Anirudh Balasubramanian BT17CME011

Bhavesh Sarode BT17CME020

Eashan Bhat BT17CME025
Ojas Hanwat BT17CME045
Pranav Gadhave BT17CME051

Polymer Processing Assignment-1

A) Polymerization reaction mechanism and its types

I) Addition Polymerization
1) Free Radical Polymerization
In free radical polymerization there is successive addition of free radical
monomer units which is initiated by various mechanisms leading to the
formation of a polymer.
The mechanism of free radical polymerization is as follows:
An active free radical species is formed by thermal or photochemical
decomposition of organic peroxides, hydroperoxides, azo and diazo
compounds.
It then attacks a monomer molecule which has a double bond leading to the
formation of a new free radical.
The polymer chain continues to grow as monomers get consumed.
This growth of chain is stopped either when two chains combine with each
other or a chain transfers a hydrogen radical to other chain.
2) Ionic Polymerization
In ionic polymerization there is successive addition of ionic (cationic or
anionic) monomer units which is initiated by various mechanisms leading to
the formation of a polymer.
Ionic polymerization is of two types based on the type of charge on the
monomer units; cationic polymerization and anionic polymerization.
The mechanism of cationic polymerization is as follows:
Cationic polymerization is generally initiated by a carbocation which is
formed in the presence of a strong proton donor (acids).
The chain propagation is terminated when a proton transfer occurs from the
main chain to a monomer molecule which can reinitiate polymerization again.

The mechanism of anionic polymerization is as follows:

Anionic polymerization is generally initiated by a carbanion which is generally
formed by organolithium compounds.
The chain propagation can be terminated by adding a proton donor like an
alcohol or the reaction will proceed till all the monomer is consumed.
3) Coordination Polymerization
In coordination polymerization there is successive addition of monomer units
which is catalysed by transition metal salts and complexes leading to the
formation of a polymer.
The mechanism of coordination polymerization is as follows:
The catalyst forms a complex with a monomer molecule and chain
propagation continues till all the monomer units are exhausted or an active
hydrogen is introduced.
II) Addition Polymerization
1) Polyaddition Polymerization
In polyaddition polymerization there is successive addition of functional
groups inside of molecular structures with double bonds which is initiated by
various mechanisms leading to the formation of a polymer.
The mechanism of coordination polymerization is as follows:
Two functional groups of different monomers undergo addition after initiated
by heat or any other agent.
The newly formed intermediate starts polymerisation with one of the
monomers which ends when all the monomer units are exhausted.

2) Polycondensation Polymerization
In polycondensation polymerization there is successive addition of functional
groups inside of molecular structures with double bonds which is initiated by
various mechanisms leading to the formation of a polymer and condensed
molecule for each bond.
The mechanism of coordination polymerization is as follows:
The reaction starts by the transfer of proton followed by the condensation of
the two different monomers which yields a chain of polymer and a condensed
molecule.
3) Ring Opening Polymerization
In ring opening polymerization there is successive addition of cyclic
monomers at terminal end of a polymer chain which is initiated by various
mechanisms.
The mechanism of coordination polymerization is as follows:
The reaction starts when nucleophile attacks the cyclic compound leading to
the formation of anion.
Monomer units attack this new nucleophile leading to the formation of a
chain.

The reaction can also start when electrophile attacks the cyclic compound
leading to the formation of cation.
Monomer units attack this new electrophile leading to the formation of a
chain.
B) Industrial preparation of polymer techniques
I) Bulk Polymerization
Bulk Polymerization is a homogenous polymerization which is done by adding
a soluble radical initiator to pure monomer in liquid state.
The reaction is started by heating or exposing to radiation. As the reaction
proceeds the mixture becomes more viscous. The reaction is exothermic and a
wide range of molecular masses are produced.
This method is used for most step-growth polymers and many types of chain-
growth polymers such as Polystyrene, Polyurethanes, Polycaprolactam (Nylon
6,6), Polycarbonates and Polyester (PET), etc.

Bulk Polymerization of Styrene

II) Solution Polymerization
Solution Polymerization is a homogenous polymerization which is done by
adding a radical initiator and monomer in a solvent in liquid state.
The reaction is started by heating or exposing to radiation. As the reaction
proceeds the mixture becomes more viscous. The reaction is exothermic and a
wide range of molecular masses are produced.
This method is used for chain-growth polymers such as Polyacrylonitrile (PAN),
Polyacrylic acid (PAA), Polyethylene, etc.

Solution Polymerization of Polyvinyl acetate

III) Suspension Polymerization
Suspension Polymerization is a heterogenous polymerization which is done by
adding monomer and initiator in liquid state in an immiscible solvent like water.
Suspension polymerization is of two types:
i) In bead polymerization, the polymer is soluble in its monomer and the
result is a smooth, translucent bead.
ii) In powder polymerization, the polymer is not soluble in its monomer and
the resultant bead will be porous and irregular.
This method is used in the production of many commercial resins such as
polyvinyl chloride (PVC), poly(styrene-acrylonitrile), poly(methyl methacrylate),
etc.

Suspension Polymerization of Polyvinyl chloride

IV) Emulsion Polymerization
Emulsion Polymerization is a heterogenous polymerization which is done by
adding monomer and initiator in liquid state in an immiscible solvent like water
along with surfactants.
A common type of this process is an oil-in-water emulsion where monomer (oil)
is emulsified with surfactants in water. The polymerization takes place in the
colloid particles that are formed in the process. The particles are prevented from
coagulating with each other because of the surfactants.
This method is used to make various rubbers and plastics like Styrene-
butadiene rubber, Nitrile rubber, Acrylic rubber, Polyvinyl fluoride, PTFE, etc.

Emulsion Polymerization of Polyvinyl fluoride

C) Molecular weight of polymers
Let Ni be the number of molecules with weight Mi,
∞

Total number of molecules = ∑ Ni

i=1
∞

Total weight of molecules = ∑ Ni Mi

i=1

I) Number average molecular weight (MN)

The number average molecular weight is defined as the total weight of polymer
divided by the total number of molecules.
It is given by,
∞
Ni Mi
̅̅̅̅
M N =∑
Ni
i=1

and can also be written as,

∞
̅̅̅̅
M N = ∑ x i Mi
i=1

where xi is the mole fraction of polymer with weight Mi.

II) Weight average molecular weight (MW)

The weight average molecular weight is defined as the second power of total
weight of polymer divided by the total weight of the polymer.
It is given by,
∞
Ni Mi 2
̅̅̅̅̅
MW = ∑
Ni Mi
i=1

and can also be written as,

∞
̅̅̅̅̅
MW = ∑ wi Mi
i=1

where wi is the weight fraction of polymer with weight Mi.

III) Viscosity average molecular weight (MV)

The viscosity average molecular weight is defined as the intrinsic viscosity
exponent in the power of total weight of polymer divided by the total weight of
the polymer.
It is given by,
1
∞ 1+a a
Ni Mi
̅̅̅̅
MV = ∑ [ ]
Ni Mi
i=1
The Staudinger-Mark-Houwinks equation is,
[η] = k M a
where [η] is intrinsic viscosity
k is a constant for a polymer solution
M is the molecular weight
a is the exponent
From the above equation a can be calculated for known value of viscosity which
helps to determine molecular weight.