Stereoselective Ring-Opening (Co)polymerization of β-Butyrolactone and ε-Decalactone Using an Yttrium Bis(phenolate) Catalytic System.

Jiraya Kiriratnikom,Vincent Guérineau,Carine Robert,Christophe M Thomas,Vincenzo Venditto

doi:10.3389/fchem.2019.00301

Abstract

An effective route for ring-opening copolymerization of β-butyrolactone (BBL) with ε-decalactone (ε-DL) is reported. Microstructures of the block copolymers characterized by 13C NMR spectroscopy revealed syndiotactic-enriched poly(3-hydroxybutyrate) (PHB) blocks. Several di- and triblock copolymers (PDL-b-PHB and PDL-b-PHB-b-PDL, respectively) were successfully synthesized by sequential addition of the monomers using (salan)Y(III) complexes as catalysts. The results from MALDI-ToF mass spectrometry confirmed the presence of the copolymers. Moreover, thermal properties of the block copolymers were also investigated and showed that the microphase separation of PDL-b-PHB copolymers into PHB- and PDL-rich domains has an impact on the glass transition temperatures of both blocks.

Highlights

Polyhydroxyalkanoates (PHAs) comprise a group of naturally occurring aliphatic polyesters produced by bacteria and other living organisms (Reddy et al, 2003; Tan et al, 2017)
In our search for new copolymerization catalysts, we focused our efforts on investigating the catalytic activity ofY(III) complexes known to be active for PHB formation (Fang et al, 2013)
We decided to study the potential of such a catalytic system in a copolymerization procedure, aiming to produce PDL-PHB block copolymers with a one-pot sequential methodology

Summary

Introduction

Polyhydroxyalkanoates (PHAs) comprise a group of naturally occurring aliphatic polyesters produced by bacteria and other living organisms (Reddy et al, 2003; Tan et al, 2017). By doubling the monomer-to-metal ratio, the resultant polymer revealed a double experimental Mn value, indicating a controlled polymerization reaction (Table 2, Entries 1 and 2).

Results

Conclusion