Polyethylene

Ken Anderson
Polyethylene R&D
The Dow Chemical Company
Freeport, Texas

Invited Lecture for Chem 470 Industrial Chemistry

Prof. Michael Rosynek, Texas A&M University

April 7, 2006
 My background
B.S. Chemistry, Tarleton State Univ., Stephenville, TX, 1978
Ph.D. Polymer Science, Univ. of Southern Mississippi, 1984
Joined Dow Chemical in 1983 in Epoxy Products R&D then
moved to Polyethylene Product Research in 1996
My present role at Dow
Product Research Leader for Solution PE; technical mentor to
younger members of Product Development group
Design of molecular architecture for new product development
and development of structure-property-performance
interrelationships
Interface with catalysis, characterization, material science,
intellectual property, process development, pilot plants,
fabrication, Manufacturing, TS&D, and Marketing, with
occasional customer interaction to execute product development
R&D rep on North American Films Market Management Team
 Part of The Ethylene Chain
Natural Gas Liquids (Ethane, Propane)
or Naphtha (from Crude Oil)

Steam Cracking

Ethylene, Propylene

Other Polymers Chemicals

POLYETHYLENE
H H
C=C -(-CH2-CH2-)n-
H H

Ethylene Polyethylene

Any Questions?
Polyethylene The Largest Volume Thermoplastic

2004 Annualized Capacity Billions of Pounds

151

92 90
75

31
 PE Demand by Region
2004 Global PE Demand: 136 Billion Pounds
 Markets/Applications for PE
Rigid and flexible packaging
Films, Bottles, Food Storage, Shrink film
Hygiene and medical (nonwovens)
Pipe, Conduit, and Tubing
Fibers
Consumer and industrial liners
Automotive applications
Stretch film and heavy duty shipping sacks (HDSS)
Agricultural films silage, mulch, bale wrap
Elastomers, Footwear
Wire and Cable
Durables, Toys
 Fabrication Versatility
Film (blown and cast) extrusion
Injection molding
Blow molding
Sheet, profile, or pipe extrusion
Thermoforming
Rotomolding
Extrusion coating - Lamination
Foaming
Fiber spinning
Wire & Cable
PE Demand by Conversion Process
2004 Global PE Demand: 136 Billion Pounds

Food Packaging
Hygiene & Medical
Fil Consumer & Ind. Liners
Stretch Films
m Agricultural Films
HDSS
World Leaders in Polyethylene Production
Dow
ExxonMobil
SABIC
Sinopec
Innovene
Chevron Phillips
Basell
Lyondell/Equistar
Borealis
Total
Formosa Plastics
NOVA Chemical
Polimeri Europa
PetroChina
 Types of Polyethylene

HDPE (0.940-0.965) LLDPE (0.860-0.926)

High Density Linear Low Density

O O
O
C-OH O

O O O
O
O O O
LDPE (0.915-0.930)
High Pressure Copolymers
Low Density
(AA, VA, MA, EA)
 Other Ethylene-Containing Polymers

EPDM rubber
Ethylene-Propylene rubber
Impact copolymer polypropylenes
Random copolymer polypropylenes

Chlorinated PE
Maleic Anhydride-grafted PE
Ionomeric salts of EAA or EMA
 Classification of PE by Molecular Architecture

PE resins can be distinguished by their unique

combinations of the following attributes:
molecular weight distribution (MWD)
short chain branch distribution (SCBD)
interrelation of SCBD across MWD
degree of long chain branching
comonomer type and level

These are dictated by polymerization chemistry and

reaction conditions.
Classification of PE by Polymerization Chemistry

Free radical polymerization

LDPE

Coordination Polymerization via Catalyst

HDPE and LLDPE
 Classification of PE by Polymerization Chemistry

Free radical polymerization LDPE

extremely high pressures, using organic
peroxides
formation of both long & short branches by
side reactions
can utilize polar comonomers, e.g. AA, VA
first practical form of PE, discovered in 1930s
 Discovery of LDPE Reaction

Date: March, 1933

Company: Imperial Chemical Industries (ICI)
Location: Winnington, England
Inventors: R. O. Gibson and E. W. Fawcett

High pressure research program (effects on reaction rates)

Ethylene/benzaldehyde system at 170 deg C and 29,000 psi
Unexpected loss of reaction pressure
Obtained minute quantities of waxy, white solid (LDPE)
Two years of research and explosions to reliably reproduce result
Trace oxygen initiated ethylene polymerization
First commercial autoclave train started up in 1939 in England.
Tubular reactor technology developed by UCC during WW II
 Free Radical Polymerization of LDPE
Typical Propagation Mechanism

H H
CH2 . + C=C CH2-CH2-CH2 .
H H

The active center is transferred from the end of the

growing chain to a position on one of the ethylene
carbons and the process continues forming longer
and longer polyethylene chains
 Free Radical Polymerization of LDPE
Back-biting Mechanism Short Chain Branching
CH2 CH2 CH2 CH2

CH CH2 CH CH2
.
H CH2 CH3
.
Butyl branch

The active center is transferred from the end of the

growing chain to a position along the back of the
chain and chain growth proceeds from this position.
 Free Radical Polymerization of LDPE

Chain Transfer to Polymer Long Chain Branching

.
CH2 . + R-CH2-R CH3 + R-CH-R

The active center is transferred from the end of the

growing chain to a position on a dead chain that
allows that chain to begin forming a long chain
branch.

Your class notes have these reactions illustrated in greater detail.

 Typical High Pressure, Low Density PE Process

Low pressure recycle

Purge to LHC
High pressure recycle
CTA

Reactor HPS
(16-39,000 psi)
Compressor
LPS

Secondary or Extruder
Ethylene
Hypercompressor

Compression Reaction Devolatilization Extrusion

Example of Autoclave PE Reactor
Ethylene

Peroxide

Peroxide

Peroxide

Peroxide

To HPS
 Classification of PE by Polymerization Chemistry

Coordination Polymerization via Catalyst

Used for
HDPE
LLDPE, when using alpha-olefin comonomers
Can use solution, slurry, or gas phase processes
Much lower pressures than free radical
Lower reaction temperatures, esp. in slurry and
gas phase (particle-form processes)
Must manage heat of reaction to maintain
reaction temperature, esp. in particle-form
Lower capital cost than LDPE
 Three major coordination catalyst types
Chromium oxide types so-called Phillips type
restricted to slurry and gas phase
dominant type in conventional slurry HDPE
can be used for LLDPE
Ziegler-Natta conventional LLDPE
discovered in 1950s for HDPE and PP
effectively commercialized in 1970s for LLDPE
still predominant type for LLDPE
density limited to ca. 0.900 and above
Single site catalysts
constrained geometry and metallocene types (mLLDPE)
both can be used as homogeneous (soluble) or supported for
particle-form processes (gas, slurry)
relatively recent innovation, commercialized in 1992
enables densities all the way down to that of amorphous
enabling rapid growth in specialty polyolefins

Your class notes illustrate the catalyst chemistry and polymerization mechansims.
Typical Gas Phase PE Process Vent
Recovery

Reaction
System
Catalyst
Resin
Purging

Additive
Addition
Raw Pelleting
Material System
Handling

To Resin
Storage
and
Loading
Typical Solution PE Process

Comonomer Solvent
Recovery
Ethylene

Reacto
r
Polymer
Devo Devo
1 2

Your class notes also illustrate the Phillips slurry loop process.
 Linear Low Density Polyethylene (LLDPE)

LLDPE is ethylene/alpha-olefin copolymer.

-olefin typically 1-butene, 1-hexene and 1-octene

-CH2-CH2-CH2-CH-CH2-CH2-CH2-CH2-
CH2
CH2 Branch length =
CH2 Comonomer length - 2

CH2
CH2
CH3
 INSITE* Catalyst Technology
A novel constrained geometry, single-site catalyst
technology introduced in 1992 that has transformed the
polyolefins industry
An innovation that continues to deliver new families of
plastics offering new combinations of performance and
processability
Exceptional control of molecular architecture and polymer
design sparking innovation and unique solutions

Si
N Ti

* Trademark of The Dow Chemical Company

 LLDPE Molecular Structure Comparison

Heterogeneous chain length Homogeneous chain length

distribution + Heterogeneous distribution + Homogeneous
short chain branch distribution short chain branch distribution

Conventional LLDPE INSITE* Technology Polymer

(typical mLLDPE lacks long
via Ziegler-Natta chain branches)

* Trademark of The Dow Chemical Company

 Semi-Crystalline
Morphology
Since SCB disrupt crystallinity, more branching means fewer and
smaller crystals. Conventional LLDPE is a mixture of small and large
crystals while metallocene LLDPE has more uniform crystal size
distribution
TIE CHAIN

INTERFACE

CRYSTAL CORE AMORPHOUS

MATERIAL

A 3-d representation of chain-folded lamellae in semi-crystalline PE is shown in your class notes.

DSC Melting Endotherms
 Solid State Properties

Solid state properties are determined by:

Percent crystallinity (density) & crystal size
distribution
Amount of Short Chain Branching
Tie-chain concentration (Toughness)
Short Chain Branching Distribution
Molecular Weight
Orientation of both crystalline and amorphous
phases
Molecular Weight Distribution
Long Chain Branching
 Engineering Stress-Strain Response - ITP resins

(Strain Rate - 2.4 min-1)

Samples were cooled at 1 oC/min.

Decreasing the Crystallinity (Density)

Is accomplished by...
Increasing the amount of short chain branching by
adding comonomer
And results in...
Decreasing the modulus (stiffness)
Decreasing the yield strength
Improving optics (haze, gloss, clarity)
Lowering the melting & softening points
 Increasing Tie Chain Concentration

Is accomplished by
Optimizing Short Chain Branching Distribution
Increasing the molecular weight
Increases
Toughness
Impact
Tear (needs balance of tie chain & high dens)
Environmental Stress Crack Resistance (ESCR)
 Properties vs. Density

Gloss, Clarity, Haze Impact Modulus (stiffness),

strength, Tear strength, Softening point, Moisture
ESCR Barrier

Density
 What is Molecular Weight ?

One of the most important properties of a

polymer is molecular weight.
The MW is simply the weight of all the atoms
in a molecule. (The weight of the chain).
Due to the random nature of the
polymerization process, all of the polymer
chains are not exactly the same length.
This requires that molecular weight be defined
as an average and as a distribution function
(MWD).
Molecular Weight Distribution Comparison
by Gel Permeation Chromatography
Mw = 73800, Mn = 37400, MWD = 2.0 Typical mLLDPE
Mw = 124600, Mn = 33200, MWD = 3.8

Conventional LLDPE

16 18 20 22 24 26 28
ELUTION VOLUME (mls)

Increasing Molecular Weight

 Melt properties are determined by:
Molecular Weight, esp. viscosity = k M3.6
Doubling Molecular weight leads to ten fold increase in viscosity

Molecular Weight Distribution

Long Chain Branching
As molecular weight increases:
Processability becomes more difficult
Melt strength, bubble stability improves
Tensile strength improves
Impact strength improves
ESCR increases