Step Growth Polymerization

Syllabus
• UNIT II (Step and Miscellaneous Polymerization)

• . Polycondensation: Role of functionality – Cyclic vs. linear

polymers. Ring opening polymerization: Initiation, propagation
and termination - Different types of polymers made through step
polymerization including Nylon 6,6 and Nylon 6.

• Electrochemical polymerization - Metathesis polymerization -

Group transfer polymerization - Enzyme-catalyzed
polymerization - Polymers made through these polymerizations
Nomenclature
Nomenclature
Nomenclature
Nomenclature
Nomenclature
Nomenclature
Nomenclature
Step Growth Polymerizations

• Bifunctional • AB monomers
monomers

A A + B B A B

a a b b a b
n
n
Example Polymers via Step
Growth Reactions

O O
N CH2 N C CH2 C
x y
H H n

O O
O O
HO C C OH
C C O CH2CH2 O
H n
+ +
HO CH2CH2 OH H2O

DacronTM, MylarTM
 Importance of Equal Reactivity
A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B

A—ba—B + A—B + A—ba—B + A—ba—B + A—ba—B + A—B

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

————————————————
 Importance of Equal Reactivity

A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B + A—B

p = 0.0 Xn = 1
A—ba—B + A—B + A—ba—B + A—ba—B + A—ba—B + A—B

p = 0.4 Xn = 1.67
A—ba—ba—ba—B + A—ba—B + A—ba—ba—B + A—B

p = 0.6 Xn = 2.5
A—ba—ba—ba—B + A—ba—ba—ba—ba—B + A—B

p = 0.7 Xn = 3.33
A—ba—ba—ba—B + A—ba—ba—ba—ba—ba—B

p = conversion = 1 – FA / FA° p = 0.8 Xn = 5

X = average degree of polymerization
 MW and Conversion
Given that: p = conversion = 1 – FA / FA°
[M] = [M]0 - [M]0 p Xn = average degree of polymerization

Rewriting:
[M] = [M]0 (1 – p)

Rewriting: Knowing:
1 [M]0 [M]0
=
Xn =
(1 – p) [M] [M]

1
Xn =
(1 – p)
 Implications of Carothers
Equation
1
• Conversion Xn =
Xn (1 – p)
– 50% 2
– 80% 5
– 90% 10
– 95% 20
– 99% 100
– 99.5% 200

p = conversion = 1 – FA / FA° Xn = average degree of polymerization

 Weight Average and Number
Average Molar Masses

p = conversion = 1 – FA / FA° Xn = average degree of polymerization

 MW Evolution of Step vs. Chain Growth Polymerization

MW MW

Conversion Conversion

Step Growth Evolution of MW Chain Growth Evolution of MW

Reaction of difunctional monomers 4-Elementary reactions (initiation, propagation,
With complementary functional termination, transfer) of reactive monomer +
groups (A2 + B2) initiator (vinylic- -systems, strained rings)
High polymer formed only at very High polymer formed at low
high conversion conversion
C-C bonds for vinylic monomers,
Heteroatom backbones Heteroatom backbones for cyclic
monomers
Step-growth Polymerization
Requirements for Step-Growth Polymerization

High polymer formed only

at very high conversion!!!
very high conversion!!!
MW

99 +
Conversion

High monomer purity

Difunctionality
Stoichiometry
Quantitative conversion of monomer to
polymer!
No side Reactions
Factors Involved in the Synthesis of High MW
Linear Polymers via Step-Growth Reactions

• 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
 Direct Reaction
O

C OH + HO

C O + H2O

• “Le Chatelier’s Principle”

 Overall Reaction

O O
H
R C OH + R' OH R C O R' + H2O

• Self-catalyzed

Rp [OH] [COOH] [COOH]

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

 Equilibrium Considerations:
Closed System

O O
H
R C OH + R' OH R C O R' + H2O

[ester] [H2O]
Keq = ————————
[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
( p [M]0)2 p2 [M]02 p2
Keq = ———————— = ———————— = ————
( [M]0 – p [M]0)2 [M]02 ( 1– p )2 ( 1– p )2
 Equilibrium Considerations:
Closed System

O O
H
R C OH + R' OH R C O R' + H2O

[ester] [H2O]
Keq = ————————
[RCOOH] [ROH]

• Solve for p yields:

K½
p = ————
1+ K½

Xn = 1 + K½
• Knowing that:
1
Xn =
(1 – p)
Effect of Equilibrium Constant on “p”
and Degree of Polymerization:
Closed System
 Effect of Equilibrium Constant on “p”
and Degree of Polymerization:
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 K
Polyesters 1 - 10
Polycarbonates 15
Transesterifications 0.1 – 1.0
Polyamidation 102 - 103

• Therefore must drive the equilibrium

 Open System
• 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
1
[H2O] = p [M]0 Xn =
(1 – p)
( p [M]0)2 p [H2O] p [H2O] (Xn)2
Keq = ———————— = —————— = ——————
– Solve for( [H
[M]O]
0 – p [M]0)
2
[M]0 ( 1– p )2 [M]0
2

1
K [M]0 [H2O] ——
[H2O] = ————— Xn2
Xn ( Xn – 1)
 Drive the Equilibrium
• 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
 How best to drive the
Equilibrium?
• 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
 Cyclization

1. Thermodynamic stability
Rings of: 3,4,8 < 11 < 7, 12 << 5 << 6

2. Kinetic Control
Propagation more rapid than cyclization
Reduce probability of collision for rings 12

Non-reversible propagation process

 Nylon-6,6
O O O O
NaOH
Cl Cl H2N NH2 H
4 4 Cl 4
N 4 N
H H
Adipoyl chloride 1,6-Diaminohexane

O O
Adipoyl chloride H
in hexane HO N N
4 4
H H n
Nylon 6,6
6 carbon 6 carbon
diacid diamine
Diamine, NaOH, in H2O
Nylon-6,6
 Nylon-6,6
Since the reactants are in different
phases, they can only react at the
Since the reactants are in different
phase boundary. Once a layer of
phases, they can only react at the
polymer forms, no more reaction
phase boundary. Once a layer of
occurs. Removing the polymer
polymer forms, no more reaction
allows more reaction to occur.
occurs. Removing the polymer
allows more reaction to occur.

Adipoyl chloride
in hexane

Nylon 6,6

Diamine, NaOH, in H2O

 Hydrogen bonds between chains

Supramolecular
Structure of
nylon

Intermolecular
hydrogen bonds
give nylon
enormous tensile
strength

35
Nylon
 Polyesters, Amides, and Urethanes

Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester
O O O O
H
HO 4
OH H2N 4
NH2 HO N 4 N
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene

H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
Chain Length: 4,000 – 8,000
Polyethylene Terephthalate (PETE)
“Polyester”

Ester
 Kevlar

Strong Network of Covalent Bonds

And Polar Hydrogen Bonds
 SILOXANE
• Siloxane Prepared by hydrolysis of dichloro
dialkylsiloxanes e.g. dichlorodimethylsiloxene.  
CH3 CH3
nCl-Si-Cl + (n+1) H2O HO [ Si-O ] H   + 2nHCl
CH3 CH3

Poly dimethylsiloxane) (PDMS): Initially

hydrolysis occurs after that we can have both
RA2 + RB2 polymerized (CH3)2 SiCl2 react with
(CH3)2 Si(OH)2 or (CH3)2 Si(OH2) can condense by
itself (RA2) polymer.
 POLYADDITION

• Step polymerization in which the monomers

react together without the elimination of other
molecules.
• Example
• 1) Polyurethanes by the RA + RB reaction of
2 2
diisocyanate with diols.

O = C = N = R1 - N = C = O + HO - R2 - OH
  O O 
[ C - NH-R1 - NH-C - OR2-O ]n
• 2) Polyureas

O O
C - N - R1 - N = C + H2N - R2-NH2

O O
[ C - NH-R1 - NH-C-NH-R2-NH ]n
 Types of Condensation Reactions

Polyesters
O O
O O - n H2O
HO R OH + R' * R O R' O *
HO OH n
O O
O O - n CH3OH
HO R OH + R' * R O R' O *
H3CO OCH3 n
O O O
H2O -n H2O
O HO (CH2)5 C OH (CH2)5 C O
trace
caprolactone

-n H2O
HO R OH +

O O O O O O
O HO R O OH * R O O *
Phthalic anhydride n
 Preparation of Aromatic Polyesters

O O
+ CH3OH
H3C O C C O CH3

O O
xs HO-CH 2CH2 OH
-
Dimethyl Terephthalate (DMT) O C C O
CH2 CH2
O O CH2OH CH2OH
H O C C O H

Terephthalic Acid O O O O
1 mm Hg 280 C
O C C O O C C O
CH2 CH2 SbO3 or Ti(OR)4
CH2
CH2OH CH2OH
CH2O

+ HOCH2CH2OH

Stoichiometry and DP controlled by extent

of glycol removed.
 Types of Condensation Reactions

Polyamides
O O
O O - n H2O H
H2N R NH2 + R' * R N R' N *
HO OH H n

O O
O O - n HCl H
H2N R NH2 + R' * R N R' N *
Cl Cl H n

O O O
H2O -n H2O
NH H2N (CH2)5 C OH (CH2)5 C N
trace H
 Polyamides via Condensation -- Nylon 66

H O O O O
O C-(CH2)4-C O C-(CH2)4-C
O- O-
H
+ NH3+ NH3+
NH2 CH2-(CH2)4-CH2 NH2 CH2 CH2
(CH2)4
slight excess
Nylon Salt

60% Slurry

mp. 265 °C, 200 C, 15 Atm. 1 hr

Tg 50 °C, MW O O
NH3+(CH2)6-NH-C-(CH2)4-C-NH-(CH2)6-NH-C-(CH2)4-C O
-

12-15,000 O 8-10 O

Unoriented 270-300 C, 1hr

elongation H2O
-

780 % NH-(CH2)6-NH-C-(CH2)4-C
O

O
Nylon 6 6
 Lexan Polycarbonate
Interfacial Process
-O - Aq NaOH
O + Cl-C-Cl
Na+ Na+ CHCl2
O
CH3 CH3

Tm = 270C, O O + NaCl
C
Tg = 145-150C CH3 CH3 O
x
10-40 % Lexan

Crystalline, O
C
O OH

Brittle Temp. - O 1) 200 C/20mm

Lexan +

10C H
+
2) 300 C. <1mm
O O
H
Ester Interchange CH3 CH3

No Solvent, Pure Polymer

with MW > 30,000 Formed
Types of Condensation Polymers

O O O O
R O C R' C O
R' C O C
n n
Polyesters Polyanhydrides

O O O
O
n
O n R
Polycarbonates Polyacetals
Types of Condensation Polymers
O CH3
H
R O N R' N O
C H O
O
CH3
polyurethanes
polyphenylene oxide

O Ar O

R
S
polyarylenes O O
polyarylene ether sulfones
Types of Condensation Polymers

O O
O O
H
R N C R' C N N N
H
O O
polyamides
polyimides

O O S S
Ar Ar
N N N N

polybenzthiazoles
polybenzoxazoles
Low Temperature Condensation Polymerization

• Interfacial or Solution in Polar Aprotic Solvents

Parameter Low Temp High Temp

Intermediates
Purity Moderate High
Stoichiometry Not Essential Essential
Heat Stability Not Essential Essential
Structure Highly Thermally
Reactive stable
Cost High Moderate
 Interfacial or Solution Polymerization in
Polar Aprotic Solvents (Con’t)

Conditions Low Temp High Temp

Time Minutes to hours Hours to days
Temperature 0 – 150 C >250 C
Pressure Atmospheric High to vacuum
Yield Low to moderate Quantitative
By-products Salts Volatiles
Solvents Required None
Applications of Low Temperature Condensations

• Prep. of Infusible Thermally Stable Polymers

• Prep. of Thermally Unstable Polymers

Prep. of Polymers Containing Functional Groups with

Differing Reactivity
Formation of Block or Ordered Polymers
(No equilibration of polymer in melt allowed)
Direct Production of Polymer Solutions for
Coatings, Spinning into Fibers, Solvent Blending to
form Composites
 POLYETHERSULFONES

K2CO3
HO K+-O
Bis-nucleophile
Bis-Phenol-A OH O- K +

K+-O O Polymerize by
Cl S
+
O SnAr2
O- K+
Cl
DMSO/Toluene
Monofunctional
160 C

2) CH Cl terminator to stabilize
3
CH O 3 polymer
O
S Use Temperature
O
O
100 to + 175C
Molecular Weight = 65,000 - 250,000 Stable in air to
Amorphous Material, Tg  200C, 500C, Self
Films pressed at 280C Extinguishing
 Polyphenylene Oxide (PPO)

Oxidative
Coupling R1 R1 R1

Process OH +
n/2 O2
cat
O O

R2 R2 R2

+ n H2O
CH3
cat = or N CH3 Cu +
N CH3 N Amine Complex
CH3
10:1 3:1
Mn 30,000 to 120,000
Noryl is a blend with Amorphous , Tg  210C
polystyrene Crystalline, Tm  270C
Brittle point  -170C
Thermally Stable to 
370C