非对称链状端基二烯和七元环烯含磷分子合成

Asymmetric Chain Terminated Diene and Heterocyclic Alkene Molecules Containing Phosphorus: Synthesis and Polymerization

摘要:

以Michaelis–Arbuzov反应制备的烯丙基膦酸二乙酯为主要的反应底物，将其与草酰氯、3-丁烯-1-醇反应，得到非对称的链状端基二烯含磷分子，该分子在Grubbs二代催化剂的作用下，既可发生非环二烯复分解聚合（ADMET）得到主链含磷的高聚物，又可发生闭环复分解反应（RCM）制备得到七元含磷、含氧杂环烯烃分子。对于目标分子主要通过核磁共振氢谱来证实其成功制备与提纯，而对于非对称链状端基二烯的ADMET产物和七元含磷杂环烯烃的开环易位聚合（ROMP）产物，主要利用凝胶渗透色谱（GPC）对聚合体系的相对分子量及多分散性指数（PDI）进行分析，表明聚合的发生。这对于烯丙基含磷单体的转化、杂环分子的制备以及后期的含磷高聚物应用有重要的指导意义。

Abstract:

Allyl phosphonic acid diethyl ester, prepared by Michaelis-Arbuzov reaction, reacted as the main reaction substrate with oxalyl chloride, 3-buten-1-ol and asymmetric chain terminated diene molecule containing phosphoru BEAPH was repared.The monomer can be transformed to the polymer having phosphoru in the main chain by non-cyclic diene metathesis polymerization, or be used for preparing heterocyclic alkene molecules containing phosphoru with closed loop metathesis polymerization. Successful preparing and purification of unsaturated monomers was confirmed using H NMR Spectrum. The condensation between molecules was proved by GPC curve and molecular weight, PDI datas,which have very important guiding significance to a conversion of allyl phosphorus-containing monomers and polymers preparation that contains phosphorus.