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Nickel-Catalyzed Propylene/Polar Monomer Copolymerization

机译:镍催化的丙烯/极性单体共聚

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摘要

Nickel complexes bearing bidentate alkylphophine-phenolate ligands were synthesized and applied to the polymerization of propylene and the copolymerization of propylene and polar monomers. Therein, the use of bulky alkyl substituents on the phosphorus atom was crucial for the formation of highly regioregular polypropylenes. Theoretical calculations suggested that the 1,2-insertion of propylene is favored over the 2,1-insertion in these nickel-catalyzed (co)polymerization reactions. The substituent at 'the ortho position relative to the oxido group greatly influences the polymerization activity, the molecular weight, and stereoregularity of the polypropylenes. This method delivers moderately isotactic ([mm] = 68%) crystalline polypropylenes. The present system represents the first example for a nickel-catalyzed regiocontrolled copolymerization of propylene and polar monomers such as but-3-en-1-ol, but-3-en-1-yl acetate, and tert-butyl allylcarbamate.
机译:合成含有二齿烷基苯酚酚酸盐配体的镍复合物并施加到丙烯和丙烯和极性单体的共聚的聚合中。 在其中,在磷原子上使用庞大的烷基取代基对于形成高度摄影聚丙烯的形成至关重要。 理论计算表明,在这些镍催化(CO)聚合反应中的2,1插入中,1,2-插入的1,2-插入丙烯。 “相对于氧化钒基团的邻位的取代基极大地影响聚丙烯的聚合活性,分子量和立体性。 该方法以适度的全同立构([mm]& = 68%)结晶聚丙烯提供。 本系统代表丙烯和极性单体的镍催化的RemioControlled共聚的第一实施例,例如-3-烯-1-醇,但-3-烯-1-基乙酸酯和叔丁基烯丙基甲酸酯。

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  • 来源
    《ACS Macro Letters》 |2018年第2期|共9页
  • 作者单位

    Japan Polychem Corp Aoba Ku 1000 Kamoshida Cho Yokohama Kanagawa 2278502 Japan;

    Univ Tokyo Grad Sch Engn Dept Chem &

    Biotechnol Bunkyo Ku 7-3-1 Hongo Tokyo 1138656 Japan;

    Univ Tokyo Grad Sch Engn Dept Chem &

    Biotechnol Bunkyo Ku 7-3-1 Hongo Tokyo 1138656 Japan;

    Univ Tokyo Grad Sch Engn Dept Chem &

    Biotechnol Bunkyo Ku 7-3-1 Hongo Tokyo 1138656 Japan;

    Japan Polychem Corp Aoba Ku 1000 Kamoshida Cho Yokohama Kanagawa 2278502 Japan;

    Japan Polychem Corp Aoba Ku 1000 Kamoshida Cho Yokohama Kanagawa 2278502 Japan;

    Japan Polychem Corp 1 Toho Cho Yokaichi Mie 5100848 Japan;

    Japan Polychem Corp 1 Toho Cho Yokaichi Mie 5100848 Japan;

    Univ Tokyo Grad Sch Engn Dept Chem &

    Biotechnol Bunkyo Ku 7-3-1 Hongo Tokyo 1138656 Japan;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 有机化学;
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