Exploring mild enzymatic sustainable routes for the synthesis of bio‐degradable aromatic‐aliphatic oligoesters

Abstract

The application of Candida antarctica lipase B in enzyme-catalyzed synthesis of aromatic-aliphatic oligoesters is here reported. The aim of the present study is to systematically investigate the most favorable conditions for the enzyme catalyzed synthesis of aromatic-aliphatic oligomers using commercially available monomers. Reaction conditions and enzyme selectivity for polymerization of various commercially available monomers were considered using different inactivated/activated aromatic monomers combined with linear polyols ranging from C2 to C12 . The effect of various reaction solvents in enzymatic polymerization was assessed and toluene allowed to achieve the highest conversions for the reaction of dimethyl isophthalate with 1,4-butanediol and with 1,10-decanediol (88 and 87% monomer conversion respectively). Mw as high as 1512 Da was obtained from the reaction of dimethyl isophthalate with 1,10-decanediol. The obtained oligomers have potential applications as raw materials in personal and home care formulations, for the production of aliphatic-aromatic block co-polymers or can be further functionalized with various moieties for a subsequent photo- or radical polymerization.

Renewable building blocks for sustainable polyesters: new biotechnological routes for greener plastics

“…Some of these hydrolases were found to be stable in organic solvents where they are able to catalyse reverse reactions, namely esterification and transesterification . Hence, these enzymes were studied regarding synthesis of aliphatic – and to a lesser extent of aromatic – polyesters …”

“…58 Hence, these enzymes were studied regarding synthesis of aliphatic -and to a lesser extent of aromatic -polyesters. 59 Hydrolases for polyester production are relatively stable, commercially available and easily produced. Among lipases, undoubtedly the most widely used biocatalyst for polyester synthesis is lipase B from Candida antarctica (CaLB), due to its commercial availability as a free and an immobilized catalyst.…”

“…For example, IA (or its derivatives) was polymerized with several polyols to give side-chain-functionalized polyesters where the vinyl moiety was preserved after the reaction and could therefore be used for further functionalizations/crosslinking of the polymer. 59,96 In particular, IA was successfully polymerized with 1,6-hexanediol leading to a mixture of products with M w of around 30 kDa. 97 Similar polyesters containing a lateral epoxy moiety were also reported after a polycondensation carried out using CaLB as catalyst.…”

Biocatalytic Route for the Synthesis of Oligoesters of Hydroxy-Fatty acids and ϵ-Caprolactone

“…MALDI‐TOF MS analysis was carried out for composition analysis of polymers, using an UltrafleXextreme Bruker spectrometer with FlexControl and FlexAnalysis software packages for acquisition and processing of the data (BrukerDaltonics, Germany), at an acceleration voltage of 25 kV, using DCTB as matrix and KTFA as ionization agent. The sample preparation and analysis were performed as previously described . The number average molecular weight M n (C), weight average molecular weight M w (C) of the copolymers (non‐cyclic and cyclic), as well as the polydispersity index PDI have been calculated as described elsewhere …”

“…Lipases have been framed as powerful tool for polyester synthesis, including the ring‐opening polymerization of lactones, and several comprehensive reviews were addressed in this topic . Polyester synthesis catalyzed by lipases also opens the route for the manufacture of fully biobased polymers obtained from renewable resources, but also for specialty products like aromatic‐aliphatic oligoesters and functional aliphatic oligoesters . The lipase from Candida antarctica B demonstrated special ability to catalyze the synthesis of linear and star oligomers.…”