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Article Dans Une Revue European Polymer Journal Année : 2024

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

Résumé

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 < 0.06) poly(BPLMe) (P(BPLMe), aka PHB for polyhydroxybutyrate) segments, starting from rac-BPLMe or (S)-BPLMe, respectively, as assessed by detailed NMR analyses of the copolymer samples. The amount of BPLOP incorporated within the P[(BPLMe)x-co-(BPLOP)y] samples were in line with the initial comonomer loadings (1.8–8.1 mol% vs. 2–10 mol%). The ROCOP was rather well-controlled affording linear α-isopropoxy, ω-crotonyl telechelic and cyclic random copolymers with Mn,NMR up to 15,000 g.mol−1 and ÐM = 1.34–1.95. Detailed MALDI and high-resolution ESI mass spectrometric analyses evidenced the formation of three major series of macromolecules, namely the cyclic one and two linear ones end-capped with an α-isoproxy and either an ω-hydroxy or a ω-crotonate groups; for each of these series, the populations containing y = 0, 1 or 2 BPLOP repeating units were unambiguously distinguished. The thermal characteristics of the P[(BPLMe)x-co-(BPLOP)y] 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 BPLOP content.

Dates et versions

hal-04506365 , version 1 (15-03-2024)

Identifiants

Citer

Ali Dhaini, Rama M. Shakaroun, Jérôme Ollivier, Ali Alaaeddine, Sophie M. Guillaume, et al.. Phosphorus-containing stereocontrolled polyhydroxyalkanoates by yttrium-mediated ring-opening copolymerization of β-lactones. European Polymer Journal, 2024, European Polymer Journal, 209, pp.112919. ⟨10.1016/j.eurpolymj.2024.112919⟩. ⟨hal-04506365⟩
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