Reactive Extrusion of

Polymers: A Review

Costas Tzoganakis
Du Pont Canada, Inc.
Research Center
P . O . Box 5000
Kingston, Ontario K7L 5.45, Canada

ABSTRACT This paper is an attempt to present a survey of recent

During the last 30 years the plastics industry has ex-
perienced enormous rates of growth. Due to an in-
creasing demand for high performance plastic mate-
rials, the use of extruders as continuousflow reactors
for polymers has attracted considerable attention in
polymerization and polymer mod@caiion applications.
literature on the reactive extrusion of polymers. Ex-
perimental and modeling studies for various polymer
systems are reviewed and some rheobgkai, modeling,
and design aspects of reactive extrusion systems are
addressed.

INTRODUCTION control systems are also at the forefront of the evolving

Traditionally, extruders are used to melt, homogenize,
and pump polymers through certain dies. During the last
three decades and due to the increasing scale of appli-
cations of high performance polymeric materials, direc-
tions of polymer R&D have been changing gradually.
The rate of introductions of new polymers has slowed
down considerably. Instead of pursuing new materials,
polymer scientists are faced with the challenge of filling
some of the performance gaps in the diversity of existing
plastic materials through modifying, reactive blending,
reinforcing, and other methods that improve properties.
As a result, single and twin-screw extruders have been
increasingly used as continuous flow reactors for poly-
mer modification. Polymer modification is intended to
introduce certain chemical changes that result in pre-
ferred properties of the modified material such as en-
hanced thermal stability, improved mechanical, adhesive
and optical properties, degradability, etc. To accom-
modate reactive extrusion processes, machinery sup-
pliers are continuously fine-tuning their compounding
equipment. New process-monitoring and sophisticated
Advances in Polymer Technology, Vol. 9, No. 4, 321330 (1989)
0 1989 by John Wiley & Sons, Inc.
extrusion machinery.
In a reactive extrusion (REX) process, the synthesis
or modification of a polymeric material takes place si-
multaneously with its processing and shaping into a fin-
ished plastic product. Reaction extrusion is now being
viewed as an efficient means of continuously polymer-
izing monomers as well as chemically modifying existing
polymers and it is defined as the engineering specialty
that combines two traditionally separate operations: the
chemical reactions for the formation or modification of
polymeric macromolecules and the processing of the
polymer for the purpose of structuring into shaped plastic
products.* REX processes, in addition to melting, in-
volve introducing reactive agents at optimum points in
the reaction sequence, homogenizing the ingredients, and
allowing sufficient time for the completion of the reac-
tions. In a typical REX process, the reactants are fed into
the extruder, usually through a feed hopper. However,
various liquid or gaseous reactants can be introduced at
specific points in the reaction sequence by using injection
ports along the extruder barrel. The reactive mixture is
conveyed through the extruder and the reaction is driven
CCC 0730-6679/89/040321-10$04.00
REACTIVE EXTRUSION OF POLYMERS
MONOMER
INITIATOR
REACTOR
EXTRUDER
FIGURE 1 Completion of polymerization reaction in an
to the desired degree of completion. At this point, and
after the removal of any volatile byproducts, the molten
polymeric product is pumped through a die and subse-
quently quenched, solidified, and pelletized. Thus, pro-
duction and processing can be integrated in one step.
Reactions that previously required several large pieces
of equipment, particularly with batch operations, can be
completed in a more efficient continuous way via reac-
tive extrusion. The advantages associated with reactive
polymer extrusion have been discussed in several publi-
c a t i o n ~ ~ and
- ' ~ they are based upon criteria such as im-
proved controlled processing, economic factors, and the
enhancement of material properties.
Extruders have been used to resolve heat and mass
transfer problems that arise from dramatic viscosity in-
crease (from about 50 to lo00 Pa s) in batch polymeri-
zation processes. In a batch reactor, as the polymerization
proceeds, the viscosity increases and after a certain point
the material becomes unmanageable in terms of mixing
and heat transfer. At that stage, the reacting material can
be transferred into an extruder (Figure 1) for completion
of the reaction. The ability of these machines to contin-
uously create new thin surface layers can increase the
degree of mixing and minimize temperature gradients
within the polymer being produced. Another factor that
can be controlled via operating conditions and geometr-
ical specifications of screw extruders is the residence time
in the system. Generally, the residence time is substan-
tially lower as compared to that required in a batch reactor
for the same reaction. Thus, long exposure to high tem-
peratures that can cause polymer degradation is greatly
avoided. The ability of an extruder to handle materials
of high viscosities without any solvents results in a dra-
matic cost reduction in raw materials and in solvent-
recovery equipment, and polymers produced are in a
322
BELT
FEEDERS
XL, 1 F T I V E AGENT
T-7
- 6 - -
MOTOR
- -
u PRODUCT
FIGURE 2 Schematic representation of a reactive extrusion
process.28
ready-to-use form. Finally, for polymer modification re-
actions, reactive extrusion processes offer natural means
for chemical crosslinking and grafting via the inherent
capability of stage-feeding of reactive agents (Figure 2).
This way, one can tailor-make speciality polymers that
are uneconomical to produce in large scale operations.
REACTION TYPES
Work performed by various research groups has shown
that the following - types
.-
of reactions can be carried out
in an e ~ t r u d e l s , ~ , ~ ~ :
a. Free radical, anionic, cationic, condensation, and co-
ordination polymerization of monomers or oligomers
to high molecular weight polymers.
b. Controlled degradation and crosslinking of polymers
(usually polyolefins) by means of a free radical ini-
tiator for the purpose of producing a product with
controlled molecular weight distribution and a higher
concentration of reactive sites for grafting.
C. Functionalizationof commodity polymers for the pur-
pose of producing materials to be used in grafting
applications.
d. Polymer modification by grafting of monomers or
mixture of monomers onto the backbone of existing
polymers for the purpose of improving various prop-
erties of the starting material. Free radical initiators
and ionizing radiation can be used to initiate the graft-
ing reactions.
e. Interchain copolymer formation. Usually, this type of
reaction involves combination of reactive groups from
several polymers to form a graft copolymer.
f. Coupling reactions which involve reaction of a ho-
mopolymer with a polyfunctional coupling agent or a
condensing agent to build molecular weight by chain
extension or branching.
VOL. 9,NO. 4
 REACTIVE EXTRUSION OF POLYMERS

TABLE I such as homogenizing, dispersing pigments and addi-

Typical Reactive Extrusion Applications tives, alloying, reactive compounding, concentrating,
devolatilizing, polymerizing, etc. The major difference
Reaction Type Reactants Products
between single- and twin-screw extruders is the convey-
Polyaddition Polyol plus Polyurethane ing mechanism. Although in single-screw machines, it
diisocyanate plus depends on frictional forces in the solids conveying zone
aromatic diamine and viscous forces in the melt pumping zone, in twin-
Polycondensation Bis(hydroxybuty1) Poly(ethy1ene screw extruders it is largely dependent on the screw geo-
terephthalate terephthalate)
Polycondensation Precondensate Polyamide metrical configuration, and it is of a positive displace-
Free radical Styrene + SAN ment character. The relative merits and the performance
copolymerization acrylonitrile of twin-screw extruders have been appraised.15*16
prepolymer Depending on the direction of rotation of the two screws,
Grafting +
Polystyrene maleic Polystyrene maleic twin-screw extruders can be distinguished in corotating
anhydride anhydride
adduct
and counter rotating machines. In simple terms, it can
Ionic polymerization Caprolactam Nylon 6 be said that corotating screws have a radial and coun-
Anionic 1,3-diene + aromatic Block copolymers terrotating have an axial shearing and plasticating effect.
copolymerization vinyl compound of 1,3-diene As corotating screws are rotating in the same direction,
and aromatic the material is transported from one screw to the other.
vinyl
compounds
This results in a good dispersion and because of the high
Hydrolysis Polyurethane scrap Polyol, amines speed, a high shear rate is achieved; conveying is similar
to a single screw through an open channel. Likewise,
both devolatilizing and feeding behavior can be retarded
as required to obtain the desired end product. It must be
Typical reactive extrusion applications are shown in
remembered that the typical high speed of the corotating
Table I.
machine results in a high output, much higher than that
of a counterrotating machine, according to the process
involved. By contrast, the screws of the counterrotating
METHODS AND INSTRUMENTATION extruder turn in opposite directions and the product is
moved forward axially and is partially kneaded in the
The design of extruders of REX applications involves kneading slot as in a rolling mill. To achieve good lon-
the manipulation and integration of information and gitudinal mixing, the system is divided into zones with
knowledge from several distinct areas. Extruders for re- great flight clearance and into others with special shearing
active processing must deal with the continuouslychang- elements. Important criteria, depending on the materials
ing nature of the reactive melt. Mixing phenomena are being processed, are flight clearance and kneading slot
considerably retarded when the reactive mixture is highly size. Typical of the counterrotating system is the wide
viscous, and the resulting inhomogeneities in chemical variety of screw layouts regarding thread depth, number
composition and temperature can lead to poor product of starts, and flight and core gap (kneading slot) which
quality. Mixing is an important factor when using an are available. Tangential twin-screw extruders provide
extruder as a reactor. Especially longitudinal mixing must more free volume on average than other twin screw ma-
be given significant consideration for radical reactions chines. This makes easier component addition and de-
since backmixing can influence the residence time dis- volatilization, as well as accommodating longer resi-
tribution (RTD), therefore, the course of the reaction, dence times that are often required for REX processes.
and can affect the molecular weight distribution (MWD) Although each type of twin-screw extruder (Figure 3)
of the final product. has a certain uniqueness regarding ingredients, type of
Although both single and twin-screw extruder config- reaction, and polymer produced, and although no ma-
urations are used in REX processes, twin-screw ones are chine design (counter- or corotating) provides the com-
increasingly being favored over the single-screw ones. plete solution, corotating intermeshing twin-screw extru-
The main reasons for this are the extended control of ders have been found to be suitable for many continuous
RTD and mixing they offer and their superior heat and REX processes. In this particular configuration, the two
mass transfer capabilities. The single-screw extruder is screws are set side by side with minimum clearance be-
best suited to the simpler jobs like melting, plasticizing, tween them. The crest of one screw completely wipes
and discharging melt for the production of films, pipes, the flights and the root of the other one. This self-wiping
profiles, etc. The twin-screw extruders, according to their feature eliminates dead regions where material can stag-
specific characteristics, can tackle the more complex tasks nate during processing. Due to the corotating design of
ADVANCES IN POLYMER TECHNOLOGY 323
REACTIVE EXTRUSION OF POLYMERS
(c 1 (b)
FIGURE 3 Twin-screw extruder configurations:
(a) intermeshing counterrotating; (b) intermeshing corotating;
(c) nonintermeshing counterrotating; (d) nonintermeshing
corotating.
the screws, high speeds and thus strong shearing forces
and high outputs can be obtained. Compared with the
counterrotating twin-screw extruders, no additional ra-
dial forces are produced, leading to increased wear of
the systems' screw and barrel. With the screws rotating
in the same direction, the material is transferred from
one screw to the other and undergoes a constant mixing.
This phenomenon is of special importance for a moderate
and homogeneous mixing, and for the heat transfer from
or to the surrounding inner housing wall. In addition,
the intensive and constant surface renewal creates fa-
vorable degassing conditions.
The modular design and assembly arrangement of the
screw and barrel sections of twin-screw machines, along
with the use of special feeding and venting ports provide
adequate flexibility for specific reactive extrusion tasks.
Usually the screw housing of a corotating extruder is
assembled from individual barrel segments, each equiv-
alent in length to 3 U D units.' Machines can be furnished
in lengths up to 15 barrel section, or 45:l UD. On a
vented barrel, an opening along the top connected to a
vacuum source permits separation of volatile gases, which
helps drive the reaction towards completion. Barrel seg-
ments can incorporate channels that circulate heat-trans-
fer fluids around the figure-eight-shaped bore. Using such
heat-transfer systems, overall heat transfer coefficients
range from 400 to 450 kcal/m2/h/"C.' Screw elements
are designed to complement and function with specific
324
barrel sections. The sequence of screw elements mainly
affects the degree of fill along the screw. Three types of
elements are widely used in corotating intermeshingtwin-
screw extruders: kneading blocks, mixing gears, and con-
veying screw elements. Kneading blocks are primarily
used for the dispersion of partially melted polymer par-
ticles and solid additives or reactive agents into the melt.
Mixing gears are superior to kneading blocks for the
thorough distribution of finely divided particles, for
achieving isothermal conditions at a given location in the
barrel, and for the homogenization of two or more feed
streams.I2 Conveying elements are the ones that move
the material through the extruder. The arrangement of
the screw elements is what determines the RTD in twin-
screw extruders. This distribution resembles that of a
plug-flow reactor with only an extended small tail. The
maximum practical residence time capability of a typical
corotating intermeshing 45: 1 LID twin-screw extruder is
about 7 min, at low screw speeds and with short-pitch
elements. Designs with even longer residence times (10-
75 min) are also available.'
RHEOLOGICAL CONSIDERATIONS
Rheology is largely concerned with the study of poly-
mer solutions and melts whose properties do not change
with time. However, in reactive extrusion systems, the
properties of the reacting material undergo severe changes.
For example, one distinguishing feature of bulk polym-
erization processes is their dramatic increase in viscosity
that occurs along the extruder. The processing behavior
of reactive systems is strongly dependent on their rheo-
logical and thermal properties. However, the rheological
and kinetic behavior of the material being processed de-
pends on the particular operating conditions and pro-
cessing history imposed. In order to be able to charac-
terize such reactive materials, one has to understand the
interactions between flow and reaction phenomena and
their evolution in time.
In such a system it is reasonable to compare three time
constants as suggested by MalkinI7: the material relax-
ation time (tl), the reaction characteristic time (tJ, and
the experimental time scale (t3). If t3 4 t2 and t3 < tl,
the chemical reaction does not proceed at all on the ex-
perimental time scale and a relaxation occurs during the
time of observation. In this case, the reactive material
behaves as a stable viscoelastic one. However, when
t2 > t3 and t3 S tl, the material is rheologically unstable
and one has to consider simultaneouslythe kinetic aspects
of the chemical reaction and the rheology of the polym-
erization medium.
The rheological characterization of reactive materials
is quite complex due to the large number of variables
VOL. 9, NO. 4

that affect their properties. The viscosity of a reactive
system is the most important property whose knowledge
is vital in the design of the processing equipment. Al-
though there is no general unifying model to describe
the viscosity of reactive systems which span a wide range
of values from polymer solutions to polymer melts, it
may be regarded as a function of several variables:
where y denotes the shear rate, T denotes temperature,
P represents pressure, M represents molecular weight,
and 6 is a measure of the extent of the reaction. Such
relationships are essential for the simulation of reactive
extrusion because they embody the crucial interactions
between flow field, temperature field, and chemical re-
action. In the past, derivation of such functional rela-
tionships was based on separate measurements of q and
5 as functions of time in different instruments and sub-
sequent elimination of time, with y, T, P, and M as
parameters. Such relationships have been developed both
for thermoplastic and thermosetting systems and their
importance has been d i s c ~ s s e d ~ * while
' ~ . ' ~ some rela-
tionships for polystyrene and polyurethane systems have
been summarized by Sebastian and Biesenberger.l9
A more desirable alternative for the derivation of vis-
cosity relationships is the simultaneous measurement of
viscosity and reaction rate, which eliminates the major
difficulty of synchronizing the separate experiments in
the time domain. For this purpose, a rheocalorimeter was
developed by Biesenberger and his co-workers.20-23 This
instrument was designed based on the combined prin-
ciples of isothermal calorimetry and viscosity in sealed
chambers. Data reported on polyurethane and epoxy type
reactions, as well as styrene acrylonitrile and methyl
methacrylate polymerizations, seem to indicate that the
instrument design is valid and that it can be used for the
characterization of reactive materials.
MODELING CONSIDERATIONS
The modeling of conventional extrusion processes has
been covered extensively in the literature, especially for
single-screw extruders, both for melt and plasticating
extruders. Modeling of a plasticating extruder should
i. Gravitational flow behavior of particulate solids in
feed hoppers
ii. Stress and temperature distribution in the solids
conveying zone
iii. Rate of melting, width profile of the solid bed, and
temperature of the melt flow into the melt pool in
the melting zone
ADVANCES IN POLYMER TECHNOLOGY
REACTIVE EXTRUSION OF POLYMERS
iv. Drag-induced pressurization and laminar mixing of
the melt in both the melt conveying and in the
melting zone
v. Power consumption in the solids conveying, melt-
ing, and melt pumping zones
vi. Pressure flow in the die
vii. Surging conditions
viii. Extrudate swelling at the die exit
In more general terms, one should be able to obtain
velocity, temperature, and pressure profiles in both the
solid and melt phases, from which all other variables of
interest could then be calculated. In addition to the afore-
mentioned factors, in reactive extrusion, the presence of
the reaction has to be included in the modeling. In con-
trast to conventional extrusion processes, in REX the
properties of the extruded material change continuously
due to the interaction between flow, heat transfer, and
reaction phenomena. Depending on the particular reac-
tive system, complex interactions may occu8' (Figure
4). In these cases, the flow pattern affects the heat and
mass transfer fields through viscous dissipation, reaction
heat, convection, and residence time distribution while
it itself is affected by the temperature distribution and
the chemorheology of the materials.27
All these interactionshave to be considered when mod-
eling REX systems. The foundation of such a modeling
approach are the general conservation laws for mass,
momentum, energy, and species concentrations and the
constitutive equations concerning the physical and ther-
mochemical behavior of the polymeric reactive mix-
EXPERIMENTAL STUDIES
The idea of using an extruder as a reactor is not new.
Historically, screw type machines were first used in the
early 1920sfor rubber polymerization and were described
in the patent literature in the 1930s. Although during the
past two decades reactive extrusion is increasingly being
used for the production and chemical modification of
polymers (see Table I), the number of publications on
the subject appears to be limited, mainly because of the
proprietary nature of the various REX processes devel-
oped.
In one of the earliest experimental works, Gouinlock
et al.29studied the production of copolyesters from bis-
phenol, neopentyl glycol, and terephthaloyl chloride in
a counterrotating twin-screw extruder. The extruder had
a diameter of 20 mm, with a length to diameter ratio
(UD) of 37:l and was manufactured by Welding Engi-
neers. The extruder feed consisted of a low molecular
weight copolyester which was prepared in a conventional
reactor and was fed to the extruder before development
325
REACTNE EXTRUSION OF POLYMERS
Convective
Micromixing
Effects
Effect o f MW
Thermal Effects
on Rheology
FIGURE 4 Transport interactions in reactive extrusion.27
of excessive viscosity. Some properties of the copolyes-
ters produced were measured and it was found that the
melt viscosity was higher and the impact strength was
lower as compared to the corresponding properties of
copolyesters produced by a conventional method. These
property differences were attributed to chain branching
reactions that possibly take place during melt polymer-
ization in the extruder.
Illing30studied the continuous, direct polymerization
of lactam into nylon-6 in the corotating twin screw ex-
truder. An important feature of this machine, manufac-
tured by Werner and Pfleiderer, was an adjustable valve
by which the effect of variable shear forces on the poly-
mer could be controlled. Thus, it was possible to adjust
the melt viscosity and the average molecular weight. By
means of this method, high molecular weight nylon fil-
aments, films, and profiles could be produced which ex-
hibited high tensile and impact strengths.
Martens and White3' carried out experiments on the
spandex polyurethane production in a single-screw ex-
truder, employing a solution polymerization method. Re-
action was carried out at room temperature (26-28 "C)
in a Prodex extruder having a 1.75 in. diameter and a
24:l WD ratio. Spandex samples from the extruder and
a batch reactor were compared in terms of molecular
weights. It was observed that the extruder yielded a broader
molecular weight distribution, a higher weight average
molecular weight, and a lower number average molecular
weight for relatively long reaction times.
Szamborski3' used reactive extrusion to modify nylon
6 for the purpose of producing a material suitable for
blow molding applications. An acrylic polymeric mod-
ifier was reacted with the amine end groups of the nylon
during compounding in a single-screw extruder. This
326
Effect of MW on Thermal Effects
Diffusion Parameters o n Diffusion
modification was found to result in an increase of the
melt and impact strength of the starting nylon. Also,
extruder processing conditions had a profound influence
on the course of the modification reaction. It was sug-
gested that, for best performance product, high compres-
sion screws, shallow flight depths in the metering zone,
and high L/D ratios should be used. Venting of the water,
produced during the reaction, was found to be a signif-
icant factor as well.
Schott and S a n d e r f ~ r dstudied
~~ the interchange re-
actions between acid/amide, amine/amide, and
amide/amide groups that take place during coextrusion
of nylon 6 and nylon 66. They used a Brabender labo-
ratory extruder having a 0.75 in. diameter and a standard
24:l U D nylon type screw. Differential scanning calo-
rimetry measurements were performed on product sam-
ples. It was found that, in a majority of cases, the reactive
blending made the melting point peak of nylon 6 dis-
appear.
Using a Haake plastograph, Lambla et al.34 studied
the condensation reactions between the anhydride groups
of a copolymer containing maleic anhydride links and
--OH groups on different molecules, in the molten state.
Siadat et al.35examined the feasibility of preparation
of a sulfonated ethylene-propylene terpolymer elastomer
(EPDM) in a continuous melt extrusion process. A mix-
ture of sulfuric acid and acetic anhydride was used as
the sulfonating agents in a Brabender laboratory single-
screw extruder with a diameter of 0.75 in. High con-
versions at relatively short residence time with good de-
grees of homogeneity of the product were achieved and
it was shown that the continuous melt sulfonation of
EPDM polymer may be used as a more efficient alter-
native to the batch solution methods previously reported.
VOL. 9, NO.4

Lambla and D r ~ studied
z ~ ~ the crosslinking of HDPE
and grafting of reactive oligomeric species onto a sty-
rene-maleic anhydride copolymer in the molten state. A
Rheometrics mechanical spectrometer was used to mea-
sure the elastic modulus of the reactive melt at temper-
atures between 120 and 21OoC, and the changes of the
elastic modulus were correlated with the progress of the
reactions.
An experimental feasibility program was carried out
by Gale3' for the production of crosslinked polyethylene
using direct silane injection. A single-screw extruder
(D=38 mm, L/D=24:1) was used and the silane was
injected into a cavity transfer mixer attached to the end
of the extruder. Samples were collected and hot defor-
mation tests were carried out to measure the extension
under load which was used to evaluate the effect of sil-
icone concentration.
Ishida and Huang3' presented a systematic study of
the graft polymerization of a chlorinated paraffin and
polypropylene in a single-screw extruder (D = 0.75 in.,
L/D = 25: 1). Fourier transform infrared spectroscopywas
used in the analysis of the product for the purpose of
following the grafting reaction and evaluating the effects
of addition of MgO, addition of peroxide, and residence
time in the extruder.
Stuber and Tirrel13' studied the continuous polymeri-
zation of methy methacrylate in a twin-screw extruder.
A 34-mm Leistritz fully intermeshing counterrotating ex-
truder was used to study the effect of processing con-
ditions on the molecular weight distribution of the prod-
uct and on the residence time distribution in the extruder.
In parallel with the experimental work, they employed
a segregated reactor model and a series of CSTR models
to simulate the experimental results and it was suggested
that the second model could provide satisfactory predic-
tions after further refinement.
Bouilloux et a1.@ studied the chemical modification
of ethylene-vinyl acetate (EVA) copolymers using a
transesterification reaction in the melt phase. Experi-
ments were carried out in a 30 mrn diameter Werner and
Plleiderer fully intermeshing corotating twin-screw ex-
truder and the extent of the reaction was followed by
infrared spectroscopy in order to examine the effects of
temperature, reaction time, and composition of reactive
mixture.
Lindt and Dauson4' performed visualization experi-
ments to document the developing nature of the poly-
merizing urethane flow in a partly filled extruder screw
channel. An analytical interpretation of the experimental
results was obtained by using a computerized drag flow
model accompanied by a polymerization reaction.
Fritz and Stohref2 presented a control scheme for the
controlled-peroxide degradation of polypropylene in a
twin-screw extruder. Peroxide concentrations were in
ADVANCES IN POLYMER TECHNOLOGY
REACTNE EXTRUSION OF POLYMERS
the range 0.01-0.1% and the process was controlled via
continuous on-line measurements of the viscosity of the
product. Pabedinskas et al.43 carried out a thorough
study and developed process control schemes for the
peroxide-initiated degradation of polypropylene in an
extruder. A single screw extruder was used in the ex-
periments and the pressure drop through the exit die
was used as a measure of the degradation extent. Tzo-
ganakis et al.28*w49 carried out peroxide promoted
polypropylene degradation experiments in a 1.5 in.
Killion single-screw plasticating extruder. Runs were
performed under a wide peroxide concentration range
(0.01-0.6%) and controlled-rheology (CR) polypropyl-
enes having tailor-made MWD were produced. The ef-
fect of screw speed, barrel temperature, and peroxide
level on the residence time distribution (RTD) was
determined by employing a tracer technique for the
measurement of the RTD. Similar experimental studies
for the same system were carried out by Suwanda et
al.50-52 on a single-screw extruder, who studied the ef-
fects of the same parameters but at low peroxide con-
centrations.
Dey and Bie~enberge?~ carried out experimental stud-
ies of the nonisothermal polymerization of methyl meth-
acrylate in a 34 mm Leistritz counterrotating twin-screw
extruder while Shah et al.54studied the reactive extrusion
of polyamide blended with MDI in a Leistritz extruder
as well.
Van Ballegooie and Rudin5' studied the reactive ex-
trusion of polyethylene/polystyrene blends at the pres-
ence of various levels of dicumyl peroxide and triallyl
isocyanurate which were used to promote grafting and
crosslinking reactions. It was found that these blends
inherited the strength of polyethylene and the brittleness
of polystyrene. Also, the fracture surfaces of these blends
did not exhibit the characteristic fibrillar nature of the
additive-free parent blends. Baker and Saleem56studied
the reactive mixing of polystyrene and polyethylene melt
blends with oxazoline and carboxylic acid functionalities.
The properties of these blends were examined and cor-
related with the composition and mixing conditions such
as shear rate, temperature, and time.
Hyun and Kim57studied experimentally and numeri-
cally the reactive extrusion of a thermoplastic polyure-
thane. The reaction kinetics and viscosity function were
obtained experimentally on a laboratory scale extruder.
Experimental data were in agreement with predictions
the model developed. Jerard and Ravens5' carried out
studies of the continuous reactive extrusion of polyure-
thane foams and they developed a model to describe the
process. The model was proven useful in selecting startup
conditions and properly adjusting the barrel temperature.
Finally, a list of some recent patents on reactive ex-
trusion processes is given in Table 11.
327
 TABLE I1
Summary of Recent Patents on Reactive Extrusion
Patent No. Author(s) Company Subject

U.S. 3,233,025 B. F. Frye Mobay Chemical Co. Method of making polyurethanes

(1966) K. A. Pigott
J. H. Saunders
U.S. 3,484,414 G. G. Joris Allied Chemical Cop. Process for the continuous polymerization of lactams
( 1969) R. H. Miller
U.S. 3,536,680 G. Illing Werner and Plleiderer Method for producing polymerizates comprising the essential
(1970) steps of kneading the reaction mixture and shearing the
polymers formed
U.S. 3,608,001 R. C. Kowalski Exxon Research and Controlled degradation of polypropylene in an extruder reactor
J. W. Harrison Eng. Co.
J. C. Staton
P. Keller
U.S. 3,634,574 K. Reinking Bayer Process for the continuous production of polyamide sections or
(1972) H. Vogel profiles
W. Hechelhammer
K. Schneider
U.S. 3,642,964 K. W. Rausch, Jr. Upjohn Continuous process for the one-shot preparation of a
(1972) T. R. McClellan thermoplastic noncellular polyurethane
U.S. 3,780,139 H. Sutter Bayer Segment copolymers of 1,3-dienes and aromatic vinyl
(1973) K. Northen compounds
F. Haas
U.S. 4,001,172 R. A. Steinkamp Exxon Research and Polymers with improved properties and process thereof
( 1977) T. J. Grail Eng. Co.
U.S. 4,011,198 T. Takekoshi General Electric Method for making polyetherimides
(1977) J. E. Kochanowski
U.S. 4,058,654 H. Sutter Erdolchemie GmbH Process for the bulk polymerization of a-olefins
(1977) R. Peuker
U.S. 4,067,861 M. Biensan Ato Chemie Anionic polymerization of lactams in an extruder with
(1978) P. Potin controlled output rate
U.S. 4,073,773 E. G. Banucci General Electric Melt polymerization method for making polyetherimides
(1978) G. A. Mellinger
U.S. 4,245,081 B. Quiring Bayer m e s s for the production of thermoplastic polyurethane
(1981) G. Niederdellmann elastomers
H. Wagner
U.S. 4,443,592 L. R. Schmidt General Electric Method for making polyetherimide
(1984) E. M. Lovgren
P. G. Meissner
U.S. 4,463,137 C. L. Bodolus Standard Oil Co. Process for the preparation of rubbermodified thermoplastic
(1984) W. J. Miloscia resins
U.S. 4,486,575 N. F. Newman Exxon Research and Process for the manufacture of halogenated elastomers
(1984) R. C. Kowalski Eng. Co.
U.S. 4,501,859 N. F. Newman Exxon Research and Rocess for the manufacture of halogenated polymers
(1985) R. C. Kowalski Eng. Co.
U.S.4,508,874 W. L. Hergenrother Fmstone Tm and Impact-resistant polymeric compositions containing maleic
(1985) M. G. Matlock Rubber Co. anhydride adducts of hydrogenated polymers and graft
R. J. Ambrose copolymers thereof
U.S. 4,532,310 D. C. Christensen Contacting arylene sulfide polymer with oxygen in extruder by
(1985) R. G. Voss continuous processing
U.S. 4,563,506 R. C. Kowalski Exxon Research and Extrusion process for preparing improved brominated butyl
(1986) W. M. Davis Eng. Co. rubber
N. F. Newman
Z. A. Foroulis
F. P. Baldwin
EPA" 0,028,914 R. W. Lee Standard Oil Co. Manufacture of rubber-modified copolymers in an extruder type
(1981) W. J. Miloscia reactor
EPA 0,124,279 R. C. Kowalski Exxon Research and Improved process for the manufacture of halogenated polymers
(1984) W. M. Davis Eng. Co.
N. F. Newman
E. Lewis
EPA 0,160,394 T. A. Kotnour Minnesota Mining and Continuous free radical polymerization in a wiped surface
(1985) R. L. Barber Manufacturing Co. reactor
W. L. Krueger
EPA 0,172,650 G. White Du Pont Canada Inc. Polyolefin blends containing reactive agents
(1986)
.Europen Patent Application.

MODELING STUDIES
Modeling of reactive extrusion systems is of great sig-
nificance because from a practical point of view it can
assist in choosing favorable operating conditions. Efforts
to model reactive extrusion systems by using classical
reactor design methods would be inadequate, the reason
being that the fluid mechanics and their interactions should
be given special consideration.
Siadat et a1.6 were the first to address the problem.
They made comparative calculations for several flow re-
actors for a polycondensation reaction and they con-
cluded that the melt extruder behaves nearly as plug flow
reactor in terms of residence time distribution. They also
discussed the effect of viscous heating and developed a
simple model for the effect of viscous heating on the
conversion.
LindtS9analyzed theoretically the flow of a polymer-
izing fluid between rotating concentric cylinders. Using
an RIM type urethane system, he demonstrated the ap-
plicability of that analysis to reactive processing systems.
Chella and Ottinom studied the simultaneous interac-
tions between mechanical mixing, molecular diffusion,
and chemical reaction in terms of a lamellar mixing model.
Their results for prototype chemical reaction schemes
indicate that mixing can significantly alter conversion
and product distribution.
In an extension of his earlier work, Lindt6' analyzed
the polymerizing flow in an extruder channel as drag
flow between parallel plates. Although this work consists
of a first basic step towards modeling of reactive extru-
sion systems, the omission of pressure gradients was
totally unfounded. One would normally expect genera-
tion of pressure gradients due to viscosity changes. This
was taken into account in a more complete work by Elbirli
and Lindt.62In that model, the dependence of viscosity
on shear rate and temperature was neglected, and, after
certain simplifying assumptions were introduced, the
conservation equations of mass, momentum, energy, and
species were solved using the finite difference method.
HineP3 developed a model for a thermosettingreactive
system following conventional plasticating extrusion the-
ory and considering the effect of temperature, shear rate,
and degree of cure on the apparent viscosity. He studied
the effect of kinetic parameter values on the model pre-
dictions by performing a sensitivity analysis. However,
no experimental verification of the model predictions were
presented.
Tzoganakis et a1.28*44*49 developed a general kinetic
model for the peroxide-promoted degradation of poly-
propylene in a single-screwextruder. Although plug flow
conditions were assumed to prevail in the extruder, the
predictions of the average molecular weights of the de-
graded polymer were satisfactory.
ADVANCES IN POLYMER TECHNOLOGY
REACTNE EXTRUSION OF POLYMERS
At the same time Bake et a L 5 0 s 5 ' developed a similar
kinetic model for the peroxide degradation of polypro-
pylene. This simplified model could predict the molecular
weight distribution of the polypropylene produced by
using residence time distribution measurements in a sin-
gle-screw extruder. Finally Tzoganakis, Vlachopoulos,
and Hamielec?Vw developed a complete rheokinetic model
for the same process. Development of the model was
based on the previously developed kinetic model and on
the plasticating extrusion model developed by A g ~ r . ~ ~
That model could predict not only pressure, temperature,
and molecular weight profiles but also the residence time
distribution in the extruder as verified by experimental
measurements.@
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VOL. 9,NO. 4