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Polymerization of monomers containing functional silyl groups. 12. Anionic polymerization of styrene derivatives para‐substituted with pentamethyldisilyl (Si‐Si), heptamethyltrisilyl (Si‐Si‐Si), and nonamethyltetrasilyl (Si‐Si‐Si‐Si) groups
Author(s) -
Hirao Akira,
Ando Yushi,
Nakahama Seiichi
Publication year - 1995
Publication title -
macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 1022-1360
DOI - 10.1002/masy.19950950125
Subject(s) - silylation , polymerization , monomer , silicon , styrene , polymer chemistry , materials science , chemistry , copolymer , organic chemistry , polymer , catalysis , composite material , optoelectronics
Three styrene derivatives, para ‐substituted pentamethyldisilyl (Si‐Si), heptamethyltrisilyl (Si‐Si‐Si), and nonamethyltetrasilyl (Si‐Si‐Si‐Si) groups 1 ‐ 3 were synthesized and polymerized in tetrahydrofuran (THF) at −78°C and in benzene at 40°C. The polymerizations of 1 and 2 in THF were found to proceed without transfer and termination reactions to afford stable living polymers. The Si‐Si and Si‐Si‐Si bonds are found to be completely stable under the conditions. Under the same conditions, novel block copolymers with well‐defined structures were synthesized by sequential addition of 1 or 2 and styrene. By contrast, side reactions occurred during the polymerizations of 1 and 2 in benzene at 40°C, although polymer yields were quantitative. More seriously, polymer was not obtained in the polymerization of 3 both in THF and in benzene. Thus, the effect of chain length of the oligosilyl group is found to be critical in the anionic polymerization of 1 ‐ 3 .