【作者】 李华；

【导师】 张宝砚；

【作者基本信息】 东北大学 ， 有机化学， 2009， 硕士

【摘要】 双环笼状磷酸酯类化合物由于其独特的结构和强的生物活性,多年来一直引起人们极大的关注,在医药、农药、塑料助剂等方面,其衍生物的合成及性能研究已有大量报道。三氯氧磷与季戊四醇反应生成1-氧基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷(PEPA),其在偏矾酸铵的催化下被浓硝酸氧化为相应羧酸,经二氯亚砜作用生成酰氯。本文利用此酰氯分别与4’-(4-十一烯酰氧基)苯甲酰氧基联苯酚单酯和4’-(4-十一烯酰氧基)苯甲酰氧基苯酚单酯反应,合成两种含磷酸酯的液晶单体,对其进行了分析表征。并以所合成的含磷酯液晶单体与含羟基向列液晶单体及手性胆甾液晶单体分别与聚甲基含氢硅油进行了接枝聚合,制备了三个系列的液晶高分子,讨论了其性能。本论文所合成的单体分别为：1-氧基磷杂-4-[4’-(4-十一烯酰氧基)苯甲酰氧基联苯氧]酰基-2,6,7-三氧杂双环[2.2.2]辛烷(M1)、1-氧基磷杂-4-[4’-(4-十一烯酰氧基)苯甲酰氧基苯氧]酰基-2,6,7-三氧杂双环[2.2.2]辛烷(M2)、4’-(4-十一烯酰氧基)苯甲酰氧基联苯酚单酯(M3)、十一烯酰氧基胆甾醇酯(M4)。除单体M3和M4外其余单体和聚合物均未见国内外报道。在分子设计上具有一定创新性。采用红外光谱仪(FT-IR)、核磁共振仪(1H-NMR)、差示扫描量热仪(DSC)、热失重分析仪(TGA)及偏光显微镜(POM)等技术对所合成的手性单体、液晶单体、液晶高分子等的结构与性能讲行了研究。这些研究内容不仅具有一定的实践意义,而且也为进一步开展含磷酯液晶研究提供了一定的宝贵的经验和借鉴意义。更多还原

【Abstract】 The study on the synthesis and biological activity of caged bicyclic phosphate derivatives is one of the active fields in organic phosphorus chemistry. Caged bicyclic phosphates would be a new type of pesticides because of their unusual mode of bioaction. Also they would be widely used as fire-proofing agents, resin-stabilizers and oil-addnets.1-oxo-4-hydroymethyle-2,6,7-trioxa-l-phosphabicyclo[2.2.2]octane were synthesized by the reaction of flame retardant with phosphorus oxychloride, thus the reaction product was oxidized with concentrated nitric acid to form the correspon-ding acid and reacted with dichlorosulfane to give the corresponding aryl chloride. In this paper, the monomers containing caged bicyclic phosphates were synthesized by the reaction of the aryl chloride with4-hydroxybiphenyl-4’-(10-undecylen-l-yloxy) benzoate and4-hydroxybenzene-4’-(10-undecylen-1-yloxy)benzoate and their respe-ctive side-chain liquid crystal homopolymers were synthesized.The monomers in this paper contain:1-oxo-4-{4’-[4-(4’-undecylenic acyl)bezoic acyl]biphenol}methylene-2,6,7-trioxa-l-phosphabicyclo[2.2.2]octane(M1),1-oxo-4-{4’-[4-(4’-undecylenic acyl)bezoic acyl]benzoyl}methylene-2,6,7-trioxa-l-phosphai-cyclo[2.2.2]octane(M2),4-abieticbiphenyl-4’-carbonylsebacic acid(M3),4-cholesteryl-esters-4’-(10-undecylen-l-yloxy)benzoate(M4). Moreover, the obtained monomers an-d all the polymers, except M3and M4, are novel.FT-IR spectroscopy,1H-NMR spectroscopy, differential scanning calorimetry (DSC), thermo gravimetric analyses (TGA) and polarizing optical microscopy (POM) were used to study the structure, liquid crystal properties of this polymer and monom-er. Their structure property relationships were discussed in detail.更多还原