Saturated branched fatty compounds: Proven industrial processes and new alternatives

Abstract

This paper reviews properties and synthesis of saturated branched fatty compounds and their application. Especially industrially established processes based on the Guerbet reaction, Fatty acid isomerization, Oxo‐ and Koch synthesis will be presented. Also new laboratory methods will be discussed, e.g., the Lewis acid‐induced hydroalkylation of oleic acids. Recently, another new process has been developed and tested in miniplant scale, the homogeneously catalyzed co‐oligomerization of linoleic acid with ethylene. This process combines the co‐oligomerization step with the heterogeneously catalyzed hydrogenation and an additional extraction to recycle the catalyst. Practical applications: This review presents synthesis routes of saturated branched fatty compounds based on both, established processes in industry and recent research results on alternative routes. A new developed process on the co‐oligomerization of fatty acids or esters is highlighted as an alternative route to form saturated branched fatty compounds. Reformulation of mineral oil based lubricants for improved biodegradability in, e.g., high‐loss lubrication systems and high‐risk hydraulic systems is highly encouraged by the oleo industry. Therefore, chemical modification of vegetable oils is also interesting for recent research on biolubricants. In addition the paper reviews latest scientific papers and patents on already industrially established processes or synthesis routes, like the fatty acid isomerization, hydroformylation, and the formation of Guerbet alcohols or Neo acids. Covering the respective reactions this review combines interesting synthesis routes for both, oleo‐ and petrochemistry. Saturated branched fatty compounds can be synthesized from both, petro‐ and oleochemical feedstock. Respective industrial processes and new synthesis routes are reviewed. New modification methods of vegetable oils represent interesting alternatives for, e.g., the formation of biolubricants.

Convenient and Environmentally Friendly Production of Isostearic Acid with Protonic Forms of Ammonium Cationic Zeolites

“…More recently, large‐pore zeolites such as faujasite and Beta structure (pore size >6 Å) and mesoporous zeolites (>15 Å) have been used for skeletal isomerization of ulc‐FA with better yield of bc‐FA. Some other synthetic methodologies have also been reported to introduce alkyl branches in fatty acid chains such as thermally initiated addition of alkanes to unsaturated fatty acids, three step synthesis of iso‐fatty acid through the addition of methylmagnesium bromide, Lewis acid induced hydroalkylation or co‐oligomerization of fatty acids . However in these procedures, high catalyst loadings, expensive synthetic methods, inadequate regeneration of used catalyst, low conversion of starting fatty acids, and suppression of dimer acid formation are issues that still need to be addressed.…”

Producing Cyclopropane Fatty Acid in Plant Leafy Biomass via Expression of Bacterial and Plant Cyclopropane Fatty Acid Synthases

“…stearic acid Tm = 69.3°C, tuberculostearic acid Tm = 20-26°C; Schmidt and Shirley, 1949;Haynes, 2016; Figure 1). Compared to either monounsaturated fatty acids or saturated fatty acids, SMCBFAs have high oxidative stability with lubricity at low temperatures, features that are sought after in many oleochemicals (Kinsman, 1979;Zhang et al, 2004;Ngo et al, 2011;Hasselberg and Behr, 2016). One such example of SMCBFA is tuberculostearic acid, where the methyl group is found midway along the fatty acyl chain (Figure 1).…”

The Role of Copper in the Upgrading of Bioalcohols

“…This reaction, developed more than a hundred years ago, yields β‐branched hydrophobic molecules with a high degree of regiospecificity (Figure ). Its products, namely Guerbet alcohols (GA), Guerbet acids and Guerbet esters have since then been the object of continuous interest owing to their unique branching pattern, which gives them low aquatic toxicity and easy biodegradability, high oxidative stability and liquidity at very low temperature . These peculiar features make Guerbet products suitable for a wide range of applications, from metal lubrication to paper processing and personal care products.…”