环状聚合物合成新路线：分子内受阻Lewis酸碱对催化下的高浓度合成

王献红; 宛新华

doi:10.11777/j.issn1000-3304.2022.22449

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环状聚合物合成新路线：分子内受阻Lewis酸碱对催化下的高浓度合成

亮点评述 | 更新时间：2023-03-08

- 环状聚合物合成新路线：分子内受阻Lewis酸碱对催化下的高浓度合成
- The Synthesis of Cyclic Bio-based Acrylic Polymers by an Intramolecular Trifunctional Lewis Pair
- 高分子学报 2023年54卷第4期页码：409-412
- 作者机构：
  
  1.中国科学院长春应用化学研究所长春 130022
  2.北京分子科学国家研究中心高分子化学与物理教育部重点实验室北京大学化学与分子工程学院北京 100871
- 作者简介：
  
  E-mail: xhwang@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2022.22449
  中图分类号：
- 纸质出版日期：2023-04-20，
  
  收稿日期：2022-12-27，
扫描看全文
王献红,宛新华.环状聚合物合成新路线：分子内受阻Lewis酸碱对催化下的高浓度合成[J].高分子学报,2023,54(04):409-412.

Wang Xian-hong,Wan Xin-hua.The Synthesis of Cyclic Bio-based Acrylic Polymers by an Intramolecular Trifunctional Lewis Pair[J].ACTA POLYMERICA SINICA,2023,54(04):409-412.
王献红,宛新华.环状聚合物合成新路线：分子内受阻Lewis酸碱对催化下的高浓度合成[J].高分子学报,2023,54(04):409-412. DOI： 10.11777/j.issn1000-3304.2022.22449.

Wang Xian-hong,Wan Xin-hua.The Synthesis of Cyclic Bio-based Acrylic Polymers by an Intramolecular Trifunctional Lewis Pair[J].ACTA POLYMERICA SINICA,2023,54(04):409-412. DOI： 10.11777/j.issn1000-3304.2022.22449.

摘要

与传统线形聚合物的合成不同，环状聚合物的合成通常需要特殊的催化剂设计且容易引入主体单体以外的其他化学结构. 最近，吉林大学张越涛团队将两分子硼路易斯酸(LA)与一分子磷路易斯碱(LB)以共价键相连，合成出分子内受阻路易斯酸碱对B-P-B三官能催化剂，通过分子内和分子间的双重协同作用实现了1+1

2的催化效果，进而成功以

-甲基-

-亚甲基-

-丁内酯(MMBL)为单体合成了完全由一种丙烯酸酯类单体构成的环状聚合物

-PMMBL. 值得指出的是，与合成环状聚合物的传统策略不同，该催化剂可以在较高浓度下简单快速地合成环状聚合物，开创了环状聚合物宏量高效合成的新路线.

Abstract

Cyclic polymers exhibit unique properties in comparison with their linear analogs. However

it remains challenging to develop highly efficient and controllable strategy for synthesis of cyclic polymers. Recently

Prof. Zhang group from the State Key Laboratory of Supramolecular Structure and Materials at Jilin University

designs and synthesizes an intramolecularly

covalently tethered B-P-B trifunctional frustrated Lewis pair catalyst/initiator

composed of two acidic B sites and one basic P sites. Through both the intramolecularly-and intermolecularly synergistic effect

such B-P-B system exhibits "one plus one is greater than two" effect

thus successfully polymerizing

-methyl-

-methylene-

-butyrolactone (MMBL) into an authentic cyclic polymer

-PMMBL composed entirely of acrylate monomer units. Compared with traditional strategies

this method exhibits good generality and can be employed for rapid synthesis of cyclic polymers

suggesting its potential application in the scalable synthesis of cyclic polymers in the future.

关键词

环状聚合物受阻路易斯酸碱对三官能催化剂分子内协同效应分子间协同效应

Keywords

Cyclic polymerFrustrated Lewis pairTrifunctional catalystIntramolecular synergistic effectIntermolecular synergistic effect

references

Hong M.; Chen E. Y. X. Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone. Nat. Chem., 2016, 8(1), 42-49. doi:10.1038/nchem.2391http://dx.doi.org/10.1038/nchem.2391

Wang T. W.; Golder M. R. Advancing macromolecular hoop construction: recent developments in synthetic cyclic polymer chemistry. Polym. Chem., 2021, 12(7), 958-969. doi:10.1039/d0py01655ahttp://dx.doi.org/10.1039/d0py01655a

Oga Y.; Hosoi Y.; Takasu A. Synthesis of cyclic poly(methyl methacrylate) via N-heterocyclic carbene (NHC) initiated-anionic polymerization and subsequent ring-closing without need of highly dilute conditions. Polymer, 2020, 186, 122019. doi:10.1016/j.polymer.2019.122019http://dx.doi.org/10.1016/j.polymer.2019.122019

McGraw M. L.; Clarke R. W.; Chen E. Y. X. Synchronous control of chain length/sequence/topology for precision synthesis of cyclic block copolymers from monomer mixtures. J. Am. Chem. Soc., 2021, 143(9), 3318-3322. doi:10.1021/jacs.1c00561http://dx.doi.org/10.1021/jacs.1c00561

Song Y. J.; He J. H.; Zhang Y. T.; Gilsdorf R. A.; Chen E. Y. X. Recyclable cyclic bio-based acrylic polymer via pairwise monomer enchainment by a trifunctional Lewis pair. Nat. Chem., 2022, DOI: 10.1038/s41557-022-01097-7.http://dx.doi.org/10.1038/s41557-022-01097-7.

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