The Liquid Crystalline State Copolymerization

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Abstract
Mixtures of p-cetyloxybenzoic acid, p-methacrylyloxybenzoic acid (M1) and styrene (M2) exist in the liquid crystalline state over a relatively wide range of temperatures and compositions. Copolymerization of M1 and M2 in the liquid crystalline state and dioxane and dimethyl formamide (DMF) solution was studied. Tert-butyl peroxide was used as initiator at a polymerization temperature of 105°C. The copolymerization rate in the liquid crystalline state considerably exceeds that in the liquid phase. The molecular weight of copolymer formed in the liquid crystalline state is about 3–4 times higher than for copolymer formed in the liquid phase. The monomer reactivity ratios for the liquid crystalline state copolymerization are equal to r 1 = 1.24, r 2 = 0.32 and differ from the corresponding values for the liquid phase copolymerization (r 1 = 0.84, r 2 = 0.13 in DMF solution). The value of r 1 > 1 in the liquid crystalline state copolymerization may be accounted for by the existence of mobile monomer (M1) arrays in liquid crystal layers. The mechanism of copolymer formation in the liquid crystalline state is discussed.