Enzymatic syntheses of unsaturated polyesters based on isosorbide and isomannide

Abstract

The search for materials produced from renewable sources aiming at the substitution of petroleum‐based derivates is an area of intense investigation. In this work, the enzymatic copolymerization of isosorbide or isomannide with diethyl adipate and fractions of different unsaturated diesters (diethyl itaconate, diethyl fumarate, diethyl glutaconate, and diethyl hydromuconate) were examined using CAL‐B as catalyst. The polyesters prepared using one‐step syntheses were characterized by SEC, NMR, and MALDI‐TOF MS. In addition, syntheses with linear diols were carried out in bulk to evaluate the reactivity of cyclic diols in producing unsaturated polyesters using enzymatic catalysis, as well as to evaluate the occurrence of addition side reactions on the double bonds. Isosorbide and isomannide yielded unsaturated polymers with Mtrue¯normalw values in the order of 4,000‐16,000 when fumarate or glutaconate esters were added in 5 mol % ratio against adipate. In all cases MALDI‐TOF confirmed the presence of unsaturated units. Although these polyesters have unreacted double bonds they are prone to crosslinking and ready to further functionalization, like anchoring bioactive molecules. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3881–3891

Structural and thermal properties of poly(1,4-cyclohexane dimethylene terephthalate) containing isosorbide

“…With such characteristics, ISB has been used to synthesize various polyesters, [20][21][22][23][24][25][26][27] epoxy adhesives, [28][29][30] polyurethanes, [31][32][33][34] polycarbonates [35][36][37][38] and medicines. It is one of the promising biomass monomers derived from glucose and it has a diol structure suitable for conden-sation reactions.…”

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

“…As shown in Figure 3, the off-diagonal peak C e /H e possessed a slightly lower position than that of C b /H b . According to this, the carbon resonance at 25 Aliphatic polyesters with the desired chemical compositions were produced from the enzymatic polymerization involving diacid ethyl esters having a chain length of more than 2 (n > 2) (see Table S1 in the Supporting Information). The values of the molar percentage were in good agreement with their feed ratios.…”

“…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.…”