双(环戊二烯基)二氯化锆催化合成乙烯-笼型倍半硅氧烷杂化共聚物及其结构表征  

Synthesis and Properties of Ethylene-polyhedral Oligomeric Silsesquioxane Copolymer with Bis(cyclopentadienyl) Zirconium Dichloride Catalyst

作　　者：张贺新[1] 张浩[1,2] 张春雨[1] 郝秀峰[1,3] 张学全[1] 

机构地区：[1]中国科学院长春应用化学研究所高性能合成橡胶工程技术中心,长春130022 [2]北京化工大学材料科学与工程学院,北京100029 [3]吉林大学化学学院,长春130012

出　　处：《高等学校化学学报》2012年第8期1850-1853,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:51073067)资助

摘　　要：通过双(环戊二烯基)二氯化锆(Cp2ZrCl2)催化剂和改良的甲基铝氧烷(MMAO)助催化剂,合成了无机-有机杂化共聚物.研究了2种具有不同单乙烯基反应基团的笼型倍半硅氧烷(POSS)与乙烯的聚合.对共聚产物的结构、热力学性质、分子量及其分布等进行了研究.共聚单体(POSS)的插入率在0.01%～0.30%之间,随着共聚单体在共聚物中摩尔分数的增大,聚合物的熔点和熔解热降低.共聚物的热重分析结果显示,乙烯-POSS共聚物拥有更高的热分解温度以及较高的热分解残留量.随着POSS的加入,聚合物的分子量明显提高,聚合物的分子量分布变宽.An organic/inorganic hybrid copolymer was prepared with a bis （cyclopentadienyl） zirconium dichloride（ Cp2ZrCl2 ） in conjunction with modified methylaluminoxane （MMAO） cocatalyst. Two kinds of monovinyl substituted polyhedral oligomeric silsesquioxane （POSS） monomers were used to copolymerize with ethylene （E）. The copolymers were characterized with 1H NMR, DSC, TGA and GPC to know the composition, thermal properties, molecular weight and its distribution, respectively. The comonomer content（POSS） was in the range of 0. 01%--0. 30% （molar fraction）. With the increase of POSS content in copolymer, the melting temperature and heat of fusion decreased. Thermogravimetric analysis of E/POSS copolymers exhibited an improved thermal stability with a higher degradation temperature and char yields, demonstrating that the inclusion of inorganic POSS nanoparticles made the organic polymer matrix more thermal robust. Increasing the feed ratio of POSS, the molecular weight increased, while the molecular weight distribution broadened.

关 键 词：杂化共聚物 纳米复合材料 乙烯 笼型倍半硅氧烷 双(环戊二烯基)二氯化锆催化剂 

分 类 号：O632.12[理学—高分子化学]