Polymer processing

Polymers prepared by the different methods are generally obtained in the form of granules, powder or
chips. To convert these polymer into usable articles it must be processed. During processing the
following substances are added. These substance are known as additives.
(a) Binders
(b) Fillers
(c) Dyes or pigments
(d) plasticizer and
(e) Lubricants
(a) Binders: A binder is any material or substance that holds or draws other materials together to form a
cohesive whole mechanically, chemically, by adhesion or cohesion. The main function of binder is to
hold the other ingredients of the plastic together. It provides adhesion to a substrate, binds pigments
and extenders together, and determines important properties such as durability, flexibility and gloss.
In most cases synthetic resins, natural resins or cellulose derivatives are used as binders. Some
examples of binders are shellac, copal, gum arabic, epoxy resin, alkyd resin etc.
(b) Fillers: These are also called extenders. There are two important functions of the fillers, which are
common for all industrial products. (i) It reduces the cost of the product per unit weight, and (ii) It
imparts certain specific properties to the finished product. The commonly used binder are corn-husks,
graphite, carbon black, clay, paper pulp, wood flour, metallic oxides like ZnO, PbO, metal powder
sush as Fe, Cu, Pb, Al etc. The proportion of the fillers may be up to 50% of the plastic materials.
Some common examples of fillers with specific function:
 Barium salts are used to render the polymer impervious to X-rays.
 Quartz and mica are used to improve hardeness.
 Asbestos are added to improve heat resistence. Asbestos is a heat- and fire-resistant mineral that was
commonly used in building materials like flooring, ceilings, roofs, and automotive parts.
 Shredded textiles are used to increase impact strength.

(c) Dyes and pigments: The main function of dyes and pigments is to increase aesthetic appeal of the
polymer product. Both organic and inorganic substances are used as dyes and pigments. Some of these
also work as fillers.
(d) Plasticizer: The important function of the plasticizer is to improve the flexibility and plasticity of the
polymer so as to reduce the moulding temperature and pressure. The properties of the finished product
are also greatly influenced by the plasticizer. The proportion of plasticizer can be increase up to 60% of
the polymer. A variety of organic materials are used as plasticizer. These are mainly semidrying and non-
drying oil (fish oil, castor oil, linseed oil), tributyl phosphate, triphenyl phosphate, camphor, ester of oleic
acid, stearic acid etc.
(e) Lubricants: Oils, waxes and soaps are usually used as lubricants in the polymer processing. Their
main function is to make the moulding process easy and to impart elegant finish to the final product.
Some important industrial polymers:
Industrially used polymers are mainly classified into two classes:
(a) Plastic polymer
(b) Fibrous polymer
Plastic polymers may be defined as the polymer, which can be moulded or given shape by applying heat
and pressure. The following are the most important properties of plastic polymer:-
 Light weight
 Low thermal and electrical conductance
 Resistance to the action of water and acid etc.
 Easy of fabrication and high corrosion resistance
 Resistance to the attack of small insects and microorganisms like fungi, moths etc .
 High resistance to the action of light, oils etc.
 High resistance to abrasion
 Transparent as well as translucent
 Low coefficient of thermal expansion
 Low m.p. but high refractive index
 Good shock absorber
 Impermeable to water and other liquids
 Low maintenance cost, do not require protective coating
 Good mechanical Properties
 Good ability to mix with pigments and other additives.
Polythene or polyethylene (PE):
Polythene is the most common plastic material used in making shopping bag. Polythene sheet is
also used in wrapping garments materials. It is the polymer of ethylene (CH2=CH2).Ethylene is
the first member of olefins (unsaturated hydrocarbon). The simplest unsaturated hydrocarbon,
ethylene, id polymerized to form polyethylene. Polyethylene is a thermo-plastic created from the
polymerization of ethylene.

It is categories into two types:

Low Density Polyethylene (LDPE) High Density Polyethylene (HDPE)

LDPE (Low Density Polyethylene):
 LDPE has the most long- and short-chain branching of any form of PE, resulting in its lower density of
0.91–0.94g/cm3.
 LDPE is partially crystalline substance. Its m.p is 115 oC. It is practically insoluble in any solvent at RT.
But at high temperature (100 oC) it is soluble in many solvents like CCl4, toluene, Xylene etc.
 However, strong oxidizing agents like concentrated nitric acid, K2Cr2O7 are able to oxidize LDPE.
Oxidation may takes place in air exposure to UV light and at elevated temperature.
Uses of LDPE:
Because of its inertness, LDPE is used for many purposes e.g. for packing and
wrapping frozen food, textile products etc. The branching keeps the molecular chains
from packing tightly in its crystalline form, so LDPE has less tensile strength but
greater ductility. That makes LDPE particularly useful for a range of applications,
from rigid products like plastic bottles, buckets and bowls to filmy ones like plastic
grocery bags and plastic cling-wrap. Pipes made of LDPE are used for both
agricultural irrigation and domestic water line connections. The non-polar nature of
LDPE makes it ideal for providing electric cable insulator.
LDPE is produced through free-radical polymerization.
The different steps involved in the synthesis of LDPE are
Initiation:
Free radical formation from initiator: I-I → 2I•
Reaction between monomer and initiator: I• + CH2=CH2 → I-CH2-CH 2•
Propagation:
Radicals interact with monomer to form a bigger radical.
I-CH2-CH2• +CH2=CH2 → I- CH2-CH2-CH2-CH2• → → I- (CH2-CH2)n-1-CH2-CH2•
Chain termination:
Chain termination is usually occurred by two different ways
(a) Mutual interaction
I- CH2-CH2-CH2-CH2• + I- CH2-CH2-CH2-CH2• → (-CH2-CH2-CH2-CH2-)n + I-I
(b) Disproportionation: It is a reaction where reduction and oxidation takes place
simultaneously.
～CH2-CH2～ + ～CH2-CH2～ → CH3-(CH2-CH2)n-CH3 + CH3- CH=CH-(CH2-CH2)n-CH3
Manufacturing procedure of LDPE
The raw material use for the manufacture of polyethylene is ethylene, which in turn prepared by the following
reactions.
(i) Dehydration of ethanol:- CH3-CH2OH → CH2=CH2 + H2O
(ii) Dehydro halogenations of ethyl chloride:- CH3-CH2Cl → CH2=CH2 + HCl
(iii) Hydrogenation of acetylene:- CH≡CH + H2 → CH2=CH2 etc.

LDPE is normally manufactured at high pressure (-

2000 atm) and high temperature ∼300oC. The initiator
used in this process are traces of oxygen, benzoyl
peroxide etc. When oxygen is used as initiator, the
operating pressure and temperature for the
polymerization are ∼1500 atm and ∼200oC
respectively. Benzene and chlorobenzene are used
as solvents.
The reaction is highly exothermic. So the mechanism
for heat dissipation should be included in the
manufacturing process. In a typical process, 10-30%
of monomer is converted into polymer. The rest of
monomer is recycled.
A flow char diagram of manufacturing LDPE is shown
in the right side figure. Flow diagram for the manufacture of LDPE
HDPE (High Density Polyethylene):

 HDPE is well-defined by a density of larger or equal to 0.941 g/cm3. It has a liner polymer and lower
degree of branching.
 Because of its low cost, and easy of processing it has become a most widely used polymer.
 This results in molecules to be packed closer and intermolecular bonds are stronger than in highly
branched polymers such as LDPE. The absence of branching also results in a higher density and
somewhat higher chemical resistance than LDPE.
 With a high tensile strength, HDPE is used in products like garbage containers, baby toys, water
pipes, jugs and jars as well as packaging's such as milk jugs, butter tubs, and detergent bottles.
 HDPE is also more durable and more opaque and can tolerate higher temperatures mainly compared
to LDPE.
 Industrially, HDPE is synthesized from ethylene by a catalytic procedure.
 The high density polyethylene (HDPE) is linear and is manufactured at low pressure (2-4 atm) and at
moderate temperature in the range of 50-70 oC.
 Usually, the polymerization is carried out in an inert atmosphere and in the presence of Ziegler-Natta
catalyst. This catalyst is based on tri-alkyl-aluminium and titanium chloride. The solvents used in this
polymerization process are liquid hydrocarbons.

Initiation:

Propagation:

Chain termination:
(i) Internal transfer of hydride
Cat-CH2- CH2-CH2-CH2-CH2-CH3 → Cat-H + CH2=CH(-CH2-CH2-)n-CH2-CH3

(ii) Transfer to monomer

Cat-CH2-CH2(-CH2-CH2-)n-CH2-CH2 → Cat-CH2-CH3+ (-CH2-CH2-)n-CH2-CH3
Manufacturing procedure of HDPE
Raw materials is mixed with 1-butene (co-
monomer) and then fed into a fluid bed reactor in
which the temperature and pressure are
maintained at 100oC and 0.7-2.0 Mpa,
respectively. The reaction is carried out in the
gas phase. The unreacted ethylene flowing out
from the top of the reactor is passed through a
compressor, cooling tower and then returned to
the reactor.
The polyethylene is taken out from the bottom
of the reactor in the form of granules. These are
then passed through extruder, quench cooler
separator and dryer.
The polymer in the form of pellet is then sent to
the storage chamber.
A simple flow sheet diagram is presented in the
right side figure. Flow diagram for the manufacture of HDPE