Polymerization of mesomorphic monomers, 2. Bulk polymerization of 4‐(2‐vinyloxyethoxy)benzoic acid

A new thermotropic liquid crystalline vinyl ether, 4‐(2‐vinyloxyethoxy)benzoic acid ( 1a ), was obtained by hydrolysis of the corresponding methyl ester 1b . The radical bulk polymerization of this acid was carried out at 130–195°C in the solid, the mesomorphic, and the isotropic liquid phases with 2,2′‐azoisobutyronitrile to study the effect of monomer ordering on polymerization rate and polymer properties. No significant effect on the rate of polymerization and the intrinsic viscosity of the products appeared to be associated with the existence of the mesomorphic phases. The rate increased with increasing temperature, i.e., decreasing ordering or enhanced mobility of the monomer. The intrinsic viscosity was 0,06–0,10 dl g −1 in N , N ‐dimethylformamide at 30°C. High crystalline polymers were obtained in the solid and the mesomorphic phases, whereas the polymer formed in the isotropic liquid phase was a less crystalline solid.