1990 Fiscal Year Annual Research Report

機能性材料作製のための反応設計

Research Project

Project/Area Number	02204006
Research Institution	The University of Tokyo
Principal Investigator	井上祥平東京大学, 工学部, 教授 (20010762)
Co-Investigator(Kenkyū-buntansha)	平野真一名古屋大学, 工学部, 教授 (30016828) 石川満夫広島大学, 工学部, 教授 (20025985) 中浜精一東京工業大学, 工学部, 教授 (90016410) 杉本豊成京都大学, 工学部, 助教授 (30093256)
Keywords	イモ-タル重合 / 有機磁性体 / ミクロ相分離 / 秩序構造 / 導電性ポリマ- / 有機ケイ素ポリマ- / 圧電体 / 薄膜
Research Abstract	本研究では、新しい機能を示す材料の創製をめざし、新しい反応プロセスを設計し、以下に示すような研究成果を得た。 (1)メタクリル酸エステル、ヘテロ環状モノマ-などを金属ポルフィリン錯体を用いて、今までにない高い効率において重合することに成功した。またイモ-タル重合性も明らかとなった。 (2)純粋な有機化合物では未知の強磁性体の達成を目指し、硫黄置換トリメチレンメタンジカチオンとジアニオンとの1:1電荷移動錯体及びスピロ架橋したTTFのポリマ-を合成し、磁気的性質を検討した。 (3)リビングアニオン重合法により、両未端にアミノ基およびカルボキシル基を有する分子量分布の狭いポリスチレンおよびポリエチレンオキシドをそれぞれ合成した。両者を種々の溶媒中で混合し、膜にキャストするとアミノ基とカルボキシル基の強い相互作用により、ミクロ相分離構造に類似の秩序性の高い構造が形成されることを電子顕微鏡観察、小角および広角X線散乱、溶解度測定、熱分析から明らかにした。 (4)テトラシアシクロオクタジインのアルキルリチウム触媒による開環重合により高重合度のポリマ-の合成に成功した。本法で合成したポリマ-は従来法のクロロシラン類のナトリウムによる縮合で合成したもよりも立体規則性に優れていることが示された。又、ポリマ-の薄膜のSbFt処理により、高い導電性を示すことに成功した。 (5)鉛含有複合ペロブスカイト型化合物、PZT、PLZT圧電体薄膜を合成するために、有機金属化合物を原料として均一溶液を調製した。単結晶及びPtをコ-ティングしたSi基板においても、パイロクロア相の生成を抑制し、配向性膜合成に成功した。またPZT(53/47)薄膜の誘電率は、膜厚に大きく依存することが明らかとなった。

Research Products

(21 results)

All Other

All Publications (21 results)

[Publications] 渡辺喜彦・相田卓三・井上祥平: "Novel Visible LightーMediated Living and Immortal Polymerizations of Epoxides with Zinc Complexes of NーSubstituted Porphyrins." Macromolecules. 23. 2612-2617 (1990)
[Publications] 杉本裕・相田卓三・井上祥平: "RingーOpening Polymerizations of Lactone and Epoxide Initiated with Aluminum Complexes of Substituted Tetraphenylporphyrins.Molecular Desing of Highly Active Initiators." Macromolecules. 23. 2869-2875 (1990)
[Publications] 相田卓三・川口健一・井上祥平: "Zinc NーSubstituted Porphyrins as Novel Initiators for the Living and Immortal Polymerizations of Episulfide." Macromolecules. 23. 3887-3892 (1990)
[Publications] Z.Yoshida,T.Sugimoto,and Y.Misaki: "Electronーdonating Radialenes.Potential Donors for Molecular Organic (Super)Conductors and Ferromagnets" Materials Research Society Symposium Proceedings. 173. 3-14 (1990)
[Publications] T.Sugimoto,Y.Yamamoto,and Z.Yoshida: "Synthesis and Electrical Conductive Property of New Tellurium Polymers Containing Thiocarbonyl Group" Chemistry Letters. 2111-2114 (1990)
[Publications] T.Sugimoto,K.Ikeda,and J.Yamauchi: "Tris(ethylenedithio)ー and Tris(1,2ーbenzodithio)ーsubstituted Trimethylenemethanes" Chemistry Letters. 29-32 (1991)
[Publications] T.Sugimoto,A.Kawachi,K.Ikeda,and J.Yamauchi: "Synthesis of Tetrakis(1,2ーbenzodithio)tetramethyleneethane Dication Salt and Its Twoーelectron Reduction" Chemistry Letters. (1991)
[Publications] T.Sugimoto,M.Sakaguchi,H.Ando,Y.Arai,T.Tanaka,Z.Yoshida,J.Yamauchi,A.A.BothnorーBy,and M.Lisicki: "Unexpected Participation of an Excited Diradical Structure in the Ground state of Cyclic Bicalicene" Journal of the American Chemical Society. 113. (1991)
[Publications] K.Ueda,A.Hirao,S.Nakahama: "Synthesis of Polymers with Amino End Groups.3.Reactions of Anionic Living Polymers with ーHaloーーaminoalkanes with a Protected Amino Functionality" Macromolecules. 23. 939-945 (1990)
[Publications] K.Takenaka,K.Kato,T.Hattori,A.Hirao,S.Nakahama: "Polymerization of Monomers Containing Functional Silyl Groups.8.Catalytic Hydrogenation of Poly(2ーsilylーsubstitutedー1,3ーbutadiene)s" Macromolecules. 23. 3619-3625 (1990)
[Publications] T.Taki,A.Hirao,S.Nakahama: "Polymerization of Monomers Containing Functional Silyl Groups.9.Anionic Living Polymerization of (4ーVinylphenyl)(n,Nーciethylamino)ーdimethylsilane" Macromolecules.
[Publications] T.Ishizone,R.Kato,Y.Ishino,A.Hirao,S.Nakahama: "Protection and Polymerization of Functional Monomers.15.Aniionic Living Polymerization of 2ー(3ーVinylphenly)ー1,3ーdioxolane and the Related Monomers" Macromolecules.
[Publications] T.Ishizone,A.Hirao,S.Nakahama: "Anionic Polymerization of Monomers Containing Functional Groups.2.Anionic Living Polymerization of 4ーCyanostyrene" Macromolecules.
[Publications] S.Nakahama,A.Hirao: "Protection and Polymerization of Functinal Monomers:Anionic Living Polymerization of Protected Monomers" Prof.Poly.Sci. 15. 299-335 (1990)
[Publications] Joji Ohshita,Daisuke Kanaya,Mitsuo Ishikawa,Toru Yamanaka: "POLYMERIC ORGANOSILICON SYSTEMS.PART 9.SYNTHESIS AND CONDUCTING PROPERTY OF POLY[(DISILANYLENE)FURYLENE]" Chem.Express. 5. 489-492 (1990)
[Publications] Joji Ohshita,Daisuke Kanaya,Mitsuo Ishikawa,Tuneaki Koike,Toru Yanamaka: "Polymeric Organosilicon Systems.10.Synthesis and Conducting Properties of Poly[2,5ー(disilanylene)ーthienylenes]" Macromolecules.
[Publications] Atsutaka Kunai,Toshihiro Kawakami,Eiji Toyoda,Mitsuo Ishikawa: "Electrochemistry of Organosilicon Compounds.2.Synthesis of Polysilane Oligomers by Copper Electrode System" Organometallics.
[Publications] S.Hirano,K.Kikuta and W.Sakamoto: "Solーgel Processing of Pb(Mg,Nb)O_3 Dielectrics" Ceramic Transactions. 12. 717-724 (1990)
[Publications] S.Hirano,K.Kikuta and K.Kato: "Processing of Stoichiometric and Ti Doped LiNbO_3 Films with Preferred Orientation from Metal Alkoxides" Mat.Res.Soc.Symp.Proc.200. 3-11 (1990)
[Publications] 遠藤剛、中浜精一他: "反応性ポリマ-の合成と応用" シ-・エム・シ-, (1989)
[Publications] 中浜精一、井上隆、千葉一正: "高性能ポリマ-アロイ" 丸善, (1991)

1990 Fiscal Year Annual Research Report

機能性材料作製のための反応設計

Principal Investigator

井上 祥平 東京大学, 工学部, 教授 (20010762)

Research Products

[Publications] 渡辺 喜彦・相田 卓三・井上 祥平: "Novel Visible LightーMediated Living and Immortal Polymerizations of Epoxides with Zinc Complexes of NーSubstituted Porphyrins." Macromolecules. 23. 2612-2617 (1990)

[Publications] 杉本 裕・相田 卓三・井上 祥平: "RingーOpening Polymerizations of Lactone and Epoxide Initiated with Aluminum Complexes of Substituted Tetraphenylporphyrins.Molecular Desing of Highly Active Initiators." Macromolecules. 23. 2869-2875 (1990)

[Publications] 相田 卓三・川口 健一・井上 祥平: "Zinc NーSubstituted Porphyrins as Novel Initiators for the Living and Immortal Polymerizations of Episulfide." Macromolecules. 23. 3887-3892 (1990)

[Publications] Z.Yoshida,T.Sugimoto,and Y.Misaki: "Electronーdonating Radialenes.Potential Donors for Molecular Organic (Super)Conductors and Ferromagnets" Materials Research Society Symposium Proceedings. 173. 3-14 (1990)

[Publications] T.Sugimoto,Y.Yamamoto,and Z.Yoshida: "Synthesis and Electrical Conductive Property of New Tellurium Polymers Containing Thiocarbonyl Group" Chemistry Letters. 2111-2114 (1990)

[Publications] T.Sugimoto,K.Ikeda,and J.Yamauchi: "Tris(ethylenedithio)ー and Tris(1,2ーbenzodithio)ーsubstituted Trimethylenemethanes" Chemistry Letters. 29-32 (1991)

[Publications] T.Sugimoto,A.Kawachi,K.Ikeda,and J.Yamauchi: "Synthesis of Tetrakis(1,2ーbenzodithio)tetramethyleneethane Dication Salt and Its Twoーelectron Reduction" Chemistry Letters. (1991)

[Publications] T.Sugimoto,M.Sakaguchi,H.Ando,Y.Arai,T.Tanaka,Z.Yoshida,J.Yamauchi,A.A.BothnorーBy,and M.Lisicki: "Unexpected Participation of an Excited Diradical Structure in the Ground state of Cyclic Bicalicene" Journal of the American Chemical Society. 113. (1991)

[Publications] K.Ueda,A.Hirao,S.Nakahama: "Synthesis of Polymers with Amino End Groups.3.Reactions of Anionic Living Polymers with ーHaloー ーaminoalkanes with a Protected Amino Functionality" Macromolecules. 23. 939-945 (1990)

[Publications] K.Takenaka,K.Kato,T.Hattori,A.Hirao,S.Nakahama: "Polymerization of Monomers Containing Functional Silyl Groups.8.Catalytic Hydrogenation of Poly(2ーsilylーsubstitutedー1,3ーbutadiene)s" Macromolecules. 23. 3619-3625 (1990)

[Publications] T.Taki,A.Hirao,S.Nakahama: "Polymerization of Monomers Containing Functional Silyl Groups.9.Anionic Living Polymerization of (4ーVinylphenyl)(n,Nーciethylamino)ーdimethylsilane" Macromolecules.

[Publications] T.Ishizone,R.Kato,Y.Ishino,A.Hirao,S.Nakahama: "Protection and Polymerization of Functional Monomers.15.Aniionic Living Polymerization of 2ー(3ーVinylphenly)ー1,3ーdioxolane and the Related Monomers" Macromolecules.

[Publications] T.Ishizone,A.Hirao,S.Nakahama: "Anionic Polymerization of Monomers Containing Functional Groups.2.Anionic Living Polymerization of 4ーCyanostyrene" Macromolecules.

[Publications] S.Nakahama,A.Hirao: "Protection and Polymerization of Functinal Monomers:Anionic Living Polymerization of Protected Monomers" Prof.Poly.Sci. 15. 299-335 (1990)

[Publications] Joji Ohshita,Daisuke Kanaya,Mitsuo Ishikawa,Toru Yamanaka: "POLYMERIC ORGANOSILICON SYSTEMS.PART 9.SYNTHESIS AND CONDUCTING PROPERTY OF POLY[(DISILANYLENE)FURYLENE]" Chem.Express. 5. 489-492 (1990)

[Publications] Joji Ohshita,Daisuke Kanaya,Mitsuo Ishikawa,Tuneaki Koike,Toru Yanamaka: "Polymeric Organosilicon Systems.10.Synthesis and Conducting Properties of Poly[2,5ー(disilanylene)ーthienylenes]" Macromolecules.

[Publications] Atsutaka Kunai,Toshihiro Kawakami,Eiji Toyoda,Mitsuo Ishikawa: "Electrochemistry of Organosilicon Compounds.2.Synthesis of Polysilane Oligomers by Copper Electrode System" Organometallics.

[Publications] S.Hirano,K.Kikuta and W.Sakamoto: "Solーgel Processing of Pb(Mg,Nb)O_3 Dielectrics" Ceramic Transactions. 12. 717-724 (1990)

[Publications] S.Hirano,K.Kikuta and K.Kato: "Processing of Stoichiometric and Ti Doped LiNbO_3 Films with Preferred Orientation from Metal Alkoxides" Mat.Res.Soc.Symp.Proc.200. 3-11 (1990)

[Publications] 遠藤 剛、中浜 精一他: "反応性ポリマ-の合成と応用" シ-・エム・シ-, (1989)

[Publications] 中浜 精一、井上 隆、千葉 一正: "高性能ポリマ-アロイ" 丸善, (1991)

井上祥平東京大学, 工学部, 教授 (20010762)

[Publications] 渡辺喜彦・相田卓三・井上祥平: "Novel Visible LightーMediated Living and Immortal Polymerizations of Epoxides with Zinc Complexes of NーSubstituted Porphyrins." Macromolecules. 23. 2612-2617 (1990)

[Publications] 杉本裕・相田卓三・井上祥平: "RingーOpening Polymerizations of Lactone and Epoxide Initiated with Aluminum Complexes of Substituted Tetraphenylporphyrins.Molecular Desing of Highly Active Initiators." Macromolecules. 23. 2869-2875 (1990)

[Publications] 相田卓三・川口健一・井上祥平: "Zinc NーSubstituted Porphyrins as Novel Initiators for the Living and Immortal Polymerizations of Episulfide." Macromolecules. 23. 3887-3892 (1990)

[Publications] K.Ueda,A.Hirao,S.Nakahama: "Synthesis of Polymers with Amino End Groups.3.Reactions of Anionic Living Polymers with ーHaloーーaminoalkanes with a Protected Amino Functionality" Macromolecules. 23. 939-945 (1990)

[Publications] 遠藤剛、中浜精一他: "反応性ポリマ-の合成と応用" シ-・エム・シ-, (1989)

[Publications] 中浜精一、井上隆、千葉一正: "高性能ポリマ-アロイ" 丸善, (1991)