Cationic ring-opening polymerization. 2, synthetic by Stanislaw Penczek, Przemyslaw Kubisa, Krzysztof

By Stanislaw Penczek, Przemyslaw Kubisa, Krzysztof Matyjaszewski, J.P. Kennedy

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These data have been interpreted in terms of the influence of the dielectric constant of the solvent, assuming that the strongest solvent-monomer interactions occur for compounds of similar polarity. e. with solvent acidity expressed by pKa). CH2CI2 as the most acidic among the studied solvents may form complexes with monomers whereas other solvents give weaker interactions. n-Decane is the weakest acid and it gives the lowest [TXN]o. Similar behaviour is observed for T T X N which is more strained and thus gives lower values of equilibrium concentration.

Dainton, F. , Ivin, K. J. : Quart. Rev. 12, 61 (1958) 41. Cairns, T. , Joyce, R. M. 1948) 42. Kazanskij, K. S. : in: Soviet Encyclopedia of Polymers, Vol. I, p. 413, Moscow 1974 43. , Hatano, M. : J. Chem. Soc. , Ind. Chem. Sect. 61,904 (1958) 44. Farthing, A. C. : J. Chem. Soc. 1955, 3648 45. , Riande, E. : Macromolecules 14, 1132 (1981) 46. : J. Polym. Sci. A1, 6, 137 (1968) 47. Pihlaja, K. : Acta Chim. Scand. 25, 451 (1971) 48. , Kubisa, P. : ACS Symp. Ser. 59, 60 (1977) 49. : Makromol. Chem.

Therefore, both 6-membered lactones and lactams are able to polymerize. Heterocycles containing sulfur atoms are usually less strained than the corresponding ethers. Thus, the 5-membered cyclic sulfide-tetrahydrotiophene (THT) does not polymerize in contrast to THF (cf. additional discussion on THF on p. 23). 2 Entropy of Polymerization The following factors affecting the entropy of polymerization have to be considered: translational, rotational, and vibrational entropy. Conversion of a cyclic monomer into a chain segment is accompanied by the decrease of translational and external rotational entropy.

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