Lewis酸碱对催化的可再生环状缩醛酯单体的开环聚合研究

汤家栋; 李茂盛; 陶友华

doi:10.11777/j.issn1000-3304.2022.22271

您当前的位置：

首页 >

文章列表页 >

Lewis酸碱对催化的可再生环状缩醛酯单体的开环聚合研究

研究论文 | 更新时间：2023-11-27

- Lewis酸碱对催化的可再生环状缩醛酯单体的开环聚合研究
- Lewis Pair-catalyzed Ring-opening Polymerization of Renewable Cyclic Acetal Ester Monomers
- 高分子学报 2023年54卷第3期页码：356-364
- 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：
  
  E-mail: youhua.tao@ciac.ac.cn
- 基金信息：
  
  国家自然科学基金(基金号U21A2089;51873211)
- DOI：10.11777/j.issn1000-3304.2022.22271
  中图分类号：
- 纸质出版日期：2023-03-20，
  
  网络出版日期：2022-10-10，
  
  收稿日期：2022-08-07，
  
  录用日期：2022-09-05
扫描看全文
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)

references

Kamber N. E.; Jeong W.; Waymouth R. M.; Pratt R. C.; Lohmeijer B. G.; Hedrick J. L. Organocatalytic ring-opening polymerization. Chem. Rev., 2007, 107, 5813-5840. doi:10.1021/cr068415bhttp://dx.doi.org/10.1021/cr068415b

Li M.; Tao Y.; Tang J.; Wang Y.; Zhang X.; Tao Y.; Wang X. Synergetic organocatalysis for eliminating epimerization in ring-opening polymerizations enables synthesis of stereoregular isotactic polyester. J. Am. Chem. Soc., 2019, 141, 281-289. doi:10.1021/jacs.8b09739http://dx.doi.org/10.1021/jacs.8b09739

Wang J.; Tao Y. Synthesis of sustainable polyesters via organocatalytic ring-opening polymerization of O-carboxyanhydrides: advances and perspectives. Macromol. Rapid Commun., 2021, 42, e2000535. doi:10.1002/marc.202000535http://dx.doi.org/10.1002/marc.202000535

Zhou T.; Guo Y. T.; Du F. S.; Li Z. C. Ring-opening polymerization of 2-oxabicyclo[2.2.2]octan-3-one and the influence of stereochemistry on the thermal properties of the polyesters. Chinese J. Polym. Sci., 2022, 40(10), 1173-1182. doi:10.1007/s10118-022-2725-1http://dx.doi.org/10.1007/s10118-022-2725-1

Lian J. W.; Chen J. L.; Luan S. F.; Liu W.; Zong B. N.; Tao Y. H.; Wang X. H. Organocatalytic copolymerization of cyclic lysine derivative and ε-caprolactam toward antibacterial nylon-6 polymers. ACS Macro. Lett., 2022, 11, 46-52. doi:10.1021/acsmacrolett.1c00658http://dx.doi.org/10.1021/acsmacrolett.1c00658

Chen J. L.; Dong Y. L.; Xiao C. S.; Tao Y. H.; Wang X. H. Organocatalyzed ring-opening polymerization of cyclic lysine derivative: sustainable access to cationic poly(epsilon-lysine) mimics. Macromolecules, 2021, 54, 2226-2231. doi:10.1021/acs.macromol.0c02689http://dx.doi.org/10.1021/acs.macromol.0c02689

Wang Y.; Li M.; Chen J.; Tao Y.; Wang X. O-to-S substitution enables dovetailing conflicting cyclizability, polymerizability, and recyclability: dithiolactone vs. Dilactone. Angew. Chem. Int. Ed., 2021, 60, 22547-22553. doi:10.1002/anie.202109767http://dx.doi.org/10.1002/anie.202109767

Yuan P.; Sun Y.; Xu X.; Luo Y.; Hong M. Towards high-performance sustainable polymers via isomerization-driven irreversible ring-opening polymerization of five-membered thionolactones. Nat. Chem., 2022, 14(3), 294-303. doi:10.1038/s41557-021-00817-9http://dx.doi.org/10.1038/s41557-021-00817-9

Abel B. A.; Snyder R. L.; Coates G. W. Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals. Science, 2021, 373, 783-789. doi:10.1126/science.abh0626http://dx.doi.org/10.1126/science.abh0626

Qiu H.; Yang Z.; Köhler M.; Ling J.; Schacher F. H. Synthesis and solution self-assembly of poly(1,3-dioxolane). Macromolecules, 2019, 52, 3359-3366. doi:10.1021/acs.macromol.9b00302http://dx.doi.org/10.1021/acs.macromol.9b00302

安泽胜, 陈昶乐, 何军坡, 洪春雁, 李志波, 李子臣, 刘超, 吕小兵, 秦安军, 曲程科, 唐本忠, 陶友华, 宛新华, 王国伟, 王佳, 郑轲, 邹文凯. 中国高分子合成化学的研究与发展动态. 高分子学报, 2019, 50, 1083-1132. doi:10.11777/j.issn1000-3304.2019.19136http://dx.doi.org/10.11777/j.issn1000-3304.2019.19136

陈学思, 陈国强, 陶友华, 王玉忠, 吕小兵, 张立群, 朱锦, 张军, 王献红. 生态环境高分子的研究进展. 高分子学报, 2019, 50, 1068-1082. doi:10.11777/j.issn1000-3304.2019.19124http://dx.doi.org/10.11777/j.issn1000-3304.2019.19124

袁鹏俊, 洪缪. “非张力环”γ-丁内酯及其衍生物开环聚合的研究进展. 高分子学报, 2019, 50, 327-337. doi:10.11777/j.issn1000-33042018.18232http://dx.doi.org/10.11777/j.issn1000-33042018.18232

Houk K. N.; Jabbari A.; Hall H. K.; Alemán C. Why δ-valerolactone polymerizes and γ-butyrolactone does not. J. Org. Chem., 2008, 73, 2674-2678. doi:10.1021/jo702567vhttp://dx.doi.org/10.1021/jo702567v

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

Zhao N.; Ren C.; Li H.; Li Y.; Liu S.; Li Z. Selective ring-opening polymerization of non-strained γ-butyrolactone catalyzed by a cyclic trimeric phosphazene base. Angew. Chem. Int. Ed. Engl., 2017, 56, 12987-12990. doi:10.1002/anie.201707122http://dx.doi.org/10.1002/anie.201707122

Zhang C. J.; Hu L. F.; Wu H. L.; Cao X. H.; Zhang X. H. Dual organocatalysts for highly active and selective synthesis of linear poly(γ-butyrolactone)s with high molecular weights. Macromolecules, 2018, 51, 8705-8711. doi:10.1021/acs.macromol.8b01757http://dx.doi.org/10.1021/acs.macromol.8b01757

Lin L.; Han D.; Qin J.; Wang S.; Xiao M.; Sun L.; Meng Y. Nonstrained γ-butyrolactone to high-molecular-weight poly(γ-butyrolactone): facile bulk polymerization using economical ureas/alkoxides. Macromolecules, 2018, 51, 9317-9322. doi:10.1021/acs.macromol.8b01860http://dx.doi.org/10.1021/acs.macromol.8b01860

Li M. S.; Zhang S.; Zhang X. Y.; Wang Y. C.; Chen J. L.; Tao Y. H.; Wang X. H. Unimolecular anion-binding catalysts for selective ring-opening polymerization of O-carboxyanhydrides. Angew. Chem. Int. Ed., 2021, 60, 6003-6012. doi:10.1002/anie.202011352http://dx.doi.org/10.1002/anie.202011352

Wu Y.; Zhang D.; Ma P.; Zhou R.; Hua L.; Liu R. Lithium hexamethyldisilazide initiated superfast ring opening polymerization of α-amino acid N-carboxyanhydrides. Nat. Commun., 2018, 9, 5297. doi:10.1038/s41467-018-07711-yhttp://dx.doi.org/10.1038/s41467-018-07711-y

Yuan J.; Zhang Y.; Li Z.; Wang Y.; Lu H. A S-Sn Lewis pair-mediated ring-opening polymerization of α-amino acid N-carboxyanhydrides: fast kinetics, high molecular weight, and facile bioconjugation. ACS Macro. Lett., 2018, 7, 892-897. doi:10.1021/acsmacrolett.8b00465http://dx.doi.org/10.1021/acsmacrolett.8b00465

He W.; Tao Y. Bifunctional fluoroalcohol catalysts enabled sustainable synthesis of poly(amino acid)s. Chin. J. Chem., 2021, 39, 2119-2124. doi:10.1002/cjoc.202100205http://dx.doi.org/10.1002/cjoc.202100205

Song Z.; Tan Z.; Cheng J. Recent advances and future perspectives of synthetic polypeptides from N-carboxyanhydrides. Macromolecules, 2019, 52, 8521-8539. doi:10.1021/acs.macromol.9b01450http://dx.doi.org/10.1021/acs.macromol.9b01450

Wu Y.; Chen K.; Wu X.; Liu L.; Zhang W.; Ding Y.; Liu S.; Zhou M.; Shao N.; Ji Z.; Chen J.; Zhu M.; Liu R. Superfast and water-insensitive polymerization on α‍-amino acid N-carboxyanhydrides to prepare polypeptides using tetraalkylammonium carboxylate as the initiator. Angew. Chem. Int. Ed. Engl., 2021, 60, 26063-26071. doi:10.1002/anie.202103540http://dx.doi.org/10.1002/anie.202103540

Wang Y.; Li M.; Wang S.; Tao Y.; Wang X. S-carboxyanhydrides: ultrafast and selective ring-opening polymerizations towards well-defined functionalized polythioesters. Angew. Chem. Int. Ed. Engl., 2021, 60, 10798-10805. doi:10.1002/anie.202016228http://dx.doi.org/10.1002/anie.202016228

Bannin T. J.; Kiesewetter M. K. Poly(thioester) by organocatalytic ring-opening polymerization. Macromolecules, 2015, 48, 5481-5486. doi:10.1021/acs.macromol.5b01463http://dx.doi.org/10.1021/acs.macromol.5b01463

Suzuki M.; Makimura K.; Matsuoka S. I. Thiol-mediated controlled ring-opening polymerization of cysteine-derived β‑thiolactone and unique features of product polythioester. Biomacromolecules, 2016, 17, 1135-1141. doi:10.1021/acs.biomac.5b01748http://dx.doi.org/10.1021/acs.biomac.5b01748

McGraw M. L.; Chen E. Y. X. Lewis pair polymerization: perspective on a ten-year journey. Macromolecules, 2020, 53, 6102-6122. doi:10.1021/acs.macromol.0c01156http://dx.doi.org/10.1021/acs.macromol.0c01156

宋艳娇, 何江华, 张越涛. 基于氮杂环烯烃的Lewis酸碱对催化二氢香豆素基聚酯合成的机理研究. 高分子学报, 2022, 53(9): 1112-1122. doi:10.11777/j.issn1000-3304.2022.22111http://dx.doi.org/10.11777/j.issn1000-3304.2022.22111

Wang Q.; Zhao W.; He J.; Zhang Y.; Chen E. Y. X. Living ring-opening polymerization of lactones by N-heterocyclic olefin/Al(C6F5)3 pairslewis: Structures of intermediates, kinetics, and mechanism. Macromolecules, 2017, 50, 123-136.

Bai Y.; Wang H.; He J.; Zhang Y. Rapid and scalable access to sequence-controlled DHDM multiblock copolymers by FLP polymerization. Angew. Chem. Int. Ed. Engl., 2020, 59, 11613-11619. doi:10.1002/anie.202004013http://dx.doi.org/10.1002/anie.202004013

Zhao W.; Li F.; Li C.; He J.; Zhang Y.; Chen C. Lewis pair catalyzed regioselective polymerization of (E,E)-alkyl sorbates for the synthesis of (AB)n sequenced polymers. Angew. Chem. Int. Ed. Engl., 2021, 60, 24306-24311. doi:10.1002/anie.202111336http://dx.doi.org/10.1002/anie.202111336

白云, 张越涛. Lewis酸碱对催化极性乙烯基单体聚合. 高分子学报, 2019, 50, 233-246. doi:10.11777/j.issn1000-3304.2019.18269http://dx.doi.org/10.11777/j.issn1000-3304.2019.18269

Bai Y.; Wang H.; He J.; Zhang Y.; Chen E. Y. X. Dual-initiating and living frustrated lewis pairs: expeditious synthesis of biobased thermoplastic elastomers. Nat. Commun., 2021, 12, 4874. doi:10.1038/s41467-021-25069-6http://dx.doi.org/10.1038/s41467-021-25069-6

Bai Y.; Wang H.; He J.; Zhang Y. Living polymerization of naturally renewable butyrolactone-based vinylidenes mediated by a frustrated lewis pair. Polym. Chem., 2021, 12, 5548-5555. doi:10.1039/d1py00924ahttp://dx.doi.org/10.1039/d1py00924a

Wan Y.; He J.; Zhang Y.; Chen E. Y. X. One-step synthesis of lignin-based triblock copolymers as high-temperature and UV-blocking thermoplastic elastomers. Angew. Chem. Int. Ed. Engl., 2022, 61, e202114946. doi:10.1002/anie.202114946http://dx.doi.org/10.1002/anie.202114946

Stapleton R. A.; Al-Humydi A.; Chai J.; Galan B. R.; Collins S. Sterically hindered aluminum alkyls: weakly interacting scavenging agents of use in olefin polymerization. Organometallics, 2006, 25, 5083-5092. doi:10.1021/om060474shttp://dx.doi.org/10.1021/om060474s

Lu X. B.; Ren B. H. Partners in epoxide copolymerization catalysis: approach to high activity and selectivity. Chinese J. Polym. Sci., 2022, 40(11), 1331-1348. doi:10.1007/s10118-022-2744-yhttp://dx.doi.org/10.1007/s10118-022-2744-y

Hormnirun P.; Marshall E. L.; Gibson V. C.; Pugh R. I.; White A. J. P. Study of ligand substituent effects on the rate and stereoselectivity of lactide polymerization using aluminum salen-type initiators. Proc. Natl. Acad. Sci. USA, 2006, 103, 15343-15348. doi:10.1073/pnas.0602765103http://dx.doi.org/10.1073/pnas.0602765103

更多指标>

浏览量

109

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

生物基δ-己内酯与L-丙交酯顺序开环共聚制备热塑性弹性体及其性质研究

结晶性生物可降解聚羟基脂肪酸酯的化学合成

苯甲氧基氧杂环内酯的合成及开环聚合研究