含碗形CTV侧基的甲基丙烯酸酯类单体和聚合物

A POLYMETHYACRYLATE CONTAINING BOWLIC CTV SIDE GROUPS AND IT'S MONOMER

采用三聚法合成外围基团中含羟十一碳氧基的CTV衍生物(CTV-H),然后结合柱层析分离技术合成和分离出外围基团中含单甲基丙烯酸酯基团的CTV衍生物(CTV-M).以CTV-M为单体,本体聚合得到含碗形CTV侧基的甲基丙烯酸酯类聚合物(BPM).CTV-H和CTV-M都具有热致液晶性,是新的碗状液晶.SAXS和WAXD测定表明,液晶结构为六方柱相(Φh),柱直径为4.4 nm和4.8 nm,与理论计算结果相符.而BPM没有液晶性,呈非晶态.

A CTV （cyclotriveratrylene） derivative with 11-hydroxyl-undecyloxide group as peripheral group （CTV-H） was synthesized by trimerization Then another CTV derivative with single methacrylate group as peripheral group （CTVM） was synthesized and purfied by silica gel column chromatography, purification is the key step of this synthesis. Their chemical structures were verified by 1H-NMR, 13C-NMR, element analysis and mass spectroscopy- Both CTV-H and CTV-M are new thermotropic bowlic liquid crystals. They all demonstrated liquid crystalline textures under polarized optical microscope （POM） at room temperature.The DSC determination showed the glass transition temperature, and the clearing point of CTV-H was -20℃ and 49℃, respectively. But a wide endo-thermal DSC peak of -16~78℃ mixed up the contributions of the glass transition temperature, clearing point and curing temperature of CTV-M. Their SAXS and WAXD peaks appeared at 2θ=3.0°, 5.0°, 6.0°, 21.0° and 2θ=2.7°, 4.6°, 5.5°, 20.5°, respectively.The results indicated that their mesophase all belongs to hexagonal columnar phase （Φh）. The diameter of the column was 4.4 nm and 4.8 nm,respectively, which agreed with the results of theoretical calculation. CTV-M was used as a monomer to synthesize polymethacrylate containing bowlic CTV side groups （BPM）by means of bulk polymerization.The number average molecular weight of BPM （GPC） was 14900, and the glass transition temperature of polymethacrylate main chain and β relaxation temperature of CTV side groups were measured to be 104℃ and 6℃, respectively-However, BPM had no liquid crystalline behavior, which presented amorphous state