MEC467-POLYMER SCIENCE AND

ENGINEERING

HINDUSTAN – ALBA – DIP - © COPYRIGHT 2017

 UNIT-I

POLYMERIZATION

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 TEXTBOOKS

1. G. Griskey, “Polymer Process Engineering”, Chapman & Hall,

New York ,1995.
2. D. H. Morton Jones, “Polymer Processing”, Chapman & Hall,
New York,1995.

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 REFERENCES BOOKS
 
1. Billmayer Jr. and Fred. W., “Textbook of Polymer Science”, WileyTappers,
1965.
2. David, J. W., “Polymer Science and Engineering”, Prentice Hall,1971. 38
3. Schmidt, A. K. and Marlies, G. A., “High Polymers - Theory and Practice”,
McGraw Hill, 1948.
4. McKelvey, J. M., “Polymer Processing”, John Wiley, 1962.
5. Rodriguez, F., Cohen.C., Oberic.K and Arches, L.A., Principles of Polymer
6. Systems, 5th edition, Taylor and Francis, 2003.
7. Crawford R.J, Plastics Engineering (3rd Ed), Pergamon Press, London (1987)

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 Factors that affects physical properties of polymers

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 Classification of polymers

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 Classification of polymers

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 Polymers are further classified by the reaction
mode of polymerization, these include

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 Classification of polymers into two groups
Condensation polymers
Addition polymers

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 Addition polymers
• Addition polymers are those in which loss of a small molecule
does not take place. The most important group of addition
polymers includes those derived from unsaturated vinyl
monomers
• Addition polymers ordinarily result from chain reactions
involving some sort of active centre

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 Condensation polymers

• Condensation polymers are those in which the molecular

formula repeat unit of the polymer chain lacks certain atoms
present in the monomer from which it is formed (or to which it
can be degraded).
• For example, a polyester is formed by typical condensation
reactions between bifunctional monomers, with the elimination
of' water
• Condensation polymers are usually formed by the stepwise
intermolecular condensation of reactive group
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Comparison between addition and condensation polymerization
S.no Addition polymerization condensation polymerization

1 Chain reaction Stepwise reaction

2 Only growth reaction adding one unit at a time Any two molecular species can react

3 Monomer decrease steadily Monomer disappears early

4 High polymers at once Polymer DP ( Degree of polymerization) rises steadily

5 Long reaction times give high yields Long reaction times give high DP

6 Only polymer and monomer present All molecular species present

7 No by product By product

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 Addition of polymerization

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 Cationic polymerization

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 Cationic polymerization

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 Cationic polymerization

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 Cationic polymerization

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 Cationic polymerization
Cationic polymerization
In this case, strong electron acceptors in the form of strong
Lewis acids initiate the chain reaction. These catalysts include
SnCl4 , H2SO4, AlCl3, AlBr3 AND BF3. A characteristic of this form of
polymerization is a high rate at low temperature.

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 Anionic polymerization

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 Anionic polymerization

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 Anionic polymerization

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 Anionic polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Coordination polymerization

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 Copolymerization

• In many instances, polymers are synthesized with only one

monomer or mer repeating unit. These are called
homopolymers.
• On the other hand, if more than one monomers is used, the
result is a copolymer.
• The purpose of copolymerization is to synthesize a material
with special properties. The term copolymerization covers all
combinations of two or more monomers.

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 Copolymerization

• Random copolymer, mers can appear anywhere in the chain

• -A-B-B-A-B-A-A-
• Block copolymers,regular runs of the mers appear.
• -AABB-BBAA-AABB-
• Graft copolymer attaches the other mers as branches.
• -AAA-AAA-AAA-
• B B B
• B B B
• I I I
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 Copolymerization

• Polymeric materials offer the practitioner a wide range of

potential products that can be utilized effectively to meet the
pressing needs of modern technology.
• The possibilities of physical and chemical modification, as
well as copolymerization, means that a polymer can literally
be tailor made for given end uses.

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 STEP-REACTION (CONDENSATION)
POLYMERIZATION
• Classification of polymers into two groups
• Condensation polymers
• Addition polymers

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 Condensation polymers

• Condensation polymers are those in which the molecular

formula repeat unit of the polymer chain lacks certain atoms
present in the monomer from which it is formed (or to which it
can be degraded).
• For example, a polyester is formed by typical condensation
reactions between bifunctional monomers, with the elimination
of' water
• Condensation polymers are usually formed by the stepwise
intermolecular condensation of reactive group
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 Addition polymers
• Addition polymers are those in which loss of a small molecule
does not take place. The most important group of addition
polymers includes those derived from unsaturated vinyl
monomers
• Addition polymers ordinarily result from chain reactions
involving some sort of active centre

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• The classification based on the reaction mechanism:
– Step reactions or condensation polymers
– Chain reactions

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 Carothers Equation

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 Interfacial Condensation
• The reaction of an acid halide with a glycol or a diamine proceeds
rapidly to high-molecular-weight polymer . If carried out at the
interface between two liquid phases, each containing one of the
reactants.
• The polymer formed at the interface can be pulled off as a continuous
film or filament. The method has been applied to the formation of
polyamides, polyurethanes, polyureas, polysulfbnamides and
polyphenyl esters.
• It is particularly useful for preparing polymers that are unstable at the
higher temperatures usual in step reaction polymerization
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 Kinetics of Stepwise Polymerization
• The formation of a polyester from a glycol and a dibasic acid may
be taken as an example
• It is well known that this reaction is catalyzed by acids In the
absence of added strong acid, a second molecule of the acid being
esterified acts as a catalyst
• The reaction is followed by measuring the rate of disappearance of
carboxyl groups

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 Case 1: Polymerization without Added Strong Acid:

• Consider esterification — the formation of a polyester from a

glycol and a dibasic acid. The progress of reaction is easily
followed by titrating the unreacted carboxyl groups in samples
removed from the reaction mixture.
• This polyesterification and other simple esterifications are acid-
catalyzed. In the absence of an added strong acid, a second
molecule of the acid being esterified acts as the

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 Case II: Polymerization with Added Strong Acid:

• The kinetic expression can be greatly simplified if the

polyesterification is carried out in the presence of a small
amount of strong acid, e.g.,p –toluene sulfonic acid.

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 Statistics of Linear Step-Reaction Polymerization
• The statistical analysis of stepwise polymerization yields results that are
equivalent to and in some cases more easily obtained than those of
kinetic considerations
• The method assumes independence of reaction rate and molecular size.
• The extent of reaction p is defined as the probability that a functional
group has reacted at time t.
• This definition is entirely equivalent to the previous definition of p as the
fraction of the functional groups that has reacted.
• It follows that the probability of finding a functional group unreacted is 1 -
p
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 Branch Point
• The reaction between a dibasic acid and glycerol, which has two
primary and one secondary hydroxyl groups (functionality of 3).
• A monomer that possesses such a functionality is referred to as a
branch unit.
• Every reaction of such a molecule introduces a branch point for the
development of the three-dimensional network.
• The portion of a polymer molecule lying between two branch
points or a branch point and a chain end is called a chain section or
segment.
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 Gel point
• As polymerization proceeds many branch points are formed. Reaction between
large molecules considerably increases the number of reaction groups per
polymer chain.
• The size of the polymer molecules increases rapidly, culminating in the
formation of a three-dimensional network polymer of infinite molecular
weight.
• During this process, the viscosity of the reaction medium increases gradually at
first and experiences a sudden and enormous increase just before the
formation of the three-dimensional network .
• The reaction medium loses fluidity, and bubbles cease to rise through it.
Gelation is said to have occurred at this point, which is referred to as the gel
point.
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 Prediction of the Gel Point
• In order to calculate the point in the reaction at which gelation
takes place, a branching coefficient α is defined as the
probability that a given functional group on a branch unit (i e . ,
a unit of functionality greater than 2) is connected to another
branch unit.

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• The
  value of α at which gelation becomes possible can be
deduced from statistical considerations to be just 1 l(f - 1);
hence the critical value of α for gelation is
αc
• Here f is the functionality of the branch units; if more than one
type of branch unit is present, an average f over all types of
branch units may be used in above equation

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 THANK YOU

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