Polyethylene

Polypropylene
Polybutylene
Properties
Manufacturing of LDPE & HDPE
Differentiate LDPE & HDPE
 Part of The Ethylene Chain
Natural Gas Liquids (Ethane, Propane)
or Naphtha (from Crude Oil)

Steam Cracking

Ethylene, Propylene

Other Polymers Chemicals

POLYETHYLENE
 Ethylene, the interesting molecule
Ethylene, because of its double bond, is more reactive
than ethane. Double bonded carbons make molecule
more susceptible to bonding with other molecules.
When approached by another molecule, the double
bond splits; the carbons are joined by a single bond,
leaving the the molecule free to bond with both
carbons.
Ethylene is used in the ripening of fruit; it stimulates
the metabolic processes of the fruit by dissolving into
the cell membrane, therefore increasing its
permeability
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 Formation and Structure

Ethylene-Ethylene
bond yields
polyethylene
(CH2CH2)n
polyethylene

Crystalline regions lie Pure

in alternating fashion polyethylene, low-
with amorphous and high-density
regions, which creates polyethylene
scattering of light (LDPE, HDPE)
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 Properties of Polyethylene

Poylethylene is a solvent
for fats, oils, and grease.
Dissolving occurs slowly.
Electrons are tightly
trapped in their C-C and
C-H bonds, which results
in an inability of electrical Thin film of polyethylene photographed
current to flow. using polarized light. The pattern arises
Also results in inability for form the presence of spherulites, or
regions where the polymer molecules
water and ions to have aggregated into spheres.
penetrate interior of solid. Picture and caption from Molecules

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 Properties of Polyethylene

Polyethylene is a
thermoplastic. That is, it
becomes soft and
malleable when heated,
and hard and solid when
cooled. (So, basically, its a plastic. Wow.)
Polyethylene is an
addition polymer. The
double bonds allow for
splitting and bonding
with other molecules.

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 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)
 Classification of PE by Polymerization Chemistry

Free radical polymerization

LDPE

Coordination Polymerization via Catalyst

HDPE and LLDPE
 Manufacturing of LDPE
Polyethylene was first produced by British company Imperial
Chemical Industries. Preparation required temperatures up to
200 deg C and pressures up to 2000atm.
Karl Ziegler prepared a high molecular weight polyethylene at
room temperature in 1952 while working at Dacron
Industries.
ICI polyethylene had shorter, branched chains, and was waxy
and easily deformed.
Giulio Natta extended Zieglers research, eventually showing
how the geometry of polyethylene could be controlled by
certain catalysts (produced by Ziegler).

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 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.
 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
 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.
 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
 Differentiate High-Density Polyethylene
Absence of branching results in a more closely packed
structure, more crystalline, higher density, and chemical
resistance slightly higher than that of LDPE.
Resists alcohols, acids, bases, esters, and aldehydes
Specific Gravity: 0.94 to 0.97
Melting point 130 to 135 deg C
Carbon chains can are 10,000 to 100,000 carbon atoms long
Translucent
Tensile strength 3000-5000 psi
Applications include trash liners, grocery bags, industrial
pipe, gas tanks, and shipping containers

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 Low-density Polyethylene (LDPE)
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
Tensile strength 1500-2500 psi
More prone to oxidation as compared to HDPE
Used for plastic food or garment bags, spray bottles,
plastic lids.
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 Polypropylene History
Prior to 1954 most attempts to produce plastics
from polyolefins had little commercial success
PP invented in 1955 by Italian Scientist F.J. Natta
by addition reaction of propylene gas with a
sterospecific catalyst titanium trichloride.
Isotactic polypropylene was sterospecific
(molecules are arranged in a definite order in
space)
Polypropylene is similar in manufacturing
method and in properties to PE
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 Chemical Structure
Propylene
H H

C C

CH3 H
n

Isotactic- CH3 on one side of polymer chain

(isolated). Commercial PP is 90% to 95% Isotactic
H H H H H H H H H H

C C C C C C C C C C

CH3 H CH3 H CH3 H CH3 H CH3 H 20

 Polypropylene Stereostatic Arrangements
Atactic- CH3 in a random order (A- without; Tactic- order) Rubbery and of
limited commercial value.
H H H CH3 H CH3 H H H CH3

C C C C C C C C C C

CH3 H H H H H CH3 H H H

Syndiotactic- CH3 in a alternating order (Syndio- ; Tactic- order)

H H H CH3 H H H CH3 H H

C C C C C C C C C C

CH3 H H H CH3 H H H CH3 H 21

 Addition Polymerization of PP
Polypropylene produced with low pressure process (Ziegler)
Polypropylene produced with linear chains
Polypropylene is similar in manufacturing method and in
properties to PE
Differences between PP and PE are
Density: PP = 0.90; PE = 0.941 to 0.965
Melt Temperature: PP = 176 C; PE = 110 C
Service Temperature: PP has higher service temperature
Hardness: PP is harder, more rigid, and higher brittle point
Stress Cracking: PP is more resistant to environmental stress cracking

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 Disadvantages of Polypropylene

Disadvantages
High thermal expansion
UV degradation
Poor weathering resistance
Subject to attack by chlorinated solvents and
aromatics
Difficulty to bond or paint
Oxidizes readily
flammable
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Mechanical Properties of Polypropylene
Mechanical Properties of Polypropylene
Polypropylene LDPE HDPE
(For Comparison) (For Comparison)
Density 0.90 0.91- 0.925 0.959-0.965

Crystallinity 30% to 50% 30% to 50% 80% to 91%

Molecular Weight 200K to 600K 10K to 30K 250K to 1.5M

Molecular Weight Range of Range of MWD Range of MWD

Dispersity MWD MWD for for processing for processing
(Mw/Mn) processing
Tensile Strength, 4,500 5,500 600 - 2,300 5,000 6,000
psi
Tensile Modulus, 165K 225K 25K 41K 150K 158 K
psi
Tensile 100% - 600% 100% - 650% 10% - 1300%
Elongation, %
Impact Strength 0.4 1.2 No break 0.4 4.0
ft-lb/in
Hardness, Shore R80 - 102 D44 D50 D66 D73
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 Physical Properties of Polyethylene
Physical Properties of Polypropylene
Polypropylene LDPE HDPE
Optical Transparent to Transparent to Transparent to opaque
opaque opaque
Tmelt 175 C 98 115 C 130 137 C

Tg -20 C -100 C -100 C

H2 0 0.01 0.03 Low < 0.01 Low < 0.01
Absorption

Oxidation Low, oxides Low, oxides Low, oxides readily

Resistance readily readily
UV Resistance Low, Crazes Low, Crazes Low, Crazes readily
readily readily
Solvent Resistant Resistant below Resistant below 60C
Resistance below 80C 60C
Alkaline Resistant Resistant Resistant
Resistance
Acid Oxidizing Oxidizing Acids Oxidizing Acids
Resistance Acids
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 Polyolefin_Polybutylene
History H H
PB invented in 1974 by Witco Chemical
Ethyl side groups in a linear backbone C C
Description
Linear isotactic material CH2 H

Upon cooling the crystallinity is 30% CH3

Post-forming techniques can increase crystallinity to 55%
Formed by conventional thermoplastic techniques
Applications (primarily pipe and film areas)
High performance films
Tank liners and pipes
Hot-melt adhesive
Coextruded as moisture barrier and heat-sealable packages
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 Properties of Polybutylene
Mechanical Properties of Polybutylene
Polybutylene Polypropylene LDPE HDPE
(For Comparison) (For Comparison)
Density 0.908 -.917 0.90 0.91- 0.925 0.959-0.965

Crystallinity 30% to 50% 30% to 50% 30% to 50% 80% to 91%

Tensile Strength, 4,000 4,500 5,500 600 - 2,300 5,000 6,000

psi
Tensile Modulus, 10K 40K 165K 225K 25K 41K 150K 158 K
psi
Tensile 300% - 400% 100% - 600% 100% - 650% 10% - 1300%
Elongation, %
Impact Strength No break 0.4 1.2 No break 0.4 4.0
ft-lb/in
Hardness Shore D55 D65 R80 - 102 D44 D50 D66 D73

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