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Development of Living Radical Emulsion Polymerization

Research Project

Project/Area Number 12555260
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section展開研究
Research Field 高分子合成
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

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

Co-Investigator(Kenkyū-buntansha) NISHIZAWA Satoru  Mitsubishi Chem., Inc. Team Leader, ポリマー材料研究所, プロジェクトリーダー
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥6,000,000 (Direct Cost: ¥6,000,000)
Fiscal Year 2002: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 2001: ¥3,000,000 (Direct Cost: ¥3,000,000)
KeywordsLiving Radical Polymerization / Emulsion Polymerization / Dispersion Polymerization / RAFT Polymerization / High Molecular Weight / Low Polydispersity / Monodisperse Particles / Degenerative Transfer / 1-フェニルエチルヨウ素 / クミルジチオベンゾエート / RAFT剤 / ヨウ素移動重合 / RAFT重合 / 移動速度定数 / 均一系
Research Abstract

It is theoretically predicted that the degenerative chain transfer-mediated living radical polymerization (LRP) carried out in an emulsion or dispersion polymerization system under specific conditions will provide an elongated radical lifetime and an increased frequency of degenerative chain transfer. In other words, LRP carried out in the inhomogeneous system is predicted to give longer chains with a lower polydispersity and a higher fraction of chain end activity (livingness) than LRP carried out in a homogeneous system. In order to test these theoretical predictions, polymerization of methyl methacrylate (MMA) and styrene were carried out in an emulsion and a dispersion system. Notable results obtained in the dispersion system will be reported below.
Optimization of the aqueous-phase solvent (75% ethanol), dispersant (polyacrilic acid), and temperature (70℃), resulted in PMMA with a number-average molecular weigh about 1.0 x 10^5 and a polydispersity index M_w/M_n about 1.1, verifying the theory. However, some mutual adhesion of the PMMA particles was observed, which remains to be a problem to be solved. In the styrene polymerization, in which polyvinyl pyrrolidone was used as a dispersant, no such adhesion of the particles was observed. The polymerization gave polystyrene particles of controllable and homogeneous size (typically 2μm) composed of well defined polystyrene. For both MMA and styrene, the polymerization was completed in a short time, meaning that the effective radical concentration was exceptionally high, and thus increasing the performance, and making better use, of the degenerative chain transfer type of LRP.

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (40 results)

All Other

All Publications (40 results)

  • [Publications] A.Goto: "Mechanism and Kinetics of RAFT-Based Polymerizations of Styrene and Methyl Methacrylate"Macromolecules. 34. 402-408 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Tsujii: "Mechanism and Kinetics of RAFT-Mediated Graft Polymerization of Styrene on a Solid Surface. 1. Experimental Evidence of Surface Radical Migration"Macromolecules. 34. 8872-8878 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Fukuda: "Penultimate Unit Effects in Free Radical Copolymerization"Macromol. Symp.. 182. 53-64 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y.Kwak: "A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition-Fragmentation Chain Transfer"Macromolecules. 35. 3026-3029 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A.Goto: "Comparative Study on Decomposition Rate Constants for Some Alkoxyamines"Macromolecules. 35. 3520-3525 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C.Yoshikawa: "Reactions of Polystyryl Radicals in A Monomer-Free Atom Transfer Radical Polymerization System"e-Polymers. 013. (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C.Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated Polymerization"Macromolecules. 35. 5801-5807 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C.Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 2. Atom Transfer Radical Polymerization"Macromolecules. 36. 908-912 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Fukuda: "Mechanisms and Kinetics of Living Radical Polymerization : Absolute Comparison of Theory and Experiment"ACS Symp. Ser.. 854. 24-40 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Fukuda: ""Handbook of Radical Polymerization", K. Matyjaszewski, T. P. Davis, Ed."John Wiley & Sons, New York. 70 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Goto: "Mechanism and Kinetics of RAFT-Based Polymerizations of Styrene and Methyl Methacrylate"Macromolecules. 34. 402-408 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Tsujii: "Mechanism and Kinetics of RAFT-Mediated Graft Polymerization of Styrene on a Solid Surface. 1. Experimental Evidence of Surface Radical Migration"Macromolecules. 34. 8872-8878 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Fukuda: "Penultimate Unit Effects in Free Radical Copolymerization"Macromol. Symp,. 182. 53-64 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Y. Kwak: "A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition-Fragmentation Chain Transfer"Macromolecules. 35. 3026-3029 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] A. Goto: "Comparative Study on Decomposition Rate Constants for Some Alkoxyamines"Macromolecules. 35. 3520-3525 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C. Yoshikawa: "Reactions of Polystyryl Radicals in A Monomer-Free Atom Transfer Radical Polymerization System"e-Polymers. no.013. (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C. Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated Polymerization"Macromolecules. 35. 5801-5807 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C. Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 2. Atom Transfer Radical Polymerization"Macromolecules. 36. 908-912 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Fukuda: "Mechanisms and Kinetics of Living Radical Polymerization: Absolute Comparison of Theory and Experiment"ACS Symp. Ser.. 854. 24-40 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T. Fukuda, K. Matyjaszewski, T. P. Davis, Ed.: "Handbook of Radical Polymerization"John Wiley & Sons. (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] C.Yoshikawa: "Reactions of Polystyryl Radicals in a Monomer-Free Atom Transfer Radical Polymerization System"e-Polymer. 013. (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Kwak: "A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition-Fragmentation Chain"Macromolecules. 35. 3026-3029 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Goto: "Comparative Study on Decomposition Rate Constants for Some Alkoxyamines"Macromolecules. 35. 3520-3525 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Fukuda: "Penultimate Unit Effects in Free Radical Copolymerization"Macromol. Symp.. 182. 53-64 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] C.Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated"Macromolecules. 35. 5801-5807 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] C.Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 2. Atom Transfer"Macromolecules. 36. 908-912 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Fukuda: "Handbook of Radical Polymerization "Matyjaszewski, K. ; Davis, T.P.Ed"John Wiley & Sons, New York. 70 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] K.Yamada: "Amphiphilic Blocck and Statistical Copolymers with Pendant Glucose Residues : Controlled Synthesis by Living Radical Cationic Polymerizayion and The Effects of Copolymer Architecture on Their Properties"J.Polym.Sci., Polym.Chem. 39. 459-467 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.-D.Ma: "Free-Radical Copolymerization of Styrene and Diethyl Fumarate. Penultimate-Unit Effects on Both Propagation and Termination Processes"Macromolecules. 34. 4749-4756 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Fukuda: "Penultimate Unit Effects in Free Radical Copolymerization"Macromol.Symp. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Kwak: "A Kinetic Study on the Rate Retardation in Radical Polymerization of Styrene with Addition-Fragmentation Chain Transfer"Macromolecules. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Goto: "Comparative Study on Decomposition Rate Constants for Some Alkoxyamines"Macromolecules. (印刷中). (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] C.Yoshikawa: "Reactions of Polystyryl Radicals in A Monomer-Free Atom Transfer Radical Polymerization System"e-Polymers. 013. (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] 福田 猛: "最近のリビングラジカル重合"未来材料. 1. 14-21 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Fukuda: "Handbook of Radical Polymerization", K. Matyjaszewski, T. P. Davis, Ed."John Wiley & Sons, New York. 70 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Fukuda: "(Feature Article) Mechanisms and Kinetics of Controlled Radical Polymerizations."Macromol.Rapid Commun.. 21. 151-165 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Goto: "Comparative Study on Activation Rate Constants for Some Styrene/Nitroxide Systems."Macromol.Chem.Phys.. 201. 2138-2142 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] T.Fukuda: "Kinetics of Living Radical Polymerization."ACS Symp.Ser.. 768. 27-3 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Goto: "Effects of Acetic Anhydride on the Activation and Polymerization Rates in Nitroxide-Mediated Polymerization of Styrene."Chem.Lett.. 788-789 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] A.Goto: "Mechanism and Kinetics of RAFT-Based Polymerization of Styrene and Methyl Methacrylate."Macromolecules. 34. 402-408 (2001)

    • Related Report
      2000 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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