By Mellor J.W.
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22. 23. 24. 25. 26. ; Mc Grath, J. E . Adv. Polym. Sci. 1988, 86, 1. Wagener, K . ; Wanigatunga, S. Trends Polymer Sci. 1996, 4, 157. ; Matyjaszewski, K. ACS Polymer Preprints 1997, 38, 701. ; Möller, M. Macromolecules 1996, 29, 3397. Chang, T. ; Chen, H. ; Chiu, Y. S. J. Polym. Sci. Part A 1996, 34, 2613, 3313. Chojnowski, J. In Siloxane Polymers Clarson, S. ; Semlyen, J. 3-71. Chojnowski, J. J. Inorg. Organometal. Polym. 1991, 1, 199. Jungst, C . D . ; Weber, W . P. J. Polym. Sci. Part A 1987, 25, 1967.
Trimethylsilyltrifluoromethane sulphonate is added to assist the acid as suggested by Lebrun, Sauvet and Sigwalt . The D is dried as in the Brown and Slusarczuk reaction but the dichloromethane (methylene chloride) solvent is not, as in this case a trace amount of water is required for the reaction to proceed. The reaction is carried out at room temperature under a nitrogen atmosphere (to prevent the introduction of excess water) for up to 48hrs. ch004 Si—0 \ / Si 0 \ \ /; s - c , + H 0 «. 2 f / Si—O-H + H O — / - S i — -0 \ / / // w S; CK + H-0 0 Si— - O - H + Si \ CF3SO3H \ 0 / \ + CF3SO3H 1 Si \ / Si— 0 \ J Si + H,0 \ Figure 4; Chojnowski reaction mechanism.
The end group is reversibly transformed with the participation o f acid to the tertiary oxonium ion, which is the active propagation center. The fast equilibrium 5b lies strongly on the side o f the ester which creates conditions for a controlled stepwise growth of the polymer chain. However, the data presented in Table I indicate that the above mechanism is oversimplified for the polymerization o f monomer 1. The polydispersity factor is higher than that expected for the controlled polymerization and the process leads to a high yield o f cyclic oligomers.
A Comprehensive Treatise Inorganic and Theoretical Chemistry by Mellor J.W.