POLYMERIZATION

REACTIONS

Polymerization is the
chemical process occurring
when simple molecules react
to form polymers

Polymerization occurs by
the sequential reactions of
monomers, which means
that a successive series of
reactions occurs as the
repeating units are linked
together.

This can proceed by the reaction

of monomer to form a dimer,
which in turn reacts with another
monomer to form a trimer and so
on.
Reaction may also be between
dimers, trimers, or any molecule
species within the reaction
mixture to form progressively
larger molecule.

In either case, a series of

linkages is built between the
repeating units, and the
resulting polymer molecule is
often called a polymer chain, a
description that emphasizes its
physical similarity to the links in
a chain.

Low-molecular-weight polymerization
products such as dimers, trimers,
tetramers, etc., are referred to as
oligomers. They generally possess
undesirable thermal and mechanical
properties.
A high degree of polymerization is
normally required for a material to
develop useful properties and before it
can be appropriately described a
polymer.

Example: polystyrene
DP = 7 - a viscous liquid
(not of much use)
DP > 1000 a solid commercial grade

However, there is no
demarcation has been
established between the
sizes of oligomers and
polymers.

Polymerization
mechanism

The classification of polymers depending on the

reaction involved in their formation :
a) step-reaction (condensation)
b)chain-reaction (addition)
polymerization.
These terms focus more on the manner in which
the monomers are linked together during
polymerization.

Step polymerization
(condensation)
Involves a series of reactions in which
any two species (monomers, dimers,
trimers, etc.) can react at any time
leading to a larger molecule.
Most step polymerization involves a
classical condensation reaction such
as esterification, ester interchange or
amidization.

In step polymerization, the stepwise

reaction occurs between pairs of
chemically reactive or functional
groups on the reacting molecule.
In the process, a small molecule,
usually water or ammonia, is
eliminated.

The formation of a
polyester

R and R are the unreactive part

of the molecules

Step polymerization generally

involve either one or more
types of monomers. In either
case, each monomer has at
least two reactive (functional)
groups.

A-B step polymerization

One type of monomer is involved :
the functional groups on the
monomer are different and capable
of intramolecular reactions.

Example : the formation of an aliphatic

polyester by the self-condensation of hydroxycaproic acid

A-A/B-B step polymerization

When more than one type of
molecule is involved, the
functional groups on each
type of monomer are the
same, but capable of
intermolecular reaction with
the other type of monomer.

Synthesis of Polyesters:

Other commercially important

polyesters:

Polycarbonates:

Complete the polymerization reaction

Identify the type of polymerization reaction

Polyamides:

Polyamides:

Step polymerization can be divided

into two main categories:
a) Polycondensation in which a
small molecule is eliminated at each
step
A-R-A + B-R-B A-R-R-B + AB
b) Polyaddition- monomers react
without the elimination of a small
molecule
A-R-A + B-R-B A-R-AB-R-B

Example of polyaddition
polymerization : preparation of
polyurethane
nHO-(CH2)4-OH + nO=C=N-(CH2)6-N=C=O
basic catalyst
O H
H O
|| |
| ||
O-(CH2)4-OC-N-(CH2)6-N-C

Chain polymerization
(addition)
Is an important industrial method of
polymer preparation
Polymers are produced by reactions in
which monomers are added one after
another to a rapidly growing chain.
Monomer generally employed in
addition polymerization are
unsaturated (usually with C=C).

The most common unsaturated compounds

that undergo chain reaction polymerization
are olefins, as exemplified by the following
reaction of a generalized vinyl monomer.

nCH2 = CH
|
R

-CH2-CH|
R

Examples of addition
polymers:
a)Polystyrene
b)Polyethylene
c)Polyacrylonitrile
d)poly(methyl methacrylate)
e)poly(vinyl chloride).

Chain reaction polymerization

may be classified as (depending
on the nature of the reactive
centre):
a)free-radical
b)cationic
c)anionic
d) coordination polymerization

Chain reactions, involved

three fundamental steps:
initiation , propagation and
termination

Free-radical
Polymerization
The growing polymer in chainreaction polymerization is a free
radical, and polymerization proceeds
via chain mechanism.
Chain reaction polymerization is
induced by the addition of freeradical-forming reagents.

Initiation
Involves the acquisition of an active
site by the monomer. This may occur
spontaneously by the absorption of
heat, light (ultraviolet), or high
energy irradiation.

But, most frequently, initiation of free radical

polymerization is brought about by the
addition of small quantities of compounds
called initiators such as:
a) peroxides: [Dialkyl peroxides (ROOR),
Diacylperoxides (RCO-O-O-CO-R),
hydroperoxides (ROOH)]. Example : Benzoyl
peroxide and t-butylperoxide are commonly used
free-radical initiators
b)azo compounds : [RN=NR] . Example: azobisisobutyronitrile
a) Lewis acids (AlCl3,BF3, SnCl4, SbCl5, ZnCl2,
TiCl4) and
b) organometallic reagents (RAlCl2, R2AlCl,
R Cl).

Initiators are not exactly catalyst since they changed

chemically in the course of polymerization.
An initiator usually a weak organic compound that
can be decomposed thermally or by irradiation to
produce free radicals (molecules containing atoms
with unpaired electrons).
Peroxides such as benzoyl peroxide can be
decomposed thermally between 60 and 90C. On
the other hand, azo compounds such as azobisisobutyronitrile is decomposed photochemically
(short-wavelenght visible light or near-ultraviolet
radiation).

The thermal decomposition of organic compound

is appropriate only for polymerizations carried out
at room temperature or higher.
In free-radical polymerization carried out in
aqueous medium, the decomposition of peroxides
and persulfate (K2S2O8) is generally accelerated
by the presence of a reducing agent (bisulfite ion
(from NaHSO3) or ferric ion). This method of free
radical initiation is referred to as redox initiation.
The enhance rate of free-radical formation in redox
reactions permits polymerization at relatively low
temperature. Example: emulsion polymerization

High energy irradiation (as X-rays, rays and -rays ) of monomers can be
carried out in bulk or in solution. It is
not as selective as photolytic initiation.

When choosing an initiator for free-radical

polymerization, the most important parameters that
must be considered are the temperature range to be
used for the polymerization and the reactivity of the
radicals formed.
The presence of certain promoter and accelerators
and the nature of the monomer often affect the rate
of decomposition of initiators.
Free-radical initiation processes do not require
stringent exclusion of atmospheric moisture, but can
be inhibited by substances such as oxygen. Free
radicals are inactivated by reaction with oxygen to
form peroxides or hydroperoxides.

The initiation of polymerization

occurs in 2 successive steps :

a)the formation of radicals :

I-I 2 I

O-centered radicals (oxyl radicals)

are un-stable and transformed into
relatively stable C-centered radicals

Nitrogen gas

2 C centered radicals

b) the addition of the initiator

radical to a vinyl monomer :
H
H
|
|
I + CH2=C I-CH2-C
|
|
R
R
Initiator fragments have been shown by endgroup analysis to become part of the growing
chain.

Propagation
During propagation, the initiated
monomer described above adds
other monomers - usually thousands
of monomer molecules-in rapid
succession.
This involves the addition of a free
radical to the double bond of a
monomer, with generation of
another radical.

H
H
|
|
I-CH2-C + CH2=CHR I-CH2-CH-CH2-C
|
|
|
R
R
R
The active centre is thus continuously relocated at
the end of the growing polymer chain
Propagation continues until the growing chain radical is
deactivated by chain termination or transfer

3 possible ways for the

propagation step to occur:
head to tail
H
H
H
|
|
|
I-CH2-C + CH2=CHR I-CH2-C-CH2-C
|
|
|
Tail
R
R
R
Head

The substituted carbon atom is regarded as the head

and the unsubstituted carbon atom the tail of the
vinyl monomer.

head to head
H
H H
|
| |
I-CH2-C + CH2=CHR I-CH2-C-C CH2
|
| |
R
R R

tail to tail
H
H
H
|
|
|
I-CH2-C + CH2=CHR I-C-CH2-CH2-C
|
|
|
R
R
R

A random distribution of these species

along the molecular chain might be
expected.
It is found, however, that head-to-tail
linkages in which the substituents occur
on alternate carbon atoms predominate;
only occasional interruptions of this
arrangement by head-to-head and tail-totail linkages occur.
In addition, exclusive head-to-head or
tail-to tail arrangements of monomers in
the chain are now known.

Termination
In termination, the growth activity of
a polymer chain radical is destroyed
by reaction with another free radical
in the system to produce polymer
molecule(s).

Termination can occur by the reaction of the

polymer radical with initiator radicals. This type
of termination process is unproductive and can
be controlled by maintaining a low rate of
initiation.

I-

H
|
-CH2-C + I I|
R

H H
| |
- CH2-C-C-I
| |
R R

The termination reaction that are more important in

polymer production are:
a) Combination (or coupling)
Two growing polymer chains react with the mutual
destruction of growth activity
H
I-

|
-CH2-C + C-CH2|
|
R
R

H H
-I I

| |
-CH2-C-C-CH2
| |
R R

Coupling reactions produce a single polymer

combination of growing polymer radicals predominates at
low temperature

b)
Disproportionation.
A labile atom (usually hydrogen) is transferred from
one polymer radical to another.

I-

H
H
|
|
-CH2-C + C-CH2|
|
R
R

-I IR

H H
|
|
-CH2-C-H + C=CH
|
|
R

Produce two polymers from the

two reacting polymer chain
radicals

The predominant termination reaction

depends on the nature of the reacting
monomer and the temperature.
Since disproportionation requires
energy for breaking of chemical bonds,
it should become more pronounced at
high reaction temperatures

Chain transfer
a fourth step called chain transfer is
usually involved.
In chain-transfer reactions, a growing polymer
chain is deactivated or terminated by
transferring its growth activity to previously
inactive species (TA) (monomer / polymer /
solvent molecule or other molecules
deliberately or inadvertently introduced into the
reaction mixture)

I-

H
-CH2|-C + TA I|
R

H
-CH |-C-T + A
2

|
R

 Depending on its reactivity, the new

radical, A may or may not initiate the
growth of another polymer chain:
If the reactivity of A is comparable to that
of the propagating chain radical, then a
new chain may be initiated.
If its reactivity toward a monomer is less
than that of the propagating radical , then
the overall reaction rate is retarded .
If A is un-reactive toward a monomer,
the entire reaction could be inhibited .

 Transfer reactions do not result in the

creation or destruction of radicals ; at any
instant the overall number of growing
radicals remains unchanged.
However, the occurrence of transfer
reactions results in the reduction of the
average polymer chain length, and in the
case of transfer to a polymer it may result
in branching.

Exercise 1:
Prepare a styrene polymer via radical
polymerization using benzoyl peroxide as
the initiator, head to tail propagation and
termination via
a) coupling
b) chain transfer to another polymer
c) dispropotionation

Exercise 2:
Prepare a vinyl chloride polymer via radical
polymerization using benzoyl peroxide as
the initiator (4 marks), tail to tail
propagation (3 marks). In the termination
step describe on how the following type of
PVC can be obtained:
a) A high molecular weight PVC (3 marks)
b) An un-saturated PVC (4 marks)
c) A branched PVC (6 marks)

Exercise 3:
Show the initiation steps in a
polymerization of ethylene using the
following technique:
a) Gamma rays
b) Cl2

Ionic Polymerization
The growing polymer molecule is associated
with counterions in ionic (cationic and anionic)
polymerization
Involves chain carriers or reactive centers that
are organic ions or charged organic groups.
The mechanism of ionic polymerization is more
complex and is not as clearly understood as
those of free radical polymerization.
Initiation of ionic polymerization usually
involves the transfer of an ion or an electron
TO or FROM the monomer

Cationic Polymerization
In cationic polymerization, the growing chain
end carries a positive charge or carbonium
(carbenium) ion.
Monomers with electron donating groups like
isobutylene form stable positive charges and
are readily converted to polymers by cationic
catalyst.
Any strong lewis acid (AlCl3,BF3, SnCl4, SbCl5,
ZnCl2, TiCl4) or Friedal-Crafts catalyst such as
AlCl3 can readily initiate cationic polymerization
in the presence of cocatalyst like water which
serve as a Lewis Base or source of protons.

During initiation
a proton adds to the monomer to form a
carbonium ion, which forms an
association with the counterion.
Example :
isobutylene and boron
trifluoride

First, the catalyst and

cocatalyst (e.g. water)
form a complex:
BF3 + H2O H+(BF3OH)-

The complex then donates a

proton to an isobutylene
molecule to form a carbonium
ion:

Propagation
involves the consecutive additions of
monomer molecules to the carbonium ion
at the growing chain end :

 Since cationic polymerization is generally carried

out in hydrocarbon solvents that have low
dielectric constant, separation of the ions would
require a large amount of energy.
Consequently, the anion and cation remain in
close proximity as an ion pair.
Therefore, the growth rate and subsequent
reaction (termination) are affected by the nature
of the ion pair. If the intimate association of the
ion pair is too strong, however, monomer
insertion during propagation will be prevented

Termination
a)

Rearrangement to produce a polymer

with an unsaturated terminal unit and
the original complex

2. Chain Transfer (to a monomer).

 Cationic polymerization are usually conducted in

solutions and frequently at temperatures as low as -80
to - 100C .
Polymerization of isobutylene (IB) was studied using
the 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4/2,6
-di-tert-butylpyridine (DTBP) system in hexane
(Hex)/methyl chloride (MeCl) at -25 to -80C
Therefore, the choice of solvent has to be made
carefully; a linear increase in polymer chain length an
exponential increase in the reaction rate usually occur
as the dielectric strength of the solvent increases.
Polymerization rates at these low temperatures
conditions are usually fast

Exercise:
Prepare poly(methyl methacrylate) via
cationic polymerization using AlBr3 as
the initiator and BrC(CH3)3 as the co
initiator. Show the termination step by:
a) chain transfer to a monomer
b) rearrangement

Exercise 2:
Explain the following:
a) It is difficult to separate the ion pair of
the propagating species in cationic
polymerization.
b) The choice of solvent to conduct
cationic polymerization is crucial
c) The rate of reaction of a cationic
polymerization usually very fast

Anionic Polymerization
In anionic polymerization, the growing chain
end carries a negative charge or carbanions .
Monomers that are suitable for ionic
polymerization generally contain electronwithdrawing substituent groups such as CN,
-COOR, -C6H5, -CH=CH2. The
electronegative group pulls electrons from the
double bond and consequently renders the
monomer susceptible to attack by an electron
donor.

Initiations
involves the addition of the initiator
to the double bond of the monomer.
The initiator may be any compound
including Grignard reagents (RMgBr), organosodium compounds
(NaOCH3), alkali metal amides
(LiN(CH3H7)2
,
alkoxide
and
hydroxides (OH).
Initiation may occur in two ways:

a) direct attack of a base

on the monomer to form a
carbanion

b)
transfer of electron from
a donor molecule to the
monomer to form an anion
radical:

 The reaction produces a carbanion at the head

end to which is associated the positively
charged counterion.
M+B- may be a metal amide, alkoxide, alkyl,
aryl and hydroxide depending on the nature of
the monomer.
The effectiveness of the catalyst in the initiation
process depends on its basicity and the acidity
of the monomer. For example, in the anionic
polymerization of styrene, the ability to initiate
reaction decreases in the order
-CH2- - NH2- > NH2- >> OH-. Indeed OH- will
not initiate anionic polymerization of styrene.

TWO EWGs are so effective in stabilizing anions. Therefore, weak base

such as water can initiate this monomer

EGW = Electron Withdrawing Group

Propagation
occurs by the successive insertion of
monomer molecules by anionic attack of
the carbanion.
No chain transfer or branching occurs in
anionic polymerization, particularly if
reactions are carried out at low
temperature:

Termination
of the growth activity of the polymer
chain takes place either by the
deliberate or accidental introduction
into the system of oxygen, carbon
dioxide, methanol, water or other
molecules that are capable of
reacting with the active chain ends.

 In general, termination by transfer to the

solvent predominates in anionic
polymerization.
In ionic as well as free-radical
polymerization, the initiator or part of it
becomes part of the resulting polymer
molecule, attached to the non-growing
chain end. Unlike cationic polymerization,
the catalyst is regenerated at the
termination step.

Living polymerization
In some anionic polymerization system,
termination can be avoided if the starting
reagents are pure and the polymerization reactor
is purged of all oxygen and traces of water.
This produces polymer molecules that can
remain active even after all the monomer
molecules are consumed. When fresh monomer
is added, polymerization resumes.
Such polymeric molecules are referred to as
living polymers because of the absence of
termination.

MW in living polymerization
:
Since the chain ends grow at the same rate ,
the molecular weight of living polymer is
determined simply by the ratio of monomer
concentration to that of the initiator:
DP = [monomer] / [initiator]
The MW is predictable
Polymers produced by living polymerization are
characterized by very narrow molecular weight
distribution. The polydispersity, D (approaches
1, typically 1.05-1.2)

Block Copolymerization
The absence of termination in living
polymerization permits the synthesis of
unusual and unique block polymers.
If a living polymer with one active end
from monomer A can initiate the
polymerization of monomer B, then an AA-B-B type copolymer can be obtained
(e.g. styrene-isoprene copolymer)

 If both ends of polymer A are active, a

copolymer of the type B-BA-AB-B results.
(e.g. polystyrene-polyisoprenepolystyrene)

Functionalization of the
Chain Ends
Living polymerization can also be
employed to introduce a variety of
desired functional groups at one or both
ends of polymeric chains both in homoand block polymers.

Carboxylation of end groups:

Alcohol end groups via ethylene oxide:

 In particular, living polymerization

techniques provide a vital and versatile
tool to control the architecture of a
polymer; complicated macromolecules
can be synthesized to meet the rigid
specification imposed by a scientific or
technological demand.
However, the reactive end groups in
living polymerization may be annihilated
by a choice of suitable reactants by the
experimenter at a desired stage of the
polymerization process.

EXERCISE 1:
Explain the following:
a) CH3ONa is un able to initiate MMA
b) Is it possible to initiate polycyanoacrylate using
water? Explain?
c) Write the polymerization mechanism of
polyacrylonitrile using butyl lithium:
i) with termination in the presence of CO2
ii) termination by proton transfer
iii) without termination
a) Explain the polymer that is obtained in c(iii)
b) Differentiate between anionic, cationic and radical
polymerization

Example 2:
Prepare a polyacrylonitrile polymer via anionic
polymerization using n-butyllithium as an
initiator.
a) Describe the initiation of the polymerization
by transfer of electron and termination by the
addition of water.
b) If the above polymerization takes place in an
inert condition whereby oxygen and traces of
water are purged out from the reactor; state:
i) the type of polymer that is produced
ii) the advantages of preparing this type of
polymerization process
iii) the carboxylation of end group

Exercise 3:
Synthesis the following polymer:
CH3(CH2)3-(CH2CH(C6H5))n-(CH2)5OH

Exercise 4:
Prove that a branched polymer of PVC can
be obtained from the free radical
polymerization of PVC

Coordination
Polymerization

the mechanism of coordination polymerization

is also complex and are not clearly understood
Coordination polymerization may be anionic or
cationic.
Relatively fewer examples of cationic
coordination polymerization leading to the
formation of stereo regular polymers currently
exists. These are limited almost exclusively to
the polymerization of monomers containing
heteroatoms with lone pair electrons such as
oxygen or nitrogen.

 In any case, the growth reaction in

coordination polymerization is considered
to be controlled by the counterion of the
catalysts, which first involves the
formation of a coordination compound
between the catalyst, monomer and
growing chain.
The polarized double bond of the
monomer is inserted in the polarized
bond between the counter ion and the
end of the growing chain.

 Coordination involves the overlap of the

electrons of the monomer with a vacant
sp orbital in the case of groups I-III
metals or a vacant d orbital in the case of
transition metals

A typical catalyst complex is

formed by trialkyl aluminum and
titanium trichloride

The catalysts function by forming transient -complexes

between the monomers and the transition metal species.

initiating
The initiating species is a metal-alkyl
complex

Propagation
involves the consecutive insertion of
monomer molecules into a polarized
titanium-carbon bond.
The proposed
propagation mechanisms for both the
monometallic and bimetallic catalyst are
shown below:

Termination
by introducing poisons such as water,
hydrogen, aromatic alcohols, or metals
like zinc into the reacting system.

 Monomers with side groups asymmetrically

disposed with respect to the double bond are
capable of producing polymers in which the side
groups have a specific stereochemical or spatial
arrangement (isotactic or syndiotactic).
Unbranced and stereospecific polymers are
produced by the use of Ziegler-Natta catalyst.
These are complex catalyst systems derived
from a transition metal compound from groups
IVB to VIIIB of the periodic table and an
organometallic compound usually from a group
IA or IIIA metal.
Monoolefins such as propylene and dienes such
as butadiene and isoprene can be polymerized
using Ziegler-Natta coordination catalysts.

Example:

i) Show the polymerization of PVC by

coordination polymerization using Z-N
[Al(CH2CH3)3 and TiCl4] catalyst by
a) monocatallic using the d orbital as the
overlapping orbital.
b) bimetallic
ii) Show the termination step by :
a) chain transfer
b) addition of water
iii) Name the stereoisomerism of PVC obtained
from this type of polymerization.

Step polymerization

Chain polymerization

Any two molecular species can react.

Growth occurs only by addition of

monomer to active chain end

Monomer disappears early.

Monomer is present throughout, but its

concentration decreases.

Polymer MW rises throughout.

Polymer begins to form immediately.

Growth of chains is usually slow Chain growth is usually very rapid

(minutes to days).
(second to microseconds).
Long reaction times increase MW, but
yield of polymer hardly changes.

MW and yield depend on mechanism

details.

All molecular species are present

throughout.

Only monomer and polymer are

present during reaction.

Usually (but not always) polymer Usually (but not always) polymer
repeat unit has fewer atoms than had repeat unit has the same atoms as had
the monomer.
the monomer