Mechanism & Applications of

Polymerization in Aromatic
compounds
Dr. Muhammad Tahir Saddique
Assistant Professor (Chemistry)
Department of Applied Sciences
 Contents
Introduction to Polymers
Mechanism of Polymerization reactions
Applications of Polymerisation
 Polymers
Polymer is a large molecule composed of many smaller
repeating units(the monomers) bonded together.
Classes of Syntheyic Polymers
The two major classes of synthetic polymers are chain
growth polymers and step growth polymers. In chain
growth polymerization, elongation of chain takes place
only at the end of chain. This occurs by rapid addition
of one monomer at a time to a reactive intermediate
(cation, radical or anion) at growing end of chain.
Chain growth polymers are usually addition
 Classes of Syntheyic Polymers
polymers, which result from monomers adding together
without the loss of any molecules. Monomers of chain
growth polymerization are commonly alkenes and
polymerization involves successive additions across the
double bonds. Poly(vinyl chloride), widely used as
[ H ]
  
synthetic leather, is a chain growth addition polymer
that is often made by free-radical polymerization.
In a step growth polymerization, any two monomers
having the correct functionality can
Classes of Syntheyic Polymers
 Classes of Syntheyic Polymers
react with each other, or two polymer chains can
combine. Most step growth polymers are
condensation polymers bonded by some kind of
condensation (bond formation with loss of a small
molecule) between the monomers or polymer
segments. The most commen condensation
involve the formation of amides and esters.
Dacron polyester is an example of step-growth
condensation polymer.
 Chain Growth Polymers
Many alkenes undergo chain-growth polymerization
when treated with small amounts of suitable initiators.
The products are addition polymers, resulting from
repeated additions across the double bonds of the
monomers. The chain growth mechanism involves
addition of reactive end of growing chain across the
double bond of the monomer. Depending on the
monomer and initiator used, the reactive intermediates
may be free radicals, carbcations or carbanions.
Most Important Addition Polymers
 Free radical Polymerization
It results when a suitable alkene is heated with a
radical initiator. For example styrene polymerizes
to polystyrene when it is heated to 100 oC.
Mechanism of Free radical Polymerization
 Polymeization
Polymerization is a process through which a
large number of monomer molecules react
together to form a polymer. The macromolecules
produced from a polymerization may have a
linear or a branched structure. They can also
assume the shape of a complex, three-
dimensional network. There exist several
different categories of polymerization reactions,
the most notable of which being step-growth
polymerization, chain-growth polymerization
 Polymerization
(both of which fall under the category of addition
polymerization), and condensation polymerization.
A polymer is a substance that is made up very large
molecules that are, in turn, made up of many repeating
units called monomers. Polymerization is the process
through which these monomers come together to form
the macromolecules that constitute polymers. An
illustration detailing the polymerization of the
monomer styrene into the polymer known as
polystyrene is provided below.
Polymerization in Styrene
 Polymerization
Depending on the functional groups present in the
reacting monomers, the complexity of the
mechanism of the polymerization reaction may
vary. The most simple polymerization reactions
involve the formation of polymers from alkenes
via free-radical reaction. Polyethylene, which is
one of the most commercially important polymers,
is prepared via such a polymerization process (the
reactant monomer used here is ethylene).
It can be noted that polymerizations involving
 Polymerization
only one type of monomer are called homopolymerizations
whereas those involving more than one type of monomer are
called copolymerization processes. Polymerization in the
simplest form can be described as a chemical process that
results in the formation of polymers. Polymerization as the
process of creating polymers. When polymerization occurs,
the smaller molecules which are known as monomers via
chemical reaction are combined to form larger molecules. A
collection of these large molecules form a polymer. The term
polymer in general means “large molecules” with higher
molecular mass. They are also referred to as macromolecules.
 Polymerization
These monomers add together to form a long
chain to form a product with specific properties.
This whole process of formation of polymers is
polymerization. Polythene and Nylon 66 are
some examples of polymers.
 Condensation Polymerization
In condensation polymerization, the formation of
the polymer occurs when there is a loss of some
small molecules as byproducts through the
reaction where molecules are joined together. The
byproducts formed may be water or hydrogen
chloride. Polyamide and proteins are examples of
condensation polymers.
Some of the different types of condensation
polymerization are given below
 Polyamides
They are synthetic fibres and are called as nylons. These
polymers have an amide linkage between them. Condensation
polymerization of di-amines with di-carboxylic acid and also of
amino acids and their lactams will create a polyamide.
Nylon 66: This polymer is prepared under the condition of high
pressure and temperature by the condensation polymerization of
hexamethylenediamine with adipic acid.
Nylon 6: Prepared by heating of caprolactam with water under
high temperature. It is used for tyre cords, fabrics and ropes.
 Polyesters
When dicarboxylic acids and diols undergo
polycondensation, polyesters are formed.
Prepared by heating a mixture of terephthalic
acid and ethylene glycol at 460 k by using zinc
acetate antimony trioxide as a catalyst. Dacron
or terylene are the best-known examples for
polyesters. And also they are used for glass
reinforcing materials in safety helmets.
Phenol-Formaldehyde Polymerization
These are obtained by condensation polymerization of
phenol with formaldehyde in the presence of either an
acid or base as a catalyst.
Phenol-Formaldehyde Polymerization
Novolac on heating with formaldehyde undergoes
crosslinking and forms an infusible sold mass
named as Bakelite. They are used for combs,
electric switches and phonograph records.
Melamine – Formaldehyde Polymer
It is formed by the condensation polymerization of
melamine and formaldehyde in certain conditions.
They are used for the manufacture of unbreakable
crockery.
Polymeriztion in 2,7- Dimethylpyrene
(DMPY)
 Polymeriztion in 2,7- Dimethylpyrene
(DMPY)
First, methyl transfer is identified as a major reaction
pathway by examining the resolved monomers. The
observation of many isomers of methylpyrenes (1–11),
including unsubstituted pyrene (1), indicates methyl
transfers or migrations. Substituted methyl groups are
scrambled on pyrene and are different from their original
2,7-positions. Dealkylation is evident based on structures
1–3 by the loss of one or both methyls. Transfer of methyls
occurs both intra- and intermolecularly, evidenced by
structures 8–11, which contain 3–4 methyls. Methyl
transfers are evidently predominant in fused products as
well.
 Polymeriztion in 2,7- Dimethylpyrene
(DMPY)
Second, the coupling or condensation reaction is evident from
dimer products. Several types of dimerization can be
identified by examining their molecular structures. (a) Most
of the dimer products can be considered as a direct coupling
between two pyrene units via an aromatic hexagonal ring, and
this accounts for about half of the dimers (12–18, 21). The
sites of fusion in product structures are different from the
original substitution positions (ipso) of methyl groups. Direct
coupling via an aromatic five-membered ring is observed in
only one molecule (22), suggesting that this coupling is
infrequent. Surprisingly, the anticipated predominant
 Mechanism of Polymerization
( Mechanism of Polymerization. Generally,
polymerization consists of three steps which
include initiation, propagation, and
termination. As for the reaction mechanism,
the process of polymerization mainly
involves two different methods. These
include the step-growth mechanism and
chain-growth mechanism.
Mechanism of Polymerization
Different Types of Polymeriztion
Homopolymers: These polymers are formed by
the polymerization of single monomeric species,
e.g. formation of polythene from ethene as: nCH 2
= CH2 → (CH2-CH2)
Copolymers: These polymers are formed by the
polymerization of two different monomers, e.g.
formation of buna-S from styrene and buta-1,3-
diene
 Important Steps in Polymerization
Step-growth polymerization refers to a type of
polymerization mechanism in which bi-
functional or multifunctional monomers react to
form first dimers, then trimers, longer oligomers
and eventually long chain polymers.
 Applications of Polymerization
Clothing, floor coverings, garbage disposal bags,
and packaging are other polymer applications.
Automobile parts, windshields for fighter planes,
pipes, tanks, packing materials, insulation, wood
substitutes, adhesives, matrix for composites,
and elastomers are all polymer applications used
in the industrial market.
 Mechanism of Polymeriztion in 1,5-
Naphthyridine
Hydrogenated carbon nitride is synthesized by polymerization of
1,5-naphthyridine, a nitrogen-containing heteroaromatic
compound, under high-pressure and high-temperature conditions.
The polymerization progressed significantly at temperatures above
573 K at 0.5 GPa and above 623 K at 1.5 GPa. The reaction
temperature was relatively lower than that observed for pure
naphthalene, suggesting that the reaction temperature is
considerably lowered when nitrogen atoms exist in the aromatic
ring structure. The polymerization reaction largely progresses
without significant change in the N/C ratio. Three types of
dimerization are identified; naphthylation, exact dimerization, and
dimerization with hydrogenation as determined from the gas
chromatograph–mass spectrometry analysis of soluble products.
Infrared spectra suggest that hydrogenation products were likely to
be formed with sp3 carbon and NH bonding.
Mechanism of Polymeriztion in 1,5-
Naphthyridine
 Polymerization in β- Pinene

polymerization mechanism involving a reaction

between Lewis acid and water, followed by the
protonation of the pinene molecule. The
carbenium ion rearranges to form a p-
menthane-type carbocation responsible for the
propagation reaction. This process is extremely
rapid and highly exothermic.
Polymerization in β- Pinene
 Radical Polymerization

The transformation of cationic polymerization to ATRP

is utilization of PSt with chlorine termini, synthesized by
living cationic polymerization without any additional
reaction, in ATRP of St, MMA, and MA
Radical Polymerization