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PROBLEMS 3-1 When one considers the various polymers produced from carbon carbon double bond monomers, the following generalizations are apparent: a. The polymers are produced almost exclusively from ethylene, monomers that have one substituent on the double bond, or monomers that have two substituents on the same carbon atom of the double bond. Monomers containing one substituent on each carbon of the double bond seldom polymerize. b. Most of the chain polymerizations are carried out by radical initiation; relatively few are produced by ionic initiation. Why Are there good reasons for these generalizations or are they simply a matter of chance Discuss. 3-2 3-3 Show by chemical equations the polymerization of acrylonitrile initiated by the thermal decomposition of cumyl hydroperoxide. Using 14C-labeled AIBN as an initiator, a sample of styrene is polymerized to an number-average degree of polymerization of 1:52 104 . The AIBN has an activity of 9:81 107 counts min 1 mol 1 in a scintillation counter. If 3.22 g of the polystyrene has an activity of 203 counts min 1 , what is the mode of termination Poly(vinyl acetate) of number-average molecular weight 100,000 is hydrolyzed to poly(vinyl alcohol). Oxidation of the latter with periodic acid to cleave 1,2-diol linkages yields a poly(vinyl alcohol) with X n 200. Calculate the percentages of head-to-tail and head-to-head linkages in the poly(vinyl acetate). The benzoyl peroxide initiated polymerization of a monomer follows the simplest kinetic scheme, that is, Rp kp M fkd I =kt 1=2 with all rate constants and f being independent of conversion. For a polymerization system with M 0 2 M and I 0 10 2 M, the limiting conversion p1 is 10%. To increase p1 to 20%: a. Would you increase or decrease M 0 and by what factor b. Would you increase or decrease I 0 and by what factor How would the rate and degree of polymerization be affected by the proposed changes in I 0 c. Would you increase or decrease the reaction temperature for the case of thermal initiated polymerization For the case of photopolymerization (assuming that an increase in temperature does not cause thermal decomposition of initiator) Ed , Ep , and Et are 124, 32, and 8 kJ mol 1 , respectively. 3-6 For a radical polymerization with bimolecular termination, the polymer produced contains 1.30 initiator fragments per polymer molecule. Calculate the relative extents of termination by disproportionation and coupling, assuming that no chain-transfer reactions occur.
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