Anionic polymerization of 4-(tert-butyldimethyIsilyloxy)styrene (2) was investigated under high vacuum conditions mbar). 2 was readily polymerized by lithium naphthalide to form a "living polymer" at -78 "C. By subsequent acid hydrolysis of the resulting polymer, a linear, nearly monodisperse polymer of 4-vinylphenol of known molecular weight was obtained. Block copolymers of 2 with a-methylstyrene were also prepared by means of this living system.
This paper describes the synthesis of side-chain liquid crystalline polymers and block copolymers by living anionic polymerization and their thermotropic phase behavior. The polymers were successfully prepared with a narrow distribution of molecular weight. The thermotropic transition behavior between crystal, smectic A, and isotropic phases was examined with a function of the molecular weight. Living anionic polymerization also allowed the preparation of well-defined block copolymers with amorphous polystyrene. In these block copolymers, microphase separation due to liquid crystalline and amorphous blocks was observed by electron microscopy and small-single X-ray methods. Effects of the microphase separation were also examined on the thermotropic phase behavior and structure.
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