Kinetics of Radical Chain

Polymerization
In order to obtain a kinetic
expression for the rate of
polymerization, it is necessary to
assume that kp and kt are
independent of the size of the
radical
The rate of monomer disappearance,
which is synonymous with the rate of
polymerization, is given by

 However, the number of monomer

molecules reacting in the initiation step is
far less than the number in the propagation
step for a process producing high polymer
Ri can be neglected and the polymerization
rate is given simply by the rate of
propagation:

The rate of propagation, and therefore the

rate of polymerization, is the sum of many
individual propagation steps

 Since the rate constants for all the

propagation steps are the same,
one can express the polymerization
rate by:

(
Where: [M] is the monomer
concentration and [M.] is the total
concentration of all chain radicals,
that is, all radicals of size M1. and
larger

 Equation 3.9 for the polymerization rate

is not directly usable because it contains
a term for the concentration of radicals
Radical concentrations are difficult to
measure quantitatively, since they are
very low, and it is therefore desirable to
eliminate [M.] from Equation 3.9
Over the course of polymerization (at
steady state), the total radical
concentration remains constant. This
means that radicals are being produced
and destroyed at equal rates (i.e., R i =
Rt)

 Nm
The right side of Equation 3.10
represents the rate of termination
Rearrangement of Equation 3.10 for
[M.] and substitution into Equation
3.9 yields an expression for rate of
polymerization as:

 The differences in the decomposition

rates of various initiators can be
conveniently expressed in terms of
the initiator half-life t1/2
defined as the time for the
concentration of initiator I to
decrease to one half its original value

 The rate of initiator disappearance is

given by:
Where: [I] 0 is the initiator
concentration at the start of
polymerization. Setting I = [I]
half time (t1/2) is obtained as:

/2 the

The rate of producing primary

radicals by thermal homolysis of an

 By:

The initiation reaction in

polymerization is composed of two
steps as discussed previously
The homolysis of the initiator is the
rate-determining step in the initiation
sequence, and the rate of initiation is
then given by

 By:
Substitution of Equation 3.13 into
Equation 3.11 for Ri yields an
expression for rate of free radical
chain polymerization as:

Example

The following are data for the

polymerization of styrene in benzene
at 60C with benzoyl peroxide as the
initiator.
[M] = 3.34 x 103 mol/m3
[I] = 4 .0 mol/m3
Kp2/Kt = 0.95 x 10-6 m3/mol-s
If the spontaneous decomposition rate
of benzoyl peroxide is 3.2 10 6 m3/mols1, calculate the rate of polymerization

Solution

Example 2
The data for the polymerization of styrene
at 60C with benzoyl peroxide as initiator
are:
[M] = 8.35 x 103 mol/m3
[I] = 4 .0 mol/m3
Kp2/Kd = 1.2 x 10-6 m3/mol-s

If the rate of polymerization of styrene is

0.026 mol/m3-s and the spontaneous
decomposition of benzoyl peroxide in
styrene is 2.8 106 s1, what is the
efficiency of the initiator?

Solution