1995 Fiscal Year Annual Research Report

導電性強誘電液晶高分子の創製

Research Project

Project/Area Number	07455377
Research Category	Grant-in-Aid for General Scientific Research (B)
Research Institution	University of Tsukuba
Principal Investigator	白川英樹筑波大学, 物質工学系, 教授 (40016720)
Co-Investigator(Kenkyū-buntansha)	赤木和夫筑波大学, 物質工学系, 助教授 (20150964)
Keywords	導電性高分子 / 強誘電液晶高分子 / ポリアセチレン誘導体 / 光学活性 / 自発分極 / カイラルスメクティックC相 / 筋付扇状模様 / 電場応答
Research Abstract	近年、我々は、共役系高分子の側鎖に液晶基を有する導電性高分子液晶を合成し、剪断応力や外部磁場による液晶基の巨視的配向とそれに伴う主鎖の配向により、電気伝導度の二桁以上の上昇を達成した。外部応力として電場を用いる場合、強誘電性液晶は通常の液晶と比べて、電場に対して極めて敏速に応答する。そのため、側鎖に強誘電性液晶が導入できれば、主鎖のポリエン骨格の配向もより高速に制御することが期待される。本研究では、ポリアセチレンの側鎖に不斉(キラル)炭素を有する光学活性液晶基を導入することで、液晶側鎖に強誘電性を付与させ、導電性と強誘電液晶性をあわせもつ新規な高分子化合物を合成し、その液晶性、光学的性質および電気的性質の向上を意図した。 (1)光学活性液晶基を持つアセチレン誘導体モノマーの合成:液晶コアとしてビフェニル系を用い、光学活性を有する置換基を液晶コアーの末端に導入することで、光学活性液晶分子を合成した。次に三重結合を有する5-クロロ-1-ペンチンをこの液晶分子とカップリングさせアセチレン誘導体モノマーを合成した。合成物は、NMR,IR,UV-VIS,および元素分析により同定した。 (2)アセチレン誘導体モノマーの重合:重合触媒として一置換アセチレンの重合に有効なメタセシス触媒[MoCl_5-Ph_4Sn]を用いて重合を行い、光学活性側鎖型液晶ポリアセチレン誘導体を合成した。モノマーおよびポリマーの光学活性の存在は円偏光二色性スペクトルの測定を通じて確認した。 (3)液晶性の確認:偏光顕微鏡による光学的模様の観察および示差走査熱量計(DSC)による相転移温度の解析を通じて、合成したポリマーは降昇温過程においてスメクティックA(S_A)相ならびにカイラルスメクティックC(S_C^)相を示すことを明らかにした。後者の液晶相は強誘電性液晶に特有なめものであり、これにより目的物である導電性と強誘電液晶性をあわせもつ高分子化合物が合成できたことを確認した。 (4)強誘電液晶相の温度領域拡大の試み:上記のS^_C相の温度領域は約5℃と極めて狭いものであったため、安定したS_C^*相を実現すべく、液晶基のスペ-サ長を長くしたもの、さらには、より強い自発力分極を付与すべく、液晶基にカルボニル部位を導入したものをそれぞれ合成したが、S_A相の温度領域が拡大したに留まった。今後、さらなる分子設計が必要である。

Research Products

(28 results)

All Other

All Publications (28 results)

[Publications] Kazuo Akagi: "Side-Chain Liquid Crystalline Conjugated Polymers, Poly(Mono-Substituted Acetylenes)" Trans. Mat. Res. Soc. Jpn.15A. 259-262 (1994)
[Publications] Kazuo Akagi: "Syntheses of Thiophene Derivatives with Liquid Crystalline Substituents and Their Polymerizations" Trans. Mat. Res. Soc. Jpn.15A. 513-516 (1994)
[Publications] Hideki Shirakawa: "Various Factors Affecting the Synthesis of Highly Conducting Polyacetlene" Synthetic Metals. 60. 93-101 (1994)
[Publications] Hideki Shirakawa: "Synthesis of Liquid CrystallinePolyacetylene Derivatives" Mol. Cryst. Liq. Cryst.255. 132-219 (1994)
[Publications] Kazuo Akagi: "Synthesis and Properties of Liquid Crystalline Polyacetylene Derivatives" Synthetic Metals. 69. 13-16 (1995)
[Publications] Kazuo Akagi: "Fused State ^<13>C-NMR Studyon Liquid Crystalline Polyacetylene DerivativesMagnetically Forced Alignment and Orientational Behavior." Synthetic Metals. 69. 33-34 (1995)
[Publications] Ryouichi Toyoshima: "Synthesis and Properties of Polythiophenes Derivatives with Liquid Crystalline Substituents." Synthetic Metals. 69. 289-290 (1995)
[Publications] Katsumi Yoshino: "Unique Electrical and Optical Properties of Polyacetylene Derivatives in Liquid Crystal Phase" Synthetic Metals. 69. 49-50 (1995)
[Publications] Hiromasa Goto: "Thermotropic Liquid CrystallineConjugated Polymers,Poly( cyclohexylphenoxyacetylenes)-Synthesis and Properties." Synthetic Metals. 71. 1899-1990 (1995)
[Publications] Kazuo Akagi: "Electrically Conducting Liquid Crystalline Polymers, Mono-Substituted Polyacetylene Derivatives." Mol. Cryst. Liq. Cryst.267. 277-282 (1995)
[Publications] Kazuo Akagi: "Polyacetylene Films Prepared byIntrinsic Non-Solvent Polymerzation Method-Mechanica-l Properties and Electrical Conductivties." Synthetic Metals. 69. 29-30 (1995)
[Publications] Kouichi Sakamaki: "Thermodynamic Behavior of Cis-Trans Isomerization in S- and N-type Polyacetylene Films. DSC study." Synthetic Metals. 69. 57-58 (1995)
[Publications] C. O. Yoon: "Effect of Anisotropy on the Temperature Dependence of Conductivity and Magnetoconductance in Heavily Doped Polyacetylene" Synthetic Metals. 69. 79-80 (1995)
[Publications] Yoshikazu Tanabe: "Isothermal Cis-Trans Isomerzation of Polyacetylene" Synthetic Metals. 69. 45-46 (1995)
[Publications] E. B. Park: "Positive Thermoelectric Power ofAlkali-Metal-Doped Polyacetylene" Synthetic Metals. 69. 61-62 (1995)
[Publications] Kenji Mizoguchi: "Analysis of the ESR Linewidth in Pristine Trans-Polyacetylene" Phys. Rev. B. 51. 8864-8873 (1995)
[Publications] Katsumi Yoshino: "Unique Liquid Crystalline Behavior of Conducting Polyacetylene Derivatives" Mol. Cryst. Liq. Cryst.(in press). (1995)
[Publications] Hiroko Kyotani: "Isothermal Cis-Trans Isomerization Behavior of Polyacetylene Films" J. Polym. Sci. Part B, Polym. Phys.32. 581-585 (1995)
[Publications] Hiroko Kyotani: "Thermal Isoerization and Morphology of Various Polyacetylene Films" J. Polym. Sci. Part B, Polym. Phys.32. 587-593 (1995)
[Publications] Yoshikazu Tanabe: "Machanism of Cis-Trans Thermal Isomerization of Polyacetylene" Macromolecules. 28. 4173-4178 (1995)
[Publications] Kazuo Akagi: "Morphological Alignment of Liquid Crystalline Conducting Polyacetylene Derivatives," Macromolecular Symposia. (in press). (1996)
[Publications] 赤木和夫: "導電性ポリアセチレン類の配向制御" 表面. 32. 32-45 (1994)
[Publications] 赤木和夫: "導電性液晶高分子" 高分子. 43. 741- (1994)
[Publications] 赤木和夫: "一番導電性の高い高分子は?" 高分子. 44. 456-457 (1995)
[Publications] 赤木和夫: "液晶性をもつ導電性高分子の開発と展開" 応用物理. 65. 265-269 (1996)
[Publications] Kazuo Akagi: "The Polymeric Materials Encyclopedia.Synthesis, Properties and Applications" Liquid Crystalline Polyacetylene Derivatives CRC Press,Inc. (in press), (1996)
[Publications] Kazuo Akagi: "The Polymeric Materials Encyclopedia. Synthesis, Properties and Applications" Polyacetylene Films CRC Press, Inc. (in press), (1996)
[Publications] 木和夫: "光・電子機能有機材料ハンドブック" 編集代表、堀江一之、谷口彬雄、朝倉書店, 20 (1995)

1995 Fiscal Year Annual Research Report

導電性強誘電液晶高分子の創製

Principal Investigator

白川 英樹 筑波大学, 物質工学系, 教授 (40016720)

Research Products

[Publications] Kazuo Akagi: "Side-Chain Liquid Crystalline Conjugated Polymers, Poly(Mono-Substituted Acetylenes)" Trans. Mat. Res. Soc. Jpn.15A. 259-262 (1994)

[Publications] Kazuo Akagi: "Syntheses of Thiophene Derivatives with Liquid Crystalline Substituents and Their Polymerizations" Trans. Mat. Res. Soc. Jpn.15A. 513-516 (1994)

[Publications] Hideki Shirakawa: "Various Factors Affecting the Synthesis of Highly Conducting Polyacetlene" Synthetic Metals. 60. 93-101 (1994)

[Publications] Hideki Shirakawa: "Synthesis of Liquid CrystallinePolyacetylene Derivatives" Mol. Cryst. Liq. Cryst.255. 132-219 (1994)

[Publications] Kazuo Akagi: "Synthesis and Properties of Liquid Crystalline Polyacetylene Derivatives" Synthetic Metals. 69. 13-16 (1995)

[Publications] Kazuo Akagi: "Fused State ^<13>C-NMR Studyon Liquid Crystalline Polyacetylene DerivativesMagnetically Forced Alignment and Orientational Behavior." Synthetic Metals. 69. 33-34 (1995)

[Publications] Ryouichi Toyoshima: "Synthesis and Properties of Polythiophenes Derivatives with Liquid Crystalline Substituents." Synthetic Metals. 69. 289-290 (1995)

[Publications] Katsumi Yoshino: "Unique Electrical and Optical Properties of Polyacetylene Derivatives in Liquid Crystal Phase" Synthetic Metals. 69. 49-50 (1995)

[Publications] Hiromasa Goto: "Thermotropic Liquid CrystallineConjugated Polymers,Poly( cyclohexylphenoxyacetylenes)-Synthesis and Properties." Synthetic Metals. 71. 1899-1990 (1995)

[Publications] Kazuo Akagi: "Electrically Conducting Liquid Crystalline Polymers, Mono-Substituted Polyacetylene Derivatives." Mol. Cryst. Liq. Cryst.267. 277-282 (1995)

[Publications] Kazuo Akagi: "Polyacetylene Films Prepared byIntrinsic Non-Solvent Polymerzation Method-Mechanica-l Properties and Electrical Conductivties." Synthetic Metals. 69. 29-30 (1995)

[Publications] Kouichi Sakamaki: "Thermodynamic Behavior of Cis-Trans Isomerization in S- and N-type Polyacetylene Films. DSC study." Synthetic Metals. 69. 57-58 (1995)

[Publications] C. O. Yoon: "Effect of Anisotropy on the Temperature Dependence of Conductivity and Magnetoconductance in Heavily Doped Polyacetylene" Synthetic Metals. 69. 79-80 (1995)

[Publications] Yoshikazu Tanabe: "Isothermal Cis-Trans Isomerzation of Polyacetylene" Synthetic Metals. 69. 45-46 (1995)

[Publications] E. B. Park: "Positive Thermoelectric Power ofAlkali-Metal-Doped Polyacetylene" Synthetic Metals. 69. 61-62 (1995)

[Publications] Kenji Mizoguchi: "Analysis of the ESR Linewidth in Pristine Trans-Polyacetylene" Phys. Rev. B. 51. 8864-8873 (1995)

[Publications] Katsumi Yoshino: "Unique Liquid Crystalline Behavior of Conducting Polyacetylene Derivatives" Mol. Cryst. Liq. Cryst.(in press). (1995)

[Publications] Hiroko Kyotani: "Isothermal Cis-Trans Isomerization Behavior of Polyacetylene Films" J. Polym. Sci. Part B, Polym. Phys.32. 581-585 (1995)

[Publications] Hiroko Kyotani: "Thermal Isoerization and Morphology of Various Polyacetylene Films" J. Polym. Sci. Part B, Polym. Phys.32. 587-593 (1995)

[Publications] Yoshikazu Tanabe: "Machanism of Cis-Trans Thermal Isomerization of Polyacetylene" Macromolecules. 28. 4173-4178 (1995)

[Publications] Kazuo Akagi: "Morphological Alignment of Liquid Crystalline Conducting Polyacetylene Derivatives," Macromolecular Symposia. (in press). (1996)

[Publications] 赤木和夫: "導電性ポリアセチレン類の配向制御" 表面. 32. 32-45 (1994)

[Publications] 赤木和夫: "導電性液晶高分子" 高分子. 43. 741- (1994)

[Publications] 赤木和夫: "一番導電性の高い高分子は?" 高分子. 44. 456-457 (1995)

[Publications] 赤木和夫: "液晶性をもつ導電性高分子の開発と展開" 応用物理. 65. 265-269 (1996)

[Publications] Kazuo Akagi: "The Polymeric Materials Encyclopedia.Synthesis, Properties and Applications" Liquid Crystalline Polyacetylene Derivatives CRC Press,Inc. (in press), (1996)

[Publications] Kazuo Akagi: "The Polymeric Materials Encyclopedia. Synthesis, Properties and Applications" Polyacetylene Films CRC Press, Inc. (in press), (1996)

[Publications] 木和夫: "光・電子機能有機材料ハンドブック" 編集代表、堀江一之、谷口彬雄、朝倉書店, 20 (1995)

白川英樹筑波大学, 物質工学系, 教授 (40016720)