Chapter 5: Polymer Production

5.1 Introduction to Polymerization Process

5.2 Production of LDPE
5.3 Production of HDPE and LLDPE
5.4 Production of PP
Introduction to Polymerization Process
Introduction to Polymerization Process
 History of Polymer Processing
 Theterm "polymer" derives from the ancient Greek word
polus, meaning "many, much“ and meros, meaning "parts“.

 The term was coined in 1833 by Jöns Jacob Berzelius.

 History of Polymer Processing
 Themodern concept of polymers as covalently bonded
macromolecular structures was proposed in 1920
by Hermann Staudinger.
 History of Polymer Processing
 Natural polymers began to be chemically modified during
the 1800s to produce many materials.

 The most famous of these were vulcanized rubber, gun

cotton and celluloid.

Guncotton
 History of Polymer Processing
 Thefirst semi-synthetic polymer produced was Bakelite in
1909 and was soon followed by the first synthetic fiber,
Rayon, which was developed in 1911.
 Malaysian History
 Through efforts provided by the government and
Petroliam Nasional Berhad (PETRONAS), Malaysia has
attracted investors and major industry players.

 Shell, ExxonMobil, Dow Chemical, ConocoPhilips,

Kaneka, Polyplastic, Toray, Dairen, Mitsui, BP, BASF,
Idemitsu, Titan and Eastman Chemicals.
 Malaysian History
 The development of petrochemicals industry has been in
great progress since the early 1990s.

 There are three integrated petrochemicals complexes

(IPCs) established in Kerteh, Terengganu; Gebeng,
Pahang, and Pasir Gudang-Tanjung Langsat, Johor.

 Malaysia is currently a net exporter of plastic products.

The main products exported were plastic containers,
plates, films, sheets, foils, strips and other articles of
plastics.
Chapter 5: Polymer Production
5.2 Production of LDPE
Background
 First
synthesized by the German chemist Hans von
Pechmann by accident 1898.

 He accidently heated diazomethane  CH2N2, producing a

white, waxy material.
 Background
 Due to the nature of diazomethane being a toxic material if
inhale, other approach were tested using different material
of raw materials.

 In an attempt to produce PE by using ethylene and

benzaldehyde, two scientists had found by accident a new
type of material, which is LDPE.
 Background
 It was the first produced in 1933 by Eric Fawcett and
Reginald Gibson at Imperial Chemical Industries (ICI),
Norwich, England using a high pressure process via free
radical polymerization.
 Production of LDPE
LDPE Characteristics
 LDPEis defined by a density range of 0.910–0.940 g/cm3.
Compare to HDPE of 0.93 to 0.97 g/cm3.

 LDPE has a high degree of short- and long-chain

branching.

 The high degree of branching with long chains gives

molten LDPE unique and desirable flow properties.
Production of LDPE
 Production of LDPE
LDPE Characteristics
Mechanical Properties
 LDPE has more branching than HDPE, so
its intermolecular forces are weaker, its tensile strength is
lower and its resilience is higher.

Chemical Properties
 Excellent resistance to dilute and concentrated acids,
alcohols, bases and esters.

 Good resistance to aldehydes, ketones and vegetable oils.

 Background
Image of LDPE pellets
 Production of LDPE
Malaysian context
 One of the biggest plant located in Kertih, Terengganu.

 Itis owned by PETLIN (Malaysia) Sdn Bhd, a subsidiary

company under Petronas Chemicals Group Berhad.

 Establish
in 1999, it has the capability of producing 255k
tonne LDPE/year.
 Production of LDPE
PETLIN Plant in Kerteh, Terengganu
 Production of LDPE
Process Reaction
 Free radical polymerization
 Production of LDPE
Industrial Process
 Operating parameter; reactor temperature at 195~295
Celsius and pressure at 1500~3500 bar.

 High pressure is required to initiate the reaction since no

catalyst is applied.

 Initiator for in the reaction is peroxide chemical, H2O2.

 Due to extremely high pressure condition, the wall of the

piping is at least 10cm thick.
 Production of LDPE
Industrial Process
 Production of LDPE
Industrial Process
 Ethane conversion had to be remained low (>20%) to
ensure no additional temperature increase and to maintain
the product viscosity at flowable condition.
Applications
Chapter 5: Polymer Production
5.2 Production of HDPE and LLDPE
 Background
History
 Due to condition of LDPE process that require high
pressure operation, scientist had research new methods to
operate a lower pressure by using catalyst.

 Inthis pursuit they found, again by accident a new material

which is HDPE.
 Background
History
 In 1953, Karl Ziegler and Erhard Holzkamp invented
HDPE. The process included the use of catalysts and low
pressure.

 For his successful invention of HDPE, Ziegler was awarded

the 1963 Nobel Prize for Chemistry.
 Background
 Highdensity polyethylene HDPE is a thermoplastic made
from the same compound as LDPE which
is monomer ethylene.

 HDPE is used in the production of plastic bottles,

corrosion-resistant piping, geomembranes, and plastic
lumber.

 Such application in construction material is due to its high

strength to density ratio.
 Production of HDPE
HDPE Characteristics
 HDPE is defined by a density range of 0.93 to 0.97 g/cm3.

 HDPE has a low degree of branching.

 Although the density of HDPE is only marginally higher

than that LDPE, HDPE has little branching, giving it
stronger intermolecular forces and tensile strength than
LDPE.
 Production of HDPE
HDPE Characteristics
 HDPE is also harder and more opaque and can withstand
higher temperatures (120 °C for short periods, 110 °C
continuously) compare to PE and also LDPE.

Chemical Properties
 Excellent resistance to dilute and concentrated acids,
alcohols, bases and esters.

 Good resistance to aldehydes, ketones and vegetable oils.

 Production of HDPE
Malaysian context
 One of the biggest plant located in Kertih, Terengganu.

 It is owned by Polyethylene Malaysia Sdn Bhd , a

subsidiary company under Petronas Chemicals Group
Berhad.

 Establish
in 1995, it has the capability of producing 200k
tonne HDPE/year.
 Production of HDPE
Polyethylene Plant in Kerteh, Terengganu
Production of LLDPE
 Background
History
 LLDPE was firstly produced by DuPont Canada in 1959.

 Achieved this substance by copolymerization ethylene with

longer chain olefins.
 Production of LLDPE
LLDPE Characteristics
 LLDPE is defined by a density range around 0.915~0.93
g/cm3.

 LLDPE has a high degree of branching, but with shorter

chain.
 Production of LLDPE
Mechanical Properties
 LLDPE has higher tensile strength and higher impact
and puncture resistance than does LDPE.

 It is very flexible and elongates under stress.

Chemical Properties
 Slightly better chemical resistance compare to LDPE
Production of LLDPE
Application
 Production of LLDPE
Malaysian context
Refinery and Petrochemical Integrated
Development will establish a LLDPE plant that
have the capacity to produce 350k Ton/year.

Expected to be completed in 2019.

The bigges LLDPE plant is currently owned by

Petronas in Kertih with a production rate of 200k
Ton/year.
 Production of LLDPE
Polyethylene Plant in Kerteh, Terengganu
Production of Polypropylene (PP)
Production of Propylene
History
Phillips Petroleum chemists J. Paul Hogan and
Robert L. Banks first polymerized propylene in
1951.

Full large scale production was pioneered by an

Italian firm Montecatini in1957.
Production of Propylene
Synthesis Process
 PP is made from monomer propylene through
application of catalyst.

 Depending on the type of raw material the operation

usually involved temperature around 300~360K and
pressure around 8~30atm.
Production of Propylene
Industrial Process
 The bulk process - Polymerization takes place in liquid
propylene.

 The gas phase process - A mixture of propylene and

hydrogen is passed over a bed containing the Ziegler-
Natta catalyst
Production of Propylene
Industrial Process
 The gas phase process
Production of Propylene
Mechanical Properties
 The density of PP is between 0.895~0.92 g/cm³.

 Polypropylene is normally tough and flexible,

especially when copolymerized with ethylene.

 Polypropylene has good resistance to fatigue.

Production of Propylene
Chemical Properties
 Polypropylene is at room temperature resistant to fats
and almost all organic solvents, apart from strong
oxidants.

 Polypropylene is liable to chain degradation from

exposure to heat and UV radiation such as that present
in sunlight.
Production of Propylene
Applications
Production of Propylene
Malaysian Context
 Biggest plant is located in Kuantan, owned by Petronas
Chemicals Sdn Bhd
 Production rate 300k/year.
Finish!!