POLYMER PROCESS Dr Wan Zaireen Nisa

Yahya
ENGINEERING Email: zaireen.yahya@utp.edu.my

CDB4423 Office: 05-3687584 ( 04-03-24)

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 CDB 4423
POLYMER
PROCESS
ENGINEERING
Chapter 3:
Polyethylene
Polymerisation

2
 1. Free radical polymerization

CONTENTS 2. Coordination polymerization via catalyst

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LESSON OUTCOME
At the end of this lecture, students should be able to;
•Describe the two types of polyethylene polymerization:
Free radical polymerization and coordination
polymerisation
•Calculate amount of initiator, rate of reaction, initial
activity of catalyst
•Understand the role of catalyst and causes of catalyst
deactivation

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 POLYETHYLENE
POLYMERIZATION
5
OVERVIEW ON PETROCHEMICAL INDUSTRY
qMalaysia has the world’s 16th largest natural gas reserves and 28th largest crude oil reserves

qThe petroleum and petrochemical industry covers natural gas, petroleum products and petrochemicals. The
industry is an important sector in Malaysia with investments totaling RM182.9 billion as at 2015.

qMalaysia is a net exporter of polyolefin (LDPE, HDPE, LLDPE, PP) with export volume recorded around 774 KMT
in the year 2010 (estimated) while import volume recorded around 589 KMT. The major export destinations
were China, South East Asia countries and India Sub-Continent.

qThe presence of world renowned petrochemical companies, such as Shell, BASF, Eastman Chemicals, Toray,
Mitsubishi, Idemitsu, Polyplastics, Kaneka, Dairen and Lotte in collaboration with Malaysia's national petroleum
company, PETRONAS.

qA wide range of petrochemicals are produced in Malaysia such as olefins, polyolefins, aromatics, ethylene
oxides, glycols, oxo-alcohols, , acrylic acids, phthalic anhydride, acetic acid, styrene monomer, high impact
polystyrene, ethyl benzene, vinyl chloride monomer and polyvinyl chloride and polybutylene terephthalate.
Providing a steady supply of feedstock material for the plastic industry.

qThree major petrochemical zones have been established in Kertih, Terengganu; Gebeng, Pahang; and Pasir
Gudang/Tanjung Langsat, Johor. Acrylonitrile butadiene styrene plant in Pulau Pinang; the nitrile-butadiene
rubber plant in Kluang, Johor. New petrochemical zone is being established in Pengerang, Johor planned to be
operational by 2019.

qAs at 2015, there are 1,837 plastic companies in operation, producing products ranging from common
household items, packaging materials and conveyance articles to parts and components for the electrical and
electronics, automotive, office automation, computer and telecommunications industries.
 Wide range of processes
• Polymer material properties can be tailored by choice of
– Raw materials; Process; Catalyst (or no catalyst); Co-monomer; Mixing (”alloying”) of polymers
 Polymerization technology

• Tailoring depends on detailed knowledge of the structure –property

relationships
• Catalyst system is the key
 POLYETHYLENE OVERVIEW
• Poly(ethene) is produced in three main forms: low density
(LDPE) (< 0.930 g cm-3) and linear low density ( LLDPE)
(ca 0.915-0.940 g cm-3) and high density (HDPE)
(ca 0.940-0.965 g cm-3).
• The LDPE or LLDPE form is preferred for film packaging
and for electrical insulation. HDPE
• HDPE is blow-moulded to make containers for household
chemicals such as washing-up liquids and drums for
industrial packaging. It is also extruded as piping.
Process HDPE LDPE LLDPE
Food packaging Cling film
Making film Stretch film
Shopping bags Milk carton lining
Dustbins Buckets
Injection moulding Food boxes
Crates Bowls
Detergent bottles
Blow moulding Squeezable bottles
Drums
Flexible water pipes, LDPE/LLDPE
Extrusion Water pipes Cable coating
Cable jacketing
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
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.
 Thermodynamics

• Very high heat of reaction combined with low heat capacity: high T-
increase
• Cooling important
• If temperature increases above about 300 °C ethene decomposition

C2H4 ®C + H2 +CH4 ∆H= -120kJ/mol

can occur, leading to increased heat release and increased pressure
Classification of PE by Polymerization Chemistry

Free radical polymerization

­ LDPE

Coordination Polymerization via Catalyst

­ HDPE and LLDPE
 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)
FREE RADICAL POLYMERISATION

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 1930’s
The addition reaction for producing polyethylene from ethylene
molecules. The unsaturated double bond in the monomer is broken to
produce active sites, which then attract additional repeat units to either
end to produce a chain.
Benzoyl Peroxide Peroxide radical

Initiation of a
polyethylene chain by
chain-growth may
involve (a) producing free
radicals from initiators
such as benzoyl peroxide,
(b) attachment of a
polyethylene repeat unit
to one of the initiator
radicals, and (c)
attachment of additional
repeat units to propagate
the chain.
 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.
TERMINATION

Termination of polyethylene
chain growth:
(a) the active ends of two
chains come into close
proximity,
(b) the two chains undergo
combination and
become one large
chain, and
(c) rearrangement of a
hydrogen atom and
creation of a double
Rxn 1 Rxn 2 covalent bond by
disproportionation
cause termination of
two chains.
• The termination by Rxn 1 (combination) can bring about a considerable increase
in the molecular weight of the final polymer.
• The termination by Rxn 2 (disproportionation) two chemically different types of
polymer molecules are produced.
• Rxn 1 & 2 depend on the nature of the monomer and on the temperature.

Probability of combination (c) kc Ac ( Ed - Ec ) / RT

Probability of disproportionation (d)
= = e
k d Ad
 Typical High Pressure, Low Density PE Process
HPS: High Pressure Separator
LPS: Low Pressure Separator
Low pressure recycle

Purge to LHC
Chain transfer agent 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
 PROBLEM 1

The following results have been obtained for the temperature dependence
of the percentage of chain termination by disproportionation in metyl methacrylate:

T (°C) 40 60 80

% Disproportionation 50 59 70

(a) Calculate the difference in activation energy between disproportionation

and combination.

Probability of combination (c) kc Ac ( Ed - Ec ) / RT

Probability of disproportionation (d)
= = e
k d Ad

(b) At what temperature will termination be 90% by combination?

PROBLEM 2
Calculation of Initiator Required
1. Calculate the amount of benzoyl peroxide initiator required to produce 1
kg of polyethylene with an average molecular weight of 200,000 g/mol.
2. What is the degree of polymerization? Assume that 20% of the initiator is
actually effective and that all termination occurs by the combination
mechanism.
SOLUTION
The molecular weight of ethylene = (2 C)(12) + (4 H)(1) = 28 g/mol. Therefore,
the degree of polymerization is:

200,000 g/mol = 7143 ethylene molecules per average chain

28 g/mol
(1000 g polyethylene)(6.02´1023 monomers/mol) = 215´1023 monomers
28 g/mol
SOLUTION (Continued)

The combination mechanism requires the number of benzoyl

peroxide molecules to be:

23
215 ´ 10 ethylene molecules 23
= 0.03 ´ 10
7143 ethylene / chain
The molecular weight of benzoyl peroxide is (14 C)(12) + (10 H)(1) + (4
O)(16) = 242 g/mol. Therefore, the amount of initiator needed to form
the ends of the chains is:

23
(0.03 ´ 10 )(242 g/mol)
23
= 1.206 g
6.02 ´ 10
POLYMERISATION BY CATALYST
 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 1950’s for HDPE and PP
­ effectively commercialized in 1970’s 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
TYPICAL GAS PHASE PE PROCESS
Vent
Recovery

Reaction
System ü No solvent is used.
Catalyst
ü Ethylene monomer, hydrogen and
Resin supported catalyst are blown into
Purging
the reactor. (ex: Philips catalysts)
ü Polymerization reaction takes
place in fluidized bed reactor.
ü Ethene polymerizes to form grains
of HDPE, suspended in the flowing
Additive
Pelleting
Addition gas, which pass out of the reactor
Raw
Material System when the valve is released.
Handling

To Resin
Storage
and Loading
 TYPICAL SOLUTION PE PROCESS

Comonomer Solvent
Recovery
Ethylene

Reactor

Polymer
Devo Devo
1 2

• Both catalyst (ex: Ziegler Natta) and resulting polymer remain dissolved in a
solvent (ex: C10 or C12 alkane ) that must be removed to isolate the polymer.
• Polymerization reaction takes place in a CSTR (Continuous Stirred Tank Reactor).
 PE SLURRY PROCESS

qCatalyst and polymer formed during production remains suspended in a liquid medium but
never dissolving. Ex: Ziegler-Natta catalyst, Philips catalyst
qThe catalyst, as granules, is mixed with a liquid hydrocarbon (for example, 2-methylpropane
(isobutane) or hexane), which simply acts as a diluent. A mixture of hydrogen and ethene is
passed under pressure into the slurry and ethene is polymerized to HDPE.
qPolymerization reaction takes place in CSTR or tubular reactor.
 Linear Low Density Polyethylene (LLDPE)
• LLDPE is ethylene/alpha-olefin copolymer.
• a-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
 Modes of Termination
Using Catalyst-Gas phase polymerization

1. β-hydride shift

C H CH2
CH2 H CH2
CH2
Al Al Ti Al
Ti Ti
R R R

2. Reaction with H2 (Molecular weight control!)

C H CH2
H H CH3 H
CH2 CH2
Al Al Ti Al
Ti Ti
R R R

Coordination Polymerization via Catalyst

ROLES OF CATALYST:

1. Initiate the reaction

2. Influence on the chain termination step by producing narrow
or wide MWD.

For example in LLDPE or HDPE Gas phase polymerisation:

v Ziegler based catalyst will produce narrow MWD

v Chromium based catalyst will produce broad MWD
 Molecular Weight

q Concentration of Hydrogen
q Reaction Temperature
q Type of catalyst

Density

q introduction of butene (C4) or Hexene (C6)

on the PE back-bone
Formation of branches alter the density
Calculation of average Melt Index (MI) and Density of Bimodal PE pellets

Reactor A Reactor B

MIA + MIB
BIMODAL
Density,rA Density,rB

Average MI: MI = wA MI A + wB MI B
1 wA wB
Average density: = +
r rA rB
Where wA,B is the weight fraction
• The melt flow index (MFI) is a measure of the ease of flow of the melt of
a thermoplastic polymer. It is defined as the mass of polymer, in grams, flowing in 10 minutes
through a capillary of a specific diameter and length.
• A higher MFI indicates a lower material viscosity, and when comparing polymers of the same
class, a lower melt flow rate corresponds to a higher molecular weight and/or less branching.
 Reactor Control
MI Model
æ [H 2 ] ö
log( MI ) = k i + ao log(T ) + a1 logçç ÷÷ + a 2 FC 4C 2
è [C 2 ] ø

Where
T is the temperature,
[H2] and [C2] are the concentration of hydrogen and ethylene
FC4C2 is the feed ratio of co-monomer to ethylene
PE based on Ti catalyst-
Ti is the active site

The polymer yield, t, or the amount of polymer powder

produced per millimole of Ti at time t, is given :
t
t = ò adt
0

Where a is the initial catalyst activity :

a = (g PE/mmol Ti-hr)
 Reactor Types
• The most important factors for the choice and design of a reactor for
heterogeneous catalysis are:

– The number and type of phases involved (G/S, G/L, G/L/S, L/L/S)
• Appropriate mass and heat transport between the phases, e.g.
determined by degree of mixing and contacting patterns (co-current,
counter-current, cross-current)

– The kinetics of the main and side reactions:

• This determine the desired temperature and concentration profile, the
residence time distribution (degree of mixing), etc.

– The heat of reaction – measure to be taken for heat transfer

– Catalyst deactivation - the rate of catalyst removal and addition and the need
for regeneration
 Catalyst deactivation
Causes, mechanism, and treatments
• Catalyst deactivation (time-scale of deactivation) is important
in the choice of reactor and operation of the commercial
process

• Deactivation is the loss of catalyst with time, can be either

– Poisoning
– Fouling
– Thermal degradation
– Attrition
 Poisoning
• Is the strong chemisorption of species or
impurities on catalytic sites rendering them
inactive for reaction
• A species acts as a poison depends upon its
adsorption strength relative to other species
competing for catalytic sites
Mechanism
e.g. Sulfur
 Poisoning
• Strongly adsorbed poison – physically blocks
reaction site
• Because of its strong chemical bond, it
electronically modifies its nearest neighbor
metal atoms
• The restructuring of the surface by the
strongly adsorbed poison – change the
properties
• Prevents or slows the surface diffusion of
adsorbed reactants
Effect of poison vs. activity
Ziegler catalyst for PE polymerization
Example
Calculate the initial catalyst activity, a, if the powder
contained 5 ppm Ti (Molar mass Ti = 48 g/mol) is
produced after 4 hours in the reactor.

5 ppm = 5 mgTi / 1000 gPE

= in 1000gPE
5 ´ 10 -3 g
48 g / molTi
t = 0.104 mmole Ti in 1000 gPE or
9600 gPE/mmole Ti. in 4 hr
OR
Ti (ppm) = 48000/t = 48000/5
=9600 gPE/mmole Ti. in 4hr
Therefore a = 9600/4 = 2400 gPE/mmole Ti.hr
PROBLEM :

1. Calculate the average density and melt index of the

PE powder after blending 3000kg from silo A with
50000 kg from silo B
PE from silo A: MI= 20 g/10 min & density = 0.936 g/ml
PE from silo B: MI = 30 g/10 min & density = 0.948 g/ml

2. If the Ti in PE powder is found to be 30 ppm in one of the

production period, explain:
a) the activity of the catalyst compared to the powder that
contained 5 ppm Ti
b) why for that period the powder has high Ti content.