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1. Rate constants for temination kt may be order of 108 liter/mol sec in free-radical
polymerizations. Consider the polymerization of styrene initiated by di-t-butyl
peroxide at 600C. For a solution of 0.01 M peroxide and 1.0 M styrene in benzene, the
initial rate of polymerization is 1.5x 10-7 mol/liter sec and M n of the polymer
produced is 138 000.
(a) From the above information estimate kp for styrene at 600C.
(b) What is the average lifetime of a macromolecule during initial stages of
polymerization in this system?
H
CH2
C.
H
+
.C
CH2
ktc
CH2
CH2
Ce3++ H+ + R-CHOH
Mn. + M
kp
Mn+1
Mn . + Ce4++
Using the steady-state assumption, derive a useful expression for the rate of
polymerization. Take the initiator efficiency = f and assume that the propagation reaction
is the only one which uses significant quantities of monomer.
5. For acrylamide, kp2/kt = 22 liter/ mol sec at 250C and termination is by coupling alone.
At this temperature the half-life of isobutylryl peroxide is 9.0h and its efficiency in
methanol can be taken to equal to 0.3 A solution of 100 g/liter acrylamide in methanol is
polymerized with 10-1 M isobutyryl peroxide.
(a) what is the initial steady-state rate of polymerization?
(b) How much polymer has been made in the first 10 min of reaction in 1 liter of
solution?
6. One hundred liter of methyl methacrylate is reacted with 10.2 mol of an initiator at
600C.
(a) What is the kinetic chain length in this polymerization?
(b) How much polymer has been made in the first 5 h of reaction?
kp= 5.5 liter/mol sec kt= 25.5 x 106 liter/ mol sec
Density of monomer = 0.94 g cm3
t1/2 for this initiator= 50 h
f = 0.3
100 L methyl methacrylate ( Mo )= C5H8O2 = 100 g/mol) 10.2 moles of an initiator at
60oC.
7. Redox initiation is often used in polymerization in aqueous system. Thus H2O2 and Fe2+
ion can be used to initiate the polymerization of acrylamide in water. Derive an expresiion
for the steady-state rate of polymerization.
In this case:
H2O2 + Fe2+