Chemo-enzymatic epoxidation of oleic acid and methyl oleate in solvent-free medium

Chemo-enzymatic epoxidation of oleic acid (OA) and its methyl ester has been performed using hydrogen peroxide and immobilized lipase from Candida antarctica (Novozym® 435). The purpose of the study was to characterize the reaction under solvent-free conditions. The reaction temperature had a significant impact on epoxidation of OA. At lower temperatures, the substrate conversion was hindered by the formation of solid epoxystearic acid product. Nearly 90% conversion of OA to the epoxide product was obtained after 6 h at 50°C. Longer reaction times at 40°C and above resulted in by-product formation and eventually lowered the product yield. In contrast, the reaction with methyl oleate (MO) was less influenced by temperature. Almost complete epoxidation was achieved at 40–60°C; the higher the temperature the shorter was the reaction time. The main epoxidation product obtained was epoxystearic acid methyl ester (EME), and the remaining was epoxystearic acid (EA) formed by the hydrolytic action of the lipase. Recycling of the lipase for epoxidation of MO at 50°C indicated that the immobilized enzyme was prone to activity loss.

[1]  Richard P. Wool,et al.  Development of a bio‐based composite material from soybean oil and keratin fibers , 2005 .

[2]  R. Joseph,et al.  Studies on epoxidised rubber seed oil as secondary plasticiser/stabiliser for polyvinyl chloride , 2004 .

[3]  S. Warwel,et al.  Glucamine-based gemini surfactants II: Gemini surfactants from long-chain N-alkyl glucamines and epoxy resins , 2004 .

[4]  Rein V. Ulijn,et al.  Biocatalysis in reaction mixtures with undissolved solid substrates and products , 2003 .

[5]  Ying Yu,et al.  Enzymatic Synthesis of Ethyl-glucoside Monooleate with Lipase in Solvent-free Medium , 2003 .

[6]  G. Gelbard,et al.  Stabilization of PVC by epoxidized sunflower oil in the presence of zinc and calcium stearates , 2003 .

[7]  R. B. Turner,et al.  Characterization of polyurethane foams from soybean oil , 2002 .

[8]  V. Svedas,et al.  Penicillin Acylase‐Catalyzed Solid‐State Ampicillin Synthesis , 2002 .

[9]  Sevim Z. Erhan,et al.  Epoxidized soybean oil as a potential source of high-temperature lubricants , 2002 .

[10]  A. Hasnat,et al.  Studies on corrosion protective epoxidised oil modified DGEBA epoxy paint , 2002 .

[11]  Richard P. Wool,et al.  Development and application of triglyceride‐based polymers and composites , 2001 .

[12]  W. Friedt,et al.  New Syntheses with Oils and Fats as Renewable Raw Materials for the Chemical Industry. , 2000, Angewandte Chemie.

[13]  G. Buisman.  Biodegradable binders and cross-linking agents from renewable resources , 1999 .

[14]  V. Balcão,et al.  Modification of butterfat by selective hydrolysis and interesterification by lipase: Process and product characterization , 1998 .

[15]  Gao,et al.  Regioselective synthesis of ethoxylated glycoside esters using beta-glucosidase in supersaturated solutions and lipases in organic solvents , 1998, Biotechnology and bioengineering.

[16]  M. Legoy,et al.  An original transesterification route for fatty acid ester production from vegetable oils in a solvent-free system , 1997 .

[17]  M. R. G. Klaas,et al.  Chemo-enzymatic epoxidation of unsaturated carboxylic acids , 1995 .

[18]  M. Zur,et al.  The effect of temperature on oil quality and yield parameters of high- and low-erucic acid Cruciferae seeds (rape and mustard) , 1995 .

[19]  F. Petrus Cuperus,et al.  Paints and coatings from renewable resources , 1995 .

[20]  P. Halling,et al.  Solvent effects on biocatalysis in organic systems: Equilibrium position and rates of lipase catalyzed esterification , 1991, Biotechnology and bioengineering.

[21]  K. D. Carlson,et al.  Chemical epoxidation of a natural unsaturated epoxy seed oil fromVernonia galamensis and a look at epoxy oil markets , 1985 .

[22]  D. Swern.  Electronic Interpretation of the Reaction of Olefins with Organic Per-acids , 1947 .