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Polymer
chemistry
2
Chapter 2
Step-Growth Polymerization
3
Part 1 An Introduction to Polycondensation
4
2.1
Introduction
2.1.1How to Prepare Polymer ?
One way is from monomer

Suitable Monomer &
Suitable method (polymerization)
Another way is from a given polymer

5
No low molecular weight material is produced.

The composition of the newly produced
material is the same as the monomer.
There are only reactions between increasing

chains and the monomers
6
Classification 2
By the reaction mechanism
A. Step-Growth Polymerization
B. Chain Polymerization
7
8
2.1.3 Why do we study the

Step-Growth Polymerization ?
Great Industrial Value

Examples
Polyester
Linear saturated polyester: plasticizer,
Linear unsaturated polyester: glass fiber laminate,
casting resin, solventless lacquer
Network polyester: surface coating
9
Polycondensation reactions are taken as

examples to illustrate the Step-Growth
Polymerization.
10
B. Polycondensation
Polycondensation is the abbreviation of

condensation polymerization.
many times of repeated condensation
Monomers with
functional group
Polymer
11
B.
Functionality ( f )
the number of functional groups in the molecule
which take part in the reaction.

(monomer,oligomer).
12
general reaction
n aRa + n bRb
a[RR]nb + (2n1)ab
ab functional group RRconstruction unit

ab micromolecule
These reactions involve two different functional

groups.
One type of the functional group in each monomer.
Forming linear polycondensation polymer
13
Summary
1) monomers f 2
2) Changeable factors :
functional groups (OH,COOH,COOR,Cl,
NH2),
f (linear or cross linking polycindensation)
R, and R
Huge sorts of polycondensation polymers
3) The polycondensation polymers are usually the

heterochain polymers with N,O,S,P in the
backbone and the functional groups in the end.
eg.
O,CONH,COOetc
14
Industrially, polycondensation can be

divided into many types according to the
group in the polymer chain.
polyester, polyamide, polyether reaction
15
4) The compositions and structures of the polymers

are different from those of the monomer, because
of the byproducts in the reaction.
5) The conversion of monomer does not increase with

the reaction time in the polycondensation reactions.
16
Essentially, the key of polycondensation is the reactions between the function

groups. Only with the efficient reaction, the macromolecules can be prepared.
Practically, polycondensation should be described by the extent of reaction.
(Notes: conversion for the chain polymerization. Chapter 3)
17
2.2.4
Classifications of
Polycondensation
(2) mixed polycondensation, f = 2,2
Two kinds of bifunctional monomers.

Only one type of functional group in each monomer.
Example: diamine / diacid, dihydric alcohol / diacid
H2N(CH2)6NH2 + HOOC(CH2)4COOH
[NH(CH2)6NHOC(CH2)4CO]n + (2n1)H2O
18
2.2.4
Classifications of
Polycondensation
2. By Structure of polymer
linear polycondensation
Bifunctional monomer
The chain increases to two directions along the ends of the chain.
19
2.2.4
Classifications of
Polycondensation
Systems of f = 2 and f = 2, 2 are linear
polycondensation.
The key of linear polycondensation is to
control the molecular weight of the products.
20
2.2.4
Classifications of
Polycondensation
cross linking polycondensation

At least one monomer has more than two functional
groups (f = 2, 3 or 2,43,3 )
The molecule increases towards more than two
directions. The crosslinking polymer forms.
Example:
glycerol / phthalic anhydride alkyd resin,
phenol / formaldehyde phenolic-formaldehyde
resin.
21
2.2.4
Classifications of
Polycondensation
The viscosity will be suddenly increased as reaction
goes to the certain degree, forming the gel. -------gelation
This critical point is called the gel point.

The key of cross-linking polycondensation is to
forecast and crontrol the gel point

22
2.2.4
Classifications of
Polycondensation
3. By Thermodynamics
balanced polycondensation
the rate of reverse reaction is not equal to zero

K103 .
unbalanced polycondensation
the rate of reverse reaction is little or equal to zero.

K103 .
23
2.3 Characteristic of linear polycondensation
Characteristic I.
The increasement of macromolecule chain is
step by step.
24
Any molecule with different functional group can react

to each other.
There are no particular active centers in

the reaction.
The molecular weight of the polymer gradually increases with the decrease of the number
of the groups.
25
The monomers dispear at the early stage of reaction far

before forming any polymer with sufficiently high
molecular weight for practical utility.
High conversion of monomer is reached at early stage of
reaction followed by the reaction between oligomers.

As the time increases,
X n increases instead of the
conversion.
Contrarily, the conversion increases with time in the
chain polymerization.
26
HOROH + HOOCR`COOH
dimer
HOROCOR`COOH + H2O
HOROH
HOOCR`COOH
HOROCOR`COOROH
HOOCR`COOROCOR`COOH
trimer
trimer
tetramer
27
Firstly, the diol and the diacid monomer reacts

to form dimer.
.
aAa + bBb
a [ A B ] b + ab
Then the dimer reacts with itself to form tetramer

or with unreacted monomer to yield trimer.
a[A B]b + aAa
a[A B]b + bBb

a[A B]b + a[A B]b
a[A B A]a + ab
b[B A B]b + ab
a[A B A B]b + ab
aAa:
dihydric alcohol(diol); bBb: diacid
28
The tetramer and trimer continues to react with
themselves, with each other, and with monomer and

dimer.
The polymerization proceeds in the stepwise manner,
resulting the continuously increases of the molecular

weight of the polymer.
29
All polycondensations are characterized by the stepwise.

The mechanism of polycondensation is rather different to that of chain polymerization which will be
discussed in Chapter 3.
The reactivity of a functional group is independent of the size of the molecule.
30
the degree of polymerization
P, the fraction of the functional groups that have

reacted
N0 N
N
1
N0
N0
where,
N0 the total of the certain groups at the initial stage
N the quantity of unreacted groups at time of t
31
X n the number everage of construction units in
each macromolecule
Xn
the total of constru ction unit s
the number of macromo lecules
N0N
N
P=
= 1
N0
N0
1
P = 1
Xn
1
Xn
1 P
P0. 9X = 10
n
= 100 ~ 200 P 0. 99 ~ 0. 995
X nadmission.edhole.com
32
Characteristic II.
Linear polycondensation is
reversible equilibrium.
The equilibrium constants (K) of different
linear polycondensation is different.
33
K410, e.g kinds of polyester

the existance of micromolecule will greatly affect the degree of polymerization.
K300400, e.g kinds of polyamide
the existance of micromolecule will affect the degree of polymerization to some extent.
K103 e.g phenol ~ methanal
the reaction is irreversible
It is clear that the synthesize art depends on the equilibrium constant, K, will affect.
34
In the closed system, the high molecular weight

polymer is hardly obtained, due to the existence of
byproducts and residual micromolecule.
Industrially, the micromolecules can be removed by
reducing pressure method in order to change the
equilibrium for preparing high molecular weight
polymer.
e.g. The vacuum degree of the system, i.e., the
quantity of residual micromolecules, control the
molecular weight of terylene.
35
2.5 The degree of polymerization

P, the fraction of the functional groups that have reacted
N0 N
N
1
N0
N0
where,
N0 the total of the certain groups at the initial stage
N the quantity of unreacted groups at time of t
X n the number everage of construction units in
each macromolecule
Xn
36
Example 1polyester reaction

nHORCOOH [ORCO]n + (n1)H2O
t=0the total of the initial groups
COOHN0
t=tthe quantity of unreacted groups COOHN

POHPCOOH N 0 N 1 N P
N0
Xn
(22)
N0
N0
N
(23)
37
Xn

1
from (23)
Xn
N0
N0
N
(23)
(24)
substitutes (22) for (24)

POHPCOOH N 0 N 1 N P
N0
P 1
N0
(22)
1
Xn
1
Xn
1 P
(25)
38
Example 2HOROH + HOOCRCOOH

Case : the same mole ratio
t=0
OH: N0 COOH N0,
the total of construction unitsN0
t=t
OH: N COOH N
the quantity of macromoleculesN
POHPCOOH
Xn
N0 N
N
1
N0
N0
N0
1
1 P
39
In the polycondensation reactionincrease of

the degree of reaction depends on
1. prolonging the reaction time
2. increasing the reaction temperature
3. removing the micromolecule intensively
4. using high active monomer
40
2.5.2
The equilibrium constant (K) and

the degree of polymerization
The equilibrium polycondensation reactions

consist of a series of equilibrium reactions.
As the reactivity of functional groups are
assumed to be equal to each other, all reactions
can be expressed by the same K
COOH OH
OCO H2O
[OCO ][H 2O]

k1
K
[COOH ][OH ]
k 1
41
COOH OH
t0
tt
C0
C0(1-P)
OCO H2O
C0
C0(1-P)
C 0P
C 0P
the closed system
C0 P C0 P
K=
C0 (1 P) C0 (1 P)
P
1 P
P2
(1 P ) 2
Xn
1
1 P
42
Thus,
Xn
K 1
K + 1
(26)
(27)
X n has relations not only with Pbut also with K.
43
To polyesterK
4P(equilibrium)2/3
X3
n
To polyamide: K 400P(equilibrium)0.95X n 21
K 104
Xn
100
Thus
1. In the closed systems especially that with small K,

the high molecular weight polymer is hard to be
prepared.
2. Try to remove the micromolecules is key for increasing the molecular weight of the polymer.
44

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Part 1 An Introduction to Polycondensation

2.1.1How to Prepare Polymer ?

One way is from monomer

Suitable method (polymerization)

Another way is from a given polymer

No low molecular weight material is produced.

There are only reactions between increasing

2.1.3 Why do we study the

Great Industrial Value

Polycondensation reactions are taken as

Polycondensation is the abbreviation of

many times of repeated condensation

the number of functional groups in the molecule

which take part in the reaction.

ab functional group RRconstruction unit

These reactions involve two different functional

3) The polycondensation polymers are usually the

Industrially, polycondensation can be

4) The compositions and structures of the polymers

5) The conversion of monomer does not increase with

Essentially, the key of polycondensation is the reactions between the function

(2) mixed polycondensation, f = 2,2

Two kinds of bifunctional monomers.

Systems of f = 2 and f = 2, 2 are linear

The key of linear polycondensation is to

control the molecular weight of the products.

cross linking polycondensation

directions. The crosslinking polymer forms.

The viscosity will be suddenly increased as reaction

goes to the certain degree, forming the gel. -------gelation

This critical point is called the gel point.

forecast and crontrol the gel point

the rate of reverse reaction is not equal to zero

the rate of reverse reaction is little or equal to zero.

2.3 Characteristic of linear polycondensation

2.3 Characteristic of linear polycondensation

Any molecule with different functional group can react

There are no particular active centers in

2.3 Characteristic of linear polycondensation

The monomers dispear at the early stage of reaction far

reaction followed by the reaction between oligomers.

X n increases instead of the

Firstly, the diol and the diacid monomer reacts

Then the dimer reacts with itself to form tetramer

a[A B]b + aAa

a[A B]b + bBb

The tetramer and trimer continues to react with

themselves, with each other, and with monomer and

resulting the continuously increases of the molecular

All polycondensations are characterized by the stepwise.

the degree of polymerization

P, the fraction of the functional groups that have

X n the number everage of construction units in

the total of constru ction unit s

the number of macromo lecules

2.3 Characteristic of linear polycondensation

K410, e.g kinds of polyester

In the closed system, the high molecular weight

2.5 The degree of polymerization

Example 1polyester reaction

t=tthe quantity of unreacted groups COOHN

the total of constru ction unit s

the number of macromo lecules