Study on the development of resinous-restoration-system without a polymerization contraction.

无聚合收缩树脂修复体系的开发研究。

• 批准号: 15390604
• 负责人: MIYAZAKI Koji
• 金额: $ 5.76万
• 依托单位: Fukuoka Dental College
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15390604/
• 关键词: Gas-solid phase reaction; Oxirane; Cyclic carbonates; Benzyltributylammonium; Block copolymer; Cationic polymerization; Ring-opening polymerization; Benzyltributylammonium chloride; オキセタン; スピロオルソカーボネート; カチオン重合; 膨張性樹脂; 膨張性モノマー; スピロ化合物; サイクリック

1)The appropriate choice of catalysts and comonomers improved the selectivity of the gas-solid phase reaction of carbon dioxide into copolymers from glycidyl methacrylate, which transforms the pendant oxirane moieties Benzyltributylammonium chloride exhibited good and selective catalytic behavior owing to its appropriate moiety in the copolymer film and moderate catalytic activity. N-Butyl methacrylate proved to be an effective comonomer, resulting in higher incorporation efficiency and better selectivity by preventing the cross-linking reaction, allowing one to obtain soluble polymers bearing cyclic carbonate structure.2)Pseudo block and triblock copolymers were synthesized by cationic ring-opening copolymerization of 1,5,7,11-tetraoxaspiro[5.5]undecane(SOC1) with trimethylene oxide(OX) via one-shot and two-shot procedures, respectively. When SOC1 and OX were copolymerized cationically using boron trifluoride etherate(BF3OEt2) as an initiator in CH2Cl2 at 25*, OX was consumed faster than SOC1. SOC1 was polymerized from the OX-rich gradient copolymer produced in the initial stage of the copolymerization to afford the corresponding pseudo block copolymer, poly[(OX-grad-SOC1)-b-SOC1]. We also succeeded the synthesis of a pseudo triblock copolymer by the addition of OX during the course of the polymerization of SOC1 before its complete consumption, which provided the corresponding pseudo triblock copolymer, poly[SOC1-b-(OX-grad-SOC1)-b-SOC1].

1)通过选择合适的催化剂和共聚单体，提高了二氧化碳与甲基丙烯酸缩水甘油酯气固相反应生成共聚物的选择性，使环氧环己烷基苯基三丁基氯化铵在共聚物膜中含量适中，催化活性适中，表现出良好的选择性催化性能。1)1，5，7，11-四氧杂螺[5.5]十一烷(SOC1)与环氧丙烷(OX)的阳离子开环共聚合成了1，5，7，11-四氧杂螺[5.5]十一烷(SOC1)的拟嵌段和三嵌段聚合物。在25℃的CH2Cl2溶液中，以三氟化硼乙醚(BF3OEt2)为引发剂，SOC1与OX发生阳离子共聚反应时，OX的消耗速度快于SOCl2。由共聚初期产生的富含OX的梯度共聚物聚合得到相应的拟嵌段共聚物Poly[(OX-GRAD-SOC1)-b-SOC1]。我们还成功地在SOC1完全消耗前的聚合过程中加入OX合成了一种拟三嵌段共聚物，得到了相应的拟三嵌段共聚物聚[SOC1-b-(OX-GRAD-SOC1)-b-SOC1]。

项目成果

T.Hino, T.Endo: "A Novel Synthetic Approach to Networked Polymers without Voleme Shrinkage on Cross-Linking Polymerization : Cationic Coplolymerization of a Monofunctional Epoxide and a Spiro Orthocarbonate Bearing Norbornene Backbone"Macromolecules. 36(1

T.Hino、T.Endo：“一种在交联聚合时无体积收缩的网络聚合物的新型合成方法：单官能环氧化物和带有降冰片烯主链的螺环原碳酸酯的阳离子共聚”大分子。

Effect Gas-Solid Phase Reaction of Atmospheric Carbon Dioxide into Copolymers with Pendant Oxirane Groups

大气二氧化碳气固相反应生成带有环氧乙烷侧基的共聚物

• 发表时间: 2005
• 期刊: Macromolecules 38
• 作者: Ochiai B;Iwamoto T;Miyazaki K;Endo T
• 通讯作者: Endo T