The

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The polymerization of methacrylates of methyl, ethyl, butyl, hexyl, octyl, dodecyl, and octadecyl alcohols was studied with 2,2′‐azobisisobutyronitrile in the smectic, nematic, cholesteric, and isotropic liquid phases at 50–75°C. N‐(4‐Methoxyphenylmethylene)phenylamine, N‐(4‐ethoxyphenyl‐methylene)‐4‐butylphenylamine, cholesteryl octadecanoate, and benzene were used as the solvents. The viscosities of the polymers were enhanced in the mesomorphic solvents. The polymer was converted to the corresponding poly(methyl methacrylate) through hydrolysis and esterification. Tacticities of the resultant poly(methyl methacrylates) were determined by nuclear magnetic resonance spectroscopy. The isotacticities of the polymers obtained in the smectic and the nematic phases were basically the same and appeared to be larger than those of the polymers in the cholesteric and isotropic liquid states. The polymerization of the methacrylates of butyl and longer‐chain alcohols deviated from Bernoullian statistics and gave polymers more isotactic than those of methyl and ethyl methacrylates.

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