Glycerol-based enzymatically synthesized renewable polyesters: Control of molecular weight, degree of branching and functional endgroups

Enzymatic Synthesis of Hydroxy-Functionalized Glycerol-Based Polyesters: A Study of Functionalization, Regioselectivity Control, and Catalyst Reuse

“…The regioselectivity of lipases toward primary alcohols in polyols has previously been reported to occur within a specific range of time and temperature. 5 Thus, the regioselectivity results align with previous observations made under similar conditions. In a study using divinyl ester and glycerol with Candida antarctica immobilized on microporous acrylic resin at 40 °C for 24 h in THF, a yield of 65% of polymer (after dissolution in acetone and precipitation in diethyl ether) was achieved.…”

“…Previous investigations have shown that analyses of 1 H NMR spectra can indicate end groups and repeating units of low molar mass polymers. 5 Therefore, the polymer was analyzed by 1 H NMR to provide an approximation of the configuration of the glycerol units in the polymeric chains. Figure 2 shows the PDO and DS protons with emphasis on the assignments of the terminal glycerol and linear and dendritic glycerol units.…”

“…4 Furthermore, all these hydroxy-functionalized polyesters increase biodegradability and enable sequential functionalization and controlled crosslinking, which is interesting for controlled drug delivery applications. 5 Among the various polyols, glycerol is attractive because, apart from being naturally synthesized from plants and microorganisms, it can also be obtained as a byproduct of biodiesel synthesis. Therefore, glycerol is an economically accessible and biocompatible monomer and can also be used as a substrate in fermentative pathways to produce succinic acid and 1,3-propanediol.…”

“…26−28 Reactions with acids or esters in the presence of various polyols and enzymatic catalysts have been previously investigated. 5,8,29 Temperature, monomer feed ratio, and enzyme origin influence the regioselectivity of the polymerization between divinyl sebacate and glycerol in bulk. 26 A similar behavior in the synthesis of poly(octamethylene adipate-co-glycerol adipate) copolymers with various molar masses has been observed.…”

Harnessing the power of polyol-based polyesters for biomedical innovations: synthesis, properties, and biodegradation

“…28,51 Through the enzymatic polycondensation approach, PGS synthesis predominantly employs the enzyme Candida antarctica lipase B (CALB). 55 Enzymatic polycon-densation offers several advantages over thermal polycondensation, such as the ability to proceed at slightly lower temperatures due to the catalytic action of the enzyme. 56 Additionally, this process results in a more linear polymer structure, which can influence the polymer's properties and potential applications.…”