Stereospecific Living Radical Polymerization and Synthesis of Stereoblock Polymers

立构活性自由基聚合及立构嵌段聚合物的合成

• 批准号: 16350062
• 负责人: KAMIGAITO Masami
• 金额: $ 8.96万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16350062/
• 关键词: Living Polymerization; Radical Polymerization; Stereospecific Polymerization; Transition Metal Complex; Lewis Acid; Methacrylate; Vinyl Acetate; Block Polymer; リビンク重合; アクリルアミド

This research is directed to developing the stereospecific living radical polymerization by effectively combining the living and stereospecific radical polymerizations for the simultaneous control of the molecular weights and tacticity. The key to the success is to find appropriate combinations where one of the controls should not be lost by the other component. We found that several combinations induced stereospecific living radical polymerizations of various monomers such as methacrylates, acrylamides, vinyl acetate, and N-vinylpyrrolidone. The followings summarize each system.(1) Ruthenium-catalyzed living radical polymerizations of methacrylates in fluoroalcohols and aprotic solventsMethyl methacrylate was polymerized with Ru(Cp^*)Cl(PPh_3)_2 in (CF_3)_3COH to give polymers with narrow molecular weight distributions (MWDs) and high syndiotacticity (M_w/M_n=1.07, r=88%). For the polymerization of 2-hydroxyethyl methacrylate, DMF as a solvent induced syndiospecific living radical polymerization in the presence of Ru(Cp^*)Cl(PPh_3)_2. By using the polymerizations, stereoblock polymers were obtained.(2) Iron-catalyzed living radical polymerizations of acrylamides in the presence of metal triflatesN,N-Dimethylacrylamide was polymerized with [FeCp(CO)_2]_2 in the presence of Y(OTf)_3 to result in the polymers with controlled molecular weights and high isotacticity (M_w/M_n=1.87, m=82%).(3) Iodine-transfer radical polymerizations of vinyl acetate in fluoroalcoholsIodine-transfer radical polymerization of vinyl acetate was done in m-C_6H_4{C(CF_3)_2OH}_2 to result in the polymers with narrow MWDs and relatively high syndiotacticity (M_W/M_n=1.20, r=59%).(4) Xanthate-mediated radical polymerizations of N-vinylpyrrolidone in fluoroalcoholsXanthate was employed for the control of molecular weight in radical polymerization of N-vinylpyrrolidone in (CF_3)_3COH to result in the polymer with controlled molecular weights and high syndiospecificity (M w/M_n=1.28, r=60%).

这项研究致力于通过有效结合生命和立体特定的自由基聚合，以同时控制分子量和战术性，来开发立体生命的自由基聚合。成功的关键是找到适当的组合，其中另一个组件不应丢失其中一个控件。我们发现，几种组合诱导了各种单体的立体生命自由基聚合，例如甲基丙烯酸酯，丙烯酰胺，乙酸乙烯酯和N-乙烯基吡咯烷酮。以下总结了每个系统。（1）用RU（CP^*）Cl（CP^*）Cl（PPH_3）_2在（CF_3）_3 goh的（CF_3）_3 goh的范围（CF_3）_2 colliment contripticationt（CF_3）_2 goh的范围（cf_3）_3 goh的含量（cf_3）_3醇（MWD）clsriment（CF_3）_3醇（MW）clonticatiot contripticatirate（cf_3）_3醇（MW），将氟醇和代氧化甲基丙烯酸甲基丙烯酸甲基甲基丙烯酸甲基甲基丙烯酸酯和较低分数分配（MW）与MIRECTRICT（MW （m_w/m_n = 1.07，r = 88％）。对于2-羟基乙基甲基丙烯酸酯的聚合，DMF作为溶剂诱导的syndioppific Living Live Live Live Pridical聚合，在RU（CP^*）CL（PPH_3）_2的存在下。通过使用聚合物，获得了刻板聚合物。（2）在存在金属三烯二烯的情况下，丙烯酰胺的铁催化生命的激进聚合物，N-二甲基丙烯酰胺与[FECP（co）_2] _2在y（otf）的存在下与y（otf）的较高级别_3一起聚合。 （M_W/M_N = 1.87，M = 82％）。（3）乙酸乙酸乙烯酯在氟醇 - 二烷二二烷二丁二二氧二氧乙烯 - 转移乙酸乙烯基乙酸乙烯酯中的自由基聚合在M-C_6H_4 {CF_3）{CF_3）_2OH} _2 ONS _2 iN的范围内进行了M-C_6H_4 {C（CF_3）_2OH} _2 iN的含量，进行了ioncetration-_2 _2 Ont and-im in the in cons Inter Inter Ins Incrimer syndiotioticiti（M_W/M_N = 1.20，r = 59％）。（4）在氟醇中，N-乙烯基吡咯烷酮在荧光酒精中介导的自由基化的自由基聚合，用于控制N-乙烯基丙烯酮的自由基聚合物中的分子体重，以控制分子量。分子量和较高的综合性（m w/m_n = 1.28，r = 60％）。

项目成果

Metal-Catalyzed Stereospecific Living Radical Polymerization of Acrylamides

金属催化丙烯酰胺立体定向活性自由基聚合

• 发表时间: 2004
• 期刊: IUPAC ICOS-15 : Conference Program and Abstracts
• 作者: Decheng Wan;et al.;J.Taninaka;香村 和彦;K.Urita;柴田 拓哉;Y.Kurokawa;上垣外 正己;H.Kato;上垣外 正己;Masami Kamigaito;Masami Kamigaito
• 通讯作者: Masami Kamigaito

Iodine transfer radical polymerization of vinyl acetate in fluoroalcohols for simultaneous control of molecular weight, stereospecificity, and regiospecificity

• DOI: 10.1021/ma0602775
• 发表时间: 2006-05
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Kazuhiko Koumura;K. Satoh;M. Kamigaito;Y. Okamoto

水酸基を有するモノマーの遷移金属錯体を用いた立体特異性リビングラジカル重合系の開発

使用含羟基单体的过渡金属配合物开发立体定向活性自由基聚合体系

• 发表时间: 2005
• 期刊: 高分子学会予稿集 54(印刷中)
• 作者: Decheng Wan;et al.;J.Taninaka;香村 和彦;K.Urita;柴田 拓哉;Y.Kurokawa;上垣外 正己
• 通讯作者: 上垣外 正己

水酸基を有するモノマーの立体特異性リビングラジカル重合

含羟基单体的立体定向活性自由基聚合

• 发表时间: 2005
• 期刊: 高分子学会予稿集 54
• 作者: Decheng Wan;et al.;J.Taninaka;香村 和彦;K.Urita;柴田 拓哉
• 通讯作者: 柴田 拓哉

鉄錯体とルイス酸を用いた立体特異性リビングラジカル重合

使用铁配合物和路易斯酸进行立体定向活性自由基聚合

• 发表时间: 2004
• 期刊: 高分子学会予稿集 53・1
• 作者: Decheng Wan;et al.;J.Taninaka;香村 和彦;K.Urita;柴田 拓哉;Y.Kurokawa;上垣外 正己;H.Kato;上垣外 正己;Masami Kamigaito;Masami Kamigaito;上垣外 正己
• 通讯作者: 上垣外 正己