摘要
分别以3-(三乙氧基硅基)丙基异氰酸酯、环己二胺、乙二胺、氨丙基三乙氧基硅烷、草酰氯为原料,通过分子间的加成反应和加成产物在微酸性环境中的水解反应,制备得到三种微形貌和结构差异的硅氧倍半聚合物。将二氯二茂锆(Cp_(2)ZrCl_(2))负载于合成的三种硅氧倍半聚合物表面,制备得到三种负载型茂金属催化剂。研究发现,上述三种负载型催化剂对乙烯均聚和乙烯与辛烯共聚均表现出较高的催化活性,尤其是Cp_(2)ZrCl_(2)负载于螺旋状硅氧倍半聚合物(环己二胺加成并水解的产物)表面催化乙烯聚合产物(聚乙烯)的熔点达到139.2℃,系目前所报道的熔点较高的聚乙烯产品,显示出优异的工业应用价值。
In this paper,three kinds of silica sesquimers with different micro morphologies and structures were prepared by the reaction between 3-(triethoxysilyl)propyl isocyanate and cyclohexanediamine or ethylenediamine,and the reaction between aminopropyl triethoxysilane and oxalyl chloride.The raw products were hydrolyzed in slightly acidic environment.Zirconium dichloride(Cp_(2)ZrCl_(2))was loaded on surface of the three silica sesquimers respectively to prepare three kinds of supported metallocene catalysts.Research results indicate that the three supported catalysts have high catalytic activity for olefin homopolymerization and copolymerization,especially Cp_(2)ZrCl_(2) supported on the surface of helical siloxane hemipolymer(product from the addition and hydrolysis of cyclohexanediamine),and the melting point of ethylene polymerization product(polyethylene)was 139.2℃,higher than most of polyethylene catalyzed by other Cp_(2)ZrCl_(2) supported catalysts.The composite catalyst shows excellent industrial application value.
作者
董晓龙
李素云
高玉李
祖凤华
义建军
郝海军
徐庆红
DONG Xiaolong;LI Suyun;GAO Yuli;ZU Fenghua;YI Jianjun;HAO Haijun;XU Qinghong(College of Chemistry,Beijing University of Chemical Technology,Beijing 100029,China;Petrochemical Research Institute of PetroChina Company Limited,Beijing 102206,China)
出处
《化学研究》
CAS
2022年第4期306-316,共11页
Chemical Research
基金
中国石油天然气股份有限公司科技开发基金资助项目。
关键词
硅氧倍半聚合物
螺旋
茂金属
均聚
共聚
silica sesquimer
spiral
metallocene
homopolymerization
copolymerization
