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

通过茂金属基催化剂合成结构受控的新型聚合物。

基本信息

批准号：
10450356
负责人：
ENDO Kiyoshi
金额：
$ 7.94万
依托单位：
OSAKA CITY UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B).
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

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

本论文主要研究了以降冰片烯为催化剂合成结构可控的新型高分子材料.本文从合成新型聚合物和精确聚合的角度出发，介绍了在均相过渡金属催化剂（如茂金属催化剂）作用下的大分子单体聚合。大分子单体在均相催化剂作用下的聚合反应，得到了新型的具有长支链的有规立构聚合物，如间同立构和全同立构接枝共聚物。苯乙烯封端的大分子单体在茂金属催化剂下均聚产生有规立构多支化聚合物。从本体性质的角度讨论了所得有规立构接枝共聚物的多晶型行为. Cp^*TiClX_3-MAO（X：Cl和OCH_3）催化剂用于氯乙烯的可控聚合 ...更多信息裂解物引发氯乙烯的聚合，尽管分子聚合速率很慢。Cp^*Ti（OCH_3）_3-MAO催化剂在二氯甲烷中以良好的产率得到高质量的聚合物。通过对聚合物的元素分析和~ 1H NMR谱的研究，发现Cp^*Ti（OCH_3）_3-MAO催化剂可以得到主链上没有异常结构的、由规则的首尾单元组成的聚合物，目前正处于合成有规立构聚合物的研究中.镍基催化剂用于多种乙烯基单体的聚合研究了Ni（acac）2-MAO催化剂用于甲基丙烯酸甲酯和甲基丙烯酸叔丁酯的聚合。发现这些单体的聚合控制聚合物的分子量。用Ni（acac）_2-MAO催化丁二烯-苯乙烯共聚合，得到了顺式-1，4含量高、序列无规的共聚物。与Ni基催化剂相比，Co（acac）_3-MAO和V（acac）_3-MAO催化剂能控制聚丁二烯的微观结构。此外，Cr（acac）_3-MAO催化剂还可得到由1，2-结构组成的聚合物。少