Polymer Chemistry 2 Exercise Problem Set#2

(Due on Oct 25th)

(1) Rate constants for termination kt may be of the order of 108L/mol s in free radical
polymerizations. Consider the polymerization of styrene initiated by di-t-butyl peroxide at 60 oC.
For a solution of 0.01 M peroxide and 1 M styrene in benzene, the initial rate of
polymerization is 1.5 x 10-7 mol/L s and Mn of the polymer product is 138,000.
(a) From the above information estimate kp for styrene at 60oC.
(b) What is the average life time of a macroradical during initial stages of polymerization in
this system?
(2) For a particular application, the molecular weight of the polymer made in Problem (1) is too
high. What concentration of t-butyl mercaptan should be used to lower the molecular weight of
the polymer to 85,000? For this, transfer constant C is 3.7 in the polymerization of styrene.
(3) Redox initiation is often used in polymerizations in aqueous systems. Thus H 2O2 and Fe+2 ion
can be used to initiate the polymerization of acrylamide in water. Derive an expression for the
steady state rate of polymerization in this case.
H2O2 + Fe +2 ------- k ------- HO* + OH- + Fe

+3

k ; rate constant

(4) In a free radical polymerization in solution the initial monomer concentration is increased by a
factor of 10:
(a) How is the rate of polymerization affected quantitatively?
(b) What change takes place in the number average degree of polymerization?
If the monomer concentration was not changed but the initiator concentration was halved
instead:
(a) What is the change in the rate of polymerization?
(b) What is the change in the number average degree of polymerization?
(5) One hundred liters of methyl methacrylate is reacted with 10.2 moles of initiators at 60oC.
(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 L/mol s, kt=25.5 x 106 L/mol s
Density of monomer= 0.94 g cm-3
t 1/2 for the initiator=50 h, f=0.3, t 1/2 =half life of initiator
(6) An engineer is studying the AIBN-initiated polymerization of butyl acrylate in solution. She
wants to change the initiator and monomer concentrations so as to double the initial steady
state polymerization without changing the number average degree of polymerization of the
polymer or reaction temperature. How should she proceed?
(7) Discuss the following phenomena in radical chain polymerization
(a) Methods of generating radicals
(b) Inhibition and retardation
(c) The temperature dependence of rate and degree of polymerization
(d) Radical life time
(e) How to distinguish between termination by combination and by disproportionation
(f) How to distinguish between transfer to monomer and to initiator