Green Synthesis of Chemically Recyclable Polyesters <italic style="font-style: italic">via</italic> Dehydrogenative Copolymerization of Diols

Wei-Ming Xu; Yuan-Dong Yu; Meng-Xiang Ma; Hui-Du Xu; Rui-Qin Wang; Yu-Peng Pan; Ke-Qin Wu; Wei-Ran Yang; Chang-Guang Yao

doi:10.1007/s10118-023-2903-9

Your Location：

Home >

Browse articles >

Green Synthesis of Chemically Recyclable Polyesters via Dehydrogenative Copolymerization of Diols

RESEARCH ARTICLE | Updated：2023-07-18

- Green Synthesis of Chemically Recyclable Polyesters via Dehydrogenative Copolymerization of Diols
- Chinese Journal of Polymer Science Vol. 41, Issue 8, Pages: 1206-1214(2023)
- Affiliations：
  
  a.School of Chemistry and Chemical Engineering, Nanchang University, Nanchang 330031, China
  b.School of Resource & Environment, Nanchang University, Nanchang 330031, China
  c.Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen 518055, China
- Author bio：
  
  wyang16@ncu.edu.cn (W.R.Y.)
  cgyao@ncu.edu.cn (C.G.Y.)
- Funds：
- DOI：10.1007/s10118-023-2903-9
  CLC：
- Received：12 October 2022，
  
  Revised：2022-11-8，
  
  Accepted：14 November 2022，
  
  Online First：31 January 2023，
  
  Published：01 August 2023
- Accepted：
Scan QR Code
Xu, W. M.; Yu, Y. D.; Ma, M. X.; Xu, H. D.; Wang, R. Q.; Pan, Y. P.; Wu, K. Q.; Yang, W. R.; Yao, C. G. Green synthesis of chemically recyclable polyesters via dehydrogenative copolymerization of diols. Chinese J. Polym. Sci. 2023, 41, 1206–1214

Wei-Ming Xu, Yuan-Dong Yu, Meng-Xiang Ma, et al. Green Synthesis of Chemically Recyclable Polyesters via Dehydrogenative Copolymerization of Diols[J]. Chinese Journal of Polymer Science, 2023, 41(8): 1206-1214. DOI: 10.1007/s10118-023-2903-9.
Xu, W. M.; Yu, Y. D.; Ma, M. X.; Xu, H. D.; Wang, R. Q.; Pan, Y. P.; Wu, K. Q.; Yang, W. R.; Yao, C. G. Green synthesis of chemically recyclable polyesters via dehydrogenative copolymerization of diols. Chinese J. Polym. Sci. 2023, 41, 1206–1214 DOI： 10.1007/s10118-023-2903-9.

Wei-Ming Xu, Yuan-Dong Yu, Meng-Xiang Ma, et al. Green Synthesis of Chemically Recyclable Polyesters via Dehydrogenative Copolymerization of Diols[J]. Chinese Journal of Polymer Science, 2023, 41(8): 1206-1214. DOI: 10.1007/s10118-023-2903-9. DOI：

摘要

Abstract

Preparation of chemically recyclable polyesters by ring-opening polymerization (ROP) has made a considerable progress over the past few years. However

this method involves cumbersome synthesis and minimal functional diversity of cyclic monomers. Therefore

it is of great significance to develop novel polymerization methods for direct polymerization of commercially available monomers to prepare recyclable polyesters with versatile functionalities. In present work

we report dehydrogenative copolymerization of commercial

-diols to afford high molecular weight chemically recyclable aliphatic copolyesters (65.7 kg·mol

−1

) by using commercially available Milstein catalyst precursor. The thermal properties of the obtained copolymers could be finely tuned by simply adjusting the feeding ratio of two monomers. The incorporation of aliphatic or aromatic rings into polyester mainchain

via

copolymerization of 1

10-decanediol with 1

4-cyclohexanedimethanol and 1

4-benzenedimethanol could significantly improve the thermal properties of the resulting copolymers. More importantly

the obtained copolyesters were able to completely depolymerize back to original diols

via

hydrogenation by the same catalyst in solvent-free and mild conditions

thus offering a green and cost-effective route toward the preparation of widely used polyesters.

关键词

Keywords

references

Geyer,R.;Jambeck,J.R.;Law,K.L.Production,use,andfateofallplasticsevermade. Sci. Adv. 2017 , 3 ,e1700782..

Stubbins,A.;Law,K.L.;Muñoz,S.E.;Bianchi,T.S.;Zhu,L.PlasticsintheEarthsystem. Science 2021 , 373 ,51−55..

Hillmyer,M.A.;Tolman,W.B.Aliphaticpolyesterblockpolymers:renewable,degradable,andsustainable. Acc. Chem. Res. 2014 , 47 ,2390−2396..

Korley,L.T.J.;Epps,T.H.,III;Helms,B.A.;Ryan,A.J.Towardpolymerupcycling-addingvalueandtacklingcircularity. Science 2021 , 373 ,66−69..

Kamber,N.E.;Jeong,W.;Waymouth,R.M.;Pratt,R.C.;Lohmeijer,B.G.G.;Hedrick,J.L.Organocatalyticring-openingpolymerization. Chem. Rev. 2007 , 107 ,5813−5840..

Feng,Z.;Wu,L.;Dong,H.;Liu,B.;Cheng,R.Copolyestersof ε -caprolactoneandL-lactidecatalyzedbyatetrabutylammoniumphthalimide- N -oxylorganocatalyst. RSC Adv. 2021 , 11 ,19021−19028..

Tang,X.;Shi,C.;Zhang,Z.;Chen,E.Y.X.Tougheningbiodegradableisotacticpoly(3-hydroxybutyrate) via stereoselectivecopolymerizationofadiolideandlactones. Macromolecules 2021 , 54 ,9401−9409..

Tang,X.;Westlie,A.H.;Caporaso,L.;Cavallo,L.;Falivene,L.;Chen,E.Y.X.Biodegradablepolyhydroxyalkanoatesbystereoselectivecopolymerizationofracemicdiolides:stereocontrolandpolyolefin-likeproperties. Angew. Chem. Int. Ed. 2020 , 59 ,7881−7890..

Tang,X.;Westlie,A.H.;Watson,E.M.;Chen,E.Y.X.Stereosequencedcrystallinepolyhydroxyalkanoatesfromdiastereomericmonomermixtures. Science 2019 , 366 ,754−758..

Kocen,A.L.;Cui,S.L.;Lin,T.W.;LaPointe,A.M.;Coates,G.W.Chemicallyrecyclableester-linkedpolypropylene. J. Am. Chem. Soc. 2022 , 144 ,12613−12618..

Häußler,M.;Eck,M.;Rothauer,D.;Mecking,S.Closed-looprecyclingofpolyethylene-likematerials. Nature 2021 , 590 ,423−427..

Coates,G.W.;Getzler,Y.D.Y.L.Chemicalrecyclingtomonomerforanideal,circularpolymereconomy. Nat. Mater. 2020 , 5 ,501−516..

Zhao,J.Z.;Yue,T.J.;Ren,B.H.;Liu,Y.;Ren,W.M.;Lu,X.B.Recyclablesulfur-richpolymerswithenhancedthermal,mechanical,andopticalperformance. Macromolecules 2022 ,10.1021/acs.macromol.2c01628..

Liao,X.;Cui,F.C.;He,J.H.;Ren,W.M.;Lu,X.B.;Zhang,Y.T.AsustainableapproachforthesynthesisofrecyclablecyclicCO 2 -basedpolycarbonates. Chem. Sci. 2022 , 13 ,6283−6290..

Liu,Y.;Zhou,H.;Guo,J.Z.;Ren,W.M.;Lu,X.B.Completelyrecyclablemonomersandpolycarbonate:approachtosustainablepolymers. Angew. Chem. Int. Ed. 2017 , 56 ,4862−4866..

Yuan,P.;Sun,Y.;Xu,X.;Luo,Y.;Hong,M.Towardshigh-performancesustainablepolymers via isomerization-drivenirreversiblering-openingpolymerizationoffive-memberedthionolactones. Nat. Chem. 2021 , 14 ,294−303..

Fan,H.Z.;Yang,X.;Chen,J.H.;Tu,Y.M.;Cai,Z.;Zhu,J.B.Advancingthedevelopmentofrecyclablearomaticpolyestersbyfunctionalizationandstereocomplexation. Angew. Chem. Int. Ed. 2022 , 61 ,e202117639..

Tu,Y.M.;Wang,X.M.;Yang,X.;Fan,H.Z.;Gong,F.L.;Cai,Z.;Zhu,J.B.Biobasedhigh-performancearomatic-aliphaticpolyesterswithcompleterecyclability. J. Am. Chem. Soc. 2021 , 143 ,20591−20597..

Zhu,J.B.;Watson,E.M.;Tang,J.;Chen,E.Y.X.Asyntheticpolymersystemwithrepeatablechemicalrecyclability. Science 2018 , 360 ,398−403..

Hong,M.;Chen,E.Y.X.Completelyrecyclablebiopolymerswithlinearandcyclictopologies via ring-openingpolymerizationof γ -butyrolactone. Nat. Chem. 2016 , 8 ,42−49..

Zhu,J.B.;Chen,E.Y.X.Livingcoordinationpolymerizationofasix-fivebicycliclactonetoproducecompletelyrecyclablepolyester. Angew. Chem. Int. Ed. 2018 , 57 ,12558−12562..

Zhu,J.B.;Chen,E.Y.X.Catalyst-sidearm-inducedstereoselectivityswitchinginpolymerizationofaracemiclactoneforstereocomplexedcrystallinepolymerwithacircularlifecycle. Angew. Chem. Int. Ed. 2019 , 58 ,1178−1182..

Tang,X.;Hong,M.;Falivene,L.;Caporaso,L.;Cavallo,L.;Chen,E.Y.XThequestforconvertingbiorenewablebifunctional α -methylene- γ -butyrolactoneintodegradableandrecyclablepolyester:controllingvinyl-addition/ring-opening/cross-linkingpathways. J. Am. Chem. Soc. 2016 , 138 ,14326−14337..

Hong,M.;Chen,E.Y.X.Towardstrulysustainablepolymers:ametal-freerecyclablepolyesterfrombiorenewablenon-strained γ -butyrolactone. Angew. Chem. Int. Ed. 2016 , 55 ,4188−4193..

Hong,M.;Tang,X.;Newell,B.S.;Chen,E.Y.X.“Nonstrained” γ -butyrolactone-basedcopolyesters:copolymerizationcharacteristicsandcomposition-dependent(thermal,eutectic,cocrystallization,anddegradation)properties. Macromolecules 2017 , 50 ,8469−8479..

Xiong,M.Y.;Schneiderman,D.K.;Bates,F.S.;Hillmyer,M.A.;Zhang,K.C.Scalableproductionofmechanicallytunableblockpolymersfromsugar. Proc. Natl. Acad. Sci. U.S.A 2014 , 111 ,8357−8362..

Fahnhorst,G.W.;Hoye,T.R.ACarbomethoxylatedpolyvalerolactonefrommalicacid:synthesisanddivergentchemicalrecycling. ACS Macro. Lett. 2018 , 7 ,143−147..

Li,J.;Liu,F.;Liu,Y.;Shen,Y.;Li,Z.Functionalizableandchemicallyrecyclablethermoplasticsfromchemoselectivering-openingpolymerizationofbio-renewablebifunctional α -methylene- δ -valerolactone. Angew. Chem. Int. Ed. 2022 , 61 ,e202207105..

Li,C.;Wang,L.;Yan,Q.;Liu,F.;Shen,Y.;Li,Z.Rapidandcontrolledpolymerizationofbio-sourced δ -caprolactonetowardfullyrecyclablepolyestersandthermoplasticelastomers. Angew. Chem. Int. Ed. 2022 , 61 ,e202201407..

Zhang,J.;Leitus,G.;Ben-David,Y.;Milstein,D.Facileconversionofalcoholsintoestersanddihydrogencatalyzedbynewrutheniumcomplexes. J. Am. Chem. Soc. 2005 , 127 ,10840−10841..

Ben-Ari,E.;Leitus,G.;Shimon,L.J.;Milstein,D.Metal-ligandcooperationinC-HandH 2 activationbyanelectron-richPNPIr(I)system:facileliganddearomatization-aromatizationaskeysteps. J. Am. Chem. Soc. 2006 , 128 ,15390−15391..

Gunanathan,C.;Ben-David,Y.;Milstein,D.DirectsynthesisofamidesfromalcoholsandamineswithliberationofH 2 . Science 2007 , 317 ,790−792..

Zeng,H.;Guan,Z.Directsynthesisofpolyamides via catalyticdehydrogenationofdiolsanddiamines. J. Am. Chem. Soc. 2011 , 133 ,1159−1161..

Gnanaprakasam,B.;Balaraman,E.;Gunanathan,C.;Milstein,D.SynthesisofpolyamidesfromdiolsanddiamineswithliberationofH 2 . J. Polym. Sci., Part A: Polym. Chem. 2012 , 50 ,1755−1765..

Hunsicker,D.M.;Dauphinais,B.C.;McIlrath,S.P.;Robertson,N.J.Synthesisofhighmolecularweightpolyesters via in vacuo dehydrogenationpolymerizationofdiols. Macromol. Rapid Commun. 2012 , 33 ,232−236..

Zhang,J.;Leitus,G.;Ben-David,Y.;Milstein,D.Efficienthomogeneouscatalytichydrogenationofesterstoalcohols. Angew. Chem. Int. Ed. 2006 , 45 ,1113−1115..

Balaraman,E.;Gnanaprakasam,B.;Shimon,L.J.;Milstein,D.Directhydrogenationofamidestoalcoholsandaminesundermildconditions. J. Am. Chem. Soc. 2010 , 132 ,16756−16758..

Krall,E.M.;Klein,T.W.;Andersen,R.J.;Nett,A.J.;Glasgow,R.W.;Reader,D.S.;Dauphinais,B.C.;McIlrath,S.P.;Fischer,A.A.;Carney,M.J.;Hudson,D.J.;Robertson,N.J.Controlledhydrogenativedepolymerizationofpolyestersandpolycarbonatescatalyzedbyruthenium(II)PNNpincercomplexes. Chem. Commun. 2014 , 50 ,4884−4887..

Kumar,A.;vonWolff,N.;Rauch,M.;Zou,Y.Q.;Shmul,G.;Ben-David,Y.;Leitus,G.;Avram,L.;Milstein,D.Hydrogenativedepolymerizationofnylons. J. Am. Chem. Soc. 2020 , 142 ,14267−14275..

Tang,X.;Chen,E.Y.X.Towardinfinitelyrecyclableplasticsderivedfromrenewablecyclicesters. Chem 2019 , 5 ,284−312..

Gusev,D.G.Dehydrogenativecouplingofethanolandesterhydrogenationcatalyzedbypincer-typeYNPcomplexes. ACS Catal. 2016 , 6 ,6967−6981..

Gusev,D.G.Rethinkingthedehydrogenativeamidesynthesis. ACS Catal. 2017 , 7 ,6656−6662..

Morris,S.A.;Gusev,D.G.RethinkingtheClaisen-Tishchenkoreaction. Angew. Chem. Int. Ed. 2017 , 56 ,6228−6231..

Nguyen,D.H.;Trivelli,X.;Capet,F.;Swesi,Y.;Favre-Réguillon,A.;Vanoye,L.;Dumeignil,F.;Gauvin,R.M.DeepermechanisticinsightintoRuPincer-mediatedacceptorlessdehydrogenativecouplingofalcohols:exchanges,intermediates,anddeactivationspecies. ACS Catal. 2018 , 8 ,4719−4734..

Gusev,D.G.RevisedmechanismsofthecatalyticalcoholdehydrogenationandesterreductionwiththeMilsteinPNNcomplexofruthenium. Organometallics 2020 , 39 ,258−270..

Li,H.;Hall,M.B.Computationalmechanisticstudiesonreactionsoftransitionmetalcomplexeswithnoninnocentpincerligands:aromatization–dearomatizationornot. ACS Catal. 2015 , 5 ,1895−1913..

Cho,D.;Ko,K.C.;Lee,J.Y.Catalyticmechanismfortheruthenium-complex-catalyzedsynthesisofamidesfromalcoholsandamines:aDFTstudy. Organometallics 2013 , 32 ,4571−4576..

Li,H.;Wang,X.;Wen,M.;Wang,Z.X.Computationalinsightintothemechanismofselectiveimineformationfromalcoholandaminecatalyzedbytheruthenium(II)-PNPPincercomplex. Eur. J. Inor. Chem. 2012 , 2012 ,5011−5020..

Views

132

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Development of Rapid Environment Degradable and Recyclable Poly(1,3-propylene glycol oxalate) via Ring-opening Polymerization of Seven-Membered Cyclic Oxalate

Ring Opening Polymerization of ω-Pentadecalactone by Weakly Oxophilic Fe(II)-based Catalytic Systems Bearing Bulky α-Diimine Ligands

Light-responsive Self-Immolative L-glutamic Acid-based Polyester Nanoparticles for Controlled Drug Release via Passerini Three-Component Polymerization

Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides

Special Topic: Chirality in Polymers

Related Author

Zhi-Bo Li

Ya-Lei Liu

Xiang-Bin Sun

Yue-Yuan Qian

Li-Jia Liu

Wen-Peng Zhao

Li-Shuang Ma

Chun-Yu Zhang

Related Institution

State Key Laboratory of Chemical Engineering and Low-carbon Technology, College of Chemical and Biological Engineering, Zhejiang University

College of Chemistry, Chemical Engineering and Materials Science, Zaozhuang University

Shandong Key Laboratory of High Performance Polyolefin Materials and Recycling; College of Polymer Science and Engineering, Qingdao University of Science and Technology

College of Chemistry and Chemical Engineering, China University of Petroleum (East China)

Shandong Provincial College Laboratory of Rubber Material and Engineering/Key Laboratory of Rubber-Plastics, Ministry of Education, School of Polymer Science and Engineering, Qingdao University of Science & Technology

⁰

Green Synthesis of Chemically Recyclable Polyesters via Dehydrogenative Copolymerization of Diols

DOI：10.1007/s10118-023-2903-9

摘要

Abstract

关键词

Keywords

references