Polymerisation

Types of Polymerization reactions

The process of formation of a macromolecule from monomers is called
polymerisation.
Based on the nature of the monomer polymerisation may be classified as

1. Addition Polymerization
2. Condensation Polymerization
3. Copolymerization

Addition Polymerization / Chain growth polymerization

Addition polymerization is the process of formation of addition polymers

from monomers without the loss of small molecules. Unsaturated monomers
usually undergo addition polymerisation. The mechanism of addition
polymerization is similar to that of chain reaction. It consists of three distinct
steps namely initiation, propagation and termination.
The reaction is initiated by the application of heat, light, pressure or a catalyst
that breaks the double bond. Monomers add on to give polymer. The polymer
product is formed at once.
Important characteristics of chain growth / addition polymerisation:
i. Once the initiation occurs , the polymer chains form very quickly ( 10-1 to
10-6 secs.)
ii. Low concentration of catalyst is sufficient
iii. Monomers will be present till the last stage of reaction
iv. The process is exothermic.
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v. High molecular weight polymers can also be prepared ( 10,000 to 10

million can be formed)

Mechanism of Addition polymerization

It proceeds via an intermediate and based on the charge on the intermediate
it can be sub divided as cationic, anionic and free radical polymerization.
By all these methods stereo specificity cannot be achieved (i.e.)
syndiotactic / isotactic polymers cannot be prepared.
In order to prepare stereo specific polymers, Zeigler Natta Catalyst is used.
However, this type of polymerization can proceed via cationic or anionic
mechanism and is often referred as co-ordination polymerization.

The three vital steps of addition polymerisation are

Initiation:

Formation of ion / free radical

Propagation :

Combining of monomers to form chains

Termination:

Elimination of ions / free radicals

The actual method of initiation, propagation and termination will affect final
properties of the polymer

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Cationic polymerization is a type of chain growth polymerization in

which a cationic initiator transfers charge to a monomer which then
becomes reactive. This reactive monomer goes on to react similarly with
other monomers to form a polymer

Cationic polymerization is used in the production of polyisobutylene (used

in inner tubes) and poly(N-vinylcarbazole ) (PVK)

Ethylene

PE

Propylene

Initiation

PP

(Step 1)

Initiation is the first step in cationic polymerization. During initiation, a

carbonium ion is generated from which the polymer chain is made. There are
a variety of initiators available for cationic polymerization, and some of them
require a co -initiator to generate the needed cationic species.

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Lewis acids are the most common compounds used for initiation of cationic
polymerization. The more popular Lewis acids are SnCl4, AlCl3, BF3, and
TiCl4.
Propagation (Step 2)
Propagation proceeds via addition of monomer to the active species, i.e. the
carbonium ion. The monomer is added to the growing chain in a head-to-tail
fashion; in the process, the cationic end group is regenerated to allow for the
next round of monomer addition.
Termination (Step 3)

During termination the growing polymer chain is terminated by removing a

proton or by adding a nucleophile. This can be done at any desired stage as
per the molecular weight requirement. Generally phase transfer reagents are
used as terminators to bring termination by removal of proton.
Step 1 and 2

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Step 3

Anionic polymerization is a type of chain growth polymerization in

which an anion initiator transfers charge to a monomer which then
becomes reactive. This reactive monomer goes on to react similarly with
other monomers to form a polymer

This polymerization is carried out through a carbanion active species. Like

all chain-growth polymerizations, it takes place in three steps: chain
initiation, chain propagation, and chain termination
Anionic polymerizations are used in the production of polydiene synthetic
rubbers, styrene/butadiene rubbers (SBR), and styrenic thermoplastic
elastomers
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Step 1

Step 2

Step 3

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Mechanism of free radical polymerization

Example: Synthesis of Low density polyethylene

In free radical polymerization, an initiator containing a weak O-O / N-N is

used.
For example AIBN (Azobis Iso Butyro Nitrile ) is used as initiator for the
synthesis of LDPE.
Monomer: Ethylene and small amount of Oxygen (0.1% to 5%)
Initiator: AIBN / Benzoyl Peroxide
Temperature: 200oC
Reaction Time: Few minutes
Pressure: 500 atmospheres
Terminator: Alcohols / Ketones
Reactor: Tower / Autoclave type
Yield: 15 30 %
Step 1 : Initiation
(i) : Decomposition of initiator (AIBN / Peroxide)

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(ii) Formation of Carbon radical

Step 2: Propagation

Step 3: Termination
(i) By Combination / Coupling: Dead Polymer is formed

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(ii) By Disproportionation: Mixture of Dead and live polymer

Dead Polymer

Live Polymer

Depending upon the pressure, temperature and time of polymerization

during termination, branching occurs resulting in the formation of a
branched polymer (LDPE)
(i)

Formation of a radical in the middle of a chain due to transfer/

migration of H

(ii)

Addition of monomer to the newly formed monomer leading to

branching ( though the monomer is only bifunctional)

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Note on AIBN
AIBN - Azobisisobutyronitrile is an organic compound with the formula
[(CH3)2C(CN)]2N2. It is a white powder soluble in alcohols and common
organic solvents but insoluble in water. It is often used as a foaming agent in
plastics and rubber. It is also used as initiator for the synthesis of polymers
through radical polymerization.

AIBN is safer to use than benzoyl peroxide (another radical initiator) because
the risk of explosion is far less. It decomposes easily and forms nitrogen in the
process which maintains the reaction in an inert atmosphere. It does not
undergo secondary reaction, hence the yield and purity of the product is much
better compared to peroxide initiators.

In addition, the rate of formation is also high with AIBN. However, it is not
safe to use it at temperatures > 50 C as it decomposes above 65 C which
could cause an explosion . A respirator dust mask, protective gloves and
safety glasses are recommended for reducing the health hazards.

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Addition Polymerisation Summary

Polymerisation
conditions

Initiator

Propagating
Species

Terminator

Cationic

Lewis acid and

Water

Carbo cation
(C+)

Toluene

Anionic

Lewis base and

Water

Carb anion
(C)

Ammonia and
EtOH

Free radical

AIBN (Azobis Iso Butyro Nitrile ) ,

Peroxides
(acetyl or benzoyl
peroxide )
Free radical
(C)

Nitrobenzene / alcohols /
ketones

(i) Coupling : Dead polymer

Product

Live polymer

Dead polymer
(ii) Disproportionation :
Mixture of live and dead
polymers

Example

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PP

PVC

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LDPE

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Condensation polymerization / Stepwise polymerization

The word "condensation reaction " refers to a process in which two or more
chemicals are brought "together" (Latin "con") to form a product that is more
"dense" than the starting material. There are no distinct initiation, propagation
and termination reactions during condensation
Condensation reaction usually occurs in two steps:
i. Substitution (seldom addition)
ii. Elimination

Monomers must have at least two identical or different functional groups to

undergo condensation polymerization. Monomers condense to give polymers
and by products like H2O, HCl, MeOH etc. are formed. .
Condensation of same type of monomers (self condensation) leads to homo
polymers while the condensation of more than one type of monomer ( cross /
co- condensation) results in hetero or co polymers.

During condensation polymerization the monomers disappear (concentration

decreases) at an early stage due to the formation of low molecular weight
oligomers. The molecular weight of the polymer chain increases successively
throughout the course of reaction and is less than the integral multiple of the
monomers. The reaction time for condensation polymerization is much greater
compared to that of addition polymerization.

Examples: Nylon 6.6, Polyester, Polycarbonate.

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Copolymerization
The process of combining two or more than two types of monomers together
is called co-polymerization. Depending on the nature of the monomers
involved (saturated / unsaturated) it can be formed by addition or
condensation reaction. The product possesses different properties compared to
the monomers.

It is superior to other polymerization reactions due to its versatility. With two

types of monomers say butadiene and styrene different types of polymers with
wide spectrum of properties can be prepared.

Copolymerization is mainly carried out to vary the polymer properties such as

strength, hardness, heat resistance, crystallization tendency etc.

Example: Styrene butadiene copolymer.

Block SBR copolymer (1:3 ratio) High abrasion resistance (used for
making tyres)
Graft SBR copolymer porous and high water retention ( used as ion
exchange resin for treating water)

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Co-polymer : SBR

Co-polymer : Nylon6,6

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