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1998 Fiscal Year Final Research Report Summary

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
KeywordsLiving radical / Mechanisms / Kinetics / Nitroxides / RAFT / ATRP / New polymers / Precistion Synthesis
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.

  • Research Products

    (40 results)

All Other

All Publications (40 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 1999-12-08  

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