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Basic and Applicative Studies on Controlled Radical Polymerization

Research Project

Project/Area Number 09450351
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

FUKUDA Takeshi  Kyoto Univ., Inst.Chem.Res., Assoc.Prof., 化学研究所, 教授 (00111972)

Co-Investigator(Kenkyū-buntansha) MINODA Masahiko  Kyoto Univ., Inst.Chem.Res., Instructor, 化学研究所, 助手 (30229786)
TSUJII Yoshinobu  Kyoto Univ., Inst.Chem.Res., Instructor, 化学研究所, 助手 (00217308)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥12,700,000 (Direct Cost: ¥12,700,000)
Fiscal Year 1998: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 1997: ¥9,900,000 (Direct Cost: ¥9,900,000)
KeywordsLiving radical / Mechanisms / Kinetics / Nitroxides / RAFT / ATRP / New polymers / Precistion Synthesis / 活性化速度定数 / 精密重合 / 表面グラフト / 均一ゲル / 糖鎖高分子 / リビングラジカル重合 / 安定ニトロキシル / 重合機構 / 精密反応解析 / フラーレン誘導体 / スチレン系グリコポリマー
Research Abstract

[I] Mechanisms and Kinetics of Controlled Radical Polymerizations
The mechanisms and kinetics of variants of controlled radical polymerization (CRP) were experimentally and theoretically studied and systematized. Main results include :
(1) Two general GPC methods for determining the rate constants of activation in CRPs were established.
(2) The GPC methods were applied to various CRP systems, and the activation rate constants and activation mechanism were established. In particular, it was confirmed that the thermal dissociation for the nitroxide system, the exchanging chain transfer for the PS-I and PS-SCSMe systems, and the atom transfer for the bromide/CuBr system are virtually the only mechanism of activation for the respective systems.
(3) A general equation describing the polymerization rates of CRP systems was developed and partly confirmed by experiments
[II] Precision Synthesis of New Polymer Materials by CRPs
(1) Low-polydispersity copolymers (randoms, blocks, polymacromonomers) and homopolymers (glucose residue-carrying styrenics, acrylates and methacrylates, fullerene-terminated polymers) with well-defined structure were synthesized mostly for the first time.
(2) Polymer gels, structurally much more homogeneous than conventional ones, were prepared for the first time.
(3) Polymer brushes with controlled chain length and chain length distribution, densely grafted on a silicon wafer, were successfully prepared for the first time.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (66 results)

All Other

All Publications (66 results)

  • [Publications] T.Fukuda: "Gel Permeation Chromatographic Determination of Activation Rate Constants in Nitroxide-Controlled Free Radical Polymerization, 2. Analysis of Evolution of Polydispersities" Macromol.Rapid Commun.18. 683-688 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Minoda: "Atom Transfer Radical Polymerization of Poly(vinyl ether)Macromonomers" Polymer Prepr.(Div.Polum.Chem., Am.Chem.Soc.). 40. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda: "Kinetics of Controlled Radical Polymerization" Polymer Prepr.(Div.Polum.Chem., Am.Chem.Soc.). 40. (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Tsujii: "Computer Simulation on the Kinetics of Nitroxide-Controlled Free Radical Polymerization" Polym.Prepr.(Div.Polym.Chem., Am.Chem.Soc.). 38. 657-658 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 福田 猛: "“リビング"ラジカル重合による高分子材料の新しい合成" 日化繊研究所講演集. 54. 1-10 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda: "Gel Permeation Chromatographic Determination of Activation Rate Constants in Nitroxide-Controlled Free Radical Polymerization, 2. Analysis of Evolution of Polydispersities" Macromol.Rapid Commun.18. 683-688 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda: "Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization" American Chemical Society, 20 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 福田 猛: "ラジカル重合-高分子の精密合成と新材料" NTS (印刷中), (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, Y.Tsujii, T.Fukuda: ""Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization. Thermal Degradation of 2,2,6,6-Tetramethyl-1-polystyroxy-piperidines"" Macromolecules. 30. 2503-2506 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Ide, T.Fukuda: ""Nitroxide-Controlled Free Radical Copolymerization of Vinyl and Divinyl Monomers. 1. Evaluation of Pendant-Vinyl Reactivity"" Macromolecules. 30. 4268-4271 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Goto, T.Fukluda: ""Effects of Radical Initiator on Polymerization Rate and Polydispersity in Nitroxide-Controlled Free Radical Polymerization"" Macromolecules. 30. 4272-4277 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Goto, T.Fukuda: ""Mechanism and Kinetics of Activation Processes in a Nitroxyl-Mediated Polymerization of Styrene"" Macromolecules. 30. 5183-5186 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Goto, T.Terauchi, T.Fukuda, T.Miyamoto: ""Gel Permeation Chromatographic Determination of Activation Rate Constants in Nitroxide-Controlled Free Radical Polymerization, 1.Direct Analysis by Peak Resolution"" Macromol.Rapid Commun.18. 673-682 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda, A.Goto: ""Gel Permeation Chromatographic Determination of Activation Rate Constants in Nitroxide-Controlled Free Radical Polymerization, 2.Analysis of Evolution of Polydispersities"" Macromol.Rapid Commun.18. 683-688 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Okamura, T.Terauchi, M.Minoda, T.Fukuda, K.Komatsu: ""Synthesis of 1,4-Dipolystryryldihydro[60]fullerenes by Using 2,2,6,6-Tetramethyl-1-polystyroxypiperidine as a Radical Source"" Macromolecules. 30. 5279-5284 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Tsujii, T.Fukuda, T.Miyamoto: ""Computer Simulation on the Kinetics of Nitroxide-Controlled Free Radical Polymerization"" Polym.Prepr.(Div.Polym.Chem., Am.Chem.Soc.). 38, (No.1). 657-658 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda, K.Ohno, A.Goto, Y.Tsujii, T.Miyamoto: ""Novel Synthesis of Polymer Materials by Living Radical Polymerization"" Proc.Ann.Meeting Inst.Chem.Fib.Jpn.54. 1-10 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, M.Ejaz, T.Fukuda, T.Miyamoto, Y.Shimizu: ""Nitroxide-Controlled Free Radical Polymerization of p-tert-Butoxystyrene. Kinetics and Applications"" Macromol.Chem.Phys.199. 291-297 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, Y.Tsujii, T.Miyamoto, T.Fukuda, M.Goto, K.Kobayashi, A.Akaike: ""Synthesis of a Well-Defined Glycopolymer by Nitroxide-Controlled Free Radical Polymerization"" Macromolecules. 31. 1064-1069 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Okamura, N.ide, M.Minoda, K.Komatsu, T.Fukuda: ""Solubility and Micellization Behavior of C60 Fullerenes with Two Well defined Polymer Arms"" Macromolecules. 31. 1859-1865 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, A.Goto, T.Fukuda, J.Xia, K.Matyjaszewski: ""Kinetic Study on the Activation Process in an Atom Transfer Radical Polymerization"" Macromolecules. 31. 2699-2701 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Goto, K.Ohno, T.Fukuda: ""Mechanism and Kinetics of Iodide-Mediated Polymerization of Styrene"" Macromolecules. 31. 2809-2814 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Ejaz, S.Yamamoto, K.Ohno, Y.Tsujii, T.Fukuda: ""Controlled Graft Polymerization of Methyl Methacrylate on Silicon Substrate by Combined Use of the Langmuir-Blodgett and Atom Transfer Radical Polymerization Techniques"" Macromolecules. 31. 5934-5936 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, Y.Tsujii, T.Fukuda: ""Synthesis of a Well-Defined Glycopolymer by Atom Transfer Radical Polymerization"" J.Polym.Sci., Polym.Chem.Ed., 36. 2473-2481 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, T.Fukuda, H.Kitano: ""Free Radical Polymerization of a Sugar Residue-Carrying Styryl Monomer with a Lipophilic Alkoxyamine Initiator : Synthesis of a Well-Defined Novel Glycolipid"" Macromol.Chem.Phys.199. 2193-2197 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, T.Fukuda: ""Synthesis of New Polymer by Living Radical Polymerization"" Polymer Applications. 47. 419-425 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, K.Fujimoto, Y.Tsujii, T.Fukuda: ""Synthesis of a Well-Defined Anthracene-Labeled Polystyrene by Atom Transfer Radical Polymerization"" Polymer. 40. 759-763 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] N.Ide, T.Fukuda: ""Nitroxide-Controlled Free-Radical Copolymerization of Vinyl and Divinyl Monomers.2.Gelation"" Macromolecules. 32. 95-99 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Goto, T.Fukuda: ""Kinetic Study on Nitroxide-Mediated Free Radical Polymerization of tert-Butyl Acrylate"" Macromolecules. 32. 618-623 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Yamada, M.Miyazaki, K.Ohno, T.Fukuda, M.Minoda: ""Atom Transfer Radical Polymerization of Poly(vinyl ether)Macromonomers"" Macromolecules. 32. 290-293 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda, A.Goto: ""Kinetics of Controlled Radical Polymerization"" Polymer Prepr.(Div.Polum.Chem., Am.Chem.Soc.). 40. (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Goto, K.Sato, T.Fukuda, G.Moad, E.Rizzardo, S.H.Thang: ""Mechanism and Kinetics of RAFT(Reversible Addition-Fragmentation Chain Transfer)-Based Controlled Radical Polymerization of Styrene"" Polymer Prepr.(Div.Polum.Chem., Am.Chem.Soc.). 40. (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] S.Yamamoto, M.Ejaz, K.Ohno, Y.Tsujii, M.Matsumoto, T.Fukuda: ""Preparation of Well-Defined Polymer Brushes on Silicon Substrate by the Surface-Initiated ATRP Technique and Their Characterization"" Polymer Prepr.(Div.Polum.Chem., Am.Chem.Soc.). 40. (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Minoda, K.Yamada, M.Miyazaki, M.Endo, K.Ohno, T.Fukuda: ""Atom Transfer Radical Polymerization of Poly(vinyl ether)Macromonomers"" Polymer Prepr.(Div.Polum.Chem., Am.Chem.Soc.). 40. (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Okamura, M.Minoda, T.Fukuda, T.Miyamoto, K.Komatsu: ""Solubility Characteristics of C60 Fullerenes with Two Well-Defined Polystyrene Arms in a Polystyrene Matrix"" Macromol.Rapid.Commun.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno, Y.Izu, S.Yamamoto, T.Miyamoto, T.Fukuda: ""Nitroxide-Controlled Free Radical Polymerization of a Sugar-Carrying Acryloyl Monomer"" Macromol.Chem.Phys.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda, A.Goto, K.Ohno: ""Feature Article : Mechanisms and Kinetics of Controlled Radical Polymerizations"" Macromol.Chem.Phys.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda, A.Goto, K.Ohno, Y.Tsujii: ""Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization"" Controlled Radical Polymerization(ACS Symposium Series 685, K.Matyjaszewski, Ed.), Chapter 11. 180-199 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Fukuda: ""Radical Polymerization-Precision Synthesis of Polymers and New Materials"" Chapter 2.2.2, NTS,Tokyo. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ohno: ""Radical Polymerization-Precision Synthesis of Polymers and New Materials"" Chapter 4.2.1, NTS,Tokyo. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 大野工司: "リビングラジカル重合法を用いた新しい高分子の合成" 高分子加工. 47. 419-425 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Nitroxide-Controlled Free Radical Polymerization of p-tert-Butoxystyrene. Kinetics and Applications" Macromol.Chem.Phys.199. 291-297 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Okamura: "Solubitity and Micellization Behavior of C60 Fullerenes with Two Well Defined Polymer Arms" Macromolecules. 31. 1859-1865 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Kinetic Study on the Activation Process in an Atom Transfer Radical Polymerization" Macromolecules. 31. 2699-2701 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] A.Goto: "Mechanism and Kinetics of Iodide-Mediated Polymerization of Styrene" Macromolecules. 31. 2809-2814 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] M.Ejaz: "Controlled Graft Polymerization of Methyl Methacrylate on Silicon Substrate by Conbined Use of the Langmuir-Blodgett and Atom Transfer Radical Polymerization Techniques" Macromolecules. 31. 5934-5936 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Synthesis of a Well-Defined Glycopolymer by Atom Transfer Radical Polymerization" J.Polym.Sci.,Polym.Chem.Ed.36. 2473-2481 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Free Radical Polymerization of a Sugar Residue-Carrying Styryl Monomer with a Lipophilic Alkoxyamine Initiator: Synthesis of a Well-Defined Novel Glycolipid" Macromol.Chem.Phys.199. 2193-2197 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Synthesis of a Well-Defined Anthracene-Labeled Polystyrene by a Arom Transfer Radical Polymerization" Polymer. 40. 759-763 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Ide: "Nitroxide-Controlled Free-Radical Copolymerization of Vinyl and Divinyl Monomers.2.Gelation" Macromolecules. 32. 95-99 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] A.Goto: "Kinetic Study on Nitroxide-Mediated Free Radical Polymerization of tert-Buryl Acrylate" Macromolecules. 32. 618-623 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Yamada: "Atom Transfer Radical Polymerization of Poly(vinyl ether) Macromonomers" Macromolecules. 32. 290-293 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Okamura: "Solubility Characteristics of C60 Fullerenes with Two Well-Defined Polystyrene Arms in a Polystyrene Matrix" Macromol.Rapid Commun.(in press). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Nitroxide-Controlled Free Radical Polymerization of a Sugar-Carrying Acryloyl Monomer" Macromol.Chem.Phys.(in press). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Fukuda: "Feature Article: Mechanisms and Kinetics of Controlled Radical Polymerizations" Macromol.Chem.Phys.(in press). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Fukuda: "Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization" American Chemical Society, 20 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 福田 猛: "ラジカル重合-高分子の精密合成と新材料" NTN, 印刷中

    • Related Report
      1998 Annual Research Report
  • [Publications] 大野工司: "ラジカル重合-高分子の精密合成と新材料" NTN (印刷中),

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Ohno: "Mechanism and Kinetics of Nitroxide-Controlled Free Radical Polymerization. Thermal Degradation of 2,2,6,6-Tetramethyl-1-polystyroxy-piperidines" Macromolecules. 30. 2503-2506 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Ide: "Nitroxide-Controlled Free Radical Copolymerization of Vinyl and Divinyl Monomers. Evaluation of Pendant-Vinyl Reactivity" Macromolecules. 30. 4268-4271 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Goto: "Effects of Radical Initiator on Polymerization Rate and Polydispersity in Nitroxide-Controlled Free Radical Polymerization" Macromolecules. 30. 4272-4277 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Goto: "Mechanism and Kinetics of Activation Processes in a Nitroxyl-Mediated Polymerization of Sryrene" Macromolecules. 30. 5183-5186 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] A.Goto: "Gel Permeation Chromatographic Determination of Activation Rate Constants in Nitroxide-Controlled Free Radical Polymerization. 1. Direct analysis by Perk Resolution" Macromol.Rapid Commun.18(8). 673-682 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Fukuda: "Gel Permeation Chromatographic Determination of Activation Rate Constants in Nitroxide-Controlled Free Radical Polymerization. 2. Analysis of Evolution of Polydispersities" Macromol.Rapid Commun.18(8). 683-688 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Okamura: "Synthesis of 1,4-Dipolystyryldihydro [60] fullerenes by Using 2,2,6,6-Tetrmethyl-1-polystyroxypiperidine as a Radical Source" Macromolecules. 30. 5279-5284 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Ohno: "Synthesis of a Well-Defined Glycopolymer by Nitroxide Controlled Free Radical Polymerization" Macromolecules. 31. 1064-1069 (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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