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| 基于降冰片二烯半酯衍生物的ROMP聚合制备两亲性聚合物的研究 |
| Study on Preparation of Amphiphilic Polymers Based on Norbornadiene Half-ester Derivatives via ROMP Polymerization |
| 投稿时间：2024-03-17 修订日期：2024-04-10 |
| DOI： |
| 中文关键词: 开环易位聚合 聚降冰片二烯 两亲性聚合物 氢化加成 环氧化反应 |
| 英文关键词: Ring-opening metathesis polymerization Polynorbornadiene Amphiphilic polymer Hydrogenation addition Epoxidation reaction |
| 基金项目:海南省热带作物栽培生理学重点实验室/农业农村部儋州热带作物科学观测实验站开放课题(NO.RRI-KLOF202303)；海南省自然科学基金(NO.521RC1058,NO.223RC475) |
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| 中文摘要: |
| 两亲性聚合物因其同时含有亲水和疏水链段的独特结构，在生物医药、纳米技术等领域有广泛的用途。本文通过开环易位聚合（ROMP），使用Grubbs第三代催化剂（[Ru]-Ⅲ催化剂）以活性可控的方式，合成了同时含有酯基和羧酸基两亲性聚降冰片烯。以高选择性单水解反应制备了半酯单体，使用[Ru]-Ⅲ催化剂一步实现结构规整两亲性聚合物的制备，所得聚合物具有反式构型和窄的分子量分布指数。氢化反应和环氧化反应制备了饱和聚合物，以提高两亲性聚降冰片烯的热稳定性，饱和聚合物原结构，而不形成新的立构分离。选择性单水解作为功能化单体设计的工具，应用于活性ROMP，可控制备功能性两亲性聚合物。 |
| 英文摘要: |
| Amphiphilic polymers have a wide range of applications in biomedicine and nanotechnology because of their unique structures with both hydrophilic chains and hydrophobic chains. In this work, amphiphilic polynorbornenes containing both ester groups and carboxylic acid groups were synthesized through ring-opening metathesis polymerization (ROMP) using Grubbs' third-generation catalyst ([Ru]-Ⅲ catalyst) in an activity-controlled manner. The half-ester monomers were prepared through a highly selective monohydrolysis reaction, and the [Ru]-III catalyst was used to prepare structurally regular amphiphilic polymers in one step. The resulting polymer had a trans configuration and narrow molecular weight distribution indexes. Saturated polymers were prepared by hydrogenation and epoxidation reactions to improve the thermal stability of amphiphilic polynorbornenes, and the original structure of the polymers were remained without forming new stereosegregation. The selective monohydrolysis, as a tool for functionalized monomer design, is applied for the active ROMP to the preparation of functional amphiphilic polymers. |
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