Yttrium-Mediated Ring-Opening Copolymerization of Oppositely Configurated 4-Alkoxymethylene-β-Propiolactones: Effective Access to Highly Alternated Isotactic Functional PHAs

Abstract

The ring-opening copolymerization (ROCOP) of functional 4-alkoxymethylene-β-propiolactones (BPL^OR s) by yttrium-bisphenolate complexes was investigated. The ROCOP of equimolar mixtures of BPL^OR s of opposite configurations, namely (R)-BPL^OR1 /(S)-BPL^OR2 [R¹ , R² =OMe, OAllyl, OCH₂ Ph (=OBn), OSiMe₂ tBu (=OTBDMS)], by the syndioselective Y{ONOO^cum }/iPrOH catalyst/initiator system affords P(HB^OR1 -alt-HB^OR2 ) copolymers with high alternation degrees (altern.=89-94 %), as determined by comprehensive kinetic, ¹³ C{¹ H} NMR spectroscopy, MALDI-ToF MS and ESI MS/MS fragmentation studies. The ROCOP of the (R)-BPL^OMe /(S)-BPL^OTBDMS combination, featuring a large difference in the substituents' bulkiness, constitutes the only observed exception to this trend (altern.=64 %). On the other hand, the isoselectivity of the Y{ONNO^Cl }/iPrOH catalyst/initiator system has been exploited to generate, in a one-pot/one-step procedure, original mixtures of isotactic poly(hydroxyalkanoate)s (PHAs). This system efficiently transforms equimolar mixtures of (R)-BPL^OAll /(S)-BPL^OMe into a 1:1 mixture of the corresponding isotactic iso-(R)-PHB^OAll and iso-(S)-PHB^OMe homopolymers; almost no copolymerization defects are observed. This new approach has been extended successfully to the ROCOP of equimolar mixtures of racemic monomers, rac-BPL^OAll /rac-BPL^OMe .

Keywords: homogeneous catalysis; polyhydroxyalkanoates; polymerization; ring-opening copolymerization; yttrium catalyst.