昇温溶離分別法を用いたMgCl_2担持型Ziegler触媒におけるイソ特異的活性点の特性分布解析  [in Japanese] Investigation of the Distribution of Isospecificity of Active Sites on the MgCl_2-Supported Ziegler Catalyst by Temperature Rising Elution Fractionation Analysis  [in Japanese]

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Author(s)

    • LIU Boping
    • 北陸先端科学技術大学院大学材料科学研究科 School of Materials Science, Japan Advanced Institute of Science and Technology
    • 寺野 稔 TERANO Minorou
    • 北陸先端科学技術大学院大学材料科学研究科 School of Materials Science, Japan Advanced Institute of Science and Technology

Abstract

本研究では, 昇温溶離分別法 (TREF) を用いて分析したポリプロピレン (PP) の立体規則性 (イソタクチック) 分布を基に, MgCl<SUB>2</SUB>担持型Ziegler触媒が有するイソ特異的活性点の特性分布と内部および外部ドナーがその分布に及ぼす効果を調べた. 内部および外部ドナーを含まないMgCl<SUB>2</SUB>担持型Ziegler触媒系を用いた, ストップフロー法によるプロピレン重合で得られたポリマーのTREF噺から, Ti, Mg, Clのみからなる触媒からも, 高イソタクチックPPをはじめ, 異なる立体規則性をもつポリマーが得られ, 本触媒においても活性点の立体特異性に分布のあることがわかった. ドナーの添加効果に関する検討では, 内部ドナーは非立体特異的活性点の生成を抑制する効果があるのみならず, もっとも立体特異性の高い活性点の創製に重要な役割を果たしており, 一方, 外部ドナーは非立体特異的活性点をイソ特異的活性点へ変換させることはできるものの, その効果は低く, しかももっとも立体特異性の高い活性点への変換には効果をもたないことがわかった.

The distribution and transformation of isospecificity of active sites of MgCl<SUB>2</SUB>-supported Ziegler catalyst were investigated on the basis of the isotacticity distribution of the polypropenes (PPs) analyzed using the temperature rising elution fractionation method (TREF). PPs were prepared by the stopped-flow method using various MgCl<SUB>2</SUB>-supported Ziegler catalyst systems. The result of the electron donor-free catalyst system shows that the highly isospecific active sites derived from the highest isotactic fraction (elution temperature by TREF is over 112°C) exist in this catalyst system. The isospecificity of active sites in the donor-free catalyst might be originated from surface monolayer multinuclear titanium species, namely “Island” of titanium species. Addition of internal donor can transfer a significant amount of aspecific active sites as well as the second highest isospecific sites into the highest isospecific active sites. Whereas, addition of external electron donor converted some part of aspecific active sites into the second highest isospecific active sites, but showed no effect on the highest isospecific active sites.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(6), 402-405, 2002-06-25

    The Society of Polymer Science, Japan

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Codes

  • NII Article ID (NAID)
    10008834639
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    ART
  • ISSN
    03862186
  • NDL Article ID
    6200569
  • NDL Source Classification
    ZP16(科学技術--化学・化学工業--高分子化学・高分子化学工業)
  • NDL Call No.
    Z17-92
  • Data Source
    CJP  NDL  J-STAGE 
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