Study of New Polymer Synthesis in Aqueous Solutions or in Plain water

水溶液或清水中合成新型聚合物的研究

• 批准号: 08455444
• 负责人: NISHIKUBO Tadatomi
• 金额: $ 4.29万
• 依托单位: Kanagawa University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455444/
• 关键词: Polymer Synthesis; Ionic Reaction; Plain Water; Aqueous Solution; Polycondensation; Polyaddition; Polymer Reaction; ポリスルフィド; 不均一反応系; ポリ(アミドースルフィド); 選択的酸価反応; ビスオキサゾリン; ジチオール; DBU; ジカルボン酸; ビスアルキルハライド

Water and aqueous solutions seem to have great promise as reaction media in chemical industries, especially in the synthetic polymer industry, from the viewpoints of incombustibility, safety and economy. In fact, the radical reactions such as suspension polymerization and emulsion polymerization of various hydrophobic vinyl monomers and solution polymerization of various hydrophilic monomers with corresponding radical initiators have long been performed using water as a reaction medium. However, the careful removal of water has been required in many cases of organic synthesis and polymer synthesis based on ionic reactions, because most ionic reactions are ordinarily hindered or blocked by the presence of water. On the other hand, we found recently that esterification reaction of poly(methacrylic acid) with benzyl bromide proceeded quantitatively using DBU as a base in water. This meant that aqueous solutions or water can be used as reaction media for ionic reactions, when appropriate r … More eaction conditions including suitable catalyst system can be designed.This research project investigated the synthesis of polymers by following polycondensation or by polyaddition reactions in aqueous solutions or in plain water under appropriate reaction conditions.In 1996, the polyaddition of bis(4-mercaptophenyl)sulfide (BMPS) with m-phenylenebis (2-oxazoline) (MPBO) was investigated. The reaction proceeded smoothly in the mixtures of NMP with water to produce the corresponding poly(amide-sulfide). The polycondensation of adipic acid with mxylylene dibromide was also performed using DBU as a base in the mixed solvents of DMSO with water or in plain water. The reaction proceeded even in water to give the corresponding polyesters, although the rate of the reaction decreased gradually with increasing water in the mixture.In 1997, the heterogeneous oxidation of poly(amide-sulfide), which was prepared by the polyaddition of BMPS with BMPO in plain water, was performed with 1-3 times the amount of hydrogen peroxide in a dispersion of water at 60=, and it was found that poly(amide-sulfone) was prepared by the oxidization of the polymer.In 1998, polycondensations of bisphenols such as bisphenol-A (BPA), bisphenol-AF (BPAF), and bisphenol-S (BPS) with bis(4-chloro-3-nitrophenyl)sulfone (BCNPS) were examined using various organic or inorganic bases in mixed solvents of DMAc with water or in plain water. The reactions of bisphenols (BPA, BPAF and BPS) with BCPNS proceeded smoothly to give the corresponding polyethers in mixed solvents of DMAc with water at 60= using DBU as a base, although the rate of the reaction decreased gradually as the water in the solvent increased. Poly(sulfone-sulfide) with high molecular weight was also synthesized with good yields by the reaction of BMPS with BCNPS in the same mixed solvents or in plain water using appropriate organic bases such as DBU and tripropylamine. Less

从不燃性、安全性和经济性的观点来看，水和水溶液似乎在化学工业中，特别是在合成聚合物工业中作为反应介质具有很大的前景。事实上，自由基反应例如各种疏水性乙烯基单体的悬浮聚合和乳液聚合以及各种亲水性单体与相应的自由基引发剂的溶液聚合长期以来一直使用水作为反应介质进行。然而，在基于离子反应的有机合成和聚合物合成的许多情况下，需要小心地除去水，因为大多数离子反应通常被水的存在阻碍或阻断。另一方面，我们最近发现，聚（甲基丙烯酸）与苄基溴的酯化反应定量进行使用DBU作为碱在水中。这意味着在适当的情况下，水溶液或水可以用作离子反应的反应介质。 ...更多信息 本课题研究了在适当的反应条件下，通过后续缩聚反应或在水溶液或纯水中的加聚反应合成聚合物，1996年，研究了双（4-巯基苯）硫醚（BMPS）与间亚苯基双（2-恶唑啉）（MPBO）的加聚反应。反应在NMP与水的混合物中顺利进行，生成相应的聚（酰胺-硫化物）。以DBU为碱，在DMSO和水的混合溶剂中或在纯水中进行了己二酸与间二溴代二甲苯的缩聚反应。反应甚至在水中进行，得到相应的聚酯，尽管反应速率随着混合物中水的增加而逐渐降低。（酰胺-硫化物），其通过BMPS与BMPO在普通水中的加聚反应制备，在60 ℃下用1-3倍量的过氧化氢在水分散体中进行，1998年，在DMAc与水的混合溶剂或普通水中，使用各种有机或无机碱，研究了双酚如双酚A（BPA）、双酚AF（BPAF）和双酚S（BPS）与双（4-氯-3-硝基苯基）砜（BCNPS）的缩聚反应。双酚（BPA、BPAF和BPS）与BCPNS在以DBU为碱的DMAc和水的混合溶剂中，在60 ℃下反应顺利，生成相应的聚醚，但反应速率随溶剂中水的增加而逐渐降低。在相同的混合溶剂中或在纯水中，用DBU和三丙胺等有机碱，BMPS和BCNPS反应，也可得到高分子量的聚砜-硫醚，产率较高。少

项目成果

T.Nishikubo: "Synthesis of Polymers in Aqueous Solutions : Synthesis of Polyesters by Reactions of Dicarboxylic Acids with Alkylene Dihalides using 1,8-Diazabicyclo [5.4.0.] undec-7-ene in Aqueous Solution" Polym.J.29. 899-903 (1997)

T.Nishikubo：“水溶液中聚合物的合成：使用 1,8-二氮杂双环 [5.4.0.] undec-7-ene 在水溶液中通过二羧酸与亚烷基二卤化物反应合成聚酯”Polym.J.29。

T.Nishikubo: "Synthesis of Polymers in Aqueous Solutions : Selective addition Reaction of Poly (2-isopropenyl-2-oxazoline) with Thiols and Carboxylic Acids in Aqueous Solution" Polym.J.28. 134-138 (1996)

T.Nishikubo：“水溶液中聚合物的合成：聚（2-异丙烯基-2-恶唑啉）与硫醇和羧酸在水溶液中的选择性加成反应”Polym.J.28。

T.Nishikubo et al.: "Synthesis of Polymers in Aqueous Solutions : Selective Addition Reaction of Poly(2-isopropenyl-2-oxazoline) with Thiols and Carboxylic Acids in Aqueous Solution" Polym.J.,. 28. 134-138 (1996)

T.Nishikubo 等人：“水溶液中聚合物的合成：聚(2-异丙烯基-2-恶唑啉)与硫醇和羧酸在水溶液中的选择性加成反应”Polym.J.,。

T.Nishikubo: "Synthesis of Polymers in Aqueous Solutions : Esterification Reaction of Poly (methacrylic acid) with Alkyl Halides using DBU in Aqueous Solution" J.Polym.Sci.Part A.Polym.Chem.34. 3531-3537 (1996)

T.Nishikubo：“水溶液中聚合物的合成：在水溶液中使用 DBU 进行聚（甲基丙烯酸）与烷基卤化物的酯化反应”J.Polym.Sci.A 部分.Polym.Chem.34。

T.Nishikubo et al.: "Synthesis of Polymers in Aqueous Solutions : Polyaddition of Bis (oxazoline) with Dithiol in Aqueous Solution" J.Polym.Sci.Part A. Polym.Chem.,. 35. 2711-2717 (1997)

T.Nishikubo 等人：“水溶液中聚合物的合成：双（恶唑啉）与二硫醇在水溶液中的加聚”J.Polym.Sci.A 部分 Polym.Chem.,。