화학공학소재연구정보센터
Macromolecules, Vol.43, No.21, 8942-8949, 2010
Steric Interaction between Flexible Main Chain and Nonmesogenic Cyclic Pendants Leading to Thermotropic Liquid Crystalline Property
Nonmesogenic cyclic alkylidene terephthalate is directly connected to flexible polyethylene main chain at every second carbon atom via the phenyl ring to obtain a novel vinyl polymer, poly(alkylidene vinylterephthalate) (PAVT-n), where n (= 10-14 and 16) denotes the number of methylene groups in the side chain. When the molecular weight is large enough, stable hexagonal columnar phases are generated from melt by the PAVT-n polymers with n = 10-13, but not by those containing 14 or 16 methylene groups. Compared with its open-ring counterpart, i.e., poly(dialkyl vinylterephthalate) (PDAVT-n) with linear side chains, PAVT-n has a glass transition temperature (T-g) over 100 degrees C higher, a much larger persistence length, and a much lower critical molecular weight to form a mesophase. In addition, PDAVT-n enters into isotropic liquid at T-g and becomes ordered at temperatures well above T-g, whereas PAVT-n forms mesophases immediately above T-g. The strong steric interaction between cyclic pendants and the flexible main chain, which causes PAVT-n to take an extended chain conformation, is considered as the main driving force for PAVT-n to generate mesophases. In a sharp contrast, the mesophase formation of PDAVT-n is known to be an entropy-driven process.