State Key Laboratory for Supramolecular Structure and Materials, School of Chemistry, Jilin University, 2699 Qianjin Street, Changchun, 130012, People's Republic of China.
Dalton Trans. 2010 Mar 14;39(10):2525-35. doi: 10.1039/b921617k. Epub 2010 Jan 22.
A number of cyclopentadienyltitanium aryloxide complexes, 1-Ar-2,3,4,5-Me(4)-Cp(2,6-(i)Pr(2)C(6)H(3)O)TiCl(2) (Ar = 4-Me(3)SiPhenyl (5), 4-(i)PrPhenyl (6), 4-MePhenyl (7), 3,5-(CF(3))(2)Phenyl (8)) and (1-Ar-2,3,4,5-Me(4)CpTiCl(2))(2)(OAr'O) (Ar' = 4,4'-(3,3',5,5'-(i)Pr(4)C(6)H(2)-C(6)H(2)), Ar = 4-SiMe(3)Phenyl (9), 4-MePhenyl (10)) were synthesized from the reaction of a corresponding cyclopentadienyl titanium trichloride derivative with the lithium salt of a relevant phenol. The molecular structures of complexes 6, 7 and 8 were determined by X-ray crystallography. Upon activation with (i)Bu(3)Al and Ph(3)CB(C(6)F(5))(4), all mononuclear complexes 5-8 exhibit good catalytic activities for propylene polymerization, whereas the binuclear complexes 9 and 10 show lower catalytic activities under the same polymerization conditions. (13)C NMR, DSC and GPC analysis indicates the produced polymers are atactic polypropylene with relatively high molecular weight. It was found that the substituents on both the cyclopentadienyl and aryloxy ligands of these complexes show obvious influence on the molecular weight of the resultant polymers with complex 5 producing the highest molecular weight atactic polypropylene. Complexes 5, 6 and 7 were also tested as catalysts for copolymerization of propylene with 1-hexene and copolymers with 1.2-10.1% comonomer incorporation were obtained in reasonable catalytic activity.
一系列环戊二烯基钛芳氧基配合物，1-Ar-2,3,4,5-Me(4)-Cp(2,6-(i)Pr(2)C(6)H(3)O)TiCl(2)（Ar=4-Me(3)Si 苯基(5)，4-(i)Pr 苯基(6)，4-Me 苯基(7)，3,5-(CF(3))(2)苯基(8))和(1-Ar-2,3,4,5-Me(4)CpTiCl(2))(2)(OAr'O)（Ar'=4,4'-(3,3',5,5'-(i)Pr(4)C(6)H(2)-C(6)H(2))，Ar=4-SiMe(3)苯基(9)，4-Me 苯基(10))是由相应的环戊二烯基钛三氯化物衍生物与相关酚的锂盐反应合成的。配合物 6、7 和 8 的分子结构通过 X 射线晶体学确定。用(i)Bu(3)Al 和 Ph(3)CB(C(6)F(5))(4)活化后，所有单核配合物 5-8 均对丙烯聚合表现出良好的催化活性，而双核配合物 9 和 10 在相同的聚合条件下显示出较低的催化活性。(13)C NMR、DSC 和 GPC 分析表明，所得到的聚合物是无规聚丙烯，具有相对较高的分子量。发现这些配合物中环戊二烯基和芳氧基配体上的取代基对所得聚合物的分子量有明显的影响，配合物 5 得到的无规聚丙烯分子量最高。配合物 5、6 和 7 也被测试为丙烯与 1-己烯共聚的催化剂，并获得了具有 1.2-10.1%共聚单体的共聚物，具有合理的催化活性。
