Development of novel organic reaction and polymer synthesis using CO_2

利用CO_2开发新型有机反应和聚合物合成

• 批准号: 13450376
• 负责人: ENDO Takeshi
• 金额: $ 9.66万
• 依托单位: Yamagata University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450376/
• 关键词: carbon dioxide; tertiary amine; environment; organic chemistry; polymer synthesis; fixation of CO_2; 第3級アミン

Development of efficient methods for CO_2 recovery from industrial waste gases is important in relation to both reutilization of CO_2 as carbon resources and atmospheric environmental issue concerned with greenhouse effect. One of the most commonly used processes for CO_2 recovery is chemically reversible CO_2 trapping by primary or secondary amines, however, CO_2 trapping by tertiary amine has not been reported. In this work, we report the development of CO_2 trapping by tertiary amine.Pyridine, triethylamine, 4-(dimethylaminopyridine), and l,4-diazabicyclo[2,2,2]octane (Dabco) could not react with CO_2. On the other hand, l,8-diazabicyclo[5,4,0]-undec-7-ene (DBU) could react with CO_2 to give the corresponding zwitter ion adduct: We also found that N-methyltetrahydropyrimidine containing amidine moiety could trap CO_2.Next, we synthesized polystyrene derivatives bearing amidine moiety (polymer-1) and CO_2 trapping experiments by it were attempted. Polymer-1 could trap CO_2 in N,N-dimethylformamide to give the corresponding polymer bearing zwitter ion adduct. Furthermore, polymer-1 could trap CO_2 in the solid state, and the film of polymer-1 could trap and release CO_2 reversibly, which might be applicable to novel CO_2 trapping materials.

从工业废气中回收CO_2的有效方法的开发，不仅关系到CO_2作为碳资源的再利用，而且关系到与温室效应有关的大气环境问题。伯胺或仲胺化学可逆捕集CO_2是最常用的CO_2回收方法之一，而叔胺捕集CO_2的方法尚未见报道。本文报道了叔胺捕集CO_2的研究进展，吡啶、三乙胺、4-二甲氨基吡啶和1，4-二氮杂双环[2，2，2]辛烷（Dabco）不能捕集CO_2。另一方面，1，8-二氮杂双环[5，4，0]-十一碳-7-烯（DBU）能与CO_2反应生成相应的两性离子加合物：我们还发现含脒基的N-甲基四氢嘧啶能捕集CO_2。聚合物-1在N，N-二甲基甲酰胺中能捕集CO_2，得到相应的两性离子聚合物加合物。聚合物-1可以在固态下捕集CO_2，且聚合物-1膜可以可逆地捕集和释放CO_2，有望成为新型的CO_2捕集材料。

项目成果

田中 正剛: "Samarium Enolate on Crosslinked Polystyrene Beads. An Anionic Initiator for the Well-Defined Synthesis of Poly(allyl methacrylate) on a Solid Support"Journal of Polymer Science Part A: Polymer Chemistry. 41巻. 853-860 (2003)

Masatake Tanaka：“交联聚苯乙烯珠上的烯醇化钐。用于在固体载体上明确合成聚（甲基丙烯酸烯丙酯）的阴离子引发剂”《聚合物科学杂志》A 部分：聚合物化学，第 41 卷，853-860。 ）

大塚 英幸: "Pinacol Rearrangement in the Polymer Backone : Synthesis of Novel Reactive Polymers with Condensed Benzopinacol Units in the Main Chain and Their Complete Rearrangement of Poly(benzopinacolone)s"Macromolecular Chemistry and Physics. 203巻. 1824-183

Hideyuki Otsuka：“聚合物主链中的频哪醇重排：主链中具有稠合苯频哪醇单元的新型反应性聚合物的合成及其聚苯频哪酮的完全重排”《高分子化学与物理》，第 203 卷，1824-183。

根本修克: "Cationic Ring-Opening Polymerization of Cyclic Monothiocarbonates:Varying the Polymer Main Chain by Neighboring Group Participation"Macromolecules. 34巻. 7642-7647 (2001)

Osamu Nemoto：“环状单硫代碳酸酯的阳离子开环聚合：通过邻近基团参与改变聚合物主链”《高分子》第 34 卷。7642-7647 (2001)

工藤宏人: "Efficient Synthesis of Macrocycles by Oxidation of Cysteine-Based Dithiols"Tetrahedron Letters. 42巻. 7847-7850 (2001)

Hiroto Kudo：“通过基于半胱氨​​酸的二硫醇的氧化有效合成大环”四面体快报第 42 卷。7847-7850 (2001)

三田文雄: "Star Polymer Synthesis from ε-Caprolactone Utilizing Polyol/Protonic Acid Initiator"Macromolecules. 35巻. 680-683 (2002)

Fumio Mita：“利用多元醇/质子酸引发剂合成 ε-己内酯”《高分子》，第 35 卷，680-683 (2002)