Synthesis of Novel Polymers with Controlled Structure by Metallocene-Based Catalysts.

通过茂金属催化剂合成新型可控结构聚合物的研究，获得了以下结果。茂金属催化剂等均相过渡金属催化剂与大分子单体的立体定向聚合从合成新型聚合物和精密聚合的角度阐述了大分子单体与均相过渡金属催化剂的聚合。大分子单体在均相催化剂作用下聚合，得到了新型的具有长支链的立体规则聚合物，如间同立构和等同立构接枝共聚物。在茂金属催化剂作用下，以苯乙烯为端基的大单体均聚合成了立体规整的多支化聚合物。从本体性质的角度讨论了所得立体规则接枝共聚物的晶型行为。Cp^*TiClX_3-MAO(X：CL和OCH_3)Cata…催化氯乙烯可控聚合较多的赖氨酸引发了氯乙烯的聚合，但分子聚合速度较慢。在二氯甲烷中，Cp^*Ti(OCH3)3-MAO催化剂以较高的产率得到了高质量的聚合物。通过对聚合物的元素分析和核磁共振氢谱分析，发现Cp^*Ti(OCH3)3-MAO催化剂的主链由规则的头尾重复单元组成，主链没有异常结构，立体规则聚合物的合成正在进行中。不同乙烯基单体在镍基催化剂上的聚合研究了Ni(Acac)2-MAO催化甲基丙烯酸甲酯和甲基丙烯酸叔丁酯的聚合反应。发现这些单体的聚合控制了聚合物的相对分子质量。在Ni(Acac)_2-MAO催化剂作用下，丁二烯和苯乙烯发生共聚反应，得到具有较高顺-1，4含量和较高顺式-1，4含量的S结构的共聚物。与镍基催化剂相比，Co(Acac)_3-MAO和V(Acac)_3-MAO催化剂对聚丁二烯的微观结构有明显的控制作用。此外，Cr(Acac)_3-MAO催化剂还得到了1，2-结构的聚合物。较少

The following results were obtained from the study of synthesis of novel polymers with controlled Structure by metallocene-based catalysts.1. Stereospecific polymerization using well-defined macromonomers with metallocence catalystsThe polymerizations of macromonomers with homogeneous transition metal catalysts such as metallocene catalysts were described from the viewpoints of not only synthesis of novel polymers but also precision polymerization. Polymerizations of macromonomers with homogeneous catalysts yielded novel stereoregular polymers with long branched chains such as syndiotactic and isotactic graft copolymers. Homopolymerization of the styrene-terminated macromonomer with metallocene catalyst produced a stereoregular multi-branched polymer. Polymorphic behavior of the obtained stereoregular graft copolymer was discussed from the viewpoint of the bulk property.2. Controlled polymerization of vinyl chloride with metallocence catalystsThe Cp^*TiClX_3-MAO (X : Cl and OCH_3) cata … More lysts initiated the polymerization of vinyl chloride, although the molecular polymerization rate was slow. The Cp^*Ti (OCH_3)_3-MAO catalyst in methylene chloride gave high weight polymers in good yields. From elemental analysis and ^1H NMR spectra of the polymers, the Cp^*Ti (OCH_3)_3-MAO catalyst was found to give polymers consisting of repeating regular head-to-tail units without anomalous structure in the main chain.The synthesis of stereoregular polymer is now in progress.3. Polymerization of various vinyl monomer with Ni-based catalystsThe polymerization of methyl methacrylate and t-butyl methacrylate with Ni (acac)2-MAO catalyst was investigated. The polymerization of these monomers was found to control the molecular weight of the polymers. The copolymerization of butadiene and styrene with Ni(acac)_2-MAO catalyst gave the copolymers with s fairly random sequence and high cis-1,4 contents. In relation to Ni-based catalyst, Co (acac)_3-MAO and V (acac)_3-MAO catalysts were found to control the microstructure of poly (butadiene). In addition, Cr (acac)_3-MAO catalyst gave a polymer consisting of 1,2-structure. Less