Basic and Applicative Studies on Controlled Radical Polymerization

受控自由基聚合的基础与应用研究

• 批准号: 09450351
• 负责人: FUKUDA Takeshi
• 金额: $ 8.13万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450351/
• 关键词: Living radical; Mechanisms; Kinetics; Nitroxides; RAFT; ATRP; New polymers; Precistion Synthesis; 活性化速度定数; 精密重合; 表面グラフト; 均一ゲル; 糖鎖高分子; リビングラジカル重合; 安定ニトロキシル; 重合機構; 精密反応解析; フラーレン誘導体; スチレン系グリコポリマー

[I] Mechanisms and Kinetics of Controlled Radical PolymerizationsThe 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.

[I] 受控自由基聚合的机理和动力学对受控自由基聚合（CRP）的变体的机理和动力学进行了实验和理论研究并系统化。主要结果包括：(1)建立了测定CRP活化速率常数的两种通用GPC方法。(2)将GPC方法应用于各种CRP体系，建立了活化速率常数和活化机制。特别是，已证实硝基氧体系的热解离、PS-I和PS-SCSMe体系的交换链转移以及溴化物/CuBr体系的原子转移实际上是各个体系的唯一活化机制。（3）建立了描述CRP体系聚合速率的通用方程，并通过实验得到了部分证实[II]新型聚合物材料的精密合成 CRPs(1) 首次合成了结构明确的低多分散性共聚物(无规、嵌段、聚大分子单体)和均聚物(带有葡萄糖残基的苯乙烯类、丙烯酸酯和甲基丙烯酸酯、富勒烯封端聚合物)。(2) 首次制备了结构比常规凝胶更均匀的聚合物凝胶。 (3)首次成功制备了在硅片上密集接枝的具有可控链长和链长分布的聚合物刷。

项目成果

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)

K.Ohno、Y.Tsujii、T.Miyamoto、T.Fukuda、M.Goto、K.Kobayashi、A.Akaike：“通过氮氧化物控制的自由基聚合合成明确的糖聚合物”大分子。

T.Fukuda: "Feature Article: Mechanisms and Kinetics of Controlled Radical Polymerizations" Macromol.Chem.Phys.(in press). (1999)

T.Fukuda：“专题文章：受控自由基聚合的机理和动力学”Macromol.Chem.Phys.（出版中）。

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)

A.Goto、K.Sato、T.Fukuda、G.Moad、E.Rizzardo、S.H.Thang：“基于 RAFT（可逆加成-断裂链转移）的苯乙烯受控自由基聚合的机理和动力学”聚合物制备。

大野工司: "リビングラジカル重合法を用いた新しい高分子の合成" 高分子加工. 47. 419-425 (1998)

Koji Ohno：“利用活性自由基聚合合成新聚合物”聚合物加工 47. 419-425 (1998)。

M.Ejaz: "Controlled Graft Polymerization of Methyl Methacrylate on Silicon Substrate by Conbined Use of the Langmuir-Blodgett and Atom Transfer Radical Polymerization Techniques" Macromolecules. 31. 5934-5936 (1998)

M.Ejaz：“结合使用 Langmuir-Blodgett 和原子转移自由基聚合技术，在硅基底上控制甲基丙烯酸甲酯的接枝聚合”大分子。