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

Your Location：

Home >

Browse articles >

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
- Chinese Journal of Polymer Science Vol. 42, Issue 2, Pages: 168-175(2024)
- 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：
- DOI：10.1007/s10118-023-3040-1
  CLC：
Scan for full text
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 42(2):168-175(2024)
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 42(2):168-175(2024) DOI： 10.1007/s10118-023-3040-1.

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 ,T,g, 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),2, 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.

关键词

Keywords

PolyesterPolyetherAlternative copolymerRing-opening polymerization

references

Zhu,Y.;Romain,C.;Williams,C.K.Sustainablepolymersfromrenewableresources.Nature2016, 540,354−362..

Haussler,M.;Eck,M.;Rothauer,D.;Mecking,S.Closed-looprecyclingofpolyethylene-likematerials.Nature2021, 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.Macromolecules2017, 50,2714−2723..

Liu,D.;Bielawski,C.W.Synthesisofdegradablepoly[(ethyleneglycol)- co-(glycolicacid)] viathepost-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 viaswitchablecatalysis.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.Macromolecules2017, 50,4198−4205..

Hu,S.;Dai,G.;Zhao,J.;Zhang,G.Ring-openingalternatingcopolymerizationofepoxidesanddihydrocoumarincatalyzedbyaphosphazenesuperbase.Macromolecules2016, 49,4462−4472..

Jung,H.J.;Goonesinghe,C.;Mehrkhodavandi,P.Temperaturetriggeredalternatingcopolymerizationofepoxidesandlactones viapre-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.Macromolecules2000, 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.Macromolecules2023, 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 viachemicalupcyclingofbioplastic.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.Polymers2019, 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 viaconcurrenttransesterificationandring-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/CO2andlactidebyadinuclearsalen-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.Macromolecules2015, 48,6121−6126..

Spink,S.S.;Kazakov,O.I.;Kiesewetter,E.T.;Kiesewetter,M.K.Rateacceleratedorganocatalyticring-openingpolymerizationofl-lactide viatheapplicationofabis(thiourea)H-bonddonatingcocatalyst.Macromolecules2015, 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.Macromolecules2019, 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.Macromolecules2018, 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..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Synthesis of Sulfur/Selenium-containing Polyester with Recyclability and Controllable Hydrophilicity and Glass Transition Temperature

Ring-opening Polymerization of 2-Oxabicyclo[2.2.2]octan-3-one and the Influence of Stereochemistry on the Thermal Properties of the Polyesters

Related Author

No data

Related Institution

Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University

Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polym. Chem. & Physics of Ministry of Education, Department of Polymer Science & Engineering, College of Chemistry and Molecular Engineering, Center for Soft Matter Science and Engineering, Peking University

Faculty of Materials Science and Engineering, South China University of Technology

Key Laboratory of Biobased Polymer Materials, Shandong Provincial Education Department; School of Polymer Science and Engineering, Qingdao University of Science and Technology

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University

⁰

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