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ion-exchange resins Styrene-butadiene rubbers (SBR) produced by free-radicalinitiated emulsion polymerization478 played an important role in World War II to supply synthetic rubber for tire-tread production Known as Buna-S in Germany and GR-S in the United States it was manufactured in a water-monomer two-phase system that also contained an initiator and emulsifier at 50 C (hot polymerization)184,223 A molecular weight modifier was also used to avoid the formation of unprocessably high-molecular-weight polymer Because of the relatively high temperature, crosslinking resulted in significant gel formation Later the use of more active initiators operating at lower temperatures allowed to perform polymerization at about 5 C, thus significantly reducing crosslinking Continuous operation was an additional important development 479 The nonterminating nature of living anionic polymerization allows the synthesis of block copolymers,480,481 which are useful thermoplastic elastomers.

22 What is the essential difference between the Langmuir Hinshelwood and Eley Rideal mechanisms Which of the two is the more likely mechanism 223 Can a catalytic reaction be an elementary step 224 In solving the kinetics of a catalytic reaction, what is the difference between the complete solution, the steady-state approximation, and the quasi-equilibrium approximation What is the MARI (most abundant reaction intermediate species) approximation 225 Does the reaction order of a catalytic reaction depend on pressure and temperature 226 Does the apparent activation energy depend on pressure and temperature 227 Why can reaction orders in catalytic reactions change sign when the reaction conditions are changed 228 Can the activation energy of a catalytic reaction have a negative value If so, under what conditions 229 Why does the quasi-equilibrium approximation fail in the low-pressure limit of a reactant 2.

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They have many properties of rubber (softness, flexibility, resilience) but in contrast to rubber can be processed as thermoplastics 482,483 Block copolymers can be manufactured by polymerizing a mixture of two monomers or by using sequential polymerization When a mixture of styrene and 1,3-butadiene (or isoprene) undergoes lithiuminitiated anionic polymerization in hydrocarbon solution, the diene polymerizes first It is unexpected, since styrene when polymerized alone, is more reactive than, for example, 1,3-butadiene The explanation is based on the differences of the rates of the four possible propagation reactions: the rate of the reaction of the styryl chain end with butadiene (crossover rate) is much faster than the those of the other three reactions 484,485 (styryl with styrene, butadienyl with butadiene or styrene) This means that the styryl chain end reacts preferentially with butadiene.

30 Under what conditions may reactions start to oscillate Give some examples of oscillating reactions 231 Compare the Michaelis Menten expression for the rate of an enzyme-catalyzed reaction with the Langmuir Hinshelwood expression for the same reaction on a metal surface Are the two expressions equivalent 232 Suppose two mechanisms have been proposed for a certain catalytic reaction Discuss to what extent it is possible to prove that the mechanisms are right or wrong on the basis of kinetic analysis..

In hydrocarbon solution butadiene polymerizes first, incorporating only a small amount of styrene; then the residual styrene homopolymerizes into the polybutadieny 1lithium The resulting copolymer (termed solution styrene-butadiene rubber) contains long blocks of polybutadiene and polystyrene The first such polymer containing 75% butadiene and 25% styrene was marketed by Phillips as Solprene 1205 With increasing relative concentration of styrene, or by the addition of polar substances (ethers, tertiary amines), more styrene can be incorporated from the beginning of polymerization changing the block nature into a more random copolymer Styrene-l,3-butadiene-styrene (SBS) or styrene-isoprene-styrene (SIS) triblock copolymers are manufactured by a three-stage sequential polymerization One possible way of the synthesis is to start with the polymerization of styrene Since all polystyrene chains have an active anionic chain end, adding butadiene to this reaction mixture resumes polymerization, leading to the formation of a polybutadiene block.

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The third block is formed after the addition of styrene again The polymer thus produced contains glassy (or crystalline) polystyrene domains dispersed in a matrix of rubbery polybutadiene 120 ,481,486.

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