AB_X型モノマーのヒドロシリル化反応による位置および立体規則性ポリ(シリレンアリーレンビニレン)の合成および特性  [in Japanese] Synthesis of Regio- and Stereoregular Poly(silylenearylenevinylene)s by the Hydrosilylation of AB_X Type Monomers and Properties of the Formed Polymers  [in Japanese]

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Author(s)

    • 郭 起燮 GISEOP Kwak
    • 京都大学大学院工学研究科 Department of Polymer Chemistry, Graduate School of Enigineering, Kyoto University
    • 増田 俊夫 MASUDA Toshio
    • 京都大学大学院工学研究科 Department of Polymer Chemistry, Graduate School of Enigineering, Kyoto University

Abstract

トルエン中25および80℃でRhI (PPh<SUB>3</SUB>) <SUB>3</SUB>触媒により<I>p</I>- (ジメチルシリル) フェニルアセチレンを重合したところそれぞれ98%シスおよび99%トランスビニレンを有する位置および立体規則性ポリ (ジメチルシリレンフェニレンビニレン) (<B><I>cis</I>-2, <I>trans</I>-2</B>) が生成した. 同様に, 74%シスおよび89%トランス構造を有するポリ (ジメチルシリレンビフェニレンビニレン) (<B><I>cis</I>-rich5, <I>trans</I>-rich5</B>) を合成した. トランスタイプのポリマーはシスタイプのポリマーに比べUV-可視スペクトルにおいて深色移動および濃色効果を示した. <B><I>cts</I>-2, <I>trans</I>-2</B>のいずれも紫外光照射によりシスリッチな混合物を与え, 平衡に達した. 異性化の程度は, 光照射前後の溶液のUVスペクトルから正確に計算することができた. トランスおよびシスポリマーは異なる発光特性を示した. 例えば, <B><I>trans</I>-2</B>の発光極大は400nmでその量子収率は3.4×10<SUP>-3</SUP>であり, 一方, <B><I>cis</I>-2</B>の発光極大は380nmでその量子収率は1.5×10<B>-3</B>であった. 特に<B><I>trans</I>-rich 5</B>の量子収率は0.15にまで達した. 興味深いことに, <B><I>cis</I>-2</B>の重量損失開始温度は約510℃であり, <B><I>trans</I>-2</B>のそれ (約280℃) に比べてはるかに大きかった. さらに, RhI (PPh<SUB>3</SUB>) <SUB>3</SUB>触媒によるビス (4-エチニルフェニル) メチルシランの重合は95%トランスビニレン構造を有する位置および立体規則性多分岐ポリ (ジメチルシリレンフェニレンビニレン) を生成した. このポリマーでは275nm付近でπ-π*遷移に由来する吸収が肩として見られ, さらに対応する直鎖ポリマー, <B><I>trans</I>-2</B>ではほとんど見られなかったπ-to-σ電荷移動に由来する弱い吸収が330nm付近で見られた.

Polymerization of <SUB>p</SUB>- (dimethylsilyl) phenylacetylene in toluene at 25 and 80°C using RhI (PPh<SUB>3</SUB>) <SUB>3</SUB> catalyst afforded highly regio-and stereoregular poly (dimethylsilylenephenylenevinylene) s (<B><I>cis</I>-2 and <I>trans</I>-2</B>) containing 98% <I>cis</I>-and 99% <I>trans</I>-vinylene moieties, respectively. Similarly, poly (dimethylsilylenebiphenylenevinylene) s (5′s with 74% cis-and 89% trans-structures) were prepared. The trans-type polymers showed red shifts and hyperchromic effects in the UV-visible spectrum compared to the cis-type counterparts. Photoirradiation of both <B><I>cis</I>-2 and <I>trans</I>-2</B> gave cis-rich mixtures at the equilibrium state. The degree of photoisomerization could be exactly evaluated by comparing the UV spectra of solutions of <B><I>cis</I>-2 and <I>trans</I>-2</B> before and after photoirradiation. The trans and cis polymers exhibited different emission properties; e. g., <B><I>trans</I>-2</B>: emissn λ<SUB>max</SUB>=400nm, quantum yield=3.4×10<SUP>-3</SUP>; <B><I>cis</I>-2</B>: emissn λ<SUB>max</SUB>=380nm, quantum yield=1.5×10<SUP>-3</SUP>. The quantum yield of the <B><I>trans</I>-rich 5</B> was especially high and reached 0.15. Interestingly, the onset temperature of weight loss of <B><I>cis</I>-2</B>was <I>ca</I>. 510°C, and much higher than that (<I>ca.</I> 280°C) of <B><I>trans</I>-2</B>. In addition, polymerization of bis (4-ethynylphenyl) methylsilane catalyzed by RhI (PPh<SUB>3</SUB>) <SUB>3</SUB> afforded a regio-and stereoregular hyperbranched poly (dimethylsilylenephenylenevinylene) containing 95% transvinylene moiety. This polymer displayed an absorption due to π-π* transition around 275 nm as a shoulder and a weak absorption around 330 nm due to π-to-σ* charge transfer, which was hardly seen with the corresponding linear polymer, <B><I>trans</I>-2</B>.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(6), 332-341, 2002-06-25

    The Society of Polymer Science, Japan

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Codes

  • NII Article ID (NAID)
    10008834380
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    REV
  • ISSN
    03862186
  • NDL Article ID
    6200384
  • 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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