Development of thc catalysts for elhylene-butadiene copolymerization and their aoolicalion for functional poly olefins

乙烯-丁二烯共聚催化剂的研制及其对功能聚烯烃的应用

基本信息

批准号：
13650930
负责人：
SHIONO Takeshi
金额：
$ 1.92万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

A SiO_2-supported (η^5-cyclopentadienyl) titanium trichloride was prepared and applied for copolymerization of ethylene and 1,3-butadiene using the mixture of triisobutylaluminum and triphenylmethyl tetralkis (pentafluorophenyl) borate as an activator. The system was found to give copolymers with selectivities of 80 % at 40 ℃ and more than 99 % at ℃. The butadiene contents, of which structure was trans-1,4-addition, was varied from 0.5 to 2.5 mol %. The trans-1,4-addition units in the copolymer were selectively oxidized with potassium permanganate, which produced α,ω-dicarboxypolyethylene. The polydispersity of the gegradation products, M_W/M_n = 2, indicated that the butadiene units were distributed randomly in the main chain. A series of zirconocene compounds activated by the mixture of triisobutylaluminum and triphenylmethyl tetralkis (pentafluorophenyl) borate was then applied for the copolymerization of ethylene and 1,3-butadiene at 40℃. The polymerization activity strongly depend … More ed on the structure of zirconocene compounds : bridged and non-bridged C_<2v>-symmetric zirconocenes did not give polymers, whereas C_2-symmetric and C_3-symmetric bridged zirconocenes produced copolymers with more than 90 % selectivity. Among the zirconocenes used, diphenymethyl(η^5-cyclopentadienyl(η^5-cyclopentadienyl)zirconium dichloride (I) showed the highest activity and gave the copolymer with the highest butadiene content. The copolymer contained ca. 8 mol % of frans-1,4-addition unit and ca. 20 mol % of cyclopentane unit., that is, the structure of the copolymer was very similar to that of ethylene-butadiene-cyclopentene copolymer. The butadiene contents of the copolymer showed a good relation with the activity and decreased in the following order : I > other C_5-symmetric zirconocenes > C_2-symmetric zirconocenes. When the copolymerization was condacted with I at O ℃, the copolymer was selectively obtained. Copolymerization of ethylene and 1,3-butadiene was also conducted with cobalt dichloride activated by methylaluminoxane. Although the copolymerization did not proceed, cobalt dichloride-methylauminoxane was found to effective for cis-specific living polymerization of 1,3-butadiene. Less

制备了三氯化二氯化钛的SIO_2支撑（η^5-胞糖二烯基），并使用三甲基苯甲酰氨基氨基氨基氨基氨基甲基和三甲基甲基甲基甲基甲基甲基甲基甲基甲基甲基甲基和甲基甲基甲基甲基甲基甲基甲基和1,3-丁二烯的共聚作用（pentafluorophisyl）（pentafluorophenylyyl）byational in Acticators as octicatorsator。发现该系统可在40°C下的选择性为80％，在℃时为99％以上。丁二烯含量是trans-1,4-添加的，从0.5到2.5 mol％变化。共聚物中的反式聚合物中的反式1,4 - 成熟单元用高峰钾选择性氧化，该钾可产生α，ω-二羧基甲基乙烯。 Gegradation产品的多分散性，M_W/M_N = 2，表明丁二烯单元是随机分布在主链中的。然后将一系列锆化化合物通过三甲基甲基铝和三苯基四甲基四烷基（五氟苯基）硼酸盐的混合物激活。聚合活性在很大程度上取决于……更多地介绍了锆循环化合物的结构：桥接和非桥接的C_ <2v> - 对称锆烯烯不能给出聚合物，而C_2-摩擦和C_3对称和C_3对称的齐甲基齐布尔式齐罗匹烯与比90％更高的选择。在所使用的锆烯基二苯基甲基（η^5-胞元二烯基（η^5-胞糖基二烯基）二氯化二氯化锆（I）显示出最高的活性，并给出了最高的共聚物，并具有最高的丁二烯含量。共聚物的含量最高。共聚物的共聚物含有最高的共聚物。含有二摩托的单位量为4摩尔。 structure of the copolymer was very similar to that of ethylene-butadiene-cyclopentene copolymer. The butadiene contents of the copolymer showed a good relationship with the activity and improved in the following order: I > other C_5-symmetric zirconocenes > C_2-symmetric zirconocenes. When the copolymerization was condacted with I at O ℃, the copolymer was selectedly获得的