Sunflower-based Feedstocks in Nonfood Applications: Perspectives from Olefin Metathesis

Abstract

Sunflower (Helianthus annuus L.) oil remains under-utilised albeit one of the major seed oils produced world-wide. Moreover, the high oleic sunflower varieties make the oil attractive for applications requiring high temperature processes and those targeting the C=C double bond functionality. Herein an overview of the recent developments in olefin metathesis of sunflower-based feedstocks is presented. The improved performance of olefin metathesis catalysts leading to high turnover numbers, high selectivity and catalyst recyclability, opens new opportunities for tailoring sunflower-based feedstocks into products required for possible new niche market applications. Promising results in biofuel, biopolymers, fragrances and fine chemicals applications have been reported.

Synthesis of industrially important platform chemicals via olefin metathesis of palash fatty acid methyl esters

“…Self-metathesis of a mixture of sunflower fatty acids resulted in cyclo-hexa-1,4-diene, alkenes mono and dicarboxylic acids [9,10]. Soybean oil subjected to self-metathesis resulted in polycondensation that lead to branching, with increased molecular weight, thereby the viscosity and drying properties.…”

Production of Dicarboxylic Acids and Flagrances by Yarrowia lipolytica

“…Angelica archangelica L.)) or alkaline cleavage of the 12-hydroxylated ricinoleic acid) or through olefin metathesis of unsaturated oils (e.g. sunflower oil with Grubbs-or Hoveyda-type catalysts) (Marvey 2008;Schörken and Kempers 2009). However, these routes are not satisfying to produce unsaturated dicarboxylic acids.…”

Metathesis of 9-octadecenoic acid methyl ester: diversity and mechanism of product formation at various Grubbs’ catalyst concentrations

“…Marvey observed that the functional group had a significant effect on the catalyst activity Marvey et al carried out self-metathesis of sunflower-based biodiesel (ethyl ester) using a homogenous WCl6/SnMe4 catalyst [21]. They have also employed 3% Re2O7/SiO2-Al2O3 heterogeneous catalyst for the metathesis of sunflower bio-diesel [13]. Both catalysts resulted in high conversion of olefins, mono and diesters from biodiesel.…”

“…In this context, metathesis of unsaturated fatty acid methyl esters provides a convenient route to synthesize organic intermediates useful for the production of polymers, biolubricants and biosurfactants. Self-metathesis of unsaturated fatty acids with double bonds at different positions as found in alkenes, cyclodienes, monocyclic and bicyclic esters [13] result in a number of important oleochemicals for a variety of polymer applications [14]. Self-metathesis of long chain fatty acids namely oleic, 11-eicosenoic, erucic, 10-undecenoic, ricinoleic and linoleic acids was carried out to synthesize symmetrical long chain unsaturated α,ώ-dicarboxylic acids (C18-C26) in high conversions by Ngo et al [15,16].…”

“…Ngo et al [15] carried out self-metathesis of long chain unsaturated fatty acids, C18-C26 to prepare α,ώ-dicarboxylic acids and hydrocarbons with 80% conversion employing 0.315 mmol of Grubbs' second generation catalyst. Two types of ruthenium carbene catalysts were employed to carry out self-metathesis of oleate-type fatty acids containing ester, hydroxyl, epoxy type of functional groups [13] to obtain a variety of intermediates for polymer, pharmaceutical and petrochemical industries. Marvey observed that the functional group had a significant effect on the catalyst activity Marvey et al carried out self-metathesis of sunflower-based biodiesel (ethyl ester) using a homogenous WCl6/SnMe4 catalyst [21].…”