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1989 Fiscal Year Final Research Report Summary

Development of Living Cationic Polymerization: Novel Methods for Controlled Polymer Synthesis

Research Project

Project/Area Number 63470099
Research Category

Grant-in-Aid for General Scientific Research (B)

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

Principal Investigator

HIGASHIMURA Toshinobu  Kyoto University Professor, 工学部, 教授 (20025860)

Co-Investigator(Kenkyū-buntansha) SAWAMOTO Mitsuo  Kyoto University Research Instructor, 工学部, 助手 (90150325)
Project Period (FY) 1988 – 1989
KeywordsCationic Polymerization / Living Polymerization / Initiator / Carbocation / Living Polymer / Block Copolymer / Vinyl Ether / Styrene Derivative
Research Abstract

This research project was directed toward three objectives: (a) to establish general principles of living cationic polymerization; (b) to develop new initiating systems for high-temperature living cationic processes; and (c) to expand the scope of living cationic polymerization to a variety of monomers.
(a) General Principles of Living Cationic Polyrarization. Living cationic polymerization has been difficult because of the iherent instability of the carbocationic intermediate therein. We theorized that "nucleophilic stabilization" of the unstable growing carbocation might lead to living pationic polymerization. On the basis of this hypothesis, we have proposed two methods to stabilize the growing carbocations; (A) stabilization by a suitably nucleophilic counteranion; and (B) stabilization by a added weak Lewis base. Both principles have been shown valid and thus led to a variety of new initiating systems.
(b) High-Temperature Living Cationic Polymerization in the Presence of Added Base … More s. In general, strongly acidic metal halides (like EtAlCl_2) cannot induce living cationic polymerization, because they generate counteranions too weakly nucleophilic to stabilize the growing carbocations. Our principle (B) turned out specifically effective for these systems; and addition of such weak Lewis bases as esters, ethers, and pyridine derivatives was found to stabilize the growing cation through nuclephilic interaction and thereby allows living cationic polymerization of vinyl ethers at temperatures as high as +70 ゚C.
(c) Living Cationic Polyrarization of Styrene Derivatives. With use of the hydrogen iodide/zinc iodide (HI/ZnI_2) initiating system, which is based on our principle (A), living cationic polymerization has been achieved not only for vinyl ethers but also for styrene derivatives. Specifically, well-defined living polymers were obtained from p-t-butoxystyrene even at room temperature, though it carries an acid-sensitive alkoxyl group. Hydrolysis of the polymer led to poly(p-vinylphenol) of a controlled molecular weight. Block copolymers of p-t-butoxystyrene with various vinyl monomers were also synthesized. Less

  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] 東村敏延: "New Initiators for Living Cationic Polymerization of Vinyl Compounds" Makromol.Chem.,Macromol.Symp.13/14. 457-471 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 東村敏延: "Living Cationic Polymerization of Vinyl Monomers:Control of Propagating Species with Added Bases" Frontiers of Macromolecular Science(T.Saegusa,T.Higashimura,A.Abe,eds.,Blackwell,Oxford). 67-72 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [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)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 岸本恭尚: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides.4.Living Polymerization of Isobutyl Vinyl Ether by EtAlCl_2 in the Presence of Ester Additives" Macromolecules. 22. 3877-3882 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 東村敏延: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides.5.Living Polymerization of Isobutyl Vinyl Ether by EtAlCl_2 in the Presence of 2,6-Dimethylpyridine and Related Amines" Polymer Journal. 21. 725-732 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 東村敏延: "Living Cationic Polymerization of 4-tert-Butoxystyrene and Synthesis of Poly(4-vinylphenol)with Narrow Molecular Weight Distribution" Makromol.Chem.,Suppl.15. 127-136 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 小島和重: "Block Copolymers of p-t-Butoxystyrene with Isobutyl Vinyl Ether or Styrene Derivatives:Synthesis of Amphiphilic Macromolecules" Macromolecules (投稿中).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T. Higashimura, S. Aoshima, and M. Sawamoto: "New Initiators for Living Cationic Polymerization of Vinyl Compounds" Makromol. Chem., Macromol. Symp., 13/14, 457-471 (1988).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Higashimura, M. Sawamoto, S. Aoshima, Y. Kishimoto, and E. Takeuchi: "Living Cationic Polymerization of Vinyl Monomers: Control of Propagating Species with Added Bases" Frontier of Macromolecular Science, Blackwell, Oxford, pp. 66-72 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S. Aoshima and T. Higashimura: "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).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Kishimoto, S. Aoshima, and T. Higashimura: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides. 4. Living Polymerization of Isobutyl Vinyl Ether by EtAlCl_2 in the Presence of Ether Additives" Macromolecules, 22, 3877-3883 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Higashimura, S. Okamoto, Y. Kishimoto, and S. Aoshima: "Living Cationic Polymerization of Vinyl Monomers by Organoaluminum Halides. 5. Living Polymerization of Isobutyl Vinyl Ether by EtAlCl_2 in the Presence of 2,6-Dimethylpyridine and Related Amines" Polymer Journal, 21, 725-732 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T. Higashimura, K. Kojima, and M. Sawamoto: "Living Cationic Polymerization of 4-tert-Butoxystyrene and Synthesis of Poly(4-vinylphenol) with Narrow Molecular Weight Distribution" Makromol. Chem., Suppl., 15, 127-136 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K. Kojima, M. Sawamoto, and T. Higashimura: "Block Copolymers of p-t-Butoxystyrene with Isobutyl Vinyl Ether or Styrene Derivatives: Synthesis of Amphiphilic Macromolecules" Macromolecules.

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1993-03-26  

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