Aluminum<sup> </sup>Porphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO<sub>2</sub>/Epoxides

Zhen-zhen Zhou; Shun-jie Liu; Tao-tao Lang; Feng-xiang Gao; Xian-hong Wang

doi:10.11777/j.issn1000-3304.2023.23282

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AluminumPorphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO₂/Epoxides

Research Article | 更新时间：2024-04-16

- AluminumPorphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO₂/Epoxides
  增强出版
- Acta Polymerica Sinica Vol. 55, Issue 4, Pages: 396-406(2024)
- 作者机构：
  
  1.中国科学院长春应用化学研究所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：
  
  Shun-jie Liu, E-mail: sjliu@ciac.ac.cn
  Xian-hong Wang, E-mail: xhwang@ciac.ac.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23282
  CLC：
- Published：20 April 2024，
  
  Published Online：09 February 2024，
  
  Received：12 December 2023，
  
  Accepted：26 December 2023
- 稿件说明：
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周振震, 刘顺杰, 郎涛涛, 高凤翔, 王献红. 铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应. 高分子学报, 2024, 55(4), 396-406

Zhou, Z. Z.; Liu, S. J.; Lang, T. T.; Gao, F. X.; Wang, X. H. Aluminum porphyrin foldamer catalyst enables efficient copolymerization of CO₂/epoxides. Acta Polymerica Sinica, 2024, 55(4), 396-406
周振震, 刘顺杰, 郎涛涛, 高凤翔, 王献红. 铝卟啉折叠催化剂催化二氧化碳/环氧化物共聚反应. 高分子学报, 2024, 55(4), 396-406 DOI： 10.11777/j.issn1000-3304.2023.23282.

Zhou, Z. Z.; Liu, S. J.; Lang, T. T.; Gao, F. X.; Wang, X. H. Aluminum porphyrin foldamer catalyst enables efficient copolymerization of CO₂/epoxides. Acta Polymerica Sinica, 2024, 55(4), 396-406 DOI： 10.11777/j.issn1000-3304.2023.23282.

摘要

折叠催化剂因具有“类酶”的二级结构，被广泛应用于小分子化合物合成，然而其在高分子合成中的应用却鲜有报道. 基于双氨基功能化的铝卟啉与2

5-吡啶二甲酰氯的缩聚反应，本文报道了一种铝卟啉芳香酰胺折叠体催化剂，有效(300~1250 h

-1

)、高选择性(99%)地催化了二氧化碳(CO

)与环氧化物的共聚反应. 值得一提的是，该催化剂可以实现无助催化剂条件下CO

和环氧丙烷的共聚，催化活性可达525 h

-1

，同时聚合物选择性在95%以上，并且在80 ℃下表现出“类酶”的最佳温度特性. 在催化CO

与环氧环己烷共聚时，催化活性与二氧化碳压力(1~7 MPa)呈线性正相关关系，催化活性最高可达1250 h

-1

，聚合物选择性和碳酸酯单元含量保持在99%以上. 本文报道的铝卟啉折叠体催化剂为芳香酰胺折叠体在催化领域的发展提供了借鉴，同时也进一步拓展了折叠催化在高分子合成中的应用.

Abstract

Foldamer catalysts have been extensively applied in the synthesis of small molecules due to the "enzyme-like" secondary structure

while their contributions in polymer synthesis were rarely reported. Based on the polycondensation reaction of aluminum bis-aminoporphyrin and 2

‍5-diacylchloropyridine

we reported an aluminum porphyrin aromatic amide foldamer catalyst (AAF)

and its foldamer structure was verified by the circular dichroism spectrum. The foldamer catalyst AAF effectively (turnover frequency

TOF=300‍‒‍1250 h

-1

) catalyzed the copolymerization of carbon dioxide and epoxides with high polymer selectivity (99%). It is worth mentioning that

this catalyst can realize the copolymerization of carbon dioxide and propylene oxide even in the absence of cocatalyst with a TOF of 525 h

-1

and polymer selectivity of 95%

which also exhibits an enzyme-like optimum temperature of 80 ℃. Additionally

it could also catalyze the copolymerization of carbon dioxide and cyclohexane oxide

the catalytic activity (TOF=550‍‒‍1250 h

-1

) was linearly positively correlated with carbon dioxide pressure (1‍‒‍7 MPa)

and the polymer selectivity and carbonate units were all over 99%. Herein

we reported an aluminum porphyrin based aromatic amide foldamer catalyst

which broadens the application of foldamer catalysis in polymers and opens up new avenues for the study of aromatic amide foldamers in the field of catalysis.

关键词

铝卟啉芳香酰胺折叠体二氧化碳环氧化物协同催化

Keywords

Aluminum porphyrinAromatic amide foldamerCarbon dioxideEpoxidesCooperative catalysis

references

Girvin Z. C.; Gellman S. H. Foldamer catalysis. J. Am. Chem. Soc., 2020, 142(41), 17211-17223. doi:10.1021/jacs.0c07347http://dx.doi.org/10.1021/jacs.0c07347

Yashima E.; Maeda K.; Iida H.; Furusho Y.; Nagai K. Helical polymers: synthesis, structures, and functions. Chem. Rev., 2009, 109(11), 6102-6211. doi:10.1021/cr900162qhttp://dx.doi.org/10.1021/cr900162q

Zhang G.; Cheng X. X.; Wang Y. F.; Zhang W. Supramolecular chiral polymeric aggregates: construction and applications. Aggregate, 2023, 4(1), e262. doi:10.1002/agt2.262http://dx.doi.org/10.1002/agt2.262

Andrews M. K.; Liu X. Y.; Gellman S. H. Tailoring reaction selectivity by modulating a catalytic diad on a foldamer scaffold. J. Am. Chem. Soc., 2022, 144(5), 2225-2232. doi:10.1021/jacs.1c11542http://dx.doi.org/10.1021/jacs.1c11542

Girvin Z. C.; Andrews M. K.; Liu X. Y.; Gellman S. H. Foldamer-templated catalysis of macrocycle formation. Science, 2019, 366(6472), 1528-1531. doi:10.1126/science.aax7344http://dx.doi.org/10.1126/science.aax7344

Bécart D.; Diemer V.; Salaün A.; Oiarbide M.; Nelli Y. R.; Kauffmann B.; Fischer L.; Palomo C.; Guichard G. Helical oligourea foldamers as powerful hydrogen bonding catalysts for enantioselective C―C bond-forming reactions. J. Am. Chem. Soc., 2017, 139(36), 12524-12532. doi:10.1021/jacs.7b05802http://dx.doi.org/10.1021/jacs.7b05802

Kang S. M.; Han S. S.; Zhu Y. Y.; Wu Z. Q. Cobalt(III) porphyrin-decorated stereoregular polyisocyanides enable highly effective cooperative catalysis for hydration of alkynes. ACS Catal., 2021, 11(22), 13838-13847. doi:10.1021/acscatal.1c04062http://dx.doi.org/10.1021/acscatal.1c04062

Wang X. H. Biodegradable polymers, history tells polymer science's fortune. Chinese J. Polym. Sci., 2022, 40(5), 431-432. doi:10.1007/s10118-022-2737-xhttp://dx.doi.org/10.1007/s10118-022-2737-x

Liu J.; Ren W. M.; Lu X. B. Fully degradable brush polymers with polycarbonate backbones and polylactide side chains. Sci. China Chem., 2015, 58(6), 999-1004. doi:10.1007/s11426-014-5263-zhttp://dx.doi.org/10.1007/s11426-014-5263-z

游怀, 严硕, 宋学霖, 卓春伟, 刘顺杰, 王献红. 有机催化精准制备聚酯多元醇: 环氧化物原位缓释与捕捉策略. 高分子学报, 2023, 54(3), 327-335.

曹晓瀚, 吕俊奇, 赵佳, 张成建, 孙悦, 虞卿磊, 侯家祥, 张兴宏. 氧化异丁烯与CO2共聚物的合成及其结构与性能. 高分子学报, 2022, 53(9), 1104-1111. doi:10.11777/j.issn1000-3304.2022.22109http://dx.doi.org/10.11777/j.issn1000-3304.2022.22109

Li Y.; Zhang Y. Y.; Hu L. F.; Zhang X. H.; Du B. Y.; Xu J. T. Carbon dioxide-based copolymers with various architectures. Prog. Polym. Sci., 2018, 82, 120-157. doi:10.1016/j.progpolymsci.2018.02.001http://dx.doi.org/10.1016/j.progpolymsci.2018.02.001

Zhang X. Y.; Fevre M.; Jones G. O.; Waymouth R. M. Catalysis as an enabling science for sustainable polymers. Chem. Rev., 2018, 118(2), 839-885. doi:10.1021/acs.chemrev.7b00329http://dx.doi.org/10.1021/acs.chemrev.7b00329

Lu X. B.; Shi L.; Wang Y. M.; Zhang R.; Zhang Y. J.; Peng X. J.; Zhang Z. C.; Li B. Design of highly active binary catalyst systems for CO2copolymerization/epoxide: polymer selectivity, enantioselectivity, and stereochemistry control. J. Am. Chem. Soc., 2006, 128(5), 1664-1674. doi:10.1021/ja056383ohttp://dx.doi.org/10.1021/ja056383o

S, S.; Min, J.; Seong, J.; Na, S.; Lee, B. A highly active and recyclable catalytic system for CO2/propylene oxide copolymerization. Angew. Chem. Int. Ed., 2008, 47(38), 7306-7309. doi:10.1002/anie.200801852http://dx.doi.org/10.1002/anie.200801852

Klaus S.; Vagin S. I.; Lehenmeier M. W.; Deglmann P.; Brym A. K.; Rieger B. Kinetic and mechanistic investigation of mononuclear and flexibly linked dinuclear complexes for copolymerization of CO2 and epoxides. Macromolecules, 2011, 44(24), 9508-9516. doi:10.1021/ma201387fhttp://dx.doi.org/10.1021/ma201387f

Fiorentini F.; Diment W. T.; Deacy A. C.; Kerr R. W. F.; Faulkner S.; Williams C. K. Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers. Nat. Commun., 2023, 14(1), 4783. doi:10.1038/s41467-023-40284-zhttp://dx.doi.org/10.1038/s41467-023-40284-z

Zhang R. Y.; Kuang Q. X.; Cao H.; Liu S. J.; Chen X. S.; Wang X. H.; Wang F. S. Unity makes strength: constructing polymeric catalyst for selective synthesis of CO2/epoxide copolymer. CCS Chem., 2023, 5(3), 750-760. doi:10.31635/ccschem.022.202201952http://dx.doi.org/10.31635/ccschem.022.202201952

Zhuo C. W.; Cao H.; Wang X. S.; Liu S. J.; Wang X. H. Polymeric aluminum porphyrin: controllable synthesis of ultra-low molecular weight CO2-based polyols. Chin. Chem. Lett., 2023, 34(8), 108011. doi:10.1016/j.cclet.2022.108011http://dx.doi.org/10.1016/j.cclet.2022.108011

Cao H.; Qin Y. S.; Zhuo C. W.; Wang X. H.; Wang F. S. Homogeneous metallic oligomer catalyst with multisite intramolecular cooperativity for the synthesis of CO2-based polymers. ACS Catal., 2019, 9(9), 8669-8676. doi:10.1021/acscatal.9b02741http://dx.doi.org/10.1021/acscatal.9b02741

Chen P.; Zhou H.; Cao H.; Zhuo C. W.; Liu S. J.; Wang X. H. Polymeric catalyst with polymerization-enhanced Lewis acidity for CO2-based copolymers. Chin. Chem. Lett., 2023, 34(12), 108630. doi:10.1016/j.cclet.2023.108630http://dx.doi.org/10.1016/j.cclet.2023.108630

卓春伟, 曹瀚, 周振震, 刘顺杰, 王献红. 高分子铝卟啉体系: 二氧化碳基多元醇的高效可控合成. 高分子学报, 2023, 54, 601-611. doi:10.11777/j.issn1000-3304.2022.22349http://dx.doi.org/10.11777/j.issn1000-3304.2022.22349

Yang G. W.; Zhang Y. Y.; Wu G. P. Modular organoboron catalysts enable transformations with unprecedented reactivity. Acc. Chem. Res., 2021, 54(23), 4434-4448. doi:10.1021/acs.accounts.1c00620http://dx.doi.org/10.1021/acs.accounts.1c00620

Kuang Q. X.; Zhang R. Y.; Zhou Z. Z.; Liao C.; Liu S. J.; Chen X. S.; Wang X. H. A supported catalyst that eanables the synthesis of colorless CO2-polyols with ultra-low molecular weight. Angew. Chem. Int. Ed., 2023, 62, e202305186. doi:10.1002/anie.202308125http://dx.doi.org/10.1002/anie.202308125

Lidston C. A. L.; Severson S. M.; Abel B. A.; Coates G. W. Multifunctional catalysts for ring-opening copolymerizations. ACS Catal., 2022, 12(18), 11037-11070. doi:10.1021/acscatal.2c02524http://dx.doi.org/10.1021/acscatal.2c02524

George K. L.; Horne W. S. Foldamer tertiary structure through sequence-guided protein backbone alteration. Acc. Chem. Res., 2018, 51(5), 1220-1228. doi:10.1021/acs.accounts.8b00048http://dx.doi.org/10.1021/acs.accounts.8b00048

Zhou Z. Z.; Liu S. J.; Yang L. H.; Kuang Q. X.; Zhou H.; Zhuo C. W.; Wang X. H. Dynamic foldamer catalyst enables efficient copolymerization of CO2 and epoxides. ACS Catal., 2023, 13(22), 15116-15125. doi:10.1021/acscatal.3c04274http://dx.doi.org/10.1021/acscatal.3c04274

Zhang D. W.; Zhao X.; Hou J. L.; Li Z. T. Aromatic amide foldamers: structures, properties, and functions. Chem. Rev., 2012, 112(10), 5271-5316. doi:10.1021/cr300116khttp://dx.doi.org/10.1021/cr300116k

Violette A.; Averlant-Petit M. C.; Semetey V.; Hemmerlin C.; Casimir R.; Graff R.; Marraud M.; Briand J. P.; Rognan D.; Guichard G. N,N'-linked oligoureas as foldamers: chain length requirements for helix formation in protic solvent investigated by circular dichroism, NMR spectroscopy, and molecular dynamics. J. Am. Chem. Soc., 2005, 127(7), 2156-2164. doi:10.1021/ja044392bhttp://dx.doi.org/10.1021/ja044392b

郭洪辰, 秦玉升, 王献红. 乙酸/氧气法高效合成取代卟啉. 应用化学, 2020, 37(3), 264-270. doi:10.11944/j.issn.1000-0518.2020.03.190271http://dx.doi.org/10.11944/j.issn.1000-0518.2020.03.190271

Solleder S. C.; Zengel D.; Wetzel K. S.; Meier M. A. R. A scalable and high-yield strategy for the synthesis of sequence-defined macromolecules. Angew. Chem. Int. Ed., 2016, 55(3), 1204-1207. doi:10.1002/anie.201509398http://dx.doi.org/10.1002/anie.201509398

Gellman, S. H. Foldamers: a manifesto. Acc. Chem. Res., 1998, 31(4), 173-180. doi:10.1021/ar960298rhttp://dx.doi.org/10.1021/ar960298r

Horne W. S.; Gellman S. H. Foldamers with heterogeneous backbones. Acc. Chem. Res., 2008, 41(10), 1399-1408. doi:10.1021/ar800009nhttp://dx.doi.org/10.1021/ar800009n

Rogers J. M.; Kwon S.; Dawson S. J.; Mandal P. K.; Suga H.; Huc I. Ribosomal synthesis and folding of peptide-helical aromatic foldamer hybrids. Nat. Chem., 2018, 10(4), 405-412. doi:10.1038/s41557-018-0007-xhttp://dx.doi.org/10.1038/s41557-018-0007-x

Nair R. V.; Vijayadas K. N.; Roy A.; Sanjayan G. J. Heterogeneous foldamers from aliphatic-aromatic amino acid building blocks: current trends and future prospects. Eur. J. Org. Chem., 2014, 2014(35), 7763-7780. doi:10.1002/ejoc.201402877http://dx.doi.org/10.1002/ejoc.201402877

Li C.; Jiang H. M.; Liu P. X.; Zhai Y.; Yang X. Q.; Gao L. C.; Jiang L. One porphyrin per chain self-assembled helical ion-exchange channels for ultrahigh osmotic energy conversion. J. Am. Chem. Soc., 2022, 144(21), 9472-9478. doi:10.1021/jacs.2c02798http://dx.doi.org/10.1021/jacs.2c02798

de Witte P. A. J.; Castriciano M.; Cornelissen J. J. L. M.; Monsù Scolaro L.; Nolte R. J. M.; Rowan A. E. Helical polymer-anchored porphyrin nanorods. Chem, 2003, 9(8), 1775-1781. doi:10.1002/chem.200390204http://dx.doi.org/10.1002/chem.200390204

Liu S. J.; Miao Y. Y.; Qiao L. J.; Qin Y. S.; Wang X. H.; Chen X. S.; Wang F. S. Controllable synthesis of a narrow polydispersity CO2-based oligo(carbonate-ether) tetraol. Polym. Chem., 2015, 6(43), 7580-7585. doi:10.1039/c5py00556fhttp://dx.doi.org/10.1039/c5py00556f

Liu S. J.; Qin Y. S.; Chen X. S.; Wang X. H.; Wang F. S. One-pot controllable synthesis of oligo(carbonate-ether) triol using a Zn-Co-DMC catalyst: the special role of trimesic acid as an initiation-transfer agent. Polym. Chem., 2014, 5(21), 6171-6179. doi:10.1039/c4py00578chttp://dx.doi.org/10.1039/c4py00578c

Jutz F.; Buchard A.; Kember M. R.; Fredriksen S. B.; Williams C. K. Mechanistic investigation and reaction kinetics of the low-pressure copolymerization of cyclohexene oxide and carbon dioxide catalyzed by a dizinc complex. J. Am. Chem. Soc., 2011, 133(43), 17395-17405. doi:10.1021/ja206352xhttp://dx.doi.org/10.1021/ja206352x

Deng J. Y.; Ratanasak M.; Sako Y.; Tokuda H.; Maeda C.; Hasegawa J. Y.; Nozaki K.; Ema T. Aluminum porphyrins with quaternary ammonium halides as catalysts for copolymerization of cyclohexene oxide and CO2: metal-ligand cooperative catalysis. Chem. Sci., 2020, 11(22), 5669-5675. doi:10.1039/d0sc01609hhttp://dx.doi.org/10.1039/d0sc01609h

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Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

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⁰

Aluminum Porphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO2/Epoxides

DOI：10.11777/j.issn1000-3304.2023.23282

摘要

Abstract

关键词

Keywords

references

AluminumPorphyrin Foldamer Catalyst Enables Efficient Copolymerization of CO₂/Epoxides