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Watts, D. G., H. N. Linsen, and J. Schrijner, J. Polym. Sci. Polym. Chem. Ed., 18, 1285 (1980). Wilks, E. S., Prog. Polym. Sci., 25, 9 (2000). Williams, R. J. J. and C. I. Vallo, Macromolecules, 21, 2571 (1988). Wood, K. B., V. T. Stannett, and P. Sigwalt, Makromol. Chem. Suppl., 15, 71 (1989). Wu, C., R. Brambilla, and J. T. Yardley, Macromolecules, 23, 997 (1990). Yee, L. H., J. P. A. Heuts, and T. P. Davis, Macromolecules, 34, 3581 (2001). Yoshimura, X., H. Mikawa, and Y. Shirota, Macromolecules, 11, 1085 (1978). Young, L. J., Copolymerization Reactivity Ratios, pp. 105 386 in Chap. II in Polymer Handbook, J. Brandrup and E. H. Immergut, with W. McDowell, eds., Wiley-Interscience, New York, 1975. Yuki, H., K. Kosai, S. Murahashi, and J. Hotta, J. Polym. Sci., B2, 1121 (1964). Zetterlund, P. B., S. Tagashira, K. Izumi, Y. Nagano, M. Azukizawa, H. Yamazoe, M. Kumagai, and B. Yamada, Macromolecules, 35, 8209 (2002).
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PROBLEMS 6-1 6-2 6-3 Discuss the differences in the structures of random, alternating, graft, and block copolymers. What is the difference between the ideal and alternating behaviors in copolymerization Consider the following monomer reactivity ratios for the copolymerization of various pairs of monomers: Case 1 2 3 4 5 6 7 r1 0.1 0.1 0.1 0 0 0.8 1 r2 0.2 10 3 0.3 0 2 15
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What is the composition of the copolymer that would be formed at low conversion from equimolar mixtures of the two monomers in each case 6-4 Using the r1 and r2 values from Table 6-2, construct plots showing the initial copolymer composition as a function of the comonomer feed composition for the radical copolymerizations of methyl acrylate methyl methacrylate and styrene maleic anhydride. Are these examples of ideal or alternating copolymerization Calculate the composition of the initial terpolymer that would be produced from the radical polymerization of a solution containing acrylonitrile, styrene, and 1,3-butadiene in mole fractions of 0.47, 0.47, and 0.06, respectively. Ferrocenylmethyl acrylate (FMA) and 2-ferrocenylethyl acrylate (FEA) have been synthesized and copolymerized with styrene, methyl acrylate, and vinyl acetate [C. U. Pittman, Jr., Macrmolecules, 4, 298 (1971)]. The following monomer reactivity ratios were found:
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M1 FEA FEA FEA FMA FMA FMA
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M2 Styrene Methyl acrylate Vinyl acetate Styrene Methyl acrylate Vinyl acetate
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r1 0.41 0.76 3.4 0.020 0.14 1.4
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r2 1.06 0.69 0.074 2.3 4.4 0.46
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a. Predict whether FEA or FMA will have the higher kp in homopolymerization. Explain the basis of your prediction. How can the difference in kp values be explained in relation to the structures of FEA and FMA b. Which of the comonomer pairs above could lead to azeotropic copolymerization c. Is styrene monomer a more or less reactive monomer than FMA monomer toward the FMA propagating center By what factor d. List styrene, methyl acrylate, and vinyl acetate in order of increasing reactivity toward the FEA propagating center. Is the trend in reactivity toward the FMA propagating center the same e. List the styrene, methyl acrylate, and vinyl acetate propagating centers in order of increasing reactivity toward FEA monomer. f. Are the copolymerization data above indicative of radical, cationic, or anionic copolymerization Explain. 6-7 Consider the radical copolymerization of a benzene solution that is 1.5 M in styrene and 3.0 M in methyl acrylate. a. What is the initial copolymer composition if the polymerization is carried out at 60 C using benzoyl peroxide at a concentration of 5:0 104 M How is the copolymer composition affected if 3:0 103 M benzoyl peroxide is used b. How will the presence of 5:0 105 M n-butyl mercaptan affect the initial copolymer composition c. What would you expect (qualitatively) for the copolymer composition if the reaction were initiated by n-butyllithium by BF3 plus water 6-8 List the following monomers in order of their increasing tendency toward alternation with 1,3-butadiene in radical copolymerization: a. n-Butyl vinyl ether b. Methyl methacrylate c. Methyl acrylate d. Styrene e. Maleic anhydride f. Vinyl acetate g. Acrylonitrile Explain the relative alternating tendencies in these copolymerizations.
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