Essentials of Polymer Engineering

(Introduction to Polymers)
Condensation (Step-Reaction)
Polymerization
 What we have covered so far…
• Introduction; Classification of Polymers
• Polymerization mechanisms (chain-reaction, ionic,
coordination, step-growth, ring-opening)
• Chemical bonding and polymer structure (primary:
monomer, secondary: polymer molecule, and tertiary:
aggregate)
• Thermal transition in polymers
• Polymer modification
• Analysis of condensation (step-reaction)
polymerization (kinetics, stoichiometry, molecular
weight control and distribution)
Review of Step Polymerization

Synthesis of polyamide involving two different

bifunctional monomers. Each monomer
posseses only one type of functional group.

Synthesis of polyamide involving a single

monomer. The single monomer contains both
types of functional groups.
 Kinetic analysis
• Kinetic analysis of polymerization is necessary for
practical synthesis of high polymers
• Step polymerization proceeds by a slow increase
in molecular weight (involves many separate
reactions such as monomer+monomer,
dimer+monomer, dimer+dimer,
trimer+monomer, etc)
• Kinetic analysis of innumerable, separate
reactions in step polymerization is greatly
simplified by Flory’s equal reactivity principle
 Principle of Equal Reactivity of
Functional Groups
• Reactivities of both functional groups of a
bifunctional monomer are the same
• Reactivity of one functional group of a
bifunctional reactant is the same irrespective
of whether the other functional group has
reacted
• Reactivity of a functional group is
independent of the size of the molecule to
which it is attached
Experimental Evidence of Flory’s Equal
Reactivity Principle - 1
Esterification of a series of homologous carboxylic acids

Rate constant independent of molecular size (k independent of x)

Experimental Evidence of Flory’s Equal
Reactivity Principle - 2
Polyesterification of sebacoyl chloride with α,ω-alkane diols

Rate constant independent of molecular size (k independent of x)

 Kinetics of Condensation
Polymerization - 1
Polyesterification of a diacid and a diol; acid-catalyzed

Proposed reaction mechanism:

Protonation of carboxylic acid

Reaction of I with alcohol to produce ester

 Kinetics of Condensation
Polymerization - 2

- For practical applications, we have to

shift the equilibrium to the production
of polymer (e.g. removal of by-product
water) to make the overall reaction
seem irreversible

Rate of polymerization = rate of

disappearance of carboxyl groups;
also similar to rate of production of
species II During practical synthesis, k4 is very
small; k1, k2, and k5 > k3
 Kinetics of Condensation
Polymerization - 3

Rate of polymerization in terms of

experimentally measurable
concentration of specie; we can
perform titration of carboxyl groups to
monitor the extent of reaction vs time

Two cases to consider: 1) Polymerization w/o added strong acid, and

2) Polymerization w/ added strong acid
 Case 1: Polymerization without
Added Strong Acid
In the absence of an added strong acid, a
second molecule of the acid being esterified
acts as the catalyst:
For most polymerizations, the concentrations
of the two functional groups are very nearly
stoichiometric:
Integration yields third-order reaction
expression:
Introduce extent of reaction p; C0 = initial
concentration of hydroxyl or carboxyl groups:

Solve the constant (t = 0; c = C0); then

substitute C (p) in the third-order reaction
expression:
 Case 1: Polymerization without
Added Strong Acid

Reaction of diethylene glycol with adipic acid (DE-A) and of diethylene glycol with
caproic acid(DE-C). Time values at 202°C have been multiplied by two.
 Case II: Polymerization with
Added Strong Acid

where k’ = k [catalysts]

Reaction of decamethylene glycol with adipic

acid at the temperature indicated, catalyzed by
0.10 eq% of p-toluenesulfonic acid. The time
scale for the results at 82.8°C is to be
multiplied by two.
 Stoichiometry in Linear Systems
Structural unit - residue from each diol and each diacid (separately, not together) in the
polymer chain

Repeating unit
The total number of structural units in any particular system equals the total number of
bifunctional monomers initially present.
The number-average degree of polymerization is defined as the average number of
structural units per polymer chain.

Number-average
molecular
Carothers weight
equation M0 – average molecular weight of the structural unit
 Example 1
For condensation polymerization between a dibasic acid and a glycol, show that M0 is
the average molecular weight of the structural units.

SOLUTION:
Assume we start w/ 10 moles of each monomer; suppose the extent of reaction at time t
equals p = 0.5.
Example 1
 Example 1
To know which of the above definitions of M0 is correct, we need to carry out a simple
mass balance:
 Example 2
A 21.3 g sample of poly(hexamethylene adipamide) is found to contain 2.50 × 10–3 mol
of carboxyl groups by both titration with base and infrared spectroscopy. From these data
calculate: a) The number-average molecular weight; b) The extent of reaction

SOLUTION: repeating unit

This is possible since we assume

each polymer molecule contains
one –COOH group:
 Molecular Weight Control
• To control MW is to adjust precisely the
stoichiometric imbalance of the
bifunctional/monofunctional monomers
• Too large nonstoichiometry
low MW
• We have to understand the quantitative effect
of stoichiometric imbalance of reactants on
the polymer MW
 Case of excess B-B monomer
Numbers of A and B functional groups
Total number
of monomer
molecules
fraction of B groups that have reacted = rp
fraction of unreacted A groups = (1 – p)
fraction of unreacted B groups = (1 – rp)
Total unreacted A and B = NA(1 - p) + NB(1 - rp)
r – stoichiometric
ratio or imbalance
Extent of reaction p or PA -
fraction of the limiting
groups (A groups) that
have reacted at a particular
time
total number of polymer chain ends is
the sum of the total number of
unreacted A and B; total number of
polymer molecules is half total
number of chain ends =
[NA(1 - p) + NB(1 - rp)]/2
 Case of excess B-B monomer
The number-average degree of polymerization is the total number of A-A and B-B molecules
initially present divided by the total number of polymer molecules

This shows the degree of polymerization as function of stoichiometric imbalance and extent
of reaction.

When the two bifunctional monomers are

present in stoichiometric amounts (r = 1):

When conversion is 100% (p = 1):

In actual practice, p may approach but never becomes equal to unity.

 Molecular Weight Distribution in Linear
Polymerization – Derivation of Size Distributions
We want to find the probability of finding a polymer molecule containing x structural units.
By principle of equal reactivity, this is also synonymous with the probability of finding a
molecule with (x – 1) A groups reacted and one A group unreacted.
Extent of reaction p = probability that an A group has reacted at time t
px-1 = probability that (x – 1) A groups have reacted is the product of (x – 1) separate
probabilities
1 – p = probability of an A group being unreacted
total probability, Px, that a given polymer
molecule contains X units

mole or number fraction of molecules in

the polymer mixture that are x-mers
N is the total number of polymer molecules
Nx is the number that are x-mers
N0 is total number of structural units present initially
 Molecular Weight Distribution in Linear
Polymerization – Derivation of Size Distributions
Number distribution Weight distribution
function function

weight fraction of
the molecules
that contains x
structural units

most probable or Flory

or Flory–Schulz
distributions
 Molecular Weight Distribution in Linear
Polymerization – Derivation of Size Distributions

Number-fraction distribution curve for Weight fraction distribution plot for

linear polymerization. Plot 1, p = 0:9600; linear polymerization. Plot 1, p = 0:9600;
plot 2, p = 0:9875; plot 3, p = 0:9950. plot 2, p = 0:9875; plot 3, p = 0:9950.
 Molecular Weight Distribution in Linear
Polymerization – Breadth of MWD
number-average degree of
polymerization

weight-average degree of
polymerization

breadth of the molecular weight distribution

Measure polydispersity of polymer sample

Approaches the limit of 2 as p increases
Polydispersity Index (PDI)
 Example
a) Polyester fibers for “lace” material can, in principle, be
produced from ω-hydroxycaproic acid. If the initial 100
moles of the hydroxyacid are reduced to 2 moles after 10
h reaction time, calculate:
1) number average molecular weight
2) weight average molecular weight
3) probability that the reaction mixture contains tetramers
4) weight fraction of these tetramers

b) As a result of extraneous reactions of the hydroxyl groups, a

5% excess of the carboxylic acid is present in the reaction
mixture. Calculate the number-average molecular weight
for the same extent of reaction in a.
 Solution

1. number average molecular weight Note: 114 is the molecular weight of the
repeating unit; in A-B polymer, the average
molecular weight of structural units M0 is equal
to the molecular weight of repeating unit
2. weight average molecular weight

3) probability that the reaction

mixture contains tetramers
 Solution
4) Weight fraction of these tetramers

b) As a result of extraneous reactions of the hydroxyl groups, a 5% excess of the carboxylic

acid is present in the reaction mixture. Calculate the number-average molecular weight for
the same extent of reaction in a.

1 + 0.95
Xn = = 22.16
1 + 0.95 − 2(0.95 × 0.98)

Notice the depression of number-average molecular weight of the polymer due

to stoichiometric imbalance (from 5700 to 2526)