Classification of Polymers

The word ‘Polymer’ is coined from two Greek words: poly means many and mer means
unit or part. The term polymer is defined as very large molecules having high molecular mass.
These are also referred to as macromolecules, which are formed by joining of repeating structural
units on a large scale. The repeating structural units are derived from some simple and reactive
molecules known as monomers and are linked to each other by covalent bonds. This process of
formation of polymers from respective monomers is called polymerization. The transformation of
ethene to polythene and interaction of hexamethylene diamine and adipic acid leading to the
formation of Nylon 6, 6 are examples of two different types of polymerisation reactions.

There are several ways of classification of polymers based on some special considerations.
The following are some of the common classifications of polymers:

Classification Based on Source: [1] Natural Polymers: These polymers are found in
plants and animals. Examples are proteins, cellulose, starch, resins and rubber.
[2] Semi-synthetic Polymers: Cellulose derivatives as cellulose acetate (rayon) and cellulose
nitrate, etc. are the usual examples of this sub category. [3] Synthetic Polymers: A variety of
synthetic polymers as plastic (polythene), synthetic fibres (nylon 6,6) and synthetic rubbers
(Buna - S) are examples of man-made polymers.

Classification Based on Structure of Polymers: [1] Linear Polymers: These polymers

consist of long and straight chains. The examples are high density polythene,
polyvinyl chloride, etc. [2] Branched Polymers: These polymers contain linear chains having
some branches, e.g., low density polythene. [3] Cross-linked Polymers: These are usually formed
from bi-functional and tri-functional monomers and contain strong covalent bonds between
various linear polymer chains, e.g. vulcanized rubber, urea-formaldehyde resins, etc.

Linear Polymers Branched Polymers Cross-linked Polymers

1
 Homopolymer: A polymer resulting from the polymerization of a single monomer;
a polymer consisting substantially of a single type of repeating unit.

Copolymer: When two different types of monomers are joined in the same polymer chain,
the polymer is called a copolymer.

Let's imagine now two monomers, which we'll call A and B. A and B can be made into a
copolymer in many different ways.

When the two monomers are arranged in an alternating fashion, the polymer is called an
alternating copolymer.

In a random copolymer, the two monomers may follow in any order.

In a block copolymer, all of one type of monomers are grouped together, and all of the
other are grouped together. A block copolymer can be thought of as two homopolymers
joined together at the ends:

Branched copolymers with one kind of monomers in their main chain and another kind of
monomers in their side chains are called graft copolymers.

Alternating
Random
Block

Graft

Copolymerization: A heteropolymer or copolymer is a polymer derived from two (or

more) monomeric species, as opposed to a homopolymer where only one monomer is used.
Copolymerization refers to methods used to chemically synthesize a copolymer. Commercially
relevant copolymers include ABS plastic, SBR, Nitrile rubber, styrene-acrylonitrile, styrene-
isoprene-styrene (SIS) and ethylene-vinyl acetate.
2
 Tacticity: The orientation of monomeric units in a macromolecule can take an orderly or
disorderly fashion with respect to the chain.

If all the side groups lie on the same side of the chain (cis arrangement), it is called an
‘isotactic’ polymer, e.g., natural rubber

If the monomers have entered the chain in a random fashion, it is called an ‘atactic’
polymer, e.g., polypropylene.

If the arrangement of side groups is in alternating fashion (trans arrangement), it is called a

‘syndiotactic’ polymer, e.g., Guttapercha

Isotactic

Atactic

Syndiotactic

Classification Based on Mode of Polymerisation: Polymers can also be classified on the

basis of mode of polymerisation into two sub groups; (a) Addition Polymers and
(b) Condensation Polymers.

Addition Polymers: The addition polymers are formed by the repeated addition of
monomer molecules possessing double or triple bonds, e.g., the formation of polythene from
ethene and polypropene from propene. However, the addition polymers formed by the
polymerisation of a single monomeric species are known as homopolymer, e.g., polythene.

The polymers made by addition polymerisation from two different monomers are termed
as copolymers, e.g., Buna-S, Buna-N, etc.

3
 Condensation Polymers: The condensation polymers are formed by repeated
condensation reaction between two different bi-functional or tri-functional monomeric units.
In these polymerisation reactions, the elimination of small molecules such as water, alcohol,
hydrogen chloride, etc. take place. The examples are terylene (dacron), nylon 6, 6, nylon 6, etc.
For e.g., nylon 6, 6 is formed by the condensation of hexamethylene diamine with adipic acid.

Classification Based on Molecular Forces: A large number of polymer applications in

different fields depend on their unique mechanical properties like tensile strength, elasticity,
toughness, etc. These mechanical properties are governed by intermolecular forces,
e.g., van der Waals forces and hydrogen bonds, present in the polymer. These forces also bind the
polymer chains. Under this category, the polymers are classified into the following three sub
groups on the basis of magnitude of intermolecular forces present in them. They are
(i) Elastomers (ii) Fibers (iii) Plastics [(a) Thermoplastic and (b) thermosetting plastic]
Depending on its ultimate form and use, a polymer can be classified as elastomers, fibre, plastic
and liquid resins.

Elastomers: These are rubber – like solids with elastic properties. In these elastomeric
polymers, the polymer chains are held together by the weakest intermolecular forces. These weak
binding forces permit the polymer to be stretched. A few ‘crosslinks’ are introduced in between
the chains, which help the polymer to retract to its original position after the force is released as
in vulcanised rubber. The examples are buna-S, buna-N, neoprene, etc.

Fibers: If drawn into long filament like material whose length is at least 100 times its
diameter, polymers are said to have been converted into ‘fibre’. Fibres are the thread forming
solids which possess high tensile strength and high modulus. These characteristics can be
attributed to the strong intermolecular forces like hydrogen bonding. These strong forces also
lead to close packing of chains and thus impart crystalline nature. The examples are polyamides
(nylon 6, 6), polyesters (terylene), etc.

Plastics: A polymer is shaped into hard and tough utility articles by the application of heat
and pressure; it is used as a ‘plastic’. Typical examples are polystyrene, PVC and polymethyl
methacrylate.

Liquid Resins: Polymers used as adhesives, potting compound sealants, etc. in a liquid
form are described liquid resins. Examples are epoxy adhesives and polysulphide sealants.
4
 Thermoplastic Polymers: Some polymers soften on heating and can be converted into
any shape that they can retain on cooling. The process of heating, reshaping and retaining the
same on cooling can be repeated several times. Such polymers, that soften on heating and stiffen
on cooling, are termed ‘thermoplastics’. These are the linear or slightly branched long chain
molecules capable of repeatedly softening on heating and hardening on cooling. These polymers
possess intermolecular forces of attraction intermediate between elastomers and fibres.
Polyethylene, PVC, nylon and sealing wax are examples of thermoplastic polymers.

Thermosetting Polymers: Some polymers, on the other hand, undergo some chemical
change on heating and convert themselves into an infusible mass. They are like the yolk of egg,
which on heating sets into a mass, and, once set, cannot be reshaped. Such polymers, that become
infusible and insoluble mass on heating, are called ‘thermosetting” polymers. These polymers are
cross linked or heavily branched molecules, which on heating undergo extensive cross linking in
moulds and again become infusible. These cannot be reused. Some common examples are
bakelite, urea-formaldelyde resins, etc. 3D networks made from trifunctional monomers.

3D networks
Organic and Inorganic Polymers: A polymer whose backbone chain is essentially made
of carbon atoms is termed as organic polymer. The atoms attached to the side valencies of the
backbone carbon atoms are, however, usually those of hydrogen, oxygen, nitrogen, etc.
The majority of synthetic polymers are organic. In fact, the number and variety of polymers are
so large that is why we refer to ‘polymers.’ On the other hand, generally chain backbone contains
no carbon atom is called inorganic polymers. Glass and silicone rubber are examples of it.

The importance of polymers in our life is almost breathtaking. Proteins and carbohydrates,
which constitute two of the three principal classes of human foodstuffs, are natural polymers of
high molecular weight. Nucleic acids are responsible for transmission of genetic characteristics in
living organisms. Natural rubber, synthetic elastomers (synthetic rubbers), plastics, synthetic
fibers, and resins are all polymers having uses that reach into every part of our lives. Most of the
structural tissues of living things are composed of polymers. In plants these are chiefly cellulose
(a polysaccharide) and lignins. In animals the main structural polymers are proteins, which take
different forms as skin, hair, muscle, etc.
5
 Additional Notes: If the main chain is made up of same species of atoms, the polymer is
called homochain polymer, and if the main chain is made up of different atoms is called
heterochain polymer

The functionality of a monomer is the number of sites it has for bonding to other
monomers under the given conditions of the polymerization reaction. Thus, a bifunctional
monomer, i.e., monomer with functionality two, can link to two other molecules under suitable
conditions. A polyfunctional monomer is one that can react with more than two molecules under
the conditions of the polymerization reactions.

It is also possible, with three functional groups (or two different monomers at least one of
which is tri-functional), to have long linkage sequences in two (or three) dimensions and such
polymers are distinguished as cross linked polymers.

Linear polymers are commonly relatively soft, often rubbery substances, and often likely
to soften (or melt) on heating and to dissolve in certain solvent, whereas cross linked polymers
are hard and do not melt, soften or dissolve in most cases.

The number of repeating units (n) in the chain so formed is called the
‘degree of polymerization’ (DP = n). Polymers with a high degree of polymerization are called
‘high polymers’ and those with low degree of polymerization are called oligopolymers
(short chain polymers or oligomers). Polymers do not exhibit strength for n < 30 and that the
optimum strength of most of the polymers is obtained at n around 600. The useful range of n is
from 200 to 2000.

Molecular Weight of Polymers: Polymerization reactions lead to the chains with many
different lengths. Hence, one must talk in terms of average chain lengths and average molecular
weights. It gives the term average molecular weights and molecular weight distributions.
The two most important molecular weight averages are the number-average molecular weight,
Mn and the weight average molecular weight, Mw

where Ni is the number of molecules of molecular weight Mi

The ratio Mw/Mn, sometimes called the polydispersity index, provides a simple definition
of the molecular weight distribution.

6
 Types of Polymerization

There are four types of polymerisation reactions; (a) Addition or chain growth
polymerisation (b) Condensation or step growth polymerisation (c) Copolymerization and
(d) Coordination polymerisation

Addition Polymerisation: In this type of polymerisation, the molecules of the same

monomer or different monomers add together on a large scale to form a polymer. The monomers
used are unsaturated compounds, e.g., alkenes and their derivatives. This mode of polymerisation
leading to an increase in chain length or chain growth can take place through the formation of
either free radicals or ionic species. Addition polymerisation, the main type with which this
volume is concerned, is essentially a chain reaction, and may be defined as one in which only a
small initial amount of initial energy is required to start an extensive chain reaction converting
monomers into polymers. A chain reaction consists of three stages, initiation, propagation and
termination.

The monomers normally employed in this type of polymerization contain a carbon-carbon

double bond that can participate in a chain reaction. As in the chain reactions studied in organic
chemistry, e.g., the free-radical halogenation of alkanes, the mechanism of the polymerization
consists of three distinct steps.

In the initiation Step an initiator molecule(s) is thermally decomposed or allowed to

undergo a chemical reaction to generate an "active species." This "active species," which can be a
free radical, a cation, an anion, then initiates the polymerization by adding to the monomer's
carbon-carbon double bond. The reaction occurs in such a manner that a new free radical, cation,
or anion is generated. The initial monomer becomes the first repeat unit in the incipient polymer
chain.

In the propagation Step, the newly generated "active species" adds to another monomer in
the same manner as in the initiation step. This procedure is repeated over and over again until the
final step of the process, termination, occurs.

In the termination step, the growing chain terminates through reaction with another
growing chain, by reaction with another species in the polymerization mixture, or by the
spontaneous decomposition of the active site. Under certain conditions, anionic can be carried out
without the termination step to generate so-called "living" polymers.

7

The following are several general characteristics of addition polymerization:

1) Once initiation occurs, the polymer chain forms very quickly, i.e., 10-1 to 10-6 sec

2) The concentration of active species is very low. For example, free radical polymerisations, the
concentration of free radicals is approximately 10-8 M. Hence, the polymerisation mixture
consists of primarily of newly-formed polymer and unreacted monomer.

3) Since the carbon-carbon double bonds in the monomers are, in effect, converted to two single
carbon-carbon bonds in the polymer energy is released making the polymerization exothermic
with cooling often required.

41 Chain-reactions normally afford polymers with high molecular weights, i.e., 104 to 107

5) Polymers can be obtained that contain secondary chains (branches) attached to the main chain
(backbone). Crosslinked systems can form where all the primary chains are interconnected with
secondary chains.

The mechanism of addition polymerisation can be divided broadly into two main classes,
free radical polymerisation and ionic polymerisation, although there are some others.
Ionic polymerisation was probably the earliest type to be noted, and is divided into cationic and
anionic polymerisations.

Free radical polymerisation: A variety of alkenes or dienes and their derivatives are
polymerised in the presence of a free radical generating initiator (catalyst) like benzoyl peroxide,
acetyl peroxide, tert-butyl peroxide, etc. For example, the polymerisation of ethene to polythene
consists of heating or exposing to light a mixture of ethene with a small amount of benzoyl
peroxide initiator.

Cationic polymerisation depends on the use of catalysts (or cationic initiators) which are
good electron acceptors. Typical examples are the Friedel–Crafts catalysts such as aluminium
chloride (AlCl3) or boron trifluoride (BF3). Monomers that polymerise in the presence of these
catalysts have substituents of the electron releasing type. They include styrene (C6H5CH=CH2)
and the vinyl ethers (CH2=CHOCnH2n+1).

Anionic polymerisation depends on the use of anionic initiators which include reagents
capable of providing negative ions. Typical catalysts include sodium in liquid ammonia, alkali
metal alkyls, Grignard reagents and triphenylmethyl sodium [(C6H5)3C-Na]. they are effective
with monomers containing electronegative substituents such as acrylonitrile and methyl
methacrylate [CH2=C(CH3)COOCH3]. Styrene may also be polymerised by an anionic method.

8
 Free radical polymerisation: A free radical may be defined as an intermediate compound
containing an odd number of electrons, but which do not carry an electric charge and are not free
ions. A free radical mechanism is the basis of addition polymerisation where these types of
initiator are employed. For a transient free radical the convention will be used of including a
single dot after or over the active element with the odd electron.

The first stage of the chain reaction is the initiation process, consists of the attack of the
free radical on one of the doubly bonded carbon atoms of the monomer. One electron of the
double bond pairs with the odd electron of the free radical to form a bond between the latter and
one carbon atom. The remaining electron of the double bond shifts to the other carbon atom
which now becomes a free radical.

The process starts with the addition of phenyl free radical formed by the peroxide to the ethene
double bond thus generating a new and larger free radical. This step is called chain initiating step

The second stage of the chain reaction is the propagation process, the new free radical
can, however, in its turn add on extra monomer units, and a chain reaction occurs, representing
the propagation stage.

As the radical reacts with another molecule of ethene, another bigger sized radical is formed. The
repetition of this sequence with new and bigger radicals carries the reaction forward and the step
is chain propagating step termed as chain propagating step

The final stage of the chain reaction is the termination process, which may take place by
one of several processes. One of these is combination of two growing chains reacting together.

The product radical formed reacts with another radical to form the polymerised product. This step
is called the chain terminating step
An alternative is disproportionation through transfer of a hydrogen atom:

9
 Ionic Polymerisation: The addition polymerisation that takes place due to
ionic intermediate is called ionic polymerisation. Based on the nature of ions used for the
initiation process ionic polymerisation classified into two types; (a) Cationic polymerisation and
(b) Anionic polymerisation

a) Cationic polymerisation: Cationic polymerisation is initiated by an acid (Lewis acids

such as BF3, AlCl3, FeCl3, SnCl4, H2SO4 and HF in presence of small amount of H2O.
Examples are isobutylene – butyl rubber, polystyrene. polyvinyl ether.
H2SO4 → H+ + HSO−4
HF → H+ + F–

BF3 + H2O → H+ + BF3(OH–)

i) Chain Initiation: Proton (H+) adds to C – C double bond of alkene to form stable carbocation.

ii) Chain Propagation: Carbocation add to the C – C double bond of another monomer molecule
to from new carbocation.

iii) Chain Termination: Reaction is terminated by combination of carbocation with negative ion
(or) by loss of proton

10
 b) Anionic Polymerization: Anionic polymerisation is initiated by anion [may be base
(or) nucleophiles such as n-butyl lithium (or) Potassium amide]. Monomer containing
electron withdrawing groups like phenyl (–C6H5), nitrile (–CN) etc undergo anionic addition
polymerisation. Examples are polystyrene, poly acylonitrile. Anionic polymerisation has no chain
termination reaction. So it is called living polymerization.

i) Chain Initiation: Potassium amide (K+NH2-) adds to C – C double bond of alkene to form
stable carbanion.

where W is electron withdrawing group

ii) Chain Propagation: Carbanion adds to the C – C double bond of another monomer molecule
to from new carbanion.

Cationic
Polymerization

Anionic
Polymerization

11
 Coordination polymerization: It is also a subclass of addition polymerization.
Here, the "active species" is a coordination complex, which initiates the polymerization by
adding to the monomer’s carbon-carbon double bond.

In coordination polymerization, usually transition-metal catalysts are involved. A growing

polymer chain is coordinatively bound to a metal atom that has another coordinative vacancy
(partially empty d-orbitals). A new ethene molecule is inserted by the creation of bonds between
one of its carbon atoms and the metal and between the other carbon atom and the innermost
carbon atom of the existing chain. Branching will not occur through this mechanism since no
radicals are involved; the active site of the growing chain is the carbon atom directly bonded to
the metal. High density polyethene (HDPE) is produced by this type of polymerization.

The most important catalyst for coordination polymerization is so-called Ziegler-Natta

catalyst discovered to be effective for alkene polymerization. Ziegler-Natta catalysts combine
transition-metal compounds such as chlorides of titanium with organometallic compounds.
An important property of these catalysts is that they yield stereoregular polymers when higher
alkenes are polymerized, e.g. polymerization of propene produces polypropene
with high selectivity.

Zeigler-Nata catalysts: These are a special type of coordination catalysts, comprising two
components, which are generally referred to as the catalyst and the cocatalyst. The catalyst
component consists of halides of IV-VIII group elements having transition valence and the
cocatalysts are organometallic compound such as alkyls, aryls and hydrides of group I-IV metals
(Zeigler-Nata Catalysts).

Although there are organo aluminium compounds such as triethyl aluminium (AlEt3) or
diethyl aluminium chloride (AlEt2Cl) in combination with titanium chlorides—both tri and tetra
(TiCl3 and TiCl4)—are, by far, the most commonly used.

Aluminium alkyls act as the electron acceptor whereas the electron donor is titanium
halides and the combination, therefore, readily forms coordination complexes. The complex
formed is insoluble in the solvent and is, hence, heterogeneous in nature. Many structures have
been proposed for these complexes are:

12
 The active centres, from where the polymer chain growth propagates are formed at the
surface of the solid phase of the catalyst complex, and the monomer is complexed with the metal
ion of the active centre before its insertion into the growing chain.

The complex formed, now acts as the active centre. The monomers then attached towards
the Ti—C bond (C from the alkyl group R) in the active centre, when it forms a π complex with
the Ti ion.

The bonds between R and Ti opens up producing an electron deficient Ti and

a carbanion at R.

The Ti ion attracts the π electrons pair or the monomer and forms σ bond

This transition state now gives rise to the chain growth at the metal carbon bond,
regenerating the active centre:

13
 Repeating the whole sequence, with the addition of second monomer molecule, we will
get the structure of the resultant chain growth as:

Therefore, on the basis of the above, polymerization is characterized by the initiation

propagation and termination reaction as follows:

Here Mt denotes transition metals such as Ti, Mo, Cr, V, Ni, or Rh.
Zeigler Natta polymerization is used to prepare polypropylene, polyethylene, polydiene, etc.
14
 Condensation Polymerisation: This type of polymerisation generally involves a
repetitive condensation reaction between two bi-functional monomers. These polycondensation
reactions may result in the loss of some simple molecules as water, alcohol, etc., and lead to the
formation of high molecular mass condensation polymers. In these reactions, the product of each
step is again a bi-functional species and the sequence of condensation goes on. Since, each step
produces a distinct functionalised species and is independent of each other; this process is also
called as step growth polymerisation.

Condensation polymerization, a form of step-growth polymerization, is a process by which

two molecules join together, resulting loss of small molecules which is often water. The type of
end product resulting from a condensation polymerization is dependent on the number of
functional end groups of the monomer which can react.

Monomers with only one reactive group terminate a growing chain, and thus give end
products with a lower molecular weight. Linear polymers are created using monomers with two
reactive end groups and monomers with more than two end groups give three dimensional
polymers which are cross linked.

Polyester is created through ester linkages between monomers, which involve the
functional groups carboxyl and hydroxyl (an organic acid and an alcohol monomer). The
formation of polyester like terylene or dacron by the interaction of ethylene glycol and
terephthalic acid is an example of this type of polymerisation.

Polyamide is created through amide linkages between monomers, which involve the
functional groups carboxyl and amine (an organic acid and an amine monomer). Nylon is an
example which can be manufactured by the condensation polymerisation of
hexamethylenediamine with adipic acid under high pressure and at high temperature.

15
 This type of polymerization normally employs two difunctional monomers that are
capable of undergoing typical organic reactions. For example, a diacid can be allowed to react
with a diol in the presence of an acid catalyst to afford polyester. In this case, chain growth is
initiated by the reaction of one of the diacid's carboxyl groups with one of the diol's hydroxyl
groups. The free carboxyl or hydroxyl group of the resulting dimer can then react with an
appropriate functional group in another monomer or dimer. This process is repeated throughout
the polymerization mixture until all of the monomers are converted to low molecular weight
species, such as dimers, trimers, tetramers, etc. These molecules, which are called oligomers, can
then further react with each other through their free functional groups. Polymer chains that have
moderate molecular weight can he built in this manner. The high molecular weights common to
chain-reaction polymerizations are usually not reached. This is due to the fact that as the
molecular weight increases the concentration of the free functional groups decreases
dramatically. In addition, the groups are attached to the ends of chains and, hence, are no longer
capable of moving- freely through the viscous reaction medium.

The following are several general characteristics of this type of polymerization:

(1) The polymer chain forms slowly, sometimes requiring several hours to several days.
(2) All of the monomers are quickly converted to oligomers, thus, the concentration of growing
chains is high. (3) Since most of the chemical reactions employed have relatively high energies of
activation, the polymerization mixture is usually heated to high temperatures. (4) Step-reaction
polymerizations normally afford polymers with moderate molecular weights, i.e., <100,000.
(5) Branching or crosslinking does not occur unless a monomer with three or more functional
groups is used

16
 Copolymerization: It is a polymerisation reaction in which a mixture of more than one
monomeric species is allowed to polymerise and form a copolymer. The copolymer can be made
not only by chain growth polymerisation but by step growth polymerisation also. It contains
multiple units of each monomer used in the same polymeric chain. For example, a mixture of 1, 3
– butadiene and styrene can form a copolymer.

17
 Copolymers have properties quite different from homopolymers. For example, butadiene -
styrene copolymer is quite tough and is a good substitute for natural rubber. It is used for the
manufacture of autotyres, floortiles, footwear components, cable insulation, etc.

Two or more different monomers are often employed in a chain-reaction polymerization to

yield a polymer containing the corresponding repeat units. Such a process is referred to as
copolymerization, and the resulting product is called a copolymer. By varying the
copolymerization technique and the amounts of each monomer, one can use as few as two
monomers to prepare a series of copolymers with considerably different properties. The amount
of different materials that can be prepared increases dramatically as the number of monomers
employed increases. Thus, it is not too surprising that the majority of synthetic polymers used
today are copolymers.

As a general principle it should not be assumed that, because two or more monomers
copolymerise completely, the resultant copolymer is reasonably homogeneous.
The term ‘copolymer’ is sometimes confined to a polymer formed from two monomers only. In a
more general sense, it can be used to cover polymers formed from a larger number of monomers.
The term ‘terpolymer’ is sometimes used when three monomers have been copolymerised.

18
 Technology of Polymerisation

Monomers may be polymerised by the following methods (1) polymerization in

homogeneous systems (2) polymerization in heterogeneous systems

Polymerization in Homogeneous systems: The homogeneous polymerization techniques

involve pure monomer or homogeneous solutions of monomer and polymer in a solvent. These
techniques can be divided into two methods: (i) the bulk and (ii) the solution polymerizations.

Bulk polymerization: Bulk polymerization is the simplest technique and produces the
highest-purity polymers. Only monomer, a monomer-soluble initiator (and chain transfer agent to
control the molecular weight) are used. This method helps easy polymer recovery and minimum
contamination of product. The viscosity of the mixture is low initially to allow ready mixing, heat
transfer, and bubble elimination. This method is used for the preparation of polyethene,
polystyrene, polymethyl methacrylate, etc.

Disadvantages: Reaction medium becomes increasingly viscous as reaction goes to higher

conversion, making stirring, heat removal and processing more difficult. It leads to uneven
polymerization and loss of monomer. Free-radical polymerizations are typically highly
exothermic. An increase temperature will increase the polymerization rate; generate heat
dissipation and a tendency to develop of localized “hot spots”. Near the end of polymerization,
the viscosity is very high and difficult to control the rate as the heat is “trapped” inside. It leads to
the autoacceleration process (Trommsdroff or gel effect) in which the propagation rate is very
higher than that of termination rate. This method is seldom used in commercial manufacture.

Solution polymerization: This method is used to solve the problems associated with the
bulk polymerization because the solvent is employed to lower the viscosity of the reaction, thus
help in the heat transfer and reduce autoacceleration. It requires the correct selection of the
solvents. Both the initiator and monomer be soluble in each other and that the solvent are suitable
for chain-transfer characteristics and melting and boiling points, regarding the solvent-removal
steps. It is often used to produce copolymers. This method is used for the preparation of
polyvinyl acetate, poly (acrylic acid), and polyacrylamide.

Advantages: (i) Solvent has low viscosity, reaction mixture can be stirred (ii) Solvent acts
as a diluent and aids in removal of heat of polymerization (iii) Solvent reduces viscosity, making
processing easier (iv) Thermal control is easier than in the bulk and (v) “Cheap” materials for the
reactors (stainless steel or glass lined).

19
 Disadvantages: (i) Reduce monomer concentration which results in decreasing the rate of
the reaction and the degree of polymerization (ii) Mobility is reduced and this can affect
termination events, so the rate of reaction is increased (iii) Solvent may cause chain transfer,
leading to low molecular weight polymers (iv) Difficult to remove solvent from final form,
causing degradation of bulk properties (v) Clean up the product with a non solvent or evaporation
of solvent (vi) Small production per reactor volume (vii) Not suitable for dry polymers.

Polymerization in Homogeneous systems

Bulk polymerization Solution polymerization

Polymerization in heterogeneous systems: Polymerization occurs in disperse phase as

large particles in water or occasionally in another non-solvent (suspension polymerisation), or
dispersed as fine particles. The last-named process is usually known as emulsion polymerisation.

Suspension (Bead or Pearl) polymerisation: Suspension polymerisation may be

described as a water-cooled bulk polymerisation. Suspension polymerization n consists of an
aqueous system with monomer as a dispersed phase and results in polymer as a dispersed solid
phase. It is similar to bulk polymerization where the reaction mixture is suspended as droplets in
an inert medium. Monomer, initiator and polymer must be insoluble in the suspension media such
as water. This method is used for the preparation of polystyrene, polymethyl methacrylate,
polyvinyl chloride, polyvinyl acetate, etc

Method: A reactor fitted with a mechanical agitator is charged with a water insoluble
monomer and initiator (and a chain-transfer agent to control molecular weight). Droplets of
monomer (containing the initiator and chain-transfer agent) are formed. As the polymerization
proceeds, the viscosity of dispersed phase increases and they become sticky. Aggregation of these
sticky droplets is prevented by the addition of a dispersing agent (protective colloid,
e.g., water-soluble colloid such as gum acacia). Near the end of polymerization, the particles are
hardened, are then recovered by filtration, and followed by washing step.

The function of the dispersing agent is that of forming an ‘envelope’ around the beads as
formed by stirring and preventing their coagulation and fusion during polymerisation.
An intermediate or ‘sticky’ state occurs in almost all polymerisations in which a solution of
20
polymer in monomer of high viscosity is formed, and the beads would fuse together very readily,
except for the energy supplied by the stirring in keeping them apart and the stabilising action of
the dispersing agent. This type of polymerisation is sometimes referred to as ‘bead’
polymerisation.

Advantages: (i) Polymerisation to high conversion (ii) Low viscosity due to the
suspension (iii) Easy heat removal due to the high heat capacity of water (iv) Excellent heat
transfer because of the presence of the solvent (v) Solvent cost and recovery operation are cheap
(vi) Polymerization yields finely divided, stable latexes and dispersions to be used directly in
coatings, paints, and adhesives. Disadvantages: (i) Contamination by the presence of suspension
and other additives low polymer purity (ii) Must separate and purify polymer, or accept
contaminated product (iii) Reactor cost may higher than the solution cost

Emulsion polymerisation: This is similar to suspension polymerization except that the

initiator is soluble in water (suspension media) and insoluble in the monomer. The reaction
product is colloidally stable dispersion known as latex. The polymer particles have diameter in
the range of smaller than suspension. An emulsion polymerization consists of water (as the heat-
transfer agent), monomer, water-soluble initiator, a chain-transfer agent, a surfactant or emulsifier
(such as sodium salt of long-chain fatty acid). This method is used for the preparation of
polyvinyl acetate, polychloroprene, butadiene/styrene/acrylonitrile copolymers, etc

Method: A typical recipe for emulsion polymerization consists of water, monomer,

fatty acid soap (emulsifying agent), and water soluble initiator. When a small amount of soap is
added to water, the soap ionizes and the ions move around freely. The soap anion consists of
a long oil-soluble portion (R) terminated at one end by the water-soluble portion.
In other words, soap anions consist of both hydrophilic and hydrophobic groups.
In water containing a partially soluble monomer molecule, the soap anion molecules orient
themselves at the water–monomer interfaces with the hydrophilic ends facing the water,
while the hydrophobic ends face the monomer phase.

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 Above a critical concentration of the emulsifying agent known as the critical micelle
concentration (CMC), only a small fraction of the emulsifying agent is dissolved in the water.
The bulk of the emulsifier molecules arrange themselves into colloidal particles called micelles.
The shape of the micellar aggregate favors a spherical arrangement with the hydrophilic (polar)
groups on the surface facing the aqueous phase while the hydrophobic chains are arranged
somewhat irregularly at the interior. The presence of soap or emulsifying agents considerably
enhances the solubility of a water insoluble or sparingly soluble monomer. The bulk of the
monomer is dispersed as droplets are stabilized by the emulsifier. Consequently, when a water
insoluble or sparingly soluble monomer is emulsified in water with the aid of soap and agitation,
lead to the monomer-swollen micelles.

When the water-soluble initiator undergoes thermal decomposition to form the water-
soluble radicals react with monomer dissolved in interior of the micelle. Emulsion polymerization
takes place almost exclusively in the micelles. This is because of two reasons: (1) A micelle has a
much greater total surface area and (2) The concentration of the micelles is higher than that of the
monomer droplets.

Polymerization is initiated in only a small number of the micelles present initially.

As polymerization proceeds, the active micelles consume the monomers within the micelle.
Monomer depletion within the micelle is replenished first from the aqueous phase and
subsequently from the monomer droplets. The active micelles grow in size with polymer
formation, to preserve their stability; these growing polymer particles absorb the soap of the
parent micelles.

Advantages: (i) Overcomes many environmental problems: “solvent” is water

(ii) If final desired product is polymer is washed with water to remove the soap (or emulsifying
agent) phase by coagulation (iii) Kinetics, molecular weight : more complex and often quite
different from solution and bulk polymerizations

Emulsion Micelle without

Micelle with monomer Polymer inside the micelle
polymerization monomer
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Representation of stages of an ideal emulsion polymerization. An emulsifier molecule (–O),
a monomer molecule (M), a polymer molecule (P), and a free radical (R·).
(a) Prior to initiation
(b) Polymerization Stage I → shortly after initiation;
(c) Polymerization Stage II → all emulsifier micelles consumed;
(d) Polymerization Stage III →monomer droplets disappear; and
(e) End polymerization

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 Polymerization in heterogeneous systems
Suspension polymerization Emulsion polymerization
Features
Features
• Heterogeneous system
• A heterogeneous system • Nucleation site is inside the micellar
• Nucleation site is monomer phase (droplet) • Polymerization time is fast
• Polymerization time is long (more than 10 h) • High Molecular weight
• Surfactant-free is possible

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 Melting and Glass Transition Temperature: The glass transition temperature is the
point at which the polymer hardens into an amorphous solid. This term is used because the
amorphous solid has properties similar to glass. Melting of a crystalline polymer: Transforming
solid with an ordered structure to a viscous liquid with a highly random structure. Amorphous
glass transitions: Transformation from a rigid material to one that has rubberlike characteristics
and temperature has large effect on chain flexibility. Below glass transition temperature, Tg,
polymers are usually brittle and glass-like in mechanical behavior. Above glass transition, Tg,
polymers are usually more elastic. Why is That? Bond rotations are “freezing” which means
chains can’t slip past each other so polymer becomes brittle, (no plastic deformation)

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 Crystallinity in polymers: Although it may at first seem surprising, Polymers can form
crystal structures (all we need is a repeating unit, which can be based on molecular chains rather
than individual atoms). Some parts of structure align during cooling to form crystalline regions
(chains align alongside each other). Around crystallites get amorphous regions. Most real
polymers contain both amorphous and crystalline regions, called semicrystaline.

The morphology of most polymers is semi-crystalline. That is, they form mixtures of
small crystals and amorphous material and melt over a range of temperature instead of at a single
melting point. The crystalline material shows a high degree of order formed by folding and
stacking of the polymer chains. An amorphous solid is formed when the chains have little
orientation throughout the bulk polymer. The amorphous or glass-like structure shows no long
range order, and the chains are tangled as illustrated below.

Crystalline Amorphous
There are some polymers that are completely amorphous, but most are a combination with
the tangled and disordered regions (amorphous regions) surrounding the crystalline areas called
semicrystaline. Such a combination is shown in the following diagram.

Semicrystaline
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 In the crystallization process, it has been observed that relatively short chains organize
themselves into crystalline structures more readily than longer molecules. Therefore, the degree
of polymerization (DP) is an important factor in determining the crystallinity of a polymer.
Polymers with a high DP have difficulty organizing into layers because they tend to become
tangled.

The cooling rate also influences the amount of crystallinity. Slow cooling provides time
for greater amounts of crystallization to occur. Fast rates, on the other hand, such as rapid
quenches, yield highly amorphous materials. Subsequent annealing (heating and holding at an
appropriate temperature below the crystalline melting point, followed by slow cooling) will
produce a significant increase in crystallinity in most polymers, as well as relieving stresses.

Low molecular weight polymers (short chains) are generally weaker in strength. Although
they are crystalline, only weak Van der Waals forces hold the lattice together. This allows the
crystalline layers to slip past one another causing a break in the material. High DP (amorphous)
polymers, however, have greater strength because the molecules become tangled between layers.
In the case of fibers, stretching to 3 or more times their original length when in a semi-crystalline
state produces increased chain alignment, crystallinity and strength. In most polymers, the
combination of crystalline and amorphous structures forms a material with advantageous
properties of strength and stiffness.

Also influencing the polymer morphology is the size and shape of the monomers'
substituent groups. If the monomers are large and irregular, it is difficult for the polymer chains
to arrange themselves in an ordered manner, resulting in a more amorphous solid. Likewise,
smaller monomers, and monomers that have a very regular structure (e.g. rod-like) will form
more crystalline polymers.

% crystallinity depends on several factors: Rate of cooling (faster cooling – less

crystallinity). Type of polymer (simple structures – more crystallinity, Copolymers – less
crystallinity). Linear polymers more easily form crystals. Degree of Crystallinity ranges from 5 -
95% - The higher % Crystallinity → higher strength. When polymers are crystallized they form
spherical structures called spherulites.

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 Syllabus

Polymers – classification – Types of polymerization → addition, condensation,

co-polymerisation and co-ordination polymerization – Mechanism → cationic, anionic and free
radical – Polymerisation techniques → Bulk, solution, suspension and emulsion –
Structure relation to properties

Previous University Questions

[1] How would you classify polymers based on source and applications? {10 marks}

[2] Differentiate between thermoplastic and thermosetting plastic {2 marks}

[3] Discuss the mechanism of addition polymerization {10 marks}

[4] Explain cationic, anionic and free radical mechanism of polymerization {10 marks}

[5] Distinguish between polymerization by addition and condensation processes {10 marks}

[6] Discuss the mechanism of coordination polymerization {10 marks}

[7] Briefly explain the techniques of polymerization {10 marks}

[8] Explain the structure relation to properties of polymers {5 marks}

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