Two-Step Biocatalytic Route to Biobased Functional Polyesters from ω-Carboxy Fatty Acids and Diols

Abstract

Biobased omega-carboxy fatty acid monomers 1,18-cis-9-octadecenedioic, 1,22-cis-9-docosenedioic, and 1,18-cis-9,10-epoxy-octadecanedioic acids were synthesized in high conversion yields from oleic, erucic and epoxy stearic acids by whole-cell biotransformations catalyzed by C. tropicalis ATCC20962. Maximum volumetric yields in shake-flasks were 17.3, 14.2, and 19.1 g/L after 48 h conversion for oleic acid and 72 h conversions for erucic and epoxy stearic acids, respectively. Studies in fermentor with better control of pH and glucose feeding revealed that conversion of oleic acid to 1,18-cis-9-octadecenedioic acid by C. tropicalis ATCC20962 occurred with productivities up to 0.5 g/L/h. The conversion of omega-carboxy fatty acid monomers to polyesters was then studied using immobilized Candida antarctica Lipase B (N435) as catalyst. Polycondensations with diols were performed in bulk as well as in diphenyl ether. The retension of functionality from fatty acid, to omega-carboxy fatty acid monomer and to corresponding polyesters resulted in polymers with with unsaturated and epoxidized repeat units and M(w) values ranging from 25000 to 57000 g/mol. These functional groups along chains disrupted crystallization giving materials that are low melting (23-40 degrees C). In contrast, saturated polyesters prepared from 1,18-octadecanedioic acid and 1,8-octanediol have correspondingly higher melting transitions (88 degrees C). TGA results indicated that all synthesized polyesters showed high thermal stabilities. Thus, the preparation of functional monomers from C. tropicalis omega-oxidation of fatty acids provides a wide range of new monomer building blocks to construct functional polymers.

Polymer precursors from catalytic reactions of natural oils

“…[66][67][68] Finally, polyesters from natural oils can be obtained from biologically-based reactions. 69,70 However, these processes are out of the scope of the present introduction.…”

Production of biodegradable polyesters via enzymatic polymerization and solid state finishing

“…19,20,[25][26][27][28] In the current work, a two-step process was suggested to prepare aliphatic PEs, derived from diols and diacids. The examined repeating units were long-chain PEs based on 1,8-octanediol, cited in literature for high reactivity during enzymatic processes, 29,30 with sebacic (poly(octylene sebacate), PE 8.10), 1,12-dodecanedioc (poly(octylene dodecanate), PE 8.12), and 1,14-tetradecanedioc acids (poly(octylene tetradecanate), PE 8.14), which may be derived from renewable resources. 30,31 In addition, the preparation of poly(butylene succinate) (PE 4.4) from 1,4-butanediol and diethyl succinate was examined due to the very limited literature on its enzymatic polymerization, 15,32 combined with its high potential for future development and applications.…”

Bio-Material Analyses of Two Canola Cultivars Applied with Foliar Surfactant

“…Oil containing increased saturation of erucic fatty acids will require additional processing for biodiesel production which will increase production cost. Having higher erucic acid concentrations could be adventitious depending on the oil end use, high fatty acid concentrations may be favourable; oleic and erucic fatty acids have been previously sought for the utilization in bio-based polyesters (Yang et al 2009). …”