Preparation of Chemically Recyclable Poly(ether-<italic style="font-style: italic">alt</italic>-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides

Feng Ren; Zhuang-Zhuang Liang; Ming-Xin Niu; Chen-Yang Hu; Xuan Pang

doi:10.1007/s10118-023-3040-1

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

RESEARCH ARTICLE | Updated：2024-01-12

- Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides
- Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides
- 高分子科学（英文版） 2024年42卷第2期页码：168-175
- Affiliations：
  
  a.Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
- Author bio：
  
  cyhu@ciac.ac.cn (C.Y.H.)
  xpang@ciac.ac.cn (X.P.)
- Funds：
  
  This work was financially supported by the National Key R&D Program of China (No. 2021YFA1501700), the Science and Technology Development Plan of Jilin Province (Nos. 20230101042JC and 20210201059GX), the National Natural Science Foundation of China, Basic Science Center Program (No. 51988102), and the National Natural Science Foundation of China (Nos. 52203017 and 52073272).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-3040-1.
- DOI：10.1007/s10118-023-3040-1
  中图分类号：
- 收稿：2023-07-07，
  
  修回：2023-7-27，
  
  录用：2023-7-27，
  
  网络首发：2023-11-15，
  
  纸质出版：2024-02-01
- Accepted：
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Ren, F.; Liang, Z. Z.; Niu, M. X.; Hu, C. Y.; Pang, X. Preparation of chemically recyclable poly(ether-alt-ester) by the ring opening polymerization of cyclic monomers synthesized by coupling glycolide and epoxides. Chinese J. Polym. Sci. 2024, 42, 168–175

Feng Ren, Zhuang-Zhuang Liang, Ming-Xin Niu, et al. Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides[J]. Chinese Journal of Polymer Science, 2024, 42(2): 168-175. DOI: 10.1007/s10118-023-3040-1.
Ren, F.; Liang, Z. Z.; Niu, M. X.; Hu, C. Y.; Pang, X. Preparation of chemically recyclable poly(ether-alt-ester) by the ring opening polymerization of cyclic monomers synthesized by coupling glycolide and epoxides. Chinese J. Polym. Sci. 2024, 42, 168–175 DOI： 10.1007/s10118-023-3040-1.

Feng Ren, Zhuang-Zhuang Liang, Ming-Xin Niu, et al. Preparation of Chemically Recyclable Poly(ether-alt-ester) by the Ring Opening Polymerization of Cyclic Monomers Synthesized by Coupling Glycolide and Epoxides[J]. Chinese Journal of Polymer Science, 2024, 42(2): 168-175. DOI: 10.1007/s10118-023-3040-1. DOI：

摘要

Here

we reported that 1

4-dioxan-2-one with different substituents was successfully synthesized by coupling glycolide with epoxide using Salen-Cr(Ⅲ)/PPNCl as catalyst. The monomers underwent ROP to form poly(ester-alt-ether)s with alternating glycolic acid and epoxides using thiourea/base. The poly(ester-alt-ether)s showed low

and chemical recyclability to monomers in the presence of catalysts.

Abstract

Polyester and polyether are two key oxygenated polymers

and completely alternative sequence of poly(ester-

alt

-ether) could efficiently combine the advantages (including flexibility

degradability

etc

.) of both segments. Currently

despite their copolymers could be synthesized from one-pot mixture of cyclic esters and epoxides

perfectly alternative microstructure is very challenging to realize and typically restricted to certain monomer pairs. Moving forward

synthesizing poly(ester-

alt

-ether) from commercially available and largescale monomers would be a significant advance. For example

successfully commercialized poly(glycolic acid) (PGA)

which is not easily soluble in polymers due to its high crystallinity and is brittle and difficult to control the degradation cycle

would encounter a new paradigm if engineered into poly(ester-

alt

-ether). In this work

starting from the design of monomer with hybrid structures

we successfully synthesized a series of 1

4-dioxan-2-one containing different substituents based on glycolide (GA) and epoxides using commercially available Salen-Cr(III) and PPNCl catalytic systems. The new monomers underwent ring-opening polymerization (ROP) to form a series of poly(ester

-alt-

ether) with perfectly alternating glycolic acid and propylene glycol repeat units under catalytic system of thiourea/base. The poly(ester-

alt

-ether) have significantly lower glass-transition temperature than PGA. Additionally

the poly(ester-

alt

-ether) can be chemically recovered to monomer using Sn(Oct)

or 1

8-diazabicyclo[5.4.0]undecane-7-ene (DBU) as a catalyst in solution

thus establishing a closed-loop life cycle. From monomers derived from GA and epoxides

this work furnishes a novel strategy for the synthesis of poly(ester-

alt

-ether) with chemical recyclability.

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references

Zhu,Y.;Romain,C.;Williams,C.K.Sustainablepolymersfromrenewableresources. Nature 2016 , 540 ,354−362..

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

Masutani,K.;Kimura,Y.;Li,S.M.;Hu,Y.F.;Müller,A.J.;Ávila,M.;Saenz,G.;Salazar,J.;Raquez,J.M.;Ramy-Ratiarison,R.;Murariu,M.;Dubois,P.;Ruellan,A.;Ducruet,V.;Domenek,S.;Peponi,L.;Mújica-García,A.;Kenny,J.M.;Bitinis,N.;Verdejo,R.;López-Manchado,M.A.;Lagarón,J.M.;Cabedo,L.;Zhou,Q.;Berglund,L.A.;Catalá,R.;López-Carballo,G.;Hernández-Muñoz,P.;Gavara,R.;Armentano,I.;Fortunati,E.;Mattioli,S.;Rescignano,N.;Fukushima,K.;Camino,G.;Fiori,S.;Peltzer,M.A.;Beltrán-Sanahuja,A. Poly(lactic acid) Science and Technology: Processing, Properties, Additives and Applications .TheRoyalSocietyofChemistry: 2014 ..

Coulembier,O.;Martin-Vaca,B.;Bourisso,D.;Fastnacht,K.V.;Datta,P.P.;Kiesewetter,M.K.;Naumann,S.;Lecomte,P.;Jérôme,C.;Guillaume,S.M.;Fukushima,K.;Taton,D.;Siefker,D.;Zhang,D.H.;Wolf,T.;Wurm,F.R.;Zhao,W.C.;Zhang,Y.T.;Bossion,A.;Heifferon,K.V.;Zivic,N.;Long,T.E.;Sardon,H.;Ryan,M.D.;Pearson,R.M.;Miyake,G.M.;Jehanno,C.;Demarteau,J.;Dove,A.P. Organic Catalysis for Polymerisation .TheRoyalSocietyofChemistry: 2018 ..

Li,J.;Stayshich,R.M.;Meyer,T.Y.ExploitingsequencetocontrolthehydrolysisbehaviorofbiodegradablePLGAcopolymers. J. Am. Chem. Soc. 2011 , 133 ,6910−6913..

Lu,Y.;Swisher,J.H.;Meyer,T.Y.;Coates,G.W.Chirality-directedregioselectivity:anapproachforthesynthesisofalternatingpoly(lactic- co -glycolicacid). J. Am. Chem. Soc. 2021 , 143 ,4119−4124..

Diaz,C.;Ebrahimi,T.;Mehrkhodavandi,P.Cationicindiumcomplexesforthecopolymerizationoffunctionalizedepoxideswithcyclicethersandlactide. Chem. Commun . 2019 , 55 ,3347−3350..

Chwatko,M.;Lynd,N.A.Statisticalcopolymerizationofepoxidesandlactonestohighmolecularweight. Macromolecules 2017 , 50 ,2714−2723..

Liu,D.;Bielawski,C.W.Synthesisofdegradablepoly[(ethyleneglycol)- co -(glycolicacid)] via thepost-polymerizationoxyfunctionalizationofpoly(ethyleneglycol). Macromol. Rapid Commun. 2016 , 37 ,1587−1592..

Li,Z.;Tan,B.H.;Lin,T.;He,C.RecentadvancesinstereocomplexationofenantiomericPLA-basedcopolymersandapplications. Prog. Polym. Sci. 2016 , 62 ,22−72..

Stosser,T.;Sulley,G.S.;Gregory,G.L.;Williams,C.K.Easyaccesstooxygenatedblockpolymers via switchablecatalysis. Nat. Commun. 2019 , 10 ,2668..

Ren,W.M.;Wang,R.J.;Ren,B.H.;Gu,G.G.;Yue,T.J.Mechanism-inspireddesignofheterodinuclearcatalystsforcopolymerizationofepoxideandlactone. Chinese J. Polym. Sci. 2020 , 38 ,950−957..

Kerr,R.W.F.;Williams,C.K.Zr(IV)Catalystforthering-openingcopolymerizationofanhydrides(A)withepoxides(B),oxetane(B),andtetrahydrofurans(C)tomakeABB-and/orABC-poly(ester- alt -ethers). J. Am. Chem. Soc. 2022 , 144 ,6882−6893..

Zhang,H.;Hu,S.;Zhao,J.;Zhang,G.Phosphazene-catalyzedalternatingcopolymerizationofdihydrocoumarinandethyleneoxide:weakerisbetter. Macromolecules 2017 , 50 ,4198−4205..

Hu,S.;Dai,G.;Zhao,J.;Zhang,G.Ring-openingalternatingcopolymerizationofepoxidesanddihydrocoumarincatalyzedbyaphosphazenesuperbase. Macromolecules 2016 , 49 ,4462−4472..

Jung,H.J.;Goonesinghe,C.;Mehrkhodavandi,P.Temperaturetriggeredalternatingcopolymerizationofepoxidesandlactones via pre-sequencedspiroorthoesterintermediates. Chem. Sci. 2022 , 13 ,3713−3718..

VanZee,N.J.;Coates,G.W.Alternatingcopolymerizationofdihydrocoumarinandepoxidescatalyzedbychromiumsalencomplexes:anewroutetofunctionalpolyesters. Chem. Commun. 2014 , 50 ,6322−6325..

Ren,W.M.;Gao,H.J.;Yue,T.J.Flexiblegradientpoly(ether-ester)fromthecopolymerizationofepoxidesand ε -caprolactonemediatedbyahetero-bimetalliccomplex. Chinese J. Polym. Sci. 2021 , 39 ,1013–1019..

Nishida,H.;Yamashita,M.;Endo,T.;Tokiwa,Y.Equilibriumpolymerizationbehaviorof1,4-dioxan-2-oneinbulk. Macromolecules 2000 , 33 ,6982−6986..

Li,K.;Li,Z.;Duan,S.;Shen,Y.;Li,Z.Organobase/ureacatalyzedringopeningpolymerizationof3-methyl-1,4-dioxan-2-onetopreparechemicallyrecyclablepoly(etherester). J. Polym. Sci. 2021 , 60 ,3331−3340..

MacDonald,J.P.;Shaver,M.P.Anaromatic/aliphaticpolyesterpreparedviaring-openingpolymerisationanditsremarkablyselectiveandcyclabledepolymerisationtomonomer. Polym. Chem. 2016 , 7 ,553−559..

Li,M.Q.;Luo,Z.X.;Yu,X.Y.;Tian,G.Q.;Wu,G.;Chen,S.C.;Wang,Y.Z.Ring-openingpolymerizationofaseven-memberedlactonetowardabiocompatible,degradable,andrecyclablesemi-aromaticpolyester. Macromolecules 2023 , 56 ,2465−2475..

Bechtold,K.;Hillmyer,M.A;Tolman,W.B.Perfectlyalternatingcopolymeroflacticacidandethyleneoxideasaplasticizingagentforpolylactide. Macromolecules. 2001 , 34 ,8641−8648..

Li,Z.;Shen,Y.;Li,Z.Chemicalupcyclingofpoly(3-hydroxybutyrate)intobicyclicether–estermonomerstowardvalue-added,degradable,andrecyclablepoly(etherester). ACS. Sustainable Chem. Eng. 2022 , 10 ,8228−8238..

Li,Z.;Zhao,D.;Shen,Y.;Li,Z.Ring-openingpolymerizationofenantiopurebicyclicether-estermonomerstowardclosed-looprecyclableandcrystallinestereoregularpolyesters via chemicalupcyclingofbioplastic. Angew. Chem. Int. Ed. 2023 , 62 ,e202302101..

Xu,J.B.;Chen,Y.;Xiao,W.H.;Zhang,J.;Bu,M.L.;Zhang,X.Q.;Lei,C.H.Studyingthering-openingpolymerizationof1,5-dioxepan-2-onewithorganocatalysts. Polymers 2019 , 11 ,1642..

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

Grablowitz,H.;Lendlein,A.Synthesisandcharacterizationof α,ω -dihydroxy-telechelicoligo( p -dioxanone). J. Mater. Chem. 2007 , 17 ,4050−4056..

Fan,H.Z.;Yang,X.;Wu,Y.C.;Cao,Q.;Cai,Z.Z.;Zhu,J.B.Leveragingthemonomerstructureforhigh-performancechemicallyrecyclablesemiaromaticpolyesters. Polym. Chem. 2023 , 14 ,747–753..

Hu,S.;Liu,L.;Li,H.;Pahovnik,D.;Hadjichristidis,N.;Zhou,X.;Zhao,J.Tuningthepropertiesofester-baseddegradablepolymersbyinsertingepoxidesintopoly( ε -caprolactone). Chem. Asian J. 2023 , 18 ,e202201097..

Hu,S.;Zhao,J.;Zhang,G.Noncopolymerizationapproachtocopolymers via concurrenttransesterificationandring-openingreactions. ACS Macro Lett. 2016 , 5 ,40−44..

Balasanthiran,V.;Chatterjee,C.;Chisholm,M.H.;Harrold,N.D.;RajanBabu,T.V.;Warren,G.A.Couplingofpropyleneoxideandlactideataporphyrinchromium(III)center. J. Am. Chem. Soc. 2015 , 137 ,1786−1789..

Liang,Z.Z.;Li,X.;Hu,C.Y.;Duan,R.L.;Wang,X.H.;Pang,X.;Chen,X.S.CopolymerizationofPO/CO 2 andlactidebyadinuclearsalen-Cr(III)complex:gradientandrandomcopolymerswithmodificablemicrostructure. Chinese J. Polym. Sci. 2022 , 40 ,1028−1033..

Datta,P.P.;Pothupitiya,J.U.;Kiesewetter,E.T.;Kiesewetter,M.K.CoupledequilibriainH-bonddonatingring-openingpolymerization:Theeffectivecatalyst-determinedshiftofapolymerizationequilibrium. Eur. Polym. J. 2017 , 95 ,671−677..

Kazakov,O.I.;Kiesewetter,M.K.Cocatalystbindingeffectsinorganocatalyticring-openingpolymerizationofl-lactide. Macromolecules 2015 , 48 ,6121−6126..

Spink,S.S.;Kazakov,O.I.;Kiesewetter,E.T.;Kiesewetter,M.K.Rateacceleratedorganocatalyticring-openingpolymerizationofl-lactide via theapplicationofabis(thiourea)H-bonddonatingcocatalyst. Macromolecules 2015 , 48 ,6127−6131..

Hewawasam,R.S.;Kalana,U.L.D.I.;Dharmaratne,N.U.;Wright,T.J.;Bannin,T.J.;Kiesewetter,E.T.;Kiesewetter,M.K.BisureaandbisthioureaH-bondingorganocatalystsforring-openingpolymerization:cuesforthecatalystdesign. Macromolecules 2019 , 52 ,9232−9237..

Lin,L.;Han,D.;Qin,J.;Wang,S.;Xiao,M.;Sun,L.;Meng,Y.Nonstrained γ -butyrolactonetohigh-molecular-weightpoly( γ -butyrolactone):facilebulkpolymerizationusingeconomicalureas/alkoxides. Macromolecules 2018 , 51 ,9317−9322..

Dharmaratne,N.U.;Pothupitiya,J.U.;Kiesewetter,M.K.Themechanisticdualityof(thio)ureaorganocatalystsforring-openingpolymerization. Org. Biomol. Chem. 2019 , 17 ,3305−3313..

Zhang,X.;Jones,G.O.;Hedrick,J.L.;Waymouth,R.M.Fastandselectivering-openingpolymerizationsbyalkoxidesandthioureas. Nat. Chem. 2016 , 8 ,1047−1053..

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

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

DOI：10.1007/s10118-023-3040-1

摘要

Abstract

关键词

Keywords

references