Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

Qi-Yuan Wang; Li-Peng Sang; Zhen Zhang; Yang Jiang; Hui Tian; Xia Zhao; Xiang Guo; Shi-Hui Li

doi:10.1007/s10118-023-3047-7

Your Location：

Home >

Browse articles >

Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

RESEARCH ARTICLE | Updated：2024-01-12

- Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts
- Chinese Journal of Polymer Science Vol. 42, Issue 2, Pages: 223-229(2024)
- Affiliations：
  
  a.State Key Laboratory of Polymer Physics and Chemistry, 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
  c.Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemotechonology, Xiangyang 441003, China
  d.Shanxi Coal Chemical Industry Technology Research Institute, Xi’an 710000, China
  e.Hubei Institute of Aerospace Chemotechonology, Xiangyang 441003, China
- Author bio：
  
  guoxcasc@163.com (X.G.)
  shihui-li@ciac.ac.cn (S.H.L.)
- Funds：
- DOI：10.1007/s10118-023-3047-7
  CLC：
Scan for full text
Wang, Q. Y.; Sang, L. P.; Zhang, Z.; Jiang, Y.; Tian, H.; Zhao, X.; Guo, X.; Li, S. H. Regio- and stereoselective polymerization of bio-based ocimene by rare-earth metal catalysts. Chinese J. Polym. Sci. 2024, 42, 223–229

Qi-Yuan Wang, Li-Peng Sang, Zhen Zhang, et al. Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts. [J]. Chinese Journal of Polymer Science 42(2):223-229(2024)
Wang, Q. Y.; Sang, L. P.; Zhang, Z.; Jiang, Y.; Tian, H.; Zhao, X.; Guo, X.; Li, S. H. Regio- and stereoselective polymerization of bio-based ocimene by rare-earth metal catalysts. Chinese J. Polym. Sci. 2024, 42, 223–229 DOI： 10.1007/s10118-023-3047-7.

Qi-Yuan Wang, Li-Peng Sang, Zhen Zhang, et al. Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts. [J]. Chinese Journal of Polymer Science 42(2):223-229(2024) DOI： 10.1007/s10118-023-3047-7.

摘要

A new type of isotactic cis-1,4-polyocimene is synthesized by coordination polymerization of renewable ,β,-ocimene using complex ,3, which is readily transformed into epoxidized and hydroxylated products. The excellent isotactic ,trans,-1,2-polyocimene is produced by complex ,5c,. ,Cis,-1,4-PIP-b-,cis,-1,4-POc and ,cis,-1,4-PBD-b-,cis,-1,4-POc is obtained in one-pot reactions of ,β,-ocimene with isoprene and butadiene.

Abstract

Coordination polymerization of renewable ,β,-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex ,1,β,-diketiminate yttrium complex ,2, bis(phosphino)carbazolide yttrium complex ,3, half-sandwich benzyl fluorenyl scandium complex ,4, and pyridyl-methylene-fluorenyl rare-metal complexes ,5a,–,5c,. Complexes ,1,4, and ,5a,–,5c, show ,trans,-1,2-regioselectivities and high activities, of which ,5c, exhibits excellent isoselectivity (,mmmm,>,99%). Conversely, complexes ,2, and ,3, promote ,β,-ocimene polymerization to produce isotactic ,cis,-1,4-polyocimenes (,cis,-1,4,>,99%,mm,>,95%). Diblock copolymers ,cis,-1,4-PIP-block-,cis,-1,4-POc and ,cis,-1,4-PBD-block-,cis,-1,4-POc are obtained in one-pot reactions of ,β,-ocimene with isoprene and butadiene using complex ,3,. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced ,T,g, (from −20 °C to 79 °C and 74 °C) and hydrophilicity.

关键词

Keywords

Biobased monomerTerpenesOcimeneRare-earthsPolymerizationRegio/stereoselectivityElastomer

references

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

Gibb,B.C.Plasticsareforever.Nat. Chem.2019, 11,394−395..

Wang,Z.;Yuan,L.;Tang,C.Sustainableelastomersfromrenewablebiomass.Acc. Chem. Res.2017, 50,1762−1773..

Llevot,A.;Grau,E.;Carlotti,S.;Grelier,S.;Cramail,H.Fromlignin-derivedaromaticcompoundstonovelbiobasedpolymers.Macromol. Rapid Commun.2016, 37,9−28..

Lambert,S.;Wagner,M.Environmentalperformanceofbio-basedandbiodegradableplastics:theroadahead.Chem. Soc. Rev.2017, 46,6855−6871..

John,G.;Nagarajan,S.;Vemula,P.K.;Silverman,J.R.;Pillai,C.K.S.Naturalmonomers:amineforfunctionalandsustainablematerials—occurrence,chemicalmodificationandpolymerization.Prog. Polym. Sci.2019, 92,158−209..

Hong,M.;Chen,E.Y.X.Futuredirectionsforsustainablepolymers.Trends Chem.2019, 1,148−151..

Gandini,A.Polymersfromrenewableresources:achallengeforthefutureofmacromolecularmaterials.Macromolecules2008, 41,9491−9504..

Winnacker,M.Pinenes:abundantandrenewablebuildingblocksforavarietyofsustainablepolymers.Angew. Chem. Int. Ed.2018, 57,14362−14371..

Stempfle,F.;Ortmann,P.;Mecking,S.Long-chainaliphaticpolymerstobridgethegapbetweensemicrystallinepolyolefinsandtraditionalpolycondensates.Chem. Rev.2016, 116,4597−4641..

Schneiderman,D.K.;Hillmyer,M.A.50thAnniversaryperspective:thereisagreatfutureinsustainablepolymers.Macromolecules2017, 50,3733−3750..

Jiang,Y.;Zhang,Z.;Li,S.;Cui,D.Coordinationpolymerizationofrenewable( E)-4,8-dimethyl-1,3,7-nonatrienebyrare-earthmetalcatalysts.Chin. J. Chem.2022, 40,1939−1944..

Jiang,Y.;Kang,X.;Zhang,Z.;Li,S.;Cui,D.Syndioselective3,4-polymerizationof1-phenyl-1,3-butadienebyrare-earthmetalcatalysts.ACS Catal.2020, 10,5223−5229..

Liu,B.;Li,S.;Wang,M.;Cui,D.Coordinationpolymerizationofrenewable3-methylenecyclopentenewithrare-earth-metalprecursors.Angew. Chem. Int. Ed.2017, 56,4560−4564..

Wahlen,C.;Frey,H.Anionicpolymerizationofterpenemonomers:newoptionsforbio-basedthermoplasticelastomers.Macromolecules2021, 54,7323−7336..

Wadgaonkar,S.P.;Wagner,M.;Baptista,L.A.;Cortes-Huerto,R.;Frey,H.Mueller,A.H.E.,Anionicpolymerizationoftheterpene-baseddienebeta-ocimene:complexmechanismduetostereoisomerreactivities.Macromolecules2023, 56,664−677..

Sahu,P.;Bhowmick,A.K.Redoxemulsionpolymerizationofterpenes:mappingtheeffectofthesystem,structure,andreactivity.Ind. Eng. Chem. Res.2019, 58,20946−20960..

Radchenko,A.V.;Bouchekif,H.;Peruch,F.Triflateestersas in-situgeneratedinitiatingsystemforcarbocationicpolymerizationofvinylethers,isoprene,myrceneandocimene.Eur. Polym. J.2017, 89,34−41..

Peng,D.;Du,G.;Zhang,P.;Yao,B.;Li,X.;Zhang,S.Regio-andstereochemicalcontrolinocimenepolymerizationbyhalf-sandwichrare-earthmetaldialkylcomplexes.Macromol. Rapid Commun.2016, 37,987−992..

Lamparelli,D.H.;Paradiso,V.;DellaMonica,F.;Proto,A.;Guerra,S.;Giannini,L.;Capacchione,C.Towardmoresustainableelastomers:stereoselectivecopolymerizationoflinearterpeneswithbutadiene.Macromolecules2020, 53,1665−1673..

Lamparelli,D.H.;Paradiso,V.;Capacchione,C.Newelastomericmaterialsfrombiomass:stereoselectivepolymerizationoflinearterpenesandtheircopolymerizationwithbutadienebyusingacobaltcomplexwithphosphaneligands.Rubber Chem. Technol.2020, 93,605−614..

Valencia,L.;Enríquez-Medrano,F.J.;LópezGonzález,H.R.;Handa,R.;Caballero,H.S.;Carrizales,R.M.;Olivares-Romero,J.L.;DíazdeLeónGómez,R.E.Bio-elastomersbasedonpolyocimenesynthesized viacoordinationpolymerizationusingneodymium-basedcatalyticsystems.RSC Adv.2020, 10,36539−36545..

Naddeo,M.;Buonerba,A.;Luciano,E.;Grassi,A.;Proto,A.;Capacchione,C.Stereoselectivepolymerizationofbiosourcedterpenes β-myrceneand β-ocimeneandtheircopolymerizationwithstyrenepromotedbytitaniumcatalysts.Polymer2017, 131,151−159..

Zhang,S.;Han,L.;Ma,H.;Liu,P.;Shen,H.;Lei,L.;Li,C.;Yang,L.;Li,Y.Investigationonsynthesisandapplicationperformanceofelastomerswithbiogenicmyrcene.Ind. Eng. Chem. Res.2019, 58,12845−12853..

Zhang,J.;Lu,J.;Su,K.;Wang,D.;Han,B.Bio-basedbeta-myrcene-modifiedsolution-polymerizedstyrene-butadienerubberforimprovingcarbonblackdispersionandwetskidresistance.J. Appl. Polym. Sci.2019, 136,48159..

Ren,X.;Guo,F.;Fu,H.;Song,Y.;Li,Y.;Hou,Z.Scandium-catalyzedcopolymerizationofmyrcenewithethyleneandpropylene:convenientsynthesesofversatilefunctionalizedpolyolefins.Polym. Chem.2018, 9,1223−1233..

Loughmari,S.;Hafid,A.;Bouazza,A.;ElBouadili,A.;Zinck,P.;Visseaux,M.Highlystereoselectivecoordinationpolymerizationofbeta-myrcenefromalanthanide-basedcatalyst:accesstobio-sourcedelastomers.J. Polym. Sci. Part A: Polym. Chem.2012, 50,2898−2905..

Liu,B.;Liu,D.;Li,S.;Sun,G.;Cui,D.High trans-1,4(co)polymerizationofbeta-myrceneandisoprenewithaniminophosphonamidelanthanumcatalyst.Chinese J. Polym. Sci.2016, 34,104−110..

Liu,B.;Li,L.;Sun,G.;Liu,D.;Li,S.;Cui,D.Isoselective3,4-(co)polymerizationofbio-renewablemyrceneusingNSN-ligatedrare-earthmetalprecursor:anapproachtoanewelastomer.Chem. Commun.2015, 51,1039−1041..

Liu,B.;Han,B.;Zhang,C.;Li,S.;Sun,G.;Cui,D.Renewablebeta-myrcenepolymerizationinitiatedbylutetiumalkylcomplexesligatedbyimidophosphonamidoligand.Chinese J. Polym. Sci.2015, 33,792−796..

Li,W.;Zhao,J.;Zhang,X.;Gong,D.CapabilityofPN3-typecobaltcomplexestowardselective(co-)polymerizationofmyrcene,butadiene,andisoprene:accesstobiosourcedpolymers.Ind. Eng. Chem. Res.2019, 58,2792−2800..

Lamparelli,D.H.;Kleybolte,M.M.;Winnacker,M.;Capacchione,C.Sustainablemyrcene-basedelastomers viaaconvenientanionicpolymerization.Polymers2021, 13,838..

Kitphaitun,S.;Chaimongkolkunasin,S.;Manit,J.;Makino,R.;Kadota,J.;Hirano,H.;Nomura,K.Ethylene/myrcenecopolymersasnewbio-basedelastomerspreparedbycoordinationpolymerizationusingtitaniumcatalysts.Macromolecules2021, 54,10049−10058..

Jia,X.;Li,W.;Zhao,J.;Yi,F.;Luo,Y.;Gong,D.Dualcatalysisoftheselectivepolymerizationofbiosourcedmyrceneandmethylmethacrylatepromotedbysalicylaldiminatocobalt(II)complexeswithapendantdonor.Organometallics2019, 38,278−288..

Hulnik,M.I.;Vasilenko,I.V.;Radchenko,A.V.;Peruch,F.;Ganachaud,F.;Kostjuk,S.V.Aqueouscationichomo-andco-polymerizationsof-myrceneandstyrene:agreenroutetowardterpene-basedrubberypolymers.Polym. Chem.2018, 9,5690−5700..

Hahn,C.;Wagner,M.;Mueller,A.H.E.;Frey,H.MyrDOL,aProtecteddihydroxyfunctionaldienemonomerderivedfrombeta-myrcene:functionalpolydienesfromrenewableresources viaanionicpolymerization.Macromolecules2022, 55,4046−4055..

Glatzel,J.;Noack,S.;Schanzenbach,D.;Schlaad,H.Anionicpolymerizationofdienesin'green'solvents.Polym. Int.2021, 70,181−184..

Georges,S.;Toure,A.O.;Visseaux,M.;Zinck,P.Coordinativechaintransfercopolymerizationandterpolymerizationofconjugateddienes.Macromolecules2014, 47,4538−4547..

Gan,Q.;Xu,Y.;Huang,W.;Luo,W.;Hu,Z.;Tang,F.;Jia,X.;Gong,D.Utilizationofbio-sourcedmyrceneforefficientpreparationofhighly cis-1,4regularelastomer viaaneodymiumcatalyzedcopolymerizationstrategy.Polym. Int.2020, 69,763−770..

Dev,A.;Roesler,A.;Schlaad,H.Limoneneasarenewableunsaturatedhydrocarbonsolventforlivinganionicpolymerizationofbeta-myrcene.Polym. Chem.2021, 12,3084−3087..

Bolton,J.M.;Hillmyer,M.A.;Hoye,T.R.Sustainablethermoplasticelastomersfromterpene-derivedmonomers.ACS Macro Lett.2014, 3,717−720..

Avila-Ortega,A.;Aguilar-Vega,M.;Bastarrachea,M.I.L.;Carrera-Figueiras,C.;Campos-Covarrubias,M.Anionicsynthesisofamineomega-terminatedbeta-myrcenepolymers.J. Polym. Res.2015, 22,226..

You,F.;Shi,W.;Yan,X.;Wang,X.;Shi,X.Polymerizationofbio-derivedconjugateddieneswithrare-earth-metalcomplexes.Chem. Asian. J.2022, 17,e202200892..

Banda-Villanueva,A.;LuisGonzalez-Zapata,J.;EduardoMartinez-Cartagena,M.;Magana,I.;Cordova,T.;Lopez,R.;Valencia,L.;GarciaMedina,S.;MedinaRodriguez,A.;Soriano,F.;DiazdeLeon,R.Synthesisandvulcanizationofpolymyrceneandpolyfarnesenebio-basedrubbers:influenceofthechemicalstructureoverthevulcanizationprocessandmechanicalproperties.Polymers2022, 14,1406..

Luk,S.B.;Maric,M.Polymerizationofbiobasedfarneseneinminiemulsionsbynitroxide-mediatedpolymerization.ACS Omega2021, 6,4939−4949..

You,F.;Kang,X.;Nishiura,M.;Zhai,J.;Xu,S.;Wang,J.;Shi,X.;Hou,Z.Living3,4-isoselective(co)polymerizationofbiobasedbeta-farnesenecatalyzedbyphosphine-functionalizedfluorenylrare-earthmetal.Macromolecules2022, 55,5049−5057..

Luk,S.B.;Maric,M.Farneseneandnorbornenylmethacrylateblockcopolymers:applicationofthiol-eneclickingtoimprovethermalandmechanicalproperties.Polymer2021, 230,124106..

CepedaTovar,V.A.;RubioRios,A.;SaenzGalindo,A.;RosalesMarines,L.;FariasCepeda,L.Bio-basedelastomersbyvinylacrylate(vac)- co-farnesene(fa)emulsioncopolimerization.Afinidad2022, 79,44−48..

Sahu,P.;Oh,J.S.Biobasedelastomerfromrenewablebiomassbeta-farnesene:synthesis,characterization,andproperties.Ind. Eng. Chem. Res.2022, 61,11815−11824..

Lamparelli,D.H.;Winnacker,M.;Capacchione,C.Stereoregularpolymerizationofacyclicterpenes.ChemPlusChem2022, 87,e202100366..

Liu,B.;Li,L.;Sun,G.;Liu,J.;Wang,M.;Li,S.;Cui,D.3,4-PolymerizationofisoprenebyusingNSN-andNPN-ligatedrareearthmetalprecursors:switchingofstereoselectivityandmechanism.Macromolecules2014, 47,4971−4978..

Valente,A.;Stoclet,G.;Bonnet,F.;Mortreux,A.;Visseaux,M.;Zinck,P.Isoprene-styrenechainshuttlingcopolymerizationmediatedbyalanthanidehalf-sandwichcomplexandalanthanidocene:straightforwardaccesstoanewtypeofthermoplasticelastomers.Angew. Chem. Int. Ed.2014, 53,4638−4641..

Bonnet,F.;Visseaux,M.;Pereira,A.;Bouyer,F.;Barbier-Baudry,D.StereospecificpolymerizationofisoprenewithNd(BH4)3(THF)3/MgBu2ascatalyst.Macromol. Rapid Commun.2004, 25,873−877..

Liu,B.;Wang,X.;Pan,Y.;Lin,F.;Wu,C.;Qu,J.;Luo,Y.;Cui,D.Unprecedented3,4-isopreneand cis-1,4-butadienecopolymerswithcontrolledsequencedistributionbysingleyttriumcationicspecies.Macromolecules2014, 47,8524−8530..

Gao,W.;Cui,D.Highly cis-1,4selectivepolymerizationofdieneswithhomogeneousZiegler-NattacatalystsbasedonNCN-pincerrareearthmetaldichlorideprecursors.J. Am. Chem. Soc.2008, 130,4984−4991..

Kaita,S.;Hou,Z.;Nishiura,M.;Doi,Y.;Kurazumi,J.;Horiuchi,A.C.;Wakatsuki,Y.Ultimatelyspecific1,4- cispolymerizationof1,3-butadienewithanovelgadoliniumcatalyst.Macromol. Rapid Commun.2003, 24,179−184..

Wang,Q.;Huang,J.;Li,S.;Cui,D.Preparationofhydroxylfunctionalized cis-1,4polydienes.Acta Polymerica Sinica(inChinese)2022, 53,474−481..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes

Stabilize and Reinforce Hydrogen-Bonded Polymer Complex Elastic Fiber by Catechol Chemistry and Coordination

Long-Range Ordered Nanostructures of Assembling Macromolecules via Rational Design of Kinetic Pathways: A Computational Perspective

Related Author

No data

Related Institution

Shanghai Key Laboratory of Functional Materials Chemistry and Laboratory of Organometallic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Center for Advanced Low-Dimension Materials, College of Materials Science and Engineering, Donghua University

Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology

Shandong Artificial intelligence Institute and Shandong Computer Science Center, Qilu University of Technology

Department of Chemistry and Physics, La Trobe Institute for Molecular Science, La Trobe University

⁰