Phosphorus-containing stereocontrolled polyhydroxyalkanoates by yttrium-mediated ring-opening copolymerization of β-lactones

[Display omitted] •Poly(3-hydroxybutyrate) (PHB) polymers bearing pendent diphenylphosphinate moieties can be prepared by the simultaneous ring-opening copolymerization (ROCOP) of β-butyrolactone (BPLMe) with a phosphinate-functionalized β-lactone (BPLOP).•By tuning the ligand substituents on the yt...

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Bibliographic Details
Published in:European polymer journal 2024-04, Vol.209, p.112919, Article 112919
Main Authors: Dhaini, Ali, Shakaroun, Rama M., Ollivier, Jérôme, Alaaeddine, Ali, Guillaume, Sophie M, Carpentier, Jean-François
Format: Article
Language:English
Subjects:
Chemical Sciences
Copolymers
Mass spectrometry
Phosphinate
Poly(3-hydroxybutyrate) (PHB)
Polyhydroxyalkanoate (PHA)
Polymers
Ring-opening copolymerization (ROCOP)
β-Lactone
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Summary:[Display omitted] •Poly(3-hydroxybutyrate) (PHB) polymers bearing pendent diphenylphosphinate moieties can be prepared by the simultaneous ring-opening copolymerization (ROCOP) of β-butyrolactone (BPLMe) with a phosphinate-functionalized β-lactone (BPLOP).•By tuning the ligand substituents on the yttrium catalyst, copolymers containing syndio-enriched, atactic and highly isotactic PHB segments were obtained. Copolymers constituted of one or several phosphinate moieties within the PHB macromolecular chains, with controlled molar mass and narrow dispersities, were thus synthesized.•Detailed MALDI-ToF and ESI mass spectrometric studies proved quite insightful to elucidate the nature of the various population formed and to evidence the incorporation of the phosphinate-functionalized β-lactone.•The thermal characteristics of the copolymers were investigated by DSC and TGA, revealing in comparison to those of the parent PHB homopolymers, tunable features as a function of their molar mass, tacticity and phosphinate comonomer content. Poly(3-hydroxybutyrate) (PHB) polymers functionalized with pendent diphenyl-phosphinate moieties were prepared by the simultaneous ring-opening copolymerization (ROCOP) of racemic or enantiopure β-butyrolactone (rac- or (S)-BPLMe, respectively) with racemic-(4-oxooxetan-2-yl)methyl diphenylphosphinate (rac-BPLOP). The reactions were mediated by yttrium catalysts which tunable ancillary structure enabled preparing copolymers containing syndio-enriched (Pr up to 0.84; Pr is the probability of racemic linkage), atactic (Pr ∼ 0.50) and highly isotactic (Pr 
ISSN:0014-3057
1873-1945
DOI:10.1016/j.eurpolymj.2024.112919