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以2-(6-氧化-6-氢-二苯基(c,e)<1,2>氧杂膦酰基)-1,4-二羟基苯(ODOPB)结构单元为中心,在两侧通过酯化反应分别引入4-(4-戊炔氧基)苯甲酰基和4-丁氧基苯甲酰基,得到了1-戊炔衍生物单体M-34,同时合成了不含9,10-二氢-9-氧杂-10-膦杂菲-10-氧化物(简称膦酰杂菲,DOPO)基元的M-34模型化合物M-0.分别以[Rh(nbd)Cl]2和Rh(nbd)B(C6H5)4为催化剂,研究了催化剂浓度和聚合时间对M-34和M-0聚合反应收率的影响.结果表明,由于DOPO存在较大π共轭结构和较强极性效应,降低了催化剂的活性,使得聚合产物P-34分子量较低,但改善了P-34的溶解性,并诱导P-34主链基本采取全反式构型,从而有利于增强侧基之间的相互作用,使这种含有DOPO的聚1-戊炔衍生物呈现良好的热稳定性,且优于其不含DOPO模型聚合物P-0的热稳定性.但同时DOPO的引入也增加侧基的体积,为链段运动提供了较大的自由体积,使得P-34的Tg低于不含DOPO模型聚合物P-0的Tg.
(2-oxo-6-oxo-diphenyl (c, e) <1,2> oxaphosphonyl) -1,4-dihydroxybenzene (ODOPB) In the esterification reaction, 4- (4-pentynyloxy) benzoyl group and 4-butoxybenzoyl group were introduced respectively to obtain 1-pentyne derivative monomer M-34. At the same time, - M-34 model compound M-0 of the dihydro-9-oxa- 10-phosphaphenanthrene 10-oxide (abbreviated phosphonophenanthroline, DOPO) And Rh (nbd) B (C6H5) 4 as catalyst, the effects of catalyst concentration and polymerization time on the yields of M-34 and M-0 polymerization were investigated. The results showed that due to the large π-conjugated structure and strong Polarity effect, reducing the activity of the catalyst, making the polymer product P-34 molecular weight lower, but to improve the solubility of P-34 and P-34 main chain to induce the basic all-trans configuration, thereby enhancing the side The interaction between the DOPO-containing poly-1-pentyne derivatives shows good thermal stability and is superior to the DOPO-free polymer P-0 in thermal stability, but at the same time the introduction of DOPO Also increases the volume of pendant groups and provides a larger free volume for segment movement such that the Tg of P-34 is lower than that of D OPO Model Polymer P-0 Tg.