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New insight into the polymerization mechanism of 1,3-dienes cationic polymerization. IV. Mechanism of unsaturation loss in the polymerization of isoprene

dc.rights.licenseopen
hal.structure.identifierRussian Acad Sci, Inst Ecol Volga River Basin
dc.contributor.authorROZENTSVET, Victor A.
hal.structure.identifierRussian Acad Sci, Inst Ecol Volga River Basin
dc.contributor.authorKOZLOV, Valery G.
hal.structure.identifierRussian Acad Sci, Inst Ecol Volga River Basin
dc.contributor.authorSABLINA, Nelly A.
hal.structure.identifierRussian Acad Sci, Inst Ecol Volga River Basin
dc.contributor.authorSTOTSKAYA, Olesya A.
hal.structure.identifierLaboratoire de Chimie des Polymères Organiques [LCPO]
hal.structure.identifierTeam 1 LCPO : Polymerization Catalyses & Engineering
dc.contributor.authorPERUCH, Frédéric
IDREF: 152900748
hal.structure.identifierRes Inst Phys Chem Problems, Belarusian State Univ
dc.contributor.authorKOSTJUK, Sergei V.
dc.date.accessioned2020
dc.date.available2020
dc.date.issued2017
dc.identifier.issn1759-9954
dc.identifier.urihttps://oskar-bordeaux.fr/handle/20.500.12278/20135
dc.description.abstractEnThe cationic polymerization of isoprene with the tBuCl/TiCl4 initiating system in the presence of a high excess of tBuCl over TiCl4 ([tBuCl]/[TiCl4] > 100) in CH2Cl2 is reported. It is shown that the polymerization follows first-order kinetics, which indicates that the main chain-breaking process is the chain transfer to the initiator. The number-average functionalities with respect to the tert-butyl head group and chlorine-containing end group are determined to be considerably higher than unity. In addition, unsaturation of the polymer chain is found to be always less than 100%. It is also shown that unsaturation of the polyisoprene chain decreases with a simultaneous increase in polydispersity upon treatment of the polymer using the tBuCl/TiCl4 initiating system. Based on these observations, the mechanism to obtain a polymer with reduced unsaturation is proposed, which includes multiple interactions of growing cations with double bonds of "own" or/and "alien" macromolecules with the formation of branched structures.
dc.language.isoen
dc.publisherRoyal Society of Chemistry - RSC
dc.subject.enIsoprene
dc.subject.enBreaking process
dc.subject.enChain transfer
dc.subject.enFirst order kinetics
dc.subject.enMultiple interactions
dc.subject.enNumber average
dc.subject.enPolymer chains
dc.subject.enPolymerization mechanisms
dc.subject.enBranched structures
dc.subject.enCationic polymerization
dc.title.enNew insight into the polymerization mechanism of 1,3-dienes cationic polymerization. IV. Mechanism of unsaturation loss in the polymerization of isoprene
dc.typeArticle de revue
dc.identifier.doi10.1039/c6py01736c
dc.subject.halChimie/Polymères
bordeaux.journalPolymer Chemistry
bordeaux.page926-935
bordeaux.volume8
bordeaux.hal.laboratoriesLaboratoire de Chimie des Polymères Organiques (LCPO) - UMR 5629*
bordeaux.issue5
bordeaux.institutionBordeaux INP
bordeaux.institutionUniversité de Bordeaux
bordeaux.peerReviewedoui
hal.identifierhal-01473824
hal.version1
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-01473824v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Polymer%20Chemistry&rft.date=2017&rft.volume=8&rft.issue=5&rft.spage=926-935&rft.epage=926-935&rft.eissn=1759-9954&rft.issn=1759-9954&rft.au=ROZENTSVET,%20Victor%20A.&KOZLOV,%20Valery%20G.&SABLINA,%20Nelly%20A.&STOTSKAYA,%20Olesya%20A.&PERUCH,%20Fr%C3%A9d%C3%A9ric&rft.genre=article


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