Fundamental Studies on Molecular Design for Specialty Polymeric Materials by Ring-Opening Polymerization of Heterobicyclic Compounds

杂双环化合物开环聚合特种高分子材料分子设计的基础研究

• 批准号: 63044062
• 负责人: OKADA Masahiko
• 金额: $ 2.56万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Overseas Scientific Survey.
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-63044062/
• 关键词: Bicyclic Lactone; Bicyclic Lactam; Ring-Opening Polymerization; Polyester; Polyamide; Oligomer; Biodegradability

1. Synthesis and Ring-Opening Polymerization of Novel Bicyclic OxalactamsTwo new bicyclic oxalactams, 2-oxa-5-azabicyclo[2.2.2]octan-6-one (2,5-BOL) and 2-oxa-6-aza-bicyclo[2.2.2]octan-5-one (2,6-BOL) were synthesized and their ring-opening polymerizabilities were examined. 2,5-BOL was anionically polymerized to give a polyamide having cis-2,5-linked tetrahydropyran rings in the main chain. 2,6-BOL did not undergo anionic polymerization, and afforded only a dimeric adduct in a low yield. In contrast, 2,6-BOL was easily polymerized with cationic initiators to give oligoethers containing 6-membered lactam rings in the main chain.2. Synthesis of Polyesters Having Tetrahydropyran Rings in their Main ChainsThree 2,6-dioxabicyclo[2.2.2]octan-3-one derivatives having an ester group at 4-position were newly prepared. These monomers underwent cationic polymerization to produce polyesters having 2,5-linked tetrahydropyran rings in their backbones and the corresponding ester groups as the side chains. These polyesters showed much improved solubilities compared with the parent polyester. Hydrolysis of these polyesters were examined at 30 ﾟC in a buffer solution at pH 7.2.

1. 合成了2-氧-5-氮杂环[2.2.2]辛烷-6- 1 （2,5- bol）和2-氧-6-氮杂-双环[2.2.2]辛烷-5- 1 （2,6- bol）两种新型双环草内酰胺，并对其开环聚合性能进行了研究。2,5- bol经阴离子聚合得到主链上有顺式2,5-四氢吡喃环的聚酰胺。2,6- bol不进行阴离子聚合，只产生二聚体加合物，收率低。相比之下，2,6- bol很容易与阳离子引发剂聚合，得到主链中含有6元内酰胺环的低聚醚。主链含四氢吡喃环聚酯的合成新制备了3个具有4位酯基的2,6-二氧杂环[2.2.2]辛烷-3- 1衍生物。这些单体经过阳离子聚合得到具有2,5-键四氢吡喃环的聚酯骨架和相应的酯基作为侧链。与母聚酯相比，这些聚酯的溶解度有了很大的提高。在pH 7.2的缓冲溶液中，在30°C的温度下对这些聚酯进行水解。

项目成果

M. Okada: "Synthesis and Ring-Opening Polymerization of Novel Bicyclic Oxalactams. 2-Oxa-5-azabicyclo[2.2.2]octan-6-one" J. Polym. Sci.in press.

M. Okada：“新型双环草内酰胺的合成和开环聚合。2-Oxa-5-azabicyclo[2.2.2]octan-6-one”J. Polym。

M.Okada: "Synthesis and Ring-Opening Polymerization of Novel Bicyclic Oxalactams.2-Oxa-6-azabicyclo[2.2.2]octan-5-one" Macromolecules. (1990)

M.Okada：“新型双环草内酰胺.2-Oxa-6-azabicyclo[2.2.2]octan-5-one”大分子的合成和开环聚合。

岡田鉦彦: "ヘテロ双環化合物の開環重合" 有機合成化学協会誌. 47. 1040-1050 (1989)

Kazuhiko Okada：“杂二环化合物的开环聚合”有机合成化学学会杂志 47. 1040-1050 (1989)。

H.Sumitomo: "Ring-Opening Polymerization of Bicyclic Oxalactams.Telechelics,Macromers,and Block and Graft Copolymers,in “Frontiers of Macromolecular Science"" Blackwell Scientific Publications, 6 (1989)

H. Sumitomo：“双环草内酰胺的开环聚合。遥爪、大分子单体和嵌段接枝共聚物，载于“大分子科学前沿””Blackwell Scientific Publications，6 (1989)

M.Okada: "Synthesis and Ring-Opening Polymerization of Novel Bicyclic Oxalactams.2-Oxa-5-azabicyclo[2.2.2]octan-5-one" J.Polymer Science,Part A. (1990)

M.Okada：“新型双环草内酰胺的合成和开环聚合。2-Oxa-5-azabicyclo[2.2.2]octan-5-one”J.Polymer Science，A 部分（1990 年）