Development and Application of Precise-Stereocontrolled Polymerization of Novel Acrylic Monomers

新型丙烯酸单体精密立体控制聚合技术的开发及应用

• 批准号: 11450355
• 负责人: OKAMOTO Yoshio
• 金额: $ 8.13万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450355/
• 关键词: Stereospecfic Polymerization; α-Substituted Acrylate; Radical Polymerization; Anionic Polymerization; Poly(Crown Ether); Lewis Acid; Helix; Ion channel; マクロ環状モノマー; ナノチューブ; アルカリ金属抽出能; オルト置換スチレン; タクチシチー; ルイス酸触媒; らせん構造; 構造制御重合; 立体規則性

α-Substituted acrylates are the monomers that have two polar substituents on an olefin. We reported that the anionic polymerization using the organolithium reagents proceeded in an isotactic-specific manner by designing the substituents at the α-position of the monomer. In this study, the highly stereocontrolled polymerization method based on the monomer design was further developed, and followings are the results.1. The anionic polymerization of ocsubstituted acrylates having various polar groups, such as aromatic heterocycles, thioethers, and secondary amino groups, at the α-position produced polymers with a high stereoregularlity, due to the successful design of the monomer structures and polymerization systems.2. Although it is very difficult to control the stereochemistry during the radical polymerization, poly[α-(alkoxymethyl)acrylates] rich in isotacticity, syndiotacticity, and heterotacticity are synthesized by the radical method using a catalytic amount of Lewis acids as an additive. This method was successfully applied to the isotactic-specific radical polymerization of acrylamides.3. The anionic polymerization of the designed styrenes bearing optically active diamines at the ortho-position gave polymers with a high stereoregularity and chiral conformation based on the stereoregular backbone structure.4. Macrocyclic α(alkoxymethyl)acrylates having a crown ether structure were anionically polymerized to produce novel poly(crownether)s, which showed characteristic functions due the structure with a pore or nanotube.

α-取代的丙烯酸酯是在烯烃上具有两个极性取代基的单体。我们报道了使用有机锂试剂的阴离子聚合是通过设计单体α-位上的取代基以全同立构特异性的方式进行的。本研究进一步发展了基于单体设计的高度立体控制聚合方法，主要研究结果如下：1.由于单体结构和聚合体系的成功设计，α-位上带有芳杂环、硫醚和仲氨基等极性基团的α-取代丙烯酸酯的阴离子聚合得到了高度立构规整的聚合物.虽然在自由基聚合过程中很难控制立体化学，但使用催化量的刘易斯酸作为添加剂，通过自由基方法合成了富含全同立构规整度、间同立构规整度和杂同立构规整度的聚[α-（烷氧基甲基）丙烯酸酯]。该方法成功地应用于丙烯酰胺的等规定向自由基聚合.所设计的邻位带有光学活性二胺的苯乙烯的阴离子聚合得到了基于有规立构骨架结构的具有高立构规整性和手性构象的聚合物。4.采用阴离子聚合法合成了具有冠醚结构的大环α-（烷氧基甲基）丙烯酸酯，合成了具有孔或纳米管结构的新型聚冠醚。

项目成果

Y.Okamoto, S.Habaue, Y.Isobe, T.Nakano: "Stereocontrol in Radical Polymerization of Acrylic Monomers"Macromol. Symp.. (in press). (2002)

Y.Okamoto、S.Habaue、Y.Isobe、T.Nakano：“丙烯酸单体自由基聚合中的立体控制”Macromol。

S. Habaue, H. Ajiro, and Y. Okamoto: "Anionic Polymerization of o-Substituted Styrene Derivatives : Control of Reactivity and Stereochemistry by Aminomethyl Group"J. Polym. Sci. PartA : Polym. Chem.. 38. 4088-4094 (2000)

S. Habaue、H. Ajiro 和 Y. Okamoto：“邻位取代苯乙烯衍生物的阴离子聚合：氨甲基控制反应性和立体化学”J。

S. Habaue and Y. Okamoto: "Stereocontrol in Radical Polymerization"Chem. Rec.. 1(1). 46-52 (2001)

S. Habaue 和 Y. Okamoto：“自由基聚合中的立体控制”Chem。

S.Habaue,H.Ajiro,and Y.Okamoto: "Anionic Polymerization of ο-Substituted Styrene Derivatives : Control of Reactivity and Stereochemistry by Aminomethyl Group"J.Polym.Sci.Part A : Polym.Chem.. 38. 4088-4094 (2000)

S.Habaue、H.Ajiro 和 Y.Okamoto：“ο-取代苯乙烯衍生物的阴离子聚合：氨基甲基控制反应性和立体化学”J.Polym.Sci.A 部分：Polym.Chem.. 38. 4088- 4094 (2000)

S. Habaue, M. Morita, Y. Okamoto: "Stereospecific Anionic Polymerization of α-(Alkoxymethyl)acrylate Derivatives Affording Novel Vinyl Polymers with Macrocyclic Side Chains"Polymer. 43(in press). (2002)

S. Habaue、M. Morita、Y. Okamoto：“具有大环侧链的新型乙烯基聚合物的 α-(烷氧基甲基)丙烯酸酯衍生物的立体定向阴离子聚合”聚合物 43（印刷中）。