Polymer Synthesis

CHEM 421

Reading (Odian Book):

Chapter 2-1, 2-2, 2-4

Step Growth Polymerizations

Bifunctional
monomers

Polymer Synthesis
CHEM 421

AB monomers

Example Polymers via Step

Growth Reactions

DacronTM, MylarTM

Polymer Synthesis
CHEM 421

Importance of Equal Reactivity

Polymer Synthesis
CHEM 421

AB + AB + AB + AB + AB + AB + AB + AB + AB + AB

AbaB +

AB +

AbaB +

AbaB +

AbaB +

FA = # of A groups at the beginning

FA = # of A groups at any given time
p = conversion = 1 FA / FA = 1 (6 / 10)
Xn = average degree of polymerization
total # of molecules present initially
Xn =
total # of molecules present at time t

AB

Importance of Equal Reactivity

Polymer Synthesis
CHEM 421

AB + AB + AB + AB + AB + AB + AB + AB + AB + AB

p = 0.0
AbaB +

AB +

AbaB +

AbaB +

AbaB +

p = 0.4
AbababaB

AbababaB

AbababaB

AbaB

AbabaB

AbabababaB

Xn = 1
AB

Xn = 1.67

AB

p = 0.6

Xn = 2.5

p = 0.7

Xn = 3.33

p = 0.8

Xn = 5

AB

AbababababaB

MW and Conversion

Polymer Synthesis
CHEM 421

Given that:
[M] = [M]0 - [M]0 p
Rewriting:
[M] = [M]0 (1 p)
Rewriting:
1
(1 p)

Knowing:

[M]0

Xn =

[M]

Xn =

1
(1 p)

[M]0
[M]

Polymer Synthesis
CHEM 421

Conversion

Xn

50%

80%

90%

10

95%

20

99%

100

99.5%

200

Xn =

1
(1 p)

Weight Average and Number AveragePolymer Synthesis

CHEM 421
Molar Masses

Factors Involved in the Synthesis of High MW

Linear Polymers via Step-Growth Reactions

Polymer Synthesis
CHEM 421

High purity monomers

Di-functionality
Proper stoichiometry
Very high conversions
No side reactions
Accessibility of mutually reacting groups
In general:
Suitable for bulk reactions
Moderate viscosity during much of the reaction
Incredible effort ($$) goes to pushing the reaction forward in last
stages

Methods for Polyester Synthesis

Direct reaction
Acid halide / hydroxyl
Transesterification
Melt acidolysis

Polymer Synthesis
CHEM 421

Direct Reaction

Le Chateliers Principle

Polymer Synthesis
CHEM 421

Mechanism

Polymer Synthesis
CHEM 421

Overall Reaction

Polymer Synthesis
CHEM 421

Self-catalyzed
Rp

[OH] [COOH] [COOH]

Catalyzed by added acid ( [H+] = constant)

Equilibrium Considerations:
Closed System

Keq

Polymer Synthesis
CHEM 421

[ester] [H2O]
=
[RCOOH] [ROH]

Initial hydroxyl and carboxyl concentrations are [M]0

Concentration of ester groups @ equilibrium is p [M]0
where p = extent of reaction @ equilibrium
The concentrations of hydroxyl and carboxyl groups @ equilibrium must
therefore be:
( [M]0 p [M]0)
Therefore
Keq

( p [M]0)2
p2 [M]02
p2
= = =
( [M]0 p [M]0)2
[M]02 ( 1 p )2
( 1 p )2

Equilibrium Considerations:
Closed System

Keq

Polymer Synthesis
CHEM 421

[ester] [H2O]
=
[RCOOH] [ROH]

Solve for p yields:

K
p =
1+ K

Knowing that:
Xn =

1
(1 p)

Xn = 1 + K

Effect of Equilibrium Constant on p

Synthesis
and Degree of Polymerization: Polymer
CHEM 421
Closed System

Effect of Equilibrium Constant on p

Synthesis
and Degree of Polymerization: Polymer
CHEM 421
Closed System

Indicates the limitation imposed by equilibrium on the synthesis

of high MW polymer
@ Xn = 100 (corresponding to Mn 10k) can be obtained in
a closed system only if K is 104!!!
Can not be done in a closed system for most polymers
Polymer

Polyesters

1 - 10

Polycarbonates

15

Transesterifications

0.1 1.0

Polyamidation

102 - 103

Therefore must drive the equilibrium

Open System

Polymer Synthesis
CHEM 421

Extent to which one must drive the system in the

forward reaction
can be seen by calculating the lowering of the small molecule
condensate concentration that is necessary to achieve a particular MW
Knowing that
[H2O] = p [M]0

Xn =

1
(1 p)

( p [M]0)2
p [H2O]
p [H2O] (Xn)2
Keq = = =
2
2
(
[M]

p
[M]
)
[M]
(
1
p
)
[M]0
0
0
0
Solve for [H O]
2

K [M]0
[H2O] =
Xn ( Xn 1)

[H2O]

Xn2

Drive the Equilibrium

Polymer Synthesis
CHEM 421

Need to remove the small molecule

condensate
H2O
HCl

Small molecule condensate needs to

diffuse through and eventually out of the
reaction mixture
Not easy because of high viscosity
Can lead to reactions becoming diffusion
controlled

Effect of Water Concentration on

Degree of Polymerization:
Open, Driven System

Polymer Synthesis
CHEM 421

How best to drive the

Equilibrium?

Polymer Synthesis
CHEM 421

Mixing is energy and capital intensive

Wiped film reactors to increase surface area

Increase diffusivity of the condensate

Raise the temperature to lower the viscosity
of the melt
Potential for side reactions

Swell the melt with solvents

Supercritical CO2