EP2498908A2 - Metathesis catalysts and processes for use thereof - Google Patents
Metathesis catalysts and processes for use thereofInfo
- Publication number
- EP2498908A2 EP2498908A2 EP10829029A EP10829029A EP2498908A2 EP 2498908 A2 EP2498908 A2 EP 2498908A2 EP 10829029 A EP10829029 A EP 10829029A EP 10829029 A EP10829029 A EP 10829029A EP 2498908 A2 EP2498908 A2 EP 2498908A2
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- European Patent Office
- Prior art keywords
- oil
- fatty acid
- alpha
- catalyst
- alkene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/002—Osmium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Definitions
- This invention relates to metathesis catalyst compounds and processes for the use thereof.
- the cross-metathesis of two reactant olefins, where each reactant olefin comprises at least one unsaturation site, to produce new olefins which are different from the reactant olefins is of significant commercial importance.
- the cross-metathesis reaction is usually catalyzed by one or more catalytic metals, usually one or more transition metals.
- LAOs linear alpha- olefms
- LAOs are useful as monomers or comonomers in certain (co)polymers (polyalphaolefms or PAOs) and/or as intermediates in the production of epoxides, amines, oxo alcohols, synthetic lubricants, synthetic fatty acids and alkylated aromatics.
- Olefins Conversion TechnologyTM is an example of an ethenolysis reaction converting ethylene and 2-butene into propylene. These processes use heterogeneous catalysts, such as tungsten and rhenium oxides, which have not proven effective for internal olefins containing functional groups such as cis-methyl oleate, a fatty acid methyl ester.
- Alkyl oleates are fatty acid esters that can be major components in biodiesel produced by the transesterification of alcohol and vegetable oils or animal fats. Vegetable oils containing at least one site of unsaturation include canola, soybean, palm, peanut, mustard, sunflower, tung, tall, perilla, grapeseed, rapeseed, linseed, safflower, pumpkin corn and many other oils extracted from plant seeds. Alkyl erucates similarly are fatty acid esters that can be major components in biodiesel.
- Useful biodiesel compositions are those which typically have high concentrations of oleate and erucate esters. These fatty acid esters preferably have one site of unsaturation such that cross-metathesis with ethylene yields 1- decene as a co-product.
- Biodiesel is a fuel prepared from renewable sources, such as plant oils or animal fats.
- TAG triacylglycerides
- FAE fatty acid alkyl esters
- Biodiesel fuel can be used in diesel engines, either alone or in a blend with petroleum-based diesel, or can be further modified to produce other chemical products.
- Cross-metathesis catalysts reported thus far for the ethenolysis of methyl oleate are typically ruthenium-based catalysts bearing phosphine or carbene ligands.
- Dow researchers in 2004 achieved catalysts turnovers of approximately 15,000 using the 1 st generation Grubb's catalyst, bis(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride, (Organometallics 2004, 23, p. 2027).
- researchers at Materia, Inc. have reported turnover numbers up to 35,000 using a ruthenium catalyst containing a cyclic alkyl amino carbene ligand, (WO 2008/010961).
- the instant invention's metathesis catalyst compounds provide both a mild and commercially economical and an "atom-economical" route to desirable olefins, in particular alpha-olefms, which in turn may be useful in the preparation of PAOs. More particularly, the instant invention's metathesis catalyst compounds demonstrate improved activity and selectivity towards ethenolysis products in ethylene cross-metathesis reactions.
- the inventors have found that symmetrically substituted N-heterocyclic carbene ligands linked to ruthenium alkylidenes, though known to be cross-metathesis catalysts, tend to have low activity in the ethenolysis of methyl oleate.
- an asymmetrically substituted N-heterocyclic carbene ligand linked to a ruthenium alkylidene yielded a catalyst that was more active than the symmetrical analog and very selective towards the ethenolysis of methyl oleate yielding 1-decene and methyl-9-decenoate.
- references of interest also include: a) "Synthesis and Reactivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes” Anderson et al., Angew. Chem. Int. Ed. 2007, 46, pp. 7262-7265; b) "Intramolecular 'Hydroiminiumation' of Alkenes: Applications to the Synthesis of Conjugate Acids of Cyclic Alkyl Amino Carbenes (CAACs)" jazzar et al, Angew. Chem. Int. Ed. 2007, 46, pp.
- This invention relates to an asymmetrically substituted N-heterocyclic carbene (NHC) metathesis catalyst and process for use thereof in the production of olefins, where the metathesis catalyst is represented by the following formula:
- M is a Group 8 metal; preferably Ru or Os;
- X2 are, independently, any anionic ligand, or and X2 may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
- L is a heteroatom or heteroatom-containing ligand; preferably the heteroatom is N, O, P, or S; preferably P; optionally L may be joined to R 7 and/or Rg;
- Rj, R2, R3, R4, R5, R6, R7, and Rg are, independently, hydrogen or a Cj to C30 substituted or unsubstituted hydrocarbyl;
- any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
- R j and R2 are dissimilar to each other.
- Rl is mesityl, then R 2 is not methyl or ethyl, preferably R 2 is hydrogen or C j to C 30 substituted hydrocarbyl, or a C 3 to C 30 unsubstituted hydrocarbyl (preferably a C 4 to C 30 unsubstituted hydrocarbyl, preferably a C5 to C 3 Q unsubstituted hydrocarbyl, preferably a Cg to C 3 o unsubstituted hydrocarbyl).
- the present invention comprises a novel metathesis catalyst compound useful for the cross-metathesis of olefins, and processes for the use thereof. More particularly, the present invention comprises a novel metathesis catalyst compound which comprises an asymmetrically substituted N-heterocyclic carbene group. Even more particularly, the present invention comprises a novel metathesis catalyst compound which demonstrates improved activity and selectivity towards ethenolysis products in ethylene cross-metathesis reactions.
- This invention also relates to a process comprising contacting a feed oil (typically a triglyceride or seed oil) or derivative thereof (and optional alkene) with an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm.
- a feed oil typically a triglyceride or seed oil
- an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm.
- the feed oil may be esterified or transesterified with an alcohol prior to contacting with the olefin metathesis catalyst.
- This invention also relates to a process comprising contacting a triacylglyceride or a derivative thereof with an optional alkene (such as ethylene) and an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm, typically yielding a linear alpha-olefm (such as 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
- an optional alkene such as ethylene
- an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm, typically yielding a linear alpha-olefm (such as 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
- This invention further relates to a process for producing alpha-olefms (preferably linear alpha-olefms) comprising contacting a triacylglyceride with an alcohol (such as methanol) to produce a fatty acid alkyl ester and thereafter contacting the fatty acid alkyl ester with an olefin metathesis catalyst of the types described herein (and optional alkene, such as ethylene) under conditions which yield an alpha-olefm (preferably a linear alpha-olefm, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester or acid functionalized olefin.
- an alcohol such as methanol
- This invention further relates to a process for producing alpha-olefms (preferably linear alpha-olefms) comprising contacting a triacylglyceride with water and/or an alkaline reactant (such as sodium hydroxide) to produce a fatty acid and thereafter contacting the fatty acid with an olefin metathesis catalyst of the types described herein (and optional alkene, such as ethylene) under conditions which yield an alpha-olefm (preferably a linear alpha- olefm, preferably 1-decene, 1-heptene, and/or 1-butene) and an acid functionalized olefin.
- alpha-olefms preferably linear alpha-olefms
- This invention further relates to contacting unsaturated fatty acids with an alkene
- an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm (preferably a linear alpha-olefm, preferably 1-decene, 1-heptene, and/or 1-butene) and an acid functionalized olefin.
- alpha-olefm preferably a linear alpha-olefm, preferably 1-decene, 1-heptene, and/or 1-butene
- This invention further relates to contacting an unsaturated fatty acid ester with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm (preferably a linear alpha- olefm, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester functionalized olefin.
- an alpha-olefm preferably a linear alpha- olefm, preferably 1-decene, 1-heptene, and/or 1-butene
- This invention further relates to contacting an unsaturated fatty acid alkyl ester with an alkene (such as ethylene) in the presence of an olefin metathesis catalyst of the types described herein under conditions which yield an alpha-olefm (preferably a linear alpha- olefin, preferably 1-decene, 1-heptene, and/or 1-butene) and an ester functionalized olefin.
- an alpha-olefm preferably a linear alpha- olefin, preferably 1-decene, 1-heptene, and/or 1-butene
- This invention also relates to a process to produce alpha olefins (preferably linear alpha olefins, preferably 1-decene, 1-heptene, and/or 1-butene) comprising contacting a metathesis catalyst of the types described herein with an alkene (preferably ethylene), and one or more fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate).
- alpha olefins preferably linear alpha olefins, preferably 1-decene, 1-heptene, and/or 1-butene
- alkene preferably ethylene
- fatty acid esters preferably fatty acid methyl esters, preferably methyl oleate
- this invention relates to a process to produce alpha olefin (preferably linear alpha olefin, preferably 1-decene, 1-heptene, and/or 1-butene) comprising contacting a metathesis catalyst of the types described herein with an alkene (preferably ethylene), and one or more fatty acid esters (preferably fatty acid methyl esters, preferably methyl oleate) derived from biodiesel.
- alpha olefin preferably linear alpha olefin, preferably 1-decene, 1-heptene, and/or 1-butene
- alkene preferably ethylene
- fatty acid esters preferably fatty acid methyl esters, preferably methyl oleate
- the olefin metathesis catalysts described herein may be combined directly with triacylglycerides, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters to produce alpha-olefins, preferably linear alpha olefins, preferably C4 to C24 alpha-olefins, preferably 1-decene, 1-heptene, and/or 1-butene.
- a mixture of one or more triacylglyceride, biodiesel, fatty acids, and/or fatty acid esters is used to produce alpha-olefins, preferably linear alpha olefins, preferably C4 to C24 alpha-olefins, preferably C4 to C24 linear alpha-olefins.
- alpha-olefins preferably linear alpha olefins, preferably 1-decene, 1-heptene, and/or 1-butene is produced.
- This invention relates to an asymmetrically substituted NHC metathesis catalyst compound represented by the following formula:
- M is a Group 8 metal; preferably Ru or Os;
- X2 are, independently, any anionic ligand, preferably a halogen (such as chlorine or bromine, preferably chlorine), an alkoxide or an alkyl sulfonate, or X ⁇ and X2 may be joined to form a di anionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
- a halogen such as chlorine or bromine, preferably chlorine
- X ⁇ and X2 may be joined to form a di anionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
- L is a heteroatom or heteroatom-containing group; preferably the heteroatom is N, O, P, or S; preferably P; optionally L may be joined to R7 and/or R 8 , preferably L is L*(R) q . 1 when L is not bound to R7 or R 8 or L is L*(R) q _ 2 when L is bound to R7 or R 8 , where q is 1, 2, 3, or 4 depending on the valence of L* (which may be 2, 3, 4, or 5) and L* is N, O, P, or S, preferably P and R is as defined for R 3 ;
- Rj, R 2 , R3, R4, R5, R6, R7, and Rg are, independently, hydrogen or a Cj to C30 substituted or unsubstituted hydrocarbyl, preferably Rj, R 2 , R3, R4, R5, R6, R7, and Rg are selected from the group consisting of methyl, ethyl, propyl butyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, indenylene, substituted indenylene, phenyl, substituted phenyl, and the linear, branched and cyclic isomers thereof (including mesityl, 3,5,5-trimethylhexyl, cyclohexyl, methyl cyclohexyl, cyclododecyl, diisopropylphenyl, cyclopentyl, and norbornyl; wherein any two adjacent R groups may form a single ring of up to 8
- R ⁇ and R 2 are dissimilar to each other.
- any two adjacent R groups may form a fused ring having from 5 to 8 non- hydrogen atoms.
- the non-hydrogen atoms are C and/or O.
- the adjacent R groups form fused rings of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms.
- adjacent is meant any two R groups located next to each other, for example R 7 and Rg, can form a ring.
- Group 8 metal is an element from Group 8 of the Periodic Table, as referenced by the IUPAC in Nomenclature of Inorganic Chemistry: Recommendations, G.J. Leigh, Editor, Blackwell Scientific Publications, 1990.
- a "substituted hydrocarbyl” is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom.
- a "substituted alkyl or aryl” group is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms.
- alkoxides include those where the alkyl group is a C ⁇ to C I Q hydrocarbyl.
- the alkyl group may be straight chain or branched.
- Preferred alkoxides include a C to C 10 alkyl group, preferably methyl, ethyl, propyl, butyl, or isopropyl.
- Preferred alkoxides include those where the alkyl group is a phenol, substituted phenol (where the phenol may be substituted with up to 1, 2, 3, 4, or 5 C ⁇ to C 2 hydrocarbyl groups) or a Cj to C 10 hydrocarbyl, preferably a C to C 10 alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.
- Preferred alkyl sulfonates are represe by the Formula (II):
- R9 is a C ⁇ to C30 hydrocarbyl group, fluoro-substituted hydrocarbyl group, chloro- substituted hydrocarbyl group, aryl group, or substituted aryl group, preferably a C ⁇ to C 1 2 alkyl or aryl group, preferably trifluoromethyl, methyl, phenyl, or para-methyl-phenyl.
- the invention relates to asymmetrically substituted NHC metathesis catalyst compounds wherein R j and R2 are dissimilar to each other, causing asymmetry in the NHC ligand.
- dissimilar means that R ⁇ and R2 differ by at least 1 non-hydrogen atom (preferably by at least 2, preferably at least 3, preferably by at least 4, preferably by at least 5 non-hydrogen atoms) or if R ⁇ and R2 have the same number of non-hydrogen atoms, then they differ in structure or saturation, e.g., if one is cyclic then the other is linear; or if one is linear then the other is branched; or if one is saturated (such as cyclohexyl) then the other is aromatic (such as phenyl), etc.
- R j is an aromatic group, preferably phenyl, substituted phenyl, indenylenes, and substituted indenylenes; and R 2 is an aliphatic group, preferably methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclohexyl, cyclohexylmethyl, and so on.
- R ⁇ is a mesityl group and R 2 is a methyl group.
- R ⁇ is a 2,6-diisopropylphenyl group and R 2 is a cyclohexylmethyl group.
- R j is a 2,6-diisopropylphenyl group and R 2 is a propyl group.
- R 2 is not methyl or ethyl, preferably R 2 is hydrogen or C ⁇ to C 30 substituted hydrocarbyl, or a C 3 to C30 unsubstituted hydrocarbyl (preferably a C 4 to C 30 unsubstituted hydrocarbyl, preferably a C 5 to C 30 unsubstituted hydrocarbyl, preferably a C 6 to C 30 unsubstituted hydrocarbyl).
- both R j and R 2 are a C 3 to C 30 unsubstituted or substituted hydrocarbyl (preferably a C 4 to C 30 unsubstituted or substituted hydrocarbyl, preferably a C5 to C 3Q unsubstituted or substituted hydrocarbyl, preferably a Cg to C 3Q unsubstituted or substituted hydrocarbyl).
- one of R j and R 2 is aromatic (such as phenyl, mesityl, cyclopentyl, indenyl, norbornyl) and the other is a C 3 to C 3 o unsubstituted or substituted hydrocarbyl (preferably a C4 to C 3Q unsubstituted or substituted hydrocarbyl, preferably a C5 to C 3Q unsubstituted or substituted hydrocarbyl, preferably a Cg to C 3Q unsubstituted or substituted hydrocarbyl).
- aromatic such as phenyl, mesityl, cyclopentyl, indenyl, norbornyl
- the other is a C 3 to C 3 o unsubstituted or substituted hydrocarbyl (preferably a C4 to C 3Q unsubstituted or substituted hydrocarbyl, preferably a C5 to C 3Q unsubstituted or substituted hydrocarbyl, preferably a Cg to C 3Q
- the invention relates to asymmetrically substituted NHC metathesis catalyst compounds wherein R 7 or Rg is not joined to L.
- R 7 or R 8 is at least one of a phenyl, substituted phenyl, indenylene, and substituted indenylene group.
- catalysts of the type below in Formula (III), where R 7 is not joined to L, where each G is independently, hydrogen, halogen, or C j -C 3 o substituted or unsubstituted hydrocarbyl, and R j and R 2 are dissimilar to each other are particularly useful herein.
- this invention relates to a compound represented by the formula:
- M, X 1 ? X 2 , L, R 1? R 2 , R3, R4, R5, Re, and R 8 are as defined in Formula (I) and G is independently, hydrogen, halogen, or CJ ⁇ Q substituted or unsubstituted hydrocarbyl.
- G is independently, hydrogen, halogen, or CJ ⁇ Q substituted or unsubstituted hydrocarbyl.
- any two adjacent G groups may form a fused ring having from 5 to 8 non- hydrogen atoms.
- the non-hydrogen atoms are C and/or O.
- the adjacent G groups form fused rings of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms.
- R7 and Rg are fused such that the C(R 7 )(Rg) group is a benzylidene, substituted benzylidene, indenylene, or substituted indenylene.
- a catalyst useful herein is (l-mesityl-3-methyl-2H-4,5- dihydroimidazol-2-ylidene)(tricyclohexylphosphine)-3 -phenyl- 1 H-inden- 1 -ylidene ruthenium (II) dichloride, shown below in Formula (IV), wherein R j is a mesityl group, R 2 is a methyl group, R 7 and R 8 are fused to form a phenyl-substituted indenylene group which does not join to L, L is a tricyclohexylphosphine group (represented as PCy 3 ), and X j and X 2 are chloride groups.
- Ph phenyl.
- the invention relates to asymmetrically substituted NHC metathesis catalyst compounds wherein a heteroatom of R 7 or Rg is also joined to L, as represented below in Formula (V).
- this invention relates to a compound represented by the formula:
- R 7 or Rg is at least one of a phenyl, substituted phenyl, indenylene, and substituted indenylene group.
- M, X 1 ? X 2 , L, R 1 ? R 2 , R 3 , R 4 , R 5 , R 6 , and Rg are as defined in Formula (I) and G is independently, hydrogen, halogen, or C1-C30 substituted or unsubstituted hydrocarbyl.
- G is independently, hydrogen, halogen, or C1-C30 substituted or unsubstituted hydrocarbyl.
- any two adjacent G groups may form a fused ring having from 5 to 8 non- hydrogen atoms.
- the non-hydrogen atoms are C and/or O.
- the adjacent G groups form fused rings of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms.
- R 7 and Rg are fused to form an indenylene group which is joined to L as shown in Formula (VII) below:
- M, X 1 ? X 2 , L, R 1 ? R 2 , R3, R4, R5, and Rg are as defined in Formula (I) and G is independently, hydrogen, halogen, or C1-C30 substituted or unsubstituted hydrocarbyl.
- G is independently, hydrogen, halogen, or C1-C30 substituted or unsubstituted hydrocarbyl.
- any two adjacent G groups may form a fused ring having from 5 to 8 non- hydrogen atoms.
- the non-hydrogen atoms are C and/or O.
- the adjacent G groups form fused rings of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms.
- a catalyst useful herein is 2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenylmethylene(l- cyclohexylmethyl-3-(2,6-diisopropylphenyl)- 4,5-dihydro-lH-imidazole) ruthenium (II) chloride, shown below in Formula (VIII), wherein Rl is a 2,6-diisopropylphenyl group, R 2 is a cyclohexylmethyl group, R 7 is a dimethylaminosulfonyl-substituted phenyl group which joins to L, L is an isopropoxy group, and i and X 2 are chloride groups.
- Preferred metathesis catalysts useful herein include: 2-(i-propoxy)-5-(N,N-dimethyl- aminosulfonyl)phenylmethylene(l- cyclohexylmethyl-3-(2,6-diisopropylphenyl)-4,5-dihydro- lH-imidazole) ruthenium (II) chloride, (l-mesityl-3-methyl-2H-4,5-dihydroimidazol-2- ylidene)(tricyclohexylphosphine)-3 -phenyl- lH-inden-l-ylidene ruthenium (II) dichloride, and mixtures thereof.
- the catalyst compounds described herein may be synthesized as follows.
- the NHC precursor as the imidazolium salt, can be synthesized as known in the art.
- 2,6- diisopropylaniline (R ⁇ ) is reacted with 2-bromoethylamine hydrobromide at reflux for four days.
- the resulting diamine is condensed with a suitable reagent such as cyclohexylcarboxaldehyde (3 ⁇ 4) to give the imine.
- the resulting imine is reduced to the corresponding diamine using any suitable reducing agent, such as sodium borohydride.
- Treatment with triethyl formate and ammonium chloride yields the imidazolium salt.
- the imidazolium salt upon deprotonation with the appropriate base such as lithium bis(trimethylsilyl)amide generates the NHC ligand.
- This carbene can be reacted with ruthenium alkylidene complexes such as 2-(i-propoxy)-5-(N,N-dimethyl- aminosulfonyl)phenylmethylene(tricyclohexylphosphine) ruthenium dichloride to generate the asymmetrically substituted NHC ruthenium complex, 2-(i-propoxy)-5-(N,N-dimethyl- aminosulfonyl)phenylmethylene(l-cyclohexylmethyl-3-(2,6-diisopropylphenyl)-4,5-dihydro- lH-imidazole) ruthenium (II) chloride.
- the resulting ruthenium alkylidene complex is an efficient catalyst or catalyst precursor towards for the cross-metathesis of ethylene and methyl oleate, a component of biodiesel, to generate with good selectivity 1-decene and methyl-9-decenoate.
- the metathesis catalysts described herein may be combined directly with feed oils, seed oils, triacylglycerides, biodiesel, fatty acids, fatty acid esters and/or fatty acid alkyl esters ("feed materials") to produce alpha-olefms, preferably linear alpha olefins, preferably C4 to C24 alpha-olefms, preferably C4 to C24 linear alpha- olefms, such as preferably 1-decene, 1-heptene, and/or 1-butene.
- feed oils preferably linear alpha olefins, preferably C4 to C24 alpha-olefms, preferably C4 to C24 linear alpha- olefms, such as preferably 1-decene, 1-heptene, and/or 1-butene.
- the molar ratio of alkene to unsaturated feed material is greater than about 0.8/1.0, preferably, greater than about 0.9/1.0.
- the molar ratio of alkene to feed material is less than about 3.0/1.0, preferably, less than about 2.0/1.0.
- other molar ratios may also be suitable.
- ethylene for example, a significantly higher molar ratio can be used, because the self-metathesis of ethylene produces only ethylene again; no undesirable co-product olefins are formed.
- the molar ratio of ethylene to feed material may range from greater than about 0.8/1 to typically less than about 20/1.
- the quantity of metathesis catalyst that is employed in the process of this invention is any quantity that provides for an operable metathesis reaction.
- the ratio of moles of feed material (preferably fatty acid ester and/or fatty acid alkyl ester) to moles of metathesis catalyst is typically greater than about 10: 1, preferably greater than about 100: 1, preferably greater than about 1000: 1, preferably greater than about 10,000: 1, preferably greater than about 25,000: 1, preferably greater than about 50,000: 1, preferably greater than about 100,000: 1.
- the molar ratio of feed material (preferably fatty acid ester and/or fatty acid alkyl ester) to metathesis catalyst is typically less than about 10,000,000: 1, preferably less than about 1,000,000: 1, and more preferably less than about 500,000: 1.
- the contacting time of the reagents and catalyst in a batch reactor can be any duration, provided that the desired olefin metathesis products are obtained.
- the contacting time in a reactor is greater than about 5 minutes, and preferably greater than about 10 minutes.
- the contacting time in a reactor is less than about 25 hours, preferably less than about 15 hours, and more preferably less than about 10 hours.
- the reactants for example, metathesis catalyst; feed materials; optional alkene, optional alcohol, optional water, etc.
- a reaction vessel at a temperature of 20 to 300°C (preferably 20 to 200°C, preferably 30 to 100°C, preferably 40 to 60°C) and an alkene (such as ethylene) at a pressure of 0.1 to 1000 psi (0.7 kPa to 6.9 MPa), preferably 20 to 400 psi (0.14 MPa to 2.8MPa), preferably 50 to 250 psi (0.34 MPa to 1.7MPa), if the alkene is present, for a residence time of 0.5 seconds to 48 hours (preferably 0.25 to 5 hours, preferably 30 minutes to 2 hours).
- the olefin pressure is greater than about 5 psig (34.5 kPa), preferably, greater than about 10 psig (68.9 kPa), and more preferably, greater than about 45 psig (310 kPa).
- the aforementioned pressure ranges may also be suitably employed as the total pressure of olefin and diluent.
- the aforementioned pressure ranges may be suitably employed for the inert gas pressure.
- from about 0.005 nmoles to about 500 nmoles, preferably from about 0.1 to about 250 nmoles, and most preferably from about 1 to about 50 nmoles of the metathesis catalyst are charged to the reactor per 3 mmoles of feed material (such as TAGs, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters or mixtures thereof, preferably fatty acid esters) charged.
- feed material such as TAGs, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters or mixtures thereof, preferably fatty acid esters
- the process is typically a solution process, although it may be a bulk or high pressure process. Homogeneous processes are preferred. (A homogeneous process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where reactant concentration in all feeds to the reactor is 70 volume % or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst or other additives, or amounts typically found with the reactants, e.g., propane in propylene).
- Suitable diluents/solvents for the process include non-coordinating, inert liquids.
- Examples include straight and branched-chain hydrocarbons such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as can be found commercially (IsoparTM); perhalogenated hydrocarbons such as perfluorinated C ⁇ I Q alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds such as benzene, toluene, mesitylene, and xylene.
- straight and branched-chain hydrocarbons such as isobutane, butane,
- Suitable diluents/solvents also include aromatic hydrocarbons, such as toluene or xylenes, and chlorinated solvents, such as dichloromethane.
- the feed concentration for the process is 60 volume % solvent or less, preferably 40 volume % or less, preferably 20 volume % or less.
- the process may be batch, semi-batch or continuous.
- continuous means a system that operates without interruption or cessation.
- a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
- Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe, or pump.
- the processes may be conducted in either glass lined, stainless steel, or similar type reaction equipment.
- Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruder, pipe, or pump, continuous flow fixed bed reactors, slurry reactors, fluidized bed reactors, and catalytic distillation reactors).
- the reaction zone may be fitted with one or more internal and/or external heat exchanger(s) in order to control undue temperature fluctuations, or to prevent "runaway" reaction temperatures.
- the weight hourly space velocity given in units of grams feed material (preferably fatty acid ester and/or fatty acid alkyl ester) per gram catalyst per hour (h _1 ), will determine the relative quantities of feed material to catalyst employed, as well as the residence time in the reactor of the unsaturated starting compound.
- the weight hourly space velocity of the unsaturated feed material preferably fatty acid ester and/or fatty acid alkyl ester
- the weight hourly space velocity of the unsaturated feed material is typically greater than about 0.04 g feed material (preferably fatty acid ester and/or fatty acid alkyl ester) per g catalyst per hour (h _1 ), and preferably, greater than about 0.1 tr 1 .
- the weight hourly space velocity of the feed material is typically less than about 100 h "1 , and preferably, less than about 20 h "1 .
- reactions utilizing the catalytic complexes of the present invention can be run in a biphasic mixture of solvents, in an emulsion or suspension, or in a lipid vesicle or bilayer.
- the feed material is typically provided as a liquid phase, preferably neat.
- the feed material is provided in a liquid phase, preferably neat; while the alkene is provided as a gas that is dissolved in the liquid phase.
- feed material is an unsaturated fatty acid ester or unsaturated fatty acid and is provided in a liquid phase, preferably neat; while the alkene is a gaseous alpha-olefm, such as for example, ethylene, which is dissolved in the liquid phase.
- the feed material is an unsaturated fatty acid ester or unsaturated fatty acid and is provided as a liquid at the process temperature, and it is generally preferred to be used neat, that is, without a diluent or solvent.
- a solvent usually increases recycle requirements and increases costs.
- a solvent can be employed with the alkene and/or feed material.
- a solvent may be desirable, for instance, where liquid feed material and alkene are not entirely miscible, and both then can be solubilized in a suitable solvent.
- the alkene and an unsaturated fatty acid ester or unsaturated fatty acid are co-metathesized to form first and second product olefins, preferably, a reduced chain first product alpha-olefin and a second product reduced chain terminal ester or acid-functionalized alpha-olefin.
- first and second product olefins preferably, a reduced chain first product alpha-olefin and a second product reduced chain terminal ester or acid-functionalized alpha-olefin.
- the metathesis of methyloleate with ethylene will yield cross-metathesis products of 1-decene and methyl-9-decenoate. Both products are alpha-olefms; the decenoate also terminates in an ester moiety at the opposite end of the chain from the carbon-carbon double bond.
- the conversion of feed material can vary widely depending upon the specific reagent olefins, the specific catalyst, and specific process conditions employed.
- conversion is defined as the mole percentage of feed material that is converted or reacted to the cross-metathesis alpha-olefin products.
- the conversion of feed material is greater than about 50 mole %, preferably, greater than about 60 mole %, and more preferably, greater than about 70 mole %.
- the yields of first product olefin and ester or acid- functionalized second product olefin can also vary depending upon the specific reagent olefins, catalyst, and process conditions employed.
- Yield will be defined as the mole percentage of cross-metathesis alpha-olefin product olefin formed relative to the initial moles of feed material (such as fatty acid ester and/or fatty acid alkyl ester) in the feed.
- the yield of alpha-olefin will be greater than about 35 mole %, preferably, greater than about 50 mole %.
- the yield of ester or acid-functionalized alpha-olefin will be 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more.
- the yield for reactions is defined as the moles of alpha olefin formed divided by (the moles of unsaturated R a + moles of unsaturated R ⁇ + moles of unsaturated R c ) introduced into the reactor is 30% or more, preferably 40% or more, preferably 45% or more, preferably 50% or more, preferably 55% or more, preferably 60% or more.
- R a , R b , and R c each, independently, represent a saturated or unsaturated hydrocarbon chain (preferably R a , Rb, and R c each, independently, are a C ⁇ to alkyl or alkene, preferably C ⁇ to C22 alkyl or alkene).
- productivity is defined to be the amount in grams of linear alpha-olefm produced per mmol of catalyst introduced into the reactor, per hour.
- productivity of the process is at least 200 g of linear alpha-olefm (such as decene-1) per mmol of catalyst per hour, preferably at least 5000 g/mmol/hour, preferably at least 10,000 g/mmol/hour, preferably at least 300,000 g/mmol/hour.
- selectivity is a measure of conversion of alkene and feed material to the cross-metathesis alpha-olefm product, and is defined by the mole percentage of product olefin formed relative to the initial moles of alkene or feed material.
- the selectivity of the process is at least 20 wt% linear alpha-olefm, based upon the weight to the material exiting the reactor, preferably at least 25 wt%, preferably at least 30 wt%>, preferably at least 35 wt%>, preferably at least 40 wt%>, preferably at least 45 wt%>, preferably at least 50 wt%>, preferably at least 60 wt%>, preferably at least 70 wt%>, preferably at least 80 wt%>, preferably at least 85 wt%>, preferably at least 90 wt%>, preferably at least wt95%.
- TON catalyst turnover number
- the (TON) of the process is at least 5,000, preferably at least 10,000, preferably at least 50,000, preferably at least 100,000, preferably at least 1,000,000. Feed Materials
- Feed materials useful in metathesis processes described herein include feed oils, fatty acids, fatty acid esters, triacylglycerides, and biodiesel.
- the fatty acid rich material useful in the processes described herein can be derived from plant, animal, microbial, or other sources (feed oil).
- feed oils include vegetable oils such as corn, soy, rapeseed, canola, sunflower, palm and other oils that are readily available; however, any vegetable oil or animal fat can be employed.
- Raw or unrefined oil can be used in certain embodiments; however, filtered and refined oils are typically preferred. Use of degummed and filtered feedstock minimizes the potential for emulsification and blockage in the reactors. Feedstock with high water content can be dried before basic catalyst processing.
- Feedstock with high free fatty acid content can be passed through an esterification process to reduce the free fatty acid content before the process of esterification to convert fatty acid glycerides to monoalkyl esters.
- the reduction of free fatty acids and the conversion of fatty acid glycerides can also in the same processing step.
- Feedstock containing other organic compounds such as hexane, heptane, isohexane, etc.
- Other materials containing fatty acid glycerides or other fatty acid esters can also be employed, including phospholipids, lysophospholipids, and fatty acid wax esters.
- the fatty acid rich material useful in the processes described herein typically includes a mixture of fatty acids.
- the feed oil can also include a mixture of fatty acid glycerides from different sources.
- the free fatty acid content of useful vegetable oils is preferably about 0.1 wt% or less when employed in a basic homogeneous catalyst esterification reaction. Higher levels can be utilized as well, and levels up to about 3 wt%, or even as high as 15 wt% or more can typically be tolerated.
- feed oil refers to one or more vegetable or animal oils, such as canola oil, corn oil, soybean oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, grapeseed oil, linseed oil, safflower oil, pumpkin oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic safflower oil, high-oleic sunflower oil, mixtures of animal and/or vegetable fats and oils, castor bean oil, dehydrated castor bean oil, cucumber oil, poppyseed oil, flaxseed oil, lesquerella oil, walnut oil, cottonseed oil, meadowfoam, tuna oil, and sesame oils.
- vegetable or animal oils such as canola oil, corn oil, soybean oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, peanut oil, mustard
- Vegetable oils useful herein preferably contain at least one site of unsaturation and include, but are not limited to, canola, soybean, palm, peanut, mustard, sunflower, tung, tall, perilla, grapeseed, rapeseed, linseed, safflower, pumpkin corn and other oils extracted from plant seeds.
- a combination of oils is used herein.
- Preferred combinations include two (three or four) or more of tall oil, palm oil, tallow, waste grease, rapeseed oil, canola oil, soy oil and algae oil.
- Alternate useful combinations include two (three or four) or more of soy oil, canola oil, rapeseed oil, algae oil, and tallow.
- processed oils such as blown oils
- fatty acids are the source of fatty acids useful herein. While vegetable oils are preferred sources of fatty acids for practicing disclosed embodiments of the present process, fatty acids also are available from animal fats including, without limitation, lard and fish oils, such as sardine oil and herring oil, and the like.
- a desired fatty acid or fatty acid precursor is produced by a plant or animal found in nature.
- particular fatty acids or fatty acid precursors are advantageously available from genetically modified organisms, such as a genetically modified plants, particularly genetically modified algae. Such genetically modified organisms are designed to produce a desired fatty acid or fatty acid precursor biosynthetically or to produce increased amounts of such compounds.
- Fatty acids are carboxylic acids with a saturated or unsaturated aliphatic tails that are found naturally in many different fats and oils. Any unsaturated fatty acid can be suitably employed in the process of this invention, provided that the unsaturated fatty acid can be metathesized in the manner disclosed herein.
- An unsaturated fatty acid comprises a long carbon chain containing at least one carbon-carbon double bond and terminating in a carboxylic acid group.
- the unsaturated fatty acid will contain greater than about 8 carbon atoms, preferably, greater than about 10 carbon atoms, and more preferably, greater than about 12 carbon atoms.
- the unsaturated fatty acid will contain less than about 50 carbon atoms, preferably, less than about 35 carbon atoms, and more preferably, less than about 25 carbon atoms. At least one carbon-carbon double bond is present along the carbon chain, this double bond usually occurring about the middle of the chain, but not necessarily. The carbon-carbon double bond may also occur at any other internal location along the chain. A terminal carbon-carbon double bond, at the opposite end of the carbon chain relative to the terminal carboxylic acid group, is also suitably employed, although terminal carbon-carbon double bonds occur less commonly in fatty acids. Unsaturated fatty acids containing the terminal carboxylic acid functionality and two or more carbon-carbon double bonds may also be suitably employed in the process of this invention.
- a fatty acid having more than one double bond may produce a variety of metathesis products.
- the unsaturated fatty acid may be straight or branched and substituted along the fatty acid chain with one or more substituents, provided that the one or more substituents are substantially inert with respect to the metathesis process.
- suitable substituents include alkyl moieties, preferably C 1 . 10 a lkyl moieties, including, for example, methyl, ethyl, propyl, butyl, and the like; cycloalkyl moieties, preferably, C 4 .
- cycloalkyl moieties including for example, cyclopentyl and cyclohexyl; monocyclic aromatic moieties, preferably, Cg aromatic moieties, that is, phenyl; arylalkyl moieties, preferably, C _i$ arylalkyl moieties, including, for example, benzyl; and alkylaryl moieties, preferably, C 7 _ 16 alkylaryl moieties, including, for example, tolyl, ethylphenyl, xylyl, and the like; as well as hydroxyl, ether, keto, aldehyde, and halide, preferably, chloro and bromo, functionalities.
- monocyclic aromatic moieties preferably, Cg aromatic moieties, that is, phenyl
- arylalkyl moieties preferably, C _i$ arylalkyl moieties, including, for example, benzyl
- alkylaryl moieties
- Non- limiting examples of suitable unsaturated fatty acids include 3-hexenoic (hydrosorbic), trans-2-heptenoic, 2-octenoic, 2-nonenoic, cis-and trans-4-decenoic, 9- decenoic (caproleic), 10-undecenoic (undecylenic), trans-3-dodecenoic (linderic), tridecenoic, cis-9-tetradeceonic (myristoleic), pentadecenoic, cis-9-hexadecenoic (cis-9-palmitoelic), trans-9-hexadecenoic (trans-9-palmitoleic), 9-heptadecenoic, cis-6-octadecenoic (petroselinic), trans-6-octadecenoic (petroselaidic), cis-9-octadecenoic (oleic), trans-9- octadecenoic (ela
- Fatty acid esters are formed by condensation of a fatty acid and an alcohol.
- Fatty acid alkyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by a hydrocarbyl group, typically a C to C30 alkyl group, preferably a Cj to C20 alkyl.
- Fatty acid alkyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by an alkyl group.
- Fatty acid alkyl esters useful herein are typically represented by the formula: R A -C(0)-0-R* , where R A is a C j to C 10 o hydrocarbyl group, preferably a C 6 to C 2 2 group, preferably a C 6 to C 14 1-alkene group, and R* is an alkyl group, preferably a Ci to C 2 o alkyl group, preferably methyl, ethyl, butyl, pentyl and hexyl.
- R A -CH 2 CH 2 -R A -C(0)- O-R*, where each R A is, independently a Cj to C 10 o alkyl group, preferably a C 6 to C 2 o, preferably a C 8 to C 14 alkyl group, preferably a C 9 group and R* is an alkyl group, preferably a Cj to C 2 o alkyl group, preferably methyl, ethyl, butyl, pentyl and hexyl.
- Particularly preferred fatty acid alkyl esters useful herein are represented by the formula:
- R* is an alkyl group, preferably a C j to C 2 o alkyl group, preferably methyl, ethyl, butyl pentyl and hexyl
- m and n are, independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, preferably 5, 7, 9, or 11, preferably 7.
- Fatty acid methyl esters are fatty acids where the hydrogen of the -OH of the acid group is replaced by methyl group.
- Fatty acid methyl esters useful herein are typically represented by the formula: R A -C(0)-0-CH 3i where R A is a C j to C 10 o hydrocarbyl group, preferably a Cg to C22 group, preferably a Cg to C1 4 1-alkene group.
- Preferred fatty acid methyl esters include methyl palmitoleate, methyl oleate, methyl gadoleate, methyl erucate, methyl linoleate, methyl linolenate, methyl soyate, and mixtures of methyl esters derived from soybean oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, Canola oil, palm oil, Jathropa oil, high-oleic soybean oil (e.g., 75 mole % or more, preferably 85 mole % or more, preferably 90 mole % or more), high-oleic safflower oil (e.g., 75 mole % or more, preferably 85 mole % or more, preferably 90 mole % or more), high-oleic sunflower oil (e.g., 75 mole % or more, preferably 85 mole % or more, preferably 90 mole % or more), and other plant or animal
- Alcohol also referred to as Alkanols
- Fatty acid esters are formed by condensation of a fatty acid and an alcohol.
- the alcohol used herein can be any monohydric, dihydric, or polyhydric alcohol that is capable of condensing with the feed material (such as the unsaturated fatty acid) to form the corresponding unsaturated ester (such as the fatty acid ester).
- the alcohol contains at least one carbon atom.
- the alcohol contains less than about 20 carbon atoms, preferably, less than about 12 carbon atoms, and more preferably, less than about 8 carbon atoms.
- the carbon atoms may be arranged in a straight-chain or branched structure, and may be substituted with a variety of substituents, such as those previously disclosed hereinabove in connection with the fatty acid, including the aforementioned alkyl, cycloalkyl, monocyclic aromatic, arylalkyl, alkylaryl, hydroxyl, halogen, ether, ester, aldehyde and keto substituents.
- the alcohol is a straight-chain or a branched C ⁇ . ⁇ alkanol.
- a preferred alcohol is the trihydric alcohol glycerol, the fatty acid esters of which are known as "glycerides.”
- Other preferred alcohols include methanol and ethanol.
- the alcohol employed in the esterification and/or transesterification reactions is preferably a low molecular weight monohydric alcohol such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, or t-butanol.
- the alcohol is preferably anhydrous; however, a small amount of water in the alcohol may be present (e.g., less than about 2 wt%, preferably less than about 1 wt%, and most preferably less than about 0.5 wt%; however, in certain embodiments, higher amounts can be tolerated).
- Acid esterification reactions are more tolerant of the presence of small amounts of water in the alcohol than are basic transesterification reactions. While specific monohydric alcohols are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific monohydric alcohols. Other suitable monohydric alcohols can also be employed in the preferred embodiments.
- Preferred sources of fatty acid esters for use herein include TAGs and biodiesel sources.
- Biodiesel is a mono-alkyl ester derived from the processing of vegetable oils and alcohols.
- the processing is typically carried out by an esterification reaction mechanism, and typically is performed in an excess of alcohol to maximize conversion.
- Esterification can refer to direct esterification, such as between a free fatty acid and an alcohol, as well as transesterification, such as between an ester and an alcohol.
- a fatty acid source such as free fatty acids, soaps, esters, glycerides (mono-, di- tri-), phospholipids, lysophospholipids, or amides
- a monohydric alcohol source such as an alcohol or an ester
- various combinations of these reagents can be employed in an esterification reaction.
- Alkyl oleates and alkyl erucates are fatty acid esters that are often major components in biodiesel produced by the transesterification of alcohol and vegetable oils (preferably the alkyls are a Ci to C 30 alkyl group, alternately a C j to C 2 o alkyl group).
- Biodiesel compositions that are particularly useful in this invention are those which have high concentrations of alkyl oleate and alkyl erucate esters. These fatty acid esters preferably have one site of unsaturation such that cross-metathesis with ethylene yields 1-decene as the coproduct.
- Biodiesel compositions that are particularly useful are those produced from vegetable oils such as canola, rapeseed oil, palm oil, and other high oleate oil, high erucate oils.
- vegetable oils such as canola, rapeseed oil, palm oil, and other high oleate oil, high erucate oils.
- Particularly preferred vegetable oils include those having at least 50% (on a molar basis) combined oleic and erucic fatty acid chains of all fatty acid chains, preferably 60%, preferably 70%>, preferably 80%>, preferably 90%>.
- useful fatty acid ester containing mixtures include those having at least 50% (on a molar basis) alkyl oleate fatty acid esters, preferably 60% of alkyl oleate fatty acid esters, preferably 70% of alkyl oleate fatty acid esters, preferably 80% of alkyl oleate fatty acid esters, preferably 90% of alkyl oleate fatty acid esters.
- useful fatty acid ester containing mixtures include those having at least 50% (on a molar basis) alkyl erucate fatty acid esters, preferably 60% of alkyl erucate fatty acid esters, preferably 70% of alkyl erucate fatty acid esters, preferably 80% of alkyl erucate fatty acid esters, preferably 90% of alkyl erucate fatty acid esters.
- useful fatty acid ester containing mixtures include those having at least 50% (on a molar basis) combined oleic and erucic fatty acid esters of all fatty acid ester chains, preferably 60%>, preferably 70%>, preferably 80%>, preferably 90%>.
- TAGs Triacylglycerides
- Triacylglycerides also called triglycerides, are a naturally occurring ester of three fatty acids and glycerol that is the chief constituent of natural fats and oils.
- the three fatty acids can be all different, all the same, or only two the same, they can be saturated or unsaturated fatty acids, and the saturated fatty acids may have one or multiple unsaturations.
- Chain lengths of the fatty acids in naturally occurring triacylglycerides can be of varying lengths but 16, 18, and 20 carbons are the most common.
- Natural fatty acids found in plants and animals are typically composed only of even numbers of carbon atoms due to the way they are bio-synthesized. Most natural fats contain a complex mixture of individual triglycerides and because of this, they melt over a broad range of temperatures.
- Vegetable oils include triglycerides and neutral fats, such as triacylglycerides, the main energy storage form of fat in animals and plants. These typically have the chemical structure:
- R a , R ⁇ , and R c each, independently, represent a saturated or non-saturated hydrocarbon chain (preferably R a , R ⁇ , and R c each, independently, are a Ci 2 to C28 alkyl or alkene, preferably C ⁇ to C22 alkyl or alkene).
- R a , R ⁇ , and R c each, independently, are a Ci 2 to C28 alkyl or alkene, preferably C ⁇ to C22 alkyl or alkene.
- Different vegetable oils have different fatty acid profiles, with the same or different fatty acids occurring on a single glycerol.
- an oil can have linoleic, oleic, and stearic acids attached to the same glycerol, with each of R a , Rb, and R c representing one of these three fatty acids.
- triglyceride consists of three fatty acids (e.g., saturated fatty acids of general structure of CH3(CH 2 ) n COOH, wherein n is typically an integer of from 4 to 28 or higher) attached to a glycerol (3 ⁇ 4 ⁇ 5( ⁇ )3) backbone by ester linkages.
- CH3(CH 2 ) n COOCH3 for saturated fatty acids typically, but not always, the length of the carbon backbone chain is from 12 to 24 carbon atoms.
- the esterification process can be catalyzed or non-catalyzed. Catalyzed processes are categorized into chemical and enzyme based processes. Chemical catalytic methods can employ acid and/or base catalyst mechanisms.
- the catalysts can be homogeneous and/or heterogeneous catalysts. Homogeneous catalysts are typically liquid phase mixtures, whereas heterogeneous catalysts are solid phase catalysts mixed with the liquid phase reactants, oils and alcohols.
- the conversion of TAGs to fatty acid alkyl esters ("FAAE") through transesterification of the TAG typically involves forming a reactant stream, which includes TAG (e.g., at least about 75 wt%), alkanol (e.g., about 5 to 20 wt%), a transesterification catalyst (e.g., about 0.05 to 1 wt%), and optionally, glycerol (typically up to about 10 wt%).
- Suitable alkanols may include Ci-C 6 alkanols and commonly may include methanol, ethanol, or mixtures thereof.
- Suitable transesterification catalysts may include alkali metal alkoxides having from 1 to 6 carbon atoms and commonly may include alkali metal methoxide, such as sodium methoxide and/or potassium methoxide.
- the basic catalyst is desirably selected such that the alkali metal alkoxide may suitably contain an alkoxide group which is the counterpart of the alkanol employed in the reaction stream (e.g., a combination of methanol and an alkali metal methoxide such as sodium methoxide and/or potassium methoxide).
- the reactant stream may suitably include about 0.05 to 0.3 wt% sodium methoxide, at least about 75 wt% triacylglyceride, about 1 to 7 wt% glycerol, and at least about 10 wt% methanol.
- the reactant stream may desirably include about 0.05 to 0.25 wt% sodium methoxide, at least about 75 wt% triacylglyceride, about 2 to 5 wt% glycerol, and about 10 to 15 wt% methanol.
- the rate and extent of reaction for esterification of the fatty acid glycerides or other fatty acid derivates with monohydric alcohol in the presence of a catalyst depends upon factors including but not limited to the concentration of the reagents, the concentration and type of catalyst, and the temperature and pressure conditions, and time of reaction.
- the reaction generally proceeds at temperatures above about 50°C, preferably at temperatures above 65°C; however, the catalyst selected or the amount of catalyst employed can affect this temperature to some extent. Higher temperatures generally result in faster reaction rates.
- very high temperatures such as those in excess of about 300°C, or even those in excess of 250°C, can lead to increased generation of side products, which can be undesirable as their presence can increase downstream purification costs. Higher temperatures can be advantageously employed; however, e.g., in situations where the side products do not present an issue.
- the reaction temperature can be achieved by preheating one or more of the feed materials or by heating a mixture of the feed materials. Heating can be achieved using apparatus known in the art, e.g., heat exchangers, jacketed vessels, submerged coils, and the like. While specific temperatures and methods of obtaining the specific temperatures are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific temperatures and methods of obtaining the specific temperatures. Other temperatures and methods of obtaining temperatures can also be employed in the preferred embodiments.
- the amount of alcohol employed in the reaction is preferably in excess of the amount of fatty acid present on a molar basis.
- the fatty acid can be free or combined, such as to alcohol, glycol, or glycerol, with up to three fatty acid moieties being attached to a glycerol. Additional amounts of alcohol above stoichiometric provide the advantage of assisting in driving the equilibrium of the reaction to produce more of the fatty acid ester product. However, greater excesses of alcohol can result in greater processing costs and larger capital investment for the larger volumes of reagents employed in the process, as well as greater energy costs associated with recovering, purifying, and recycling this excess alcohol.
- lower relative levels of alcohol to fatty acid result in decreased yield and higher relative levels of alcohol levels to fatty acid result in increased capital and operating expense.
- Some instances of operation at ratios of alcohol to fatty acid over a wider range include when first starting up the process or shutting down the process, when balancing the throughput of the reactor to other processing steps or other processing facilities, such as one that produces alcohol or utilizes a side stream, or when process upsets occur.
- a molar ratio of 2: 1 methanol to fatty acid is employed and a sodium hydroxide concentration of about 0.5 wt% of the total reaction mixture is employed
- the ratio of sodium hydroxide to methanol is about 2 wt% entering the reactor and about 4 wt% at the exit because about half of the alcohol is consumed in the esterification reaction.
- the amount of homogeneous catalyst is preferably from about 0.2 wt% to about 1.0 wt% of the reaction mixture when the catalyst is sodium hydroxide; at typical concentration of 0.5 wt% when a 2: 1 molar ratio of methanol to fatty acid is used; however, in certain embodiments, higher or lower amounts can be employed.
- the amount of catalyst employed can also vary depending upon the nature of the catalyst, feed materials, operating conditions, and other factors. Specifically, the temperature, pressure, free fatty acid content of the feed, and degree of mixing can change the amount of catalyst preferably employed. While specific catalyst amounts are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific catalyst amounts. Other suitable catalyst amounts can also be employed in the preferred embodiments.
- the esterification reaction can be performed batchwise, such as in a stirred tank, or it can be performed continuously, such as in a continuous stirred tank reactor (CSTR) or a plug flow reactor (PFR).
- CSTR continuous stirred tank reactor
- PFR plug flow reactor
- a series of continuous reactors can advantageously operate in series.
- batch reactors can be arranged in parallel and/or series.
- one or more of the feed materials is preferably metered into the process.
- Various techniques for metering can be employed (e.g., metering pumps, positive displacement pumps, control valves, flow meters, and the like). While specific types of reactors are discussed herein with reference to certain embodiments and examples, the preferred embodiments are not limited to such specific reactors. Other suitable types of reactors can also be employed in the preferred embodiments.
- biodiesel refers to a transesterified vegetable oil or animal fat based diesel fuel containing long-chain alkyl (typically methyl, propyl, or ethyl) esters.
- Biodiesel is typically made by chemically reacting lipids (such as vegetable oil) with an alcohol.
- Biodiesel, TAG's and derivatives thereof may be used in the processes described herein.
- preferred fatty acid methyl esters useful herein may be obtained by reacting canola oil, corn oil, soybean oil, beef tallow, tall oil, animal fats, waste oils/greases, rapeseed oil, algae oil, Canola oil, palm oil, Jathropa oil, high-oleic soybean oil, high-oleic saffiower oil, high-oleic sunflower oil, or mixtures of animal and/or vegetable fats, and oils with one or more alcohols (as described above), preferably methanol.
- the feed material is first isomerized, then combined with a metathesis catalyst as described herein.
- the processes disclosed herein may comprise providing a feed material (typically a fatty acid or fatty acid derivative), isomerizing a site of unsaturation in the feed material (typically a fatty acid or fatty acid derivative) to produce an isomerized feed material (typically a fatty acid or fatty acid derivative), and then contacting the isomerized material with an alkene in the presence of a metathesis catalyst.
- the isomerized material can be produced by isomerization with or without subsequent esterification or transesterification. Isomerization can be catalyzed by known biochemical or chemical techniques.
- an isomerase enzyme such as a linoleate isomerase
- a linoleate isomerase can be used to isomerize linoleic acid from the cis 9, cis 12 isomer to the cis 9, trans 11 isomer.
- This isomerization process is stereospecific, however, nonstereospecific processes can be used because both cis and trans isomers are suitable for metathesis.
- an alternative process employs a chemical isomerization catalyst, such as an acidic or basic catalyst, can be used to isomerize an unsaturated feed material (typically a fatty acid or fatty acid derivative) having a site of unsaturation at one location in the molecule into an isomerized, feed material (typically a fatty acid or fatty acid derivative) having a site of unsaturation at a different location in the molecule.
- a chemical isomerization catalyst such as an acidic or basic catalyst
- an unsaturated feed material typically a fatty acid or fatty acid derivative
- Metal or organometallic catalysts also can be used to isomerize an unsaturated feed material (typically a fatty acid or fatty acid derivative).
- nickel catalysts are known to catalyze positional isomerization of unsaturated sites in fatty acid derivatives.
- esterification, transesterification, reduction, oxidation, and/or other modifications of the starting compound or products can be catalyzed by biochemical or chemical techniques.
- a fatty acid or fatty acid derivative can be modified by a lipase, esterase, reductase or other enzyme before or after isomerization.
- the isomerization described above may be practiced with any triacylglycerides, biodiesel, fatty acids, fatty acid esters, and/or fatty acid alkyl esters described herein, typically before contacting with the metathesis catalyst.
- the metathesis process of this invention may require an alkene as a reactant.
- alkene shall imply an organic compound containing at least one carbon-carbon double bond and typically having less than about 10 carbon atoms.
- the alkene may have one carbon-carbon unsaturated bond, or alternatively, two or more carbon- carbon unsaturated bonds. Since the metathesis reaction can occur at any double bond, alkenes having more than one double bond will produce more metathesis products. Accordingly, in some embodiments, it is preferred to employ an alkene having only one carbon-carbon double bond.
- the double bond may be, without limitation, a terminal double bond or an internal double bond.
- the alkene may also be substituted at any position along the carbon chain with one or more substituents, provided that the one or more substituents are essentially inert with respect to the metathesis process.
- Suitable substituents include, without limitation, alkyl, preferably, C ⁇ g alkyl; cycloalkyl, preferably, C 3 . 6 cycloalkyl; as well as hydroxy, ether, keto, aldehyde, and halogen functionalities.
- suitable alkenes include ethylene, propylene, butene, butadiene, pentene, hexene, the various isomers thereof, as well as higher homologues thereof.
- the alkene is a C2_8 alkene. More preferably, the alkene is a C2_6 alkene, even more preferably, a C2.4 alkene, and most preferably, ethylene.
- the processes described herein produce a linear alpha olefin.
- the alpha-olefin, preferably linear alpha-olefin, produced herein contains at least one more carbon than the alkene used in the reaction to make the alpha-olefin.
- the processes described herein produce a blend of an alpha olefin and an ester-functionalized alpha olefin.
- a mixture of non-ester-containing alpha olefins will be produced due to the presence of mono-, di-, and tri-unsubstituted fatty acid chains.
- the major alpha olefin products are expected to be 1-decene, 1-heptene, and 1- butene.
- the major ester-containing alpha olefin product is methyl dec-9-enoate.
- the alpha olefin produced herein is 1-decene.
- the 1-decene is produced with an ester.
- the major alpha olefin produced herein is 1-decene.
- the 1-decene is produced with an ester.
- ethylene and methyl oleate are combined with the metathesis catalysts described herein (such as 2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenylmethylene(l- cyclohexylmethyl-3-(2,6-diisopropylphenyl)- 4,5-dihydro-lH-imidazole) ruthenium (II) chloride, (l-mesityl-3-methyl-2H-4,5- dihydroimidazol-2-ylidene)(tricyclohexylphosphine)-3 -phenyl- 1 H-inden- 1 -ylidene ruthenium (II) dichloride, and mixtures thereof) to produce 1-decene and methyl dec-9-enoate.
- the metathesis catalysts described herein such as 2-(i-propoxy)-5-(N,N- dimethylaminosulfonyl)phenylmethylene(l- cyclohexy
- Separation of the 1 -olefin (such as the 1-decene) from the ester may be by means typically known in the art such as distillation or filtration.
- the linear alpha-olefin (such as 1-decene or a mixture of Cg, C ⁇ Q , C ⁇ linear alpha olefins) is then separated from any esters present and preferably used to make poly-alpha- olefins(PAOs).
- PAOs may be produced by the polymerization of olefin feed in the presence of a catalyst such as A1C1 3 , BF 3 , or BF 3 complexes.
- PAOs Processes for the production of PAOs are disclosed, for example, in the following patents: US 3,149,178; 3,382,291; 3,742,082; 3,769,363; 3,780,128; 4,172,855; and 4,956,122; which are fully incorporated by reference. PAOs are also discussed in: Will, J.G. Lubrication Fundamentals, Marcel Dekker: New York, 1980. Certain high viscosity index PAO's may also be conveniently made by the polymerization of an alpha-olefin in the presence of a polymerization catalyst such as Friedel-Crafts catalysts.
- a polymerization catalyst such as Friedel-Crafts catalysts.
- PAO's can also be made using various metallocene catalyst systems. Examples include US 6,706,828; WO 96/23751; EP 0 613 873; US 5,688,887; US 6,043,401; WO 03/020856; US 6,548,724; US 5,087,788; US 6,414,090; US 6,414,091; US 4,704,491; US 6,133,209; and US 6,713,438.
- PAOs are often used as additives and base stocks for lubricants, among other things. Additional information on the use of PAO's in the formulations of full synthetic, semisynthetic or part synthetic lubricant or functional fluids can be found in "Synthetic Lubricants and High-Performance Functional Fluids", 2 nc ⁇ Ed., L. Rudnick et al., Marcel Dekker, Inc., N.Y. (1999). Additional information on additives used in product formulation can be found in "Lubricants and Lubrications", Ed. By T. Mang and W. Dresel, by Wiley- VCH GmbH, Weinheim 2001.
- this invention relates to:
- M is a Group 8 metal; preferably Ru or Os, preferably Ru;
- Xl and X2 are, independently, any anionic ligand (preferably halogen, an alkoxide or an alkyl sulfonate), or X ⁇ and X2 may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
- L is a heteroatom or heteroatom-containing ligand; preferably the heteroatom is N, O, P, or S; preferably P, optionally L may be joined to R 7 and/or R 8 , preferably L is L*(R) q . 1 when L is not bound to R 7 or R 8 or L is L*(R) q _ 2 when L is bound to R 7 or R 8 , where q is 1 , 2, 3, or 4 depending on the valence of L* (which may be 2, 3, 4, or 5) and L* is N, O, P, or S, (preferably P) and R is as defined for R 3 ;
- R2, R3, R4, R5, R6, R7, and Rg are, independently, hydrogen or a C to C30 substituted or unsubstituted hydrocarbyl;
- any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
- R j and R2 are dissimilar to each other.
- R ⁇ is an aromatic hydrocarbyl or substituted hydrocarbyl and R2 is an aliphatic hydrocarbyl or substituted hydrocarbyl, (preferably R j is a substituted or unsubstituted Cg to C 3 Q aryl, and R2 is a C j to C30 substituted or unsubstituted alkyl, preferably C3 to C30 substituted or unsubstituted alkyl, preferably C 4 to C 30 substituted or unsubstituted alkyl, C 5 to C 30 substituted or unsubstituted alkyl, C 6 to C 30 substituted or unsubstituted alkyl).
- the metathesis catalyst compound comprises one or more of: 2-(i-propoxy)-5-(N,N-dimethylaminosulfonyl)phenylmethylene(l- cyclohexylmethyl-3-(2,6-diisopropylphenyl)-4,5-dihydro- lH-imidazole) ruthenium (II) chloride, (l-mesityl-3-methyl-2H-4,5-dihydroimidazol-2-ylidene)(tricyclohexylphosphine)-3- phenyl-lH-inden-l-ylidene ruthenium (II) dichloride, and mixtures thereof.
- a process to produce alpha-olefm comprising contacting a feed material (such as a feed oil) with the catalyst compound of any of paragraphs 1 to 9.
- the feed material is selected from the group consisting of canola oil, corn oil, soybean oil, rapeseed oil, algae oil, peanut oil, mustard oil, sunflower oil, tung oil, perilla oil, tall oil, grapeseed oil, linseed oil, saffiower oil, pumpkin
- a process to produce alpha-olefm comprising contacting a triacylglyceride with an alkene and the catalyst compound of any of paragraphs 1 to 9, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
- a process to produce alpha-olefm comprising contacting an unsaturated fatty acid with an alkene and the catalyst compound of any of paragraphs 1 to 9, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
- a process to produce alpha-olefm comprising contacting a triacylglyceride with the catalyst compound of any of paragraphs 1 to 9, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
- a process to produce alpha-olefm comprising contacting an unsaturated fatty acid ester and or unsaturated fatty acid alkyl ester with an alkene and the catalyst compound of any of paragraphs 1 to 9, preferably wherein the alpha olefin produced has at least one more carbon atom than the alkene.
- R a , R b , and R c each, independently, represent a saturated or unsaturated hydrocarbon chain.
- a process to produce C 4 to C 2 4 linear alpha-olefm comprising contacting a feed material with an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene, decene, and mixtures thereof and a metathesis catalyst compound of any of paragraphs 1 to 10, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from seed oil.
- an alkene selected from the group consisting of ethylene, propylene butene, pentene, hexene, heptene, octene, nonene, decene, and mixtures thereof and a metathesis catalyst compound of any of paragraphs 1 to 10, wherein the feed material is a triacylglyceride, fatty acid, fatty acid alkyl ester, and/or fatty acid ester derived from
- Et is ethyl
- Me is methyl
- Ph is phenyl
- Cy is cyclohexyl
- THF is tetrahydrofuran
- MeOH is methanol
- DCM is dichloromethane
- TLC thin layer chromatography
- a sample of the metathesis product will be taken and analyzed by GC.
- An internal standard usually tetradecane, is used to derive the amount of metathesis product that is obtained.
- the amount of metathesis product is calculated from the area under the desired peak on the GC trace, relative to the internal standard.
- Yield is reported as a percentage and is generally calculated as 100 x [micromoles of metathesis products obtained by GC]/[micromoles of feed material weighed into reactor].
- Selectivity is reported as a percentage and was calculated as 100 x [area under the peak of desired metathesis products]/[sum of peak areas of cross-metathesis and the homometathesis products].
- TON Catalyst turnovers
- the metathesis of methyl oleate with ethylene will yield cross-metathesis products of 1-decene and methyl-9-decenoate.
- the methyl oleate may homometathesize to produce small amounts of 9-octadecene, a less desirable product, and l,18-dimethyl-9-octadecenedioate, a second less desirable product. Yield was calculated as 100 x [micromoles of etheno lysis products obtained from the GC]/[micromoles of methyl oleate weighed into reactor].
- 1-decene selectivity is shown as a percentage and was calculated as 100 x [GC peak area of 1-decene & methyl-9- decenoate]/[sum of GC peak areas of 1-decene, methyl-9-decenoate, and the homometathesis products, 9-octadecene, and l,18-dimethyl-9-octadecenedioate].
- Catalyst turnovers for production of the 1-decene was calculated as the [micromoles of 1-decene obtained from the gas chromatograph]/([micromoles of catalyst].
- Products were analyzed by gas chromatography (Agilent 6890N with auto-injector) using helium as a carrier gas at 38 cm/sec.
- a column having a length of 60 m(J & W Scientific DB-1, 60 m x 0.25 mm I.D.x 1.0 ⁇ film thickness) packed with a flame ionization detector (FID), an Injector temperature of 250°C, and a Detector temperature of 250°C were used.
- FID flame ionization detector
- Catalyst 1 The ethynolysis of methyl oleate was used as a test to determine the activity of the (l-mesityl-3-methyl-2H-4,5-dihydroimidazol-2-ylidene)(tricyclohexylphosphine)-3- phenyl-lH-inden-l-ylideneruthenium(II) dichloride complex (Catalyst 1). A 0.120 mM stock solution was made by dissolving Catalyst 1 in dichloromethane.
- Methyl oleate (0.87g, 1.0 mL), Catalyst 1 stock solution (125 nmol, 1.04 mL), dichloromethane (2.91 mL) and of tetradecane (0.152 g, used as an internal standard) were weighed out and then placed in a Fisher-Porter bottle equipped with a stir bar. The Fisher-Porter bottle was then filled with ethylene to 150 psig and placed in an oil bath heated to 40°C for 3 hours. The vessel was depressurized and 5 drops of ethyl vinyl ether was added to stop the reaction. A sample was removed and analyzed by GC.
- Comparative Catalyst A Tricyclohexylphosphine[3-phenyl-lH-inden-l-ylidene][l,3- bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II) dichloride
- Comparative Catalyst A Tricyclohexylphosphine[3-phenyl-lH-inden-l-ylidene][l,3- bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene]ruthenium(II) dichloride
- Comparative Catalyst A is a symmetrical annolog of Catalyst 1 and was purchased from Strem Chemicals. The structure of Comparative Catalyst A is shown below.
- Comparative Catalyst A stock solution (94.4 nmol, 0.679 mL), dichloromethane (3.12 mL), methyl oleate (0.87g, 1.0 mL) and tetradecane (0.152 g, used as an internal standard) were weighed out and then placed in a Fisher-Porter bottle equipped with a stir bar. The Fisher-Porter bottle was filled with 150 psig of ethylene and heated to 40°C for 3 hours. A sample was removed and analyzed by GC. The results of the ethenolysis reactions are as follows:
- the inventors have surprisingly discovered that by replacing one of the mesityl groups on the nitrogen of the NHC ligand ligated to the ruthenium alkylidene, as in Catalyst 1 above, the activity increased substantially as depicted by increased turnover numbers in excess of five-fold, with a corresponding increase in yield.
Abstract
Description
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CN112898160B (en) * | 2021-01-25 | 2021-09-24 | 南京工业大学 | Vegetable oil polyalcohol, preparation method and application thereof in polyurethane material |
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Publication number | Publication date |
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WO2011056874A2 (en) | 2011-05-12 |
BR112012010894A2 (en) | 2020-12-15 |
EP2498908A4 (en) | 2013-08-14 |
WO2011056874A3 (en) | 2011-10-06 |
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