Investigation of initiator metal efficiency in the ring-opening polymerization of lactones: an experimental and computational study

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dc.authoridkinal, armagan/0000-0002-9747-4901
dc.authorscopusid56385869300
dc.authorscopusid15119176800
dc.authorscopusid11739944700
dc.contributor.authorGumustas, Sila
dc.contributor.authorBalcan, Mehmet
dc.contributor.authorKinal, Armagan
dc.date.accessioned2023-01-12T19:49:55Z
dc.date.available2023-01-12T19:49:55Z
dc.date.issued2022
dc.departmentN/A/Departmenten_US
dc.description.abstractPoly(delta-valerolactone) (PVL) was synthesized by ring-opening polymerization (ROP), employing tin(II) acetate (SnAcet(2)), lead(II) acetate trihydrate (PbAcet(2)center dot 3H(2)O) and cadmium(II) acetate dihydrate (CdAcet(2)center dot 2H(2)O) complexes as initiators without any co-initiator. The highest molecular weight PVL (45 438 g mol(-1), 91% yield) was obtained with CdAcet(2)center dot 2H(2)O. Characterization of the synthesized products was performed by FTIR, H-1 NMR, C-13 NMR, gel permeation chromatography (GPC), matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF/TOF MS), TGA and DSC. Electrostatic data (natural bond orbital and Hirshfeld) and lowest unoccupied molecular orbital (LUMO) of the initiators were obtained by using several density functional theory methods (B3LYP, omega B97X-D, PBEPBE, BPV86, HSEH1PBE, MPW1PW91, M06 and M062X). In addition, the initiation stage of the ROP mechanism of delta-valerolactone with these metal acetate complexes was investigated at the omega B97X-D level with a mixed basis set. It was computationally determined that the most effective initiator was also CdAcet(2). The molecular weight variation of PVLs synthesized with these initiators can be associated with the combined evaluation of atomic charge, LUMO and orbital overlap analyses. The computationally obtained reaction barriers for the initiators support this idea, also. In addition, toxicity tests carried out for PVLs synthesized with acetate complexes containing Sn, Cd and Pb revealed that the Sn and Cd complexes do not have a toxic effect on cell viability at some dilution rates. (C) 2021 Society of Industrial Chemistry.en_US
dc.description.sponsorshipResearch Foundation of Ege University, Turkey [2016 FEN 041]; Ege University Planning and Monitoring Coordination of Organizational Development; Ege University Directorate of Library and Documentationen_US
dc.description.sponsorshipThis work was supported by the Research Foundation of Ege University, Turkey (No. 2016 FEN 041). The DFT calculations reported in this study were performed at TUBITAK ULAKBIM, High Performance and Grid Computing Center (TRUBA resources). We are grateful to Ege University Planning and Monitoring Coordination of Organizational Development and the Directorate of Library and Documentation for their support in the editing and proofreading service of this study.en_US
dc.identifier.doi10.1002/pi.6361
dc.identifier.endpage920en_US
dc.identifier.issn0959-8103
dc.identifier.issn1097-0126
dc.identifier.issn0959-8103en_US
dc.identifier.issn1097-0126en_US
dc.identifier.issue7en_US
dc.identifier.scopus2-s2.0-85123503121en_US
dc.identifier.scopusqualityQ2en_US
dc.identifier.startpage912en_US
dc.identifier.urihttps://doi.org/10.1002/pi.6361
dc.identifier.urihttps://hdl.handle.net/11454/75956
dc.identifier.volume71en_US
dc.identifier.wosWOS:000746562300001en_US
dc.identifier.wosqualityQ2en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.indekslendigikaynakScopusen_US
dc.language.isoenen_US
dc.publisherWileyen_US
dc.relation.ispartofPolymer Internationalen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectpoly(delta-valerolactone)en_US
dc.subjectring-opening polymerization (ROP)en_US
dc.subjectdensity functional theoryen_US
dc.subjectmetal acetatesen_US
dc.subjectbiodegradable polymersen_US
dc.subjectHirshfelden_US
dc.subjectEffective Core Potentialsen_US
dc.subjectEpsilon-Caprolactoneen_US
dc.subjectL-Lactideen_US
dc.subjectDelta-Valerolactoneen_US
dc.subjectBasis-Setsen_US
dc.subjectMolecular Calculationsen_US
dc.subjectCyclic Estersen_US
dc.subjectZincen_US
dc.subjectAcetateen_US
dc.subjectComplexesen_US
dc.titleInvestigation of initiator metal efficiency in the ring-opening polymerization of lactones: an experimental and computational studyen_US
dc.typeArticleen_US

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