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SiO_2负载的(n^5-环戊二烯基)三氯化钛，并以三异丁基铝和三苯基甲基四(五氟苯基)硼酸酯的混合物为活化剂，将其用于乙烯和1,3-丁二烯的共聚合反应，得到了共聚物。 40℃选择性80%以上，选择性99%以上其结构为反式1,4-加成的丁二烯含量在0.5至2.5mol%之间变化。共聚物中的反式1,4-加成单元被高锰酸钾选择性氧化，产生α。 ,ω-二羧基聚乙烯的聚合产物的多分散性M_W/M_n = 2,表明丁二烯单元随机分布。然后将一系列由强三异丁基铝和三苯基甲基四（五氟苯基）硼酸酯的混合物活化的锆化合物应用于乙烯和1,3-丁二烯在40℃下的共聚合反应。锆茂化合物的结构：桥联和非桥联的C_<2v>-对称锆茂不能得到聚合物，而C_2-对称和C_3-对称桥联二茂锆产生的共聚物具有超过90%的选择性，在所使用的二茂锆中，二苯甲基(η^5-环戊二烯基(η^5-环戊二烯基)二氯化锆(I)表现出最高的选择性。活性并得到具有最高丁二烯含量的共聚物。 8mol％的反式1，4-加成单元和约20mol％的环戊烷单元，即该共聚物的结构与乙烯-丁二烯-环戊烯共聚物的结构非常相似。与活性有良好的关系，并按以下顺序降低：I>其他C_5-对称二茂锆>C_2-对称当与I在O℃下进行共聚时，也用甲基铝氧烷活化的二氯化钴进行了共聚，但二氯化钴-。发现甲基铝氧烷对顺式特异性活性聚合有效1,3-丁二烯较少。