Polyethylene

HENRIQUE DE ALMEIDA TORRES

Introduction

Polyethylene is the simplest of

all commercial polymers, and
yet, it is the most popular
plastic in the world.

It is a versatile material that can

be used in grocery bags,
shampoo bottles, children's
toys, and even bullet proof vests

Where does the monomer,

ethylene (ethane) come from?

Ethane, propane, naphta, gas oil

and ethanol

http://www.elmhurst.edu/~chm/vchembook/40
1addpolymer

Types of Polyethylene

LDPE Low-density Polyethylene

HDPE High-density Polyethylene

LLDPE Linear low density Polyethylene

UHMWPE Ultra high molecular weight Polyethylene

Annual production of
Polyethylene/
Million tons
LDPE
HDPE

LLDPE

World

23.3

25.5

7.4

Europe

6.7

5.1

1.1

US

3.5

6.5

2.8

Russia

Total 1.41

Middle
East

1.9

China

3.5

Rest of
Asia

4.3

1.4

1.6

6.4

1.8

1. Federal State Statistics Service: Russian Federation 2011

Table from: www.essentialchemicalindustry.org/polymers/polyethene

LDPE Low density Polyethylene

The commercial LDPE process is a free radical polymerization that uses organic
peroxide initiators 420-570 K and 1000 - 3000 atmospheres of pressure.

Ethene (purity in excess of 99.9%) is compressed and passed into a reactor together
with the initiator. The molten polyethylene is removed, extruded and cut into
granules

Density : 0.91-0.94 g/cm 3

Average LDPE chain length: 400 40000 carbon atoms

LDPE is generally amorphous and transparent with about 50% crystallinity

LDPE has about 20 branches per 1000 carbon atoms

Representation of the LDPE Image from: www.essentialchemicalindustry.org/polymers/polyethene

HDPE- High Density Polyethylene

Image1: HDPE beads

http://www.ecvv.com/product/2377724
www.polyethylenepepipes.com

Image2: HDPE pipes

HDPE

Density: 0.94 g/cm3

Low branching allows better stacking of the molecules

HDPEs synthesis is done via Ziegler-Natta or Phillips catalysis.

Ziegler-Nattta catalyst: organometallic catalyst (titanium

compounds with an aluminum alkyl).

Phillips-type catalyst: A well-known example is chromium(VI)

oxide on silica.

HDPE is produced by three types of processes: Slurry process(2methylpropane (isobutane) or hexane as solvent), Solution
process (a C10or C12alkane as solvent) and the Gas phase
process

Slurry process (using a loop

reactor)

Image from: www.essentialchemicalindustry.org/polymers/polyethene

Gas phase process(Phillips

catalyst)

Image from:www.essentialchemicalindustry.org/polymers/polyethene

LLDPE Linear Low density

Polyethylene

LLDPE is actually a copolymer of ethylene and 1- butane (with

lesser amounts of others alkenes)

LLDPEs production is more energetically favorable energy than

the production of LDPE

The structure is essentially linear but because of the short chain

branching it has a low density. The structure gives the material
much better resilience, tear strength and flexibility without the
use of plasticizers

LLDPE is produced by the same processes as HDPE

LLDPE

Structure of LLDPE with 1-butane as copolymer and a representation of the

polymer molecule.
Images from: www.essentialchemicalindustry.org/polymers/polyethene

Polyethylene Applications
Process

HDPE

LDPE

LLDPE

Making film

Food
Cling film
packaging
Milk carton
Shopping bags lining

Stretch film

Injection
molding

Dustbins
Crates

Food boxes

Buckets
Bowls

Detergent
Blow moulding bottles
Drums

Squeezable
bottles

Extrusion

Flexible water
pipes
Cable coating
Cable
jacketing

Water pipes

Table from: www.essentialchemicalindustry.org/polymers/polyethene

UHMWPE Ultra high molecular

weight Polyethylene

Ultrahigh molecular weight polyethylene (UHMWPE) is a unique

polymer with outstanding physical and mechanical properties.
Most notable are its chemical inertness, lubricity, impact
resistance, and abrasion resistance. These characteristics of
UHMWPE have been exploited since the 1950s in a wide range of
industrial applications

Its molecular weight is generally around 4-7 millions g/mole

Density: 0.9300.935 g/cm3

UHMWPE

The polymerization is done by Ziegler- Natta catalysis (titanium

tetra chloride as catalyst). The polymerization takes place in a
solvent, used for mass and heat transfer, at low pressures.

UHMWPE is produced as powder and must be consolidated under

elevated temperatures and pressures because of its high melt
viscosity.

Schematic of a ram extruder

Image from: www.uhmwpe.org/lexicon/processing_uhmwpe

Compression Molding Press (along with the author, for scale) for production of 1 m by 2 m sheets of
UHMWPE. This press is located at Poly Hi Solidur MediTECH in Vreden, Germany, and was originally
used by Ticona in the production of Chirulen sheets of UHMWPE. The press is still used today in the
production of medical grade UHMWPE
Image from: www.uhmwpe.org/lexicon/processing_uhmwpe

Morphological features of
UHMWPE

TEM micrograph of UHMWPE showing

amorphous and crystalline regions
(lamellae)
Images from: www.uhmwpe.org/lexicon/a_primer

UHMWPEs applications

Pickers for textile machinery, lining for coal chutes and dump trucks,
runners for bottling production lines, as well as bumpers and siding
for ships and harbors. Over 90% of the UHMWPE produced in the
world is used by industry. UHMWPE is also used in orthopedics as a
bearing material in artificial joints.

Stainless steel and ultra high molecular weight polythene hip replacement
Image from: en.wikipedia.org/wiki/Polyethylene

The Dyneema brand

Dyneema is respected as the premium brand for UltraHigh Molecular Weight Polyethylene (UHMwPE), and we
manufacture and sell products in several forms including
fiber, tape and uni-directional (UD) sheets.

Image from: www.dyneema.com/americas/applications/life-protection/personal-armor

Typical Average Physical Properties of High Density

Polyethylene (HDPE), Ultra-High Molecular Weight
Polyethylene (UHMWPE)
Property

HDPE

UHMWPE

Molecular Weight (10 g/mole)

0.050.25

3.57.5

Melting Temperature (C)

130137

132138

Specific Gravity

0.9520.965

0.9250.945

Tensile Modulus of Elasticity* (GPa)

0.44.0

0.50.8

Tensile Yield Strength* (MPa)

2633

2128

Tensile Ultimate Strength* (MPa)

2231

3948

Tensile Ultimate Elongation* (%)

101200

350525

Impact Strength, Izod* (J/m of notch;

3.175 mm thick specimen)

21214

>1070 (No Break)

Degree of Crystallinity (%)

6080

3975

Table from: www.uhmwpe.org/lexicon/a_primer

True-stress strain behavior in uniaxial tension

(room temperature, 30 mm/min) for two grades of
UHMWPE, in comparison with HDPE

Graph from: www.uhmwpe.org/lexicon/processing_uhmwpe

Green Polyethylene Braskems Im GreenTM

Polyethylene

Polyethylene can be produced from renewable sources

Brazilian chemical company Braskem, produces polyethylene

from sugar cane ethanol since 2007

U$290 million dollars in the biopolymer production plant in

TriunfoRS

Image from: www.braskem.com.br/site.aspx/Onde-e-produzido

The green cycle

Image from:www.braskem.com.br/site.aspx/Como-e-

References

Polymer Chemistry: an introduction/ Malcolm P. Stevens. 2nd ed. P.271-275

www.pslc.ws/macrog/pe.htm
www.uhmwpe.org/lexicon
www.unomaha.edu/tiskochem/Chem4310/Notes/PDF_Files/Free_Radical_Synth
esis-Properties
www2.dupont.com/Tyvek/en_US/assets/downloads/tyvek_handbook
www.essentialchemicalindustry.org/polymers/polyethene
www.dyneema.com

Revision questions

List and describe two other microscopy techniques that could be

used to analyze UHMWPEs cristallinity.

What are the similarities between suspension and solution

polymerization?

Explain the differences in HDPEs and LDPEs properties

considering their chain structures.