Chapter 1

Polyethylene

Materials

Polymerization

Manufacturing methods

Structure, properties and applications

Materials Chapter 1
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
Materials Chapter 1
Introduction

Ethylene,
What is it, actually?
Its : C2H4 !!
2 carbons, 4 hydrogens
Materials Chapter 1
Introduction
The 10 plastic products
most used in the world:
Business of Polyethylene : PE
8 to 10 Billion World 130 Million
/year Capacity t/y Polypropylene: PP
(2006)

Polystyrene: PS
Polyurethane

Basic chemical for

PVC
1 billion Polyester
derivatives
Nylon
Kevlar
Perspex
Teflon
Materials Introduction Chapter 1

From ethylene to plastics & other usages

The mostly used chemical reactions from ethylene:

Polymerisation = polymers
Oxidation = polyesters, urethane, glycols, acetate,...
Halogenation: PVC
Alkylation: Styrene
Hydration: proteins, ethanol...
Oligomerisation: plasticizer
Oxo-reaction: herbicides
Pure: ripening agent
Materials Introduction Chapter 1

Polimeri Europa
Materials Introduction Chapter 1
Materials Chapter 1
Introduction
Materials Introduction Chapter 1

Olefins complex: a steam-cracking unit

Hydrogen
Utilities Mixed
Butanes
Gasoline
Material Movements
Acid Gas

Steam Compressor and Propylene

Drier Chilling
Primary NAPD Propane
Fractionator Converter

Feeds Quench Ethylene

Mixed
Products Ethane
Acetylene
Converter
Ethane

Methane
Quench

Fuel Oil

Cracking
Naphtha Furnaces
Materials Introduction Chapter 1

Characteristics of olefins production

Materials Introduction Chapter 1

Steam cracking = cracking of hydrocarbon molecules

having, at least, 2 atomes of carbon :

C C Ethane (USA, Middle East)

C C C Propane, LPG

C.. C Naphtha (CEE, Japan, Far East)

Gasoil, HVGO (Shell)
Materials Introduction Chapter 1

heat
Simple : C C C C + H2

(C2H6 800 C
Ethane) 0.1 second

In fact : C 2H 6 CH3 + CH3

C2H6+ CH3 CH4 + C2H5

C 2H 5 C 2H 4 + H

C 2H 6 + H C2H4 + H etc etc

2
Free radical, fugitive, non isolable
Steam : inert
Materials Introduction Chapter 1

Schutt formula
Y = yield in ethylene from ethane :

1.67 k 1 2 PH 2
Y= 1 + 1.2 -1
P TOTAL P TOTAL k 1 2

= disappearance of ethane

PH = hydrocarbon partial pressure

k = equilibrium constant
Materials Introduction Chapter 1

Cracking technology
Cracking is:
non-catalytic
governed by reaction kinetics
intrinsically non-selective

Hence:

looking primitive and unsophisticated, but

requires advanced engineering modelling
Very sophisticated yield prediction softwares
Materials Introduction Chapter 1

Feedstock selection and ethylene yields

Ethane C3-LPG C4-LPG Naphtha Gasoil

Feed 125 226 300 334 433

Ethylene 100 100 100 100 100

Propylene 0 35 45 52 60

Butadiene 0 6 1 14 18

Raffinate-1 0 4 4 17 21

Benzene 1 8 9 22 18

Other (fuel) 24 73 141 129 216

(Feed and Products in tons per 100 ton of ethylene product)

Materials Introduction Chapter 1

Key items: Reference Plant (80s): Mega-Cracker (2006):

600 kt/y 1000 + kt/y

Energy input 8000 kWh per ton of ethylene 5300 kWh per ton of ethylene

Product losses Less than 1% Less than 0.25%

CO2 emissions 1550 kg per ton of ethylene 790 kg per ton of ethylene
NOx emissions 180/200 mg/Nm3 effluent Less than 120 mg/Nm3 effluent

Operators 7 per shift 7 per shift

Noise ~92 dBA (compressors) ~85-87 dBA (compressors)

Materials Introduction Chapter 1

Making polymers from steam-cracking of oil & gas

Vinyl Chloride (VCM) Polyvinyl Chloride

Ethylene Polyethylenes
Ethylene Oxide (EO) Monoethylene Glycol (MEG)

Propylene Polypropylenes
Allyl Chloride Epichlorohydrin (ECH)
Olefins
Propylene Oxide (PO) Polyether Polyols

Butadiene Butadiene Rubber

Styrene Butadiene
Oil / Gas Rubber
Feedstocks Thermoplastic Rubber
To Cracker
C5 Olefins Isoprene Isoprene Rubber

Styrene (SM) Polystyrenes

Acetone

Benzene Cumene Phenol Diphenylol Propane Epoxy Resins

Aromatics
Diphenyl methane Di-Isocyanate (MDI)
Polyurethanes
Toluene Toluene Di-Isocyanate (TDI)

Xylenes Para-Xylene Terephthalic Acid (PTA) Polyethylene Terephthalate

Materials Chapter 1
Types of Polyethylene

LDPE Low-density Polyethylene

HDPE High-density Polyethylene

LLDPE Linear low density Polyethylene

UHMWPE Ultra high molecular weight Polyethylene

Materials Introduction Chapter 1

Ethyl Benzene
7%

Oxide/Glycols LLDPE/LDPE
13% 34%

EDC/VCM
14%
Polyethylene
58% HDPE
24%

Other
8%
Materials Chapter 1
Introduction

LDPE
HDPE LLDPE Low density
High density polyethylene Linear low density polyethylene polyethylene
Density 935-965 mg/cm3 Density 915-930 mg/cm3 Density 910-925
mg/cm3
Materials Chapter 1
A little History

1898

Polyethylene was first synthesized by

the German chemist Hans von Pechmann,
who prepared it by accident in 1898
while investigating diazomethane
Materials
1933 Chapter 1

The first industrially practical polyethylene synthesis

(diazomethane is a notoriously unstable substance
that is generally avoided in industrial application)
was discovered in 1933 by Eric Fawcett and Reginald
Gibson, again by accident, at the Imperial Chemical
Industries (ICI) works in Northwich, England

Preparation required temperatures up to 200 0C and

pressures up to 2000atm on a mixture of ethylene
and benzaldehyde.

White and waxy material

Materials Chapter 1
1935
1935 that another ICI chemist, Michael Perrin,
developed this accident into a reproducible high-
pressure synthesis for polyethylene that became the
basis for industrial LDPE production beginning in 1939

Polyethylene was found to have very low-loss properties at very high

frequency radio waves, commercial distribution in Britain was
suspended on the outbreak of World War II, secrecy imposed and the
new process was used to produce insulation for UHF and SHF coaxial
cables of radar sets.

Commercial production at 1944 Bakelite Corporation at Sabine, Texas,

and Du Pont at Charleston under licence of ICI
Polymerization Free radical polymerization Chapter 1

1. INITIATION (You need Initiators)

Polymerization Free radical polymerization Chapter 1

2. PROPAGATION
High pressure is needed during the propagation step in order to
bring the ethylene monomer closer to the free radicals
Polymerization Free radical polymerization Chapter 1

3. TERMINATION (Many ways)

Coupling
Polymerization Free radical polymerization Chapter 1

3. TERMINATION (Many ways)

Disproportionation
Polymerization Free radical polymerization Chapter 1

Chain Transfer
(Hydrogen Abstraction)
Polymerization Free radical polymerization Chapter 1

Side reactions (Causes Branching)

Polymerization Free radical polymerization Chapter 1

Disadvantages

Uncontrolled Process
Structure, Molecular weight
Requires high pressure
Reactions are highly
exothermic
Inefficient process (20%
ethylene polymerized)
 Chapter 1
Material 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/cm3
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
 Chapter 1
Material LDPE Low density Polyethylene

Small amount of branching on the chain gives a

more open structure

Melting point of 109 to 125 deg C

Does not react at room temperature

Resists alcohols, esters, acids, and bases.

Limited resistance to aldehydes.

Translucent to opaque
Materials Chapter 1
Development of catalyst

Breakthrough landmark in the commercial production of polyethylene

1951
Chromium trioxidebased catalyst discovered in 1951 by
Robert Banks and J. Paul Hogan at Phillips Petroleum

Crystalline polypropylene" and high-density polyethylene (HDPE)

Marlex
Materials Chapter 1

1952
Karl Ziegler prepared a high molecular weight
polyethylene at room temperature in 1952 while working
at Dacron Industries.
Zieglers puppy was had and rigid, and could easily be
easily drawn into fibers. High density polyethylene
(HDPE)
Giulio Natta extended Zieglers research, eventually
showing how the geometry of polyethylene could be
controlled by certain catalysts (produced by Ziegler).
Ziegler-Natta catalyst: titanium halides and organo-
aluminium compounds

Nobel Prize in Chemistry in 1963, with Giulio Natta, for work on polymers
Materials Chapter 1

Transition-Metal organic compounds

Many organometallic compounds derived

from transition metals have useful properties.

Typical transition metals are iron, nickel,

chromium, platinum, and rhodium.
Materials Chapter 1
Transition-Metal organic compounds

18-Electron Rule

The number of ligands attached to a metal

will be such that the sum of the electrons
brought by the ligands plus the valence
electrons of the metal equals 18.
When the electron-count is less than 18,
metal is said to be coordinately unsaturated
and can take on additional ligands.
18-Electron rule is to transition metals as
the octet rule is to second-row elements.
Materials Chapter 1
Transition-Metal organic compounds
18-Electron Rule

Example

Ni has the electron

configuration [Ar]4s23d8
CO
Ni has 10 valence
OC CO electrons
Ni
Each CO uses 2
CO electrons to bond to Ni
4 CO contribute 8
Nickel carbonyl valence electrons
10 + 8 = 18
Materials Chapter 1
Transition-Metal organic compounds
18-Electron Rule

Example

Fe Fe2+ has the electron configuration [Ar]3d6

Each cyclopentadienide anion contributes 6 p
electrons
Total 6 + 6 + 6 = 18
Ferrocene
Organometallic compounds with
cyclopentadienide ligands are called metallocenes.
Polymerization Chapter 1
Ziegler-Natta Catalysis
of Alkene Polymerization
The catalysts used in coordination polymerization are
transition-metal organic compounds.

Why using a catalyst?

http://www.elmhurst.edu/~chm/vchembook/401addpolymer
Polymerization Ziegler-Natta Catalysis of Chapter 1
Alkene Polymerization
n H2C CH2

Ethylene oligomerization Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2

Triethylaluminum catalyzes the formation of alkenes

from ethylene.
These compounds are called ethylene oligomers and
the process is called oligomerization.
Polymerization Ziegler-Natta Catalysis of Chapter 1
Alkene Polymerization
n H2C CH2

Karl Ziegler (1950) Al(CH2CH3)3

CH3CH2(CH2CH2)n-2CH CH2

Ziegler found that oligomerization was affected differently

by different transition metals.
Some gave oligomers with 6-18 carbons, others gave
polyethylene.
Polymerization Ziegler-Natta Catalysis of Chapter 1
Alkene Polymerization

The ethylene oligomers formed under Ziegler's

conditions are called linear -olefins and have
become important industrial chemicals.

The polyethylene formed under Ziegler's conditions

is called high-density polyethylene and has, in many
ways, more desirable properties than the
polyethylene formed by free-radical polymerization.
Polymerization Ziegler-Natta Catalysis of Alkene Polymerization Chapter 1

Giulio Natta
n H2C CHCH3

Natta found that polymerization of propene under Al(CH2CH3)3

Ziegler's conditions gave mainly isotactic
polypropylene. This discovery made it possible to
produce polypropylene having useful properties.
polypropylene
Polymerization Ziegler-Natta Catalysis of Alkene Polymerization Chapter 1

Ziegler-Natta Catalysts

A typical Ziegler-Natta catalyst is a

combination of TiCl4 and (CH3CH2)2AlCl, or
TiCl3 and (CH3CH2)3Al.
Many Ziegler-Natta catalyst
combinations include a metallocene.
Polymerization Chapter 1
What type of polymerization?

Coordination polymerization

Free radical polymerization

Polymerization Coordination polymerization Chapter 1

Al(CH2CH3)3 + TiCl4 ClAl(CH2CH3)2

+
CH3CH2TiCl3

CH3CH2TiCl3 + H2C CH2

CH3CH2TiCl3

H2C CH2
Polymerization Coordination polymerization Chapter 1

TiCl3

CH3CH2CH2CH2
H2C CH2

TiCl3
H2C CH2 CH3CH2TiCl3
CH3CH2CH2CH2

H2C CH2
Polymerization Coordination polymerization Chapter 1

CH3CH2CH2CH2CH2CH2

TiCl3

H2C CH2

H2C CH2
TiCl3
etc.
CH3CH2CH2CH2
Material Chapter 1
HDPE- High Density Polyethylene

Image1: HDPE beads Image2: HDPE pipes

http://www.ecvv.com/product/2377724
www.polyethylenepepipes.com
Material Chapter 1
HDPE- High Density Polyethylene
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.
Manufacturing Chapter 1
Methods HDPE- High Density Polyethylene

HDPE is produced by three types of processes:

Slurry process(2-methylpropane (isobutane) or hexane

as solvent)

Solution process (a C10 or C12 alkane as solvent)

Gas phase process

Manufacturing Chapter 1
Methods Slurry process (using a loop reactor)

Catalyst and polymer formed

during production
remains suspended in a
liquid medium but never
dissolving.

Polymerization reaction
takes place in tubular
reactor.
Manufacturing Chapter 1
Methods Solution process

Both catalyst and resulting

polymer remain dissolved in a
solvent that must be removed to
isolate the polymer.

Polymerization reaction takes

place in a CSTR (Continuous
Stirred Tank Reactor).
Manufacturing Chapter 1
Methods HDPE- High Density Polyethylene
Gas phase process(Phillips catalyst)

No solvent is used.

Ethylene monomer and

supported catalyst are blown
into the reactor.

Polymerization reaction takes

place in fluidized bed reactor.
Manufacturing
Methods Polyethylene polymerization techniques Chapter 1

Regional differences/similarities in the type of process

utilized to produce linear polyethylene
Material LLDPE Linear Low density Polyethylene Chapter 1

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
Material
LLDPE Linear Low density Polyethylene Chapter 1

Densities between 0.916 and

0.930
Contains little if any
branching
Properties include good flex
life, low warpage, and
improved stress-crack
resistance
Applications include films for
Structure of LLDPE with 1-butane as copolymer and a ice, trash, garment, and
representation of the polymer molecule. produce bags
Images from: www.essentialchemicalindustry.org/polymers/polyethene
Material Polyethylene Applications Chapter 1

Process HDPE LDPE LLDPE

Food packaging Cling film
Making film Stretch film
Shopping bags Milk carton lining

Dustbins Buckets
Injection molding Food boxes
Crates Bowls
Detergent bottles Squeezable
Blow moulding
Drums bottles

Flexible water
Extrusion Water pipes pipes Cable coating
Cable jacketing
Table from: www.essentialchemicalindustry.org/polymers/polyethene
Material Chapter 1
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

Material UHMWPE Ultra high molecular weight Polyethylene Chapter 1

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
 UHMWPE Ultra high molecular weight Polyethylene Chapter 1

TEM micrograph of UHMWPE

showing amorphous and
crystalline regions (lamellae)

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

 UHMWPE applications Chapter 1

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
 UHMWPE applications Chapter 1

The Dyneema brand

Dyneema is respected as the premium brand for Ultra-High 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), Chapter 1
Ultra-High Molecular Weight Polyethylene (UHMWPE)
Property HDPE UHMWPE
6
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* 0.44.0 0.50.8
(GPa)
Tensile Yield Strength* (MPa) 2633 2128

Tensile Ultimate Strength* (MPa) 2231 3948

Tensile Ultimate Elongation* (%) 101200 350525

Impact Strength, Izod* (J/m of 21214 >1070 (No Break)

notch; 3.175 mm thick specimen)

Degree of Crystallinity (%) 6080 3975

Manufacturing
Methods
POLYETHYLENE PRODUCTION Chapter 1

TECHNOLOGIES
Manufacturing POLYETHYLENE END USER Chapter 1
Methods TECHNIQUES
End User Processing Techniques
Manufacturing POLYETHYLENE END USER Chapter 1
Methods TECHNIQUES
End User Processing Techniques
Manufacturing POLYETHYLENE END USER Chapter 1
Methods TECHNIQUES
End User Processing Techniques
Manufacturing POLYETHYLENE END USER Chapter 1
Methods TECHNIQUES
End User Processing Techniques
Application POLYETHYLENE APPLICATIONS Chapter 1
Application POLYETHYLENE APPLICATIONS Chapter 1
Application POLYETHYLENE APPLICATIONS Chapter 1
 Chapter 1
Summary What to remember?

Ethane: steam cracking

Ethylene: polymerization (radical, coordination)

Who discovered first PE?

History Why catalyst so important?
Who get a nobel price 1963 and for what?

Forms of PE
Polymerization
Properties LDPE, LLDPE, HDPE, UHMWPE
Applications
 Chapter 1
Summary What to remember?

Polymerization techniques Production technologies

Process HDPE LDPE LLDPE

Food Cling film
Making film packaging Milk carton Stretch film
Shopping bags lining
Injection Dustbins Buckets
Food boxes
molding Crates Bowls
Detergent
Squeezable
Blow moulding bottles
bottles
Drums
Flexible water
Extrusion Water pipes pipes Cable coating
Cable jacketing

Remember next week short test!!!