One‐Component Thiol‐Alkene Functional Oligoester Resins Utilizing Lipase Catalysis

Abstract

Chemo-enzymatic methods are powerful tools for the synthesis of novel materials. By combining the fl exibility of chemical synthesis and the high selectivity of enzymes, a variety of functional materials can be achieved. In the present study, a series of α,ω-thiol telechelic oligoesters with varying amount of internal alkenes are prepared using selective lipase catalysis and are subsequently cross-linked by thiol-ene chemistry yielding alkene functional networks. Due to the reactivity of thiols and alkenes almost all present thiol-ene systems consist of two components. This work demonstrates that selective lipase catalysis in combination with renewable monomers with internal alkenes is a promising system for achieving one-component thiol-alkene functional resins with good storage stability and a high degree of thiol end-groups. The developed chemo-enzymatic route yields polymer networks with tailored amount of alkene functionalities in the fi nal thermoset, which facilitate further postmodifi cation.

Recent advances in the synthesis of biodegradable polyesters by sustainable polymerization: lipase-catalyzed polymerization

“…Recently, several research groups have constructed many multicomponent polymerization systems to prepare functional copolymers or optically active polymers using techniques such as click-chemoenzymatic-ATRP, 103 chemoenzymatic monomer transformation with ATRP, 104 light-controlled polymerization (LCP) 105 or reversible addition-fragmentation chain transfer (RAFT), [106][107][108] enzymatic ring-opening polymerization (eROP) with ATRP, 58 enzymatic polycondensation with thiol-ene chemistry, enzymatic ringopening polymerization (eROP). 109 In our previous research, block copolymers were also synthesized through a one-pot polymerization by tandem enzymatic ring-opening polymerization (eROP) and ring-opening metathesis polymerization (ROMP) (Fig. 7).…”

Enantio‐, Regio‐, and Chemoselective Lipase‐Catalyzed Polymer Synthesis

“…In the polycondensation reactions, enzymes showed obvious chemoselectivity in which esterification and transesterification have been observed for diols harboring unsaturated groups or oxetane monomers. [90,91] Through the strategy, a series of α,ωthiol telechelic oligomers could be successfully synthesized, and the polymers could be further cross-linked by thiol-ene chemistry yielding alkene functional networks. The crosslinking of polymer could also be achieved through the opening of pending oxetanes.…”

A review of progress in (bio)catalytic routes from/to renewable succinic acid

“…(a) Production of saturated and unsaturated aliphatic polyesters and oligoesters of PBS and PBSI through CaBL catalyzed polycondensation and (b) chemo‐enzymatic route to alkene functional networks …”

“…More recently, Finneveden et al . developed a chemo‐enzymatic route to synthesize alkene functional oligomeric networks based on thiol‐ene click chemistry with UV post‐modification for application as dental restorative materials . They proposed CaLB as a chemoselective catalyst to synthesize thiol‐alkene functional resins and subsequently cross‐link to form thermoset materials with varying degree of alkene functionality and different thermal properties (Fig.…”

“…(a) Conjugation of CaLB onto carboxylated multi-walled carbon nanotubes (MWCNTs) using APTES as cross-linker and SAn for production of excessive carboxylic groups prior to EDAC activation 91 and (b) synthesis of succinate hydroxyethylcellulose (HEC). (a) Production of saturated and unsaturated aliphatic polyesters and oligoesters of PBS and PBSI through CaBL catalyzed polycondensation15 and (b) chemo-enzymatic route to alkene functional networks 108. …”