Classification of Polymers

POLYMER
The polymer (poly- many; mer-unit or parts) is a high
molecular weight compound, formed by the combination
of small molecules of low molecular weight.
OR
Polymers having long chain macromolecules, which are built
up by the linking together of a large number of small
molecules, called monomer.

Basic Terms of Polymers

Polymerization: The process by which, monomer combine to
form polymers is known as polymerization.
Degree of Polymerization (DP): The numbers of repeating unit
present in it call degree of polymerization (DP).
Addition Polymerization: : When molecules just add on to form
the polymer, the process is called addition polymerization
In addition polymerisation the molecular weight of the polymer
is roughly equal, to that of all the molecules, which combine
to form the polymer.
Ex; Polyethylene, polypropylene

Condensation Polymerization: When, however, molecules do

not just add on but also undergo some reaction in
forming the polymer, the process is called condensation
polymerisation

The molecular weight of polymer is lesser by the weight

of simple molecules eliminated during the condensation
process

The condensation takes place between the two reactive

functional groups, like the carbonyl group (of an acid)
and hydroxyl group (of an alcohol) to form polyesters.

Ex. Nylon, PET

Polymer Material Properties Depends on

1. Degree of Polymerization
2. Molecular Weight of the Polymer
3. Molecular Weight Distribution
4. Glass Transition Temperature
5. Percentage of Crystallinity
6. Structure and Distribution of Chain Branching

Types of Polymers
A polymer consist of identical monomers or monomers of
different chemical structure and accordingly they are
called homopolymer and copolymers respectively. If the
main chain is made up of same species of atoms, the
polymer is called homochain polymer Graft copolymer are
branched structures in which the monomer segments on
the branches and backbone differ

The monomeric unit in a polymer may be present in a linear,

branched or cross-linked (three dimensional) structure

Tacticity
1. The head to tail configuration in which the functional
groups are all on the same side of the chain, is called
isotactic polymers.
2. If the arrangements of functional groups are at random
around the main, it is called atactic polymers e.g.
polypropylene.
3. If the arrangements of side groups is in alternating
fashion, it is called synditactic polymers

Where R = Alkyl Group

Functionality

Thermoplastics Polymers
Thermoplastics are resins that repeatedly soften when
heated and harden when cooled
Thermosetting Polymers
Thermosets are resins that undergo reaction during
processing to become permanently insoluble and infusible
due to they formed three-dimensional cross linked network
structure when heat is applied.
Characteristics of thermosetting resins:
1. During the hardening the cross-links are formed between
adjacent molecules, resulting in a complex, interconnected
network that can be related to its viscosity and performance
2. These cross-links prevent slippage of individual chains, thus
preventing plastic flow under addition of heat
3. If excessive heat is added after cross links, degradation
rather than melting will occur.
Ex: Phenolic Resin, Epoxy Resin, Polyester resin

Thermoplastics and Thermosetting Polymers

Structure of Thermoplastics and Thermosetting Polymers

Difference Between Thermoplastics and Thermosetting Polymers

Molecular weight of Polymers

Molecular weight of a polymer is defined as sum of the
atomic weight of each of the atoms in the molecules,
which is present in the polymer.
This distribution of molecular weights is caused by the
statistical nature of the polymerization process e.g.
methane (CH4) molecules have the same molecular weight
(16), but all polyethylene do not have the same molecular
weight because the statistical distribution of molecular
weight may be different for the different grade of the
polyethylene and the degree of polymerization may also be
different.

Generalization of Concept

Number-average molecular weight

Mn=

niMi = wi
ni wi/Mi

Weight-average molecular weight

2
niMi

wiMi
Mw=
=
niMi wi
z-Average molecular weight

niMi wiMi

Mz=
=
niMi wiMi
3

Where,
n=
Moles of molecules (n1 + n2 + n3 + ----------ni) i.e. weight
(w)/molecular weight (M)
w=

Weight of individual molecules (w 1 + w 2 + w 3 + ---------w i)

M=

Molecular weight of each molecules

Number Average Weight (Mn)

The number average molecular weight is not too difficult to
understand. It is just the total weight of all the polymer
molecules in a sample, divided by the total number of
polymer molecules in a sample.
Consider a polymer, which contains four molecular weight
polymers in different numbers and weight and these

Total number of polymer in containing each entity of poly-1,

poly-2, poly-3 and poly-4 is = 15
Number of Poly-1 present in the polymer = 2
Number of fraction of poly-1 = 2/15
Similarly, Number of fraction of poly-2 = 4/15, Number of
fraction of poly-3 = 6/15, Number of fraction of poly-4 = 3/15
Contribution made by poly-1 towards the average weight of
polymer = number of fraction of each polymer x weight of
each poly entity
Therefore, each poly contribution is
(2/15) x 10 =1.33g, (4/15) x 20 = 5.33g, (6/15) x 100 =40g, (3/15) x
250 = 50g
Summing up the contribution to get Number Average Molecular
Weight=
1.33 + 5.33 + 40 + 50 = 96.66g

Generalization of Concept
Total number of molecules (n) id given by

n n1 n2 n3 n4 ........... ni
Number fraction of each molecule is =

ni
ni

Number average weight contribution of each entity is =

Number average weight molecular weight is

n1M 2 n2 M 2 n3 M 3 n4 M 4

......
ni ni ni ni

n M
n
i

Mn

ni M i
ni

Weight Average Molecular Weight (Mw )

Total weight of each poly present in the polymer =1450g
Weight of poly-1 present in polymer = 20g
Weight fraction of poly-1 = 20/1450, Weight fraction of poly-2
= 80/1450, Weight fraction of poly-3 = 600/1450, Weight
fraction of poly-4 = 750/1450
Contribution made by each poly towards average weight of
polymer = weight fraction of poly-1x weight of each unit
For poly-1 (20/1450) x 10 = 0.14g
For poly-2 (80/1450) x 20 = 1.10g
For poly-3 (600/1450) x 100 = 41.38g
For poly-4 (750/1450) x 250 = 129.31g
Summing up the contribution made by each poly to get
weight average molecular weight is
0.14 + 1.10 + 41.38 + 129.31 = 171.93g

Generalization of Concept
Total number of molecules (n) id given by

n n1 n2 n3 n4 ........... ni

Total weight of the polymer is =

NWM
i

n1M 1
nM
1 1
W
n1M 1

Weight fraction of each molecule is =

2
Weight average weight contribution of each entity is = n1M 1M 1 ni M i

n M n M

Number average weight molecular weight is

2

nM
n1M 1
nM
nM
2 2 3 3 4 4 ......
ni M i ni M i ni M i ni M i

ni M i

Mw

nM

For synthetic polymers Mw is greater than the Mn. If they are

i

equal than they will consider as perfectly homogeneous.

(Each molecule has same molecular weight).

Molecular weight and degree of polymerisation

Number of repeating unit in a polymer called as degree of
polymerisation (DP). DP provides the indirect method of
expressing the molecular weight and the relation is as
follows;
M = DP x m
Where, M is the molecular weight of polymer, DP is the
degree of polymerisation and m is the molecular weight
of the monomer

(DP) n =

n i (DP)i
n

and( DP ) w =

n i (DP)i

n (DP)

Each of these averages can be related to the corresponding

molecular weight average by the following two equations;
Mn = (DP)n.m
Mw = (DP)w.m

Influence of Molecular weight of Polymers

The influence of molecular weight on the bulk properties of
polyolefin's, an increase in the molecular weight leads to
Increase in:

Melt viscosity

Impact strength

Lowers in:

Hardness

Stiffness

Softening point

Brittle point
High molecular weight polymer does not crystallize so
easily as lower molecular weight material crystallizes due
to chain entanglement and that reflect in bulk properties of
the high molecular weight polymer.

Determination of Molecular Weight

1. Number-average Molecular Weight
a) End-group Analysis:
If functional groups present in a given weight of the
sample and this is expressed as a functional group
equivalent/100 g. From knowledge of the functional group
equivalent and the functionality, The molecular weight is
calculated using the equation:

Functionality
Mn
Functionalgroupequivalent
Then the functionality of the polymer sample can be given
by the equation
Functionality = molecular weight X functional equivalent

Determination of Molecular Weight

b) Measurement of Colligative Properties

1. Depression in freezing point (cryoscopy) and elevation in
boiling point (ebulliometry). As these two properties are
Colligative (i.e. depend only on the number of moles of a
solute present in a liquid and not on their nature).
2. Colligative properties are those that depend on the number
of species present rather than on their kind. From
thermodynamic arguments it may be shown that for very
dilute ideal solutions

ln 1 X 2

Where, 1 is the activity of the solvent in a dilute ideal

solution and X2 is the mole fraction of solute. From this
relationship the solute molecular weight may be calculated
if the weight fraction W2 is known.

n2 w2 M 1
X2

n1 M 2 w1

Glass Transition Temperature (Tg)

The temperature below, which a polymer is hard and above
which it is soft, is called the glass transition temperature
(Tg).
Or
The molecular mobility is just starts above that temperature
or below which mobility arrested called Tg

Glass Transition Temperature (Tg)

Tg is unique to amorphous thermoplastics. It occurs at a
specific temperature that depends on pressure and
specific volume and is lower than melting point.

Tg

The glass transition temperature is a measure of

evaluating the flexibility of polymer molecules and the type
of response the polymeric material would exhibit to
mechanical stress.

The glass transition temperature depends on the structure

and polarity of a polymer, which affects both chain
flexibility and intermolecular interaction.

Since non-polar polymers have lower potential energy

barrier for rotation, their chain remains flexible and they
have low Tg. Chains based on aliphatic C-C bond and C-O
bond are quite flexible, on the other hand introduction of
ring structure into main chain has a marked stiffening
effect which results in higher Tg of such polymer.

Glass Transition Temperature (Tg)

Rotation about a single C-C bond is also impended by the

substitutions of attached hydrogen atoms by methyl or
other attached hydrogen atoms by methyl or other
attached to the main chain carbon atom can influence the
Tg.

Inclusion of double bonds will stiffen the chain at the point

of inclusion but at the same time decrease the flexibility of
adjacent bond. The net effect may therefore be to reduce
the glass transition temperature.

The presence of polar groups or atoms will result in high

glass transition temperature. Hydrogen bonding has a
similar effect to that of a polar group.

Glass Transition Temperature and Molecular Weight

K
Tg Tg
Mn

Where, Tg is the glass transition temperature at infinite

molecular weight and K and A are arbitrary constants.

1
1
A

Tg Tg
Mn
For a given weight of the polymer, a low molecular weight
sample will have more chain end segments than a high
molecular weight sample.

Glass Transition Temperature and Plasticizer

1. The plasticizer substantially reduces the brittleness of
many amorphous polymers because its addition even in
small quantities markedly reduces the Tg of the polymer.
2. The effectiveness of plasticizer in lowering the Tg of a
polymeric composition is directly proportional to its Tg
and volume fraction of plasticizer
Tg V1Tg1 V2Tg 2
1
w
w
1 2
Tg Tg1 Tg 2

The extent of reduction in the glass transition values is

called asplasticizer efficiency'. The extent of reduction is
depends on factors such as solubility parameter, polarity
and density

Effect of Co-polymerization on Glass Transition Temperature

1
wA
wB

Tg ( AB ) Tg ( A) Tg ( B )
Where Tg(A), Tg(B) and Tg(AB) are the glass transition
temperature of homo polymers A and B and the
copolymer AB respectively. that the glass transition
temperature of a copolymer will be in between those of
the. respective homo polymers

Glass Transition Temperature and Melting Point

1
Tg Tm
2

For symmetrical polymers

2
Tg Tm
3

For unsymmetrical polymers

A combined version of these two equations, in which the

effect of molecular symmetry is not taken into account,
is also in vogue, as now shown:

1 Tg 2

2 Tm 3
Since this relation gives a range for Tg/Tm (rather than a
sharp value), it may more realistically reflect the
thermal behavior of polymers.

Crystallinity in Polymers
A small region of a macromolecules materials in which
portions of large molecules are arranged in regular way, is
called crystalline.
1. Crystallization imparts a denser packing of molecules,
thereby increasing the intermolecular forces of attraction.
2. This accounts for a higher and sharper softening point,
greater rigidity and strength and greater density. A
completely crystalline polymer tends to acquire brittleness.
Amorphous Polymers
An amorphous polymers is characterized by completely
random arrangement of molecules of polymer chain.
While a crystalline region (called crystallites) embedded in
amorphous random matrix. e.g. Polystyrene, polyvinyl
acetate and polymethyl methacrylate (all are having bulky
side groups attached at random to the main carbon chain)
are typically amorphous.

Crystalline and Amorphous Polymers

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.

As symmetrical molecules approaches within a critical

distance, crystal begins to form in the areas where they are
most densely packed.

A crystallized area is stiffer and stronger. A non-crystalline

(amorphous) are more flexible.

Crystalline and Amorphous Polymers

An increasing crystalline in polypropylene increased in

creep, heat and stress cracking as well as increased in
mould shrinkage.

Crystallization tendency decreases by co-polymerization,

because it lowers the structural symmetry, so by
controlling the extent of co-polymerization, the relative
extent of crystallize.

The amorphous region can be adjusted to get required

hardens, rigidity, heat resistance and flexibility.

A crystallize or any amorphous polymer can also be made

flexible and plastics by adding plasticizer.

The plasticizer neutralization of intermolecular forces of

attraction between macromolecules.

Performance of Crystalline and Amorphous Polymers

Crystalline types of plastics are more difficult to process;

requiring more precise control during fabrication, have
higher melting temperature and melt viscosities, and tends
to shrink and warp more than amorphous types.

They have a relatively sharp melting point.

That is they do not soften gradually with increasing

temperature but remain hard until a given quantity of heat
has been absorbed.

Heating and sudden quenching of crystalline materials will

lead to produce amorphous material. Its properties can be
significantly different than if it is cooled properly (slowly)
and allowed to re-crystallize.

Effect of Crystallization on the properties of polymers

The properties of polymer such as density, modulus,
hardness, permeability and heat capacity will be largely
affected by its crystallinity. Semi crystalline polymer, its
crystalline and amorphous region exhibit different
properties even than both the region are chemically
same. E.g. density of crystalline region will be higher
than the density of amorphous region. Most of the
properties are dependent on the percentage of the
crystalline region present in the polymer.

Effect of Crystallization on Processability

strong crystalline forces may make the melting

temperature of crystalline polymer higher than its
thermal decomposition temperature, and thus
prevent thermal decomposition temperature.

Fast and complete crystallization must be

occurring in the mold so that the molded piece

can

be ejected rapidly without later distortion

and

shrinkage

Effect of Crystallization on Mechanical Properties

Packing of polymer molecules into crystalline lattice

generally restricts their mobility and stiffness their
reversible mechanical properties.

Elongation in polymer that is near or above the glass

transition temperature generally decreases as crystallinity
increases.

Creep and compliance creep of polymer, above the glass

transition temperature, are greatly reduced by crystallinity.

Crystallinity often decreases impact strength and large

crystallites particularly produce brittleness as explained
below

Effect of Crystallization on Mechanical Properties

Effect of Crystallization on Thermal Properties

Effect of Crystallization on Electrical Properties

Crystallinity restricts the mobility of polar groups in the

polymer molecules and thus affects dielectric properties
of the polymer.

In the molten state thermal randomization of polar groups

is greater than orienting effects of an electric field and
dielectric constant rather low.

With decreasing the temperature thermal randomization

decreases, the orienting and polarization effects of the
electric

field

increases.

remains

and

thus

dielectric

constant

Effect of Crystallization on Electrical Properties

Effect of Crystallization on Optical Properties

Crystallinity increases the density of the polymer, which

decreases the speed of light passing through it and thus
increases the refractive index

When crystals are larger than the wavelength of visible light

about 400-700m lights passes through many successive
crystalline and amorphous area is scattered and clarity of
the polymer decreased.

Large single crystal scatters light at wide angels and thus

causes haze.

Effect of Crystallization on Chemical Properties

The tigtly packed regular structure of crystalline polymers

is so stable that it is impossible to break the lattice using
chemicals

Liner amorphous polymers dissolve easily in a range of

organic solvents

Crystalline polymers are usually insoluble and can be

dissolved only under limited condition in few specific
solvents

Crystalline polymers can be dissolve above their melting

point where sufficient thermal energy has already been
supplied to separate the polymer molecules from the tight
crystalline structure.

Effect of Molecular Weight on Crystallinity

Chemistry of Polymerisations

Functionality

Chain Growth Polymerisation

1. The monomers contain at least a double bond that
participates in the polymerisation reaction.
2. The initiators for chain polymerisation may be different
depending upon the nature of initiation i.e. free radical,
cation and anion.
3. The carbon-carbon double bond in vinyl monomers and
the carbon-oxygen double bond in aldehydes and
ketones are the two main types of linkages that undergo
chain polymerisation.
4. Important characteristics of chain polymerisation
5. Once the initiation occurs, the polymer chains form very
quickly i.e. in the time scale of 10-1 to 10-6 s,
6. The catalyst concentration needed is very low and that
means during the course of polymerisation only
monomers and polymer are present,
7. The process is exothermic
8. High polymers with molecular weights of 10,000 to 10
million can be obtained,)

Polymerisation Techniques
Bulk Polymerisation
a.

The monomer is taken in the liquid state and the

initiator is dissolved in the monomer. The chain transfer
agent, whenever used to control the molecular weight, is
also dissolved in the monomer itself.

b.

The whole system is, therefore, in a homogeneous

phase. The reaction mass is heated or exposed to a
radiation source for initiating the polymerisation and is
kept under agitation for proper mass and heat transfers.

c.

As the polymerisation proceeds, the viscosity of the

medium increases and mixing becomes progressively
difficult, leading to products with very broad molecular
weight distribution.

The major Disadvantages are:

1. The medium gets viscous, the diffusibility of the
growing polymer chains becomes restricted, the probability
of chain collision becomes less, termination becomes
difficult, active radical sites accumulate and the rate of
polymerisation increases enormously.
2. This whole phenomenon is called 'auto acceleration'
and, sometimes, the uncontrolled exothermic reaction can
lead to an explosion.
Some advantages:
3. Bulk polymerisation, however, is quite simple and the
product obtained has a high purity since, except the
initiator and the chain transfer agent, no other additive that
could contaminate the product is used. The polymer
obtained can also be used as such since no isolation from
other components is involved.
4. Ex: vinyl chloride to get PVC resin

Solution Polymerisation
a. In solution polymerisation, the monomer is dissolved in a
suitable inert solvent along with the chain transfer agent.
b. The free-radical initiator is also dissolved in the solvent
medium, while the ionic and coordination catalysts, can
either be dissolved or suspended.
c. The presence of the inert solvent medium helps to
control viscosity increase and promote a proper heat
transfer.
The major disadvantage
technique is:

of

the

solution

polymerisation

1. The selected solvent cannot be completely ruled out and

hence, it is difficult to get very high molecular weight
products.

2. The polymer formed will also have to be isolated from

the solution either by evaporation of the solvent or by
precipitation in a non-solvent, and removal of their final
traces is always extremely difficult.
3. Solution polymerisation techniques, nevertheless, can
advantageously be used where the polymer is used in its
solution form, as in the case of certain adhesives and
coating compositions, or in systems where the polymer
formed is insoluble in its monomer or solvent and
precipitates out as a slurry and is amenable for easy
isolation.
4. Polyacrylonitrile by free-radical polymerisation and
that of polyisobutylene by cationic polymerisation, use the
solution technique. Block co-polymers are also made
exclusively by this technique

Suspension Polymerisation
Only water-insoluble monomers can be polymerised
by this technique. The initiators are monomer soluble.
The monomer is suspended in water, in the form of
fine droplets, which are stabilized and prevented from
coalescing by using suitable water-soluble protective
colloids, surface active agents and by stirring.
The size of the monomer droplets formed depends
on the monomer-to-water ratio, the type and
concentration of the stabilizing agents and also on the
type and speed of agitation employed.
Since each monomer droplet is isolated and
independent of the other droplets, it can be visualized to
act as an independent bulk polymerisation nucleus.
The continuous aqueous phase separating the
monomer droplets acts as an efficient heat transfer
medium and, hence, the exothermic is well controlled.

Advantages
1. Since water is used as the heat transfer medium, the
process is also economical as compared to solution
polymerisation.
2. As the entire bulk of the monomer is divided into
innumerable any droplets control on the kinetic chain length
of the polymer formed is also quite 'good, resulting in a fairly
narrow 'molecular weight distribution of the product.
3. Polymerisation proceeds to 100% conversion and the
product is obtained as spherical beads or pearls. (For this
reason, this technique is also known as bead or pearl
polymerisation).
4. Isolation of the product becomes easy as this involves
only filtration of the beads and removal of the surface-active
agents and protective colloids by water washing.
5. The water washed and dried product can be used as
such for moulding purposes or can be dissolved in a
suitable medium for use as adhesives and coatings. `

Emulsion Polymerisation
1. As in the case of suspension polymerisation, in
emulsion polymerisation too, the monomer is dispersed
in the aqueous phase not as discrete droplets, but as a
uniform emulsion.
2. The emulsion is stabilized by surface-active agents
(surfactants), protective colloids and also by certain
buffers. The surfactants can be anionic (alkali salts of
fatty acids and of aryl and alkyl sulfonic acids), cationic
(alkyl amine hydrochlorides and alkyl ammonium
halides) or non-ionic (alkyl glycosides and saccharose
esters of fatty acids).
3. Surfactants serve the purpose of lowering the
surface tension at the monomer water interface and
facilitate emulsification of the monomer in water.

1. Owing to their low solubility, surfactants get fully

dissolved or molecularly dispersed only at low
concentrations. Beyond a particular concentration, the
excess quantity does not get molecularly dispersed, out
forms molecular aggregates known as 'micelles', and an
equilibrium is set up between the dissolved surfactant
molecules and the aggregated ones.

2.The highest concentration, wherein all the molecules are

in a dispersed state, or the concentration beyond which only
micelle formation is possible, is known as the 'critical micelle
concentration' (CMC).

3. Emulsifier molecules are made of two parts: a long nonpolar hydrocarbon' chain to which is attached a polar group
such as -COONa, -S03Na, -NH2HCl or -NBr.

4. In micelle formation, the emulsifier molecules aggregate in

such a way that the polar end of the molecules align
themselves outward and. the hydrocarbon ends come close
to each other at the interior.

5. Due to the close proximity of the hydrocarbon ends of all

emulsifier molecules, the interior of the micelle acts as a
hydrocarbon phase where the monomer can be soIubilize.
When the monomer is added and agitated, emulsification
takes place.

6. The resultant emulsion is a complex system a molecular

solution of the emulsifier in water is the continuous phase
wherein the monomer droplets and micelles (having the
soIubilize monomer at their interior) are uniformly dispersed.

7. If the monomer is slightly soluble in water, then the

aqueous emulsifier solution phase will also dissolved in it.

Melt Polycondensation
1. This technique is used for the polymerisation of
monomers, which have at least one solid component, and do
not decompose around their melting points.
2. The temperatures involved in melt polycondensation are
rather high and, hence, the reaction has to be carried out in
an inert atmosphere of N2 or CO2 to avoid such side
reactions as can lead to oxidation, decarboxylation,
degradation etc.
3. The reaction is carried out under reduced pressure to
facilitate removal of the byproduct, which becomes essential
if a high molecular weight product is aimed at.
4. Removal of the byproduct becomes extremely difficult at
later stages of the reaction, as there is considerable increase
in the viscosity of the medium, like in bulk polymerisation.
5. Ex: polyethylene terephthalate, nylon 6, 6

Solution Polycondensation
1.

The reactants are taken as a solution in a suitable inert

solvent. The reaction can be carried out at comparatively
lower temperatures during which heat and mass transfer
processes are easier than in the melt technique.

2.

The solvent can also serve as an entrapping agent for the

byproduct formed and hence, the removal of the byproduct
becomes easy. Owing to the presence of the solvent phase,
however, the kinetic probability of chain growth is low and
this leads to a reduced rate and a low degree of
polymerisation.

Many of the liquid polyester resins based on glycols and unsa

turated dicarboxylic acid are prepared by this technique
using high boiling aromatic hydrocarbons as solvent with
which the water (byproduct) forms an azeotrope and, hence,
can be removed easily.

Interfacial Condensation
1.

Polymerisation is allowed to proceed at the interface

between an aqueous and an organic medium. Reactants
having highly reactive functional groups, which can readily
react at ambient temperatures to form condensation
products, are suited to this technique.

2.

The polymer formation at the interface is a diffusion

controlled process, very high molecular weight products
can be achieved by this technique.

3.

The two solutions are very thoroughly agitated so as to

form an emulsion wherein the interface surface/volume
ratio is increased tremendously and, hence, both the rate
and degree of polymerisation become very high

4.

Preparation of fully aromatic polyarnides from tereph

tholoyl chloride and paraphenylene diamine is a typical
example:

1. The diamine is dissolved in water and the acid chloride

in chloroform or carbon tetrachloride. When the two
solutions are brought in contact with each other, at the
interface, the diamine molecules diffuse into the organic
phase and react with the acid chloride, resulting in the
formation of a polymer, which precipitates out immediately.
2. The byproduct formed (HCI) diffuses back into the
aqueous phase and gets dissolved. The precipitate is
formed at the interface in the form of a thin film and, when
removed from the system, exposes a fresh surface of the
acid chloride to the organic phase resulting in the
formation of the fresh quantity of the polymer.
3. As the polymer is formed, it precipitates out and, under
the influence of high-speed agitation, forms slurry. The
polymer is isolated from the slurry and washed free of
adherent reactants.

Solid and Gas Phase Polymerisation

Solid phase polymerisation is mostly restricted to chain
polymerisation. Also, since such polymerisation is
restricted to low temperatures, thermal activation of the
reaction is quite difficult and, hence, the photo or
radiation-activation technique is resorted to.

Gas phase polymerisation is known in the case of very few

olefinic monomers. The disadvantage of the system is that
it has a very poor heat transfer. The two methods used in
the gas phase polymerisation are: (i) spraying the catalyst
(usually Zeigler-Natta type) into the gaseous monomer
and (ii) feeding the gaseous monomer into a fluidised bed
made up of the catalyst particles. In both the cases, the
polymer is obtained as a free-flowing powder. Poly
merisation of ethylene and p-xylene can be cited as
examples for gas phase polymerisation.

Thank You