————————————————————————————

Real SUPPLE Data:
$ CATALYST - FIRST SITE
$REACTION STEP( 1): CATALYST SITE ACTIVATION BY
$ COCATALYST KACT
$REACTION STEP( 2): INITIATION OF MONOMER A BY C* KICA
$REACTION STEP( 3): INITIATION OF MONOMER B BY C* KICB
$REACTION STEP( 4): PROPAGATION OF P* WITH MONOMER A KPAA
POLYMERS
$REACTION STEP( 5): PROPAGATION OF Q* WITH MONOMER A KPBA
$REACTION STEP( 6): PROPAGATION OF P* WITH MONOMER B KPAB
$REACTION STEP( 7): PROPAGATION OF Q* WITH MONOMER B KPBB
$REACTION STEP( 8): TRANSFER FROM P* TO MONOMER A
$ TO FORM RP* KMAA
$REACTION STEP( 9): TRANSFER FROM Q* TO MONOMER A
$ TO FORM RP* KMBA
$REACTION STEP(10): TRANSFER FROM P* TO MONOMER B
$ TO FORM RQ* KMAB
$REACTION STEP(11): TRANSFER FROM Q* TO MONOMER B
$ TO FORM RQ* KMBB
$REACTION STEP(12): TRANSFER FROM P* TO SOLVENT
$ TO FORM RP* KTSA
$REACTION STEP(13): TRANSFER FROM Q* TO SOLVENT
$ TO FORM RQ* KTSB

$REACTION STEP(14): TRANSFER FROM P* TO SOLVENT
$ TO FORM RP* KTHA
BATCH

$REACTION STEP(15): TRANSFER FROM Q* TO SOLVENT
$ TO FORM RQ* KTHB
$REACTION STEP(16): TRANSFER FROM P* TO COCATALYST
$ TO FORM C* KTAC
$REACTION STEP(17): TRANSFER FROM Q* TO COCATALYST
$ TO FORM C* KTBC
POLYMERS
$REACTION STEP(18): SPONTANEOUS TERMINATION OF P*

$ TO FORM C* KZA
$REACTION STEP(19): SPONTANEOUS TERMINATION OF Q*
$ TO FORM C* KZB
$REACTION STEP(20): SPONTANEOUS TERMINATION OF C*
$ TO FORM D* KSPT
$REACTION STEP(21): THERMAL DEGRADATION OF P*
$ TO FORM D* KTDA
$REACTION STEP(22): THERMAL DEGRADATION OF Q*
$ TO FORM D* KTDB
$
$ CATALYST - SECOND SITE ( IF USED )
$ REACTION(23) -> REACTION(44)
$ SUPPLE(45) -> SUPPLE(88)
$ CATALYST - THIRD SITE ( IF USED )
$ CATALYST - FOURTH SITE ( IF USED )

Using Reactor Unit US21 to Model Coordination Polymer-
ization Systems
Polymer systems that may be modeled with unit US21 are:
 Polyolefin Homopolymers and Copolymers
Example P10-1: Single-Site Coordination Homopolymeriza-

tion in a CSTR
used to model the solution polymerization of polyethylene. It is
important to note:
POLYMERS
for the polymer polyethylene, and the FILL=VANK keyword is
2. The molecular weight distribution is provided on the ATTRI-
BUTE statement. The distribution given will result in the cre-
ation of 10 polymer pseudocomponents (1MW50000 through
1MW600000).
on this statement.
5. NONLIB components MSZ and MAO represent the zircono-
cene dichloride ([C2H5]2ZrCl2) catalyst and methylaluminox-
ane ([MeAlO]x) activator system. Here the molecular weight
given for MAO is consistent for a value of x=3.
and the non-isothermal reactor operating conditions are pro-
7. Data for the coordination complex kinetics for the polymeriza-
tion reaction are taken from Table P10-2 and are provided in
the US21 units via the SUPPLE data statement.

Table P10-2: Co-ordinate Comples Kinetics for
BATCH
Step Rate Prefactor k0 Prefactor Activation

1 kact 9.999E09 (L/gmol/sec) 20000.
2 kica 1.611E10 (L/gmol/sec) 20502.
3 kicb 1.056E09 (L/gmol/sec) 25940.
4 kpaa 1.611E10 (L/gmol/sec) 20502.
5 kpba 4.722E10 (L/gmol/sec) 25940.
6 kpab 7.222E08 (L/gmol/sec) 20502.
7 kpbb 1.056E09 (L/gmol/sec) 25940.
8 kmaa 5.833E04 (L/gmol/sec) 14540.
POLYMERS
9 kmba 8.167E02 (L/gmol/sec) 19986.

10 kmab 9.917E02 (L/gmol/sec) 14540.
11 kmbb 2.722E04 (L/gmol/sec) 19986.
12 ktsa 0.000E00 (L/gmol/sec) 0.
13 ktsb 0.000E00 (L/gmol/sec) 0.
14 ktha 0.000E00 (L/gmol/sec) 0.
15 kthb 0.000E00 (L/gmol/sec) 0.
16 ktac 5.833E05 (L/gmol/sec) 14540.
17 ktbc 9.917E03 (L/gmol/sec) 14540.
18 kza 5.000E10 (sec^-1) 46420.
19 kzb 1.361E12 (sec^-1) 51860.
20 kspt 4.722E04 (sec^-1) 25104.
21 ktda 4.722E04 (sec^-1) 25104.
22 ktdb 4.722E04 (sec^-1) 25104.
Note: The heats of polymerization for this system (- ΔHaa), (-ΔHba), (-ΔHab), and
(-ΔHbb) are 94800, 89650, 89650, and 84750 joule/gmol, respectively.
References
1. Kim, Kee Jeong and Kyu Yong Choi, “Continuous Olefin
Copolymerization with Soluble Ziegler-Natta Catalysts”,
AICHE Journal, August 1991, Vol. 37, No. 8 pp. 1255-1260.

Polyethylene Input CSTR File
TITLE PROJ=HOMOPOLYMER, PROB=ETH, USER=SIM, DATE=05/08/2007
$
DIME SI
$
$ DIMENSION METRIC, STDTEMP=0, STDPRES=1.03323
$ DIMENSION ENGLISH, STDTEMP=60.0008, STDPRES=14.6959
$
OUTDIME REPLACE, SI, TIME=MIN
$
PRINT INPUT=ALL, STREAM=ALL, RATE=WT, PWRATE
$
SEGMENT DATA
POLYMERS
STRUCTURE A, 4(2)
$
$ (1)Polymer
$ (2)Monomer A (3)Monomer B (4)Solvent
$ (5)Modifier (6)1st Catalyst (7)1st CoCatalyst
$ (8)2nd Catalyst (9)2nd CoCatalyst
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,HEXANE, BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1, HPE
MWAVG 1, 100000/ 4, 292.2 / 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, &
DATA= 1, 400, 200,-457.7994, 1.76/ &
2, 400, 200,-457.7994, 1.76/ &
3, 400, 200,-457.7994, 1.76/ &
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76
$
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, &
DATA= 1, 400, 200, 900/ 2, 400, 200, 905/ &
3, 400, 200, 910/ 4, 400, 200, 915/ &
5, 400, 200, 920
$
VP(Pa) CORRELATION= 20, DATA=4, 400, 200, 0.0, 1.0 / &
5, 400, 200, 0.0, 1.0

$
LATENT (KCAL/K,WT) CORRELATION= 15, &
DATA= 4, 400, 200, 8730800., 0.3526000/ &
BATCH
5, 400, 200, 8730800., 0.3526000

$
ATTRIBUTE COMP= 1, KINE= ZN, *
MWD= 50000, 100000, 150000, 200000, 250000, &
300000, 350000, 400000, 500000, 600000, &
MMWD= psi0, psi1, psi2
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,3, 0.5 $MONOMER-SOLVENT INTERACTIONS
$
STREAM DATA
POLYMERS
PROP STRM=Feed_1, TEMP(K)=180.15, PRES(ATM)=35.0, &

$
COMP(WT,KG/MIN)=0.0/0.8/0.2/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=PE CSTReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = SITES ( 4 MAX ) ON 1ST CATALYST (=N) REQ
$ IPARM( 5) = SITES (4-N MAX) ON 2ND CATALYST (=M OR 0)
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$

$------------------------------------------------------------
IPARM 1,0,6,1,0, 0,0,0,0,0, 1,2,0,3,0, 4,5,0,0
$------------------------------------------------------------
$
POLYMERS
$ RPARM( 8) -> RPARM(19) N/A

$------------------------------------------------------------
RPARM 74800., 1000.0, 180.15, 100.0, 3.66, 150.00, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.5, 0.5, &
1.00, 1.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6
$------------------------------------------------------------
$ RPARM(22) = Type I Site Fraction
$ RPARM(23) = Fraction of Type I Sites which are Inactive
$ RPARM(24) = Fraction of Type I Sites which are Active
$
$ RPARM(25) = Type II Site Fraction
$ RPARM(26) = Fraction of Type II Sites which are Inactive
$ RPARM(27) = Fraction of Type II Sites which are Active
$
$ RPARM(28) = Type III Site Fraction
$ RPARM(29) = Fraction of Type III Sites which are Inactive
$ RPARM(30) = Fraction of Type III Sites which are Active
$
$ RPARM(31) = Type IV Site Fraction
$ RPARM(32) = Fraction of Type IV Sites which are Inactive
$ RPARM(33) = Fraction of Type IV Sites which are Active
$
$

$
$-------------------------------------------------------
SUPPLE 1, &
BATCH
$ CATALYST / 1ST (ONLY) SITE

9.999E09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
POLYMERS
Example P10-2: Multi-Site Coordination Copolymerization

in a CSTR
used to model the bulk copolymerization of ethylene and butene. It
is important to note:
1MW600000).
on this statement.

given for MAO is consistent for a value of x=3. Data describing
the NONLIB components MSZP and MAOP are identical with
that of the NONLIB components MSZ and MAO. NONLIB

components MSZP and MAOP have been introduced here to
indicate how a second catalyst-activator system is addressed.
tion reaction are taken from Table 10-2 and are provided in the
US21 units via the SUPPLE data statement.
Polyethylene-butene Input CSTR File

TITLE PROJ=COPOLYMER, PROB=Eth:But-1, USER=SIM, DATE=05/08/07
$
DIME SI
POLYMERS
$
$
$
PRINT RATE=WT
$ PRINT RATE=WT, PWRATE
$
SEGMENT DATA
SEGMENT A, PE1/B, BUT1, FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 60(1),4(1)
$
$ (1)Polymer
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,BUT1/ 4,HEXANE/ 5,DPRK, BANK=SIMSCI
NONLIB 6,MSZ/ 7,MAO/ 8,MSZP/ 9,MAOP
$
POLYMER 1,PE-BUTENE
MWAVG 1, 100000/ 6, 292.2/ 7, 580.0/ 8, 292.2/ 9, 580.0
PHASE VLS=1
$
SPGR 6, 1.6 / 7, 1.4 / 8, 1.6 / 9, 1.4
NBP(K) 6, 450.0 / 7, 450.0 / 8, 450.0 / 9, 450.0
SOLUPARA 6, 10.0 / 7, 10.0 / 8, 10.0 / 9, 10.0
$
ENTHALPY(L,K,J/G,WT) CORRELATION= 1, &

DATA= 1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
BATCH
4, 400, 200,-457.7994, 1.76/*

5, 400, 200,-457.7994, 1.76/*
6, 400, 200,-457.7994, 1.76/*
7, 400, 200,-457.7994, 1.76/*
8, 400, 200,-457.7994, 1.76/*
9, 400, 200,-457.7994, 1.76
$
DENSITY(L,K,G/LIT,WT) CORRELATION= 1, &
DATA= 1, 400, 200, 900/ 2, 400, 200, 905/ &
3, 400, 200, 910/ 4, 400, 200, 915/ &
5, 400, 200, 920/ 6, 400, 200, 925/ &
7, 400, 200, 930/ 8, 400, 200, 935/ &
9, 400, 200, 940
POLYMERS
$
VP(Pa) CORRELATION= 20, &
DATA= 6, 400, 200, 0.0, 1.0/ 7, 400, 200, 0.0, 1.0/ &
8, 400, 200, 0.0, 1.0/ 9, 400, 200, 0.0, 1.0
$
LATENT(KCAL/K,WT) CORRELATION= 15, &
DATA= 6, 400, 200, 8730800., 0.3526000/ &
7, 400, 200, 8730800., 0.3526000/ &
8, 400, 200, 8730800., 0.3526000/ &
9, 400, 200, 8730800., 0.3526000
$
ATTRIBUTE COMP= 1, KINE= ZN, *
MWD= 50000, 100000, 150000, 200000, 250000, &
300000, 350000, 400000, 500000, 600000, &
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4,0.5 / B,4,0.5 $MONOMER-SOLVENT INTERACTION
$
STREAM DATA
$
COMP(WT,KG/MIN)= 0.0/0.2/0.8/0.1/0.1/ &
1.0E-7/0.01/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=1st PE-BUT CSTReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------

$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
POLYMERS
$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 1,0,7,2,2, 0,0,0,0,0, 1,2,3,4,5, 6,7,8,9
$------------------------------------------------------------
$
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A

$ RPARM(19) = N/A
BATCH
$ RPARM(20) = INTERACTION ORDER FOR TRANSFER AGENT TO P &

$ RPARM(21) = INTERACTION ORDER FOR TRANSFER AGENT TO Q &
$-----------------------------------------------------------
RPARM 94800., 100.0, 180.15, 100.0, 36.6, 148.15, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
89650., 89650., 84750., 0.0, 0.0, 0.5, 0.5, &
0.20, 1.0E-0, 0.0E-6, 0.30, 1.0E-0, 0.0E-6, &
0.40, 1.0E-0, 0.0E-6, 0.10, 1.0E-0, 0.0E-6
$-----------------------------------------------------------
$
POLYMERS

$
$
$
$
$ CATALYST - THIRD SITE ( IF USED )
$ CATALYST - FOURTH SITE ( IF USED )
$----------------------------------------------------------
$
SUPPLE 1, &
$ CATALYST / 1ST SITE
9.999e18/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &

2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$ CATALYST / 2ND SITE
9.999e18/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
POLYMERS
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$ CATALYST / 3RD SITE
9.999e18/ 20000./ 1.611E09/ 20502./ &
1.056E09/ 25940./ 1.611E09/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$ CATALYST / 4TH SITE
9.999e18/ 20000./ 1.611E09/ 20502./ &
1.056E09/ 25940./ 1.611E09/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$

Example P10-3: Single-Site Coordination Polymerization in
a CSTR
BATCH

used to model the bulk polymerization of ethylene and butene. If
solution polymerization is of interest, this problem can be modified
easily to add an input solvent component to the reactor feed. It is
important to note:
for the polymer polyethylene and polyvinylacetate. The
FILL=VANK keyword is used to specify that van Krevelen pre-
diction methods be used for polymer properties.
POLYMERS
1MW200000).

on this statement.

Polyethylene-Butene CSTR Input File
TITLE PROJ=COPOLYMER, PROB=Eth:But-1, USER=SIM, DATE=05/08/07
$
DIME SI
$
$
$
PRINT RATE=WT
$
SEGMENT DATA
POLYMERS
SEGMENT A, PE1 /B, BUT1, FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 60(1),4(1)
$
$ (1)Polymer
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,BUT1, BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1,PE-BUT
MWAVG 1, 100000/ 4, 292.2/ 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
DATA= 1, 400, 200,-457.7994, 1.76/ &
2, 400, 200,-457.7994, 1.76/ &
3, 400, 200,-457.7994, 1.76/ &
4, 400, 200,-457.7994, 1.76/ &
5, 400, 200,-457.7994, 1.76
$
DATA= 1, 400, 200, 900/ &
2, 400, 200, 905/ &
3, 400, 200, 910/ &
4, 400, 200, 915/ &
5, 400, 200, 920

$
5, 400, 200, 0.0, 1.0
BATCH
$
DATA=4, 400, 200, 8730800., 0.3526000/&
5, 400, 200, 8730800., 0.3526000
$
ATTRIBUTE COMP= 1, KINE= ZN, &
MWD= 50000, 60000, 70000, 80000, 90000, &
110000, 130000, 150000, 170000, 200000, &
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
POLYMERS
CHI A,4, 0.5/ B,4, 0.5 $ MONOMER-SOLVENT INTERACTIONS

$
STREAM DATA
$
COMP(WT,KG/MIN)=0.0/0.2/0.8/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=1st PE-BUT CSTReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$

$------------------------------------------------------------
IPARM 1,1,7,1,0, 0,0,0,0,0, 1,2,3,0,0, 4,5,0,0
$------------------------------------------------------------
$
POLYMERS
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A
$------------------------------------------------------------
RPARM 94800., 100.0, 180.15, 100.0, 36.6, 140.00, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
89650., 89650., 84750., 0.0, 0.0, 0.5, 0.5, &
$
1.00, 1.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6
$------------------------------------------------------------
$

$
BATCH

$
$
$------------------------------------------------------------
$
SUPPLE 1, &
$
POLYMERS
9.999e09/ 20000./ 1.611E10/ 20502./ &

1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$
$
US21 UID=REACTOR2, NAME=2nd PE-BUT CSTReactor
FEED Prod_1
PROD Prod_2
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A

$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 1,1,7,1,0, 0,0,0,0,0, 1,2,3,0,0, 4,5,0,0
$------------------------------------------------------------
$
POLYMERS
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A
$----------------------------------------------------------
RPARM 94800., 100.0, 180.15, 100.0, 36.6, 160.00, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
89650., 89650., 84750., 0.0, 0.0, 0.5, 0.5, &
1.00, 1.0E-0, 0.0E-6, 0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, 0.00, 0.0E-0, 0.0E-6
$
DEFINE RPARM(22) AS US21=REACTOR1 RPARM(22)

BATCH


$
$------------------------------------------------------------
POLYMERS

$
$
$
$
$------------------------------------------------------------
$
SUPPLE 1, &
$
9.999e09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.

Example P10-4: Multi-Site Coordination Polymerization in
a PFR
used to model the solution polymerization of ethylene. It is impor-
tant to note:
POLYMERS
1MW200000).

on this statement.

Polyethylene PFR Input File
TITLE PROJ=HOMOPOLYMER, PROB=Eth, USER=SIM, DATE=12/30/98
BATCH
$
DIME SI
$
$
$
PRINT RATE=WT
$
SEGMENT DATA
STRUCTURE A, 4(2)
POLYMERS
$
$ (1)Polymer
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,HEXANE, BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1,PETH
MWAVG 1, 100000/ 4, 292.2/ 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
DATA= 1, 400, 200,-457.7994, 1.76/ &
2, 400, 200,-457.7994, 1.76/ &
3, 400, 200,-457.7994, 1.76/ &
4, 400, 200,-457.7994, 1.76/ &
5, 400, 200,-457.7994, 1.76
$
DATA= 1, 400, 200, 900/ &
2, 400, 200, 905/ &
3, 400, 200, 910/ &
4, 400, 200, 915/ &
5, 400, 200, 920

$
5, 400, 200, 0.0, 1.0
$
DATA= 4, 400, 200, 8730800., 0.3526000/ &
5, 400, 200, 8730800., 0.3526000
$
ATTRIBUTE COMP= 1, KINE= ZN, &
MWD= 50000, 60000, 70000, 80000, 90000, &
110000, 130000, 150000, 170000, 200000, &
$
THERMO DATA
METHOD SYSTEM=FLORY
POLYMERS
KVALUE
CHI A,2 ,0.5 $MONOMER-SOLVENT INTERACTION
$
STREAM DATA
$
COMP(WT,KG/MIN)=0.0/2.0/2.0/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=1st PE PFReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$

BATCH

$------------------------------------------------------------
IPARM 2,0,6,2,0, 0,0,0,0,0, 1,2,0,3,0, 4,5,0,0
$------------------------------------------------------------
$
POLYMERS

$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A
$-----------------------------------------------------------
RPARM 94800., 0.0, 140.15, 0.0, 36.6, 140.00, 0.0, &
0.0, 0.0, 0.0, 500.0, 4.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.9, 0.0, 0.5, 0.5, &
0.25, 1.0E-0, 0.0E-6, 0.75, 1.0E-0, 0.0E-6, &
0.0, 0.0E-0, 0.0E-6, &
0.0, 0.0E-0, 0.0E-6
$-----------------------------------------------------------
$

$
$
$
$
$
$RXN STEP( 1): CATALYST SITE ACTIVATION BY COCATALYST KACT
$RXN STEP( 2): INITIATION OF MONOMER A BY C* KICA
$RXN STEP( 3): INITIATION OF MONOMER B BY C* KICB
POLYMERS
$RXN STEP( 4): PROPAGATION OF P* WITH MONOMER A KPAA
$RXN STEP( 5): PROPAGATION OF Q* WITH MONOMER A KPBA
$RXN STEP( 6): PROPAGATION OF P* WITH MONOMER B KPAB
$RXN STEP( 7): PROPAGATION OF Q* WITH MONOMER B KPBB
$RXN STEP( 8): TRANSFER FROM P* TO MONOMER A TO FORM RP* KMAA
$RXN STEP( 9): TRANSFER FROM Q* TO MONOMER A TO FORM RP* KMBA
$RXN STEP(10): TRANSFER FROM P* TO MONOMER B TO FORM RQ* KMAB
$RXN STEP(11): TRANSFER FROM Q* TO MONOMER B TO FORM RQ* KMBB
$RXN STEP(12): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTSA
$RXN STEP(13): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTSB
$RXN STEP(14): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTHA
$RXN STEP(15): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTHB
$RXN STEP(16): TRANSFER FROM P* TO COCATALYST TO FORM C* KTAC
$RXN STEP(17): TRANSFER FROM Q* TO COCATALYST TO FORM C* KTBC
$RXN STEP(18): SPONTANEOUS TERMINATION OF P* TO FORM C* KZA
$RXN STEP(19): SPONTANEOUS TERMINATION OF Q* TO FORM C* KZB
$RXN STEP(20): SPONTANEOUS TERMINATION OF C* TO FORM D* KSPT
$RXN STEP(21): THERMAL DEGRADATION OF P* TO FORM D* KTDA
$RXN STEP(22): THERMAL DEGRADATION OF Q* TO FORM D* KTDB
$
$
$-------------------------------------------------------
$
SUPPLE 1, &
$
9.999e09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &

8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
BATCH
0.000E00/ 0./ 5.833E05/ 14540./ &

9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$
$ CATALYST / 2ND SITE
9.999e09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
POLYMERS
0.000E00/ 0./ 5.833E05/ 14540./ &

9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$

Chapter P11
User-Added Step Growth
Polymerization Reactor Model

systems.
POLYMERS
polymer
linear homopolymer
linear copolymer

Polymerization via Step-wise Kinetics
Stepwise or step growth polymerization refers to a kinetic mecha-
BATCH
nism in which the polymer molecular weight increases in a slow

and steplike manner as the reaction time increases. The stepwise
polymerization mechanism involves a chemical reaction between
monomer functional groups. All stepwise polymerizations fall into
two groups, depending on the structure and number of monomers
taking part in the reaction.
The first monomer group describes the reaction between the func-
tional groups of one bifunctional or polyfunctional monomer that
contains different functional groups. The monomers of this group
are labeled as ARB. A general stepwise ARB polymerization can be
represented as:
POLYMERS
( n )XA′R 1 B′Y + ( n )XA′R 1 B′Y<—> X – ( A′R 1 B′A′R 1 B′ ) n – Y + ( 2n – 1 )X:Y
in which A'X represents functional groups may include:

– NH 2 – SH – CONH 2 – OH – NOH
and B'Y represents functional groups that may include:

– COOH – COCl – PORCl – SOOCl
The second monomer group describes the reaction between two dif-
ferent bifunctional or polyfunctional monomers in which each of
the reacting monomers contains only one unique functional group.
The monomers of this group are labeled as ARA and BRB. A general
stepwise ARA and BRB polymerization can be represented as:
( n )XA′R 1 A′X + ( n )YB′R 2 B′Y<—> X – ( A′R 1 B′A′R 2 B′ ) n – Y + ( 2n – 1 )X:Y
The reacting functional groups contain the atoms X and Y and it is

these moieties that form the condensate X:Y. To simplify the step-
wise nomenclature, the following definitions have been used:
*
A = XA′ B = YB′ R = R 1 A′B′R 1 R = R 1 A′B′R 2
Note that the groups R* and R do not take place explicitly in the
polymerization, because the condensation reactions occur at the ter-
minal functional groups. The general reactions for ARB and ARA and
BRB polymerization are then greatly simplified.
ARB polymerization:
*
( n )AR 1 B<——>A – ( R ) n + ( 2n – 1 )X:Y
P11-2 User-Added Step Growth Polymerization Reactor Model

ARA + BRB polymerization:
( n )AR 1 A + ( n )BR 2 B<——>A – ( R n ) + ( 2n – 1 )X:Y
The step growth polymerization reactions are usually slow and take
on the order of 10 - 20 hours to complete. The polymerization reac-
tions may be reversible, and, if so, they are dominated by equilib-
rium considerations. Consequently, it is important to accurately
simulate a flash in which any condensate or residual monomer is
driven off. The reaction kinetics are then shifted such that increased
yield is obtained. The monomers used in the step growth polymer-
izations include esters, ethers, amines, and amides. Polymer exam-
ples are polyesters, polyethers, nylons (Nylon 6, Nylon 6,6), and
polyimides (Kevlar).
POLYMERS
Stepwise Polymerization Chain Types
Three categories of stepwise polymer chains can be identified from
the functionality of the reacting monomers and the structure of the
polymer chain formed.
If a single monomer is involved in the reaction, and the monomer is
of the bifunctional form A-B (actually A-R-B), the polymer formed
has the structure given by A-BA-BA-B. This is a Type I stepwise
polymerization.
Type I:
ARB + ARB<——> AR′R′B + C
X 1 A′RB′Y 1 + X 1 A′RB′Y 1 <——> X 1 A′B′A′RB′Y 1 + X 1 Y 1
The kinetic data for this reaction require the definition of a single
monomer along with the rate constants for the reaction between X1
and Y1.
If two monomers are involved in the reaction, and the monomers
are of the monofunctional form A-A and B-B (actually A-R-B and B-
R-B), the polymer formed has the structure given by A-BA-BA-B.
This is a Type II stepwise polymerization.
Type II:
AR 1 A + BR 2 B<——> AR1 ′R 2 ′B + C
X 1 A 1 ′R 1 A 1 ′X 1 + Y 1 B 1 ′R 2 B 1 ′Y 1 <——> X 1 A 1 ′R 1 A 1 ′B 1 ′R 2 B 1 ′Y 1 + X 1 Y 1

The kinetic data for this reaction require the definition of two
monomers along with the rate constants for a reaction between X1
and Y1.
BATCH
If a single monomer is involved in the reaction and the monomer is

of the monofunctional form A-A (actually A-R-A), the polymer
formed has the structure given by A-R-R-A. This is a Type III step-
wise polymerization.
Type III:
ARA + ARA<——> AR′R′A + C
X 1 A′RA′Y 1 + X 1 A′RA′Y 1 <——> X 1 A′RA′Y 1 + X 1 Y 1
The kinetic data for this reaction requires the definition of a single
monomer along with the rate constants for a reaction between X1
POLYMERS
and Y1.
Ultimately, it is required that a value for the number of monomer
units be incorporated into the “average” stepwise polymer and that
the number of active functional groups (X and Y) on the average
polymer chain be available. This characterization begins with the
population balance. The term Pm,a,b is introduced to indicate a lin-
ear polymer molecule containing m repeat units terminated on one
end by an a functional group and the other end by a b functional
group. The vectors m, a, and b are defined by:
 m1   X1   Y1 
     
m ≡  m2  a ≡  X2  b ≡  Y2 
     
M M M 
in which the vector components are mi = Ri, ai = XiAi', and

bi = YiBi'. The population balance is then written consistent with
these vectors and the kinetic mechanisms given in Table 11-1.
Stepwise Polymerization Kinetic Mechanisms

A stepwise polymerization can be adequately modeled by the
kinetic mechanisms presented in Table P11-1. The stepwise polym-
erization mechanisms are reversible and therefore are ultimately
determined by chemical equilibrium. Also, some mechanisms are
acid catalyzed. The kinetic constants ki, kir and Ki, which are the

forward, reverse, and equilibrium rate constants, respectively, for
reaction (i), are based on the reaction of functional groups.
Table P11-1: Stepwise Polymerization Kinetics Mechanisms
Reaction Constant Type
1 k1 Polycondensation I
P n, a, b + P m, x, y —>P n + m, a + x – δ ( i ), b + y – d ( j ) + C i, j
2 k2 Polymer addition
P n, a, b + P m, x, y —>P n + m, a + x – δ ( i ), b + y – d ( j )
3 k3 Polycondensation II
P n, a, b + P m, x, y —>P n + m, a + x – δ ( i ), b + y – d ( j ) + P δ ( k ), 2 δ ( i ) – δ ( j ), 0
POLYMERS
4 k4 Polymer-monomer unequal reactivity
P n, a, b + P δ ( k ), m δ ( i ), 0 —>P n + δ ( k ), a + ( m – 1 ) δ ( c ), b – d ( j ) + C i:j
5 k5 Scission degradation
P n, a, b —>P n – r, a – x, b – y + δ ( j ) + P r – δ ( r1 ) + δ ( r2 ), x, y
6 k6 Monomer salting
S δ ( i ) + S δ ( j ) —>P δ ( i ) + δ ( j ), a, b + C i:j
7 k7 Two-chain reformation
P n, a, b + P m, x, y —>P n – δ ( r1 ), a – δ ( i ), b + δ ( b1 ) +
P m – δ ( r2 ) + δ ( r3 ), x – δ ( j ) – δ ( a1 ), y
8 k8 Deactivation of A group
P n, a, b + Z k —>P n, a – δ ( i ), b + ( C i:k )
9 k9 Deactivation of B group
P n, a, b + Z k —>P n, a, b – δ ( j ) + ( C i:k )
10 k10 Ultimate monomer degradation

P n, a, b —>P n – δ ( k ), a – δ ( i ), b + δ ( j ) + C i:j
11 k11 Ring opening

R n + C i:j —>P n, δ ( i ), δ ( j )
12 k12 Ring addition

P n, a, b + R m —>P n + m, a – δ ( k ) + d ( i ), b added to Ak
A brief description of each mechanism is presented below.

1. Polycondensation I: This reaction is between two non-ring
linear polymer chains and involves the reaction between an Ai
end group and Bj end group. The kinetic rate constant is based
BATCH
on the reaction between the end groups Ai and Bj.

2. Polymer Addition: This reaction is identical to the polycon-
densation I reaction except that no condensate is formed.
Non-ring linear chains are involved, and the reaction is
between the Ai and Bj end groups.
3. Polycondensation II: This mechanism describes the reaction
between two end groups of the same type, which are Ai with Bj.
A condensate labeled Pδ(k), 2δ(i)-δ(j),0 is formed. The rate con-
stant is based on the rate of reaction of an Ai group reacting
with an Aj group.
4. Polymer Monomer Unequal Reactivity: This mechanism
POLYMERS
describes the reaction of two non-ring polymer chains to form

monomer end groups that have different reactivities from the
identical end groups already on the polymer chain. This reac-
tion is similar to the polycondensation I reaction, except that
the end group of the ultimate monomer unit transforms. The
kinetic rate constant is based on the rate of reaction for an Ai
end group with a Bj end group.
5. Scission Degradation: This mechanism describes the degrada-
tion of a chain linkage to form two polymer chains. The ulti-
mate monomer unit on the first chain is chemically altered
(made inactive), and an active Bj end group is created on the
second chain. The rate constant is based on the rate of reaction
of an ij linkage with a polymer chain.
6. Monomer Salting: This mechanism describes the reaction of
two salting compounds to form polymer and a condensate. The
polymer salt formed is treated as polymer dimer.
7. Two Chain Reformation: This reaction is between two A end
groups. It creates two new chain ends. The first chain has its
ultimate monomer unit stripped away, which leads to the
penultimate monomer unit and its corresponding Bi end group
being exposed. The second chain receives the stripped mono-
mer unit. The kinetic rate constant is based on reacting with the
Ai end group.
8. Deactivation of A Group: This mechanism describes the reac-
tion of a deactivating species with the polymer chain. The
result is that the polymer chain has one less active end group.
Here it is assumed no condensate is formed. This reaction deac-

tivates an Ai group. The rate constant is based on the rate of
reaction of the Ai functional group and the Zk deactivation spe-
cies.
9. Deactivation of B Group: This mechanism describes the reac-
tion of a deactivating species with the polymer chain. The
result is that the polymer chain has one less active end group.
Here it is assumed no condensate is formed. This reaction deac-
tivates a Bj group. The rate constant is based on the rate of
reaction of the Bj functional group and the Zk deactivation spe-
cies.
10. Ultimate Monomer Degradation: This mechanism describes
the degradation of the ultimate monomer unit, (Rk). The result
POLYMERS
is that the chain has one less monomer unit. The rate constant is
based on the rate of reaction of the ij linkage made by the ulti-
mate monomer unit (Rk) and the penultimate monomer unit.
11. Ring Opening: This reaction is between the condensate i:j
and the ring h-mer where the symbol h indicates the equivalent
number of linear monomers n in the ring. The reaction product
is therefore an n-mer, and it has Ai and Bj end groups. The
kinetic rate constant is based on the reaction rate between con-
densate i:j and ring h.
12. Ring Addition: This reaction is between the ring h-mer of the
previous mechanism and the polymer chain. The ring h-mer is
added to the polymer chain end group. The kinetic rate constant
is based on the rate of reaction of the ring h-mer and the func-
tional group.

BATCH
 Component data
 Components – Monomer(s), polymer, solvent, transfer agent
(optional), inhibitor (optional)
SAFT, or PHSC
POLYMERS

reactor)
 Step growth kinetic data
 Required stepwise reactions (poly-condensation reaction)


Guide.
Communicating with PRO/II for Stepwise Kinetics
POLYMERS
The keyword headers presented here describe IPARM, RPARM, and
SUPPLE input data requirements. They are quite lengthy, and do not
appear in any example problems.
IPARM integer,…. (up to 24 values)
RPARM real no,…. (up to 18 values)
SUPPLEMENTAL i,Ri/Ri+1/…/j,Rj/Rj+1…
(up to 86 Supplemental values)
Integer IPARM Data:

$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL OPTION FLAG REQ
$ = 3 STEP GROWTH POLYMERIZATION
$ (TYPE I)
$ (TYPE II)
$ (TYPE III)
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = NUMBER OF RINGS REQ
$ IPARM( 7) = BASIS FOR KINETIC RATE CONstants
$ REQ
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$ IPARM(12) = MONOMER 1 (A1-R1-B1) COMPONENT

$ IPARM(13) = MONOMER 2 (A2-R2-B2) COMPONENT(or 0)
$ IPARM(14) = MONOMER 1 - RING 1
$ ( A-R[1]-B ) COMPONENT
BATCH

$ ( A-R[2]-B ) COMPONENT (OR 0)
$ ( A-R[3]-B ) COMPONENT (OR 0)
$ IPARM(17) = P1 COMPONENT (OR 0)
$ IPARM(20) = CONDENSATE COMPONENT (OR 0)
$ IPARM(21) = CATALYST COMPONENT (OR 0)
$ IPARM(22) = DEACTIVATION AGENT COMPONENT (OR 0)
$ IPARM(23) = SALTING AGENT COMPONENT (OR 0)
$ IPARM(24) = INERT COMPONENT, N2 (OR 0)
Real RPARM Data:

POLYMERS
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa), J/GMOL

$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET
$ TEMPERATURE, K
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC,
$ J/SEC/M2/K
$ = OPERATING TEMPERATURE OF ISOTHERMAL
$ CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NON-
$ ISOTHERMAL CSTR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa),
$ (DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT of POLYMERIZATION (Hba),J/GMOL
$ RPARM(16) = HEAT of POLYMERIZATION (Hab),J/GMOL
$ RPARM(17) = HEAT of POLYMERIZATION (Hbb),J/GMOL
Real SUPPLE Data:

$
$ NON RING REVERSIBLE KINETIC DATA
$
$ REACTION 1 … POLYCONDENSATION I
$ SUPPLE( 1) = PREEXPONENTIAL FACTOR FOR
$ INTRINSIC REACTION
$ SUPPLE( 2) = ACTIVATION ENERGY

$ CATALYZED RXN
$ SUPPLE( 5) = DEL(H) FOR EQUILIBRIUM RXN
$ SUPPLE( 6) = DEL(S)
$
$ REACTION 2 … POLYMER ADDITION
$ INTRINSIC RXN
$ CATALYZED RXN
$ SUPPLE(10) = ACTIVATION ENERGY
$ SUPPLE(11) = DEL(H) FOR EQUILIBRIUM RXN
$ SUPPLE(12) = DEL(S)
$
POLYMERS
$ REACTION 3 … POLYCONDENSATION II
$ SUPPLE(13) = PREEXPONENTIAL FACTOR FOR
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 4 … POLYMER-MONOMER U. R.
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 5 … SCISSION DEGRADATION
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ NON RING IRREVERSIBLE KINETIC DATA
$
$ REACTION 6 … MONOMER SALTING
$ INTRINSIC RXN

$ CATALYZED RXN
$
BATCH
$ REACTION 7 … TWO CHAIN REFORMATION

$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 8 … DEACTIVATION
$ INTRINSIC RXN
$ CATALYZED RXN
POLYMERS
$
$ REACTION 9 … DEACTIVATION
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 10 … ULTIMATE MONOMER DEGRADATION
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ RING REVERSIBLE KINETIC DATA
$
$ REACTION 11a … RING OPENING OF MONOMER
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 11b … RING OPENING OF DIMER
$ SUPPLE(57) = PREEXPONENTIAL FACTOR
$ FOR INTRINSIC RXN
$ CATALYZED RXN

$
$ REACTION 11c … RING OPENING OF TRIMER
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 12a … POLYADDITION OF MONOMER
POLYMERS
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 12b … POLYADDITION OF DIMER
$ INTRINSIC RXN
$ CATALYZED RXN
$
$ REACTION 12c … POLYADDITION OF TRIMER
$ INTRINSIC RXN
$ CATALYZED RXN
Using Reactor Unit US21 to Model Step Growth Systems

Polymer systems that may be modeled with unit US21 are:
 Type I − Nylon 6
 Type II − Ethylene Glycol and Adipic Acid, Nylon 6,6
 Type III − BHET homopolymerization

Example P11-1: Type I Step Growth Polymerization in a CSTR
BATCH
used to model the bulk polymerization of caprolactum to Nylon 6.

If solution polymerization is of interest, this problem can be modi-
fied easily to add an input component to the reactor feed for use as a
solvent. It is important to note:
1MW200000).
POLYMERS

on this statement.
6. Data for the step growth kinetics for the polymerization reac-
tion are taken from Table 11-2 and Table 11-3 and are provided
in the US21 units via the SUPPLE data statement.
Rxn Rate Prefacto Prefactor Prefactor

Step Const. r Ao Ac Units Ea0 Eac
1 k1 1.8942e1 1.2114e10 kg/kmol/ 9.7389e 8.6504e
0 hr 4 4
11a k11a 5.9874e5 4.3075e7 kg/kmol/ 8.3198e 7.8703e
hr 4 4
12a k12a 2.8558e9 1.6377e10 kg/kmol/ 9.5606e 8.4148e
hr 4 4
Note: The heat of polymerization (-ΔHaa) for caprolactum is 16900 joule/
gmol.

Reaction Rate Enthalpy Entropy
Step Constant DH (J/kg) DS (J/kg/K)
1 K1 -2.4883e4 3.9496e0
11a K11a 8.0268e3 -3.2997e1
12a K12a -1.6923e4 -2.9068e1
Nylon 6 Input CSTR File

TITLE PROJ=POLYMER, PROB=NYLON6, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, NYLON1, FILL=VANKREVELEN
STRUCTURE A, 4(5), 231(1), 403(1)
POLYMERS
COMPONENT DATA
LIBID 2,CPLC/3,NPHT/4,H20
POLYMER 1, NYLON6
MWAVG 1, 5900
PHASE VLS = 1
ENTHALPY (L,K,J/G,WT) CORRELATION=1, *
DATA=1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, *
DATA=1, 400, 200, 910/*
2, 400, 200, 910/*
3, 400, 200, 910/*
4, 400, 200, 910
ATTRIBUTE COMP=1, KINE= SG, *
MWD = 50,100,200,500,800,1000,3000,4000,*
5000,6000,8000,10000,30000,50000,*
70000,80000,100000,200000,*
MMWD = PSI0, PSI1, PSI2
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,2, 0.00681127
ALMC A, 0.475503
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=494.15, &
PRES(ATM)=5, *
COMP(WT, KG/MIN)=0.0/9.650/0.000/0.0430
UNIT OPERATION
US21 UID=REACTOR_1, NAME=NYLON6 CSTReactor
FEED FEED_0
PROD PROD_1
$-----------------------------------------------
$ = 1 FOR CSTR

$ = 2 FOR PFR
BATCH

$ = 3 FOR STEP GROWTH POLYMERIZATION
$ ( TYPE I )
$ ( TYPE II )
$ ( TYPE III )
$ IPARM( 4) = NUMBER OF REVERSIBLE REACTION
$ STEPS REQ
$ IPARM( 5) = NUMBER OF IRREVERSIBLE REACTION
$ STEPS REQ
$ IPARM( 7) = BASIS FOR KINETIC RATE
$ CONSTANTS REQ
POLYMERS

$ IPARM( 8) = REVERSIBLE KINETICS FLAG REQ
$ = 1 FORWARD KINETIC RATE CONSTANTS
$ ONLY
$ = 2 INCLUDE REVERSE KINETIC RATE
$ CONSTANTS
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$----------------------------------------------
IPARM 1,1,3,5,5, 1,2,2,0,0, 1,0,0,2,0, &
0,3,0,0,4, 0,0,0,0
$----------------------------------------------
$ IPARM(12) = MONOMER 1 ( A1-R1-B1 ) COMPONENT
$ (OR 0)
$ IPARM(14) = MONOMER 1 - RING 1 ( A-R[1]-B )
$ COMPONENT
$ COMPONENT (OR 0)
$ COMPONENT (OR 0)
$ IPARM(20) = CONDENSATE COMPONENT (OR 0)
$ IPARM(21) = CATALYST COMPONENT (OR 0)
$ IPARM(23) = SALTING AGENT COMPONENT (OR 0)
$ IPARM(24) = INERT COMPONENT, N2 (OR 0)
$-------------------------------------------------

$ TEMPERATURE, K
$ J/SEC/M2/K
$ = OPERATING TEMPERATURE OF
$ ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR
$ NONISOTHERMAL CSTR
$ (DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
POLYMERS
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba),
$ J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab),
$ J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb),
$ J/GMOL
$---------------------------------------------
RPARM 16900.0, 6400.0, 350.0, 2.5, &
60.0, 494.15, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0, &
0.0, 0.0
$---------------------------------------------
$---------------------------------------------
SUPPLE 1,1.8942D+10/ 9.7389D+04/ &
1.2114D+10/ 8.6504D+04/ &
-2.4883D+04/ 3.9496D+00/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ &
5.9874D+05/ 8.3198D+04/ &
4.3075D+07/ 7.8703D+04/ &
8.0268D+03/ -3.2997D+01/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ &
2.8558D+09/ 9.5606D+04/ &
1.6377D+10/ 8.4148D+04/ &
-1.6923D+04/ -2.9068D+01/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0

FLASH UID=PRODUCT
FEED PROD_1
BATCH

Example P11-2: Type I Step Growth Polymerization in a PFR

used to model the bulk polymerization of caprolactum to Nylon 6.
If solution polymerization is of interest, this problem can be modi-
fied easily to add an input component to the reactor feed for use as a
solvent. It is important to note:
POLYMERS

1MW50000).
on this statement.
Nylon 6 Input PFR File

$TITLE PROJ=POLYMER, PROB=NYLON6, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, NYLON1, FILL=VANKREVELEN
STRUCTURE A, 4(5), 231(1), 403(1)
COMPONENT DATA
LIBID 2,CPLC/3,NPHT/4,H20

POLYMER 1, NYLON6
MWAVG 1, 8400
PHASE VLS = 1
ENTHALPY( L,K,J/G,WT ) CORRELATION=1,&
DATA= 1,400, 200, -457.7994, 1.676/ &
2,400, 200, -457.7994, 1.676/ &
3,400, 200, -457.7994, 1.676/ &
4,400, 200, -457.7994, 1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, &
DATA= 1, 400, 200, 897/ &
2, 400, 200, 897/ &
3, 400, 200, 897/ &
4, 400, 200, 897
ATTRIBUTE COMP=1, KINE= SG, &
MWD = 1000, 2000, 3000, 5000, 6000, &
POLYMERS
7000, 8000, 9000,10000,15000, &
20000, 30000,40000,50000, &
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,2, 0.00681127
ALMC A, 0.475503
STREAM DATA
PRES(ATM)=5, &
COMP(WT, KG/MIN)=0.0/9.650/0.000/0.0830
UNIT OPERATION
US21 UID=REACTOR_1, NAME=NYLON6 PFReactor
FEED FEED_0
PROD PROD_1
$-----------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL FLAG REQ
$ = 0 FOR NON-ISOTHERMAL REACTOR
$ ( TYPE I )
$ ( TYPE II )
$ ( TYPE III )
$ IPARM( 4) = NUMBER OF REVERSIBLE REACTION
$ STEPS REQ
$ IPARM( 5) = NUMBER OF IRREVERSIBLE REACTION
$ STEPS REQ
$ CONSTANTS REQ

$ IPARM( 8) = REVERSIBLE KINETICS FLAG REQ
BATCH
$ = 1 FORWARD KINETIC RATE

$ CONSTANTS ONLY
$ = 2 INCLUDE REVERSE KINETIC RATE
$ CONSTANTS
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$----------------------------------------------
IPARM 2,1,3,5,5, 1,2,2,0,0, 1,0,0,2,0, &
0,3,0,0,4, 0,0,0,0
$----------------------------------------------
$ IPARM(13) = MONOMER 2 ( A2-R2-B2 )
$ COMPONENT (or 0)
POLYMERS
$ COMPONENT
COMPONENT (or 0)
COMPONENT (or 0)
$ IPARM(17) = P1 COMPONENT (or 0)
$ IPARM(20) = CONDENSATE COMPONENT (or 0)
$ IPARM(21) = CATALYST COMPONENT (or 0)
$ IPARM(22) = DEACTIVATION AGENT COMPONENT (or 0)
$ IPARM(23) = SALTING AGENT COMPONENT (or 0)
$ IPARM(24) = INERT COMPONENT, N2 (or 0)
$----------------------------------------------
$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa),
$ J/GMOL
$ TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET
$ AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL
$ HTC, J/SEC/M2/K
$ (DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A

$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ J/GMOL
$ J/GMOL
$ J/GMOL
$----------------------------------------------
RPARM 16900.0, 0.0, 0.0, 0.0, &
0.0, 518.15, 0.0, 0.0, &
0.0, 0.0, 150.0, 15.0, &
0.0, 0.0, 16900., 16900., &
0.0, 0.008
POLYMERS
$----------------------------------------------
$----------------------------------------------
SUPPLE 1,1.8942D+10/ 9.7389D+04/ &
1.2114D+10/ 8.6504D+04/ &
-2.4883D+04/ 3.9496D+00/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/ &
5.9874D+05/ 8.3198D+04/ &
4.3075D+07/ 7.8703D+04/ &
8.0268D+03/ -3.2997D+01/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
2.8558D+09/ 9.5606D+04/ &
1.6377D+10/ 8.4148D+04/ &
-1.6923D+04/ -2.9068D+01/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
ISOT TEMP(K)=518.15, PRES(ATM)=5$

Example P11-3: Type II Step Growth Polymerization in a CSTR
BATCH
used to model the bulk polymerization of ethylene glycol and adipic

acid. If solution polymerization is of interest, this problem can be
modified easily to add an input solvent component to the reactor
feed. It is important to note:
for the polymer polystyrene. The FILL=VANK keyword is used
to specify that van Krevelen prediction methods be used for
polymer properties.
1MW1000).
POLYMERS

on this statement.
tion are taken from Table 11-4 and are provided in the US21
6. The product of the reactor unit is flashed isothermally in unit
Rate
Step Constant Prefactor Ac Prefactor Units Eac(J/gmol)
1 k1 2.2000e5 kg/kmol/hr 54392
Note: The heat of polymerization (-ΔHaa) for ethylene glycol and
adipic acid is 64500 joule/gmol.

Ethylene Glycol \ Adipic Acid CSTR Input File
TITLE PROJ=TYPE II, PROB=FPOLYMER, USER=SIM, DATE=12/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, EG1/B, ADIPIC1, FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 4(4), 237(2)
COMPONENT DATA
LIBID 2,EG /3,ADIPIC /4,H20
POLYMER 1, FPOLYMER
MWAVG 1, 120
PHASE VLS=1
DATA= 1,400,200,-457.7994,1.676/ &
POLYMERS
2,400,200,-457.7994,1.676/ &
3,400,200,-457.7994,1.676/ &
4,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, &
DATA= 1, 400, 200, 945/ &
2, 400, 200, 945/ &
3, 400, 200, 945/ &
4, 400, 200, 945
ATTRIBUTE COMP=1, KINE = SG,
MWD = 10, 20, 30, 40, 50, &
60, 70, 80, 90, 100, &
110, 120, 130, 150, 200, &
300, 500, 700,1000, &
THERMO DATA
METHODS SYSTEM=FLORY
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=439.15,
PRES(ATM)=10, COMP(WT, KG/MIN)= &
0.0/4.850/11.450/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=FLORY-P CSTReactor
FEED FEED_0
PROD PROD_1
$----------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ ( TYPE I )
$ ( TYPE II )

$ ( TYPE III )
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
BATCH
$ IPARM( 6) = N/A
$ CONSTANTS REQ
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$------------------------------------------------
IPARM 1,1,4,0,0, 0,2,0,0,0, 1,2,3,0,0, &
0,0,0,0,4, 0,0,0,0
$------------------------------------------------
POLYMERS
$ COMPONENT (or 0)
$ COMPONENT
$ COMPONENT (or 0)
$ COMPONENT (or 0)
$-----------------------------------------------
$ J/GMOL
$ TEMPERATURE, K
$ J/SEC/M2/K
$ (DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A

$ RPARM(12) =
PFR DIAMETER, CM
$ RPARM(13) =
N/A
$ RPARM(14) =
N/A
$ RPARM(15) =
HEAT OF POLYMERIZATION (Hba),
J/GMOL
$ J/GMOL
$ J/GMOL
$----------------------------------------------
RPARM 64500., 100.0, 350., 2.5, &
0., 439.15, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0, &
0.0, 0.0
POLYMERS
$----------------------------------------------
$----------------------------------------------
SUPPLE 1,0.0/ 0.0/2.2E+05/ 54392./0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/ 0.0/ 0.0/0.0/
FLASH UID=PRODUCT
FEED PROD_1
ISOT TEMP(K)=439.15, PRES(ATM)=10$

Example 11-4: Type II Step Growth Polymerization in a PFR
BATCH
used to model the bulk polymerization of ethylene glycol and adipic

acid. If solution polymerization is of interest, this problem can be
modified easily to add an input solvent component to the reactor
feed. It is important to note:
1MW5000).
POLYMERS

on this statement.
tion are taken from Table 11-4 and are provided in the US21
6. The product of the reactor unit is flashed isothermally in unit
Ethylene Glycol/Adipic Acid PFR Input File

TITLE PROJ=TYPE II, PROB=FPOLYMER, USER=SIM, &
DATE=1/2007
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, EG1/B, ADIPIC1 , FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 4(4), 237(2)
COMPONENT DATA
LIBID 2,EG/ 3,ADIPIC/ 4,H20
POLYMER 1, FPOLYMER
MWAVG 1, 160
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION= 1,*
DATA= 1,400, 200, -457.7994, 1.676/ &
2,400, 200, -457.7994, 1.676/ &

3,400, 200, -457.7994, 1.676/ &
4,400, 200, -457.7994, 1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, *
DATA= 1, 400, 200, 945/ &
2, 400, 200, 945/ &
3, 400, 200, 945/ &
4, 400, 200, 945
ATTRIBUTE COMP=1, KINE = SG, &
MWD = 10, 20, 30, 40, 50, &
60, 80, 100, 120, 150, &
170, 200, 500, 700, 800, &
900,1000,2000,3000,4000, &
5000, &
THERMO DATA
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=439.15,
POLYMERS
PRES(ATM)=10, &
COMP(WT, KG/MIN)=0.0/4.850/11.450/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=FLORY-P PFReactor
FEED FEED_0
PROD PROD_1
$----------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ ( TYPE I )
$ ( TYPE II )
$ ( TYPE III )
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ CONSTANTS REQ
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$----------------------------------------------
IPARM 2,1,4,0,0, 0,2,0,0,0, 1,2,3,0,0, 0,0,0,0,4,
0,0,0,0
$----------------------------------------------
$ COMPONENT (or 0)
$ COMPONENT

$ COMPONENT (or 0)
BATCH
$ COMPONENT (or 0)
$----------------------------------------------
$ J/GMOL
$ TEMPERATURE, K
POLYMERS

$ J/SEC/M2/K
$ (DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ J/GMOL
$ J/GMOL
$ J/GMOL
$----------------------------------------------
RPARM 64500., 0.0, 350., 0.0, &
0., 439.15, 0.0, 0.0, &
0.0, 0.0, 100.0, 5.0, &
0.0, 0.0, 0.0, 0.0, &
0.0, 0.3535
$----------------------------------------------
$----------------------------------------------
SUPPLE 1,0.0/ 0.0/2.2E+05/ 54392./ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &

0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
Example P11-5: Type III Step Growth Polymerization in a CSTR

used to model the bulk polymerization of BHET to form poly-
ethyleneterephthalate. If solution polymerization is of interest, this
POLYMERS
problem can be modified easily to add an input solvent component
to the reactor feed. It is important to note:
polymer properties.
1MW5000).
on this statement.
Rate
Step Constant Prefactor Ao Prefactor Units Ea (J/gmol)
3 k3 4.0800e7 kg/kmol/hr 7.7400e4
Note: Heat of polymerization (-ΔHaa) for BHET is 62500 joule/g-mol.

Equilibrium Enthalpy Entropy
Step Constant DH(J/kg) DS(J/kg/K)
BATCH
1 K3 -2.4883e4 3.9496e0
BHET CSTR Input File
TITLE PROJ=POLYMER, PROB=PRE-PET, USER=SIM, &

DATE=1/2007
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, BHET1, FILL=VANKREVELEN
STRUCTURE A, 4(2),514(1)
COMPONENT DATA
LIBID 2,BHET/3,EG
POLYMERS
PHASE VLS=1
POLYMER 1, PRE-PET
MWAVG 1, 250
ATTRIBUTE COMP=1, KINE = SG, &
MWD= 10, 20, 30, 40, 50, &
70, 100, 150, 200, 250, &
300, 500, 700, 1000, 2000, &
3000, 4000, 5000, &
MMWD= PSI0, PSI1, PSI2
THERMO DATA
STREAM DATA
PRES(ATM)=0.095, &
COMP(WT, KG/MIN)=0.0/7.150/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=PRE-PET CSTReactor
FEED FEED_0
PROD PROD_1
$----------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ ( TYPE I )
$ ( TYPE II )
$ ( TYPE III )
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 7) = BASIS FOR KINETIC RATE CONTANTS REQ

$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$----------------------------------------------
IPARM 1,1,5,0,0, 0,2,0,0,0, 1,2,0,0,0, &
0,3,0,0,0, 0,0,0,0
$----------------------------------------------
$ COMPONENT (or 0)
$ COMPONENT
$ COMPONENT (or 0)
POLYMERS
$ COMPONENT (or 0)
$----------------------------------------------
$ J/GMOL
$ TEMPERATURE, K
$ J/SEC/M2/K
$ (DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba), J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab), J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb), J/GMOL
$----------------------------------------------
RPARM 62500., 1100.0, 350., 2.5, &
0., 433.15, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0, &

0.0, 0.0, 0.0, 0.0, &
0.0, 0.0
$----------------------------------------------
BATCH

$----------------------------------------------
SUPPLE 1,0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/ &
4.08E+07/ 7.740E+04/ &
0.0/0.0/0.0/ &
20.0D+01/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
POLYMERS
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
ISOT TEMP(K)=433.15, PRES(ATM)=0.095$

Example P11-6: Type III Step Growth Polymerization in a PFR
used to model the bulk polymerization of BHET to form polyethyl-
eneterephthalate. If solution polymerization is of interest, this prob-
lem can be modified easily to add an input solvent component to the
reactor feed. It is important to note:
polymer properties.
POLYMERS
1MW10000).
on this statement.

BHET PFR Input File
TITLE PROJ=POLYMER, PROB=PRE-PET, USER=SIM, &
BATCH
DATE=01/2007
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, BHET1, FILL=VANKREVELEN
STRUCTURE A, 4(2),514(1)
COMPONENT DATA
LIBID 2,BHET/ 3,EG
PHASE VLS=1
POLYMER 1, PRE-PET
MWAVG 1, 400
ATTRIBUTE COMP=1, KINE = SG,
MWD= 10, 20, 30, 50, 70, &
100, 150, 200, 250, 300, &
350, 400, 500, 700, 800, &
1000, 2000, 3000, 5000, 7000, &
POLYMERS
10000, &
MMWD= PSI0, PSI1, PSI2
THERMO DATA
STREAM DATA
PRES(ATM)=10, *
COMP(WT, KG/MIN)=0.0/7.150/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=PRE-PET PFReactor
FEED FEED_0
PROD PROD_1
$----------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ ( TYPE I )
$ ( TYPE II )
$ ( TYPE III )
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ CONTANTS REQ
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$----------------------------------------------
IPARM 2,1,5,0,0, 0,2,0,0,0, 1,2,0,0,0, &

0,3,0,0,0, 0,0,0,0
$----------------------------------------------
$ COMPONENT (or 0)
$ COMPONENT
$ COMPONENT (or 0)
$ COMPONENT (or 0)
POLYMERS
$----------------------------------------------
$ TEMPERATURE, K
$ J/SEC/M2/K
$ RPARM( 7) = CSTR PRESSURE DROP (kPa)(DEFAULT=0.0)
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba), J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab), J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb), J/GMOL
$----------------------------------------------
RPARM 62500., 500.0, 350., 2.5, &
0., 453.15, 0.0, 0.0, &
0.0, 0.0, 1000.0, 5.0, &
1.0, 1.0, 62500., 0.0, &
0.0, 0.25
$----------------------------------------------
$----------------------------------------------
SUPPLE 1,0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
4.08E+07/ 7.740E+04/ &
0.0/0.0/0.0/ 20.0D+01/ &

0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
BATCH
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
POLYMERS

Chapter P12
Interpreting Polymer Output
Description of Polymer Report
The definitions given below will provide a better understanding of
the output reports generated for polymer systems.
Live Chains The live or growing chains contain an active center

and as such can be considered macro radicals. The
activity of the live chains has not been curtailed by a
transfer or termination reaction, and the live chains
POLYMERS
continue to incorporate monomer. In the case of the
free radical copolymer, the live chain may be termi-
nated with an active radical formed from either the A
monomer or B monomer. These radicals are labeled as
Live A and Live B Chains, respectively. In step growth
kinetics all chains are considered live.
Dead Chains The dead or polymer chains are chains that have
undergone a transfer or termination reaction and are no
longer growing. These chains are labeled as Dead
Chains.
Bulk Chains The bulk chain is defined as the “average” chain in the
product. The properties of the bulk chain are derived
from the arithmetic average of the equivalent proper-
ties of all types of chains found in the product. For free
radical kinetics, the dead chain properties dominate the
bulk material properties. For step growth kinetics, the
bulk chain properties are equivalent to the live chain
properties.
Kinetic Chain In free radical kinetics, the kinetic chain length is

Length defined as the ratio of the rate of monomer incorpora-
tion into the polymer to the rate of the generation of
free radicals. The kinetic chain length indicates the
number of monomer molecules reacted per free radical
generated.
Number Average The number average molecular weight is the molecular

Molecular weight based on the number of monomer units incor-
Weight porated into an average polymer molecule.

Weight Average The weight average molecular weight is the molecular
Molecular weight based on the weight of monomer units incorpo-
BATCH
Weight rated into an average polymer molecule.
Polydispersity The poly-dispersity index is the ratio of the weight

Index average molecular weight to the number average
molecular weight. Weight average and number average
molecular weights are defined in a subsequent section.
Poly-dispersity is an indicator of the molecular unifor-
mity of the polymer product and is reflected in the
breadth of the molecular weight distribution function.
Molecular Kinetic rate data describing initiation, propagation,

Weight transfer, and termination mechanisms have been used
Distribution to obtain number and weight average molecular
POLYMERS
weights and polydispersities. An assumed molecular

weight distribution has been described with the
ATTRIB statement of the input file. In the POLYMER
MOLECULAR WEIGHT DISTRIBUTION section of
the Polymethylmethacrylate-Polyvinylacetate CSTR
Output File, the simulated or predicted molecular
weight distribution function has been distributed into
the given molecular weight distribution function.
P12-2 Interpreting Polymer Output

Polymer Characterization via Moments
The reaction scheme followed in the production of synthetic poly-
mers can be a complicated set of series and parallel kinetic reaction
steps that lead to a distribution from chain to chain in molecular size
and shape. In this model, the distribution in molecular size or
weight is addressed by the method of moments. The distribution is
characterized by an infinite series, with the coefficients of the series
being the moments. The lower order moments are retained, and
properties of interest are extracted from the moments. The zeroth-
order moment is related to the concentration of the polymer chain
molecules, while the first-order moment is related to the number of
monomer units in the average length polymer chain model. From
these moments, the number average and weight average molecular
POLYMERS
weights can be obtained.
The definitions of the moment of the live chains terminated by an
active monomer A and an active B monomer are:
∞ *
ψk =  nk [ Pn ]
n=1
∞
*
and χ k =  nk [ Qn ]
n=1
respectively. The definition of the dead chain moment is

∞
*
: μk =  nk [ Dn ]
n=1
The number and weight average molecular weights for the dead
chains can be obtained as
μ1
M n = ------
μ0
and
μ2
M w = ------
μ1
Molecular weights and poly-dispersities from these calculations are

shown in the output reprint on the next pages. Included are live
chains terminating in monomer A, live chains terminating in mono-
mer B, and dead or inactive chains. The corresponding variables for
the bulk chains are obtained from the arithmetic average of the live

and dead chains. Also, the moments on which these calculations are
based are shown in the Stream output portion of the listing. (The
listing has been formatted slightly to fit the page size of this Guide.)
BATCH
Polymethylmethacrylate - Polyvinylacetate CSTR Output File

SIMULATION SCIENCES INC. R PAGE P-5
PROJECT COPOLYMER PRO/II 386/EM
PROBLEM PMMAC-VAC OUTPUT SIM
POLYMER CSTR SUMMARY 05/08/2007
========================================================
UNIT 1, ‘REACTOR’, ‘1st PMMAC-VAC CSTReactor’
FEED STREAM S1
PRODUCT STREAM S2
OPERATING CONDITIONS
POLYMERS
POLYMER REACTOR TYPE ISOTHERMAL CSTR
TEMPERATURE, K 333.15
VOLUME, M3 1.0000
DUTY, M*KJ/HR -8.678E-03
TOTAL HEAT OF REACTION, M*KJ/HR 8.678E-03
SPACE-TIME, HR, AT OUTLET CONDITIONS 6.9357
SPACE-VELOCITY, /HR, AT OUTLET CONDITIONS .1442
FREE RADICAL COPOLYMERIZATION DATA

POLYMER REACTOR MASS BALANCE
————— RATES, KG/HR —————
PERCENT
COMPONENT FEED CHANGE PRODUCT CONVERTED
——————— ———— —————— ——————— —————————
1 PMMAC-VA POLYMER .000 13.525 13.525
2 MMAC MONOMER A 18.000 -10.341 7.659 57.452
3 VACT MONOMER B 90.000 -3.143 86.857 3.492
4 BNZN SOLVENT 36.000 -1.042E-03 35.999 2.738E-03
5 BOBZ INITIATOR A .180 -3.966E-02 .140 22.032
TOTAL 144.180 .000 144.180
POLYMER REACTOR HEAT BALANCE

FEED PRODUCT
AT OPERATING CONDITIONS ———————— ————————
TEMPERATURE, K 333.1300 333.1500
PRESSURE, KPA 506.6265 101.3253
ENTHALPY, M*KJ/HR .0145 .0145
POLYMER CHARACTERIZATION DATA

COPOLYMER COMPOSITION
NUMBER FRACTION MONOMER A .739
NUMBER FRACTION MONOMER B .261

FREE RADICAL KINETICS
KINETIC CHAIN LENGTH .1535E+03
POLYDISPERSITY DATA
LIVE A CHAINS:
WEIGHT FRACTION IN POLYMER .2127E-04
NUMBER AVERAGE MOLECULAR WT .2865E+05
WEIGHT AVERAGE MOLECULAR WT .5709E+05
POLYDISPERSITY INDEX 1.9924
LIVE B CHAINS:
WEIGHT FRACTION IN POLYMER .1758E-07
POLYMERS
DEAD CHAINS:
WEIGHT FRACTION IN POLYMER .1000E+01
BULK CHAINS:
POLYMER MOLECULAR WEIGHT DISTRIBUTION
MOL. WT. WT FRAC

————- ———-
5.0000E+02 .0002
7.0000E+02 .0004
1.0000E+03 .0007
3.0000E+03 .0051
5.0000E+03 .0121
7.0000E+03 .0209
1.0000E+04 .0362
3.0000E+04 .1364
4.0000E+04 .1647
5.0000E+04 .1768
6.0000E+04 .1762
8.0000E+04 .1522
1.0000E+05 .1169
3.0000E+05 .0011
5.0000E+05 .0000
7.0000E+05 .0000
1.0000E+06 .0000

BATCH

STREAM WEIGHT COMPONENT RATES 05/08/2007
==============================================================
STREAM ID POLYMER_MELT S1 S2
NAME
PHASE LIQUID LIQUID LIQUID
FLUID RATES, KG/HR

1 PMMAC-VAC .0000 .0000 .0000
2 MMAC 7.6587 18.0000 7.6587
3 VACT 86.8568 90.0000 86.8568
4 BNZN 35.9990 36.0000 35.9990
5 BOBZ .1403 .1800 .1403
6 1MW500 2.8984E-03 .0000 2.8984E-03
POLYMERS
7 1MW700 5.3079E-03 .0000 5.3079E-03

8 1MW1000 .0101 .0000 .0101
9 1MW3000 .0693 .0000 .0693
10 1MW5000 .1640 .0000 .1640
11 1MW7000 .2828 .0000 .2828
12 1MW10000 .4892 .0000 .4892
13 1MW30000 1.8455 .0000 1.8455
14 1MW40000 2.2277 .0000 2.2277
15 1MW50000 2.3913 .0000 2.3913
16 1MW60000 2.3834 .0000 2.3834
17 1MW80000 2.0584 .0000 2.0584
18 1MW100000 1.5809 .0000 1.5809
19 1MW300000 .0144 .0000 .0144
20 1MW500000 4.5020E-05 .0000 4.5020E-05
21 1MW700000 1.0255E-07 .0000 1.0255E-07
22 1MW1000000 .0000 .0000 .0000
TOTAL RATE, KG/HR 144.1800 144.1800 144.1800
TEMPERATURE, K 333.1500 333.1300 333.1500

PRESSURE, KPA 506.6250 506.6250 101.3250
ENTHALPY, M*KJ/HR .0145 .0145 .0145
MOLECULAR WEIGHT 93.1723 85.4614 93.1723
WEIGHT FRAC VAPOR .0000 .0000 .0000
WEIGHT FRAC LIQUID 1.0000 1.0000 1.0000

POLYMER ATTRIBUTES 05/08/2007
=============================================================
STREAM ID POLYMER_MELT S2
NAME
PHASE LIQUID LIQUID
1 MMAC-VAC FREE RADICAL POLYMER

MMWD - LIVE CHAINS IN SINGLE A BOND IN LIQUID KG-MOL/M3
psi0 6.939E-08 6.939E-08
psi1 1.988E-03 1.988E-03
psi2 113.500 113.500
MMWD - LIVE CHAINS IN SINGLE B BOND IN LIQUID KG-MOL/M3
psi0 5.790E-11 5.790E-11
POLYMERS
psi1 1.644E-06 1.644E-06
psi2 9.383E-02 9.383E-02
MMWD - DEAD CHAINS IN SINGLE A BOND IN LIQUID KG-MOL/M3
psi0 1.722E-03 1.722E-03
psi1 93.484 93.484
psi2 7868632.111 7868632.111
POLYMER CHAIN WEIGHT FRACTIONS IN LIQUID
LIVE A 2.127E-05 2.127E-05
LIVE B 1.758E-08 1.758E-08
DEAD A 1.000 1.000

BATCH
POLYMERS

Chapter P13
Wiped Film Evaporator
WFE Overview
A wiped film evaporator (WFE) separates volatile components (e.g.
monomers, solvents, initiators, inhibitors, etc.) from a viscous liq-
uid. WFE’s are employed when the mass transfer of volatiles out of
a liquid is a rate-limited process governed by the diffusion of the
volatiles through the liquid. A standard application for a WFE is the
de-volatilization of a polymer melt.
POLYMERS
A WFE consists of a shaft that passes through the center of a verti-
cal cylindrical drum. A motor turns the shaft powers about its verti-
cal axis. A structure of wiper blades extends from the shaft towards
the interior wall of the WFE. There is a liquid inlet at the top of the
shell and a liquid outlet at the bottom. Vapor is collected in the inte-
rior space of the shell and is drawn out of the top of the WFE under
vacuum. Figure P13-1 illustrates basic WFE design.
Figure P13-1: A Wiped Film Evaporator - Outside and Inside Views

The polymer melt fed into the top of a WFE is spread over the inte-
rior wall by the rotating wiper blades. The melt is transported axi-
ally by the flow of the bow wave. The bow wave is the accumulated
BATCH
polymer melt that is pushed along on the leading edge of the wiper
blades. For polymer melts of high viscosity, it is usually beneficial
to tilt the wiper blades so that they propel the melt downward rather
than allowing pure gravity-induced flow. The melt in the bow wave
is under shear. This assists in the vertical transport of Bingham and
pseudo-plastic fluids by decreasing their viscosity in this region.
The melt devolatilizes as it advances through the WFE. The thin
film of melt on the wall provides a large surface-area-to-volume
ratio that is critical in rate-limited mass transfer. The wiper blades
serve both to transport the melt axially, as well as to remix it, thus
maintaining the maximum concentration of volatiles near the liq-
POLYMERS
uid-vapor interface. Mass transfer is increased by the periodic

remixing of the melt as it enters a bow wave and is subsequently
smeared back onto the wall.
PRO/II Wiped Film Evaporator Model

Operating Modes
There are two WFE operating modes: rating and design. In the rat-
ing mode, you specify an existing piece of equipment. The model
can then be used to evaluate the performance of that equipment
under various process conditions. In the design mode, you must
specify the desired outlet weight fraction of consecutive volatile
components. A relative tolerance around this specification may also
be given (default 10-5). The design mode calculations will predict
the required WFE diameter and height to meet the specification.
The design mode can be used with any of the combinations of feed-
back ratio, temperature profile, and blade configuration described in
this section.
One important parameter in the design mode calculations is the bow
wave to film area ratio. The bow wave area is determined by the
WFE feed volumetric flow rate. The bow wave to film area ratio is
used to determine the design diameter of the WFE directly. You can
specify this parameter or accept the default of 0.05. As this ratio
gets larger, the design diameter decreases. The implications are that
too large a diameter will result in extreme power consumption,
while too small a diameter will require a very long WFE to meet the
specification. Adjustment of this parameter is important in obtain-
P13-2 Wiped Film Evaporator

ing an acceptable design. It should be matched to real operating
data if possible.
Another important operating parameter in design mode is shaft rota-
tion speed. A faster rotation translates to greater mass transfer rates.
However, increasing the shaft speed also increases power costs. In
rating mode, a Controller unit might be employed to limit the WFE
shaft speed to the minimum value that meets the product specifica-
tion. A design mode WFE does not attempt to adjust the shaft speed
because choosing an optimum value requires knowledge of process
constraints and utility and power costs. Because of its effect on
operating costs, the shaft speed is a good target for optimization
using the PRO/II Optimizer unit. Figure P13-2 illustrates the rela-
tionship between the volatile concentration using the PRO/II Opti-
POLYMERS
mizer consumption and the shaft rotation rate for a specific,
undisclosed case. Your data will vary with each problem; however,
these trends will be similar.
Figure P13-2: Final Concentration and Power as a Function of
Rotation Rate
4500 100
90
4000 Final Concentration
80
3500 Power (%)
Concentration (ppm)
70
3000
60
2500
50
2000
40
1500
30
1000 20
500 10
0 0
0 0.5 1 1.5 2 2.5 3
Rotation Rate
Feedback Ratio
PRO/II models a Wiped Film Evaporator unit operation as a series
of levels. A level consists of a number of identical stages equal to
the number of blades in its cross section. Each stage consists of a

mixing step and a devolatilization step. The mixing step occurs in
the bow wave. The devolatilization step occurs in the film. As a
wiper blade moves through a stage, it “picks up” the devolatilized
BATCH
melt in front of it and receives the axial flow from the bow wave of
the stage above. It simultaneously lays down a film of polymer melt
behind it and loses some melt to the stage below it. A parameter
called the feedback ratio determines the degree of mixing that
occurs between the melt entering from the stage above and the melt
that is picked up from the current stage. If the feedback ratio is 1.0,
the entering and picked-up melts are thoroughly mixed. Some of
this mixed melt is then wiped behind the blade, and the rest is
passed to the next lower stage. If the feedback ratio is 0.0, the
model is called Surface Renewal. The picked up melt is passed to
the next stage and the bow wave from above is wiped behind the
blade. The PRO/II model allows continuous intermediate values of
POLYMERS
the feedback ratio to simulate imperfect mixing.

Figure P13-3: Surface Renewal Model
From stage n-2 De-volatilization step To stage
Stage n-1 Mixing step Stage n
Figure P13-4: Feedback Model

q
Evaporation element
Q Q
Mixing element
From level n-1
To level
Stage n in level n

Figure P13-5: Comparison of Feedback and Surface Renewal
Models
18
16
Surface Renewal
Concentration (1000 ppm)

14
Feedback
12
10
0
0 5 10 15 20 25 30 35 40 45 50
POLYMERS
Number of Stages
Figure P13-6: Enlargement of Fig. 13-5 Stages 30-42

320
300
Surface Renewal
280
Feedback
Concentration (ppm)
260
Equilibrium Concentration
240
220
200
180
160
140
120
30 32 34 36 38 40 42
Number of Stages
Blade Configurations
A WFE unit operation can have either vertical, pitched, or alternat-
ing blade configuration. The selection of blade configuration
depends on the properties of the polymer melt. Pitched or alternat-
ing blades are preferred for high-viscosity solutions. Note that
pitched blades with an angle of zero degrees are not the same as
vertical blades, because with vertical blades axial velocity is deter-
mined by gravity flow, while with pitched blades axial velocity is
determined by the pitch angle and rotation rate of the wiper blades.
With pitched or alternating blades, you must specify their pitch
angle or a default of 22.5 degrees will be assumed. Additionally,
you must specify the number of blades in a horizontal cross section

of the WFE or accept the default of eight. If alternating blades are
specified, there must be an even number.
BATCH
You should also specify blade length, blade width, and wall clear-
ance.
Figure P13-7: Feasible Blade Configurations
Film
Straight
Wall Pitched
Alternatin
POLYMERS
Blades
Temperature Profiles
A WFE unit operation can have one of four temperature profiles:
isothermal, adiabatic, jacketed, or user-defined. If isothermal opera-
tion is selected, you should specify the operating temperature. If an
operating temperature is not specified, the combined feed tempera-
ture will be used. An adiabatic temperature profile will not allow
heat transfer into the system other than viscous heating of the poly-
mer melt due to the action of the wiper blades. A jacketed tempera-
ture profile includes the viscous heating term as well as a heat
transfer term from a heating/cooling jacket. If the jacketed profile is
used, you should specify the jacket fluid temperature (default:
100°C) and the overall heat transfer coefficient between the jacket
fluid and polymer melt (default: 50 W/m2/°C). If a user-defined
profile is used, you must specify 11 evenly spaced temperatures, the
first being the inlet temperature and the last the outlet temperature.
Component and Melt Physical Properties

The WFE model requires that transport property calculations be
enabled for the thermodynamic set that it will use. Only liquid vis-
cosity and liquid diffusivity need to have methods selected. The
other transport property methods may be set to none, unless they are
required by another unit operation that uses the same thermody-
namic set.

Liquid Viscosity
You can specify liquid viscosity for the polymer as shown in Chap-
ter 5. Take note, however, that this release of PRO/II applies a
molar mixing rule to polymer mixtures. This will cause the system
to generate inaccurate viscosity estimates for a polymer melt con-
taining volatiles. For this reason, the WFE model allows you to
input a zero shear melt viscosity to be used in the model. This vis-
cosity is internal to the WFE model and will not be shown in any
section of the output other than the WFE report. If you do not input
the zero shear melt viscosity, the WFE will use the viscosity pre-
dicted by PRO/II as its default.
Because polymers are non-Newtonian fluids and the WFE’s wiper
blades can exert considerable shear on the polymer film, it is impor-
POLYMERS
tant to model viscosity as a function of shear rate. The WFE incor-
porates the Carreau model to evaluate viscosity as a function of
shear rate. You should specify relaxation time (default: 0.3) and
power law index (default: 0.3) for the polymer melt. The WFE will
apply the Carreau model to the zero shear melt viscosity discussed
above. The following equation shows the Carreau model for viscos-
ity as a function of shear rate:
n – 1-
-----------
μ – μ∞  2 
- = ( 1 + ( γλ ) 2 )
------------------
μo – μ∞
where m is the shear viscosity, μ o is the zero shear viscosity, μ ∞ is

the infinite shear viscosity, which is equal to zero; g is the shear
rate, l is the relaxation time, and n is the power law index.
The actual viscosity used by the WFE is taken as a weighted aver-
age between the zero shear viscosity and the shear viscosity. The
weighting is determined by the user-supplied Omega parameter. A
value of 1.0 (default) indicates that the shear viscosity will be used.
A value of 0.0 indicates that the zero shear viscosity will be used.
Intermediate values weight the average. You can enter the shear rate
to be used in these calculations or allow them to be calculated by
PRO/II. The shear rate will be calculated by assuming a linear shear
profile between the blade and the wall.
Note: If you specify the melt viscosity for the WFE, the WFE will
not consider the variance of viscosity with temperature. This is
especially important when specifying temperature profiles and
may wish to enter the zero shear melt viscosity as the average
between the inlet and outlet temperatures.

Liquid Diffusivity
The WFE model is very sensitive to the diffusivities of the volatiles
BATCH
in the polymer melt. The predictive diffusivity method within

PRO/II may give inaccurate results; therefore, you will probably
want to input diffusivity data for the specific system. Refer to the
PRO/II Keyword Manual or the PRO/II User’s Guide for informa-
tion on entering diffusivity data. Enter data for the binary pairs of
volatiles (i) diffusing through every other component (j). If the
polymer component is number 1 and the solutes are numbers 2 and
3, you must enter data for D21, D23, D31, and D32. In most cases, you
will enter the same coefficients for all “ij” pairs of the same ith
index. Example 13-1 shows the proper syntax for the DIFDATA
statement. These diffusivity values are not expected to be the exact
values for mass diffusivity. Since the film is never entirely stagnant,
it is safer to think of these values for diffusivity as “effective” diffu-
POLYMERS
sivities. The diffusivity data are probably the best choices for
attempting to tune a WFE model. For design estimates, true diffu-
sivity data will provide a conservative estimate. Values of Dij on the
order of 10-6 to 10-12 are normal. Values much less than 10-12 m2
will predict negligible transfer rates while values much greater than
10-6 m2 are inconsistent with a diffusion-limited model.
Output
Both modes will output the height, diameter, operating pressure,
mass flow of evaporate, heat duty, and shaft power requirements of
the WFE. In addition, the WFE output report will contain a zone
report that will show conditions at periodic levels within the WFE.
The diffusivities for volatile components at the entering and exiting
conditions will also be shown.
Data Required by the Wiped Film Evaporator Unit

Component Data − For information about entering
polymer component data, see Chapters 3 and 4.
Thermodynamics Data − Select a thermodynamic
method that is suitable for VLE calculations with poly-
mer systems: ALM, Flory-Huggins, UNIFAC Free Vol-
ume, SAFT, or PHSC. For information about entering
thermodynamic data, see Chapter 7. Enable transport
property calculations; the WFE needs only liquid viscos-
ity and liquid diffusivity. For information about entering

liquid viscosity and liquid diffusivity data, see the PRO/
II Keyword Manual.
WFE Unit Data
Physical Dimensions − Height1, Diameter2, Length of

Wiper Blade2, Blade-Wall Clearance2, Blade Width2,
Blade Configuration2, Number of Blades2.
Operating Parameters − Shaft Rotation Rate2, Inlet

Pressure2, Inlet Pressure Drop, Shear Rate at Blade Tip2,
Heating/Cooling Jacket Fluid Temperature2, Heat Trans-
fer Coefficient2, Temperature Profile Type2, Isothermal
POLYMERS
Temperature2, Temperature Profile Data (required if
user-defined profile is selected).
Model Parameters − Calculation Mode2, Number of

Zones to Report2, Model Selection2, Power Parameter2.
Viscosity Parameters − Viscosity Parameter (Omega)2,

Viscosity at Zero Shear2, Viscosity Relaxation Time2,
Power Law Index2.
Design Mode Parameters − Starting Component of
Design Specification3, Ending Component of Design
Specification2, Design Target Mass Fraction3, Design
Relative Tolerance2.
Using the Wiped Film Evaporator to Model Systems

The PRO/II WFE can be used to model any polymer devolatiliza-
tion process. It performs best when the volatile concentration in the
feed is at or below 10% by weight. If the volatile concentration gets
too high, the diffusion limited model is not valid, and the WFE may
get inaccurate results. In order to model a WFE with a higher
weight percent volatile streams, model the top portion of the WFE
as a concentration-specified flash, then pass the equilibrium liquid
on to a shorter WFE for the rate-limited modeling.
1. Required entry for rating mode.

2. Default used if these data are omitted.
3. Required entry for design mode.

Wiped Film Evaporator Keyword Input
Keyword Summary
BATCH
Unit Identification (required)

WFEVAPORATOR UID=uid, {NAME=text}
Feeds and Products (required)
FEED sid, {sid,…}
PROD sid1, sid2
Operating Parameters (required)
IPARM i, j, k, …
RPARM i, j, k, …
Thermodynamic Set Selection (optional)
POLYMERS
METHOD SET=setid
General Information
The wiped film evaporator unit operation provides the capability to
separate solvents and/or monomers from a polymer melt. A wiped
film evaporator should be used when the removal of volatiles from
a viscous polymer melt is diffusion limited. The blades inside the
wiped film evaporator continually mix and spread a thin film of the
melt on the wall of the evaporator. As the melt moves down the
evaporator, the volatiles diffuse out of it and into the vapor space of
the evaporator. The volatiles are pulled out of the evaporator under
vacuum.
A mixture of up to ten feed streams is allowed and the unit requires
both an overhead and a bottoms product.
The wiped film evaporator can be modeled under several heating
conditions. It can be modeled isothermally (using the combined
feed temperature or user-specified temperature), adiabatically
(allowing heat input only through friction with the wiper blades), at
steady state (allowing heat input from a heating/cooling jacket), or
with a user-specified temperature profile.
The wiped film evaporator will operate at the lowest of the feed
stream pressures unless an inlet pressure and/or inlet pressure drop
are specified.

.
Note: The wiped film evaporator models a rate-limited process. It

allows liquid feeds only. If there is vapor in the feed stream, it is
assumed to be the product of an equilibrium flash. The WFE
attempts to condense the vapor and set the feed to the non-equilib-
rium state specified by the unit operating parameters (temperature
and pressure). The wiped film evaporator then commences model-
ing the rate-limited de-volatilization of the polymer melt as it tries
to reach thermophysical equilibrium.
Keyword Description
Unit Identification (required)
POLYMERS
WFEVAPORATOR UID=uid, {NAME=text}
This must be the first statement of a Wiped Film Evaporator unit.
Section 42, Unit Operation Input, of the PRO/II Keyword Manual
describes all optional entries.
Feeds and Products (required)

FEED sid, {sid,…}
PRODsid1, sid2
One FEED and one PROD statement are required. At least one feed
stream must be supplied, and a maximum of 10 may be provided. A
bottoms product stream (sid1) and an overhead product stream
(sid2) must be provided on the PROD statement.
Operating Parameters (required)

IPARM i, j, k, …
RPARM i, j, k, …
Input variables are specified on one IPARM statement for integers
and one RPARM statement for real variables. Table P13-1 describes
the values that can be entered on each statement and the associated
outcome. Entries are separated by commas, unspecified values may
be left blank or filled with a 0 except the first entry on each state-
ment, which must be specified or filled with a zero. The numbers
listed in Table P13-1 in parentheses following the words IPARM or
RPARM indicate the element position of the array that corresponds to
the attribute described. For example, IPARM(1) indicates that the
first element of the IPARM array is associated with the rating or
design mode choice, IPARM(2) is associated with the choice of
blade pitch, and IPARM(3) is associated with the number of blades

used. The statement IPARM 1,2,8,… indicates that rating mode,
pitched blades, and eight blades are to be used.
BATCH
Variables are further divided into input and output. Real output vari-
ables begin at RPARM(144). These values may be the target of a
SPEC command in a CONTROLLER. IPARM variables are not accessi-
ble to the SPEC system.
The default units of measure defined in the DIMENSION section of
the input file are used for all input unless otherwise specified. Indi-
vidual qualifiers for units of measure are not supported.
Table P13-1: Wiped Film Evaporator Available Input Entries
Variable Rating Design Description
IPARM Input Variables
IPARM(1) In In Calculation mode 1. Rating
POLYMERS
2. Design
IPARM(2) In In Blade configuration
1. Vertical
2. Pitched
3. Alternating number of blades.In
[IPARM(3)] must be an even number
if alternating configuration is used.
IPARM(3) In In Number of blades. Default is 8; see
IPARM(2).
IPARM(4) In In Temperature profile type
1. Isothermal
2. User Defined
3. Adiabatic
4. Steady State
IPARM(5) In In Number of zones in zone report.
Default is 20
IPARM(6) In† Starting component of design
specification.
IPARM(7) In Ending component of design
specification. Default is value of
IPARM(6)
RPARM Input Variables
RPARM(1) In* Out‡ Evaporator height
Default values are underlined.
In columns 2 and 3, ‘In’ indicates the variable may be input, ‘Out’
indicates it may be output.
* Required input.
† Required input in design mode only. ‡In user input units.

RPARM(2) In Out‡ Inside evaporator diameter. Default is
0.85 m.
RPARM(3) In In Length of pitched blade. Default is
evaporator height in rating mode. In
design mode, default is evaporator
height (if given) or 0.5 m if not given.
RPARM(4) In In Blade-wall
clearance
RPARM(5) In In Blade width
RPARM(6) In In Blade pitch (radians). Default is p/8.
RPARM(7) In In Rotation rate (1.5/
s)
POLYMERS
RPARM(8) In In Inlet pressure. Default is lowest of the
feed stream pressures.
RPARM(9) In In Inlet pressure drop - pressure drop from
inlet (or lowest feed stream) and the
evaporator.
RPARM(10) In In Ratio of bow wave to film area. Default
is 0.05.
RPARM(11) In In Viscosity at zero shear. If no input is
given for viscosity, PRO/II data are
used.
RPARM(12) In In Shear rate at blade tip (1/s). Default is
calculated from the assumption of a
straight line velocity profile. If no value
is entered or if the value entered is zero
the default value will be used.
RPARM(13) In In Viscosity relaxation time. Default is
0.3.
RPARM(14) In In Power law index. Default is 0.3.
RPARM(15) In In Model selection
1. Complete feedback model;
intermediate values are acceptable
0. Complete surface renewal model
RPARM(16) In In Power parameter - Fraction of the
calculated power required to push the
bow wave. Does not effect the power
required to overcome the drag force of
the polymer on the blade. Default is 1.
* Required input.

BATCH
RPARM(17) In In Viscosity parameter, Ω, where: effective

viscosity = Ω * viscosity under shear +
(1 - Ω) * viscosity at zero shear. Default
= 1.
RPARM(18) In In Heating/cooling jacket fluid
temperature (e.g. steam temperature).
RPARM(19) In In Overall heat transfer coefficient
between jacket fluid and polymer melt.
RPARM(20) In In† Design target concentration (mass
fraction) for component numbers
IPARM(6) through IPARM(7) in the
outlet melt.
RPARM(21) In In Design mode relative tolerance for
convergence on outlet concentration
supplied in RPARM(20).
POLYMERS
RPARM(22) In In For isothermal operation, temperature 1

is the inlet temperature of the
evaporator. If no value is specified for
temperature 1, the feed stream
temperature is used.
RPARM In In Temperatures 2-11. For a user specified
(23-32) temperature profile, all these must have
values. Values begin at RPARM(22)
and are given at evenly spaced intervals
through RPARM(32).
RPARM Output Variables
RPARM(144) Out‡ Out‡ Evaporator operating pressure.
RPAMR(145) Out‡ Out‡ Shaft power required by evaporator
blades.
RPARM(146) Out‡ Out‡ Mass flow of vapor from evaporator.
RPARM(147) Out‡ Out‡ Heat duty required by evaporator.
Negative values reflect a cooling
requirement.
RPARM(151) Out‡ Out‡ Mass rate of polymer melt entering
evaporator.
RPARM(152) Out‡ Out‡ Mass rate of polymer melt leaving
evaporator.
RPARM(153) Out‡ Out‡ Density of polymer melt entering
evaporator
* Required input.

RPARM(154) Out‡ Out‡ Density of polymer melt leaving
evaporator.
RPARM(155) Out‡ Out‡ Viscosity of polymer melt entering
evaporator
RPARM(156) Out‡ Out‡ Viscosity of polymer melt leaving
evaporator.
RPARM(157) Out‡ Out‡ Volumetric flow rate of vapor from
evaporator.
* Required input.
POLYMERS
Example P13-1
This example problem describes a polystyrene polymerization and
separation process, comprised of a polymer CSTR, a flash, a con-
troller, and a WFE. The CSTR produces a continuous polymer
molecular weight distribution that it uses to calculate the polymer
pseudocomponent concentrations in its product stream. The flash
and controller work to reduce the volatile concentration in the prod-
uct stream to the point where the process becomes rate-limited. The
WFE then takes the equilibrium liquid from the flash as its feed.
Notice that the operating temperature of the WFE is higher than that
of the flash. This puts the feed stream in a non-equilibrium condi-
tion in the WFE. If an equilibrated liquid stream is fed to a WFE,
and the WFE temperature and pressure are not different (higher
and/or lower, respectively) from the feed conditions, the feed will
not devolatilize.
Example P13-1 Input File
TITLE DATE=06/01/99
PRINT STREAM=ALL, RATE=WT, FRACTION=M,WT
DIMENSION SI, STDTEMP=273.15, STDPRES=101.325
SEQUENCE SIMSCI
CALCULATION RVPBASIS=APIN, TVP=310.93
SEGMENT DATA
SEGMENT A,A, FILL=VANKREVLEN
STRUCTURE(VANKRE) A,144(1),4(1)

COMPONENT DATA
LIBID 2,STYRENE/3,EBZN/4,BOBZ, BANK=SIMSCI
POLY 1,PSTYR
BATCH
PCOMPOSITION 1,1(A)
PHASE VLS=4
MWAVG 1,31000
ATTRIBUTE COMP=1,KINETICS=FR,&
MWD=2000,4000,6000,8000,10000,20000, &
30000,40000,60000,80000,100000,120000,150000,&
200000,300000,400000, MMWD=M0,M1,M2
VISCOSITY(V,K,PAS) TABULAR=300,500/1,0.001,0.001
VISCOSITY(L,C,PAS) TABULAR=30,100,500/1,500,450,300
CONDUCTIVITY(V,K,W/MK) TABULAR=300,500/1,1,1
THERMODYNAMIC DATA
METHOD SYSTEM=ALM, TRANSPORT=PURE, DIFFUSIVITY=DATA,&
POLYMERS
SET=ALM01, DEFAULT
KVAL(VLE)
ALME 3,A,0.06555,0,0
ALMC A,1.56677
DIFFUSIVITY(L)
DIFDATA(K) &
2,1,-18.420680744,0,0 /&
3,1,-16.8112428315,0,0 /&
2,3,-18.420680744,0,0 /&
3,2,-16.8112428315,0,0 /&
2,4,-18.420680744,0,0 /&
3,4,-16.8112428315,0,0 /&
4,1,-20.7232658369,0,0 /&
4,2,-20.7232658369,0,0 /&
4,3,-20.7232658369,0,0
STREAM DATA
PROPERTY STREAM=FEED_0, TEMPERATURE=343, &
PRESSURE=1013.3, PHASE=M, &
COMPOSITION(M,KGM/H)=2,10.4188/4,0.15
UNIT OPERATIONS
PCSTR UID=PC1
FEED FEED_0
PRODUCT PROD_1
IPARM =1,1,1,,79,,,,1,3,1,2,,3,4,0,0,0,0,0,0
RPARM =69900,200,0,0,0,355,0,0.5,0,0,,,1,
SUPPLEMENTAL=1,1.58E15/128870/0/0/1.05E7/ &
29540/0/0/13,0/&
0/0/0/0/0/0/0/25,0/0/0/0/0/0/0/0/ &
37,0/0/0/0/45,0/0/0/0/53,0/0/0/0/ &
61,0/0/0/0/69,0/0/0/0/77,0/0/0/0/ &

85,1.05E7/ 29540/0/0/101,0/0/0/0/ &
109,0/0/0/0/117,0/0/0/0/125,0/0/0/&
133,0/0/0/0/141,0/0/0/0/149,0/0/0/0/ &
157,0/0/0/0/165,0/0/0/0/173,0/0/0/0/ &
181,0/0/0/0/189,0/0/0/0/213,0/0/0/0/ &
229,1.26E9/7030/0/0/245,0/0/0/0/ &
261,0/0/0/0/269,0/0/0/ 0/277,0/0/0/0/ &
285,0/0/0/0/293,0/0/0/0/301,0/0/0/0
FLASH UID=F1
FEED PROD_1
PRODUCT V=VAP1, W=PROD_2
ISO TEMPERATURE=400, PRESSURE=0.666
CONTROLLER UID=CN1
POLYMERS
SPEC STREAM=PROD_2,FRACTION(WT), COMP=2,4, VALUE=0.02
VARY FLASH=F1, TEMP, PCT2=10
CPARAMETER IPRINT, NOSTOP
WFEV UID=WFE1
FEED PROD_2
PRODUCT PROD_3,VAP4
IPARM =1,,,1
RPARM =3,0.50,0.2,,,,,,,,500,,,,,,,,,0.0001,1E-5,460
END
Example P13-1 Output File

PROJECT PRO/II 386/EM
PROBLEM OUTPUT
WIPED FILM EVAPORATOR UNIT SUMMARY 05/08/2007
========================================================================
UNIT 4, 'WFE1'
WIPED FILM EVAPORATOR - RATING MODE
TEMPERATURE PROFILE: ISOTHERMAL
FEEDS PROD_2
PRODUCTS VAPOR VAP4
LIQUID PROD_3
OPERATING CONDITIONS
INLET TEMPERATURE, DEG K 460.0000
OUTLET TEMPERATURE, DEG K 460.0000
EVPORATOR PRESSURE, KPA .6660
REQUIRED SHAFT POWER, KW 2.0861
REQUIRED HEAT DUTY, KW 4.4966
VOLUMETRIC VAPOR FLOW RATE, M3/HR 107.7954
PHYSICAL CONFIGURATION
DIAMETER, M .5000
HEIGHT, M 3.0000
NUMBER OF VERTICAL BLADES 8

BLADE LENGTH, M .2000
BLADE WIDTH, M 5.000E-03
BLADE TO WALL CLEARANCE, M 5.000E-03
BATCH
FEEDBACK RATIO 1.0000

POWER PARAMETER (GAMMA) 1.0000
VISCOSITY PARAMETER (OMEGA) 1.0000
VISCOSITY RELAXATION TIME, SEC .3000
POWER LAW INDEX .3000
BOW WAVE TO FILM AREA RATIO .0500
SHAFT ROTATION RATE, REV/SEC 1.5000
VELOCITY PROFILE, 1/SEC 471.2389
STREAM PROPERTIES
LIQUID LIQUID VAPOR
INLET OUTLET OUTLET
STREAM ID PROD_2 PROD_3 VAP4
MASS FLOW RATE, KG/HR 143.2308 140.9980 2.2328
DENSITY, KG/M3 972.6086 976.6445
VISCOSITY, PAS 500.0000 500.0000
POLYMERS
DIFFUSIVITY REPORT (DIFFUSIVITIES Ids M2/S)

LIQUID LIQUID
COMPONENT INLET OUTLET
STYRENE .1000000E-07 .1000000E-07
EBZN .5000000E-07 .5000000E-07
BOBZ .1000000E-08 .1000000E-08
ZONE REPORT
DISTANCE LIQUID LIQUID LIQUID MASS VAPOR

MASS
FROM TOP TEMPERATURE VISCOSITY DENSITY FLOWRATE
FLOWRATE
M DEG K PAS KG/M3 KG/HR KG/HR
1 .1529 460.0000 15.6210 975.3908 141.8115 .0419
2 .3061 460.0000 15.6210 976.2098 141.3456 .0138
3 .4508 460.0000 15.6210 976.4450 141.1833 6.0254E-03
4 .6041 460.0000 15.6210 976.5397 141.1040 3.6379E-03
5 .7573 460.0000 15.6210 976.5844 141.0610 1.7342E-03
6 .9021 460.0000 15.6210 976.6076 141.0372 1.0589E-03
7 1.0554 460.0000 15.6210 976.6221 141.0219 6.4036E-04
8 1.2001 460.0000 15.6210 976.6304 141.0131 4.7831E-04
9 1.3534 460.0000 15.6210 976.6359 141.0072 2.4609E-04
10 1.5067 460.0000 15.6210 976.6393 141.0036 1.5046E-04
11 1.6514 460.0000 15.6210 976.6412 141.0015 9.4541E-05
12 1.8047 460.0000 15.6210 976.6425 141.0001 6.9007E-05
13 1.9580 460.0000 15.6210 976.6433 140.9993 3.5557E-05
14 2.1028 460.0000 15.6210 976.6437 140.9988 2.2346E-05
15 2.2560 460.0000 15.6210 976.6440 140.9985 1.3662E-05
16 2.4008 460.0000 15.6210 976.6442 140.9983 1.0246E-05
17 2.5541 460.0000 15.6210 976.6443 140.9982 5.2832E-06
18 2.7074 460.0000 15.6210 976.6444 140.9981 3.2331E-06
19 2.8521 460.0000 15.6210 976.6444 140.9980 2.0327E-06
20 3.0000 460.0000 15.6210 976.6445 140.9980 5.5237E-07

Appendix A
Table A-1: van Krevelen Structural Groups

ID Group Structural Formula Name Additional Description Chain
Aliphatic hydrocarbon chain groups
000 -H —H Hydrogen Also atomic contribution -
001 >C < | Carbon, 4 -valence, Also atomic contribution -
—C— aliphatic
|
002 >CH- | Methylidene -
—C—H
|
003 -CH2- — CH2 — Methylene General contribution -
004 -CH2-main — CH2 — Methylene In an aliphatic main chain +
005 -CH2-alpha — CH2 — Methylene Alpha position in a main +
chain with hetero groups
006 -CH2-beta — CH2 — Methylene Beta position in a main +
chain with hetero groups
007 -CH2-gamma — CH2 — Methylene Gamma position in a main +
chain with hetero-groups
008 -CH2- Methylene correction Correction for hydrogen +
H-bonding bonded aliphatic main
correction chain; for each methylene
group in main chain
009 -CH2- Methylene correction Correction for main chain +
one hetero- with 1 hetero-group per
group correction unit; for each methylene
group in main chain
010 -CH2- Methylene correction Correction for main chain +
two hetero- with 2 hetero-groups per
groups unit; for each methylene
POLYMERS
correction group in main chain

011 -CH2- side — CH2 — Methylene In side chain -
012 -CH3 — CH2 — Methyl General contribution -
013 -CH3 replaces - — CH3 Methyl substitution Methyl group as +
H replacement for hydrogen
+ Indicates main chain group - Indicates side group
PRO/II Polymers User Guide Appendix A-1

Table A-1: van Krevelen Structural Groups (Continued)
BATCH
014 >CHCH< | | Ethane, 1,1,2,2- tetra- General contribution -

—C—C— substituted
| |
H H
015 -CH(CH3)- — CH(CH3)— Methylmethylene Substituted main chain or +
general contribution
016 -C(CH3)2- — C(CH3)2 — Dimethylmethylene Substituted main chain +
(free rotation) without steric hindrance for
rotation or general
contribution
017 -C(CH3)2- — C(CH3)2 — Dimethylmethylene Substituted main chain with +
(hindered) (hindered rotation) steric hindrance for rotation
from one side
018 -C(CH3)2- — C(CH3)2 — Dimethylmethylene Substituted main chain with +
(two-side (two-side hindered steric hindrance for rotation
hindered) rotation) from two sides, especially
when enclosed between
rings
019 -CH(CH3)2 — CH(CH3)2 — Isopropyl General contribution -
020 - — CH[CH(CH3)2]— Isopropylmethylene Substituted main chain or +
CH[CH(CH3)2] general contribution
-
021 -CH(CH3)2 Isopropyl substitution Replacement of hydrogen +
(subst) by isopropyl
022 -C(CH3)3 — C(CH3)3 — Tert-butyl General contribution -
023 -C(CH3)3 Tert-butyl substitution Replacement of hydrogen +
(subst) by tert-butyl
024 -CH[C(CH3)3]- — CH[C(CH3)3]— Tert-butyl-methylene Substituted main chain or +
025 -CH[CH2CH — Iso-buty-lmethylene Substituted main chain or +
(CH3)2]- CH[CH2CH(CH3)2] general contribution
—
026 -CH2C(CH3)3 Neo-pentyl Replacement of hydrogen +
(subst) substitution by neopentyl
030 -CH2- (5r) — CH2 — Methylene Contribution for a -
5-membered ring
031 -CH2- (6r) — CH2 — Methylene Contribution for a -
6-membered ring
Aliphatic hydrocarbon ring groups
Appendix A-2 van Krevelen Structural Groups

032 Ring 3 3-membered ring Correction for a 3-member -
nonaromatic ring
nonaromatic ring
nonaromatic ring
nonaromatic ring
036 Ring7 7-membered ring Correction for a 7-member -
nonaromatic ring
037 Ring(other) other ring Correction for another -
nonaromatic ring
040 -C5H9, ring Cyclo-pentyl General contribution -
041 -C6H11, ring Cyclohexyl General contribution -
042 -C6H10(cis)- 1,4-cis- Cyclic main chain unit or +

Cyclo-hexylene general contribution
043 -C6H10(trans)- 1,4-trans-Cyclo- Cyclic main chain unit or
hexylene general contribution
044 -CH(C5H9)- Cyclo-pentyl- Substituted main chain or +

methylene general contribution
045 -CH(C6H11)- Cyclo-hexyl- Substituted main chain or +

methylene general contribution
046 -C6H11, ring Cyclo-hexyl Replacement of hydrogen +

(subst) substitution by cyclo-hexyl
POLYMERS
Unsaturated hydrocarbon groups

050 >C= >C= Carbon, aliphatic with Also atomic contribution -
double bond
051 -CH= — CH = Methylidene, aliphatic General contribution -
with double bond

BATCH
052 CH2= = CH2 2 Methylene, aliphatic General contribution -

with double bond
053 =C= =C= Carbon, aliphatic with Also atomic contribution -
two double bonds
054 Double Bond Double bond Correction for double bond -
correction
055 Cis-Double Cis configuration of Correction for Cis -
Bond double bond configuration of double
bond
056 Trans-Double Trans configuration of Correction for Trans -
Bond double bond configuration of double
bond
057 Conjug-Double Conjugation of double Correction for conjugation -
Bonds bonds of double bonds
058 Conjug-Double Conjugation of double Correction for conjugation -
Bonds (Ring) bonds in ring of double bonds in ring for
each double bond
060 >C=CH- Vinylidene General contribution -
061 -CH=CH-(cis) Cis-Vinylene Vinylene group in Cis +

configuration; main chain
unit or general contribution
062 -CH=CH-(trans) Trans-Vinylene Vinylene group in Trans +
configuration; main chain
063 -CH=C(CH3)- Cis-Methylvinylene Methylvinylene group in +
(cis) Cis configuration; main
chain unit or general
contribution
064 -CH=C(CH3)- Trans-Methylvinylene Methylvinylene group in +
(trans) Trans configuration; main
contribution
065 - Cis-1,2-Di-methyl- 1,2-Di-methyl-vinylene +
C(CH3)=C(CH3 methylene group in Cis configuration;
) -(cis) main chain unit or general
contribution
066 - Trans-1,2- Di-methyl- 1,2-Di-methyl-methylene +
C(CH3)=C(CH3 vinylene group in Trans
) -(trans) configuration; main chain

070 -C —C= Carbon, aliphatic with Also atomic contribution -
triple bond
071 HC H—C= Methylidene, aliphatic General contribution -
with triple bond
072 Triple Bond Triple bond correction Correction for triple bond -
073 -CC- —C=C— Ethynyl-idene Triple bond group; main +
contribution
074 -CCH H—C=C— Ethynyl Triple bond group -
Aromatic hydrocarbon groups
100 C,ar(exo) Carbon, aromatic, Also atomic contribution -
on the edge of aromatic
system
101 C,ar(endo) Carbon, aromatic, Also atomic contribution -
inside of the aromatic
system
102 CHar Nonsubstituted carbon, Also atomic contribution -
aromatic, on the edge
of aromatic system
105 OrthoSubst Correction for ortho Correction for ortho -
substitution substitution in aromatic ring
106 MetaSubst Correction for meta Correction for meta -
107 ParaSubst Correction for para Correction for para -
110 Ph- Phenyl General contribution -
111 Ph- (subst) Phenyl substitution Replacement of hydrogen +

by phenyl
112 -Ph-(o) 1,2-Phenylene -
POLYMERS
113 -Ph-(m) 1,3-Phenylene Main chain fragment for +

non-conjugated ring or
114 -Ph-(m)c 1,3-Phenylene; one Main chain fragment +
side conjugated conjugated from one side

BATCH
115 -Ph-(m)cc 1,3-Phenylene; two Main chain fragment +

sides conjugated conjugated from both sides
116 -Ph-(p) 1,4-Phenylene Main chain fragment for +

non-conjugated ring or
117 -Ph-(p)c 1,4-Phenylene, one Main chain fragment +
side conjugated conjugated from one side
118 -Ph-(p)cc 1,4-Phenylene two Main chain fragment +

sides conjugated conjugated from both sides
120 -Ph< Phenylidene General contribution -

121 >Ph<(1,2,3,5) Phenyl tetra- General contribution -
substituted in positions
1,2,3,5
122 >Ph<(1,2,4,5) Phenyl tetrasubstituted General contribution -
in positions 1,2,4,5
123 >Ph<(1,2,3,4,5) Phenyl General contribution -

pentasubstituted
124 >Ph<(1,2,3,4,5, Phenyl hexasubstituted General contribution -

6)
130 Naph- Naphthyl -
131 Naph< Naphthylene General contribution, can +

also be used as main chain
fragment
132 Naph<(1,4) 1,4-Naphthylene General contribution, can +
also be used as main chain
fragment
140 2-MePh(1,4)< 2-Methyl-1,4- Main chain fragment or

Phenylene general contribution
141 1-MePh(2,4)< 1-Methyl-2,4- Main chain fragment or

142 1,3- 1,3-Dimethyl-2,5- Main chain fragment or +

Me2Ph(2,5)< Phenylene general contribution

143 1,3-Ph2Ph(2,5)< 1,3-Diphenyl-2,5- Main chain fragment or +
144 -CH(C6H5)- Phenylmethylene Substituted main chain unit +

or general contribution
145 -CH(p- (4- Methylphenyl) Substituted main chain unit +

C6H4CH3)- methylene or general contribution
146 - 1-Phenyl-1- Substituted main chain unit +

C(CH3)(C6H5)- methylmethylene or general contribution
147 -C(C6H5)2- Diphenylmethylene Substituted main chain unit +

150 MePh- (subst) 4-Methylphenyl Replacement of hydrogen +

substitution by 4- methylphenyl
Groups containing oxygen
200 -O-(al) —O— Oxygen atom in General contribution; also, +
aliphatic chain atomic contribution and
non-conjugated main chain
fragment, mainly in ethers
201 -O-(ar) —O— Oxygen atom General contribution; also, +
connected with atomic contribution and
aromatic ring main chain fragment,
mainly in aromatic ethers
202 -O-(acetal) —O— Oxygen atom in acetals Special contribution for +
acetals; also, a main chain
unit
POLYMERS
203 -O-(epoxide) —O— Oxygen atom in Special contribution for

epoxides epoxides; also, a main chain
unit
204 O2(ester) Oxygen atoms in esters Special atomic contribution -
for esters

BATCH
210 -OH(pri) — OH Primary hydroxyl -

group
211 -OH(sec) — OH Secondary hydroxyl -
group
212 -OH(tert) — OH Tertiary hydroxyl -
group
213 -OH(phen) — OH Phenolic hydroxyl -
group
214 -OH(hydr.bond) — OH Hydrogen bonded Special contribution for -
hydroxyl group hydrogen bonded hydroxyl
group
215 -OH(twin or Correction for twinned Correction for each -
alpha) or alpha positioned hydroxyl group on adjacent
hydroxyl group or hydroxyl- bisubstituted
carbon atoms
220 -CH(OH)- — CH(OH) — Hydroxymethylene Substituted main chain unit +
221 -CH(OH)(wet)- — CH(OH) — Hydroxymethylene - Substituted main chain unit +
wet or general contribution
222 -CH(OCH3)- — CH(OCH3) — Methoxymethylene Substituted main chain unit +
230 -CO- O Carbonyl group General contribution -
||
—C—
231 -CO-(nc) O Non-conjugated Main chain unit or general +
|| carbonyl group as main contribution
—C— chain fragment
232 -CO-(c) O One-side conjugated Main chain unit or general +
233 -CO-(cc) O Two-side conjugated Main chain unit or general +
234 -CHO O Aldehyde group General contribution -
||
—C—H
235 -COO- O Ester group General contribution (not -
|| O conjugated)
—C—

236 -COO-(acryl) O Acrylic ester group General contribution for -
|| O acrylic ester group
—C—
237 -COO-(nc) O Non-conjugated ester Main chain unit (not +
|| group as main chain conjugated) or general
—C—O fragment contribution
238 -COO-(c) O One-side conjugated Main chain unit (one-side +
|| ester group as main conjugated)
—C—O chain fragment
239 -COO-(cc) O Ester group as main Main chain contribution +
|| chain fragment (between aromatic rings -
—C—O between two aromatic rigid system)
rings
240 -COOH O Carboxylic group General contribution -
||
— C — OH
241 HCOO- O Formic group General contribution -
||
H—C—O
242 -OCOO- O Carbonate group Main chain unit or general +
|| contribution
O—C—O
243 -COOCO-(nc) O O Anhydride group (not General contribution or +
|| || conjugated) main chain unit
—C—O —C—
244 -COOCO-(c) O O Anhydride group General contribution or +
|| || (conjugated on one main chain unit
—C—O —C— side)
245 -COOCO-(cc) O O Anhydride group General contribution or +
|| || (conjugated on two main chain unit
—C—O—C— sides)
246 -OCOCOO- O O Oxylate group Main chain unit or general +
|| || contribution
- O — C — C —O-
250 - Methylene acetate Substituted main chain unit +
POLYMERS
CH(OOCCH3)- or general contribution
251 - Methyl Substituted main chain unit +

CH(COOCH3)- methylenecarboxylate or general contribution

BATCH
252 -C(CH3)(COO Methyl Substituted main chain unit

CH3)- methylmethylene or general contribution
carboxylate
Groups containing fluorine

300 -F —F Fluoride General contribution -
301 -F(disubst) —F Fluoride Each of two fluoride atoms -
(disubstituted) substituted to a carbon atom
302 -F(trisubst) —F Fluoride Each of three fluoride atoms -
(trisubstituted) substituted to a carbon atom
303 -F(double) Fluoride (double bond) Correction for fluoride -
connected to a carbon atom
with a double bond
304 -F(subst) Fluorine (aliphatic Tentative contribution for +
substitution) hydrogen replacement by
fluorine
310 -CHF- — CHF — Fluoromethylene General contribution or +
main chain fragment
311 -CF2- — CF2 — Difluoromethylene General contribution or +
main chain fragment
312 -CF2-(per) — CF2 — Difluoromethylene General contribution or +
(perfluoro) main chain fragment for
perfluoro compounds
313 -CF3 — CF3 Trifluoromethyl General contribution -
314 -CF3(per) — CF3 Trifluoromethyl General contribution for -
(perfluoro) perfluoro compounds
315 -CF(CF3)- — CH(CF3 )— Difluoromethylene General contribution or +
(perfluoro) main chain fragment
316 -CH=CF- — CH = CF — Fluorovinylene General contribution or +
main chain fragment
317 -CF=CF- — CH = CF — 1,2-Difluorovinylene General contribution or +
main chain fragment

Groups containing chlorine (or fluorine and chlorine)
320 -Cl(al) — Cl Chlorine (aliphatic) General contribution for -
chlorine in aliphatic
compound
321 -Cl(pri) — Cl Chlorine (primary) Contribution for chlorine -
connected to a primary
aliphatic carbon atom
322 -Cl(sec) — Cl Chlorine (secondary) Contribution for chlorine -
connected to a secondary
323 -Cl(disubst) — Cl Chlorine Contribution for each of two -
(disubstituted) chlorines connected to an
324 -Cl(trisubst) — Cl Chlorine Contribution for each of -
(trisubstituted) three chlorines connected to
an aliphatic carbon atom
325 -Cl(double) Chlorine (double bond) Correction for chlorine -
connected to a double
bonded carbon atom
326 -Cl(ar) — Cl Chlorine (aromatic) Contribution for chlorine -
connected to an aromatic
carbon atom
327 -Cl(subst, aliph) Chlorine (aliphatic Tentative contribution for +
substitution) hydrogen replaced by
chlorine in an aliphatic
compound
328 -Cl(subst, arom) Chlorine (aromatic Tentative contribution for +
substitution) hydrogen replaced by
chlorine in an aromatic
compound
330 -CH2Cl — CH2Cl Chloromethyl General contribution -
331 -CHCl2 — CHCl2 Dichloromethyl General contribution -
332 -CCl3 — CCl3 Trichloromethyl General contribution -
333 -CHCl- — CHCl — Chloromethylene General contribution and +
POLYMERS
main chain fragment

334 -CCl2- — CCl2 — Dichloromethylene General contribution and +
main chain fragment
335 -CFCl- — CFCl — Chlorofluoromethylen General contribution and +
e main chain fragment

BATCH
336 -CH(CH2Cl)- — CH(CH2Cl) — 2-Chloroethylene-1,1 General contribution and +

main chain fragment
337 -C(CH2Cl)2- — C(CH2Cl)2 — Di(chloromethyl)- General contribution and
methylene main chain fragment
338 -CH=CCl- — CH=CCl — Chlorovinylene General contribution and +
main chain fragment
340 2-ClPh(1,4)< 2-Chloro-1,4- General contribution and
Phenylene main chain fragment
341 1-ClPh(2,4)< 1-Chloro-2,4- General contribution and +

Phenylene main chain fragment
Groups containing bromine

350 -Br(al) — Br Bromine General contribution for -
(aliphatic) bromine in an aliphatic
compound
351 -Br(disubst) — Br Bromine Contribution for each of two -
(disubstituted) bromines connected to an
352 -Br(trisubst) — Br Bromine Contribution for each of -
(trisubstituted) three bromines connected to
353 -Br(double) — Br Bromine Correction for bromine -
(double bond) connected to a double-
bonded carbon atom
354 -Br(ar) — Br Bromine Contribution for bromine -
(aromatic) connected to an aromatic
carbon atom
355 -Br(subst) Bromine Tentative contribution for +
(substitution) hydrogen replaced by
bromine

Groups containing iodine
360 -I —I Iodine General contribution for -
iodine
361 -I(disubst) —I Iodine Contribution for each of two -
(disubstituted) iodines connected to an
362 -I(trisubst) —I Iodine Contribution for each of -
(trisubstituted) three iodines connected to
363 -I(double) Iodine Correction for iodine -
(double bond) connected to a double-
bonded carbon atom
Groups containing nitrogen (or nitrogen and oxygen)
400 -N< —N< Nitrogen atom General and atomic -
contribution
401 -N= —N= Nitrogen atom with General and atomic -
double bond contribution
402 N(ar) Nitrogen atom in General and atomic -
aromatic ring contribution
403 -NH- — NH — Imine group General contribution and +
main chain fragment
404 -NH2 — NH2 Amine group General contribution -
405 -CN —C=N Nitrile group General contribution -
406 -CN(subst) Nitrile group Hydrogen substituted by a +
(substitution) nitrile group
407 -CH(CN)- — CH(CN) — Nitrilmethylene General and main chain +
fragment contribution
408 -C(CN)2- — C(CN)2 — Dinitrilmethylene General and main chain +
fragment contribution
410 -CONH-(nc) O N-substituted non- Main chain contribution +
|| conjugated amide (not conjugated) or general
— C — NH — group as a main chain contribution
fragment
POLYMERS
411 -CONH-(c) O N-substituted one-side Main chain contribution +

|| conjugated amide (one-side conjugated)
— C — NH — group as a main chain
fragment

BATCH
412 -CONH-(cc) O N-substituted two-side Main chain contribution +

|| conjugated amide (two-side conjugated -
— C — NH — group as a main chain between rings in rigid
fragment aramides)
413 -CONH-(wet) O N-substituted wet Main chain unit or general +
|| amide group contribution
— C — NH —
414 -OCONH- O Carbonimide as main Main chain or general +
|| chain fragment contribution
— O — C — NH —
415 -NHCONH- O Urenide as main chain Main chain or general +
|| fragment contribution
— NH — C — NH
—
416 -CONH2 O Amide group General contribution -
||
— C — NH2
417 -CON< O N,N-disubstituted General contribution -
|| amide group
—C—N<
418 HCON< O N,N-disubstituted General contribution -
|| formamide group
H—C—N<
419 HCONH- O N-substituted General contribution -
|| formamide group
H — C — NH —
420 >NCON< O N,N,N’,N’- General contribution -
|| tetradisubstituted
>N—C—N< urenide group
421 -N=C=O — N =C = O Isocyanide group General contribution -
422 -NHNH- — NH — NH — Hydrazine group Main chain unit or general +
(N,N'-disubstituted) contribution
423 >NNH2 > N — NH2 Hydrazine group General contribution -
(N,N-disubstituted)
424 -NHNH2 — NH — NH2 Hydrazine group General contribution -
(N-substituted)
425 -N=N- —N=N— Azo group General contribution -
426 –N ≡ N —N=N Diazo group General contribution -
427 -N=C=N- —N=C=N— General contribution -

428 >C=N-N=C< >C=N—N=C< Azine group General contribution -

430 -NO2 (al) — NO2 Nitro group in aliphatic General contribution -
compounds
431 -NO2 (ar) — NO2 Nitro group in General contribution -
aromatic compounds
432 -ONO2 — ONO2 Nitrate group General contribution -
433 -ONO —O—N=O Nitrite group General contribution -
440 -Pyr Pyridine group General contribution -
(substituted in
position 4)
441 -Pyrrol Pyrrolidone group General contribution -
(substituted)
442 -Carbazole Carbazole group (N- General contribution -

substituted)
443 -Quinoxaline< Quinoxaline (2,3,6 - General contribution -

trisubstituted)
Groups containing sulfur (or sulfur and oxygen)

450 -S- —S— Sulphide Main chain fragment or +
451 Sar Sulphur (aromatic) General contribution -
452 -SS- —S—S— Disulphide Main chain fragment and +

453 -SH — SH Mercaptyl group General contribution -
460 -SO- O Sulphinyl group General contribution -
||
—S—
461 -SO2- O Sulphonyl group (not Main chain fragment and +
|| conjugated) general contribution
—S—
||
O
POLYMERS
462 -SO2-(c) O Sulphonyl group (one- Main chain fragment and +

|| side conjugated) general contribution
—S—
||
O

BATCH
463 -SO2-(cc) O Sulphonyl group (two- Main chain fragment and +

|| side conjugated) general contribution
—S—
||
O
464 -SO3H O Sulphonic group General contribution -
||
— S — OH
||
O
Groups containing silicon
480 Si | Silicone group General contribution -
— Si —
|
481 -Si(CH3)2- — Si(CH3)2 — Dimethylsilicone Main chain fragment and +
group (not sterically general contribution
hindered)
482 -Si(CH3)2-(sh) — Si(CH3)2 — Dimethylsilicone Main chain fragment and +
group (sterically general contribution
hindered)
Complex groups (combinations of elementary groups)
500 -1,4-C6H4- Main chain fragment and +
CH2-1,4-C6H4- general contribution
C(CH3)2- general contribution
1,4-C6H4-
C(CH3)(C6H5)- general contribution
1,4-C6H4-
C(C6H5)2- general contribution
1,4- C6H4-

1,4-C6H10- general contribution
1,4-C6H4-
505 -1,4-C6H4 Main chain fragment and +
[-C(CH3)2- general contribution
1,4- C6H4]2-
506 -1,4-C6H4- 4,4’-diphenylene Main chain fragment and +
1,4-C6H4- group general contribution

507 -1,4-C6H4-CO- Main chain fragment and +
508 -1,4-C6H4-O- Main chain fragment and +

509 -1,4-C6H4[-O- Main chain fragment and +
1,4- C6H4]2- general contribution
510 -1,4-C6H4-S- Main chain fragment and +

SO2-1,4- C6H4- general contribution
512 -CH2-1,4- Flexible main chain +
C6H4-CH2- fragment or general
contribution
513 -O-1,4-C6H4- Flexible main chain +
O- fragment or general
contribution
514 -OCO-1,4- Flexible main chain +
C6H4-COO- fragment or general
contribution
contribution
contribution
517 -NHCO-1,4- Flexible main chain +
C6H4-CONH- fragment or general
contribution
518 -NHCO-1,3- Flexible main chain +
C6H4-CONH- fragment or general
contribution
519 -O-1,4- Main chain fragment in +
C6H4-CO- rigid arylates or general
contribution
POLYMERS
520 -O-1,3-C6H4- Main chain fragment in +

CO- rigid arylates or general
contribution
521 -NH-1,4-C6H4- Main chain fragment in +
CO- rigid aramides or general
contribution

BATCH

NHCO-1,4- rigid aramides or general
C6H4-CO- contribution
NHCO-1,3- rigid aramides or general
C6H4-CO- contribution
600 -C3H4N2O- 2-Imidazolidone group Main chain fragment or +
(1,3-disubstituted) general contribution
601 -C4H2N2O2- Uracil group (1,3- Main chain fragment or +

disubstituted) general contribution
602 -C5H4N2O2- Thymine group (1,3- Main chain fragment or +

disubstituted) general contribution
603 -C2N2O- 1,2,4-oxadiazol group Main chain fragment or +

(one-side conjugated)
604 -C2N2S- 1,2,4-thiodiazol group Main chain fragment or +

(two-sides conjugated)
605 -C3HNS- Thiazol group (2,5- Main chain fragment or +

disubstituted) (two- general contribution
sides conjugated)
606 -C8H3NO2- Phthalimide group (N Main chain fragment or +

and ring disubstituted) general contribution
(not conjugated)
607 -C8H3NO2-(c) Phthalimide group (N Main chain fragment or +

and ring disubstituted) general contribution
(one-side conjugated)
608 -C9H12N2O2- 5-cyclohexylhydantoin Main chain fragment or +

group (1,3- general contribution
disubstituted)

609 -C7H4N2O- 2(3H)- Main chain fragment or +
benzimidazolone general contribution
group (1,3-
disubstituted)
610 -C11H6N2O- Main chain fragment or +

611 -C10H2N2O4- Pyromellitic diimide Main chain fragment or +

(N,N’-disubstituted) general contribution
612 -C7H4N2- Benzimidazole group Main chain fragment or +

(2- and ring general contribution
disubstituted) (two-
sides conjugated)
613 -C8H4N4- Benzimidazole group Main chain fragment or +
(2,2’-disubstituted) general contribution
614 -C8H2N2S2- Benzothiazole group Main chain fragment or +

(2,2’-disubstituted) general contribution
Special contributions of additional effects
700 Even(-O-) Special contribution of Main chain contribution +
a sequence of an even
number of CH2 units
in a main chain with
ether groups
701 Even(-S-) Special contribution of Main chain contribution +
number of CH2 units
thioether groups
702 Even(-OCOO-) Special contribution of Main chain contribution +
POLYMERS
number of CH2 units
carbonate or equivalent
groups

BATCH
703 Even(-OCONH- Special contribution of Main chain contribution +

) a sequence of an even
number of CH2 units
carbonamide or
equivalent groups
704 Odd(-O-) Special contribution of Main chain contribution +
a sequence of an odd
number of CH2 units
ether groups
705 Odd(-S-) Special contribution of Main chain contribution +
number of CH2 units
thioether groups
706 Odd(-OCOO-) Special contribution of Main chain contribution +
number of CH2 units
carbonate or equivalent
group
707 Odd(-OCONH-) Special contribution of Main chain contribution +
number of CH2 unit in
a main chain with
carbonamide or
equivalent groups
708 Backbone atom Special contribution of -
each backbone atom
(in a main chain)
709 Cross link Special contribution of -
a side-chain bivalent
group
710 Side group Special contribution of -
side-chain group
711 Small molecule Special contribution -
for a small molecule -
(not polymeric)
712 Symmetry(1p) One plane of symmetry -
- special contribution

713 Symmetry(2p) Two planes of -
symmetry - special
contribution
714 Symmetry(mp) More than two planes -
of symmetry - special
contribution
POLYMERS

BATCH

Index
A C
Addition polymerization , P1-1 Carreau model , P13-7
Additivity principle , P3-1 Chain length , P7-18
Advanced lattice model kinetic, P12-1
example, P7-7 Chain polymerization
K-value data, P7-4 See Addition polymerization
METHOD statement, P7-2 Chain propagation , P9-8
overview, P7-2
Chain termination , P9-9
pure component properties, P7-2
two liquid phase behavior, P7-2 Chain transfer , P9-8
typical usage, P7-2 Chains
Application ranges bulk, P12-1
UNIFAC free volume dead, P12-1
model, P7-8 live, P12-1
Attributes types of, P5-12, P11-3
example of MWD or Component
MMWD, P5-7 estimating polymer
example of PCFRAC, P5-8 properties, P3-1
MWD or MMWD, P5-4, P5-5 Component data
PCFRAC, P5-5, P5-6 entering, P2-3, P3-10
Average molecular weight , P2-3, estimating polymer
P12-2, P12-3 properties, P3-1
Axial velocity , P13-5 supplying polymer pure
properties, P4-1
Component properties
B liquid diffusivity, P13-7
liquid viscosity, P13-7
Binary energetic parameters , P7- options, P13-6
4 Components
Binary interaction parameters, adding, P5-11
types , P7-30 solid, P5-1
Binary temperature-dependent Concentration as a function of
parameters , P7-13 rotation rate , P13-3
Blades Condensation
configurations, P13-5 polymerization , P1-2
length, P13-6 Coordination Complex Kinetic
number of, P13-5 mechanisms, P10-4
width, P13-6
Coordination Complex Kinetics
Bow wave , P13-2 catalyst initiation, P10-7
Bulk chains , P12-1 chain propagation at catalyst
site, P10-7
Bulk polymerization , P1-4
chain termination, P10-8
PRO/II Polymers User Guide Index-1

chain transfer at catalyst typical usage, P7-17
site, P10-7 Example
Coordination complex kinetics advanced lattice model, P7-7
BATCH
polymerization via, P10-2 coordination copolymerization

Copolymer , P1-3 in a CSTR, P10-22
coordination
Correlation, gel and glass homopolymerization in a
effects , P9-11 CSTR, P10-17
Cross-linking , P1-3 coordination polymerization in
CSTR , P2-9, P8-1, P9-1, P10-1, P11-1, a CSTR, P10-28
P13-15 coordination polymerization in
coordination a PFR, P10-35
copolymerization, P10-22 equations of state, P7-25
coordination Flory-Huggins model, P7-16
homopolymerization, P10-17 free radical copolymerization
coordination in CSTR, P9-33
polymerization, P10-28 free radical copolymerization
free radical in PFR, P9-38
copolymerization, P9-33 free radical
free radical homopolymerization in
homopolymerization, P9-23 CSTR, P9-23
mass and energy balances, P8-3 free radical
type 1 step growth homopolymerization in
polymerization, P11-14 PFR, P9-29
type 2 step growth MWD or MMWD attributes, P5-
polymerization, P11-22 7
type 3 step growth PCFRAC attributes, P5-8
polymerization, P11-29 type 1 step growth
polymerization in
CSTR, P11-14
type 1 step growth
D polymerization in PFR, P11-
18
Dead chains , P12-1 type 2 step growth
Devolatilization , P13-1 polymerization in
CSTR, P11-22
Diffusivity , P13-6
type 2 step growth
polymerization in PFR, P11-
26
E type 3 step growth
polymerization in
Emulsion polymerization , P1-4, CSTR, P11-29
P5-3 type 3 step growth
Energy operating equations polymerization in PFR, P11-
33
CSTR, P8-3
UNIFAC free-volume
PFR, P8-4
model, P7-10
Energy parameter , P7-18 van Krevelen structural
Equations of state groups, P3-4
example, P7-25 wiped film evaporator, P13-15
K-values, P7-18
METHOD statement, P7-18
options, P7-17 F
pure component properties, P7-
17 Feedback model , P13-4
Index-2
Feedback ratio , P13-3 polymer attributes, P4-3
Flory-Huggins model polymer definition, P4-3
example, P7-16 temperature-dependent
properties, P4-6
K-values, P7-12
METHOD statement, P7-12 Invariant properties
overview, P7-11 input description, P4-5
typical usage, P7-11 keyword summary, P4-1
types, P4-1
Flowsheet, building the , P2-8
Ionic polymerization , P1-1
Free radical initiation , P9-7
Free radical kinetics IPARM variables , P9-13, P10-11,
P11-9
mechanisms, P9-2 definitions, P13-11
polymerization via, P9-2 entering, P2-9
user-added subroutines, P9-13
Free radical polymerization , P1-
1, P9-2 K
MWD or MMWD attributes, P5-
4
Keyword summary
PCFRAC attributes, P5-5
example, P3-4
Free radical recombination , P9-9 invariant properties, P4-1
Fugacity , P7-4, P7-13 METHOD statement, P7-2, P7-8,
P7-12, P7-18
Fugacity coefficient , P7-3, P7-9,
P7-12 polymer attributes, P4-1
POLYMER components, P3-2
polymer definition, P4-1
G PRINT statement, P6-1
stream polymers, P5-2
Gel and glass effects , P9-10 STRUCTURE statement, P3-2
temperature-dependent
Group transfer properties, P4-2
polymerization , P1-1 user-added subroutines, P9-13,
P10-11, P11-9
van Krevelen group
H contribution method, P3-1
van Krevelen structural
Hardness , P1-3 groups, P3-3
Heat VANKRE qualifier, P3-2
conditions of wiped film wiped film evaporator, P13-10
evaporator, P13-10 Kinetic chain length , P12-1
controls, P1-2 Kinetic data, entering , P2-9
removal/addition of, P1-1
Kinetic rate constants , P8-2, P11-8
Heat transfer coefficient , P8-5
Kinetic type , P2-5
Henry’s law data , P7-3, P7-9, P7-12
Kinetics
High-viscosity solutions , P13-5 Coordination complex, P10-2
Homopolymer , P1-3 free radical, P9-2
stepwise, P11-2
K-values
I advanced lattice method, P7-4
equations of state, P7-18
Input description Flory-Huggins model, P7-12
invariant properties, P4-5

UNIFAC free volume
method, P7-9
N
Non-Newtonian fluids , P13-7
BATCH
L
Live chains , P12-1, P12-3
O
Omega parameter , P13-7
M Operating data , P2-9
Operating modes, wiped film
Macromolecules , P1-2 evaporator , P13-2
Mass operating equations Operating parameters, wiped
CSTR, P8-3 film evaporator , P13-10, P13-11
PFR, P8-4 Optimizer unit , P13-3
Melt physical properties Output reports
liquid diffusity, P13-7 interpreting, P12-1
liquid viscosity, P13-7 options, P6-1
options, P13-6 PRINT statement, P6-1
METHOD statement PWRATE and PCONV
advanced lattice model, P7-2 statements, P6-2
equations of state, P7-18 Output, wiped film
Flory-Huggins model, P7-12 evaporator , P13-8
UNIFAC free volume
model, P7-8
Mole balances , P8-3, P8-4 P
Molecular weight
distribution , P12-2 Parameters
calculating, P2-4, P4-10 binary interaction, P7-4
entering data, P2-4, P4-11, P5-12 Omega, P13-7
moments, P4-1, P5-1 operating, wiped film
providing, P4-1 evaporator, P13-10, P13-11
pure chain length, P7-18
Molecular weight fractions , P5- pure energy, P7-18
12
pure size, P7-18
Molecular weight, average , P2-3, pure species, P7-29
P12-3
PCFRAC attributes
Moment expansions , P8-7
free radical, P5-5
Moments , P8-3, P8-5, P12-3 step-growth polymerization, P5-
Monomers , P1-1, P1-2, P1-3, P9-2 6
Ziegler-Natta, P5-6
MWD or MMWD attibutes
Ziegler-Natta Perturbed hard-sphere-chain
polymerization, P5-4 (PHSC) theory
See Equations of state
MWD or MMWD attributes
example, P5-7 PFR , P8-1, P9-1, P10-1, P11-1
free radical polymerization, P5- coordination
4 polymerization, P10-35
step growth polymerization, P5- free radical
5 copolymerization, P9-38
free radical
homopolymerization, P9-29
Index-4
mass and energy balances, P8-4 selecting polymer reactors, P2-8
type 1 step growth selecting the units of
polymerization, P11-18 measure, P2-1
type 2 step growth using in PRO/II, P2-1
polymerization, P11-26 Polymer properties
type 3 step growth estimating, P3-1
polymerization, P11-33
supplying pure component
PFRAC attributes, example , P5-8 data, P4-1
Phase equilibrium Polymer reactors
calculations , P7-1 selecting, P2-8
Poly(vinylchloride) , P1-1 Polymer segments
Polyamides , P1-2 definition, P1-3
entering data, P2-3, P3-10
Polydispersity index , P12-2
STRUCTURE statement, P7-8
Polyesters , P1-2
Polymer stream data , P5-1
Polyethylene , P1-1
Polymerization
Polymer addition or chain, P1-1
estimating properties, P3-1 bulk, P1-4
Polymer blend , P1-3 chain types, P11-3
Polymer chain , P1-3 condensation or step
growth, P1-2
Polymer characterization emulsion, P1-4
conversion , P6-2 exothermic reactions, P1-2
Polymer characterization free radical, P9-2
conversion utility , P5-1 MWD or MMWD attributes for
Polymer characterization via free radical, P5-4
moments , P12-3 MWD or MMWD attributes for
step growth, P5-5
Polymer components MWD or MMWD attributes for
adding, P2-3 Ziegler-Natta, P5-4
deleting, P2-4 PCFRAC attributes for free
entering distribution data, P2-5, radical, P5-5
P4-11 PCFRAC attributes for step
enterring data, P3-10 growth, P5-6
kinetic type, P2-5 PCFRAC attributes for Ziegler-
Polymer melt , P13-2 Natta, P5-6
Polymer module solution, P1-4
building the flowsheet, P2-8 suspension, P1-4
calculating molecular weight via Coordination complex
distributions, P2-4, P4-10 kinetics, P10-2
choosing thermodynamic via free radical kinetics, P9-2
methods, P2-6 via stepwise kinetics, P11-2
entering component data, P2-3 Polymers
entering polymer segment derivatives, P1-2
data, P2-3 hardness, P1-3
entering PWRATE and PCONV introduction, P1-1
values, P6-2 keyword summary, P4-1
entering stream polymer properties, P1-3
data, P5-10 synthesis methods, P1-1, P1-2
general approach for using, P2-1 terminology, P1-3
selecting a thermodynamic thermoplastic, P1-1
method, P7-27 thermosetting, P1-2

Polystyrene , P1-1 decomposition and
initiation, P9-3
Polyurethane , P1-2
free radical initiation, P9-7
BATCH
Population balance , P8-6 free radical recombination, P9-9

Power as afunction of rotation gel and glass effects, P9-10
rate , P13-3 propagation, P9-4
Poynting correction , P7-4, P7-13 side, P9-6
termination, P9-6
Predicted properties
equations of state, P7-17 Reactive center , P9-2
Pressure effects , P8-5 Reactor models or Reactors
See User-added polymer
PRINT statement , P6-1 reactor models
PRO/II Reactor unit US21 , P9-23, P10-17,
polymer characterization P11-13
conversion utility, P5-1
Reactors, selecting polymer
user-added subroutines, P9-13,
P10-11, P11-9
type , P2-8
using the polymer module Report options
in, P2-1 output, P6-1
wiped film evaporator, P13-2 PRINT statement, P6-1
Properties PWRATE and PCONV
estimating polymer, P3-1 statements, P6-2
Pseudocomponents , P2-4 Rotation rate, wiped film
evaporator , P13-3
Pure chain length parameter , P7-
18 RPARM variables , P8-5, P9-13, P10-
11, P11-9
Pure component properties , P7-
11
definitions, P13-11
advanced lattice model, P7-2 entering, P2-9
UNIFAC free volume
model, P7-8 S
Pure energy parameter , P7-18
SCHULZ-FLORY
Pure size parameter , P7-18 distribution , P5-1
Pure species parameters , P7-29 Segment data , P2-3
PWRATE and PCONV Shear rate , P13-7
statements , P6-2
Simulation
creating for a polymer
system, P2-1
R
Size correction factor , P7-4
Rate constants, kinetic , P8-2, P11- Solid components , P5-1
8 Solution polymerization , P1-4
Rate-limited process , P13-11, P13- Statistical associating fluid
15
theory (SAFT)
Reactions See Equations of state
chain propagation, P9-8
Step growth polymerization
chain termination, P9-9
chain types, P11-3
chain transfer, P9-8
kinetic mechanisms, P11-4
chain transfer and
reinitiation, P9-4 MWD or MMWD attributes, P5-
5
Index-6
PCFRAC attributes, P5-6 fugacity coefficient, P7-3, P7-9,
See Also Condensation P7-12
polymerization Henry’s law, P7-3, P7-9, P7-12
Stepwise kinetics K-values, P7-4, P7-9, P7-12
polymerization via, P11-2 METHOD statement, P7-2, P7-8,
P7-12, P7-18
user-added subroutines, P10-11,
P11-9 Poynting correction, P7-4, P7-13
selecting, P7-27
Stream data
wiped film evaporator
supplying, P5-10 keywords, P13-10
Stream output report Thermophysical properties , P7-1
options, P6-1
PRINT statement, P6-1 Thermoplastic polymer
PWRATE and PCONV creating, P1-1
statements, P6-2 definition, P1-3
Streams Thermosetting polymer
emulsion/suspension, P5-3 creating, P1-2
entering PWRATE and definition, P1-3
PCONV, P6-2 Two liquid phase behavior , P7-11
limits for wiped film advanced lattice model, P7-2
evaporator, P13-10 equations of state, P7-17
MWD or MMWD attributes, P5- UNIFAC free volume
4, P5-5 method, P7-8
PCFRAC attributes, P5-5, P5-6
polymer keyword summary, P5-
2
polymer solids in, P5-1
U
supplying data, P5-1
UNIFAC free volume model
wiped film evaporator
application ranges, P7-8
keywords, P13-10, P13-11
example, P7-10
SUPPLE variables , P9-13, P10-11, K-values, P7-9
P11-9
METHOD statement, P7-8
entering, P2-9
overview, P7-8
Surface renewal model , P13-4 pure component properties, P7-8
Suspension , P5-3 two phase behavior, P7-8
Suspension polymerization , P1-4 typical usage, P7-8
UNIFAC structures , P2-3, P3-13
Unit
T wiped film evaporator
keyword, P13-10, P13-11
Temperature profiles , P13-6 Units of measure
Temperature-dependent selecting, P2-1
properties User-added polymer reactor
input description, P4-6 models
keyword summary, P4-2 conditions, P8-1, P9-1, P10-1, P11-1
types, P4-1 energy operating equations, P8-
Terminology , P1-3 3, P8-4
Thermodynamic method heat transfer coefficient, P8-5
binary energetic parameters, P7- kinetic rate constants, P8-2, P11-
8
4
choosing, P2-6 mass operting equations, P8-3,
P8-4

mechanisms, P9-2 W
moment expansions, P8-7
overview, P8-1, P9-1, P10-1, P11-1 Wall clearance , P13-6
BATCH
polymerization via free radical

kinetics, P9-2 WFE
polymerization via stepwise See Wiped film evaporator
kinetics, P11-2 Wiped film evaporator
population balance, P8-6 axial velocity, P13-5
pressure effects, P8-5 blade configurations, P13-5
required data, P9-12, P10-10, P11-8 bow wave, P13-2
user-added subroutines, P9-13, Carreau model, P13-7
P10-11, P11-9 component properties, P13-6
user-added polymer reactor design mode calculations, P13-2
models example, P4-8, P13-15
polymerization via feedback model, P13-4
Coordination complex feedback ratio, P13-3
kinetics, P10-2 functions of rotation rate, P13-3
User-added routines general summary, P13-10
stepwise kinetics, P10-11, P11-9 heating conditions, P13-10
inside view, P13-1
User-added subroutines
keyword input, P13-10
communicating with PRO/
II, P9-13, P10-11, P11-9 liquid diffusivity, P13-7
free radical kinetics, P9-13 liquid viscosity, P13-7
keyword input, P9-13, P10-11, melt physical properties, P13-6
P11-9 number of blades, P13-5
reactor unit US21, P9-23, P10-17, operating modes, P13-2
P11-13 optimization, P13-3
Utility output, P13-8
polymer characterization outside view, P13-1
conversion, P5-1 polymer melt, P13-2
PRO/II, P13-2
rate-limited process, P13-11
V rating mode, P13-3
required entries, P13-8
van Krevelen method shear rate, P13-7
group contribution, P3-1 surface renewal model, P13-4
group contribution, temperature profiles, P13-6
example, P7-7 unit identification, P13-10, P13-11
van Krevelen structural groups
description, P3-3
example, P3-4
Z
table, A-1
Ziegler-Natta
van Krevelen structures , P2-3 polymerization , P1-1
Viscosity , P13-6
Volatiles, mass transfer of , P13-1
Index-8
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van Krevelen Group Contribution Method . . . . . . . . . . . . . . . . P3-1

PRO/II Polymers User Guide Contents-1

PRO/II Polymers User Guide Contents-3

Addition or Chain Polymerization

PRO/II Polymers User Guide P1-1

another to form larger monomers or macromolecules. These large

identical to that of the monomer. Many polymers formed by con-

P1-2 - May 2014 Introduction to Polymers

Polymer chain A high molecular weight structure made up of a large

Polymer A representative section of the polymer chain that con-

Cross-linking A process in which polymer chains react with each

Monomer A building block unit of a polymer. Monomer units

Homopolymer A polymer formed by a single type of monomer unit.

Copolymer A polymer formed by two types of monomer units.

Thermosetting A polymer that remains rigid and insoluble when

Thermoplastic A polymer that softens or hardens by the addition or

Polymer blend A non-homogeneous mixture of polymers that results

Condensation or A process in which monomer units are combined by

PRO/II Polymers User Guide P1-3

polymerization those of the monomer.

Bulk A process in which monomer units are combined in

Solution A process in which monomer units are combined in the

Suspension A process in which monomer units are combined in the

ing polymer globules from aggregating to each other.

Emulsion A process in which monomer units are combined in the

P1-4 - May 2014 Introduction to Polymers

Selecting the Units of Measure

PRO/II Polymers User Guide P2-1

 Click Initialize from UOM Library... to display the Initialize Units

P2-2 - May 2014 Using the Polymer Module with PRO/II

 Complete all the segment data by entering the segment names

PRO/II Polymers User Guide P2-3

Calculating Molecular Weight Distributions

To calculate or input the molecular weight distributions, first enter

P2-4 - May 2014 Using the Polymer Module with PRO/II

PRO/II Polymers User Guide P2-5

Choosing Thermodynamic Methods

Figure P2-6: Thermodynamic Data Dialog Box

P2-6 - May 2014 Using the Polymer Module with PRO/II

PRO/II Polymers User Guide P2-7

used in the flowsheet from the unit operation palette by clicking on

 Double-click on the polymer reactor icon on the PFD to display

P2-8 - May 2014 Using the Polymer Module with PRO/II

PRO/II Polymers User Guide P2-9

P2-10 - May 2014 Using the Polymer Module with PRO/II

van Krevelen Group Contribution Method

Component Definition (required)

PRO/II Polymers User Guide P3-1

SEGMENT α, name/…, FILL= VANKREVELEN

a Segment type letter.

name Name of segment α.

FILL This keyword is used to activate the van Krevelen

The STRUCTURE statement with a VANKRE qualifier is required for

the van Krevelen group contribution method. The default VANKRE

a Segment type letter.

igroup(n) The seven-digit identifier for an individual structural

name Name of component i (polymer).

MWAVG The molecular weight of each polymer component

P3-2 - May 2014 Estimating Polymer Properties

PHASE The polymer phase type can be defined as VLS or

i, j Component numbers continuously from