Introduction to

Polymerisation
Prepared by : Submitted to:
Nirmal Patel (17BCH036) Prof.Nikita Choksi
Ruchit Patel (17BCH037)
Shrajesh Patel (17BCH038)
Tarang Patel (17BCH039)
 CONTENT

 Introduction
 Modes of Polymerisation
 Polymer Manufacturing Process
 Introduction

 The word “Polymer” is derived from two Greek words, ‘Poly’

that means many (numerous) and ‘Mer’ which means units. In
basic terms, a polymer is a long-chain molecule that is
composed of a large number of repeating units of identical
structure.
 monomers can be simple — just an atom or two or three — or
they might be complicated ring-shaped structures containing a
dozen or more atoms.
 Classification of polymers based on
resources
 Natural polymers: Polymers which occurs in nature and are
existing in the natural source like plant and animal
e.g. cellulose, proteins, DNA, Silk etc.
 Semi-synthesis polymers: Polymers obtained by modification
in the properties of natural polymers which with stand our
requirement.
e.g. Vulcanize rubber, Cellulose diacetate etc.
 Synthesis polymers: Polymers which are human made using
different chemical process.
e.g. Polyethylene, Polystyrene, Nylon, Bakelite etc.
 Classification of polymers based on
structure
 Chain polymers: polymers whose structure are linear (long chain)
e.g. polyethylene, nylon 6-6 etc.
 Branched polymers: polymers which consisting secondary polymeric
chain to the original chain e.g. LDPE, starch, glycogen etc.
 Crosslink polymers: crosslink is a bond that links one polymer chain
to another polymer chain (three dimension network) e.g. polystyrene,
synthetic rubber
 Classification of polymers based on
Polymerization
Addition polymers
 These type of polymers are formed by the repeated addition of
monomer molecules.
 There is no elimination of small molecules like water or alcohol etc
Example: ethene n(CH2=CH2) to polyethene -(CH2-CH2)n-.
Condensation polymers
 These polymers are formed by the combination of monomers, with
the elimination of small molecules like water, alcohol etc.
 The monomers in these reactions are bi-functional or tri-functional
in nature. Example: Hexamethylenediamine and adipic acid. to
give Nylon 6-6
 Classification of polymers based on
molecular forces
Thermoplastic polymers
 Thermoplastic polymers are long-chain polymers in which inter-
molecules forces hold the polymer chains together.These polymers
when heated are softened and hardened when they are allowed to
cool down, forming a hard mass.
 They do not contain any cross bond and can easily be shaped by
heating and using moulds. e.g. Polystyrene, PVC.
Thermosetting polymer
 Thermosetting plastics are polymers which are semi-fluid in nature
with low molecular masses. They form a three-dimensional structure
on the application of heat.
 This reaction is irreversible in nature. e.g. Bakelite
Elastomer
 Elastomer are rubber-like solid polymers, that are elastic in
nature. they can be easily stretched by applying a little force.
 They have weakest intramolecular force and they also get their
original shape very easily e.g. rubber band
Fibers
 Polymers which are a thread like in nature, strong inter-
molecules forces giving them less elasticity and high tensile
strength.
 The intermolecular forces may be hydrogen bonds or dipole-
dipole interaction. Fibres have sharp and high melting points.
e.g. Nylon-6-6
 Classification of polymers based on
degradation properties
Biodegradable polymers
 Polymers which degrade by bacteria, enzyme or via
air oxidation.
 Most common biopolymers are polylecticacid (PLA),
polyglycolicacid (PGA), dextran etc.

Non-biodegradable polymers
 Polymers which do not degrade very easily.This type
of polymers create an environmental issues.
 Examples are terelin, nylon 6-6, nitrile rubber,
Bakelite etc.
 Condensation polymerization method
 Roughly follows procedures used for low molecular weight
functional group reactions
 Stoichiometric proportions of reactants chosen for desired final
properties
 Can be processed with or without solvent addition
 Mixed in batch reaction vessels with catalyst addition and heat
control to avoid premature gelation
 Major problem is to remove condensation products by azeotropic
distillation
 Condensation polymerization method

 Tri dimensional polymers are often prepared in two stages:

(1) Soluble and Fusile polymers with low cross-linkaging are
prepared as described earlier. The reaction is terminated by removal
of catalyst, lowering the temperature, or not removing the volatile
condensation product.
(2)Products are Shipped to fabricators who convert them by heat
curing to the final thermoset product.
 ADDITION POLYMERIZATION METHOD

HOMOGENEOUS HETEROGENEOUS
SYSTEM SYSTEM
BULK SUSPENSION
POLYMERIZATION POLYMERIZATION

SOLUTION EMULSION POLYMERIZATION

POLYMERIZATION
 Homogeneous Polymerization

 In a homogeneous polymerization process, all reactants,

including monomers, initiators, and solvents, are mutually
soluble and compatible with the resulting polymer.
 Bulk Polymerization

• Monomer, initiator, and polymer are miscible

monomer initiator • Generally exothermic
• The higher the conversion, the higher the
viscosity

E-1

polymer
 Bulk Polymerization
The process is carried out in two stages:

Stage Prepolymerization or polymerization initiation

1: stage, which is often carried out in a short
period (5 – 10 minutes) resulting syrup of low
degree of polymerization and low viscosity

Stage Polymerization stage, which is often carried out in

2: a mold resulting solid polymer in a relatively long
period.
 Bulk Polymerization

 An example is the polymerization of polystyrene,

which is carried out in two stages.

 In the first stage, styrene is polymerized at 80°C with

the 30 to 35% monomer conversion in a stirred reactor
known as a prepolymerizer.

 The resulting reaction mass — a viscous solution or

syrup of polymer in monomer — subsequently passes
down a tower with increasing temperature.
 Bulk Polymerization

 The increasing temperature helps to keep the

viscosity at manageable levels and also enhances
conversion, which reaches at least 95% at the exit of
the tower.

 By removal of the heat of polymerization at the top

of the tower and proper temperature control of the
finished polymer at the bottom of the tower, an
optimum molecular weight may be achieved and
channeling of the polymer may be minimized.
 Solution Polymerization

solvent catalyst • Monomer, initiator, catalyst, and

initiator resulting polymer are soluble in the
monomer solvent
• Exothermic
• The higher the conversion, the higher
the viscosity

E-1

Solution
 Solution Polymerization

 For example, a synthetic rubber process using a coordination

catalyst requires rigorous exclusion of air ,moisture, carbon
dioxide and other catalyst deactivators from the monomer,
solvent, and any other ingredient with which the catalyst will
come in contact before the reaction.

 In addition, exclusion of air prevents the tendency to form

dangerous peroxides.

 To avoid product contamination and discoloration, materials of

construction also need to be selected with the greatest care.
 Solution Polymerization

 Solution polymerization finds ready applications when the end

use of the polymer requires a solution, as in certain adhesives
and coating processes i.e., polyvinyl acetate to be converted to
polyvinyl alcohol and some acrylic ester finishes.

 Solution polymerization is used widely in ionic and coordination

polymerization.

 High-density polyethylene, polybutadiene, and butyl rubber are

produced this way.
 Heterogenous Polymerisation

 In a heterogenous polymerization process, all

reactants, including monomers, initiators, and
solvents, are insoluble, they form two separate
phases
 Emulsion Polymerisation

 Emulsion polymerization is one of the most important methods for

the polymerization
 An emulsion polymerization system consists of a dispersing
medium, monomer, emulsifier, initiator and, if necessary,
modifiers
 Common emulsifiers are anionic and non-ionic surfactants. A
combination of both anionic and non-ionic surfactants will often
improve the stability of the dispersed droplets
 This process can be divided into 3 distinct stages
 Stages of emulsion polymerisation

https://polymerdatabase.com/polymer%20chemistry/Emulsion%20Polymerization.html
Advantages
 The rate of polymerisation is high
 Heat can be easily controlled and hence viscosity
build up is low
 Conversion is almost 100%
Disadvantages
 Polymer needs purification

 Polymers such as Chloroprene, Acrylamide and Co-

polymers such as ABS is carried out using the Emulsion
polymerisation
 Suspension Polymerisation

 Suspension polymerization which is also called bead

polymerization
 A suspension polymerization system consists of a dispersing
medium, monomer, stabilizing agents and a monomer soluble
initiator
 The monomers are suspended in the form of spheroids of .5-3 mm
size in the dispersion medium and agitated in presence of
initiator
 The 3 distinct stages of the
process are as follows:

Stage 1: Agitation of the

monomers in a dispersion
medium in presence of
initiators

Stage 2: The monomers in

presence of initiators start
coalescing and form bead like
structures

Stage 3: The beads settle

down and combine to form a
polymer
http://polymerdatabase.com/polymer%20chemistry/Suspension%20Polymerization.html
Advantages
 Water as continuous phase is economical and environmental
friendly
 The rate of heat transfer is higher than other modes of
polymerisation
 Polymers formed are easy to isolate and are pure
Disadvantages
 This is only applicable to water insoluble monomers
 Control of particle size is difficult

 Polymers such has Styrene, Vinyl chloride, ethylene and

Formaldehyde are produced using this method
 Comparison of Monomers
Method Catalyst % conversion Mol. Wt.

Bulk 0.5% Benzoic Acid 54 40,000

Emulsion 0.5% Potassium 97 370,000

persulphate

Suspension 0.5% Benzoic Acid 49 67,000

Polymer: Polystyrene
Reaction conditions: 2 hours at 85°C
Dryden’s Outlines of Chemical Technology
 SBR

 Least expensive and process easily

 Good weathering resistance and resistances to oil
 Better in heat aging and ozone resistance
 Inferior in mechanical properties except wear as compared to
natural rubber
 Leading Producers

 Global  India
 Lanxess  Indian Synthetic Rubber
 LG Chem  Reliance
 Europa  Ema Rubber Industries
 Sinopec  Arihant Solvent and
Chemicals
 Production of SBR

 Two types of Polymerization reactions are used to

produce Styrene Butadiene copolymer
1. Emulsion crumb process
2. Solution type
Emulsion Crumb Process
 Process
 Involves purification with 20% aqueous caustic
 Passed through 6 to 12 reactors
 Reactors are glass lined or of stainless steel
 Residence time is 5-15 hours and reactors are
equipped with steam heating, water cooling and
refrigeration
 Product formed in this phase of reaction is known as
latex
 Both cold SBR(5℃, 1 atm gauge) and hot SBR(50 ℃,3-
4 atm gauge)
 Process
 Latex is collected in blow tank and butadiene is
removed from stripper and then to perforated plate
column to remove styrene
 Passed through blend tanks and then coagulated to
rubber crumbs by addition of mixture of brine and
acid
 Liquid and Crumbs are separated by screening
 Crumb products are separated as cake from rotary
filters
 Crumbs are dried in belt dryers with hot air and then
pressed into bales and sent for shipment
 Equipment's used in Polymer industry

 Reactors Mixers
 Equipment's used in Polymer industry

 Pumps Shaping
Equipment's used in Polymer industry

Valve
 Applications

 Sealing Requirements for hydraulic braking system

 Tires, Shoe Heels and Soles, Gaskets
 Latex form is extensively used in coating papers
 Building applications and to tank damp rooms or surfaces
 References
 http://toppr.com
 http://polymerdatabase.com/polymer%20chemistry/Suspension%20Polymerizatio
n.html
 https://nptel.ac.in/courses/103103026/module4/lec38/3.html
 http://polymerdatabase.com/polymer%20chemistry/Solution%20Polymerization.h
tml
 https://polymerdatabase.com/polymer%20chemistry/Emulsion%20Polymerization
.html
 https://en.wikipedia.org/wiki/Emulsion
 Polymeric Materials and Processing by Jean-Michel Charrier
 Nptel module 3
 CpmainIndia
 Dryden’s Outlines of Chemical Technology
Thank You
Any questions?