MSE241: Polymer Science

Dr. Nasir Ahmad

Department of Materials Engineering
School of Chemical and Materials Engineering (SCME)
National University of Sciences and Technology (NUST)
Week # 5:
Polymer Synthesis:
Step-Growth or Condensation Polymerization
Semester: Fall 2020

Contact info:
e-mail: nasir.ahmad@scme.nust.edu.pk
Tel (office): 9085-5213
Room No. 208
MSe241 Lecture Notes 1 (Dr. Nasir Ahmad)

Lecture
Step-Growth Polymerization
Young/Lovell-Book, Page: 39-41
 Step-Growth Polymerization
Flory’s Assumption
 Assumption 1
 The reactivity of a functional group is independent
of the length of a chain to which it is attached

 Assumption 2.
 the reactivity of a functional group is
unaffected by reactions/presence of other
functional groups in the Molecule
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 Was Flory Right???
 Chain reactivity is independent of its length/size. This is
experimentally proved as shown below:

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Comparison Between Step and Chain
Polymerization

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 Condensation Polymerization
Main Features
 Condensation polymers are any kind of polymers formed through a
condensation reaction, releasing small molecules as by-products
such as water or methanol, as opposed to addition polymers which
involve the reaction of unsaturated monomers. Types of condensation
polymers include polyamides, and polyesters.

 Condensation polymerization, also known as step-growth

polymerization, is a process by which two molecules join together,
resulting in 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.

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 Condensation Polymerization
Main Features-continued
 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 crosslinked.

 Polyester is created through ester linkages between monomers, which

involve the functional groups carboxyl and hydroxyl (an organic acid
and an alcohol monomer).

 Nylon is another common condensation polymer. It can be

manufactured by reacting di-amines with carboxyl derivatives. In this
example the derivative is a di-carboxylic acid, but di-acyl chlorides are
also used. Another approach used is the reaction of di-functional
monomers, with one amine and one carboxylic acid group on the
same molecule: 7
 Why We Need Bifunction Monomer?
Mono-Functional and Di-functional Molecules

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PET synthesis via Condensation
Polymerization

Formation of polyester Elimination of

with ester linkage/bond water after
condensation
reaction
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 Nylon synthesis via Condensation
Polymerization

Dicarboxylic Diamine Formation of Elimination of

acid monomer monomer nylon with water after
amide linkage condensation
reaction

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 BULK STEP-GROWTH POLYMERIZATION
 Nylon 11 can be prepared by bulk polymerization, i.e., by thermal
polymerization of the neat monomer, 10-aminodecanoic acid.

 This is an A-B monomer, thus, exact stoichiometry of the reactants in this

step-growth polymerization is assured.

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Classroom Assignment

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 Step-Growth Polymerization
Summary
 In step growth, bifunctional monomers are added systematically to form
covalent bonds. It generally involves 2 (or more) functional groups: “a” and
“b.” Molecular weight increases “slowly” as dimers become trimers, which in
turn become tetramers.
 Examples of polymers formed by chain growth: nylons,
polyesters, polypeptides (proteins)
 These are typical a and b groups:

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 Carothers Theory
 Number average Degree of Polymerization, x n:, for No initial no. and N
molecules left at time t:
No
xn 
N
 p is the extent of reaction, i.e. probability that any functional group present
initially has reacted:

number of functional groups that have reacted NO  N

p p
number of functional groups present initially NO

1
xn 
1 p
 Apply to RA2 + RB2, RAB and RA2 Polymerization: Exact Stoichiometric
balance in number of mutually –reactive functional groups.
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 Kinetics of Step Growth Polymerization
 Rate of reaction, Rate of decrease in concentration of one or other FG

 Rate of polymerization =Rp

 Assume reactant ratio, r =1, where r is the stoichiometric ratio.

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Kinetics of Step Growth Polymerization

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Kinetics of Step Growth Polymerization

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