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Unit-I
POLYMER CHEMISTRY
1. Introduction
Polymers are macromolecules having high molecular weight. The macromolecule of polymers
are either biological on non-biological orgin. Biological polymers govern and control life; synthetic or
non-biological polymers such as plastics, fibres, elastromers are widely used in industry and everyday
life. Twentieth century is called as Polymer Age since many of the conventional materials made of
wood, iron and rubber are irrevocably replaced by polymers. In Greek Poly means many and mer unit
or part.
1.1 Terms used in polymer chemistry
Few terms are repeatedly used in polymer sciences which have got significance and specific
meaning. Some of them are,
1.1.1 Monomers and Polymers
Polymer is defined as a high molecular weight compound formed by the combination of small
repetitive units called monomers.
A monomer is a small chemical entity, which forms the backbone of the polymer. The following
table illustrates some monomers and repeating units of the polymer.
Table 1.1 Monomers, repeating units, Properties and applications of the polymers
Name of the
polymer
Formula Monomer Properties Application Area
Polyethylene
low density
(LDPE)
(CH
2
-CH
2
)
n
Ethylene CH
2
=CH
2

soft, waxy
solid
Film wrap, plastic
bags
Polyethylene
high density
(HDPE)
(CH
2
-CH
2
)
n

ethylene
CH
2
=CH
2

rigid,
translucent
solid
Electrical
insulation
bottles, toys
Polypropylene
(PP) different
grades
[CH
2
-CH(CH
3
)]
n

propylene
CH
2
=CHCH
3

atactic: soft,
elastic solid
isotactic:
hard, strong
solid
Similar to LDPE
carpet, upholstery
2

Poly(ethylene
terephthlate)
(PET)

n


ethylene
CH
2
=CH
2 &
Terephthlic
acid

Transparent ,
solid
Bottles for soft
Drinks and other
Beverages.
Poly(vinyl
chloride)
(PVC)
(CH
2
-CHCl)
n

vinyl chloride
CH
2
=CHCl
strong rigid
solid
Pipes, siding,
flooring
Poly(vinylidene
chloride)
(Saran A)
(CH
2
-CCl
2
)
n

vinylidene chloride
CH
2
=CCl
2

dense, high-
melting solid
Seat covers, films
Polystyrene
(PS)
[CH
2
-CH(C
6
H
5
)]
n

styrene
CH
2
=CHC
6
H
5

hard, rigid,
clear solid
soluble in
organic
solvents
Toys, cabinets
packaging
(foamed)
Polyacrylonitrile
(PAN, Orlon,
Acrilan)
(CH
2
-CHCN)
n

acrylonitrile
CH
2
=CHCN
high-melting
solid
soluble in
organic
solvents
Rugs, blankets
clothing
Polytetrafluoroe
thylene
(PTFE, Teflon)
(CF
2
-CF
2
)
n

tetrafluoroethylene
CF
2
=CF
2

resistant,
smooth solid
Non-stick surfaces
electrical insulation
Poly(methyl
methacrylate)
(PMMA, Lucite,
Plexiglas)
[CH
2
-C(CH
3
)CO
2
CH
3
]
n

methyl methacrylate
CH
2
=C(CH
3
)CO
2
CH
3

hard,
transparent
solid
Lighting covers,
signs skylights
Poly(vinyl
acetate)
(PVAc)
(CH
2
-CHOCOCH
3
)
n

vinyl acetate
CH
2
=CHOCOCH
3

soft, sticky
solid
Latex paints,
adhesives
cis-Polyisoprene
natural rubber
[CH
2
-CH=C(CH
3
)-
CH
2
]
n

isoprene
CH
2
=CH-C(CH
3
)=CH
2

soft, sticky
solid
Requires
vulcanization
for practical use
Polychloroprene
(cis + trans)
(Neoprene)
[CH
2
-CH=CCl-CH
2
]
n

chloroprene
CH
2
=CH-CCl=CH
2

tough,
rubbery solid
Synthetic rubber
oil resistant
Polyamides(Nylo
n)

Tough, hard
engineering
plastic
Fibers, molded
objects
Polyesters
(Dacron, Mylar,
Fortrel)



Linear polyesters,
fibers, recording
tape
3

Polyesters
(Casting resin)



Cross-linked with
styrene and
benzoylperoxide,
fiberglass boat
resin, casting resin
Phenol-
formaldehyde
(Bakelite)



Mixed with fillers,
Molded electrical
cases, adhesives,
laminates, varnishes
Cellulose acetate
(cellulose is a
polymer of
glucose)


Photographic film
Silicones



Water-repellent
coatings,
Temperature-
resistant
Fluids and rubber

1.7. CLASSIFICATION OF POLYMERS
Based on the source, polymers are broadly classified into two types natural polymers and synthetic
polymers.
Chart 1.1. Classification of Polymers







1.7.1 Natural Polymers
1.7.1.1 Natural Organic Polymers
Polymer
s
Natural

Artificial
Organic

Inorganic Inorganic Organic
4

The polymers obtained from nature are called natural polymers. Examples of natural polymers
are starch, cellulose, proteins, nucleic acids, natural rubber, jute fiber etc., Starch is a polymer of
glucose. It is a chief food reserve of plants. Cellulose is also a polymer of glucose. It is a chief structural
material of the plants, both starch and cellulose are produced by plant photosynthesis. Proteins are
polymers of -amino acids. They have generally 20 to 100 -amino acids joined together in a highly
organized arrangement. These are building block of animals. Nucleic acids are polymers of various
nucleotides.RNA and DNA are common nucleotides. Natural rubber is a polymer of unsaturated
hydrocarbon, 2-methyl-1,3-butadiene, called isoprene. It is obtained from latex of rubber trees.

nCH
2
=C-CH=CH
2
-------CH
2
-C=CH-CH
2
----

CH
3
CH
3


Isoprene polyisoprene (natural rubber)
1.7.1.2 Natural Inorganic Polymers
These are polymers containing no carbon atoms. the chains of these polymers are composed of
different atoms joined by chemical bonds. Examples are poly silicon dioxide and Poly phosphoric acid.

1.7.2 Synthetic polymers.
The polymers which are prepared in the laboratories are called synthetic polymers. These are
also called man-made polymers. A few examples are PVC, polyethene, nylon, Teflon, Teflon,
Bakelite, Terylene, etc.,
Type of synthetic polymers
(i) Organic polymers
These are polymers containing hydrogen, oxygen, nitrogen, sulphur and halogen atoms.
Polyethylene, Polyvinylalcohol, PVC, Epoxy polymers, polyurethane are a few illustrative examples.
(ii) Elemento-organic (or) hetero-organic polymers
These are polymers composed of carbon atoms and hetero-atoms (like N,S & O).The main chain
consists of carbon atoms and whose side groups contain hetero atoms linked directly to the C atoms in
the chain. For example Polysiloxanes and polytitoxanes.
Classification based on molecular weight
5

Polymers classified in two types by its molecular weight or degree of polymerization. Polymers
with low degree of polymerization are known as oligomers, there molecular weight ranges from 500-
5000. Polymers with high degree of polymerization are known as high polymers, their molecular weight
ranges from 10,000- 2, 00,000.
1.6 FUNCTIOALITY AND ITS SIGNIFICANCE
The number of bonding sites or reactive sites or functional groups, present in a monomer is
known as its functionality.
Table 1.2 Functionality of monomers
S.No. Example Functionality

1
CH
2
= CH
2
(Ethylene)

2(Two Bonding sites are due to the presence of one
double bond in the monomer. Therefore ethylene is a bi
functional monomer).
2 H
2
N-(CH
2
)
6
-NH
2
Hexa methylene di amine
2 (this monomer contains two functional groups; hence
it is a bi functional monomer).
3 CH
2
-OH

CH
2
-OH

CH
2
-OH
(Glycerol)
3 (this monomer contains three functional groups; hence
it is a tri functional monomer).

1.6.1.SIGNIFICANCE OF FUNCTIONALITY
1.6.1.1. Bi functional monomers
Bi functional monomers (i.e., functionality of the monomer is 2) mainly form linear (or) straight
chain polymer. Each monomeric unit in the linear chain is linked by strong covalent bonds (primary
bonds), but the different chains are held together by weak Van der walls forces of attraction (secondary
bonds). Therefore there is no restriction to movement of one chain over another. These types of
polymers are soft and flexible. These are soluble in organic solvents












6



Fig.1.1 Morphology of bi-functional polymers
1.6.1.2. TRIFUNCTIONAL MONOMERS
When a trifunctional monometer (i.e., functionality of the monometer is 3) is mixed in small
with a bifunctional monomer, they form branched chain polymer.





Fig.1.2. Morphology of tri-functional polymers
The movement of polymer chain in branched polymer is more restricted than that of straight
chain polymers.
1.6.1.3. Poly functional monomers
Poly functional monomers form cross-linked polymer (three-dimensional network polymer). All
the monomers in the polymer are connected to each other by strong covalent bonds. Therefore the
movement of polymer chain is totally restricted .This type of polymers are hard and brittle and possess
very high strength and heat resistance. They are insoluble in almost all organic solvents.







Fig.1.3. Morphology of poly-functional polymers
x
x x
x
x
x

x
x x
x x x x
x x
x
x

x
x x
x x x x
7

1.2 POLYMERIZATION
Polymerization is a process in which a larger number of small molecules (called monomers)
combine to give a big molecule (called polymer) with or without the elimination of small molecules like
water, methanol, ammonia, HCl etc., Accordingly they are classified as addition or condensation
polymerization.
1.3 DEGREE OF POLYMERIZATION(DP)
Polymerization reaction results of polymer chains of different length is specified by number of repeating
units in the polymer chain. This is called as degree of polymerization(DP). It is represented by the
following relationship,
=



=


For example
The molecular weight is the product of molecular weight of repeating unit and DP. Using
polyethylene is an example, a polymers of DP 1000 has molecular weight of 28 X 1000 = 28000.
1000CH
2
= CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-CH
2
-
In this example 1000 repeating units are present in the polymer chain. So, the degree of
polymerization is 1000.
1.8. Polymerization Reactions
Polymers are made or polymerized by chemical reactions. Small simple undergo chemical
bond formation in the presence of catalysts to form very large molecule.
1.8.1. Addition (Chain Growth) Polymerization
Addition polymerization reactions involves a rapid chain reaction of chemically activated
monomers. Each reaction sets up the condition for another to proceed. Each step needs a reactive site a
double carbon bond or an unsaturated molecule. The three stages are: initiation, propagation,
termination In the case of the polymerization of polyethylene, initiation can come from a free radical a
single unit that has one unpaired electron such as an OH

molecule. H
2
O
2
can break up into 2 OH

8

molecules. Each can act to initiate and to terminate the reaction. The termination here would be called
recombination. The composition of resultant molecule is a multiple of the individual monomers. These
reactions most commonly produce linear structures but cannot produce network structures.
1.8.2. Condensation (Step Growth or Stepwise) Polymerization
As the term condensation involves two molecules fairly different functional groups reacts to
give a polymer product. In these reactions between reactive monomers that occur in one step at a time.
They are slower than addition polymerization needs reactive functional groups. In all condensation
polymerizations reactions involves the elimination of byproduct such as water, methanol, HCl etc., No
reactant species has the chemical formula of monomer repeating unit. Most commonly produce network
products and sometimes linear structures also. Detailed mechanisms of these reactions are discussed in
the following sections.
Table.1.3. Difference between addition polymerization and condensation polymerization
S.No. Addition Polymerization Condensation polymerization
1. The monomer must have at least
one multiple bond
Example : Ethylene ; CH
2
=CH
2

Vinyl chloride ; CH
2
=CHCl
The monomer must have two identical or
different reactive functional groups
Example : Ethylene glycol; HO-CH
2
-CH
2
-OH
Adipic acid ; HOOC-CH
2
-CH
2
-CH
2
-CH2-
COOH
2 Monomers add on to give
polymer and no other byproduct
is forms
Polymer is formed by the condensation of
reactive functional groups with the elimination
of small molecules like water, methanol, etc.,
3 Number of monomeric unit
decrease steadily throughout the
reaction
Monomers disappear at the initial stage of the
reaction
4 Molecular weight of the polymer
is an integral multiple of a
monomer.
Molecular weight of the polymer need not to be
an integral multiple of a monomer.
5 High molecular weight
compounds formed at once
Molecular weight of the polymer increases
steadly throughout the reaction.
6 Longer reaction time gives higher
yield, but have a little effect on
molecular weight.
Longer reaction is required to obtain high
molecular weight polymer.
9

7 Homo-chain polymer is obtained Hetero chain polymer is obtained.
8 Thermo plastics are produced Thermosetting polymers are produced.

Synthesis of Addition Polymers
All the monomers from which addition polymers are made are alkenes or functionally substituted
alkenes. The most common and thermodynamically favored chemical transformations of alkenes are
addition reactions. Many of these addition reactions are known to proceed in a stepwise fashion by way
of reactive intermediates, and this is the mechanism followed by most polymerizations. A general
diagram illustrating this assembly of linear macromolecules, which supports the name chain growth
polymers, is presented here. Since a pi-bond in the monomer is converted to a sigma-bond in the
polymer, the polymerization reaction is usually exothermic by 8 to 20 kcal/mol. Indeed, cases of
explosively uncontrolled polymerizations have been reported.

Scheme1.1.General addition polymerization reaction.
It is useful to distinguish four polymerization procedures fitting this general description.
Radical Polymerization The initiator is a radical, and the propagating site of reactivity (*) is a carbon
radical.
Cationic Polymerization The initiator is an acid, and the propagating site of reactivity (*) is a
carbocation.
Anionic Polymerization The initiator is a nucleophile, and the propagating site of reactivity (*) is a
carbanion.
Coordination Catalytic Polymerization The initiator is a transition metal complex, and the
propagating site of reactivity (*) is a terminal catalytic complex.
1. Radical Chain-Growth Polymerization
10

Virtually all of the monomers described above are subject to radical polymerization. Since this can
be initiated by traces of oxygen or other minor impurities, pure samples of these compounds are often
"stabilized" by small amounts of radical inhibitors to avoid unwanted reaction. When radical
polymerization is desired, it must be started by using a radical initiator, such as a peroxide or certain
azo compounds. The formulas of some common initiators, and equations showing the formation of
radical species from these initiators are presented below.

Scheme.1.2. Mechanism of formation of free radical initiators
By using small amounts of initiators, a wide variety of monomers can be polymerized. One example
of this radical polymerization is the conversion of styrene to polystyrene, shown in the following
diagram. The first two equations illustrate the initiation process, and the last two equations are examples
of chain propagation. Each monomer unit adds to the growing chain in a manner that generates the
most stable radical. Since carbon radicals are stabilized by substituent of many kinds, the preference for
head-to-tail regioselectivity in most addition polymerizations is understandable. Because radicals are
tolerant of many functional groups and solvents (including water), radical polymerizations are widely
used in the chemical industry.
11


Scheme.1.3.Mechanism of initiation of polymerization reaction
Termination may be happened by combination or disproportionation, in both types of termination
two reactive radical sites are removed by simultaneous conversion to stable product(s). Since the
concentration of radical species in a polymerization reaction is small relative to other reactants (e.g.
monomers, solvents and terminated chains), the rate at which these radical-radical termination reactions
occurs is very small, and most growing chains achieve moderate length before termination.

Scheme.1.4.Mechanism of termination of polymerization reaction
12

2. Cationic Chain-Growth Polymerization
Polymerization of isobutylene (2-methylpropene) by traces of strong acids is an example of
cationic polymerization. This process is similar to radical polymerization, as demonstrated by the
following equations. Chain growth ceases when the terminal carbocation combines with a nucleophile or
loses a proton, giving a terminal alkene (as shown here).

Scheme.1.5.Mechanism of cationic polymerization reaction

Monomers bearing cation stabilizing groups, such as alkyl, phenyl or vinyl can be polymerized
by cationic processes. These are normally initiated at low temperature in methylene chloride solution.
Strong acids, such as HClO
4
, or Lewis acids containing traces of water (as shown above) serve as
initiating reagents. At low temperatures, chain transfer reactions are rare in such polymerizations, so the
resulting polymers are cleanly linear (unbranched).

3. Anionic Chain-Growth Polymerization
Treatment of a cold THF solution of styrene with 0.001 equivalents of n-butyllithium causes an
immediate polymerization. This is an example of anionic polymerization, the course of which is
described by the following equations. Chain growth may be terminated by water or carbon dioxide, and
chain transfer seldom occurs. Only monomers having anion stabilizing substituents, such as phenyl,
cyano or carbonyl are good substrates for this polymerization technique. Many of the resulting polymers
are largely isotactic in configuration, and have high degrees of crystallinity.
13


Scheme.1.6.Mechanism of cationic polymerization reaction

Species that have been used to initiate anionic polymerization include alkali metals, alkali
amides, alkyl lithiums and various electron sources. A practical application of anionic polymerization
occurs in the use of superglue. This material is methyl 2-cyanoacrylate, CH
2
=C(CN)CO
2
CH
3
. When
exposed to water, amines or other nucleophiles, a rapid polymerization of this monomer takes place.
1.9. PLASTICS
Plastics are high molecular weight organic materials that can be moulded into any desired
shape by the application of heat and pressure in the presence of a catalyst. Originally, plastics were
discovered and then developed based on trial and error method. The present time is sometime referred as
plastic age, because the use of polymeric material is percolated in large variety of applications. This
rapid growth has taken place only in the last 50 years. It was mans desire to replace, glass, metal,
ceramic, wood and other materials of constructions. Since plastics possess the following advantages,
they have wider applications.
1.9.1.Advantages of plastics over other materials
Advantages of plastics over other materials are
i) They are light in weight.
ii) They possess low melting point.
iii) They can be easily moulded and have excellent finishing
iv) They possess very good strength and toughness.
v) They possess good shock absorption capacity.
vi) They are corrosion resistant and chemically insert.
vii) They have low co-efficient of thermal expansion and possess good thermal and electrical
insulating property.
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viii) They are very good water-resistant and possess good adhesiveness.
1.9.2 Classification of plastics
Based on the structure and type of resin used for used for the manufacture of plastics,
plastics are classified into two main types thermoplastics and thermosetting plastics. A resin is a basic
binding material, present in a plastic which undergoes polymerization reaction during moulding.
Chart 1.2.Classification of Plastics






Example are Examples are
i. Polyethylene i. Bakelite
ii. polyvinyl chloride ii. Polyester
iii. Polystyrene iii. Urea-formaldehyde
iv. Poly acrylic nitrile iv. Epoxy-resin

1.9.2.Thermoplastics
Thermoplastics are prepared by addition polymerization. they are straight chain or a slightly
branched polymers and various chains are held together by weak Van der Waals forces of attraction.
Thermoplastics can be softened on heating and hardened on cooling. They are generally soluble in
organic solvents.

1.9.4.Thermosetting plastics
Thermosetting plastics are made up by three dimensional networks. They are heat resistant and
could not be remoulded by heating. They are known for toughness. Usually they are manufactured by
condensation polymerization reactions

Table.1.4. Difference between thermal plastics and thermosetting plastics
Plastics
Thermoplastics
Thermosetting plastics
15

S.No. Thermal Plastics Thermosetting Plastics
1 They are formed by addition
polymerization
Example: Polyethylne, PVC etc.,
They are formed by condensation
polymerization
Bakelite, Nylons, epoxy resins
2 They are long linear chain
polymers
They consist of three dimentional cross
linked network
3 They soften on heating and
harden on cooling
They do not soft on heating

4 They are weak, soft and less brittle They are strong, hard and more brittle
5 All the chains of the polymer are
held by hydrogen bonding or Van
dar Walls forces.
All the polymers chains are cross linked
by strong covalent bond.
6 They can be remoulded They cannot be remoulded
7 They have low molecular weights They have high molecular weights
8 They are soluble in organic
solvents
Ther are insoluble in organic solvents

1.10. Properties of Polymers
1.10.1.The Glass Transition Temperature, Tg
Glass transition temperature is defined as the temperature bellow which a polymer is hard and
above which it is soft. The hard brittle state of a polymer is known as the glassy state and the soft
flexible state is rubbery of viscoelastic state. On further heating, the polymer (if it is un-cross linked)
becomes a highly viscous liquid and starts flowing; this state is termed as viscofluid state, the transition
takes place at its flow temperature.
16


Fig.1.4. Change of state with temperature of polymeric materials
When an amorphous material is cooled, there is no abrupt change in volume. In the case of a
crystalline material there is sudden change in volume. At the glass transition temperature, Tg, there is
change in slope of the curve or specific volume Vs temperature is moving form a low value in a glassy
state to a higher volume in the rubbery state over a range of temperature as shown in figure.1.4.

Fig.1.5.Change in volume of a polymer as a function of temperature
The following features are known to influence the glass transition temperature:(a) The presence of
groups pendant to the polymer backbone, since they increase the energy required to rotate the molecule
about primary bonds in the main polymer chain. This is especially true of side chains or branches.
( b ) The presence of inherently rigid structures in the backbone of the molecule, e.g. phenylene groups.
(c) Cross linking.
17

( d ) Hydrogen bonds between polymer chains. ( e ) Relative molar mass, which influences 7; because
higher molar mass polymers have less ease of movement and more restrictions in their overall molecular
freedom than polymers of lower molar mass. (f) The presence of plasticizers. The effects of these
different factors can be seen in the Tg values of some typical polymers. A number of these values are
particularly contributes to the relative level of the glass transition temperature.

1.10.2.POLYMER STEREOCHEMISTRY

Mono substituted vinyl monomers form polymers containing a series of asymmetric carbon
atoms along the molecule. The precise arrangement of these asymmetric carbons gives rise to three
different possible stereo chemical arrangements. Firstly, where all asymmetric carbon atoms adopt
identical configurations, the resulting polymer is described as isotactic. Secondly, where there is a
regular alternating arrangement of asymmetric carbon atoms, the polymer is described as syndiotactic.
Lastly,
where there is no regularity at all in the arrangement of asymmetric carbon atoms, the resulting structure
is known as atactic. These three steric arrangements are illustrated in Figure 1.2.
Figure 1.2 Steric arrangements of polymers

Scheme.1.7.Tacticity of polymer
1.11.Molecular weight of a polymer
18

The molecular weight is single digit for simple chemical entity but it is in the order of millions for
polymer. For example molecular weight of ethylene is 28, each of its molecules has the same chemical
structure [CH
2
=CH
2
] . But ethylene is polymerized the structure is indefinite
Wherein n can change from one polyethylene to another polyethylene in the same sample. This is
because, the number of polymer chains start growing at any instant, but all then do not get terminated
after growing the same time. The chain termination is random process, and so polymer molecules formed
can have different number of monomer units and thus different molecular weights. A polymers sample is
a mixture of molecules of same chemical type but different molecular weight. It is necessary, therefore,
to take an average molecular mass in these substances. Two types of molecular mass as reckoned with.
These are number average molecular mass(

n
) and weight average molecular mass(

w
).

1.11.1Number average concept
Consider a basket containing four vegetables: onion, brinjals, cabbages and cauliflowers. Just for
ease of understanding, let each onion of the onion lot weigh the same and so also of the other vegetables.
Assume that the number of each vegetable and its weight are tabulated.
Vegetable entity Number of units
in each entity, n
Weight of each
unit, M(g)
Total weight of each entity
W= nM(g)
Onions 2 10 20
Brinjals 4 20 80
Cabbages 6 100 600
Cauliflowers 3 250 750
Total 15 1450

Now, we have to find out the averages weight of the vegetables present in the basket. To work this
out, one might assume that that the individual vegetable entity contributes to the average weight in the
proportion of its numbers. What we can then get is the number average weight , arrived at as follows:
Total number of vegetables contained in the basket = 15
Number of onions present in the basket = 2
Therefore, the number fraction of onions = 2/15
Similarly,
Number fractions of brinjals = 4/15
Number fractions of cabbages = 6/15
Number fraction of cauliflowers = 3/15
Contribution made by 2 onions towards average weight of vegetables in the basket :
19

Number fraction of onion X weight of each onion =(2/15) X 10
= 1.33 g
Similarly
Contribution made by 4 brinjals towards average weight of vegetables in the basket = (4/15) X 20
= 5.33 g
Contribution made by 6 cabbages towards average weight of vegetables in the basket = (6/15) X 100
= 40.00 g
Contribution made by 4 brinjals towards average weight of vegetables in the basket = (3/15) X 250
= 50.00 g
Summing up the contributions made by each vegetable variety, we get the number average weight of the
total vegetables as
1.33+5.33+40+50 = 96.66
1.11.2.Weight average concept
The other method of calculation the average weight is based on the assumption that the individual
vegetable variety contributes to the total weight in the proportion not its number but its weight. What we
then get is the weight average is arrived as follows:

Total weight of all vegetables in the basket = 1450 g
Weight of onions present in the basket = 20 g
Therefore,
Weight fraction of onions = 20/1450
Similarly, weight fraction of brinjals, cabbages and cauliflowers are 80/1450, 600/1450 and 750/1450,
respectively.
Next, contribution made by onions towards average weight of the vegetables in the basket = weight
fraction of onions X average weight of onions = (20/1450) X 10 = 0.14 g
Similarly,
Corresponding contribution of brinjals = (80/1450) X 50
= 1.10 g
Corresponding contribution of cabbages = (600/1450) X 100
= 41.38 g
Corresponding contribution of cauliflowers = (7500/1450) X 250
= 129.31g
Summing up the contribution made by the each vegetable variety, we get the weight-average weight of
total vegetables as
20

0.14 + 1.10 + 41.38 + 129.31 = 171.93 g
1.11.3.Generalization of the foregoing concepts
In the calculation of molecular weights of a polymer, either we can use number-average (

n
) or
weight-average (

w
) molecular weights. The method of calculating (

n
) and (

w
) can now be easily
generalized, using simple mathematics. Assume that there is n number of polymers in a polymers sample
and n
1
of them have M
1
molecular weight; n
2
have M
2
molecular weight and so on till we get n
i
and M
i

molecular weight(see Fig.)



Fig.1.6.Polymer sample with different molecular weight
Now we have total number molecules (n) is given by n = n
1
+ n
2
+n
3
+.+n
i
= n
i
Number of molecules in fraction 1 = n1
Number fraction if fraction 1 =


Molecular weight contribution by fraction 1 =


Similarly molecular weight contribution by other fractions will be as follows:

, . . ,


Number average molecular weight of whole polymer is given by

, +

+. . +


Similarly total weight of the polymer = W = n
i
M
i
.
Weight of fraction1 = W
1
= n
1
M
1
21

Weight fraction of 1 =


Molecular weight contribution of the fraction 1 is given by

1
2


Similarly the molecular contributions of other fraction will be

2
2

3
2

, .,


The weight average molecular weight of the whole polymer will be

1
2

1
2

2
2

3
2

+. +


For synthetic polymers,

is greater than

. It they were be equal , the polymer sample may be


considered as perfectly homogeneous (i.e., each molecule has same molecular weight); but this does not
happen.
1.11.4.Poly dispersity index.
Simple chemical molecules like water, all molecules are in the same size and molecular weight, so
they are monodisperse but polymers molecules are in different size and hence different molecular mass
so they are polydisperse. Monodispersity and polydispersity is represented in the fig.1.7.


All molecules are in same size Molecules are in different size
Fig.1.7. Dispersity of polymers
The heterogeneity of the polymer sample is called polydispersity. The weight average molecular
mass (

) is always greater than number average molecular mass (

),(Figure 1.) unless the polymer


sample is monodisperse i.e.,

.
22


Fig.1.8.Ditribution of molecular weight of a polymer.
The ratio of weight average molecular mass and number average molecular mass(

) is
called the polydispersity index(P.D.I) of a polymer sample.
=


1.12. PRACTICAL METHODS OF CHAIN POLYMERISATION
Chain reactions are used to prepare a variety of high molecular mass polymers of commercial
importance and in practice may take one of four forms, namely bulk, solution, suspension, and emulsion
methods. These four methods are described in the sections that follow, together with the loop
modification which has become of commercial importance recently in producing latexes by emulsion
polymerization for the paint industry.

1.12.1 Bulk Polymerisation.
Bulk polymerization is the simple technique for the preparation of high molecular weight polymer,
which involves the addition reactions. The starting material consist pure polymer with only traces of
initiator and chain transfer agent. For the laboratory preparation of vinyl polymers this method is used.
In industry polyethylene, polystyrene and poly methyl methacrylate are prepared by using this
technique. Polyethylene is produced from gaseous monomers under pressure either high of low. In the
case of poly (styrene), bulk polymerisation is nonetheless used for the commercial production of the
polymer.
23


Fig.1.8.Bulk polymerization
Manufacture of the polymer takes place in discrete stages in different parts of the plant. The reaction
is initiated in a tank which is heated to a temperature of 80 C; styrene undergoes self-initiation on
heating, so that no extra initiator is required for this step, which is allowed to continue until about 35%
conversion to polymer. At this conversion the mixture still has a sufficiently low viscosity to enable
fairly easy stirring and transport. From this stage of 35% polymerisation the mixture is passed down a
tower in an atmosphere of nitrogen; there is a thermal gradient throughout the tower from 100 C at the
top to 200 C at the bottom. This gradient is maintained by a complicated arrangement of heaters and
coolers which compensate for the exotherm that the polystyrene undergoes itself as increasing
proportions of monomer are converted to polymer. At the bottom of the tower, the high molar mass
poly(styrene) is extruded, granulated, and cooled prior to packaging.
Some disadvantages of bulk polymerization are
i. Viscosity of polymeric material increases as polymerization occurs. These results the
difficulties in handling the polymer.
ii. Since chemical reactions are generally exothermic and the increasing viscosity inhibits the
dissipation of heat, there can be localized overheating leading to the charring and possible
degradation of the product.
1.12.2. Solution Polymerisation

In solution polymerization technique the monomer is dissolved in an appropriate solvent. It
eliminates the difficulties associated with the exotherm on polymerization may be overcome since
temperature can be more readily controlled than in the bulk technique. If the right solvent is chosen the
product may form to give a solution suitable for casting or spinning.

24


Fig.1.9.Solution polymerization
Disadvantages with solution polymerization are
i. Reaction temperature is limited by the boiling point of the solvent used which in turn restricts the
rate of reaction that may be achieved.
ii. It is difficult to free the product of the last traces of the solvent.
iii. Selection of a completely inert solvent cannot be done, of means that there is possible chain transfer
to the solvent and hence a restriction on the molar mass of the product. This last point is particularly
important and is the one that is primarily responsible for the rarity of solution techniques in the
manufacture of commercially important polymers.
Suspension Polymerization
Only water-insoluble monomers can be polymerized bb this technique. The monomer is
suspended in water, in the form of fine droplets, which are stabilized and prevented from coalescing
by using suitable water protective colloids, surface active agents by stirring. The size of monomer
droplet formed depend upon monomer water ratio, concentration of stabilizing agent and agitation
speed.
The initiators are monomer soluble. Since each monomer is independent of other droplets and
it will act as individual bulk polymerization nucleus. Aqueous phase separating monomers and
polymers act as heat transfer medium and exothermicity is well controlled.

25


Fig.1.10.suspension polymerization
Polymerization proceeds to 100 % conversion and the product obtained is spherical beads [For this
reason, this polymerization is called as bead or pearl polymerization] . Isolation of product is very easy
only water wash of beads remove all the unwanted materials. Polystyrene beads, styrene-divinyl benzene
copolymer beads, PVA beads are the main products of this technique.

1.12.3. Emulsion Polymerisation
Emulsion polymerization technique is a versatile and widely used method of polymerization. In
this technique droplets of monomer are dispersed in water with the aid of an emulsifying agent, usually a
synthetic detergent. The detergent forms small micelles 10-100 pm in size, which is much smaller than
the droplets that can be formed by mechanical agitation in suspension polymerisation. These micelles
contain a small quantity of monomer, the rest of the monomer being suspended in the water without the
aid of any surfactant. Emulsion polymerisation is initiated using a water-soluble initiator, such as
potassium per sulfate. This forms free radicals in solution which may initiate some growing chains in
solution. These radicals or growing chains pass to the micelles and diffuse into them, which causes the
bulk of the polymerisation to occur in these stabilized droplets.
As emulsion polymerisation proceeds, like the suspension technique but unlike either the bulk or
the solution techniques, there is almost no increase in viscosity. The resulting dispersed polymer is not a
true emulsion any more, but instead has become latex. The particles of the latex do not interact with the
water; hence viscosity is not found to change significantly up to about 60% solids content. Emulsion
polymerisation is used in the commercial production of synthetic diene elastomer and also to produce
commercial latexes of the type used in paints.
26

Figure. 1.1. Emulsion Polymerization

Fig.1.11.Emulsion polymerization
1.13.Nylons 6,6
The aliphatic polyamides are generally known as Nylons. There are different types of nylons
usually indicated by number system. Nylon 66 is one of the important member of the family of
Nylons. Nylon 66 is a polyamide prepared by polycondensation of hexamethylene diamine and
adipic acid, monomers having six carbon atoms each, so it is named as Nylon 66.
Scheme1. Preparation of Nylon 66


Scheme.1.8.Preparation of Nylon 66
Properties of Nylon 66
Nylon 66 is used as plastic as well as fibre. It has good tensile strength, abrasion resistance and
toughness upto 150 C. Also, it offer resistance to many solvents. However, phenols, cresols and formic
acid dissolve this polymer. Nylon 6,6 is very stable in nature. Nylon 6,6 is very difficult to dye but once
it is dyed it has a high colorfastness and is less susceptible to fading
27

Applications of Nylon 66
1. A large quantity of Nylon 66 is used to produce tyre cord.
2. Nylon 66 is used to prepare monofilaments and ropes.
3. It is used to prepare textile fibre for the use of dress
4. It is used as substitute for metal gears and bearings.
5. Nylon 6,6 is waterproof in nature so it is also used to make swimwear.
6. Other popular applications are: carpet fibres, apparel, airbags, zip ties, ropes, conveyor belts, hoses
and the outer layer of turnout blankets. Nylon 6-6 is also a popular guitar nut material
1.14.Epoxy resin
The epoxy polymers are generally poly ethers .One type of epoxy polymers is prepared from
epichlorohydrin and bisphenol-A. The reaction is carried out with the excess of epichlorohydrin. The
scheme is as follows.




Scheme.1.9.Preparation of epoxy resin
Properties of epoxy resins.
Epoxy resins possess remarkable chemical resistance and good adhesion because of the presence
of chemically inert ether linkage. They are flexible and possess heat resistivity. Epoxy resin contain
polar groups so they possess good adhesive properly.
Applications of epoxy resins
1. Epoxy resins are used as structural adhesives like araldite.
2. Epoxy resins are used in surface coatings, glass fibre reinforced plastics[FRP]
28

3. They are applied over cotton, rayon and bleached fabrics to impart crease-resistance and shrinkage
control.
4. These are used as electrical insulators and laminating materials.
5. Epoxy resin compounds are used in the production of light weight components for automobiles and
aircrafts.