Development of Polymer Emulsion Utilizing Radical Ring-Opening Polymerization

利用自由基开环聚合开发聚合物乳液

• 批准号: 10555323
• 负责人: ENDO Takeshi
• 金额: $ 3.71万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10555323/
• 关键词: polymer emulsion; radical polymerization; ring-opening polymerization; vinylcyclopropane; soap-free polymerization; soap-in polymerization; single particle size; 共重合

This work dealt with synthesis of novel polymer emulsion utilizing radical ring-opening polymerization. We examined the synthesis and radical polymerization of vinylcyclopropanes having cyclic thioacetal, amide, ester, trimethylsilyl groups. The monomer with cyclic thioacetal moiety showed low polymerizability, while the monomers with amide and ester groups underwent radical polymerization efficiently to afford the polymers consisting of 1,5-ring-opened units quantitatively. A bifunctional vinylcyclopropane afforded a crosslinked polymer. A trimethylsilylated polymer was reacted with electrophiles to afford the corresponding adducts. We examined the radical emulsion polymerization of vinylcyclopropanes, 1,1-bis(ethoxycar-bonyl)-2-vinylcyclopropane (ECVCP) and 1,1-dichloro-2-vinylcyclopropane (CVCP). ECVCP underwent soap-free and soap-in emulsion polymerization satisfactorily to afford the ring-opened polymer in good yields. Polymer emulsions were obtained in a spherical shape with single particle size distribution. Meanwhile, emulsion polymerization of CVCP proceeded in only a low conversion.

本文研究了利用自由基开环聚合法制备新型聚合物乳液。我们研究了具有环硫缩醛、酰胺、酯、三甲基硅基的乙烯基环丙烷的合成和自由基聚合。含环硫缩醛基团的单体可聚合性较低，而含酰胺基和酯基的单体可进行有效的自由基聚合，定量地得到由1,5环开环单元组成的聚合物。双官能的乙烯基环丙烷提供交联聚合物。三甲基硅基化聚合物与亲电试剂反应生成相应的加合物。研究了乙烯基环丙烷、1,1-二（乙氧基羰基）-2-乙烯基环丙烷（ECVCP）和1,1-二氯-2-乙烯基环丙烷（CVCP）的自由基乳液聚合。ECVCP经无皂和皂内乳液聚合得到开环聚合物，收率高。所得聚合物乳液呈球形，粒径分布单一。同时，CVCP的乳液聚合在低转化率下进行。

项目成果

F.Sanda,J.Murata,T.Endo: "Synthesis and Radical Ring-Opening Polymerization of Vinylcyclopropanes Bearing Vinylsilane" J.Polym.Sci.,Part A:Polym.Chem.36. 2037-2042 (1998)

F.Sanda、J.Murata、T.Endo：“带有乙烯基硅烷的乙烯基环丙烷的合成和自由基开环聚合”J.Polym.Sci.，A 部分：Polym.Chem.36。

Fumio Sanda, Junji Murata, and Takeshi Endo: "Syntheses and Radical Ring-Opening Polymerizations of 1,1-Bis(hydroxymethyl)-2-Vinylcyclopropane and 1,1-Bis(methoxymethyl)2-Vinylcyclopropane"Polym. Chem.. 36. 2037-2042 (1998)

Fumio Sanda、Junji Murata 和 Takeshi Endo：“1,1-双（羟甲基）-2-乙烯基环丙烷和 1,1-双（甲氧基甲基）2-乙烯基环丙烷的合成和自由基开环聚合”Polym。

Fumio Sanda Teruaki Komiya, and Takeshi Endo: "Radical Polyaddition-Isomerization of Bifunctional Vinylcyclopropanes with Dithiols"Macromol. Chem. Phys.. 199. 2165-2172 (1998)

Fumio Sanda Teruaki Komiya 和 Takeshi Endo：“双官能乙烯基环丙烷与二硫醇的自由基加聚异构化”Macromol。

F.Sanda,T.Miyagawa,T.Edno: "Synthesis and Radical Polymerization of 5-Methylene-2,2-Dimethy1-1,3-Doixolan-4-One"J.Polym.Sci.,Part A: Polym.Chem. 38(印刷中). (2000)

F.Sanda、T.Miyakawa、T.Edno：“5-亚甲基-2,2-二甲基1-1,3-Doixolan-4-One 的合成和自由基聚合”J.Polym.Sci.，A 部分：聚合物。化学 38（印刷中）（2000）。

F. Sanda, Y. Takamatsu, T. Endo: "Radical Ring-Opening Emulsion Polymerization of Vinylcyclopropanes"J. Appl. Polym. Sci.. 68. 497-501 (1998)

F. Sanda、Y. Takamatsu、T. Endo：“乙烯基环丙烷的自由基开环乳液聚合”J。