Ring-opening (co)polymerization of γ-butyrolactone: a review

Abstract

With increased environment concerns and the rising demands for sustainable polymers, e.g. degradable polymers and chemically recyclable polymers, studies on ring-opening polymerization (ROP) of cycle esters have been developed during last decades. Biorenewable five-membered γ-butyrolactone (γBL) could be a desirable feedstock for the chemical synthesis of poly(γ-butyrolactone) (PγBL) or for the incorporation of γBL units into polyester chains in order to modify their properties. Although γBL is traditionally considered to be "nonpolymerizable", some progresses were recently made in ROP of γBL. This mini-review is thus specially focused on the ROP of γBL and its copolymerization with other cyclic esters.

Synthesis of Poly(Ethylene Brassylate-Co-squaric Acid) as Potential Essential Oil Carrier

“…The growing interest for ring-opening (co)polymerization is entirely justified by the potential offered by the bio-based cyclic monomers, for example, cyclic esters, lactides, epoxides, etc., to form degradable or recyclable polymers with a broad range of applications and use especial in biomedical field due to their biodegradability and biocompatibility [ 5 , 6 , 7 , 8 ]. The literature in the field has developed very fast with reviews and experimental studies about monomer classes, various groups of cyclic monomers disposed for ROP processes with specific mechanisms including cationic, anionic, enzymatic, coordinative, and radical ring-opening polymerization, or catalysts to achieve ring opening under mild conditions [ 9 , 10 , 11 , 12 , 13 , 14 , 15 ]. For example, in Wilson’s review, there is evidence of the advantages brought by the ring-opening polymerization of macrolactones (MLs) derived from sustainable or renewable feed stocks that conduct to new, potentially degradable polymeric materials boasting a diversity of properties and potential applications [ 7 ].…”

Sustainable Hyperbranched Functional Materials via Green Polymerization of Readily Accessible Levoglucosenone‐Derived Monomers

“…reviewed several examples of the ring-opening polymerization (ROP) of these compounds. [24,25] Indeed, long chainsbutyrolactone ( BL) polymers were prepared through ROP using alkali metal and alkoxide/urea as catalytic systems. [24] Furthermore, unsaturated polyesters were synthesized from the ROP of BL derivatives having endocyclic C═C bond ( -angelica lactone; AL) [26] or exocyclic C═C bond ( -methylene--butyrolactone; MBL) [27] (Scheme 3).…”

“…[24,25] Indeed, long chainsbutyrolactone ( BL) polymers were prepared through ROP using alkali metal and alkoxide/urea as catalytic systems. [24] Furthermore, unsaturated polyesters were synthesized from the ROP of BL derivatives having endocyclic C═C bond ( -angelica lactone; AL) [26] or exocyclic C═C bond ( -methylene--butyrolactone; MBL) [27] (Scheme 3). Chen et al showed that MBL polymerization can lead to three types of polymers depending on the catalyst/initiator ratio that affects the polymerization pathway(s), i.e., ROP, vinyl addition polymerization (VAP) or a combination of both.…”

High pressure as a novel tool for the cationic ROP of γ-butyrolactone

“…Nevertheless, although such a great interest in the synthesis of PGBL, so far, only a few successful attempts to perform the ROP of GBL have been reported in the literature. 10,11 However, it should be mentioned that these approaches relied on the application of heavy conditions, i.e., ultra-high pressure, 12 extremely low reaction temperature, 13 or a synthetic path supported by catalytic/initiating systems based on organometallic compounds, which are not only expensive but also exhibit some level of toxicity. 13,14 Some organocatalytic compounds (including phosphazenes, 15,16 the bicyclic guanidine derivative 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 13,17 N-heterocyclic carbenes, 18 N-heterocyclic olens 19 and systems of ion pairs based on (thio) ureas and phosphazenes 20,21 /tetra-n-butyl ammonium hydroxide (TBAOH) 22 or ureas and alkoxide 23 ) turned out to be a less toxic alternative to organometallic compounds, also capable of mediating GBL polymerization.…”