含膦酰杂菲侧基聚乙炔的合成与热稳定性  

SYNTHESIS AND THERMAL STABILITY OF PHOSPHAPHENANTHRENE-CONTAINING POLYACETYLENES

作　　者：申进波[1] 佟斌[1] 赵玮[1] 潘月秀[1] 冯霄[1] 石建兵[1] 支俊格[2] 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》2009年第8期769-774,共6页Acta Polymerica Sinica

基　　金：国家自然科学重点基金(基金号20634020)资助项目

摘　　要：以2-(6-氧化-6-氢-二苯基(c,e)<1,2>氧杂磷酰基)-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-乙炔基苯甲酰基和4-烷氧基苯甲酰基,并作为乙炔单体,在[Rh(nbd)Cl]2催化下,30℃聚合得到了含磷酰杂菲(DOPO)基团的聚乙炔.1H-NMR和GPC分析表明,由于DOPO存在较大π共轭结构和较强极性效应,在诱导聚乙炔主链采取高反式构型的同时,增加了分子链内相邻侧基之间的相互作用,使整个分子链趋向二维共平面结构,有利于增强分子链之间的相互作用.TGA显示,与不含磷酰杂菲侧基的模型聚乙炔相比,DOPO的引入使聚乙炔呈现良好的热稳定性,起始热分解温度(T5%)接近400℃,说明通过增强分子链内侧基间相互作用有助于提高热稳定性.New thermal stable mono-substituted polyacetylenes （ PAT5 and PAT10 ） containing phosphaphenanthrene as side groups and end-chains of different lengths were studied. 4-Ethynylbenzoyl and 4- alkoxylbenzoyl were first introduced into the 2-（6-oxide-6H-dibenz 〈 c, e 〉 〈 1, 2 〉 oxaphos-phorin-6-yl）-dihydroxyphenylene （ODOPB） through a two-step esterification, respectively, which synthesized the phosphaphenanthrene-containing acetylenic monomers. The polymerization of novel monomers was carried out by using [Rh（nbd）Cl]2-NEt3 as the catalyst at room temperature in high yield （ 〉 90%）.The structure and optical properties of the polyphenylacetylenes were characterized by means of ^1H-NMR, FT-IR, UV-Vis and photoluminescence spectroscopy, respectively, which showed that the polyacetylenes were synthesized successfully. During the introduction of phosphaphenanthrene as side-groups, PAT5 and PAT10 are yellow-brown and soluble in common solvents. However, The model polyacetylene PA5 in the absence of phosphaphenanthrene is red and insoluble. GPC reveals two peaks for the novel polacetylenes. The first peak is attributed to the aggregation state between polymeric chains （ 10^7 ）, and the second one is to the real molecular weight （ 10^4 ）. The experimental results indicate that the regular supramolecular structures between phosphaphenanthrene-containing pendent groups are fabricated based on the strong π-π stacking and polar interactions and then induce production of the polyphenylacetylene with high trans-content configuration, which may result in the high degree of extend conjugation of the main chain and enhence the interaction between adjacent pendent groups. Comparing with the model polyphenylacetylene in the absence of phosphaphenanthrene side-groups, TGA analysis reveals the excellent thermal stability of the mono-substituted polyphenylacetylenes containing phosphaphenanthrene as side-groups because the 5 % weight loss temperatures are close to 400 ℃.

关 键 词：聚乙炔 Rh基催化剂 磷酰杂菲 热稳定性 

分 类 号：O632.1[理学—高分子化学]