CHAPTER 2

STEP-GROWTH
POLYMERIZATION

CRB30104
Dr. Noor Faizah Che Harun
 Upon comple*on of this chapter,
student should be able to
1. Discuss and evaluate the step-growth
polymeriza*on in terms of their mechanisms,
kine*cs and modes of polymeriza*on.
 Step-Growth Polymeriza*on
• All step polymeriza*ons fall into two groups
depending on the type of monomer(s)
employed.
• The first involves two different bifunc*onal
and/or polyfunc*onal monomers in which
each monomer possesses only one type of
func*onal group.
 Step-Growth Polymeriza*on
• The second involves a single monomer
containing both types of func*onal groups.
• The synthesis of polyamides illustrates both
groups of polymeriza*on reac*ons.
• Thus polyamides can be obtained from the
reac*on of diamines with diacids:
 Step-Growth Polymeriza*on
or from the reac*on of amino acids with
themselves:

The two groups of reac*ons can be represented in

a general manner by the equa*ons:

where A and B are the two different types of

func*onal groups.
Step-Growth Polymeriza*on
 Step-Growth Polymeriza*on
The successful synthesis of high polymers
using step polymeriza*on reac*on is more
difficult than the corresponding small
molecule reac*on, since high polymers can be
achieved only at very high conversions
(>98–99%).
 Step-Growth Polymeriza*on
• A conversion of 90%, which would be
considered excellent for the synthesis of
ethyl acetate or methyl benzamide.
• However, disaster for the synthesis of the
corresponding polyester or polyamide.
Step-Growth Polymeriza*on
 Step-Growth Polymeriza*on
• The need for very high conversions to
synthesize high polymer places several
stringent requirements —a favorable
equilibrium and the absence of cycliza*on and
other side reac*ons.
• An addi*onal requirement for achieving high
molecular weights is the need for the A and B
func*onal groups to be be present at very
close to stoichiometric amounts.
Step-Growth Polymeriza*on
 Reac*vity of Func*onal Groups
and Kine*cs of Step Polymeriza*on
Func*onal Groups in Organic Chemistry
 Reac*vity of Func*onal Groups
u Basis for Analysis of Polymerization
Kinetics
• Step polymerization proceeds by a relatively
slow increase in molecular weight of the
polymer.
• Consider the synthesis of a polyester from a
diol and a diacid. The first step is the reaction
of the diol and diacid monomers to form
dimer:
 Reac*vity of Func*onal Groups
• which can be expressed as the general reaction:

• The reaction mixture at any instance consists

of various-sized diol, diacid, and hydroxy acid
molecules.
• Any HO-containing molecule can react with
any COOH-containing molecule.
 Polymeriza*on Kine*cs
Kinetics: Tell us how fast the system takes various
reaction paths
Step Growth: SLOW
can use statistical methods as well as
kinetics to describe molecular weights
distributions

Chain Polymerization: FAST

Can apply statistical methods to an
analysis of the microstructure of the
products, but not the polymerization
process and things like molecular weight.
Kine*cs of Step Growth Polymeriza*on

• How long does it take to make polymer?

• Can we speed up the reaction?
• What is the relationship between kinetics
and the Molecular Weight of the product?
Kine*cs of Step Growth Polymeriza*on
Ø The reactivity of a functional group is independent
of the length of the chain to which it is attached.
Kine*cs
K I N E Tof
I CStep
S O F Growth
P O L Y C OPolymeriza*on
NDENSATION

A - A + B - B A- AB - B

Kinet ic equat ion f or t his t ype of

react ion is usually of t he f orm:

d[A]
Reaction Rate = - = k 2[A][B]
dt

N.B. [A] AND [B] ARE THE CONCENTRATIONS

OF FUNCTI ONAL GROUPS

However, esterifications are acid catalyzed

and in t he absence of added st rong acid

d[A] 2
- = k 3 [A] [B]
dt
 MORE KINETICS
d[A] 2
- = k 3 [A] [B]
dt
If [A] = [B]

c = [A] = [B]

Hence
dc
− = k3 c 3
dt
c t
dc
∫c c 3 = k3 ∫ dt
t =0
o

1 1
2 k3 t = 2 − 2
c co
 Acid Catalyzed Reac*on

• Consider the polyesterification of a diacid and

a diol
• This is an acid-catalyzed reaction.
• The reaction involves protonation of the
carboxylic acid:

(2.12)
• followed by reaction of the protonated species
I with the alcohol to yield the ester:

(2.13)
• Polyesterifications, are equilibrium reactions.
• In order to obtain high yields of high-
molecular-weight product the polymerizations
equilibrium must be in the direction of the
polymer.
• This is easily accomplished by removal of
water.
• Under these conditions the last two reactions
are irreversible.
• The rate of a step polymerization is expressed
in terms of the concentrations of the reacting
functional groups.
• Thus the polyesterification can be
experimentally followed by titrating for the
unreacted carboxyl groups with a base.
• The rate of polymerization Rp can then be
expressed as the rate of disappearance of
carboxyl groups d[COOH]/dt.
 Polyesterification Using Acid Catalysis
Polyesterifica*on using Acid Catalysis
O O
k1
Acid COH + HA C
catalyst k2 +
Acid
More active than
More active thanCOOH
-COOH
catalyst

⎡ OH ⎤
⎢ C OH ⎥
⎢ + - ⎥
k1 ⎣ A ⎦
K12 = =
k2 [HA][COOH ]

OH OH
k3
C OH + OH C OH
+ k4 -
- A +
 catalyst

⎡ OH ⎤
⎢ C OH ⎥
⎢ + - ⎥
Polyesterifica*on using Acid Catalysis
K12 =
k1 ⎣
k2
= A
[HA][COOH ]
⎦

OH OH
k3
Slow step
C OH + OH C OH
+ k4 - (rate-determining step)
- A +
A OH

.. Slow Step
OHof Polymers, Fall 2006 O
..

.. Synthesis
10.569, Lectu
OH Hammond..
Prof. Paula k
O Page 3
..

5
.. C Paulak5
Citation: Professor
C OH
OHHammond,C 10.569
.. O
CO
Synthesis
+ H
OHA Fall+2006
of Polymers
+
H2course
O + materials,
HA MIT
- - ..
OpenCourseWare k6
(http://ocw.mit.edu/index.html),
k
2
Massachusetts Institute of Technology, Date
A +A + 6
OH OH catalyst regeneration,catalyst re
Catalyst regeneration
thus [HA] will always be
constant in equilibrium
− d [COOH ]
Rp =
R = dt −d [COOH ] of disappearance
Rate
Rate
Rate
of carboxylic monomer
of disappearance of carboxylic
of disappearance monomer
of carboxylic mono
p
dt
Rp = k3 ⎡⎣C ( OH )2 ⎤⎦ ⎡⎣OH ⎤⎦
+ (from previous page)

=Rkp3K12 ⎡⎣=HA ⎡C + ⎤⎡
⎦⎣COOH
k⎤⎡
3 (
OH
⎦⎣ )
OH ⎤⎦ ⎤ ⎡OH ⎤ (from previous page)
 Polyesterifica*on using Acid Catalysis

• The polymeriza*on rate is the same as the

rate of forma*on of species II; because k4 is
very small and k1, k2, and k5 are large
compared to k3.
• The rate of polymeriza*on is given by:

(2.15)
 Polyesterifica*on using Acid Catalysis

• A more convenient expression for Rp is obtained

by subs*tu*ng for C+(OH)2 from the equilibrium
expression:

• HA such as sulfuric acid or p-toluenesulfonic acid

 Self-Catalyzed Polymeriza*on

• In the absence of an externally added strong

acid the diacid monomer acts as its own
catalyst.
• For this case [HA] = [COOH] and equa*on can
be wrigen:
 Self-Catalyzed Polymeriza*on
where K and k3 have been combined into the
experimentally determined rate constant k.
• The reac*on is third-order overall with a
second-order dependence on the carboxyl
concentra*on.
• The second-order dependence on the carboxyl
concentra*on is comprised of two first-order
dependencies—one for the carboxyl as the
reactant and one as the catalyst.
 Self-Catalyzed Polymeriza*on

• The concentra*ons of the two func*onal

groups are stoichiometric, and equa*on can
be wrigen as:

or:
 Self-Catalyzed Polymeriza*on

where [M] is the concentra*on of hydroxyl groups or

carboxyl groups.
• By integrate the equa*on yields:

where [M]0 is the ini*al concentra*on of hydroxyl or

carboxyl groups.
• The concentra*on [M] at *me t of either
hydroxyl or carboxyl groups is then given by

P = extent of reac*on (the decreased of

func*onality of monomer by *me)
thus,
2-2a-1 Experimental Observations
Experimental Observa*on

• Equa*on

indicates that a plot of 1/(1- p)2 versus t should be

linear.
Figure 2.1 The polymeriza*on of diethylene glycol, (HOCH2CH2)2O, and
adipic acid.
Reasons for Nonlinearity in Third-Order Plot

Low-Conversion Region.
• The nonlinearity in the low conversion region
is due to the large changes that take place in
the reac*on medium.
• There is a large decrease in the polarity of the
reac*on system as the polar alcohol and acid
groups are replaced by the less polar ester
groups with the simultaneous removal of
water.
Reasons for Nonlinearity in Third-Order Plot

• This may result in a change in the reac*on

rate constant or order of reac*on.
• It is also possible that extensive associa*on of
both the diol and diacid reactants in the low
conversion region lowers the reac*on rate by
effec*vely decreasing the concentra*ons of
the reac*ve species.
Reasons for Nonlinearity in Third-Order Plot

• Another possiblity for the nonlinearity in the

low conversion region is the decrease in
the volume of the reaction mixture with
conversion due to loss of one of the products
of reaction (water in the case of esterification).
2-2a-2-b High-Conversion Region.
High conversion region

• Polyesterifica*ons are carried out at high

temperatures not only to achieve fast reac*on
rates but also to aid in removal of the small
molecule by-product (ojen H2O).
• The polymeriza*on is an equilibrium reac*on
and the equilibrium must be displaced toward
the polymer to achieve high conversions and
high molecular weights.
• Par*al vacuum (ojen coupled with purging of
the reac*on system by nitrogen gas) is usually
also employed to drive the system toward
high
molecular weight.
• Under these condi*ons small amounts of one
or the other or both reactants may be lost by
degrada*on or vola*liza*on.
• In the case of polyesterifica*on, small
degrada*ve losses might arise from
dehydra*on of the diol, decarboxyla*on of
the diacid, or other side reac*ons.
• Although such losses may not be important
ini*ally, they can become significant during
the later stages of reac*on.
• A loss of only 0.3% of one reactant can lead to
an error of almost 5% in the concentration of
that reactant at 93% conversion.
• When kinetic studies were performed under
conditions which minimized the loss of
reactants by volatilization or side reactions the
reaction showed third-order behavior up to
past 98–99% conversion.
• Another possible reason for the observed
nonlinearity is an increase in the rate of
reverse reac*on.
• It ojen becomes more difficult to displace the
equilibrium toward the polymer as the
conversion increases.
• This is because of increased viscosity of the
reac*on medium at high conversions.
• This viscosity increase decreases the efficiency
of water removal and may lead to the
observed decrease in the reac*on rate with
increasing conversion.
• High viscosity may also lead to failure of the
assump*on of equal reac*vity of func*onal
groups—specifically to a decrease in
func*onal group reac*vity at very large
molecular size if there is too large a decrease
in molecular mobility.
 Molecular Weight of Polymer

• The molecular weight of a polymer is

important for unless a polymer is of
sufficiently high molecular weight it will not
have the desirable strength characteris*cs.
• It is therefore important to consider the
change in polymer molecular weight with
reac*on *me.
• The number-average degree of polymeriza*on
Xn is defined as the average number of
structural units per polymer chain.
• Xn is simply given as the total number of
monomer molecules ini*ally present divided
by the total number of molecules present at
*me t:
• This equa*on is referred to as the Carothers
equa*on.
• The number-average molecular weight Mn,
defined as the total weight of a polymer
sample divided by the total number of moles
in it is given by:
 (2.28)

where Mo is the mean of the molecular weights of

the two structural units, and Meg is the
molecular weight of the end groups
• For the polyesterifica*on of adipic acid,
HO2C(CH2)4CO2H, and ethylene glycol, HOCH2CH2OH,
the repea*ng unit is
• One half of its weight or 86 is the value of Mo.
• The end groups are H and OH and Meg is 18.
• For normal molecular weight polymer the
contribution of Meg to Mn is negligibly small,
and Eq. 2-28 becomes:

(2.29)
• Since the reac*on *me and degree of
polymeriza*on appear as the first and second
powers, respec*vely, the polymer molecular
weight will increase very slowly with reac*on
*me except in the early stages of the reac*on.
• This means that very long reac*on *mes are
needed to obtain a high-molecular-weight
polymer product.
• The right-hand ordinate of Fig. 2-1 shows the
varia*on of Xn with t.
• The slow increase of the molecular weight of
the polymer with *me is clear.
• The rate of increase of Xn with *me decreases
as the reac*on proceeds.
 External Catalysis of Polymerization

• The slow increase in molecular weight was

mistakenly thought originally to be due to the low
reac*vity of func*onal groups agached to large
molecules.
• It is, however, simply a consequence of the third-
order kine*cs of the direct polyesterifica*on
reac*on.
• The achievement of high-molecular-weight products
in reasonable reac*on *mes can be achieved by
employing small amounts of externally added strong
acids as catalysts.
• Since this remains constant throughout the
course of the polymeriza*on, the equa*on
can be wrigen as:

where k’ is the combina*on of all the

constant terms.
• It applies to reac*ons between stoichiometric
concentra*ons of the diol and diacid.
• Integra*on of that equa*on yields:

• Combining both equa*ons yields the dependence of

the degree of polymeriza*on on reac*on *me as:
 or

• Data for the polymeriza*on of diethylene

glycol with adipic acid catalyzed by p-
toluenesulfonic acid are shown in Fig. 2-2.
• The degree of polymeriza*on increasing
linearly with reac*on *me.
• There is much greater rate of increase of Xn
with reac*on *me in the catalyzed
polyesterifica*on compared to the
uncatalyzed reac*on
• The polyesterifica*on becomes a much more
economically feasible reac*on when it is
catalyzed by an external acid.
• The linearity of the plot in the higher
conversion region is a strong confirma*on of
the concept of func*onal group reac*vity
independent of molecular size.
• There is no change in the reac*vi*es of the
hydroxyl and carboxyl groups in spite of the
large increase in molecular size (and the
accompanying large viscosity increase of the
medium).
 EQUILIBRIUM CONSIDERATIONS

Closed System
• Step polymeriza*ons involve equilibrium
reac*ons.
• It is important to analyze how the equilibrium
affects the polymer molecular weight.
• A first considera*on is whether an equilibrium
polymeriza*on will yield high-molecular
weight polymer if carried out in a closed
system.
• A closed system is one where none of the
products of the forward reac*on are
removed.
• Nothing is done to push the equilibrium
toward the polymer side.
• Under these condi*ons the concentra*ons of
products (polymer and usually a small
molecule such as water) build up un*l the rate
of the reverse reac*on becomes equal to the
polymeriza*on rate.
• The reverse reac*on is referred to as a
depolymeriza*on reac*on or hydrolysis.
• The polymer molecular weight is determined
by the extent to which the forward reac*on
has proceeded when equilibrium is
established.
• Consider an external acid-catalyzed
polyesterifica*on:
• The rela*onship between the degree of
polymeriza*on and the equilibrium constant is
given by:

• Table 2-5 shows p and Xn values calculated for

various K values.
• A degree of polymeriza*on of 100
(corresponding to a molecular weight of
approximately 104 in most systems) can be
obtained in a closed system only if the
equilibrium constant is almost 104.
• The higher molecular weights that are
typically required for prac*cal applica*ons
would require even larger equilibrium
constants.
• The equilibrium constants for a polyesterifica*on
is normally no larger than 1–10
• This means that polymeriza*ons cannot be carried
out as closed systems.
Open, Driven System
• A step polymeriza*on must be carried out as
an open, driven system.
• We must remove at least one of the products
of the forward (polymeriza*on) reac*on so as
to drive the equilibrium toward high
molecular weights.
• It is usually more convenient to remove the
small molecule by-product rather than the
polymer.
• When water is the by-product, it can be
removed by a combina*on of temperature,
reduced pressure, and purging with inert gas.
• Conveniently step polymeriza*ons are carried
at temperatures near or above the boiling
point of water.
• This is usually done for purposes of obtaining desired
reac*on rates, but it has the added advantage of
facilita*ng water removal.
• Driving an equilibrium toward polymer is not easy
since the water or other small molecule must diffuse
through and out of the reac*on mixture.
• Diffusion is not so easy since the typical step
polymeriza*on system is fairly viscous at very high
conversions.
• For the polyesterifica*on,

• For large values of Xn, (Xn-1) is close to Xn and

[H2O] is inversely dependent on the square of
Xn
 Interfacial Polymerization
• Many of the polymers that are produced by
the usual high-temperature reac*ons could be
produced at lower temperatures by using the
faster Schogen–Baumann reac*ons of acid
chlorides.
• Thus polyesters and polyamides could be
produced by replacing the diacid by the
corresponding diacyl chloride
• The rate constants for these reac*ons are
greater than those for the corresponding
reac*ons of the diacid.
• This low-temperature polymeriza*on
technique is called interfacial polymeriza*on.
• Polyamida*on is performed at room temperature
by placing an aqueous solu*on of the diamine on
top of an organic phase containing the acid
chloride.
• The reactants diffuse to and undergo
polymeriza*on at the interface.
• The polymer product precipitates and is
con*nuously
withdrawn in the form of a con*nuous film or
filament
• The polymeriza*on rate is diffusion-controlled,
since the rates of diffusion of reactants to the
interface are slower than the rate of reac*on of
the two func*onal groups.
• The reac*on rates are so high that monomers will
react with the growing polymer chain ends only.
• Interfacial polymerza*on tend to produce high
molecular weight polymer.
• Interfacial polymeriza*on does not require
stoichiometry.
• Stoichiometry automa*cally exists at the
interface due to diffusion.
• An inorganic base should be added to the
aqueous phase to neutralize hydrogen
chloride.
• The choice of organic solvent is very important.
• The solvent affects the molecular weight and
rate of polymeriza*on.
• Advantages of interfacial polymeriza*on:
Bulk stoichiometry is not needed.
High-molecular-weight polymers are produced.
Fast reac*ons.
The low temperatures allow the synthesis of
polymers that may be unstable at the high
temperatures.
• Disadvantages of interfacial polymeriza*on:
The high cost of acid chloride reactants.
Large amounts of solvents that must be used
and recovered.