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

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.

[1]  J. Mol,et al.  Catalytic activity and selectivity of Ru(CHPh)Cl2(PCy3)2 in the metathesis of linear alkenes , 1999 .

[2]  Grant S. Forman,et al.  Metathesis of renewable unsaturated fatty acid esters catalysed by a phoban-indenylidene ruthenium catalyst , 2006 .

[3]  L. Kleingartner.  NuSun Sunflower Oil: Redirection of an Industry , 2002 .

[4]  C. Boelhouwer,et al.  Homogeneous catalytic metathesis of unsaturated fatty esters: New synthetic method for preparation of unsaturated mono-and dicarboxylic acids , 1974 .

[5]  Bolun Yang,et al.  Predicting the viscosity of biodiesel fuels based on the mixture topological index method , 2007 .

[6]  V. Dupont,et al.  STEAM REFORMING OF SUNFLOWER OIL FOR HYDROGEN GAS PRODUCTION / OXIDACIÓN CATALÍTICA DEL ACEITE DE GIRASOL EN LA PRODUCCIÓN DEL GAS HIDRÓGENO / REFORMAGE À LA VAPEUR DE L’HUILE DE TOURNESOL DANS LA PRODUCTION DE GAZ HYDROGÈNE , 2007 .

[7]  D. Astruc.  The metathesis reactions: from a historical perspective to recent developments , 2005 .

[8]  SonBinh T. Nguyen,et al.  Well-defined ruthenium olefin metathesis catalysts: Mechanism and activity , 1997 .

[9]  M. O. Bagby,et al.  Heats of combustion of fatty esters and triglycerides , 1989 .

[10]  M. Meier,et al.  Metathesis as a versatile tool in oleochemistry , 2008 .

[11]  C. Boelhouwer,et al.  Metathesis of unsaturated fatty acid esters by a homogeneous tungsten hexachloride–tetramethyltin catalyst , 1972 .

[12]  E. Campbell.  Sunflower oil , 1983 .

[13]  Salmiah Ahmad,et al.  Non-food applications of palm-based products - market opportunities and environmental benefits. , 2006 .

[14]  S. Erhan,et al.  Metathesis of methyl soyate with ruthenium catalysts , 2006 .

[15]  K. Burdett,et al.  Renewable monomer feedstocks via olefin metathesis: Fundamental mechanistic studies of methyl oleate ethenolysis with the first-generation grubbs catalyst , 2004 .

[16]  F. Kapteijn,et al.  Heterogeneous metathesis of unsaturated fatty acid esters , 1977 .

[17]  J. Mol.  Application of olefin metathesis in oleochemistry: an example of green chemistry , 2002 .

[18]  Cédric Fischmeister,et al.  Ethenolysis of methyl oleate in room-temperature ionic liquids. , 2008, ChemSusChem.

[19]  M. Dinger,et al.  High Turnover Numbers with Ruthenium-Based Metathesis Catalysts , 2002 .

[20]  S. Scott.  CATALYTIC TRANSFORMATION OF SEED OIL DERIVATIVES VIA OLEFIN METATHESIS / TRANSFORMACIÓN CATALÍTICA DE LOS DERIVADOS DEL ACEITE A TRAVÉS DE METÁTESIS OLEFÍNICA / TRANSFORMATION CATALYTIQUE DES DÉRIVÉS DE L’HUILE PAR LA MÉTATHÈSE D’OLÉFINES , 2007 .

[21]  L. Velasco,et al.  BREEDING FOR SPECIALTY OIL TYPES IN SUNFLOWER / SELECCIÓN DE TIPOS OLEAGINOSOS DE GIRASOL ESPECIALES / SÉLECTION DE TYPES SPÉCIAUX DE TOURNESOLS OLÉAGINEUX , 2007 .

[22]  M. Kunz,et al.  Copolymerization of Ethylene with ω‐Unsaturated Fatty Acid Methyl Esters Using a Cationic Palladium Complex , 2001 .

[23]  J. Ziller,et al.  Synthesis and Applications of RuCl2(CHR‘)(PR3)2: The Influence of the Alkylidene Moiety on Metathesis Activity , 1996 .

[24]  M. Kunz,et al.  Polyesters of ω-unsaturated fatty acid derivatives , 2001 .

[25]  R von Wedel,et al.  TECHNICAL HANDBOOK FOR MARINE BIODIESEL IN RECREATIONAL BOATS - 2ND EDITION , 1999 .

[26]  W. R. Jackson,et al.  High conversion and productive catalyst turnovers in cross-metathesis reactions of natural oils with 2-butene , 2006 .

[27]  M. Pegg,et al.  Predicting the viscosity of biodiesel fuels from their fatty acid ester composition , 1999 .

[28]  S. Nguyen,et al.  Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media , 1992 .

[29]  W. Focke,et al.  Metathesis of fatty esters derived from South African sunflower oil , 1990 .

[30]  J. D. Plessis,et al.  Metathesis of unsaturated fatty acid esters derived from South African sunflower oil in the presence of a 3 wt.% Re2O7/SiO2-Al2O3/SnBu4 catalyst , 2003 .

[31]  Pretoria South Africa Fisheries,et al.  Utilization of sunflower seed oil as a renewable fuel for diesel engines , 1981 .

[32]  J. Mol,et al.  Metathesis of fatty acid esters , 1984 .

[33]  M. Kunz,et al.  Polymers and surfactants on the basis of renewable resources. , 2001, Chemosphere.

[34]  Ulrich S Schubert,et al.  Plant oil renewable resources as green alternatives in polymer science. , 2007, Chemical Society reviews.

[35]  S. Narine,et al.  Physical Properties of Polyurethanes Produced from Polyols from Seed Oils: I. Elastomers , 2007 .

[36]  Johannes C. Mol,et al.  Industrial applications of olefin metathesis , 2004 .

[37]  Martin J. Hanton,et al.  A Stable Ruthenium Catalyst for Productive Olefin Metathesis , 2004 .

[38]  D. Rowe.  Chemistry and technology of flavors and fragrances. , 2004 .

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

[40]  A. Hoveyda,et al.  Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts , 2000 .

[41]  M. Meier,et al.  Cross-metathesis of fatty acid derivatives with methyl acrylate: renewable raw materials for the chemical industry , 2007 .

[42]  G. Terraneo,et al.  Biocatalytic production of flavors and fragrances , 2005 .

[43]  S. Warwel,et al.  Polyesters by lipase‐catalyzed polycondensation of unsaturated and epoxidized long‐chain α,ω‐dicarboxylic acid methyl esters with diols , 2001 .

[44]  G. Knothe,et al.  Biodiesel: the use of vegetable oils and their derivatives as alternative diesel fuels. , 1997 .

[45]  B. van der Boshoff,et al.  Sunflower seed oil as an extender for diesel fuel in agricultural tractors. Paper presented at Symposium of South African Institute of Agricultural Engineers, 11 June 1980. , 1980 .

[46]  E. Verkuijlen,et al.  Formation of cyclohexa-1,4-diene by metathesis of linoleic and linolenic esters , 1974 .

[47]  C. K. Segakweng,et al.  Ruthenium Carbene Mediated Metathesis of Oleate-Type Fatty Compounds , 2008, International journal of molecular sciences.

[48]  J. P. Harrity,et al.  A Recyclable Ru-Based Metathesis Catalyst , 1999 .

[49]  S. Nguyen,et al.  Syntheses and activities of new single-component, ruthenium-based olefin metathesis catalysts , 1993 .

[50]  Masahiro Aoyama,et al.  Olefin Metathesis , 2020, Name Reactions.

[51]  J. Tsuji,et al.  Metathesis reactions of unsaturated esters catalyzed by homogenous tungsten complexes. Syntheses of civetone and macrolides , 1981 .