重合反応の精密制御とその応用に関する総合的研究

1990 Fiscal Year Annual Research Report

• Project/Area Number: 01303008
• Research Institution: University of Tokyo
• Principal Investigator: 井上 祥平 東京大学, 工学部, 教授 (20010762)
• Co-Investigator(Kenkyū-buntansha): 福田 清成 埼玉大学, 理学部, 教授 (80008789) ; 平井 英史 東京理科大学, 工学部, 教授 (90010751) ; 竹本 喜一 大阪大学, 工学部, 教授 (50029170) ; 岡本 佳男 名古屋大学, 工学部, 教授 (60029501) ; 東村 敏延 京都大学, 工学部, 教授 (20025860)
• Keywords: リビング重合 / 共重合 / 立体規則性ポリマ- / 光学活性ポリマ- / 包接重合 / 薄膜 / 二分子膜 / LB膜

Research Abstract

重合反応の制御は、高性能・高機能の高分子材料の分子設計にとって最も基本的で重要な課題である。なかでも、分子量の制御とそれを応用するブロック共重合体や末端官能性ポリマ-の合成、立体化学の制御とそれを利用する光学活性ポリマ-の合成とその応用、モノマ-の集合状態における重合と生成組織体の応用などが重要である。本研究は、この見地から高分子材料の分子設計の一般的原理となり得るような重合反応の精密制御の方法を確立しその応用への基礎を築くことを目的とし、具体的には、1)分子量の制御、2)立体化学の制御、3)共重合配列の制御、4)集合状態の制御の各分野について、相互に関連させた有機的、総合的な研究を行って来た。その結果次の各項目について夫々すぐれた成果が得られた。1)<分子量の制御>___ー:i)リビングカチオン重合によるビニルポリマ-の精密制御。ii)アニオンリビング重合による反応性高分子の分子量制御。iii)リビング配位重合によるポリオレフィンの分子量制御。iv)ポルフィリン錯体による開環、付加重合の制御;これらによるブロックコポリマ-、末端官能性ポリマ-の合成。2)<立体化学の制御>___ー:i)コンホメ-ションに由来する光学活性ポリマ-の合成と応用。ii)立体制御された多糖の合成とその生理性化。iii)包接重合による立体化学の制御。3)<共重合配列の制御>___ー:i)金属塩を用いるラジカル共重合の制御。ii)高分子反応による周期コポリマ-の合成と物性。4)<集合状態の制御>___ー:i)層状組織体における重合反応の制御。ii)2分子膜の分子集合状態による重合制御。iii)導電性高分子の超ミクロ構造制御。iv)高分子LB膜の調製と光誘起電子移動反応。v)固相重付加反応による高結晶性共役高分子薄膜の合成。

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 Design 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] 青島 貞人: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides.3.Living Polymerization of Isobutyl Vinyl Ether by EtAlCl_2 in the Presence of Ester Additives" Macromolecules. 22. 1009-1013 (1989)
• [Publications] 岸本 恭尚: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides.4.Polymerization of Isobutyl Vinyl Ether by EtAlCl_2 in the Presence of Ether Additives" Macromolecules. 22. 3877-3882 (1989)
• [Publications] 東村 敏延: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides.5.Polymerization of Isobutyl Vinyl Ether with EtAlCl_2 in the Presence of 2,6ーDimethylpyridine and Related Amines" Polymer Journal. 21. 725-732 (1989)
• [Publications] 小島 和重: "Living Cationic Polymerization of Isobutyl Vinyl Ether by Hydrogen Iodide/Lewis Acid Initiating Systems:Effects of Lewis Acid Activators and Polymerization Kinetics" Macromolecules. 22. 1552-1557 (1989)
• [Publications] 小島 和重: "Living Cationic Polymerization of pーMethoxystyrene by the HI/ZnI_2 and HI/I_2 Initiating Systems:Effects of Tetrabutylammonium Halides in a Polar Solvent" Macromolecules. 23. 948-953 (1990)
• [Publications] 上垣外 正己: "Living Cationic Polymerization of Isobutyl Vinyl Ether by Me_3SiI/Lewis Acid Systems in the Presence of Acetone:Initiation via a Silyloxycarbocation" Macromolecules. 23. 4896-4901 (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] 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Vinylphenyl)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 Functional Monomers:Anionic Living Polymerization of Protected Monomers" Prof.Poly.Sci.,. 15. 299-335 (1990)
• [Publications] Y.Doi,N.Ohgizawa,N.Nunomura,K.Soga: "Synthesis and Characterization of a Diblock Copolymes of Propylene and Methyl methacrylate" Makromol.Chem.,Rapid Commun.12. (1991)
• [Publications] Yoshio Okamoto,Haruhiko Mohri,Tamaki Nakano,and Koichi Hatada: "Stereomutation of Optically Active Poly(diphenylー2ーpyridylmethyl methacrylate)" Journal of the American Chemical Society. 111. 5952-5954 (1989)
• [Publications] Yoshio Okamoto,Tamaki Nakano,Toshikage Asakura,Haruhiko Mohri,and Koichi Hatada: "Asymmetric Polymerization of Optically Active Phenylー2ーpyridylーmーtolylmethyl Methacrylate and Stereomutation of the Polymer" Journal of Polymer Science:Part A:Polymer Chemistry,in press. 29. (1991)
• [Publications] Yoshio Okamoto,Tamaki Nakano,Etsuko Ono,and Koichi Hatada: "Synthesis and Reversible Stereomutation of Optically Active Poly[(S)ーdiphenyl(1ーmethylpyrrolidinー2ーyl)methyl methacrylate]" Chemistry Letters,.
• [Publications] Tamaki Nakano,Yoshio Okamoto,and Koichi Hatada: "Asymmetric Polymerization of Triphenylmethyl Methacrylate Leading to OneーHanded Helical Polymer:Mechanism of Polymerization" Macromolecules,.
• [Publications] T.Uryu and J.ーC.Song: "Thermotropic LiquidーCrystalline Copoly(ester amides) and Copolyamides Containing a Flexible Spacer in the Main Chain" Polym.J.,. 21. 977-986 (1989)
• [Publications] Y.Kaneko,O.Yoshida,R.Nakagawa,T.Yoshida,M.Date,S.Ogiwara,S.Shioya,Y.Matsuzawa,N.Nagashima,Y.Irie,T.Mimura,H.Shinkai,N.Yasuda,K.Matsuzaki,T.Uryu,and N.Yamamoto: "Complete Inhibition of HIVー1 Infectivity with Curdlan Sulfate <in Vitro>___ー" Biochem.Pharm.,. 39. 793-797 (1990)
• [Publications] T.Yoshida,K.Hatanaka,T.Uryu,Y.Kaneko,E.Suzuki,H.Miyano,T.Mimura,O.Yoshida,and N.Yamamoto: "Synthesis and Structural Analysis of Curdlan Sulfate with a Potent Inhibitory Effect of AIDS Virus Infection" Macromolecules,. 23. 3717-3722 (1990)
• [Publications] K.Hatanaka,T.Hirobe,T.Yoshida,M.Yamanaka,and T.Uryu: "Synthesis and Sulfation of Branched Dextrans" Polym.J.,. 22. 435-441 (1990)
• [Publications] K.Hatanaka,Y.Yoshida,T.Yoshida,and T.Uryu: "Synthesis of Polymerizable Anhydro Deoxyribose Derivatives" Carbohydr.Res.,. (1990)
• [Publications] T.Yoshida,L.Song,P.C.Wu,K.Hatanaka,and T.Uryu: "Selective Synthesis of CelluloseーType Copolymers by RingーOpening Copolymerization of 1,4ーAnhydroーαーDーribopyranose Derivatives" Chem.Lett.,.
• [Publications] H.Tsutsumi,K.Okanishi,M.Miyata,K.Takemoto: "Inclusion polymerization of 1ーchlorobutadiene in a deoxycholic acid canal" J.Polymer Sci.:Part A;Polymer Chemistry. 28. 1527-1538 (1990)
• [Publications] M.Miyata,M.Shibakami,S.Chirachanchai,K.Takemoto,N.Kasai,K.Miki: "Guestーresponsive structural changes in cholic acid intercalation crystals" Nature. 343. 446-447 (1990)
• [Publications] Y.Gotoh,T.Iihara,N.Kanai,N.Toshima,H.Hirai,: "Synthesis of Highly Coheterotactic Poly(Metyl MethacrylateーaltーStyrene)" Chemistry Letters. 2157-2160 (1990)
• [Publications] H.Hirai,: "Sequence Regulation in Radical Copolymerization of Methacrylate and Styrene" J.Macromol.Sci.ーChem.
• [Publications] 平林 忠道・山内 幸二・横田 健二: "Synthesis of SequenceーOrdered Copolymer.Synthesis of EthyleneーMethyl Methacrylate Alternating Copolymer by a Polymer Reaction" Macromolecules. 23. 935-939 (1990)
• [Publications] 平林 忠道・山内 幸二・横田 健二: "Synthesis of SequenceーOrdered Copolymer.Synthesis of Alternating Copolymers Containing Some Allyl Derivatines Units" Macromolecules.
• [Publications] 平林 忠道・山内 幸二・横田 健二: "Synthesis of SequenceーOrdered Copolymer.Synthesis of Some Alternating and Periodic Copolymers by Polymer Reactions" Macromolecules.
• [Publications] 横田 健二・三輪 雅申・今泉 幸博・平林 忠道・稻井 嘉人: "Glass Transition Temperatures of SequenceーOrdered andーUnordered Copolymers" Macromolecules.
• [Publications] K.Fukuda,Y.Shibasaki,H.Nakahara and H.Endo: "Control of Polymerization Reactions and Polymer Structures through the Molecular Orientation of Amphiphilic Monomers in LangmuirーBlodgett Films." Thin Solid Films. 179. 103-108 (1989)
• [Publications] K.Fukuda,Y.Shibasaki and H.Nakahara: "Control of Polymerization Reactions by Specified Arrangements of Monomer Molecules in LB Films." Proc.The 1990 ChinaーJapan Bilateral Symposium on LangmuirーBlodgett Films(Beijing,China). 37-38 (1990)
• [Publications] Y.Shibasaki and K.Fukuda: "Surface Effects on Phase Transition Behaviour and Thermal Polymerization of LongーChain Compounds in Micro DSC Measurements." Thermochimica Acta.
• [Publications] S.Kato,T.Kunitake: "Aqueous Bilayers of GlutamateーBased DoubleーChain Ammonium Anphiphiles.II.Impraement of Polymeriy atim and Membrane Characteristics by EtherーLinhed Alkye Tailo" Polym.Jo,. 23. 135-146 (1991)
• [Publications] S.Kato,T.Kunitake: "Molecules・Design of Blach Lipid Menlrane(BLM) by Polymerized DoubleーChain Ammonium Amphiphiles" Chem.Lett.,. 1991. 261-264 (1991)
• [Publications] T.Shimidzu: "Functionalized Conducting Polymer Materials toward Molecular Device" Mol.Cryst.Liq.Cryst.190. 75-83 (1990)
• [Publications] T.Iyoda,A.Ohtani,K.Honda,T.Shimidzu: "Diaphragmatic Chemical Polymeri zation of Pyrrole in the Nafion Film" Macromolecules. 23. 1971-1976 (1990)
• [Publications] T.Shimidzu,T.Iyoda,M.Ando,K.Honda: "Ultarーanisotropic Conducting Polymer LB Multilayer" Adv.Mat.Res.1. 237-240 (1990)
• [Publications] M.Ando,Y.Watanabe,T.Iyoda,K.Honda,T.Shimidzu: "Syntheses of Conducting Polymer LangmuirーBloagett Multilayers" Thin Solid Films. 179. 225-231 (1990)
• [Publications] T.Shimidzu: "Derivatization of Conducting Polymers with Functional Molecules and Molecular Structural Control toward Molecular Device" Reactive Polymers. 11. 177-189 (1989)
• [Publications] H.Segawa,H.Nishino,T.Kamikawa,K.Honda,T.Shimidzu: "Heteroーaggregation between Gold Porphyrins and Zinc Porphyrins through Charge Transfer Interaction" Chem.Lett.1917-1920 (1989)
• [Publications] T.Miyashita,Y.Mizuta,and M.Matsuda: "Studies on LangmuirーBlodgett Multilayer Formation from Preformed Poly(Nーalkylacrylamides)" British Polymer Journal. 22. 327-331 (1990)
• [Publications] T.Miyashita,T.Yatsue,and M.Matsuda: "Polymer LB Films Containing Photofunctional Group.2.Electron Transfer Quenching in Polymer LB Films Containing Carbazole Chromophore" The Journal of Physical Chemistry. 95. (1991)
• [Publications] Eiichi Kobayashi,Toyoshi Ohashi,Junji Furukawa: "Phase transition of layer structure of poly(pーbenzenedithiolーcoーdiethynylbenzene) by heat or photon mode" Polymers for Advanced Technologies.
• [Publications] Eiichi Kobayashi,Yukihiro Terada Toyoshi Ohashi,Junji Furukawa: "Molecular interaction between 1,4ーbenzenedithiol and 1,4ーdiethynylbenzene" Polymer Journal.
• [Publications] Eiichi Kobayashi,Takatsugu Obata,Sadahito Aoshima,Junji Furukawa: "Polyaddition of dithiol compounds to diethynyl compounds:kinetics of the model addition reaction of thiophenol to ethynylbenzene" Polymer Journal. 22. 1035-1042 (1990)
• [Publications] Eiichi Kobayashi,Jian Jiang,Hirotoshi Ohta,Junji Furukawa: "Novel conjugated polymer containing anthracene backbone:addition polymer of 9,10ーdiethynylanthracene with 9,10ーanthracenedithiol and its properties" Journal of Polymer Science:Part A:Polymer Chemistry. 28. 2641-2650 (1990)
• [Publications] Toyoshi Ohashi,Eiichi Kobayashi,Junji Furukawa: "Effect of photolysis wavelength on the addition polymerization of 1,4ーbenzenedithiol to 1,4ーdiethynylbenzene in solid state" Journal of Polymer Science:Part C:Polymer Letters. 27. 247-252 (1989)
• [Publications] Eiichi Kobayashi,Toyoshi Ohashi,Junji Furukawa: "Microstructure of an addition polymer composed of 1,4ーbenzenedithiol and 1,4ーdiethynylbenzene" Polymer Journal. 21. 111-117 (1989)
• [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)
• [Publications] S.Penczek,T.Uryu: "“Polysaccharides",in “Models of Biopolymers by RingーOpening Polymerizations"," CRC Press,P133-234 (1990)
• [Publications] T.Uryu,Y.Yoshida,N.Ikushima,K.Hatanaka,Y.Kaneko,T.Mimura,H.Nakashima,and N.Yamamoto: "Sulfated Polysaccharides as a Potent and Selective Inhibitor of AIDS Virus Infection" Tata McGraw Hill,New Delhi,989-996 (1991)