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MSE241: Polymer Science: Dr. Nasir Ahmad

This document provides an overview of step-growth or condensation polymerization. It discusses Flory's assumptions about chain reactivity, key features of condensation polymerization including the elimination of small molecules as byproducts, and examples of nylon and PET synthesis using diacids and diamines. It also covers Carothers theory for calculating number average degree of polymerization and kinetics equations for step-growth polymerization. The contact is Dr. Nasir Ahmad of the National University of Sciences and Technology.

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Asim Khan
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26 views

MSE241: Polymer Science: Dr. Nasir Ahmad

This document provides an overview of step-growth or condensation polymerization. It discusses Flory's assumptions about chain reactivity, key features of condensation polymerization including the elimination of small molecules as byproducts, and examples of nylon and PET synthesis using diacids and diamines. It also covers Carothers theory for calculating number average degree of polymerization and kinetics equations for step-growth polymerization. The contact is Dr. Nasir Ahmad of the National University of Sciences and Technology.

Uploaded by

Asim Khan
Copyright
© © All Rights Reserved
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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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: [email protected]
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.

6
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

8
PET synthesis via Condensation
Polymerization

Formation of polyester Elimination of


with ester linkage/bond water after
condensation
reaction
9
Nylon synthesis via Condensation
Polymerization

Dicarboxylic Diamine Formation of Elimination of


acid monomer monomer nylon with water after
amide linkage condensation
reaction

10
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:

13
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.
14
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.

15
Kinetics of Step Growth Polymerization

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Kinetics of Step Growth Polymerization

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