2001 Fiscal Year Annual Research Report

"超高密度"ポリマーブラシの構造と物性

Research Project

Project/Area Number	12450385
Research Institution	KYOTO UNIVERSITY
Principal Investigator	福田猛京都大学, 化学研究所, 教授 (00111972)
Co-Investigator(Kenkyū-buntansha)	辻井敬亘京都大学, 化学研究所, 助教授 (00217308)
Keywords	超高密度ポリマーブラシ / 膨潤膜厚 / 圧縮弾性率 / 溶融ブラシ / ガラス転移温度 / 非スケーリング性 / グラフト膜界面特性 / グラフト膜バルク特性
Research Abstract	表面に適当な開始基を化学結合で導入した固体(シリコン基板、シリカ微粒子、金属微粒子など)に原子移動ラジカル重合(ATRP)や可逆的付加・開裂連鎖移動(RAFT)ラジカル重合などのリビングラジカル重合法(LRP)を適用し、固体表面に0.7 chains/nm^2にも達する高密度で長さおよび化学構造の制御された各種のモノマーからなるグラフト鎖(ポリマーブラシ)を形成する技術を確立した。これら高密度グラフト膜の特性を膨潤状態および乾燥状態で調べた結果、キャスト法による(通常の)高分子薄膜とは著しく異なる性質を有する新規な分子集合組織であることが判明した。例えば、良溶媒中において高密度グラフト膜中の分子鎖は膜面に垂直な方向に高度に伸張し、伸び切り鎖長の80〜90%にも達する膜厚を与える。また、膨潤膜の圧縮弾性率はグラフト鎖長とともに増大する非スケーリング性を示す。溶融状態における乾燥膜の圧縮弾性率も等価なキャスト膜に比して約50%高い。また、乾燥膜のガラス転移温度T_gは等価なキャスト膜に比べて、低分子量領域(膜厚で約50nm以下)および高分子量領域で特徴的な差異を示した。特に、実験データは分子量が無隈に大きい極限においてもポリメタクリル酸メチル(PMMA)高密度グラフト膜のT_gがバルクPMMAのそれに比して約8K高いことを示しており、表面グラフトという界面効果が膜のバルクな性質に及ぶことが判明した。

Research Products
(14 results)

All Other

All Publications (14 results)

[Publications] A.Goto: "Mechanism and Kinetics of RAFT-Based Polymerizations of Styrene and Methyl Methacrylate"Macromolecules. 34. 402-408 (2001)
[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)
[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)
[Publications] M.Ejaz: "Controlled Grafting of a Well-Defined Polymer on a Porous Glass Filter by Surface-Initiated Atom Transfer Radical Polymerization"Polymer. 42. 6811-6815 (2001)
[Publications] T.Fukuda: "Penultimate Unit Effects in Free Radical Copolymerization"Macromol. Symp.. (印刷中). (2002)
[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)
[Publications] M.Ejaz: "Fabrication of Patterned High-Density Polymer Graft Surfaces. I. Amplification of Phase-Separated Morphology of Organosilane Blend Monolayer by Surface-Initiated Atom Transfer Radical Polymerization"Macromolecules. 35. 1412-1418 (2002)
[Publications] Y.Tsujii: "Fabrication of Patterned High-Density Polymer Graft Surfaces. II. Amplification of EB-Patterned Initiator Monolayer by Surface-Initiated Atom Transfer Radical Polymerization"Polymer. (印刷中). (2002)
[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)
[Publications] A.Goto: "Comparative Study on Decomposition Rate Constants for Some Alkoxyamines"Macromolecules. (印刷中). (2002)
[Publications] C.Yoshikawa: "Reactions of Polystyryl Radicals in A Monomer-Free Atom Transfer Radical Polymerization System"e-Polymers. 013. (2002)
[Publications] C.Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated Polymerization"Macromolecules. (印刷中). (2002)
[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)
[Publications] T.Fukuda: "Handbook of Radical Polymerization", K.Matyjaszewski, T.P.Davis, Ed."John Wiley & Sons, New York. 70 (2002)

2001 Fiscal Year Annual Research Report

"超高密度"ポリマーブラシの構造と物性

Principal Investigator

福田 猛 京都大学, 化学研究所, 教授 (00111972)

Research Products

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

[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)

[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)

[Publications] M.Ejaz: "Controlled Grafting of a Well-Defined Polymer on a Porous Glass Filter by Surface-Initiated Atom Transfer Radical Polymerization"Polymer. 42. 6811-6815 (2001)

[Publications] T.Fukuda: "Penultimate Unit Effects in Free Radical Copolymerization"Macromol. Symp.. (印刷中). (2002)

[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)

[Publications] M.Ejaz: "Fabrication of Patterned High-Density Polymer Graft Surfaces. I. Amplification of Phase-Separated Morphology of Organosilane Blend Monolayer by Surface-Initiated Atom Transfer Radical Polymerization"Macromolecules. 35. 1412-1418 (2002)

[Publications] Y.Tsujii: "Fabrication of Patterned High-Density Polymer Graft Surfaces. II. Amplification of EB-Patterned Initiator Monolayer by Surface-Initiated Atom Transfer Radical Polymerization"Polymer. (印刷中). (2002)

[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)

[Publications] A.Goto: "Comparative Study on Decomposition Rate Constants for Some Alkoxyamines"Macromolecules. (印刷中). (2002)

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

[Publications] C.Yoshikawa: "Quantitative Comparison of Theory and Experiment on Living Radical Polymerization Kinetics. 1. Nitroxide-Mediated Polymerization"Macromolecules. (印刷中). (2002)

[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)

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

福田猛京都大学, 化学研究所, 教授 (00111972)

[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)