【摘要】 借助于主催剂单茂钛化合物分子设计和助催剂甲基铝氧烷改性构思，研制出几种有代表性的高活性新型单茂钛催化体系进行苯乙烯间规聚合．发现：单茂钛化合物主配体茂基和辅助配体非茂基的电子效应和空间位阻效应对苯乙烯聚合活性和聚苯乙烯的相对分子质量、间规度及熔融温度都有较大的影响．助催剂改性甲基铝氧烷（ｍＭＡＯ）中ＴＭＡ的质量分数达到一个特定值（２５１％）时，催化体系的催化活性最高，外加烷基铝（ＡｌＲ３）可以部分替代ＴＭＡ，其中外加三异丁基铝（ＴＩＢＡ）效果最好．对ＣｐＴｉ（ＯＰｒｎ）３／ｍＭＡＯ催化体系中钛的氧化态进行了分析，结果表明烷基铝的含量是影响催化体系中各种钛氧化态分配百分数的主要因素；活性中心钛的氧化态以Ｔｉ（Ⅲ）为主时有利于苯乙烯间规聚合．更多还原

【Abstract】 Novel and highly active one η 5 cyclopentadienyl ligand titanium metallocene catalytic systems for styrene syndiospecific polymerization were obtained by the molecular design of metallocene complexes and modification of methylaluminoxane(MAO). The catalytic activity, stereospecificity, molecular weight and melting temperature of polystyrene are affected by steric and electronic changes of η 5 cyclopentadienyl ligands and non cyclopentadienyl ancillary ligands of these titanocene complexes The pentamethylcyclopentadienyl ligand is beneficial for obtaining high catalytic activity and molecular weight and melting temperature of polystyrene The influences of the percentage contents of TMA in m MAO which can reduce Ti(Ⅳ) to Ti(Ⅲ) on polymerization of styrene have been investigated in detail,Ti(Ⅲ) is good for styrene syndiospecific polymerization in a higher catalytic activity. The external addition of alkylaluminium(AlR 3) to [CpTi(OPr n ) 3]/modified methylaluminoxane(m MAO) catalytic system may alternates partially TMA in m MAO, and tri isobutylaluminum(TIBA) is more effective than trimethylaluminum(TMA) and triethylaluminum(TEA).更多还原