ロジウム錯体触媒によるヘリカル置換ポリアセチレンの合成 : カラムナー形成による色制御  [in Japanese] Synthesis of Helical Substituted Polyacetylenes Using a Rhodium Complex Catalyst : Color Control through Columnar Formation  [in Japanese]

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Abstract

ヘテロ原子を側鎖に含む置換アセチレンは, 水, アルコール, アミン溶媒の存在下, ロジウム (Rh) 錯体触媒によって立体規則的に重合でき, 選択的にシス体の置換ポリアセチレンが高収率で生成する. また, 生成したポリアセチレンの主鎖は, ラセン構造を有し, それが非晶の場合とラセンのポリマーが集合したカラムナーを形成する場合がある. 後者のカラムナーポリマーは, 非晶の場合と比べ著しく長波長側に吸収を示した. カラムナーのシス体を減圧下, 加圧するとトランス体になるが, その吸収極大は, 非晶のそれに比較すると青色シフトしていた. このように, Rh錯体を用いるとラセンの共役ポリマーが生成し, その集合体の量が, 生成したポリマーの吸収波長と関係していることを新しく見いだした.

Stereospecific polymerization of substituted aromatic acetylenes such as <I>p</I>-3-methylbutoxyphenylacetylene (p3MBPA), <I>o</I>-trifluorophenylacetylene (oTFMPA), <I>p</I>-amidophenylacetylene (pAPA), 3-<I>n</I>-octylthienylacetylene (3OTA), and <I>N</I>-<I>n</I>-octyl-3-carbazolylacetylene (NOCzA) was carried out by using the Rh complex, [Rh (norbornadiene) Cl] <SUB>2</SUB> to produce the corresponding polymers. These have a <I>cis</I> isomer as the main structure and are obtained in fairly high yields in the presence of ethylalcohol, water, and triethylamine (TEA). The resulting polymers were characterized in detail using <SUP>1</SUP>H NMR, laser Raman, diffuse reflective UV-Vis, electron spin resonance, and wide angle X-ray diffraction methods. The data showed that the obtained polymers were composed of amorphous and pseudohexagonal structures, <I>i. e., </I> columnar. We found that the absorption maximum of the columnar polymer appeared at somewhat longer wavelength than that of the amorphous polymer. Further, the columnar structure composed of helical main chain can be destroyed by compression under reduced pressure to produce the <I>trans</I> isomer, even though the absorption maximum of the obtained <I>trans</I> isomer is shifted to a lower wavelength region compared to that of the original columnar polymer. Based on these data, we concluded that the color of these polymers can be easily controlled by formation of columnars which are composed of the helical polymer chains.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(4), 168-177, 2002-04-25

    The Society of Polymer Science, Japan

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Codes

  • NII Article ID (NAID)
    10008223815
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    REV
  • ISSN
    03862186
  • NDL Article ID
    6154229
  • 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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