Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs

Zhi-Kang Chen; Wu-Chao Zhao; Yi-Ling Zhao; Cong-Lei Liu; Liu-Yin Jiang; Yue-Tao Zhang; Hong-Ping Zhu

doi:10.1007/s10118-023-3039-7

Your Location：

Home >

Browse articles >

Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs

RESEARCH ARTICLE | Updated：2024-01-12

- Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs
  Enhanced Publication
- Chinese Journal of Polymer Science Vol. 42, Issue 2, Pages: 159-167(2024)
- Affiliations：
  
  a.State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
  b.State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
- Author bio：
  
  lyjiang@xmu.edu.cn (L.Y.J.)
  ytzhang2009@jlu.edu.cn (Y.T.Z.)
  hpzhu@xmu.edu.cn (H.P.Z.)
- Funds：
- DOI：10.1007/s10118-023-3039-7
  CLC：
Scan for full text
Chen, Z. K.; Zhao, W. C.; Zhao, Y. L.; Liu, C. L.; Jiang, L. Y.; Zhang, Y. T.; Zhu, H. P. Chemoselective and living/controlled polymerization of alkenyl methacrylates by the phosphonium ylide/organoaluminum Lewis pairs. Chinese J. Polym. Sci. 2024, 42, 159–167

Zhi-Kang Chen, Wu-Chao Zhao, Yi-Ling Zhao, et al. Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs. [J]. Chinese Journal of Polymer Science 42(2):159-167(2024)
Chen, Z. K.; Zhao, W. C.; Zhao, Y. L.; Liu, C. L.; Jiang, L. Y.; Zhang, Y. T.; Zhu, H. P. Chemoselective and living/controlled polymerization of alkenyl methacrylates by the phosphonium ylide/organoaluminum Lewis pairs. Chinese J. Polym. Sci. 2024, 42, 159–167 DOI： 10.1007/s10118-023-3039-7.

Zhi-Kang Chen, Wu-Chao Zhao, Yi-Ling Zhao, et al. Chemoselective and Living/Controlled Polymerization of Alkenyl Methacrylates by the Phosphonium Ylide/Organoaluminum Lewis Pairs. [J]. Chinese Journal of Polymer Science 42(2):159-167(2024) DOI： 10.1007/s10118-023-3039-7.

摘要

The P-ylide-,2,/AlMe(BHT)2 Lewis pair (LP) system initiates the highly efficient, chemoselective, living/controlled block copolymerization of allyl methacrylate (AMA) and methyl methacrylate (MMA) into the PAMA-,b,-PMMA-,b,-PAMA and the polymer is PhCH,2,SH-post-functionalized.

Abstract

Chemoselective, living/controlled polymerizations of allyl methacrylate (AMA) and vinyl methacrylate (VMA) with/without methyl methacrylate (MMA) by using the phosphonium ylide/organoaluminum based Lewis pairs (LPs) have been realized. The P-ylide-,2,/AlMe(BHT),2, (P-ylide-,2, = Ph,3,P=CHMe and BHT = 2,6-,i,Bu,2,-4-MeC,6,H,2,O) was demonstrated to be superior by which homopolymers PAMAs (,M,n,=27.6−111.5 kg/mol and ,Ð,=1.14−1.25) and PVMAs (,M,n,=28.4−78.4 kg/mol and ,Ð,=1.12−1.18) and block copolymers PMMA-,b,-PAMA, PAMA-,b,-PVMA, PAMA-,b,-PMMA, PMMA-,b,-PAMA-,b,-PMMA, PAMA-,b,-PMMA-,b,-PAMA, and PAMA-,b,-PVMA-,b,-PAMA were synthesized. In the polymerizations, all of the monomers were reacted by the conjugated ester vinyl groups leaving intactly the nonconjugated acryloxy groups. The pendant acryloxy groups attached to the main chain enable further to post-functionalization by the AIBN-induced radical “thiol-ene” reaction using PhCH,2,SH. The thiolether side group-containing polymers PAMA-SCH,2,Ph and PAMA-SCH,2,Ph-,b,-PMMA-,b,-PAMA-SCH,2,Ph were thus prepared.

关键词

Keywords

Phosphonium ylideAlkenyl methacrylateChemoselectivityLiving/controlled polymerizationPost-functionalization

references

Dong,Z.M.;Liu,X.H.;Liu,H.W.;Li,Y.S.Synthesisofnovelstarpolymerswithvinyl-functionalizedhyperbranchedcore via“arm-first”strategy.Macromolecules2010, 43,7985−7992..

Sui,X.F.;Hempenius,M.A.;Vancso,G.Redox-activecross-linkablepoly(ionicliquid)s.J. Am. Chem. Soc.2012, 134,4023−4025..

Barker,I.A.;ElHarfi,J.E.;Adlington,K.;Howdle,S.M.;Irvine,D.J.Catalyticchaintransfermediatedautopolymerizationofdivinylbenzene:towardfacilesynthesisofhighalkenefunctionalgroupdensityhyperbranchedmaterials.Macromolecules2012, 45,9258−9266..

Powell,K.T.;Cheng,C.;Wooley,K.L.Complexamphiphilichyperbranchedfluoropolymersbyatomtransferradicalself-condensingvinyl(co)polymerization.Macromolecules2007, 40,4509−4515..

Stevens,D.M.;Tempelaar,S.;Dove,A.P.;Harth,E.Nanospongeformationfromorganocatalyticallysynthesizedpoly(carbonate)copolymers.ACS Macro Lett.2012, 1,915−918..

Das,A.;Theato,P.Activatedestercontainingpolymers:opportunitiesandchallengesforthedesignoffunctionalmacromolecules.Chem. Rev.2016, 116,1434−1495..

Bermeshev,M.V.;Chapala,P.P.Additionpolymerizationoffunctionalizednorbornenesasapowerfultoolforassemblingmolecularmoietiesofnewpolymerswithversatileproperties.Prog. Polym. Sci.2018, 84,1−46..

Zhao,Y.;Wu,H.;Zhang,Y.;Wang,X.;Yang,B.;Zhang,Q.;Ren,X.;Fu,C.;Wei,Y.;Wang,Z.;Wang,Y.;Tao,L.Postpolymerizationmodificationofpoly(dihydropyrimidin-2(1 H)-thione)s viathethiourea–haloalkanereactiontopreparefunctionalpolymers.ACS Macro Lett.2015, 4,843–847..

Iha,R.K.;Wooley,K.L.;Nystrom,A.M.;Hawker,C.J.;Burke,D.J.;Kade,M.J.;Hawker,C.J.Applicationsoforthogonal“click”chemistriesinthesynthesisoffunctionalsoftmaterials.Chem. Rev.2009, 109,5620–5686..

Greenley,R.Z.,InPolymer Handbook,3rded.byImmergut,E.H.,Brandup,J.,Eds.,Wiley,NewYork, 1989 ,p.267.

Vardareli,T.K.;Keskin,S.;Usanmaz,A.Synthesisandcharacterizationofpoly(allylmethacrylate)obtainedbyfreeradicalinitiator.J. Macromol. Sci., Part A: Pure Appl. Chem.2008, 45,302−311..

Sugiyama,F.;Satoh,K.;Kamigaito,M.RegiospecificradicalpolymerizationofvinylmethacrylateinthepresenceofLewisacidsintosolublepolymerswithpendentvinylestersubstituents.Macromolecules2008, 41,3042–3048..

Ma,J.;Cheng,C.;Sun,G.;Wooley,K.L.Well-definedpolymersbearingpendentalkenefunctionalities viaselectiveRAFTpolymerization.Macromolecules2008, 41,9080–9089..

Mohan,Y.M.;Raghunadh,V.;Sivaram,S.;Baskaran,D.Reactivepolymersbearingstyrenependantsthroughselectiveanionicpolymerizationof4-vinylbenzylmethacrylate.Macromolecules2012, 45,3387–3393..

Tanaka,S.;Goseki,R.;Ishizone,T.;Hirao,A.Synthesisofwell-definednovelreactiveblockpolymerscontainingapoly(1,4-divinylbenzene)segmentbylivinganionicpolymerization.Macromolecules2014, 47,2333–2339..

Chen,Y.;Fuchise,K.;Narumi,A.;Kawaguchi,S.;Satoh,T.;Kakuchi,T.Core-firstsynthesisofthree-,four-,andsix-armedstar-shapedpoly(methylmethacrylate)sbygrouptransferpolymerizationusingphosphazenebase.Macromolecules2011, 44,9091–9098..

Sogah,D.Y.;Hertler,W.R.;Webster,O.W.;Cohen,G.M.Grouptransferpolymerization—polymerizationofacrylicmonomers.Macromolecules1987, 20,1473–1488..

Vidal,F.;Gowda,R.R.;Chen.E.Y.X.Chemoselective,stereospecific,andlivingpolymerizationofpolardivinylmonomersbychiralzirconoceniumcatalysts.J. Am. Chem. Soc.2015, 137,9469−9480..

Xu,T.;Liu,J.;Lu,X.B.Highlyactivehalf-metalloceneyttriumcatalystsforlivingandchemoselectivepolymerizationofallylmethacrylate.Macromolecules2015, 48,7428–7434..

McGraw,M.L.;Chen,E.Y.X.Lewispairpolymerization:perspectiveonaten-yearjourney.Macromolecules2020, 53,6102–6122..

Zhao,W.;He,J.;Zhang,Y.Lewispairspolymerizationofpolarvinylmonomers.Sci. Bull.2019, 64,1830–1840..

Hong,M.;Chen,J.;Chen,E.Y.X.Polymerizationofpolarmonomersmediatedbymain-groupLewisacid-basepairs.Chem. Rev.2018, 118,10551–10616..

Wang,X.;Hong,M.Precisecontrolofmolecularweightandstereospecificityinlewispairpolymerizationofsemifluorinatedmethacrylates:mechanisticstudiesandstereocomplexformation.Macromolecules2020, 53,4659–4669..

Zhang,Z.;Wang,X.;Wang,X.;Li,Y.;Hong,M.Tris(2,4-difluorophenyl)borane/triisobutylphosphinelewispair:athermostableandair/moisture-tolerantorganiccatalystforthelivingpolymerizationofacrylates.Macromolecules2021, 54,8495–8502..

Ottou,W.N.;Conde-Mendizabal,E.;Pascual,A.;Wirotius,A.L.;Bourichon,D.;Vignolle,J.;Robert.F.;Landais,Y.;Sotiropoulos,J.M.;Miqueu,K.;Taton,D.OrganicLewispairsbasedonphosphineandelectrophilicsilaneforthedirectandcontrolledpolymerizationofmethylmethacrylate:experimentalandtheoreticalinvestigations.Macromolecules2017, 50,762–774..

Wang,H.;Wang,Q.;He,J.;Zhang,Y.Livingpolymerizationofacrylamidescatalysedby N-heterocyclicolefin-basedLewispairs.Polym. Chem.2019, 10,3597–3603..

Knaus,M.G.M.;Giuman,M.M.;Pöthig,A.;Rieger,B.Endoffrustration:catalyticprecisionpolymerizationwithhighlyinteractingLewispairs.J. Am. Chem. Soc.2016, 138,7776–7781..

Bai,Y.;He,J.;Zhang,Y.Ultra-high-molecular-weightpolymersproducedbytheimmortalphosphine-basedcatalystsystem.Angew. Chem. Int. Ed.2018, 57,17230–17234..

McGraw,M.L.;Chen,E.Y.X.CatalyticLewispairpolymerizationofrenewablemethylcrotonatetohigh-molecular-weightpolymers.ACS Catal.2018, 8,9877–9887..

Clarke,R.W.;McGraw,M.L.;Gowda,R.R.;Chen,E.Y.X.Lewispairpolymerizationofrenewableindenonetoerythro-ditactichigh- Tgpolymerswithanupcyclingavenue.Macromolecules2020, 53,640–648..

Wang,X.;Zhang,Y.;Hong,M.Controlledandefficientpolymerizationofconjugatedpolaralkenesbylewispairsbasedonstericallyhinderedaryloxide-substitutedalkylaluminum.Molecules2018, 23,442–453..

Wang,Q.;Zhao,W.;Zhang,S.;He,J.;Zhang,Y.Chen,E.Y.X.Livingpolymerizationofconjugatedpolaralkenescatalyzedby N-heterocyclicolefin-basedfrustratedLewispairs.ACS Catal.2018, 8,3571–3578..

Zhang,Y.;Miyake,G.M.;Chen,E.Y.X.Alane-basedclassicalandfrustratedlewispairsinpolymersynthesis:rapidpolymerizationofMMAandnaturallyrenewablemethylenebutyrolactonesintohigh-molecular-weightpolymers.Angew. Chem. Int. Ed.2010, 49,10158–10162..

He,J.;Zhang,Y.;Falivene,L.;Caporaso,L.;Cavallo,L.;Chen,E.Y.X.Chainpropagationandterminationmechanismsforpolymerizationofconjugatedpolaralkenesby[Al]-basedfrustratedLewispairs.Macromolecules2014, 47,7765–7774..

Jia,Y.;Wang,Y.;Ren,W.;Xu,T.;Wang,J.;Lu,X.MechanisticaspectsofinitiationanddeactivationinN-heterocyclicolefinmediatedpolymerizationofacrylateswithalaneasactivator.Macromolecules 2014 ,47,1966–1972..

Jia,Y.;Ren,W.;Liu,S.;Xu,T.;Wang,Y.;Lu,X.ControlleddivinylmonomerpolymerizationmediatedbyLewispairs:apowerfulsyntheticstrategyforfunctionalpolymers.ACS Macro Lett.2014, 3,896–899..

Gowda,R.R.;Chen,E.Y.X.ChemoselectiveLewispairpolymerizationofrenewablemultivinyl-functionalized γ-butyrolactones.Phil. Trans. R. Soc. A2017, 375,20170003..

Xu,P.;Wu,L.;Dong,L.;Xu,X.Chemoselectivepolymerizationofpolardivinylmonomerswithrare-earth/phosphineLewispairs.Molecules2018, 23,360–369..

McGraw,M.L.;Clarke,R.W.;Chen,E.Y.X.Compoundedsequencecontrolinpolymerizationofone-potmixturesofhighlyreactiveacrylatesbydifferentiatingLewispairs.J. Am. Chem. Soc.2020, 142,5969–5973..

Song,Y.;He,J.;Zhang,Y.;Gilsdorf,R.A.;Chen,E.Y.X.Recyclablecyclicbio-basedacrylicpolymer viapairwisemonomerenchainmentbyatrifunctionalLewispair.Nat. Chem.2022, 15,366−376..

McGraw,M.L.;Clarke,R.W.;Chen,E.Y.X.Synchronouscontrolofchainlength/sequence/topologyforprecisionsynthesisofcyclicblockcopolymersfrommonomermixtures.J. Am. Chem. Soc.2021, 143,3318–3322..

Li,C.;Zhao,W.;He,J.;Zhang,Y.;Zhang,W.Single-stepexpeditioussynthesisofdiblockcopolymerswithdifferentmorphologiesbyLewispairpolymerization-inducedself-assembly.Angew. Chem. Int. Ed.2022, 61,e202202448..

Wan,Y.;He,J.;Zhang,Y.;Chen,E.Y.X.One-stepsynthesisoflignin-basedtriblockcopolymersashigh-temperatureandUV-blockingthermoplasticelastomers.Angew. Chem. Int. Ed.2022, 61,e202114946..

Zhang,P.;Zhou,H.;Lu,X.Livingandchemoselective(co)polymerizationofpolardivinylmonomersmediatedbybulkyLewispairs.Macromolecules2019, 52,4520–4525..

Zhao,W.;Wang,Q.;He,J.;Zhang,Y.Chemoselectiveandliving/controlledpolymerizationofpolardivinylmonomersby N-heterocyclicolefinbasedclassicalandfrustratedLewispairs.Livingandchemoselective(co)polymerizationofpolardivinylmonomersmediatedbybulkyLewispairs.Polym. Chem.2019, 10,4328–4335..

Chen,Z.;Zhao,W.;Liu,C.;Jiang,L.;Fu,G.;Zhang,Y.;Zhu,H.Phosphoniumylide/organoaluminum-basedLewispairsforthehighlyefficientliving/controlledpolymerizationofalkyl(meth)acrylates.Polym. Chem.2023, 14,2344–2354..

Transue,W.J.;Yang,J.;Nava,M.;Sergeyev,I.V.;Barnum,T.J.;McCarthy,M.C.;Cummins,C.C.Syntheticandspectroscopicinvestigationsenabledbymodularsynthesisofmolecularphosphaalkyneprecursors.J. Am. Chem. Soc.2018, 140,17985–17991..

Bestmann,H.J.;Stransky,W.;Vostrowsky,O.DarstellungLithiumsalzfreierYlidlosungenmitNatrium-bis-(trimethylsilyl)-amid.Chem. Ber.1 976 ,109,1694–1700..

Lee,C.H.;Lee,S.J.;Park,J.W.;Kim,K.H.;Lee,B.Y.;Oh,J.S.PreparationofAl(C6F5)3anditsuseforthemodificationofmethylalumoxane.J. Mol. Catal. A-Chem.1998, 132,231–239..

Stapleton,R.A.;Al-Humydi,A.;Chai,J.;Galan,B.R.;Collins,S.Stericallyhinderedaluminumalkyls:weaklyinteractingscavengingagentsofuseinolefinpolymerization.Organometallics2006, 25,5083–5092..

Faingol’d,E.E.;Bravaya,N.M.;Panin,A.N.;Babkina,O.N.;Saratovskikh,S.L.;Privalov,V.I.Isobutylaluminumaryloxidesasmetalloceneactivatorsinhomo-andcopolymerizationofolefins.J. Appl. Polym. Sci.2016, 133,43276–43284..

UsuallythePAMAshereinobtainedareoftherichsyndiotacticity,ascanbedeterminedbythecalculationoftheprotonintigationratiosoftheMesidegroupsatthemainchainfromthe1HNMRdata.See:reference18andBolig,A.D.;Chen,E.Y.X. ansa-Zirconoceneesterenolates:synthesis,structure,reactionwithorgano-Lewisacids,andapplicationtopolymerizationofmethacrylates.J. Am. Chem. Soc.2004, 126,4897–4906..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Advanced Surfaces by Anchoring Thin Hydrogel Layers of Functional Polymers

Related Author

No data

Related Institution

Provincial Key Lab of Pulp & Paper Sci and Tech, and Joint International Research Lab of Lignocellulosic Functional Materials, Nanjing Forestry University

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University

Department of Chemical Engineering, University of New Brunswick,, NB

Department of Resin and Additives, Institute for Color Science and Technology, 16765-654, Tehran

⁰