Lipase-catalyzed synthesis and post-polymerization modification of new fully bio-based poly(hexamethylene γ-ketopimelate) and poly(hexamethylene γ-ketopimelate-co-hexamethylene adipate) copolyesters

Abstract

<jats:title>Abstract</jats:title><jats:p>A novel full bio-based ketone-containing aliphatic polyester was prepared by enzyme-catalyzed polycondensation of diethyl γ-ketopimelate (DEK) with 1,6-hexanediol (HDO) using immobilized lipase B from <jats:italic>Candida antarctica</jats:italic> (CALB). The influences of polymerization conditions such as temperature, time, enzyme amount, and solvent amount on the molecular weight of poly(hexamethylene γ-ketopimelate) (PHK) were investigated. New fully bio-based poly(hexamethylene γ-ketopimelate-<jats:italic>co</jats:italic>-hexamethylene adipate) (poly(HK-<jats:italic>co</jats:italic>-HA)) copolymers with narrow polydispersity and well-defined composition were synthesized by copolymerization of DEK, HDO, and diethyl adipate. The structures of PHK and poly(HK-<jats:italic>co</jats:italic>-HA) copolymers were characterized by nuclear magnetic resonance, and their thermal characterization was examined by thermogravimetric analysis and differential scanning calorimetry. The degradation of PHK and poly(HK-<jats:italic>co</jats:italic>-HA) copolymers was studied. The post-polymerization modification of these polyketoesters via oxime click chemistry was further demonstrated.</jats:p>

Lipase-Catalyzed Fully Aliphatic Copolyesters Based on Renewable Isohexide Isomers

“…EP is known to proceed at generally low temperatures (<100 °C) and has high stereo-/regio-enantio-selectivity, which is particularly promising to minimize the thermal decomposition isohexides, particularly in IM. In recent years, enzyme catalysts have been extensively employed to catalyze different types of monomers toward the synthesis of polyesters, polyamides, and polyesteramides. , CALB has also been employed to synthesize prepolymers or polymers based on other natural compounds of sustainable or renewable sources. − In a report published by Wu et al very recently, CALB has shown to be very efficient for synthesizing a novel biobased copolyester based on diethyl γ-ketopimelate, diethyl adipate, and 1,6-hexanediol. The resulting homo-/copolyesters were obtained with fairly high MWs with M n values over 20,000 Da and narrow polydispersities.…”

“…34−36 In a report published by Wu et al very recently,34 CALB has shown to be very efficient for synthesizing a novel biobased copolyester based on diethyl γ-ketopimelate, diethyl adipate,…”

Enzymatic Synthesis of Poly(alkylene succinate)s: Influence of Reaction Conditions

“…Numerous types of polymers prepared by enzymatic polymerization have been reported, among them polyphenols by enzymatic oxidative polymerization [3], polyaniline by enzymatic catalysis in presence of hydrogen peroxide [4], polysaccharides [5,6], vinyl polymerizates (being typically chain growth polymerizates) [7], a high number of differ-ent polyesters, polythioesters, polythioetheresters, polyphosphates, or polyketoetheresters obtained by ring-opening polymerization [8][9][10][11] or by polycondensation [12][13][14]. Polyesters and polyamides attracted particular attention, reflected by various studies [1,[15][16][17][18][19][20][21][22][23][24].…”