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Unprecedented polymerization of trimethylene carbonate initiated by a samarium borohydride complex: Mechanistic insights and copolymerization with epsilon-caprolactone

dc.rights.licenseopen
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorPALARD, Isabelle
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorSCHAPPACHER, Michèle
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
dc.contributor.authorBELLONCLE, Benjamine
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
hal.structure.identifierTeam 1 LCPO : Polymerization Catalyses & Engineering
dc.contributor.authorSOUM, Alain
hal.structure.identifierLaboratoire de Chimie des polymères organiques [LCPO]
hal.structure.identifierInstitut des Sciences Chimiques de Rennes [ISCR]
hal.structure.identifierTeam 1 LCPO : Polymerization Catalyses & Engineering
dc.contributor.authorGUILLAUME, Sophie M.
dc.date.accessioned2020
dc.date.available2020
dc.date.issued2007
dc.identifier.issn0947-6539
dc.identifier.urihttps://oskar-bordeaux.fr/handle/20.500.12278/20833
dc.description.abstractEnPoly(trimethylene carbonate) (PTMC) was synthesized through ring-opening polymerization by using a rare-earth borohydride initiator, [Sm(BH4)(3)(thf)(3)]. This initiator shows a high activity to give high-molar-mass PTMCs with molar-mass distributions ranging from 1.2 to 1.4, and with a regular structure void of ether linkages. ne polymers were characterized by H-1 and C-13 NMR spectroscopy, H-1-H-1 COSY, H-1-C-13 HMQC NMR spectroscopy, size-exclusion chromatography (SEC), viscosimetry, and MALDI-TOF MS analyses. A coordination-insertion mechanism was established based on detailed NMR characterizations, especially of the polymer chain end-functions. The monomer initially coordinates the samarium to give [Sm(BH4)(3-)(tMc)(3)], 1. The monomer then opens up through cleavage of the cyclic ester oxygen-acyl bond and inserts into the Sm-HBH3 bond resulting in an alkoxide complex, [Sm{O(CH2)(3)OC(O)HBH3}(3)], 2, or [Sm{O(CH2)(3)OC(O)H)(3)], 2', which then propagates the polymerization of TMC to give the active polymer [Sm({O(CH2)(3)OC(O)(n)-O(CH2)(3)OC(O)HBH3)(3)], 3 or [Sm(O(CH2)(3)OC(O){O(CH2)(3)OC(O)}(n)O- (CH2)(3)OC(O)H)(3)], 3'. Finally, acidic hydrolysis of 3 or 3' gives HO-(CH2)(3)OC(O)[O(CH2)(3)OC(O)](n)O-(CH2)(3)OC(O)H, 4. This novel alpha-hydroxy w-formatetelechelic PTMC represents the first example of a formate-terminated polycarbonate. TMC and epsilon-caprolactone (CL) were copolymerized to afford both random PTMC-co-PCL and block PTMC-b-PCL copolymers that were characterized by H-1 NMR spectroscopy, SEC, and differential scanning calorimetry (DSC). The structure of the block copolymers depends on the order of addition of monomers: if CL is introduced first, dihydroxytelechelic HO-PTMC-b-PCL-OH polymers are formed, whereas introduction of TMC first or simultaneous addition of comonomers leads to hydroxyformatetelechelic HC(O)O-PTMC-b-PCL-OH analogues
dc.language.isoen
dc.publisherWiley-VCH Verlag
dc.subject.enring-opening polymerization
dc.subject.enblock copolymers
dc.subject.enborohydride
dc.subject.encarbonates
dc.subject.enrare earth metals
dc.title.enUnprecedented polymerization of trimethylene carbonate initiated by a samarium borohydride complex: Mechanistic insights and copolymerization with epsilon-caprolactone
dc.typeArticle de revue
dc.identifier.doi10.1002/chem.200600843
dc.subject.halChimie/Polymères
bordeaux.journalChemistry - A European Journal
bordeaux.page1511-1521
bordeaux.volume13
bordeaux.hal.laboratoriesLaboratoire de Chimie des Polymères Organiques (LCPO) - UMR 5629*
bordeaux.issue5
bordeaux.institutionBordeaux INP
bordeaux.institutionUniversité de Bordeaux
bordeaux.peerReviewedoui
hal.identifierhal-00275433
hal.version1
hal.origin.linkhttps://hal.archives-ouvertes.fr//hal-00275433v1
bordeaux.COinSctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Chemistry%20-%20A%20European%20Journal&rft.date=2007&rft.volume=13&rft.issue=5&rft.spage=1511-1521&rft.epage=1511-1521&rft.eissn=0947-6539&rft.issn=0947-6539&rft.au=PALARD,%20Isabelle&SCHAPPACHER,%20Mich%C3%A8le&BELLONCLE,%20Benjamine&SOUM,%20Alain&GUILLAUME,%20Sophie%20M.&rft.genre=article


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