POLYMERIZATION

Unit 4
 Polymers
Polymerization is one of the very important unit processes which find
application in manufacture of polymer, synthetic fibre, synthetic rubber,
polyurethane, polyethylene etc.
A polymer is a macromolecule, made up of many smaller repeating units
called monomer.
Polymers have high molecular weight in the range of 103-107
Polymers can be synthesized from various types and combinations of
monomers to yield unusual properties, both physical and chemical.
Classification
near polymer is represented by a chain with two ends.

oss-linked
linked polymer have three dimensional structures in
ich each chain is connected to all others by a sequence of
ction points and other chains. But it does not contain any
in chain when compare with branched polymer.

anched polymers have side chains, or branches, of

nificant length which are bonded to the main chain at
anch points, and are characterized in terms of the number
d size of the branches.
 Classification
lassification of Polymers by Physical Properties
Thermoplastic Polymers:
he individual chains of thermoplastic polymer are held together by van
er Waals forces.
hey are strong if the polymer chains are lined up in an ordered, closely
acked array. This region is called crystallites and the other where polym
hains are oriented randomly is called amorphous.
hermoplastic polymers have both ordered crystalline regions and
morphous non-crystalline regions.
hermoplastic polymers are hard at room temperature, but become sof
when heated, because on heating individual polymer chains slip from on
nother.
olyethylene, polystyrene, polypropene and teflon are some examples f
hermoplastic polymer.
ermosetting Polymers:
e greater the degree of cross-linking
linking makes the polymer more rigid. Such cross-link
cross
ymers are called thermosetting polymers.
ermosetting polymers are generally stronger than thermoplastic polymers due to s
valent linkage (cross-linking)
linking) between polymer chains not by weak intermolecular v
Waals forces.
ey are more brittle in nature and their shape is permanent. Once it is hardened the
nnot be recycled.
enol formaldehyde, Melmac,, Bakelite and polyurethanes are examples for thermos
ymers.
astomers:
elastomer is a randomly oriented amorphous polymer, which stretches and then re
ck to its original shape.
hen elastomers are stretched, the random chains stretch out where as the van der W
ces are not strong enough to maintain them in that arrangement and retains its ori
ape when the stress is removed.
bber, Butadiene and its derivaties,, silicones, thiokols are examples of an elastomer

bers:
ese are thread like polymers which can be used as fabrics.
e strong intermolecular forces like hydrogen bond provide high tensile strength.
ew examples are polyamides, polyester, polycarbamides,
polycarbamides polyurethanes etc
 Classification by based on sources
atural Polymers:
olymers are naturally available.
xamples : Polysaccharides (biopolymers): Nucleic Acids (DNA,RNA), Proteins, Natur
ubber
nthetic Polymers
he polymers which are synthesized in the laboratory are called as synthetic polyme
ased on the method of its preparation they can be further classified into addition
olymers and condensation polymers.
ddition polymers: Addition polymers are formed by the sequential addition of the
monomer units with the help of a reactive intermediate such as free radicals, cation
nions without loss of small molecules.
ondensation Polymers: This type of polymers is generated by the condensation of
monomer units with the loss of small molecules such as H2O, HCl, and NH3 etc. Here
monomer units must have two functional groups in order to condensation reaction
lace. Dacron, nylon 6 and nylon 66 are few examples for condensation polymers.
Addition

Condensation
 polymer chain is formed from only one type of monomer unit
alled homopolymers.. Alternatively, two of more different
omer units can combine to form a polymer chain is called
lymers.
Addition Polymerization Methods
Homogeneous Polymerization:
In case of homogeneous bulk polymerization, the feed is a gas , liquid or
solid monomer. No initiators or additives are used.
For homogeneous Solution polymerization, the monomer is completely
dissolved in a solvent.
Heterogeneous Polymerization:
In heterogeneous Emulsion polymerization, the monomer molecules are
emulsified in aqueous media in the form of micelles.
For heterogeneous Suspension polymerization, the monomer is
suspended in an aqueous or other type of media as large droplets.
 Polythene (PE)
he manufacture of polyethylene follows addition polymerization
netics involving catalysis of purified ethylene.

s molecular formula is -(CH2-CH2)n-

olecular weight of 1,500 to 100,000.
100,000
s melting point is 85 – 110oC.
ensity is 0.91 -0.93, when produced by high pressure process and
96, when produced by low pressure process.
e are three processes by which polyethylene is manufactured

Pressure Process : This process was developed in the UK. It uses peroxide catalyst at 100-300oC a
uces low density randomly oriented polymer which have a low melting point. The process is
sure of 1000 – 2500 atms.. This process yields Low Density Polyethylene (LDPE).

mediate Pressure Process : This process was developed in the USA by Phillips Petroleum Co. for
aring high density polymer with increased rigidity,, crystallinity, tensile strength and softening point
ess uses MoO3 and Cr2O3 on alumina as catalyst and is operated at 30 – 100 atms.

Pressure Process : This process was originally developed by Dr. Karl Ziegler in Germany for pre
density polyethylene (HDPE). The catalyst used in this process consists of aluminium triethyl
ated with heavy metal derivatives such as TiCl4 and is operated at 6-10 atms.

ar process developed by Dr. G. Natta in Italy is used for the production of polypropylene
nufacture of Polythene (Low
Low Pressure Ziegler Process )
Process Description
 Process Description

The flashed solvent is thereafter recycled to the catalyst make –up

unit after appropriate drying and re-distillation.
The slurry which results is then centrifuged to remove the
water, and the water is treated to remove the catalyst before
recycle.
The final products of polyethylene solids are then dried, extruded
and given the required final forms.
Phenol Formaldehyde
Uses
Process Description
 NYLONS
on is a thermoplastic silky material that can be melt-processed into
rs, films, or shapes.
made of repeating units linked by amide links
ons (i.e. nylon 6, nylon 66) are polyamides with structural units derived
dominantly from aliphatic monomers.
on polymers can be mixed with a wide variety of additives to achieve m
erent property variations.
on polymers have found significant commercial applications in fabric an
rs (apparel, flooring and rubber reinforcement), in shapes (molded par
s, electrical equipment, etc.), and in films (mostly for food packaging).
Nylon 6 and Nylon 66 are two important polyamides and find
application in woven and nonwoven industries.
Caprolactam is monomer for Nylon-6
Nylon while monomer for Nylon 66 is
nylon 66 which is made from adipic acid and hexamethylene diamine.
Nylons are exception all strong, elastic,
elastic abrasion resistant, lustrous,
easy to wash, resistant to damage from oil and many chemicals, low
in moisture absorbency
Uses
 NYLON 6,6
lon 66 (or 6,6 - Nylon) is a condensation polymer formed by the condensation
lymerization of Adipic acid (a dibasic acid) and hexamethylenediamine.
pical advantages of nylon 66 over nylon 6 are its
gher tensile strength in use,
cellent abrasion resistance, and
gher melting point. (40-45OC higher than nylon 6)
Manufacture of Nylon 6,6
Process Description
 NYLON 6
e production of Nylon–6 6 is similar to that of Nylon–66,
Nylon the only difference be
nature of polymerization. Nylon – 6 is manufactured by the step–wise
step condensat
rolactum with no net water removal
ymerization at 240-2700C in presence of water
on 6 is produced from polymerisation of caprolactam.
caprolactam Process steps involved in
duction of Nylon 6 involve the following steps:

prolactam melting and addition of additives

ymerisation:: Batch/continuous and chips production
ps washing and drying
nning of nylon
Manufacturing process of Nylon 6
 Elastomers
Elastomer is an elastic polymer which returns to original dimensions when stretched considerably from its
original shape.
Rubber is a collective term for macromolecular substances of natural (natural rubber, NR) or synthetic
(synthetic rubber, SR) origin. Natural rubber iss prepared by material produced from the milk of rubber trees,
which has been treated with more or less amounts of sulfur and vulcanized.
Synthetic rubbers are complex chemical compounds built by means of polymerization of monomers. The
synthetic rubber industry provides a high number of different synthetic rubbers which are produced in
chemical plants world wide to reflect the different applications and the wide range of requirements from the
market.
xamples are
Styrene-Butadiene Rubber (SBR),
Polybutadiene Rubber (BR)
Polyisoprene Rubber (IR)
Butyl Rubber (IIR)
Nitrile Rubber (NBR)
Halobutyl Rubber (HIIR)
Ethylene Propylene Diene Monomer (EPDM)
 Styrene-Butadiene
Butadiene Rubber (SBR)
yrene-butadiene rubber (SBR) is the most commonly produced synthe
bber obtained from styrene and butadiene.
bout 70 % of SBR is used for the manufacture of car tyres, SBR is also us
manufacture conveyor belts, flooring and carpet underlay, hoses, seals
eeting, footwear and a large number of other rubber goods.
here are two different process types utilized for SBR production: emulsi
olymerization and solution polymerization. In emulsion polymerization,
onomers polymerize in the presence of an emulsifier (fatty acid or rosin
id soap)) while in solution polymerization a solvent (n-hexane or cyclo
entane) is utilized.
mulsion polymerization of SBR or Buna-S
Buna is most commonly used.
he cold process of emulsion polymerization process has replaced the ho
olymerization process
Chemical Reaction
Manufacturing process of SBR

H2SO4 & NaCl