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DESIGN OF POLYMERIC MICROSPHERES USING MACROMONOMERS

Research Project

Project/Area Number 07555597
Research Category

Grant-in-Aid for Scientific Research (A)

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

Principal Investigator

ITO Koichi  Toyohashi University of Technology, Faculty of Engineering, Professor, 工学部, 教授 (00023119)

Co-Investigator(Kenkyū-buntansha) YABUTA Motoshi  Kansai Paint Co., Ltd., Research Laboratory, Research Manager, 技術研究所, 部長(研究職)
KAWAGUCHI Seigou  Toyohashi University of Technology, Faculty of Engineering, Research Associate, 工学部, 助手 (00204694)
ITSUNO Shinichi  Toyohashi University of Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (50158755)
薮田 元志  関西ペイント(株), 技術研究所, 部長(研究職)
Project Period (FY) 1995 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥2,500,000 (Direct Cost: ¥2,500,000)
Fiscal Year 1997: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1996: ¥1,300,000 (Direct Cost: ¥1,300,000)
KeywordsMacromonomer / Polymeric microspheres / Dispersion polymerization / Emulsion polymerization / Poly (ethylene oxide) / Poly (methacrylic acid) / Theory of particle size control / Comb polymer / ブラシ鎖 / 高分子微粒子 / 単分散ミクロスフェア / 立体安定化 / カルボキシル基 / 無公害塗料 / 両親媒性 / 分散、乳化重合 / 表面特性 / ミクロスフェア- / グラフト高分子
Research Abstract

This research project aimed at designed synthesis of polymeric microspheres by taking advantage of amphiphilic macromonomers. Poly (ethylene oxide) (PEO) and poly (methacrylicacid) (PMA) macromonomers carrying stryl or methacrylate end groups, hydrophobically enhanced by alkylene spacers, are reasonably expected and in fact found to work as effective, reactive (copolymerizable) emulsifiers and disperants in emulsion dispersion polymerizations of hydrophobic monomers in water and alcoholic media. Thus the macromonomers copolymerized with the comonomers to produce in situ the graft copolymers, the branches of which cover the particle surfaces to effect steric stabilization while the trunks serve as the anchors into the particles. This project has proposed a basic mechanism and theory of the formation of such sterically-stabilized polymeric particles and has applied the theory to various emulsion and dispersion systems using the PEO and PMA macromonomers to establish a fundamental guideli … More ne to the microspheres, design, with the main conclusions as follows.
(1) The PEO macromonomers effectively afforded monodisperse microspheres of submicron to micron size in dispersion polymerization of stirene and butyl methacrylate in methanol-water. A theory of particle size control, based on the steric stabilization by the graft-copolymerized macromonomer chains covered on the surface, reasonably accounted for the experiments ; the size changes according to 1/3rd order of conversion, 2/3rd order of the comonomer concentration, and-1/2nd order of the macromonomer concentration. Change of the grafted PEO chains from a random coil to an extended conformation was also confirmed by NMR measurement.
(2) PEO and PMA macromonomers were also effective in emulsion polymerization of stirene. The traditional theory of emulsion polymerization has to be modified to account for the macromonomers to take part in the copolymerization in addition to function as the emulsifiers.
(3) Very rapid polymerization of the PEO macromonomers in water was studied kinetically by use of ESR among others, to be ascribed to their micelle formation. The resulting comb polymer in water could be described as a semiflexible wormlike chain just like a bottle brush with a hard, hydrophobic polystirene axle with an uncountable number of soft, soluble PEO hairs which will exert an extensive excluded-volume effect.
To summarize, the macromonomer technique for design of polymeric microspheres is relatively simple both in principle and in practice, promising a variety of applications. Less

Report

(4 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • Research Products

    (59 results)

All Other

All Publications (59 results)

  • [Publications] S.Kawaguchi: "Dispersion copolymerization of n-butyl methacrylate with poly (ethylene oxide) macromonomers in methanol-water. Comparison of experiment wth theory" Macromolecules. 28. 1159-1166 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi: "Surface characterization and dissociation properties of carboxylic acid core-shell latex particles by potentiometric and conductometric titration" J.Colloid Interf.Sci.176. 362-369 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Yoshida: "Synthesia and interfacial characterization of graft copolymers from styrene and 2-hydroxyethyl methacrylate that comprise either trunks or branches" Can.J.Chem.73. 1757-1764 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Ito: "One-step synthesis of poly (methacrylic acid) macromonomers and application to soap-free emulsion copolymerization with styrene" Macromol.Symp.91. 65-72 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M B.Nugroho: "Control of particle size in dispersion polymerization using poly (ethylene oxide) macromonomers" Macromolecular Reports. A32. 593-601 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi: "^1H NMR study of dispersion copolymerization of n-butyl methacrylate with poly (ethylene oxide) macromonomers in deuterated methanol-water" Macromolecules. 29. 4465-4472 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.P.S.Farinha: "Latex film formation probed by nonradiative energy transfer. Effect of grafted and free poly (ethylene oxide) on a poly (n-butyl methacrylate) lat." J.Phys.Chem.100. 12552-12558 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Furuhashi: "Synthesis,polymerization,and dispersion copolymerization of poly-(ethylene oxide) macromonomers carrying methacryloyloxyalkyl end groups" Colloid Polym. Sci.275. 227-233 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] I.Capek: "Microemulsion radical polymerization kinetics of alkyl acrylates" Polym.Internat.43. 1-7 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] E.Nomura: "Radical polymerization kinetics of poly (ethylene oxide) macromonomers" Macromolecules. 30. 2811-2817 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi: "Aqueous solution properties of oligo-and poly (ethylene oxide) by static light scattering and intrinsic viscosity" Polymer. 38. 2885-2891 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Ito: "Polymeric design by macromonomer technigue" Prog.Polym.Sci.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Ito: "Comb polymers,poly (ethylene oxide) side chains" Polymeric Materials Encyclopedia (J. C. Salamone,ed.). 2. 1347-1351 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Ito: "Macromonomers,soap-free emulsion and dispersion polymerization" Polymeric Materials Encyclopedia (J.C.Salamone,ed.). 6. 3927-3933 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Ito: "Poly (ethylene oxide) macromonomers,micellar-polymerization" Polymeric Materials Encyclopedia (J.C.Salamone,ed.). 8. 6054-6057 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Y.Yamashita: "Surfactants,polymeric (Overview)" Polymeric Materials Encyclopedia (J.C.Salamone,ed.). 10. 8195-8201 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M Yabuta: "High solid coatings,Microspheres from nonaqueous polymer dispersions" Polymeric Materials Encyclopedia (J.C.Salamone,ed.). 5. 3017-3026 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 伊藤 浩一: "水溶性マクロモノマー" 高分子. 46. 741-742 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 伊藤 浩一(分担): "「ブロック・グラフト」,新高分子実験学2(高分子の合成と反応(1))" 高分子学会編(共立出版), 40 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 伊藤 浩一(分担): "「末端反応性高分子」,新高分子実験学4(高分子の合成と反応(3))" 高分子学会編(共立出版), 44 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi, M.A.Winnik, K.Ito: "Dispersion copolymerization of n-butyl methacrylate with poly (ethylene oxide) macromonomers in methanol-water. Comparison of experiment with theory" Macromolecules. 28. 1159-1166 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi, A.Yekta, M.A.Winnik: "Surface characterization and dissociation properties of carboxylic acid coreshell latex particles by potentiometric and conductometric titration" J.Colloid Interf.Sci.176. 362-369 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Yoshida, S.Itsuno, K.Ito: "Synthesis and interfacial characterization of graft copolymers fromstirene and 2-hydroxyethl methacrylate that comprise either trunks or branches" Can.J.Chem.73. 1757-1764 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] K.Ito, K.Sabano, S.Kawaguchi: "One-step synthesis of poly (methacrylic acid) macromonomers and application to soap-free emulsion copolymerization with stirene" Macromol.Symp.91. 65-72 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] M.B.Nugroho, S.Kawaguchi, K.Ito, M.A.Winnik: "Control of particle size in dispersion polymerization using poly (ethylene oxide) macromonomers" Macromol.Reports. A32, Suppl.5 & 6. 593-601 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi, M.A.Winnik, , K.Ito: "H NMR study of dispersion copolymerization of n-butyl methacrylate with poly (ethylene oxide) macromonomer in deuterated methanol-water" Macromolecules. 29. 4465-4472 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] J.P.S.Farinha, J.M.G.Martinho, S.Kawaguchi, A.Yekta, M.A.Winnik: "Latex film formation probed by nonradiative energy transfer : Effect of grafted and free poly (ethylene oxide) on a poly (n-butyl methacrylate) latex" J.Phys.Chem.100. 12552-12558 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Furuhashi.S.Kawaguchi, S.Itsuno, K.Ito: "Synthesis, polymerization, and dispersion copolymerization of poly (ethylene oxide) macromonomers carrying methacryloyloxyalkyl and groups" Colloid Polym.Sci.275. 227-233 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] I.Capek, V.Juranico, J.Barton, J.M.Asua, K.Ito: "Microemulsion radical polymerization of alkyl acrylates" Polym.Internat.43. 1-7 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] E.Nomura, K.Ito, A.Kajiwara, M.Kamachi: "Radical polymerization kinetics of poly (ethylene oxide) macromonomers" Macromolecules. 30. 2811-2817 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] S.Kawaguchi, G.Iami, J.Suzuki, A.Miyahara, T.Kitano, K.Ito: "Aqueous solution properties of oligo-and poly-(ethylene oxide) by static light scattering and intrinsic viscosity" Polymer. 38. 2885-2891 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) K.Ito: "Polymeric design by macromonomer technique" Prog.Polymer Sci.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) K.Ito: "Comb polymers [Poly (ethylene oxide) side chains]" Polymeric Materials Encyc.2. 1347-1351 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) K.Ito: "Macromonomers (Soap-free emulsion and dispersion polymerization)" Polymeric Materials Encyc.6. 3927-3933 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) K.Ito: "Poly (ethylene oxide macromonomers (Micellar polymerization)" Polymeric Materials Encyc.8. 6054-6057 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) Y.Yamashita, K.Ito: "Surfactants, Polymeric (Overview)" Polymeric Materials Encyc.10. 8195-8201 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) M.Yabuta, Y.Nakano, A.Tominaga: "High solid coatings (Microspheres from nonaqueous polymer dispersions)" Polymeric Materials Encyc.5. 3017-3026 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] (Review) K.Ito: "Water-soluble macromonomers" Kobunshi. 46. 741-742 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] H.Furuhashi: "Synthesis, polymerization, and dispersion copoly-merization of poly (ethylene oxide) macromonomers carrying methacryloyloxyalkyl end groups" Colloid Polym.Sci.275. 227-233 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] E.Nomura: "Radical polymerization kinetics of poly (ethylene oxide) macromonomers" Macromolecules. 30. 2811-2817 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Kawaguchi: "Aqueous solution properties of oligo-and poly (ethylene oxide) by static light scattering and intrinsic viscosity" Polymer. 38. 2885-2891 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 川口正剛: "多角度光散乱-サイズ排除クロマトグラフィーを用いる無秩序分岐ポリスチレンのキャラクタリゼーション" 高分子論文集. 54. 923-929 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 伊藤浩一: "水溶性マクロモノマー" 高分子. 46. 741-742 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Ito: "Polymeric design by macromonomer technique" Prog.Polymer Sci.(in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] S.Kawaguchi: "^1H-NMR Study of Dispersion Copolymerization of n-Butyl Methacrylate with with Poly (ethylene oxide) Macromonomers in Deuterated Methanol-Water" Macromolecules. 29. 4465-4472 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Y.Hirose: "Preparation,Characterization and Dissociation Properties of Poly (acrylic acid) and Poly (methacrylic acid) with Narrow Molecular Weight Distribution21GC02:Polymer Journal" 28. 735-741 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.P.S.Farinha: "Latex Film Formation Probed by Nonradiative Energy Transfer : Effect of Grafted and Free Poly (ethylene oxide) on a Poly (n-butyl methacrylate) Latex" Journal of Physical Chemistry. 100. 12552-12558 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] S.Kawaguchi: "Aqueous Solution Properties of Oligo-and Poly (ethylene oxide) by Static Light Scattering and Intrinsic Viscosity" Polymer. 38. in press (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Furuhashi: "Synthesis,Polymerization,and Dispersion Copolymerization of Poly (ethylene oxide) Macromonomers Carrying Methacryloyoloxyalkyl End Groups" Colloid & Polymer Science. 275. in press (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 川口正剛: "非(選択)媒体中での高分子合成-分散重合微粒子径の制御とブラシ高分子-" 海外高分子研究. 43・1. 10-11 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 伊藤浩一(分担): "新高分子実験学4.高分子の合成・反応" 共立出版, 44 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 伊藤浩一(分担): "材料システム学(三大材料の力学的性質の統一的理解のために)" 共立出版, 11 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Ito: "One-Step Snthesis of Poly(methacrylic acid)Macromonomers and Application to Soap-Free Emulsion Copolymerization with Styrene" Macromol. Symp.91. 65-72 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.B.Nugroho: "Control of Particle Size in Dispersion Polymerization Using Poly(ethylene oxide)Macromonomers" Macromolecular Reports. A32. 593-601 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Kawaguchi: "Dispersion Copolymerization of n-Butyl Methacrylate with Poly(ethylene oxide)Macromonomers in Methanol-Water. Comparision of Experiment with Theory" Macromolecules. 28. 1159-1166 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Yoshida: "Syntheses and Interfacial Characterization of Graft Copolymers from Styrene and 2-Hydroxyethy Methacrylate That Comprise Either Trunks of Branches" Can. J. Chem.73. 1757-1764 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] S.Kawaguchi: "Surface Characterization and Dissociation Properties of Carboxylic Acid Core-Shell Latex Particles by Potentiometric and Conductometric Titration" J. Colloid and Interface Sci.176. 362-369 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 伊藤浩一: "新高分子実験学2" 共立出版, 40 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 伊藤浩一: "高分子合成化学" 東京電機大学出版, 68 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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