SYNTHESIS OF OPTICALLY ACTIVE POLY(SILYETHYLENE)S CONTAINING A STEREOGENIC SILICON CENTER

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Hydrosilylation of acetylene with a chiral silane, R-(+)-methyl-l-naphthyl-phenylsilane [R-(+)-Me-NpPhSi*H], in the presence of H_2PtCl_6.xH_2O proceeds with retention of configuration of the stereogenic silicon center and produces a chiral vhiylsilane or silylethylene [S-(+)-MeNpPhSi*Vi] of high optical purity under mild condition (50℃) in high chemical yield (85%). Anionic polymerizations of the chiral silylethylene monomer by an achiral initiator n-BuLi yield optically active polymers with [a]_D^<20> up to -28.1°, while polymerizations of the racemic monomer by a chiral initiator n-BuLi/(-)-spar-teine prodluce polymers with [a]_D^<20> up to +275°. Thus the sign of optical rotation of the polymers can be controlled by different combination of monomer and catalyst. Magnitude of the optical rotation can be "tuned" by changing polymerization temperature with high temperature generally favoring random propagation. All the polymers have low rolydispersity indexes (M_w/M_n down to 1.02) or possess narrow molecular weight distributions. Spectroscopic characterization confirms the molecular structure of polymers to be poly(silylethylene), that is, a polyethylene main chain with a bulky methyl-1-naphthyl-phenykilyl side chain. The polymers are thermally stable (onset temperature for weigiit loss in air: 380℃), possess high glass transition temperature (Tg >380℃), and may rind a wide range of applications in the optical displaysystems.
社団法人電子情報通信学会の論文
1997-02-14

SYNTHESIS OF OPTICALLY ACTIVE POLY(SILYETHYLENE)S CONTAINING A STEREOGENIC SILICON CENTER

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