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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650930/
• 关键词: coordination polymerization; half titanocene; zirconocene; ethylene; 1,3-butadiene; copolymerization; cobalt dichloride; living polymerization; チーグラー触媒; 酸化分解

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SiO2负载（η^5-环戊二烯基）三氯化钛，并以三异丁基铝和三苯甲基四（五氟苯基）硼酸盐的混合物为活化剂，用于乙烯和1，3-丁二烯的共聚合。该体系在40 ℃时的选择性为80%，在℃时的选择性大于99%.丁二烯的含量为0.5 ~ 2.5mol%，其结构为反式-1，4-加成。用高锰酸钾选择性氧化共聚物中的反式1，4-加成单元，生成α，ω-二羧基聚乙烯。接枝产物的多分散性（M_W/M_n = 2）表明丁二烯单元在主链上无规分布。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，合成了一系列茂锆化合物，并在40℃下用于乙烯和1，3-丁二烯的共聚合。聚合活性强烈依赖于 ...更多信息 艾德对茂锆化合物的结构进行了研究：桥连和非桥连的C_2<2v>对称茂锆化合物不生成聚合物，而桥连的C_2对称茂锆化合物和桥连的C_3对称茂锆化合物生成聚合物，选择性大于90%。在所用的二茂锆中，二苯基甲基（η^5-双（η ^5-双）二氯化锆（I）显示出最高的活性，并且得到具有最高丁二烯含量的共聚物。共聚物含有ca. 8mol%的反式-1，4-加成单元和约. 20摩尔%的环戊烷单元，即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。共聚物中丁二烯含量与催化活性有良好的相关性，其顺序为：I &gt;其它C_5对称茂锆&gt; C_2对称茂锆。在0 ℃下与I进行共聚反应，选择性地得到共聚物。乙烯和1，3-丁二烯的共聚也进行了与氯化钴活化的甲基铝氧烷。虽然共聚没有进行，但发现氯化钴-甲基铝氧烷对1，3-丁二烯的顺式特异性活性聚合是有效的。少

项目成果

D. C. Nath, T. Shiono and T. Ikeda: "Polymerization of 1,3-butadiene by cobalt dichloride activated with various aluminoxanes"Appl. Catal. A. 238. 193-199 (2003)

D. C. Nath、T. Shiono 和 T. Ikeda：“用各种铝氧烷活化的二氯化钴聚合 1,3-丁二烯”Appl。

D.C.Nath, T.Shiono, T.Ikeda: "cis-Specific living Polymerization of 1,3-butadiene Polymerization with cobalt dichloride and methylaluminoxane"Macromol. Chem. Phys.. 203・4. 756-760 (2002)

D.C.Nath、T.Shiono、T.Ikeda：“二氯化钴和甲基铝氧烷的顺式特异性活性聚合”Macromol. 756-760 (2002)

D.C.Nath, T.Shiono, T.Ikeda: "Polymerization of 1,3-butadiene by cobalt dichloride activated with various aluminoxanes"Appl. Catal. A. 238. 193-199 (2003)

D.C.Nath、T.Shiono、T.Ikeda：“用各种铝氧烷活化的二氯化钴聚合 1,3-丁二烯”Appl。

D.C.Nath, T.Shiono, T.Ikeda: "Copolymerization of 1,3-butadiene and isoprene with cobalt dichloride-methylaluminoxane in the presence of triphenylphosphine"J.Polym.Sci., Part A : Polym.Chem.Ed.. 40・17. 3086-3092 (2002)

D.C.Nath、T.Shiono、T.Ikeda：“在三苯基膦存在下，1,3-丁二烯和异戊二烯与二氯化钴-甲基铝氧烷的共聚”J.Polym.Sci.，A 部分：Polym.Chem.Ed. 40・17。3086-3092（2002）

T.Shiono, O.Yoshino, T.Ikeda: "Copolymerization of ethene and 1,3-butadiene over a SiO_2-supported CpTiCl catalyst"Micro-Kinetics and Dynamics of Individual Active Sites in Catalytic Reactions. 131-137 (2001)

T.Shiono、O.Yoshino、T.Ikeda：“SiO_2 负载的 CpTiCl 催化剂上乙烯和 1,3-丁二烯的共聚合”催化反应中各个活性位点的微观动力学和动力学。