Isosorbide Polyesters from Enzymatic Catalysis

Abstract

The synthesis of isosorbide aliphatic polyesters is demonstrated by the use of Novozym 435, a catalyst consisting of Candida antarctica lipase B immobilized on a macroporous support. Several experimental procedures were tested and azeotropic distillation was most effective in removing low mass byproduct. Furthermore, the use of diethyl ester derivatives of diacid comonomers gave isosorbide copolyesters with highest isolated yield and molecular weights. The length of the diacid aliphatic chain was less restrictive, but with a clear preference for longer aliphatic chains. The molecular mass values of the obtained products were equivalent or higher than those obtained by nonenzymatic polymerizations, a clear illustration of the potential of enzymatic over conventional catalysis. The ability of Novozym 435 to catalyze the synthesis of isosorbide polyester with weight-average molecular weights in excess of 40 000 Da was unexpected given that isosorbide has two chemically distinct secondary hydroxyl groups. This is the first example in which isosorbide polyesters were synthesized by enzyme catalysis, opening a large array of possibilities for this important class of biomass-derived building blocks. Because these polymers are potential biomaterials, the total absence of conventional Lewis acid catalyst residues represents a major improvement in the toxicity of the material.

Enzymatic Polymerization of Furan-2,5-Dicarboxylic Acid-Based Furanic-Aliphatic Polyamides as Sustainable Alternatives to Polyphthalamides

“…As previous reported, high molecular weights polyesters were successfully produced in high yields (70+ %) via enzymatic polycondensation in the mixture of toluene/cyclohexane by azeotropic distillation. 39,59,60 In addition, the enzyme-catalyzed polycondensation of polyamides by azeotropic distillation has not been studied yet. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 20 Eight polyamide species were identified, which might differ in the abundance (see Table 2 and Figure 5, and Figures S1-S7 in Supporting Information).…”

Environmentally benign synthesis of saturated and unsaturated aliphatic polyesters via enzymatic polymerization of biobased monomers derived from renewable resources

“…Similar results were reported by Catalani el al. 24 and Papaspyrides et al 50 on the effect of the chain length of dicarboxylic acids/diacid ethyl esters on enzymatic polymerization. Catalani el al.…”

“…5 By using this approach, the energy and material consumption can be greatly reduced and the generation of hazardous waste and dianhydrohexitol-based polyesters by CALB-catalyzed azeotropic polymerization. 24, 25 Kobayashi et al enzymatically synthesized biodegradable epoxide-containing polyesters from vegetal oils. 26 Moreover, many other biobased polyesters are produced by the lipase-catalyzed polycondensation, e.g., sorbitol-based polyesters, 27,28 glucose-based polyesters 29 and furan-based polyesters.…”

Chemo-enzymatic Synthesis, Derivatizations, and Polymerizations of Renewable Phenolic Monomers Derived from Ferulic Acid and Biobased Polyols: An Access to Sustainable Copolyesters, Poly(ester-urethane)s, and Poly(ester-alkenamer)s

“…Isosorbide, readily obtained from corn (86) was first chosen for its robust bicyclic structure (87), potentially providing high thermal and mechanical properties to the resulting polymers (88,89). Classified by the US Food and Drugs Administration as a "generally recognized as safe" (aka GRAS) material (90), isosorbide was previously employed as a generic diol monomer in several polymer systems like polyester (91)(92)(93)(94), polyether (94,95), polycarbonate (94,96) and polyurethane (94,97), among others. The synthesis of isosorbide-derived polyesters could be realized using activated diacid derivatives, Lewis acid catalysts or lipase-biocatalysis coupled with the removal of low mass condensation products.…”