以膦酰杂菲为侧基的1-戊炔聚合反应及其结构与热力学性质  

POLYMERIZATION,STRUCTURES AND THERMAL PROPERTIES OF PHOSPHAPHENANTHRENE-CONTAINING POLY(1-PENTYNE)

作　　者：杨帆[1] 佟斌[1] 石建兵[1] 支俊格[2] 申进波[1] 董宇平[1] 

机构地区：[1]北京理工大学材料科学与工程学院,北京100081 [2]北京理工大学理学院,北京100081

出　　处：《高分子学报》2011年第9期1073-1078,共6页Acta Polymerica Sinica

基　　金：国家自然科学重点基金(基金号20634020);北京理工大学火安全材料与技术教育部工程研究中心开放基金(2011);北京理工大学基础研究基金(基金号20090942012)资助项目

摘　　要：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.The phosphaphenanthrene-containing 1-pentyne monomer（M-34） was synthesized through the successive esterification of 2-（6-oxide-6H-dibenzc,e1,2oxaphos-phorin-6-yl）-dihydroxyphenylene（ODOPB） with 4-（4-pentynoxy）benzoyl and 4-butyloxybenzoyl,respectively.Due to the introduction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide（DOPO） group,the catalytic ability of Rh-based catalysts（[Rh（nbd）Cl]2 and Rh（nbd）B（C6H5）4） is decreased and the yields of polymer are relatively low.The polymerization of model monomer（M-0） in the absence of phosphaphenanthrene side-group was,however,carried out in high yield at the same condition.The microstructure of the poly（1-pentyne） derivants was characterized by means of 1H-NMR.The experimental results indicate that the main-chains of poly（1-pentyne） derivants with high trans-content configuration are produced due to the strong π-π stacking and polar interactions between phosphaphenanthrene-containing pendent groups.Thus,the interaction between adjacent pendent groups is further strengthened.The molecular weights and distribution of P-34 and its model polymer P-0 were measured by GPC;Their thermal properties were evaluated by TGA and DSC.Comparing with P-0 in the absence of phosphaphenanthrene side-group,TGA analysis reveals the excellent thermal stability of P-34,losing 1% of weights during heating to 270℃ and retaining 50% of weights after pyrolyzis at 550℃.And the char yield of P-34 is over 50 wt% at 550℃.The DSC results indicate that Tg of P-34 is lower than that of P-0 because DOPO increases the volume of side-groups in P-34.

关 键 词：聚(1-戊炔) Rh基催化剂 膦酰杂菲 热力学性质 

分 类 号：O631.5[理学—高分子化学]