THE EFFECT OF MOLECULAR WEIGHT, STRUCTURE AND DENSITY ON THE CHOICE/TYPE OF APPLICATION

Case Study Polyethylene

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

H
H

-(-CH2-CH2-)n-

Ethylene

Polyethylene

Polyethylene The Largest Volume Thermoplastic

2004 Annualized Capacity Billions of Pounds

151

92

90 75 31

PE
Source: Chem Systems 2004

PP

Polyester

PVC

PS

PE Demand by Region
2004 Global PE Demand: 136 Billion Pounds
MEAF 7.8% Latin America 8.4% Western Europe 21.4% NA (US & Can) 23.5%

Asia-Pacific 34.8%

Central/Eastern Europe 4.1%

SOURCE: Nexant/Chem Systems 2005

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
Rotational Molding 1% Blow Molding 14% Sheet 2% Extrusion Coating 4% Other Extrusion Wire and Cable 2% 3%

Injection Molding 12% Pipe and Conduit 7% Other Non-Extrusion 3%

Film 51%

Film

Food Packaging Hygiene & Medical Consumer & Ind. Liners Stretch Films Agricultural Films HDSS

SOURCE: Nexant/ChemSystems 2005, PTAI 1/05

Many types of PE
HDPE: High Density PolyEthylene LDPE: Low LLDPE: Linear Low VLDPE: Very Low Applications depend on properties, combinations of
Density MWD (Molecular Weight Distribution) Comonomer and branching

The applications of PE are determined by: Molecular weight (MW) or melt flow index (MI) Density

MOLECULAR WEIGHT DISTRIBUTION MWD

MWD distribution of polymer chains lengths Broad MWD wide range of chain lengths Narrow MWD narrow range of chain lengths Catalyst and processing dependent Narrow Low warpage/shrinkage Poor processability Broad High warpage/shrinkage Good processability Good melt strength

Injection Molding
Nozzle

Hydraulic Pressure

The Injection Molding Process

Blow Moldinge.g. milk bottle

Plastic

Extruded ParisonMold Open

Mold Closed and Bottle Blown

Finished Bottle Removed from Mold

Types of Polyethylene

HDPE (0.940-0.965) High Density

LLDPE (0.860-0.926) Linear Low Density

O C-OH O

O
O

O
O O

O O

LDPE (0.915-0.930) Low Density

High Pressure Copolymers (AA, VA, MA, EA)

Amorphous: density low Crystalline : density high

Density is a measured of crystallinity/amorphous of PE solid.

Polyethylene
Amorphous vs. Crystalline

HDPE - Highly ordered = crystalline (translucent to opaque) LDPE - Random arrangements = amorphous (clear) Depends partly on polymer chain shape Depends partly on thermal history (rate of cooling) As Crystallinity increases, density increases, stiffness increases, heat tolerance increases, barrier properties improve, clarity decreases

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)
40
0.9180 0.9099 0.9016

15

30
0.8960 0.8817 0.9550

10

Stress, MPa

20
0.8730

0.8702

10

0.8630

0 0 250 500 750 1000 0 1250 0 50 100

Strain, %
Samples were cooled at 1 oC/min.

Strain, %

ALLS50. 21.3.93

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 strength, Tear strength, ESCR Modulus (stiffness), Softening point, Moisture Barrier

Density

BIMODAL MWD Outstanding final properties

- the low molecular weight part forming the crystalline and the high-molecular weight forming the amorphous part with high numbers of tie molecules per volume. Bimodal HDPE resins are used to produce thin, stiff films Conventional process,Unimodal LDPE or LLDPE is used for making film - The HDPE film thickness is less than half that HDPE film for the same application Bimodal blow molding products, such as drums and bulk container are superior with respect to cold impact and chemical resistance.

NEW CATALYST

LLDPE Molecular Structure Comparison

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

Conventional LLDPE via Ziegler-Natta

INSITE* Technology Polymer (typical mLLDPE lacks long chain branches)

* Trademark of The Dow Chemical Company