Lewis Pair-catalyzed Ring-opening Polymerization of Renewable Cyclic Acetal Ester Monomers

Jia-dong Tang; Mao-sheng Li; You-hua Tao

doi:10.11777/j.issn1000-3304.2022.22271

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Lewis Pair-catalyzed Ring-opening Polymerization of Renewable Cyclic Acetal Ester Monomers

Research Article | 更新时间：2023-11-27

- Lewis Pair-catalyzed Ring-opening Polymerization of Renewable Cyclic Acetal Ester Monomers
- ACTA POLYMERICA SINICA Vol. 54, Issue 3, Pages: 356-364(2023)
- 作者机构：
  
  1.中国科学院长春应用化学研究所中国科学院生态环境高分子材料重点实验室长春 130022
  2.中国科学技术大学应用化学与工程学院合肥 230026
- 作者简介：
  
  You-hua Tao, E-mail: youhua.tao@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2022.22271
  CLC：
- Published：20 March 2023，
  
  Published Online：10 October 2022，
  
  Received：07 August 2022，
  
  Accepted：05 September 2022
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汤家栋,李茂盛,陶友华.Lewis酸碱对催化的可再生环状缩醛酯单体的开环聚合研究[J].高分子学报,2023,54(03):356-364.

Tang Jia-dong,Li Mao-sheng,Tao You-hua.Lewis Pair-catalyzed Ring-opening Polymerization of Renewable Cyclic Acetal Ester Monomers[J].ACTA POLYMERICA SINICA,2023,54(03):356-364.
汤家栋,李茂盛,陶友华.Lewis酸碱对催化的可再生环状缩醛酯单体的开环聚合研究[J].高分子学报,2023,54(03):356-364. DOI： 10.11777/j.issn1000-3304.2022.22271.

Tang Jia-dong,Li Mao-sheng,Tao You-hua.Lewis Pair-catalyzed Ring-opening Polymerization of Renewable Cyclic Acetal Ester Monomers[J].ACTA POLYMERICA SINICA,2023,54(03):356-364. DOI： 10.11777/j.issn1000-3304.2022.22271.

摘要

从生物质原料3

4-二氢吡喃出发，合成了可再生环状缩醛酯单体(H-AE)，从结构上看，该单体在

-丁内酯中引入了缩醛单元，在开环聚合过程中，通过释放甲醛分子有希望在温和条件下得到聚(

-丁内酯). 选用合适的Lewis酸碱对催化剂，基本抑制了聚合过程中的链回咬副反应，实现了单体的可控聚合. 详细研究了催化剂的酸/碱性强度及其位阻大小对于合成的聚合物的组成和比例的影响，通过设计和优化催化剂的结构，实现了聚合物中聚丁内酯单元和聚缩醛酯单元比例的调控. 对所得聚合物进行了

H-NMR、

C-NMR及扩散排序核磁共振(DOSY)表征，结合聚合过程的核磁与SEC监测，证实所得聚合物为丁内酯与缩醛酯的无规共聚物. 根据实验数据和表征结果，推测聚合遵循Lewis酸碱对调控的阴离子开环聚合机理，酸碱催化剂共同稳定活性链末端，实现了亲核进攻和甲醛的脱除.

Abstract

A seven-membered cyclic acetal ester monomer (H-AE) was synthesized from biomass-based 3

‍4-dihydropyran. Structurally

this monomer introduces an acetal unit into

-butyrolactone

which promises to afford poly(

-butyrolactone) under mild conditions by releasing formaldehyde molecules during ring-opening polymerization. The judicious choice of Lewis pair catalysts substantially inhibits the back-biting side reactions during the polymerization process and realizes the entropy driven polymerization. We carefully studied the effects of the acid/basicity and the steric hindrance of the catalyst on the composition of the synthesized polymers. By designing and optimizing the catalyst structure

regulation of the ratio of poly(

-butyrolactone) and poly(acetal esters) units was realized. With the help of NMR and SEC characterization of the polymer and the polymerization process

we confirmed that the obtained polymer is a random copolymer of poly(

γ‍

-butyrolactone) and poly(acetal ester). Finally

based on the experimental data and characterization results

we speculate that the polymerization follows the Lewis-pair mediated anionic ring-opening polymerization mechanism. Lewis acid and Lewis base act together on the active anion chain end to afford appropriate affinity and supress the back-bite side reaction while ensuring the release of formaldehyde.

关键词

开环聚合Lewis酸碱对环状缩醛酯聚(γ-丁内酯)

Keywords

Ring-opening polymerizationLewis pairCyclic acetal esterPoly(γ-butyrolactone)

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Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department, College of Polymer Science and Engineering, Qingdao University of Science and Technology

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