单取代芳氧钛合成与催化乙烯及乙烯与α-烯烃共聚

Synthesis of TiCl_3 Complexes Containing Aryloxy Groups and Application for Ethylene Polymerization and Copolymerization

使用廉价原料和简单工艺方法合成了芳氧钛类烯烃聚合和共聚催化剂,得到了(2-OMe C6H4O)Ti Cl3(C1),(2,4-Me2C6H3O)Ti Cl3(C2),Ti Cl3(1,4-OC6H4O)Ti Cl3(C3),Ti Cl3(1,4-OC6H2O-Me2-2,5)Ti Cl3(C4)以及相应的(Ar O)2Ti Cl2类络合物Ti Cl2(OC6H4-OMe-2)2(C5)和Ti Cl2(OC6H3-Me2-2,6)2(C6).通过1H NMR,13C NMR,MS以及元素分析进行了结构表征,确认了化学组成,以甲基铝氧烷(MAO)为助催化剂,Ar OTi Cl3/MAO体系显示了对乙烯聚合和共聚的高活性,13C NMR结果表明,聚合物中1-己烯插入率最高达6.88%(摩尔分数),而且得到的聚合物呈现高度支化,除了α-烯烃支链,还有甲基、乙基和长支链,并对其形成机理进行了研究,此外,对聚合温度、时间及共聚单体浓度对聚合反应的影响也进行了探讨.

Novel olefin polymerization catalysts with lower cost and simple synthetic process were developed.Ar OTi Cl3 complexes[（ 2-OMe C6 H4 O） Ti Cl3（ C1）,（ 2,4-Me2 C6 H3 O） Ti Cl3（ C2）,Ti Cl3（ 1,4-OC6 H4 O） Ti Cl3（ C3）, Ti Cl3（ 1,4-OC6 H2 O-Me2-2,5） Ti Cl3（ C4） ] and corresponding（ Ar O）2 Ti Cl2 complexes [Ti Cl2·（ OC6 H4-OMe-2）2（ C5） and Ti Cl2（ OC6 H3-Me2-2,6）2（ C6） ]were synthesized and well characterized. When combined with methylaluminoxane（ MAO）,the Ar OTi Cl3/MAO system shows moderate activity for ethylene copolymerization with 1-hexene. The13 C NMR result of polymer indicates that the 1-hexene incorporation in polymer reached up to 6. 88%（ molar fraction）. The polymer was characterized by13 C NMR and the mechanisms of methyl,ethyl and long side chain formation were given. The effects of polymerization temperature,concentration of polymerization monomer and polymerization time on the catalytic activity were investigated.