Recent Developments in Transition Metal-Catalyzed Polymerization I. Synthesis of Helical Substituted Polyacetylenes Using a Rhodium Complex Catalyst-Color Control through Columnar Formation.

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  • TABATA Masayoshi
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University
  • MAWATARI Yasuteru
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University
  • SONE Takeyuki
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University Research Fellow of Japan Society for the Promotion of Science
  • YONEMOTO Daigo
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University
  • MIYASAKA Atsushi
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University
  • FUKUSHIMA Takashi
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University
  • SADAHIRO Yoshikazu
    Department of Molecular Chemistry, Graduate School of Engineering, Hokkaido University

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Other Title
  • 遷移金属触媒重合の新展開　Ｉ　　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
  • ロジウム サクタイ ショクバイ ニ ヨル ヘリカル チカン ポリアセチレン ノ ゴウセイ カラムナー ケイセイ ニ ヨル イロ セイギョ
  • Color Control through Columnar Formation
  • カラムナー形成による色制御

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Abstract

Stereospecific polymerization of substituted aromatic acetylenes such as p-3-methylbutoxyphenylacetylene (p3MBPA), o-trifluorophenylacetylene (oTFMPA), p-amidophenylacetylene (pAPA), 3-n-octylthienylacetylene (3OTA), and N-n-octyl-3-carbazolylacetylene (NOCzA) was carried out by using the Rh complex, [Rh (norbornadiene) Cl] 2 to produce the corresponding polymers. These have a cis 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 1H 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. e., 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 trans isomer, even though the absorption maximum of the obtained trans 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

    The Society of Polymer Science, Japan

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