POLYMER Chemistry

Addition, condensation and co polymerization, mechanism of addition and

condensation polymerisation

By
Dr.M. Sarojadevi, Professor
Department of Chemistry
Anna University, Chennai-600025
E.Mail: msrde2000@yahoo.com
 Homopolymers
PE,PP,PS

A single kind of repeat nM1 → ---M1M1M1M1M1M1M1M1M1M1M1M1--

unit is involved

-NH-R-CO- Self-reaction
-CO-R-CONH-R’-NH- of an amino
Acid or ring opening
of lactums

poly(ε-caprolactam)
Nylon 6/6 Nylon 6/10
Hexamethylene diamine Hexamethylene diamine
with with
Adipic acid Sebacic acid
 Copolymers

Two different repeat

units are involved

-CO-R-CONH-R’-NH-CO-R’’-CONH-R’’’-NH-
M1 + M2 → ---M1M2M1M2M1M2M1M2M1M2M1M2---

-NH-R-CO-NH-R’’-CO

HO2C-R-CO2H & HO2C-R’’-CO2H

Ethylene–vinyl acetate (EVA)
+
H2N-R’-NH2 & H2N-R’’’-NH2 styrene + 1,3-butadiene
Reaction between
two different amino
acids
Carothers [1929] classified Polymers into condensation and addition polymers on the
basis of Compositional difference between the polymer and the monomer(s)

Condensation Polymers
Were formed from polyfunctional monomers by the various condensation reactions of
organic chemistry with the elimination of some small molecule such as water
Polyamides

Polycarbonates
Typical Condensation Polymers
 Typical Addition Polymers

Addition polymers

Were classified by Carothers as

those formed from monomers
without the loss of a small molecule

The repeating unit has the same

composition as the monomer

Majority of them are formed by

polymerization of monomers
containing the carbon – carbon
double bond -Vinyl monomers

nCH2=CHY → -(-CH2-CHY-)n-
In summary

A polymer is classified as a condensation polymer if

Its synthesis involves the elimination of small molecules, or

It contains functional groups as part of the polymer chain, or

Its repeating unit lacks certain atoms that are present in the
(hypothetical) monomer to which it can be degraded.

If a polymer does not fulfill any of these requirements, it is

classified as an addition polymer.
Flory [1953] stressed the very significant difference in the
mechanism by which polymer molecules are built up

More recent terminology classifies polymerizations into step

and chain polymerizations

Chain and step polymerizations differ in several features

The identities of the species that can react with each

other

The manner in which polymer molecular size depends on

the extent of conversion

Step polymerizations proceed by the stepwise reaction

between the functional groups of reactants
 Step Polymerization: One Step at a Time

One proceeds from monomer to dimer, trimer,tetramer, pentamer, and so on

Monomer + monomer → dimer

Dimer + monomer → trimer
Dimer + dimer → tetramer
Trimer + monomer → tetramer
Trimer + dimmer → pentamer
Trimer + trimer → hexamer
Tetramer + monomer → pentamer
Tetramer + dimer → hexamer
Tetramer + trimer → heptamer
Tetramer + tetramer → octamer

The size of the polymer molecules increases at a relatively slow pace in such
polymerizations
Reaction occurs between any of the different-sized species present in the
reaction system
Chain (addition)polymerization
An initiator is used to produce an initiator species R* with a reactive center
The reactive center may be either a free radical, cation, or anion
Polymerization occurs by the propagation of the reactive center by the
successive additions of large numbers of monomer molecules in a chain reaction.
The polymer growth takes place by monomer reacting only with the reactive
center
Each monomer molecule that adds to a reactive center regenerates the reactive
center.
Monomer does not react with monomer and the different-sized species such as
dimer, trimer, tetramer, and n-mer do not react with each other.
The growth of the polymer chain ceases when the reactive center is destroyed by
one or more of a number of possible termination reactions
The most common example of chain polymerization is that of vinyl monomers
 DIFFERENCES BETWEEN ADDITION AND
CONDENSATION POLYMERIZATION
ADDITION CONDENSATION
Monomers add on to give a Monomers condense to give
polymer and no other by a polymer and byproducts
product is formed. such as H2O, CH3OH are
formed.
Number of monomeric Monomers disappear at the
units decreases steadily early stage of the reaction.
throughout the reaction.
High molecular weight Polymer molecular mass
polymer is formed at once. rises steadily throughout the
reaction.
Both thermosetting and thermoplastic polymers can be made by Condensation
and addition polymerisations
 FREE RADICAL MECHANISM

 Generally neutral or moderately e- withdrawing or e-

donating groups attached to ethylene undergo free
radical polymerization.
 INITIATION (INVOLVES TWO STEPS)
(1) Production of free radicals

O O O

Ph C O O C Ph 2 Ph C O

2)Addition of freeradical to the first monomer

molecule
O O
H2
Ph C O + H2C CH Ph C O C CH
X X
 PROPAGATION STEP

O O
H2 H2 H H2
Ph C O C CH + H2C CH Ph C O C C C CH

X X X X

O
H2 H H2
Ph C O C C C CH + H2C CH
n
X X X

O
H2 H H2
Ph C O C C C CH
n+1
X X
 TERMINATION 1.
1.DIMERISATION 2.
3.
O 4 O
H2 H H2 H2 H H2
Ph C O C C C CH + HC C C C O C Ph
n X X n
X X

O
O
H2 H H2 H H2 H H2
Ph C O C C C CH C C C C O C P
h
X X
X X
 2.DISPROPORTINATION

H
O O
H2 H H2 H H2
Ph C O C C C CH + HC C C C O C Ph
n H n
X X
X X

O
H2 H2 O
H H H2
Ph C O C C C CH2 + HC C C C O C Ph
n H n
X X X X
 Cationic Polymerisation
Monomers

Initiators
Strong protic acids - Phosphoric, sulfuric, fluoro-, and
triflic acids

Lewis acids/Friedel-Crafts - SnCl4, AlCl3, BF3, and TiCl4

catalysts
Mechanism

Initiation
Propagation
The initiator ion pair (consisting of the carbocation and its negative
counterion) produced in the initiation step, proceeds to propagate by
successive additions of monomer molecules
Chain transfer to monomer

1. transfer of a β-proton to monomer with the formation of terminal unsaturation in the polymer.

2. Hydride ion transfer from monomer to the propagating center

 Termination

Chain transfer to counterion - spontaneous termination - transfer of a β-

proton to the counterion. The initiator is regenerated - the polymer
molecule has a terminal double bond
Termination by Combination with Counterion
combination of the propagating center with the
counterion
ANIONIC POLYMERIZATION OF THE CARBON–CARBON DOUBLE BOND

The propagating species are anionic

Termination occurs by transfer of a positive fragment, usually a proton, from the

solvent or some transfer agent (often deliberately added), although other modes of
termination are also known. Many anionic polymerizations are living
polymerizations when the reaction components are appropriately chosen.

Basic (nucleophilic) initiators covalent or ionic metal amides such as

NaNH2 and Li N (C2H5)2 , alkoxides, hydroxides, cyanides,
phosphines, amines, and organometallic compounds such as n-
C4H9Li and PhMgBr
THANK YOU