33

CHAPTER 2. STEP-GROWTH POLYMERIZATION

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2.1 Polycondensation mechanisms

• Polymer is made up through a series of steps;

• High molecular weight materials is only made after many steps;
• If we look at these steps, each step produces a repeat unit, different
from the monomeric units, e.g. ester, amide, etc.
polyesters from diols and dicarboxylic acids
polyamides from diamides and dicarboxylic acids.
• In general for difunctional monomers A-A and B-B reacting to
form an ab linkage
n A A - A + n B B - B → A - ab - ba - ab - ba - ab - ba ab - B
→ A - ( ab) n-1 − B
nA =nB = stoichiometric balance
• It is also possible for the two functional groups to be on the same
molecule, then in general A-B monomer reacting to form an ab
linkage (stoichiometric balance assured)
n A - B → A - ab - ab - ab - ab - ab - ab ab - B
→ A - (ab) n -1 − B
• Consider that only the functionality is important, and that the
reactivity of the functional group does not depend upon chain
length. Assumption of Equal Reactivity (Justification?)
monofunctional monomer ⎯ chain stopper;
trifunctional monomer ⎯ long chain branching.

How fast can we make these polymers?

 35

Rate equation when external catalyst is used:

dV [ A] dV [B ] dV [ab]
− =− = ∝ [ A][B ]
Vdt Vdt Vdt
d [ A] d [ B] d [ab]
− =− = = K[ A][ B] K: rate constant
dt dt dt

Rate constant: incorporates the effect of diffusion.

2.2 Polymerization Kinetics

Stoichiometric balance: [A] = [B]

1 1
− = Kt
[ A] [ A] 0
Stoichiometric Imbalance [A] ≠ [B]
1 [ A][B ] 0
ln = Kt
[ A] 0 − [ B ] 0 [ A ] 0 [ B ]
Define extent of reaction (p),
[ A]0 − [ A]
p= , fraction of reacted functional groups
[ A]0
ν A0 [ A]0
and r = 0 = (r ≤ 1, B groups in excess), imbalance factor
ν B [ B]0
1
Balance: = 1 + K [ A]0 t
1− p
1− p ⎛ 1 ⎞
Imbalance: ln = K [ A]0 ⎜1 − ⎟t
1 − rp ⎝ r ⎠
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2.3. Number-Average Molecular Weight

How Big Can We Make These Polymers?

A-B Example

Consider 10 monomer units, each line represents the possible products of some of
the possible reaction steps.
Line Molecular Species Extent of Number-Average
Reaction Degree of Polymer

p Nn

1 AB AB AB AB AB AB AB AB AB AB 0.0 1

2 AbaB AbaB AbaB AbaB AB AB 4/10=0.4 10/6=1.67

3 AbababaB AbaB AbabaB AB 0.6 2.50

4 AbababaB AbabababaB AB 0.7 3.33

5 AbababaB AbababababaB 0.8 5.00

 37

6 AbababababababababaB 0.9 10.00

• Can watch either A or B functional groups to monitor the extent of reaction;
• Molecular weight increases slowly with extent of reaction;
• We assumed linear polymer, rings could be formed to consume functional
groups without a resultant increase in molecular weight (loss of functional
groups to other reactions neglected).

In general
Numberof Monomer Initially Present
Nn =
Number of Molecules Present at Time t

Stoichiometric Balance
ν A0 1
Nn = =
ν A 1− p
Applicable not only to AB case, but AA + BB case. However, in
AA +BB case, repeat unit structure is different: ab in the AB case,
aabb in the AA + BB case.

Stoichiometric Imbalance

The number of unreacted functional groups after reaction reaches

extent p is
ν A = (1 − p)ν A0 ν B = ν B0 − pν A0 = ν B0 − prν B0 = (1 − pr )ν B0

The total number of chain ends is:

1 − pr 0 1
ν ends = ν A + ν B = (1 − p + )ν A = (1 + − 2 p)ν A0
r r

The total number of chains is half the end of chain ends:

1 1 1
ν chains = ν ends = (1 + − 2 p)ν A0
2 2 r

The total number of repeat units distributed among these chains is

the number of monomer molecules present initially
1 1 1 1
ν repeat unit = ν A0 + ν B0 = (1 + )ν A0
2 2 2 r
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The number average degree of polymerization is

ν
N n = repeat units
ν chains
1
1+
= r
1
1+ − 2 p
r
1+ r
=
1 + r − 2 pr

In cases when some of the excess B groups present are in the form
of monofunctional reagents, the definition of r is modified to r´
ν A0
r= 0
ν B + 2ν B0 '
The factor of 2 for νB’ indicates the monofunctional reagent has the
same effect on the degree of polymerization as a difunctional
molecule with two B groups.
Some values of Nn calculated for values of r and p close to unity

R p = 0.95 p = 0.97 p = 0.99 p = 1.00

0.95 13.5 18.2 28.3 39.0
0.97 15.5 22.3 39.9 65.7
0.99 18.3 28.7 66.8 199
1.00 20.0 33.3 100 ∞

Effects of r and p values on Nn

• For any value of r, Nn is greater for larger values of p; this is true
regardless of the stoichiometric balance or imbalance.
• The final 0.05 increase in p has a bigger effect on Nn at r values
that are closer to unity than for less-balance mixtures.
• For any value of p, Nn is greater for larger values of r;
stoichiometric imbalance lowers Nn.
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• An 0.05 increase in r produces a much bigger increase in Nn at p =

1 than in mixtures that have reacted to a less extent.
• When p = 1, N n = 1 + r
1− r

In order to produce high MW polymers:

• Very accurate control of the stoichiometric ratio of functional

groups, r;
• Absence of side reactions;
• Availability of high-purity monomers;
• Reasonably high polymerization rate;
• Little tendency towards cyclization reactions.

Q: Esterification of hydroxycarboxylic acid

n HO − R − COOH → [−O − R − CO −]n + n H 2 O

N n = 100 required, p ?

Q: Esterification of diacid and diol

n HO − R1 − OH + n HOOC − R2 − COOH
→ [−O − R1 − O − CO − R2 − CO −]n + 2n H 2 O
[-OH]0 = 4.95 mol/L
[-COOH]0 = 5.00 mol/L

(1) At x(-OH) = 99%, N n = ?

(2) What is maximum N n ?
(3) What are the residue concentration of [-COOH] for cases (1) and (2) ?
 40

2.4 Molecular Weight Distribution

Q: Are all polymer chains in the same size?

Derivation (Statistical Approach)

Conversion p: the probability that a functional group selected at random has
reacted.
Consider again AB monomers
Ab ab ab ab aB

The number chain length distribution xi(p):

xi ( p) = p i−1 (1 − p) most probable distribution

The number of i-mer molecules in the reaction mixture (total number of

molecules is m)
ni ( p ) = mp i−1 (1 − p )
m = (1 − p)[ A]0 = (1 − p)m0 m0 = [A]0
Therefore
ni ( p) = p i−1 (1 − p) 2 m0

The number-average polymerization degree

m0 ∞
1
N n = ∑ ixi ( p) =∑ ipi−1 (1 − p) =
i =1 i =1 1− p

The weight chain length distribution wi:

ini M 0 ini
wi = = = ipi−1 (1 − p) 2
m0 M 0 m0

The number-average polymerization degree

m0 ∞
2
∑ iw ∑ ii p i−1 (1 − p) 2
1+ p
Nw = i =1
m0
= i =1
=
∞
i −1 1− p
∑w i ∑ ip (1 − p) 2
i =1 i =1
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The polydispersity index

M w Nw
= = 1+ p
M n Nn
 42

2.4 Polyesters and Polyamides

Polyester

Reactions for the formation of polyesters

Thermoplastic polyester: Dacron (fiber) and Mylar (film)

Saturated polyester:
terephthalic acid [C6H4(COOH)2]+ethylene glycol
[C2H4(OH)2-] = PET;
fibre, film, videotape, dual ovenable container, computer, and
magnetic tape, beverage bottle.
 43

PET: originally developed ICI;1953 DuPont purchased Dacron

Advantage of polyester:·
1. tough, rigid
2. processable

Disadvantage:
1. attacked by acid and base
2. low thermal resistance
3. poor solvent resistance

Polyamides (PA)

Reactions for the formation of polyamides

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1928, Wallace Hume Carothers concluded linear polyester not suitable for fiber; amino acid in
silk and natural fiber prompted Carothers to study polyamides; 1938 polyamide 6,6
(Nylon (6,6) by DuPont; condensate diacid and diamine (-CONH- repeat unit);
processed into filament, fiber, film, molded part
Nylons 6 Polycaprolactam
Nylon 6,6 Polyhexamethyleneadipamide
Nylon 6,10 Polyhexamethylenesebacamide
Nylon 11 Poly(11-aminoundecanoic acid)
Nylon 12 Poly(12-aminododecanoic acid)

Nylon-6 and 6,6 are most used; originally as fiber, now fiber, molding, compound, extrusive,
coating, adhesive, casting, shared with acetal (superior in fatigue endurance, creep
resistance, water resistance) and fluorocarbon; used as gear, bearing, valve seat, comb,
furniture caster, door catcher; wear resistance, quite operation, low friction

Advantage:
1. tough, strong, impact resistant
2. low coefficient of friction
3. abrasion resistance
4. high temperature resistance
5. .processable
6. good solvent resistance
7. resistant to bases

Disadvantage:
1. high moisture absorption
2. attacked by strong acid and oxidizing agent
3. UV sensitive
4. high shrinkage
5. electrical and mechanical properties influenced by moisture
absorption

Interfacial Polymerization (for High Molecular Weight)

Required: Extremely fast polymerization;

Two immiscible monomer solutions.

e.g. polyamidation of diamine with diacid chloride

n H2N R1 NH2 + n ClCOR2COCl
H H O O
45
N R1 N C R2 C + 2n HCl
n