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

Poly(δ‐valerolactone) (PVL) was synthesized by ring‐opening polymerization (ROP), employing tin(II) acetate (SnAcet2), lead(II) acetate trihydrate (PbAcet2·3H2O) and cadmium(II) acetate dihydrate (CdAcet2·2H2O) complexes as initiators without any co‐initiator. The highest molecular weight PVL (45 43...

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Bibliographic Details
Published in:Polymer international 2022-07, Vol.71 (7), p.912-920
Main Authors: Gümüştaş, Sıla, Balcan, Mehmet, Kinal, Armağan
Format: Article
Language:English
Subjects:
biodegradable polymers
Cadmium
Cell viability
Chemical synthesis
Computer applications
Coordination compounds
Density functional theory
Dilution
Hirshfeld
Initiators
Ions
Lactones
Lead
Lead acetates
Liquid chromatography
Mass spectrometry
Mass spectroscopy
metal acetates
Molecular orbitals
Molecular weight
NMR
Nuclear magnetic resonance
poly(δ‐valerolactone)
Polymerization
Ring opening polymerization
ring‐opening polymerization (ROP)
Tin
Toxicity
Toxicity testing
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Summary:Poly(δ‐valerolactone) (PVL) was synthesized by ring‐opening polymerization (ROP), employing tin(II) acetate (SnAcet2), lead(II) acetate trihydrate (PbAcet2·3H2O) and cadmium(II) acetate dihydrate (CdAcet2·2H2O) complexes as initiators without any co‐initiator. The highest molecular weight PVL (45 438 g mol−1, 91% yield) was obtained with CdAcet2·2H2O. Characterization of the synthesized products was performed by FTIR, 1H NMR, 13C 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, ωB97X‐D, PBEPBE, BPV86, HSEH1PBE, MPW1PW91, M06 and M062X). In addition, the initiation stage of the ROP mechanism of δ‐valerolactone with these metal acetate complexes was investigated at the ωB97X‐D level with a mixed basis set. It was computationally determined that the most effective initiator was also CdAcet2. 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. © 2021 Society of Industrial Chemistry. This paper presents experimental and theoretical studies on the determination of initiator metal efficiency in the ring‐opening polymerization of δ‐valerolactone.
ISSN:0959-8103
1097-0126
DOI:10.1002/pi.6361