COMPOSITION OF METATIZED NATURAL OIL, AS WELL AS ITS USE IN FORMULATION AND METHOD OF PRODUCTION

专利摘要:
compositions of natural oil metathesis. the present invention relates to a metatized natural oil composition comprising (i) a mixture of olefins and/or esters, or (ii) a metatized natural oil. the metatized natural oil composition has a number average molecular weight in the range of about 100 g/mol to about 150,000 g/mol, a weight average molecular weight in the range of about 1,000 g/mol to about 100,000 g/mol , a z-average molecular weight in the range of about 5,000 g/mol to about 1,000,000 g/mol and a polydispersity index of about 1 to about 20. The metatized natural oil composition is metatized at least once .
公开号:BR112014032139B1
申请号:R112014032139-6
申请日:2013-06-20
公开日:2021-08-03
发明作者:Steven A. Cohen；M. Michelle Morie-Bebel；Alexander D. Ilseman；Benjamin Bergmann；Stephen A. Dibiase；Alexander S. Christensen
申请人:Wilmar Trading Pte Ltd；
IPC主号:

专利说明:

Cross Reference to Related Orders
[001] This application claims the benefit of United States Provisional Patent Application No. 61/662,318, filed June 20, 2012 and United States Provisional Patent Application No. 61/781,892, filed March 14 of 2013; the respective descriptions are fully incorporated into this document by this citation. Background
[002] In recent years, the demand for environmentally friendly techniques for manufacturing materials typically derived from petroleum sources has increased. Due to the non-renewable nature of petroleum, it is highly desirable to provide alternatives other than petroleum for the manufacture of biofuels, waxes, plastics, cosmetics, personal care items, and such materials. One of the methods for manufacturing these materials is to create compositions through the metathesis of raw materials derived from natural oil, such as vegetable oils and seed oils. Brief Description of Drawings
[003] This application claims the benefit of United States Provisional Patent Application No. 61/662,318, filed June 20, 2012 and United States Provisional Patent Application No. 61/781,892, filed March 14 of 2013; the respective descriptions are fully incorporated into this document by this citation.
[004] Figure 1 represents a schematic diagram of a process for the production of a metatized natural oil product and a transesterified product from a natural oil.
[005] Figure 2 represents a mass spectrum of a metatized natural oil product.
[006] Figure 3 represents a mass spectrum of a metatized natural oil product.
[007] Figure 4 represents a mass spectrum of a metatized natural oil product.
[008] Figure 5 represents a mass spectrum of a metatized natural oil product.
[009] Figure 6 represents a gel permeation chromatogram of metatized natural oil products.
[010] Figure 7 represents the dynamic viscosity as a function of time for the metatized natural oil products.
[011] Figure 8 represents a layer of the gel permeation chromatogram of kinetic studies of metatized natural oil products.
[012] Figure 9 represents viscosity as a function of the combination of two different products of metatized natural oil.
[013] Figure 10 represents the kinetics of metatized natural oil products.
[014] Figure 11 represents a layer of the gel permeation chromatogram of kinetic studies of metatized natural oil products.
[015] Figure 12 represents a layer of the gel permeation chromatogram of kinetic studies of metatized natural oil products.
[016] Figure 13 represents a gel permeation chromatogram of a metatized natural oil product.
[017] Figure 14 represents a gel permeation chromatogram of a metatized natural oil product.
[018] Figure 15 represents a gel permeation chromatogram of a metatized natural oil product.
[019] Figure 16 represents a gel permeation chromatogram of a metatized natural oil product. Detailed Description
[020]Note that, unless otherwise specified herein, references to "a", "an", "the" and/or "a" may include one or more than one, and the reference a singular item can also include the plural item.
[021] The terms "natural oils", "natural raw materials", or "natural oil-derived raw materials" may be a reference to oils derived from plant or animal sources. The term "natural oil" includes derivatives of natural oil, unless otherwise indicated. Terms also include modified plant or animal sources (eg, genetically modified plant or animal sources), unless otherwise indicated. Examples of natural oils include, but are not limited to, vegetable oils, seaweed oils, fish oils, animal fats, oily wood residues, derivatives and combinations of any of the aforementioned oils, and the like. Representative non-limiting examples of vegetable oils include canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, saffron oil, sesame oil, soybean oil (“OFS”), sunflower oil, linseed oil, palm seed oil, tung oil, jatropha oil, mustard oil, thlaspi oil, camelina oil, and castor oil. Representative non-limiting examples of animal fats include lard, tallow, poultry fat, yellow grease, and fish oil. Oily wood residues are by-products of the way pulp manufacture.
[022] The term “derived from natural oil” refers to products derived from natural oil. Methods used to form natural oil derivatives may include one or more of addition, neutralization, overbasing (excess base), saponification, transesterification, esterification, amidification, hydrogenation, isomerization, oxidation, alkylation, acylation, sulfurization, sulfonation, rearrangement , reduction, fermentation, pyrolysis, hydrolysis, liquefaction, anaerobic digestion, hydrothermal processing, gasification or a combination of two or more cited methods. Examples of its natural derivatives may include carboxylic acids, gums, phospholipids, refining sludge, acidulated refining sludge, distilled or undistilled sludge, fatty acids, fatty acid esters, as well as hydroxy substituted variations, including unsaturated polyol esters. In some embodiments, the natural oil derivative can comprise an unsaturated carboxylic acid having about 5 to about 30 carbon atoms, one or more carbon-carbon double bonds in the hydrocarbon (alkene) chain. The natural oil derivative may further comprise an alkyl (e.g. methyl) ester of an unsaturated fatty acid derived from a glyceride of the natural oil. For example, the natural oil derivative may be a fatty acid methyl ester ("FAME") derived from the glyceride of the natural oil. In some embodiments, a feedstock includes canola or soybean oil, as a non-limiting example, refined, bleached, and deodorized soybean oil (i.e., RBD soybean oil).
[023] The term “low molecular weight olefin” can refer to any one or combination of straight chain, branched or cyclic unsaturated hydrocarbons in the range of C2 to C14. Low molecular weight olefins include "alpha-olefins" or "terminal olefins" in which the unsaturated carbon-carbon bond is present at one end of the compound. Low molecular weight olefins can further include dienes or trienes. Examples of low molecular weight olefins in the C2 to C6 range include, without limiting effect: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1- butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1- pentene, 4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. Other possible low molecular weight olefins include styrene and vinyl cyclohexane. In certain embodiments, it is preferable to use a blend of olefins, the blend comprising linear and branched low molecular weight olefins in the C4-C10 range. In one embodiment, it may be preferable to use a mixture of linear and branched C4 olefins (i.e., combinations of: 1-butene, 2-butene, and/or isobutene). In other modalities, the range C11-C14 can be used.
[024] The term "metathesis monomer" refers to a single entity that is the product of a metathesis reaction comprising a molecule of a compound with one or more carbon-carbon double bonds that has undergone exchange of the alkylidene unit through a or more of the carbon-carbon double bonds, within the molecule (intramolecular metathesis) and/or with a molecule of another compound containing one or more carbon-carbon double bonds, such as an olefin (intermolecular metathesis).
[025] The term "metathesis dimer" refers to the product of a metathesis reaction in which two precursor reactant compounds, which may be the same or different and each with one or more carbon-carbon double bonds, are bonded together. by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of the metathesis reaction.
[026] The term "metathesis trimer" refers to the product of one or more metathesis reactions in which three molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the trimer containing three bonded groups derived from the precursor reactant compounds.
[027] The term "metathesis tetramer" refers to the product of one or more metathesis reactions in which four molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the tetramer containing four bonded groups derived from the precursor reactant compounds.
[028] The term "metathesis pentamer" refers to the product of one or more metathesis reactions in which five molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the pentamer containing five bonded groups derived from the precursor reactant compounds.
[029] The term "metathesis hexamer" refers to the product of one or more metathesis reactions in which six molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the hexamer containing six bonded groups derived from the precursor reactant compounds.
[030] The term "metathesis heptamer" refers to the product of one or more metathesis reactions in which seven molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the heptamer containing seven bonded groups derived from the precursor reactant compounds.
[031] The term "metathesis octamer" refers to the product of one or more metathesis reactions in which eight molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the octamer containing eight bonded groups derived from the precursor reactant compounds.
[032] The term "metathesis non-namer" refers to the product of one or more metathesis reactions in which nine molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the nonamer containing nine bonded groups derived from the precursor reactant compounds.
[033] The term "metathesis decamer" refers to the product of one or more metathesis reactions in which ten molecules of two or more precursor reactant compounds, which may be the same or different and each with one or more carbon double bonds -carbon, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the decamer containing ten bonded groups derived from the precursor reactant compounds.
[034] The term "metathesis oligomer" refers to the product of one or more metathesis reactions in which two or more molecules (for example, 2 to about 10, or 2 to about 4) of two or more reactant compounds precursors, which can be the same or different and each with one or more carbon-carbon double bonds, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more reactions of metathesis, the oligomer containing some (for example, 2 to about 10, or 2 to about 4) attached groups derived from the precursor reactant compounds. In some embodiments, the term "metathesis oligomer" may include metathesis reactions in which more than ten molecules of two or more precursor reactant compounds, which may be the same or different, and each with one or more carbon-carbon double bonds, are linked together by one or more of the carbon-carbon double bonds in each of the precursor reactant compounds as a result of one or more metathesis reactions, the oligomer containing more than ten bonded groups derived from the precursor reactant compounds.
[035] As used herein, the terms "metatize" and "metathesis" may refer to the reaction of a natural oil raw material in the presence of a metathesis catalyst to form a metatized natural oil product comprising a new compound and/or olefinic esters. Metathesis can refer to cross metathesis (also known as cometathesis), autometathesis, ring-opening metathesis, polymerizations by ring-opening metathesis ("ROMP"), ring closing metathesis ("RCM"), and diene metathesis acyclic (“ADMET”). As a non-limiting example, metathesis can refer to the reaction of two triglycerides present in a natural raw material (autometathesis) in the presence of a metathesis catalyst, where each triglyceride has an unsaturated carbon-carbon double bond, thus forming an oligomer that has a new mixture of olefins and esters which may comprise one or more of: metathesis monomers, metathesis dimers, metathesis trimers, metathesis tetramers, metathesis pentamers, and higher order metathesis oligomers (eg metathesis hexamers, metathesis, metathesis heptamers, metathesis octamers, metathesis nonamers, metathesis decamers, superior to and above metathesis decamers).
[036] Metathesis is a catalytic reaction generally known in the art that involves the exchange of alkylidene units between compounds containing one or more double bonds (eg, olefinic compounds) through the formation and cleavage of carbon-carbon double bonds. Metathesis can occur between two identical molecules (often called autometathesis) and/or between two different molecules (often called cross metathesis). Autometathesis can be represented schematically by Equation A below. Equation A R1-CH=CH-R2+ R1-CH=CH-R2 θ R1-CH=CH-R1 + R2-CH=CH-R2 wherein R1 and R2 are organic groups. Cross metathesis can be represented schematically by Equation B below. Equation B R1-CH=CH-R2+ R3-CH=CH-R4 θ R1-CH=CH-R3 + R1-CH=CH-R4 + R2-CH=CH-R3 + R2-CH=CH-R4 + R1 -CH=CH-R1+ R2-CH=CH-R2+ R3-CH=CH-R3+ R4-CH=CH-R4 wherein R1, R2, R3, and R4 are organic groups.
[037] The metathesis reaction of the raw material of natural oil with polyol esters (of fatty acids) results in oligomerization of the raw material of natural oil that has a mixture of olefins and esters that may comprise one or more of: monomers of metathesis, metathesis dimers, metathesis trimers, metathesis tetramers, metathesis pentamers, and higher metathesis oligomers (eg, metathesis hexamers, metathesis heptamers, metathesis octamers, metathesis nomers, metathesis detamers beyond metathesis of the metathesis decamers).
[038]Natural oils of the type described here are typically composed of fatty acid triglycerides. These fatty acids can be saturated, monounsaturated or polyunsaturated and contain variable chain lengths between C8 and C30. The most common fatty acids include saturated acids such as lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), and lignoceric acid (acid tetracosanoic); unsaturated acids include fatty acids as palmitoleic (a C16 acid), and oleic acid (a C18 acid); Polyunsaturated acids include fatty acids such as linoleic acid (a C18 di-unsaturated acid), linolenic acid (a C18 tri-unsaturated acid), and arachidonic acid (a C20 tetraunsaturated acid). Natural oils are also made up of esters of these fatty acids randomly positioned at three sites on the trifunctional glycerin molecule. Different natural oils will exhibit different proportions of these fatty acids, with a given natural oil having a variation between such acids, in addition to depending on factors such as the place of growth of the vegetable or crop, maturity of the vegetable or crop, climate during the season. growth, etc. Therefore, it is difficult for a given natural oil to have a unique or specific structure, as the structure typically occurs as a function of some statistical mean. For example, soybean oil contains a mixture of stearic acid, oleic acid, linoleic acid, and linolenic acid in a ratio of 15:24:50:11, and an average number of double bonds of 4.4-4.7 per triglyceride. One method of quantifying the number of double bonds is the iodine value (IV) which is defined as the number of grams of iodine that will react with 100 grams of vegetable oil. Thus, for soybean oil, the iodine value is in the average range of 120-140. Soybean oil may comprise about 95% by weight or above this value (e.g. 99% by weight or above this value) of fatty acid triglycerides. The main fatty acids in soy oil polyol esters include saturated acids, as a non-limiting example, palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and unsaturated acids, as a non-limiting example, oleic acid (9- octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), and linolenic acid (9, 12, 15-octadecatrienoic acid).
[039] When a polyol ester comprises molecules with more than one carbon-carbon double bond, autometathesis can result in oligomerization or polymerization of the unsaturated in the starting material. For example, Equation C represents the oligomerization of metathesis of a representative species (eg, a polyol ester) with more than one carbon-carbon double bond. In Equation C, the autometathesis reaction results in the formation of metathesis dimers, metathesis trimers, and metathesis tetramers. Although not shown, higher oligomers such as pentamers, hexamers, heptamers, octamers, nomers, decamers, superior to the metathesis decamers, and mixtures of two or more of them, can also be formed. The number of groups or repeating units of metathesis in the metatized natural oil can range from 1 to about 100, or from 2 to about 50, or from 2 to about 30, or from 2 to about 10, or from 2 to about 4. The molecular weight of the metathesis dimer may exceed the molecular weight of the unsaturated polyol ester that gave rise to the dimer. Each of the linked polyol ester molecules may be termed a "group or repeating unit". Typically, a metathesis trimer can be formed by cross-metathesis of a metathesis dimer with an unsaturated polyol ester. Typically, a metathesis tetramer can be formed by the cross metathesis of a metathesis trimer with an unsaturated polyol ester or formed by the cross metathesis of two metathesis dimers. Equation C R1-HC=CH-R2-HC=CH-R3 + R1-HC=CH-R2-HC=CH-R3 θ R1-HC=CH-R2-HC=CH-R2-HC=CH-R3 + (other products) (metathesis dimer) R1-R2-HC=CH-R2-HC=CH-R3 + R1-HC=CH-R2-HC=CH-R3 θ R1-HC=CH-R2-HC=CH -R2-HC=CH-R2-HC=CH-R3 + (other products) (trimer of metathesis) R1-HC=CH-R2-HC=CH-R2-HC=CH-R2-HC=CH-R3 + R1-HC=CH-R2-HC=CH-R3 θ R1-HC=CH-R2-HC=CH-R2-HC=CH-R2-HC=CH-R2-HC=CH-R3 + (other products) (metathesis tetramer) where R1, R2, and R3 are organic groups.
[040]As noted, the autometathesis of natural oil occurs in the presence of a metathesis catalyst. As stated above, the term "metathesis catalyst" includes any catalyst or catalytic system that catalyzes a metathesis reaction. Any known metathesis catalyst can be used, separately or in combination with one or more additional catalysts. Suitable homogeneous metathesis catalysts include combinations of a transition metal halide or oxo-halide (eg WOCl4 or WC16) with an alkylating cocatalyst (eg Me4Sn), or alkylidene (or carbene) complexes of transition metals, particularly Ru, Mo, or W. These include first and second generation Grubbs catalysts, Grubbs-Hoveyda catalysts, and the like. The general structure of alkylidene catalysts is: M[X1X2L1L2(L3)n]=Cm=C(R1)R2 where M is a Group 8 transition metal, L1, L2, and L3 are electron-donating neutral ligands, n is 0 (so that L3 may not be present) or 1, m is 0, 1, or 2, X1 and X2 are anionic linkers, and R1 and R2 are independently selected from H, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, hydrocarbyl containing substituted heteroatom, and functional groups. Two or more of X1, X2, L1, L2, L3, R1 and R2 can form a cyclic group and any one of these groups can be attached to a support.
[041] First generation Grubbs catalysts are in this category, where m=n=0 and particular choices are made for n, X1, X2, L1, L2, L3, R1 and R2 as described in the Patent Application Publication of United States No. 2010/0145086, whose teachings regarding all metathesis catalysts are incorporated herein by means of this citation.
[042] The second generation Grubbs catalysts also have the general formula described above, however, L1 is a carbene ligand where the carbon of the carbene is flanked by N, O, S, or P atoms, preferably by two N atoms. Typically, the carbene linker is part of a cyclic group. Examples of suitable second generation Grubbs catalysts are also found in publication '086.
[043] In another class of suitable alkylidene catalysts, L1 is a strong coordinating neutral electron donor as with the first and second generation Grubbs catalysts, and L2 and L3 are weakly coordinating neutral electron donor ligands in the form of groups optionally substituted heterocyclics. Thus, L2 and L3 are pyridine, pyrimidine, pyrrole, quinoline, thiophene, or similar substances.
[044] In yet another class of suitable alkylidene catalysts, a pair of substituents is used to form a tridentate bidentate linker, such as a bisphosphine, dialkoxide or alkyldiketone. Grubbs-Hoveyda catalysts are a subgroup of this type of catalyst in which L2 and R2 are linked. Typically, a neutral oxygen or nitrogen is coordinated with the metal while bonding to a carbon that is α-, β-, or y- relative to the carbene carbon to provide the bidentate ligand. Examples of suitable Grubbs-Hoveyda catalysts are found in publication '086.
[045] The following structures provide just a few illustrations of suitable catalysts that can be used:

[046]Heterogeneous catalysts suitable for use in the autometathesis or cross-metathesis reaction include certain rhenium and molybdenum compounds as described, for example, by J.C. Mol in Green Chem. 4 (2002) 5 pages 11-12. Particular examples are catalytic systems that include Re2O7 on alumina promoted by an alkylating cocatalyst, such as a tin-lead tetraalkyl compound, germanium or silicon. Other examples include MoCl3 or MoCl5 on tetraalkyltin activated silica.
[047] For other examples of catalysts suitable for autometathesis or cross metathesis, see U.S. Patent Nos. 4,545,941, 5,312,940, 5,342,909, 5,710,298, 5,728,785, 5,728,917, 5,750,815 , 5,831,108, 5,922,863, 6,306,988, 6,414,097, 6,696,597, 6,794,534, 7,102,047, 7,378,528, and United States Patent Application Publication No. 2009/0264672 A1, and PCT/US2008/009635, pp. 18-47, all of which are incorporated herein by this citation. Several potentially advantageous metathesis catalysts employed in metathesis reactions are manufactured and sold by Materia, Inc. (Pasadena, California).
[048] A process for metatizing a natural oil and treating the resulting metatized natural oil is illustrated in Figure 1. In certain embodiments, prior to the metathesis reaction, a raw material of the natural oil can be treated to produce the most suitable natural oil for the subsequent metathesis reaction. In one embodiment, natural oil treatment involves the removal of catalytic poisons, such as peroxides, which can potentially reduce the activity of the metathesis catalyst. Non-limiting examples of natural oil feedstock treatment methods to decrease catalytic poisons include those described in PCT/US2008/09604, PCT/US2008/09635, and in U.S. Patent Applications No. 12/672,651 and 12/672,652, incorporated herein in their entirety by means of this reference. In certain embodiments, the raw material of natural oil is heat-treated by heating the raw material to a temperature above 100°C in the absence of oxygen, and maintaining this temperature long enough to reduce catalytic poisons in the raw material. . In other embodiments, the temperature is between approximately 100°C and 300°C, between approximately 120°C and 250°C, between approximately 150°C and 210°C, or between approximately 190 and 200°C. In one embodiment, the absence of oxygen is achieved by bubbling the natural oil feedstock with nitrogen, where nitrogen gas is pumped into the feedstock treatment vessel at a pressure of approximately 10 atm (150 psig).
[049] In certain embodiments, the raw material of the natural oil is chemically treated under conditions sufficient to reduce the catalytic poisons in the raw material through a chemical reaction of the catalytic poisons. In certain embodiments, the raw material is treated with a reducing agent or an inorganic cation base composition. Non-limiting examples of reducing agents include bisulfate, boron hydride, phosphine, thiosulfate, and combinations thereof.
[050] In certain embodiments, the raw material of natural oil is treated with an adsorbent to remove catalytic poisons. In one modality, the raw material is treated with a combination of thermal and adsorbent methods. In another modality, the raw material is treated with a combination of chemical and adsorbent methods. In another modality, the treatment involves a partial hydrogenation treatment to modify the reactivity of the natural oil raw material with the metathesis catalyst. Other non-limiting examples of raw material treatment are also described below during the discussion of various metathesis catalysts.
[051] Additionally, in certain embodiments, the low molecular weight olefin can also be treated prior to the metathesis reaction. Like natural oil treatment, low molecular weight olefin can be treated to remove poisons that can impact or reduce catalytic activity.
[052] As shown in Figure 1, after this optional raw material treatment of natural oil and/or low molecular weight olefin, natural oil 12 is reacted with itself, or combined with a low molecular weight olefin 14 in one metathesis reactor 20 in the presence of a metathesis catalyst. In some embodiments, natural oil 12 is soybean oil. Metathesis catalysts and metathesis reaction conditions are discussed in more detail below. In certain embodiments, in the presence of a metathesis catalyst, the natural oil 12 undergoes an autometathesis reaction with itself. In other embodiments, in the presence of the metathesis catalyst, the natural oil 12 is subjected to a metathesis cross-reaction with the low molecular weight olefin 14. In certain embodiments, the natural oil 12 is subjected to autometathesis and cross-metathesis reactions in parallel metathesis reactors. Multiple, parallel or sequential (at least one or more times) metathesis reactions can be performed. The autometathesis and/or cross-metathesis reaction forms a metatized natural oil product 22 wherein the metatized natural oil product 22 comprises olefins 32 and esters 34. In some embodiments, the metatized natural oil product 22 is metatized soybean oil (OFSM). As used herein, "metastatic natural oil product" may also refer to "metastatic natural oil composition".
[053] In certain embodiments, the low molecular weight olefin 14 is in the range C2 to C6. As a non-limiting example, in one embodiment, the low molecular weight olefin 14 can comprise at least one of the following: ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentene, 1-hexene, 2-hexene, 3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene . In another embodiment, the low molecular weight olefin 14 comprises at least styrene and/or vinyl cyclohexane. In another embodiment, the low molecular weight olefin 14 can comprise at least one of ethylene, propylene, 1-butene, 2-butene, and isobutene. In another embodiment, the low molecular weight olefin 14 comprises at least one alpha-olefin or terminal olefin in the range C2 to C10.
[054] In another embodiment, the low molecular weight olefin 14 comprises at least one branched low molecular weight olefin in the range C4 to C10. Non-limiting examples of low molecular weight branched olefins include isobutene, 3-methyl-1-butene, 2-methyl-3-pentene, and 2,2-dimethyl-3-pentene. With the use of low molecular weight branched olefins in the metathesis reaction, the metatized natural oil product will include branched olefins, which can be further hydrogenated to isoparaffins. In certain embodiments, low molecular weight branched olefins can serve to obtain the desired performance properties for a fuel composition, such as jet fuel, kerosene or diesel.
[055] As noted, it is possible to use in the reaction a mixture of several linear or branched olefins of low molecular weight to obtain the distribution of the product of the desired metathesis. In one embodiment, a mixture of butenes (1-butene, 2-butenes, and, optionally, isobutene) can be employed as a low molecular weight olefin, offering a low cost commercially available raw material in place of a purified source of a particular butene. Low cost raw materials mixed with butene are typically diluted with n-butane and/or isobutane.
[056] In certain embodiments, recycled streams from the downstream separation units can be introduced into the metathesis reactor 20 in addition to the natural oil 12 and, in some embodiments, the low molecular weight olefin 14. For example, in some embodiments, a C2C6 recycle olefin stream or a C3-C4 bottom stream from an aerial separation unit may be returned to the metathesis reactor. In one embodiment, as shown in Figure 1, a low molecular weight olefin stream 44 from an olefin separation unit 40 may be returned to the metathesis reactor 20. In another embodiment, the bottom stream C3-C4 is the Low molecular weight olefin stream 44 are combined together and returned to metathesis reactor 20. In another embodiment, a C15+ bottom stream 46 from olefin separation unit 40 is returned to metathesis reactor 20. In another embodiment, all the mentioned recycling streams are returned to the metathesis reactor 20.
[057] The metathesis reaction in the metathesis reactor 20 produces a metatized natural oil product 22. In one embodiment, the metatized natural oil product 22 enters an evaporation vessel operated under temperature and pressure conditions designed to evaporate and remove aerially compounds C2 or C2-C3. The C2 or C2-C3 light ends are mostly formed of hydrocarbon compounds with carbon numbers 2 or 3. In certain embodiments, the C2 or C2-C3 light ends are then sent to an air separation unit, where the C2 or C2 compounds -C3 are also separated aerially from the heavier compounds that evaporated along with the C2-C3 compounds. These heavier compounds are typically airborne C3-C5 compounds along with the C2 or C2-C3 compounds. After separation in the air separation unit, air stream C2 or C2-C3 can then be used as a fuel source. These hydrocarbons have their own value beyond the scope of a fuel composition and can be used or separated at this stage for other valuable compositions and applications. In certain embodiments, the bottom stream from the air separation unit containing primarily C3-C5 compounds is returned as a recycle stream to the metathesis reactor. In the evaporation vessel, the metamatized natural oil product 22 that does not air evaporate is sent downstream for separation in a separation unit 30, such as a distillation column.
[058] Prior to the separation unit 30, in certain embodiments, the metatized natural oil product 22 may be introduced into an adsorbent bed to facilitate the separation of the metatized natural oil product 22 from the metathesis catalyst. In one embodiment, the adsorbent is a bed of clay. The clay bed will adsorb the metathesis catalyst, and after a filtration step, the metatized natural oil product 22 can be sent to the separation unit 30 for further processing. Separation unit 30 may comprise a distillation unit. In some modalities, the distillation can be carried out, for example, removing, by means of steam drag, the product from the metatized natural oil. Distillation can be performed by bubbling the mixture into a typically agitated vessel, contacting the mixture with a gaseous stream in a column that may contain typical distillation fillings (eg, random or structured), by vacuum distillation, or by evaporating light ones in an evaporator, such as a thin-film evaporator. Typically, steam stripping will be conducted at reduced pressure and at temperatures between 100°C and 250°C. The temperature may depend, for example, on the degree of vacuum used, where the higher vacuum allows for a lower temperature and a more efficient and complete separation of volatile substances.
[059] In another modality, the adsorbent is a water-soluble phosphine reagent such as tris hydroxymethyl phosphine (THMP). The catalyst can be separated with a water-soluble phosphine using known liquid-liquid extraction mechanisms by decanting the aqueous phase from the organic phase. In other embodiments, the metatized natural oil product 22 can be contacted with a precursor reagent to deactivate or extract the catalyst.
[060] In the separation unit 30, in certain embodiments, the metatized natural oil product 22 is separated into at least two product streams. In one embodiment, metatized natural oil product 22 is sent to separation unit 30, or distillation column, to separate olefins 32 from esters 34. In another embodiment, a by-product stream comprising C7 and cyclohexadiene can be removed from the unit separation 30 in a side stream. In certain embodiments, the separated olefins 32 can comprise hydrocarbons with a maximum number of carbons equal to 24. In certain embodiments, the esters 34 can comprise metatized glycerides. In other words, the light olefins 32 are preferably separated or aerially distilled to be processed into olefinic compositions, while the esters 34, basically consisting of compounds with acid/carboxylic ester functionality, are carried in an underflow. Based on the quality of the separation, it is possible that some ester compounds are carried into the overhead olefin stream 32, while it is possible that some heavier olefin hydrocarbons are carried into the ester stream 34.
[061] In one embodiment, 32 olefins can be collected and sold for several known uses. In other embodiments, olefins 32 are further processed in an olefin separation unit 40 and/or hydrogenation unit 50 (where the olefinic bonds are saturated with hydrogen gas 48, as described below). In other embodiments, esters comprising heavier glycerides and free fatty acids are separated or distilled as a bottoms product for further processing to form various products. In certain embodiments, further processing can be aimed at producing the following non-limiting examples: fatty acid methyl esters; biodiesel; 9DA esters, 9UDA esters, and/or 9DDA esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earth metal salts of 9DA, 9UDA, and/or 9DDA; diacids, and/or diesters of transesterified products; and its mixtures. In certain embodiments, further processing can be aimed at producing C15-C18 fatty acids and/or esters. In other embodiments, further processing can be aimed at producing diacids and/or diesters. In additional embodiments, further processing can be aimed at producing compounds with molecular weights greater than the molecular weights of stearic acid and/or linolenic acid.
[062]As shown in Figure 1, with respect to the aerial olefins 32 derived from the separation unit 30, the olefins 32 can be further separated or distilled in the olefin separation unit 40 to separate the various components of the stream. In one embodiment, light olefins 44 primarily formed from C2-C9 compounds can be distilled into an overhead stream from olefin separation unit 40. In certain embodiments, light olefins 44 are mostly formed from C3C8 hydrocarbon compounds. In other embodiments, heavier olefins with higher carbon numbers can be air separated to form the light olefin stream 44 to target a specific fuel composition. The light olefins 44 can be recycled to the metathesis reactor 20, purged from the system for further processing and sold, or a combination of both. In one embodiment, the light olefins 44 can be partially purged from the system and partially recycled to the metathesis reactor 20. Relative to the other streams in the olefin separation unit 40, a heavier stream of compound C16+, C18+, C20+, C22+ , or C24+ can be separated as an olefin 46 bottoms stream. This olefin 46 bottoms stream can be purged or recycled to the metathesis reactor 20 for further processing, or a combination of both. In another embodiment, a central olefin stream 42 can be separated from the olefin distillation unit for further processing. Core olefins 42 can be designed to target a selected carbon number range for a specific fuel composition. As a non-limiting example, a C5-C15 distribution can be targeted for further processing into a naphtha-type jet fuel. Alternatively, a C8-C16 distribution can be targeted for further processing into a kerosene-type jet fuel. In another embodiment, a C8-C25 distribution can be targeted for further processing to form a diesel fuel.
[063] In certain embodiments, 32 olefins can be oligomerized to form poly-alpha-olefins (PAOs) or internal polyolefins (PIOs), mineral oil substitutes, and/or biodiesel fuel. The oligomerization reaction can take place after the distillation unit 30 or after the olefin aerial separation unit 40. In certain embodiments, the by-products of the oligomerization reactions can be recycled back to the metathesis reactor 20 for further processing.
[064] As mentioned, in one embodiment, the olefins 32 coming from the separation unit 30 can be sent directly to the hydrogenation unit 50. In another embodiment, the core olefins 42 coming from the olefin aerial separation unit 40 can be sent to the hydrogenation unit 50. The hydrogenation may be conducted according to any method known in the art for hydrogenating double bond containing compounds, such as olefins 32 or core olefins 42. In certain embodiments, in hydrogenation unit 50, hydrogen gas 48 is reacted with the olefins 32 or core olefins 42 in the presence of a hydrogenation catalyst to produce a hydrogenated product 52.
[065] In some embodiments, olefins are hydrogenated in the presence of a hydrogenation catalyst comprising nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, or iridium, individually or in combinations thereof. Useful catalyst can be heterogeneous or homogeneous. In some embodiments, the catalysts are supported nickel or sponge nickel catalysts.
[066] In some embodiments, the hydrogenation catalyst comprises nickel that has been chemically reduced with hydrogen to the active state (ie, reduced nickel) provided on a support. The support may comprise porous silica (for example kieselguhr, infusorial earth, diatomaceous or silica) or alumina. Catalysts are characterized by a high nickel surface area per gram of nickel.
[067]Commercial examples of supported nickel hydrogenation catalysts include those available under the tradenames "NYSOFACT", "NYSOSEL", and "NI 5248 D" (from BASF Catalysts LLC, Iselin, NJ). Additional nickel supported hydrogenation catalysts include those available under the trade designations "PRICAT 9910", "PRICAT 9920", "PRICAT 9908", "PRICAT 9936" (from Johnson Matthey Catalysts, Ward Hill, MA).
[068] Supported nickel catalysts may be of the type described in United States Patent No. 3,351,566, United States Patent No. 6,846,772, EP 0168091, and EP 0167201, incorporated herein by reference. The hydrogenation can be carried out in batch or in a continuous process, it can be a partial or complete hydrogenation. In certain embodiments, the temperature ranges from about 50°C to about 350°C, about 100°C to about 300°C, about 150°C to about 250°C, or about 100°C at about 150 °C. The desired temperature can vary, for example, with hydrogen gas pressure. Typically, a higher gas pressure will require a lower temperature. Hydrogen gas is pumped into the reaction vessel to obtain the desired H2 gas pressure. In certain embodiments, H2 gas pressure ranges from about 15 psig (1 atm) to about 3000 psig (204.1 atm), about 15 psig (1 atm) to about 90 psig (6.1 atm) , or about 100 psig (6.8 atm) to about 500 psig (34 atm). In certain embodiments, the reaction conditions are "moderate", and the approximate temperature is between about 50°C and about 100°C and the pressure of the H2 gas is less than about 100 psig. In other embodiments, the temperature is between about 100°C and about 150°C, and the pressure is between about 100 psig (6.8 atm) and about 500 psig (34 atm). When the desired degree of hydrogenation is reached, the reaction mass is cooled to the desired filtration temperature.
[069]During hydrogenation, compounds endowed with a carbon-carbon double bond in olefins are partially to fully saturated by hydrogen gas 48. In one embodiment, the resulting hydrogenated product 52 includes hydrocarbons with a centered distribution between about C10 and C12 hydrocarbons. for jet fuel compositions such as kerosene and naphtha. In another modality, the distribution is centered between about C16 and C18 for a diesel fuel composition.
[070] In certain embodiments, based on the quality of the hydrogenated product 52 produced in the hydrogenation unit 50, it may be preferable to isomerize the hydrogenated product from the olefin 52 to assist in obtaining the desired fuel properties, such as flash evaporation point, point freezing temperature, energy density, cetane number, or end-point distillation temperature, among other parameters. Isomerization reactions are well known in the art, as described in U.S. Patent Nos. 3,150,205; 4,210,771; 5,095,169; and 6,214,764, incorporated herein by reference. In one embodiment, the isomerization reaction at this stage can also crack some remaining C15+ compounds, which can help produce a fuel composition containing compounds with the desired carbon number range, such as 5 to 16 for a jet fuel composition.
[071] In certain modalities, isomerization can occur simultaneously with the hydrogenation step in the hydrogenation unit 50, thus obtaining a desired fuel product. In other embodiments, the isomerization step can take place before the hydrogenation step (i.e., the olefins 32 or core olefins 42 can be isomerized before the hydrogenation unit 50). In additional embodiments, it is possible to avoid or reduce the scope of the isomerization step by selecting the low molecular weight olefin(s) used in the metathesis reaction.
[072] In certain embodiments, the hydrogenated product 52 comprises approximately 15-25% by weight of C7, approximately <5% by weight of C8, approximately 20-40% by weight of C9, approximately 20-40% by weight of C10 , approximately <5% by weight C11, approximately 15-25% by weight C12, approximately <5% by weight C13, approximately <5% by weight C14, approximately <5% by weight C15, approximately <1 % by weight of C16, approximately <1% by weight of C17, and approximately <1% by weight of C18+. In certain embodiments, the hydrogenated product 52 comprises a minimum heat of combustion of approximately 40, 41, 42, 43 or 44 MJ/kg (as measured by ASTM D3338). In certain embodiments, the hydrogenated product 52 contains less than about 1 mg of sulfur per kg of the hydrogenated product (as measured by ASTM D5453). In other embodiments, the hydrogenated product 52 comprises an approximate density of 0.70-0.75 (as measured by ASTM D4052). In other embodiments, the hydrogenated product has an approximate final boiling point of 220-240°C (as measured by ASTM D86).
[073] The hydrogenated product 52 produced by the hydrogenation unit 50 can be used as a fuel composition, non-limiting examples include jet fuel, kerosene or diesel. In certain embodiments, the hydrogenated product 52 may contain by-products from the hydrogenation, isomerization and/or metathesis reactions. As shown in Figure 1, the hydrogenated product 52 can be further processed forming a fuel composition separation unit 60, removing any traces of by-products from the hydrogenated product 52, such as hydrogen gas, water, C2-C9 hydrocarbons, or C15+ hydrocarbons , producing an intended fuel composition. In one embodiment, the hydrogenated product 52 can be separated forming the C9-C15 product of the desired fuel 64, and a C2-C96 light fraction 62 and/or a C15+ 66 heavy fraction. Distillation can be used to separate the fractions. Alternatively, in other embodiments, as with a naphtha or kerosene-type jet fuel composition, the heavy fraction 66 can be separated from the desired fuel product 64 by cooling the hydrogenated product 52 to about -40°C, -47 °C, or -65°C, and then removing the heavy solid fraction 66 using methods known in the art, such as filtration, decantation, or centrifugation.
[074] Regarding the esters 34 from the distillation unit 30, in certain embodiments, the esters 34 can be completely removed as a stream from the ester product 36 and then processed or marketed at its own value, as shown in Figure 1. As a non-limiting example, esters 34 can comprise various triglycerides that could be used as a lubricant. Based on the quality of the separation between olefins and esters, the esters 34 may comprise some heavier olefin components carried along with the triglycerides. In other embodiments, the esters 34 can be further processed in a biorefinery or other chemical or fuel processing unit known in the art, thus producing various products such as biodiesel or specialized chemicals of greater value than triglycerides, for example. Alternatively, in certain embodiments, the esters 34 may be partially removed from the system and sold, and the remainder further processed in the biorefinery or other chemical or fuel processing unit known in the art.
[075] In certain embodiments, the ester stream 34 is sent to a transesterification unit 70. In the transesterification unit 70, the esters 34 are reacted with at least one alcohol 38 in the presence of a transesterification catalyst. In certain embodiments, the alcohol comprises methanol and/or ethanol. In one embodiment, the transesterification reaction is conducted on average at 60-70°C and 1 atm. In certain embodiments, the transesterification catalyst is a homogeneous sodium methoxide catalyst. Varying amounts of catalyst can be used in the reaction and, in certain embodiments, the transesterification catalyst is present in the approximate amount of 0.5-1.0% by weight of the esters 34.
[076] The transesterification reaction can produce transesterified products 72 which include methyl esters of saturated and/or unsaturated fatty acid (“FAME”), glycerin, methanol, and/or free fatty acids. In certain embodiments, transesterified products 72, or a fraction thereof, may comprise a source of biodiesel. In certain embodiments, the transesterified products 72 comprise 9DA esters, 9UDA esters, and/or 9DDA esters. Non-limiting examples of 9DA esters, 9UDA esters, and 9DDA esters include methyl 9-decenoate ("9-DAME"), methyl 9-undecenoate ("9-UDAME"), and methyl 9-dodecenoate ("9-DDAME"), respectively. As a non-limiting example, in a transesterification reaction, a 9DA moiety of a metatized glyceride is removed from the glycerol backbone to form a 9DA ester.
[077] In another embodiment, a glycerin alcohol can be used in reaction with a glyceride stream. This reaction can produce monoglycerides and/or diglycerides. In certain embodiments, transesterified products 72 from transesterification unit 70 can be sent to a liquid-liquid separation unit, in which transesterified products 72 (i.e., FAME, free fatty acids, and/or alcohols) are separated from the glycerin. Additionally, in certain embodiments, the glycerin by-product stream may be further processed in a secondary separation unit, where the glycerin is removed and the remaining alcohols are recycled back to transesterification unit 70 for further processing.
[078] In one modality, the transesterified products 72 are further processed in a water washing unit. In this unit, the transesterified products are subjected to a liquid-liquid extraction when washed with water. Excess alcohol, water, and glycerin are removed from the transesterified products 72. In another embodiment, a water wash step is followed by a drying unit where excess water is further removed from the desired mixture of esters (i.e. , specialized chemicals). Such specialized chemical substances include non-limiting examples such as 9DA, 9UDA, and/or 9DDA, alkali metal salts and alkaline earth metal salts of the above, individually or in combinations thereof.
[079] In one embodiment, the specialized chemical (eg, 9DA) can be further processed in an oligomerization reaction to form a lactone, which can serve as a precursor of a surfactant.
[080] In certain embodiments, transesterified products 72 from the transesterification unit 70 or specialized chemicals from the water washing unit or drying unit are sent to an ester distillation column 80 for further separation of several individual compounds or of groups of compounds, as shown in Figure 1. This separation may include, among others, the separation of 9DA esters, 9UDA esters, and/or 9DDA esters. In one embodiment, the 9DA ester 82 can be individually distilled or separated from the rest of the mixture 84 of transesterified products or specialized chemical substances. Under certain process conditions, the 9DA ester 82 must be the lightest component in the specialized chemical or transesterified product stream, and emerge at the top of the ester 80 distillation column. In another embodiment, the remaining mixture 84 or more components heavy transesterified products or specialized chemicals can be separated by the bottom of the column. In certain embodiments, this bottom stream 84 can potentially be marketed in the form of biodiesel.
[081]The 9DA esters, 9UDA esters, and/or 9DDA esters can be further processed after the distillation step in the ester distillation column. In one embodiment, under known operating conditions, the 9DA ester, 9UDA ester, and/or 9DDA ester can be subjected to a hydrolysis reaction with water to form 9DA, 9UDA, and/or 9DDA, alkali metal salts and metal salts alkaline earth of the above, individually or in their combinations.
[082] In certain embodiments, the fatty acid methyl esters from the transesterified products 72 can be reacted with each other to form other specialized chemical substances, such as dimers.
[083]It is possible to carry out the metathesis reaction in multiple and sequential steps. For example, metatized natural oil product can be generated by reacting a natural oil in the presence of a metathesis catalyst to form a first metatized natural oil product. The first metatized natural oil product can then be reacted in an autometathesis reaction to form another metatized natural oil product. Alternatively, the first metastatic natural oil product can be reacted in a cross-metathesis reaction with a natural oil to form another metastatic natural oil product. As an alternative, transesterified products, olefins and/or esters can be further metatized in the presence of a metathesis catalyst. The multi-step and/or sequential metathesis reactions can be performed as often as necessary, and at least one or more times, depending on the processing/composition requirements understood by a person skilled in the art. In some embodiments of a multiple metathesis reaction, the second metathesis or subsequent metathesis will produce a distinguishable product if the composition is changed. For example, if soybean oil is cross-metathesized with a low weight olefin, such as 1-butene, in a first metathesis, in the second metathesis it will produce a higher molecular weight oligomeric mixture if the olefins that were present during the first metathesis have been partially removed before or during the second metathesis. This is generally done by removing the olefins, in this case, from the soybean oil with butene. This “composition transfer” allows another reaction to occur during the second metathesis. In the absence of this transfer, adding more catalyst to an equilibrium system will result in little or no change.
[084] As used herein, a "metastatic natural oil product" may include products that have been metatized once and/or multiple times. These procedures can be used to form metathesis dimers, metathesis trimers, metathesis tetramers, metathesis pentamers, and higher metathesis oligomers (eg, metathesis hexamers, metathesis heptamers, metathesis octamers, metathesis nomers, metathesis, and in addition to the metathesis decamers). Such procedures may be repeated as often as desired (for example, from 2 to about 50 times, or from 2 to about 30 times, or from 2 to about 10 times, or from 2 to about 5 times, or from 2 to about 4 times, or 2 or 3 times) to provide the desired metathesis oligomer or polymer which may comprise, for example, from 2 to about 100 attached groups, or from 2 to about 50, or from 2 to about 30, or 2 to about 10, or 2 to about 8, or 2 to about 6 bonded groups, or 2 to about 4 bonded groups, or 2 to about 3 bonded groups. In certain embodiments, it may be desirable to use metatized natural products produced by cross-metathesis of a natural oil, or combination of natural oils, with a C2-C100 olefin, as a precursor reagent in an autometathesis reaction to produce another natural oil product. metatized. Alternatively, metatized natural products produced by cross-metathesis of a natural oil, or combination of natural oils, with a C2-C100 olefin can be combined with a natural oil, or combination of natural oils, and then metatized to produce another product. metatized natural oil.
[085] The number average molecular weight of the metatized natural oil product may range from about 100 g/mol to about 150,000 g/mol, or from about 300 g/mol to about 100,000 g/mol, or from about 300 g/mol to about 70,000 g/mol, or from about 300 g/mol to about 50,000 g/mol, or from about 500 g/mol to about 30,000 g/mol, or from about from 700 g/mol to about 10,000 g/mol, or from about 1,000 g/mol to about 5,000 g/mol. The weight average molecular weight of the metatized natural oil product can range from about 1,000 g/mol to about 100,000 g/mol, from about 2,500 g/mol to about 50,000 g/mol, from about 4,000 g /mol to about 30,000 g/mol, from about 5,000 g/mol to about 20,000 g/mol, and from about 6,000 g/mol to about 15,000 g/mol. The z-average molecular weight of the metatized natural oil product can range from about 5,000 g/mol to about 1,000,000 g/mol, for example, from about 7,500 g/mol to about 500,000 g/mol, from about 10,000 g/mol to about 300,000 g/mol, or from about 12,500 g/mol to about 200,000 g/mol. The polydispersion index is calculated by dividing the weight average molecular weight by the number average molecular weight. Polydispersion is a measure of the breadth of the molecular weight distribution of the metatized natural oil product, and generally such products exhibit a polydispersion index of from about 1 to about 20, or from about 2 to about 15. The number average molecular weight, weight average molecular weight, and z average molecular weight can be determined by gel permeation chromatography (CPG), gas chromatography, gas chromatography mass spectroscopy, NMR spectroscopy, vapor phase osmometry ( OFV), wet analytical techniques such as acid number, base number, saponification number or oxirane number, and the like. In some embodiments, gas chromatography and gas chromatography mass spectroscopy can be used to analyze the metastatic natural oil product by first transforming the triglycerides into their corresponding methyl esters prior to testing. If the individual triglyceride molecules have been polymerized, it can be understood that there is a direct relationship with the concentration of diester molecules found in the analyzed fatty acid methyl esters. In some embodiments, the molecular weight of the metatized natural oil product can be increased by transesterification of the metatized natural oil product with diesters. In some embodiments, the molecular weight of the metatized natural oil product can be increased by esterifying the metatized natural oil product with diacids. In certain embodiments, the metatized natural oil product has a dynamic viscosity between about 1 centipoise (cP) and about 10,000 centipoise (cP), between about 30 centipoise (cP) and about 5000 cP, between about 50 cP and about 3000 cP, and between about 80 cP and about 1500 cP.
[086] The metathesis process can be conducted under any conditions suitable for producing the desired metathesis products. For example, factors such as stoichiometry, atmosphere, solvent, temperature, and pressure can be selected by a person skilled in the art to produce a desired product and minimize unwanted by-products. The metathesis process can be carried out under an inert atmosphere. Likewise, if a reagent is supplied in gaseous form, an inert gaseous diluent may be used. The inert atmosphere or inert gaseous diluent typically is an inert gas, meaning that the gas does not interact with the metathesis catalyst to substantially impede catalysis. For example, particular inert gases are selected from the group consisting of helium, neon, argon, nitrogen, individually or in combinations thereof.
[087] In certain embodiments, the metathesis catalyst is dissolved in a solvent before carrying out the metathesis reaction. In certain embodiments, the chosen solvent can be selected to be substantially inert to the metathesis catalyst. For example, substantially inert solvents include, without limitation, aromatic hydrocarbons such as benzene, toluene, xylenes, etc.; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic solvents including pentane, hexane, heptane, cyclohexane, etc.; and chlorinated alkanes such as dichloromethane, chloroform, dichloroethane, etc., in a particular embodiment the solvent comprises toluene. The metathesis reaction temperature can be a rate-controlled variable, where the temperature is selected to provide a desired product at an acceptable rate. In certain embodiments, the temperature of the metathesis reaction is above about -40°C, above about -20°C, above about 0°C, or above about 10°C. In certain embodiments, the temperature of the metathesis reaction is below about 150°C, or below about 120°C. In one embodiment, the temperature of the metathesis reaction is between about 10°C and about 120°C.
[088]The metathesis reaction can be conducted at any desired pressure. Typically, it will be desirable to maintain a total pressure high enough to keep the cross-metathesis reagent in solution. Therefore, as the molecular weight of the cross-metathesis reagent increases, the lower pressure range typically decreases as the boiling point of the cross-metathesis reagent increases. The total pressure can be selected to be above about 0.1 atm (10 kPa), in some embodiments above about 0.3 atm (30 kPa), or above about 1 atm (100 kPa). Typically, the reaction pressure is at most about 70 atm (7000 kPa), in some embodiments it is at most about 30 atm (3000 kPa). An example of a non-limiting pressure range for the metathesis reaction is from about 1 atm (100 kPa) to about 30 atm (3000 kPa). In certain embodiments it may be desirable to carry out the metathesis reactions in a reduced pressure atmosphere. Vacuum or reduced pressure conditions can be used to remove olefins as they are generated in a metathesis reaction, thereby directing the metathesis equilibrium towards the formation of less volatile products. In the case of autometathesis of a natural oil, reduced pressure can be used to remove lighter or C12 olefins that include, without limiting effect, hexene, nonene, and dodecene, as well as by-products that include, without limiting effect, cyclohexadiene and benzene such as products of the metathesis reaction. The removal of these species can be used as a way to direct the reaction towards the formation of cross-linked diester and triglyceride groups.
[089] The metatized natural oil compositions described herein can be used independently and/or incorporated into various formulations and used as functional ingredients in dimethicone substitutes, laundry detergents, fabric softeners, personal care applications such as emollients, fixative polymers of hair, rheology modifiers, special conditioning polymers, surfactants, UV absorbers, solvents, humectants, occlusives, film formers, or end-user personal care applications such as cosmetics, lip balms, lipsticks, hair creams, products of sun care, moisturizer, scented sticks, perfume carriers, skin perception agents, shampoos/conditioners, bar soaps, hand soaps/liquids, bubble baths, body fluids, facial cleansers, shower gels, wipes, products for baby cleansers, creams/lotions, and antiperspirants/deodorants.
[090] The metatized natural oil compositions described herein can also be incorporated into various formulations and used as functional ingredients in lubricants, functional fluids, fuels and fuel additives, additives to these lubricants, functional fluids and fuels, plasticizers, asphalt additives, friction reducing agents, antistatic agents in the textile and plastic industries, flotation agents, gelling agents, epoxy curing agents, corrosion inhibitors, pigment wetting agents, in cleaning compositions, plastics, coatings, adhesives, cleaning agents skin perception, film formers, rheological modifiers, release agents, conditioning dispersants, hydrotropes, industrial and institutional cleaning products, oilfield applications, gypsum foamers, sealants, agricultural formulations, compositions for advanced oil recovery, solvent products, gypsum products, gei s, semi-solids, detergents, heavy duty liquid detergents (HDL), light duty liquid detergents (LDL), liquid detergents softeners, antistatic formulations, dryer softeners, hard surface cleaners (HSC) for household utensils, automatic washers, additives rinses, laundry additives, carpet cleaners, detergent softeners (softergents), single-rinse fabric softeners, I&I laundry, stove cleaners, car wash liquids, transport cleaners, drain cleaners, defoamers, defoamers , foam intensifiers, antidust/dust repellents, industrial cleaners, institutional cleaners, service cleaners, glass cleaners, graphite removers, concrete cleaners, metal parts/machinery cleaners, pesticides, agricultural formulations and cleaners for food services, plasticizers, asphalt additives and emulsifiers, reducing agents friction s, film formers, rheological modifiers, biocides, biocide enhancers, release agents, household cleaners, including powder and liquid laundry detergents, liquid and sheet fabric softeners, soft and hard surface cleaners, antiseptics and disinfectants, and industrial cleaning products, emulsion polymerization, including processes for latex manufacturing and for use as surfactants as wetting agents, and in agricultural applications as formulation inerts in pesticide applications or as adjuvants used together with the delivery of pesticides including crop protection peat and ornamental, home and garden, and professional applications, and institutional cleaning products, oilfield applications, including oil and gas transportation, production, drilling and stimulation chemicals, and intensification and formation of reservoir, organoclays for drilling muds, and special pumants to control or disperse foam in the manufacturing process of gypsum, cement wall board, concrete additives and firefighting foams, paints and coalescing agents, paint thickeners, or other applications that need to be performed with tolerance to cold or winterization (for example, applications that need to be run in cold weather without the inclusion of additional volatile components).
[091] The examples and given below are mere illustrations of the invention. It should be noted that its various modifications will be noticed by individuals versed in the technique when reading this descriptive report. Therefore, it is to be understood that the invention disclosed herein includes any modifications that may fall within the scope of the appended claims. EXAMPLES Multiple Metathesis Example
Physical Properties of Metatized Soybean Oil (Samples A, B and C)
Viscosity measurements for Sample C were performed at 40°C. Various fractions of OFSM composition. See Figure 2 and Figure 3 for mass spectral analyses. 1. peak at 368
2. peak at 409
3. Peak at 659
4. peak at 675
5. peak at 797
6. peak at 877.6
7. peak ~919
Metathesis reaction of Triolein (Oleyl Triglyceride) with second-generation Grubbs catalyst
[092] 1 gram of Triolein in a bottle was heated to 45°C under N2 protection. 0.01 gram of Catalyst was added. The reaction was kept at 45°C for 16 hours and cooled with ethyl vinyl ether. The mixture was dissolved in ethyl acetate and filtered through celite. The MS of the resulting samples was tested in a triple quadrupole mass spectrometer with an electrospray ionization source for Micromass Quattro LC. See Figure 4 and Figure 5 for mass spectral analyses. 1. peak at 907
M+Na (23)= 908 M+ K(39)=924 2. peak at 409
M+Na (23)= 391.51 M+ K(39)=407.51 3. Peak at ~655
M+Na (23) = 655.95 M+K (39) =671.95 4. Peak at 1051
M+Na (23) = 1036 M+K (39) = 1052 5. Peak at 1557
M+Na (23) =1541 M+ K (39) =1557 6. Peak at 2199
M+Na (23) = 2174M+ K (39) = 2190 7. Peak at ~1300 M+Na (23) = 1274 M+K (39) = 1290.88 Canola Oil Metathesis to Generate FAME and Diesters
[093] Refined, bleached and deodorized canola oil (170 g) was poured into a round flask with a capacity of 250 ml and two necks with a magnetic stir bar. The top joint of the bottle was fitted with a 320 mm cold coil condenser fed by a cooler circulator set at 15°C. A hose adapter connected to an oil bubbler by Tygon tubing was fitted to the top of the condenser. The neck of the side arm was fitted with a rubber septum through which a needle-type thermocouple and an 18 gauge stainless steel needle were introduced for the purpose of feeding a nitrogen source to the vial. The oil was heated, with magnetic stirring, for 2 hours at 200°C while being bubbled with dry nitrogen. After 2 hours, the oil cooled to 70°C, before the metathesis catalyst was added. The catalyst (Materia C827) was added through the canola oil slurry through the upper joint of the flask, maintaining the purge with nitrogen throughout the addition of the slurry. At this time, the coil condenser has been replaced. The reaction mixture was bubbled with nitrogen for an additional five minutes to ensure an inert atmosphere before the nitrogen supply was cut off. Metathesis was carried out for 3 hours at 70°C, without nitrogen purge, before the temperature of the reaction mixture was increased to 100°C in order to deactivate the catalyst. After 1 hour at 100°C, the reaction mixture cooled to room temperature overnight, slowly purging with nitrogen.
[094] The next day, the rubber septum was exchanged for the PTFE thermocouple adapter, and the coil condenser was exchanged for a short path distillation head containing a jacketed condenser equipped with a 100 ml receiving flask. The reaction mixture was removed by dragging to a vessel temperature of 250°C under 300 mTorr pressure for 4.5 hours. The drag resulted in the removal of 17.4% by weight of light substances and gave the oil product a slightly burnt appearance. The Brookfield viscosity of the final product was measured as 710 cp at 40°C. Conversion of the product to its corresponding fatty acid methyl esters was carried out prior to analysis by gas chromatography. The resulting mixture of fatty acid methyl esters was found to contain 27% by weight diesters as shown by gas chromatography. Data Set No. 1 of Metatized Natural Oil Compositions
[095] In the Data Sets below, Mn refers to number average molecular weight, Mw refers to weight average molecular weight, Mz refers to z average molecular weight, pm refers to peak molecular weight, IPD refers to index of polydispersion, ATG refers to thermogravimetric analysis, and VI refers to intrinsic viscosity. In addition, OFSM refers to metatized soybean oil, OCM refers to metatized canola oil, and 2X refers to two metatheses suffered.

Data Set #2 of Metatized Natural Oil Compositions
NOTE: Load of all catalysts = 38-42 ppm. Temperature of all reactions = 70⁰C Metatized Natural Oil Compositions Data Set #3
Data Set #4 High Molecular Weight OFSM Synthesis
[096] In some embodiments, the composition of metatized natural oil is metatized soybean oil (OFSM). The OFSM was synthesized as follows: Soybean Oil (OFS) was loaded into a 5 liter reactor with overhead mechanical agitation, nitrogen bubbling tube, and nitrogen outlet. The OFS was stirred and bubbled with nitrogen for thirty minutes at room temperature. Then, the OFS was heated at 200°C for two hours, with continuous nitrogen bubbling. The OFS was cooled to room temperature overnight.
[097] The reaction was stirred and bubbled with nitrogen at room temperature for 30 minutes. The bubbling tube was pulled above the oil level to maintain the nitrogen block during the reaction. The OFS was heated to 70°C. When the reactor reached the desired temperature, 40 ppm of ruthenium catalyst (C827) was added. The reaction was continued until the oil reached a dynamic viscosity of 235 cPs at 25°C with a spindle speed of 10 RPM. Then, 5% by weight of Oildri B80 clay was added to the reactor, and heated at 80°C for 1 hour to remove the catalyst. The oil/clay mixture was filtered through a sand bed on a pressure filter at 60 PSI. After filtration, the oil was removed at 200°C for 2 hours under vacuum.
[098]Then, the removed OFSM was loaded into a reactor equipped with a nitrogen bubbling tube, mechanical air agitation and nitrogen outlet. OFSM was bubbled with stirring at room temperature for 30 minutes. The reactor was heated to 70°C and 40 ppm of ruthenium catalyst (C827) was added. The reaction was held at this temperature until equilibrium, as determined by the stable dynamic viscosity samples (obtained at 30 minute intervals), was reached.
[099] Several samples of OFSM were analyzed using gel permeation chromatography (or CPG as used herein) and dynamic viscosity (or VD as used herein) at 40°C. The samples (10 mg/ml concentration in THF) were analyzed by CPG with Agilent 2x Oligopore columns (300 x 7.5 mm), using THF as the elution solvent at a constant flow rate of 1 ml/min at 35°C. The CPG system consisted of a Varian Pro-star 210 pump, 410 Automatic Sampling System, 325 UV-Vis dual wavelength detector and 356 RI detector. Molecular weights of the samples were determined using polystyrene CPG rigid calibration standards (Polimer Standard Service, Warwick, RI, USA) (MW = 17300 - 162) in Polymer lab and Cirrus CPG analysis software. BHT stabilized dry state THF was purchased from Pharmco-Aaper and used as received. The dynamic viscosity of these samples, shown in Table 1, indicated that 1064-6-4 has the lowest conversion. The dynamic viscosity of the removed material was lower than that of the pre-removed material (1033-96-7). Sample 1064-6-4 was used to generate the desired viscosities for the high molecular weight OFSM. Table 1. Dynamic Viscosity of the ID Retained Samples
After observing the discontinuity in dynamic viscosity, CPG was used to compare molecular weight distributions. The results are shown in Figure 6, which represents a gel permeation chromatogram of high molecular weight OFSM samples. For comparison, sample BB9001 was included as a reference to OFSM, the starting material. The CPG data shows that Sample 1064-6-4 has fewer higher molecular weight fractions than Samples 1033-96-9 and BB9007, indicating that 1064-6-4 is less convertible than the other lots of OFSM of high molecular weight. As understood, higher conversions will produce higher molecular weight polymers. Kinetic study of the high molecular weight OFSM
[0100]360 g of high molecular weight OFSM were synthesized in a 500 ml flask. The reaction was conducted using the same method described in the previous section, except for charging and stirring the catalyst with a magnetic stir bar. In an attempt to reduce the reaction rate, the catalyst charge was 30 ppm. Samples were taken every ten minutes after catalyst was added. Samples were analyzed using dynamic viscosity and CPG. The kinetic study for the high molecular weight OFSM was not performed at equilibrium, as the purpose of this study was to determine the point in time at which the target viscosity of 390 cP at 40°C would be reached. Dynamic viscosity analyzes of the kinetic samples of high molecular weight OFSM were plotted against time, as shown in Figure 7, and the relevant data are shown in Table 2. This study showed that the target viscosity was reached within 80 minutes. This did not show a direct relationship on larger scales. Scaled up to a 5 L reactor, the batch reached the target viscosity within 60 minutes. This could have resulted from the different agitation capacities. The kinetic study was carried out with magnetic agitation, whereas larger scale reactions use mechanical air agitation. CPG was also used to analyze the kinetic samples for molecular weight distributions, as shown in Figure 8 (CPG layer from high molecular weight OFSM kinetic studies with 30 ppm catalyst; BB9006DV31 @ 30 minutes, BB9006DV71 @ 70 minutes, BB9006DV81 @ 80 minutes, and BB9006DV91 @ 90 minutes). This shows that the highest molecular weight fraction is obtained over time. Through future study, CPG could be used as an analytical method to determine the completion of the reaction, in addition to the dynamic viscosity. Table 2
Study of the combination of high molecular weight OFSM and OFSM
[0101]High molecular weight OFSM was combined with OFSM to determine the feasibility of retro-combinations to achieve the desired viscosities. The initial blend was estimated using the weighted average viscosity of the blend. After measuring the initial blend, other blends were adjusted to the desired viscosity. Figure 9 below shows the properties of the combination of high molecular weight OFSM (BB9004) back-combined with OFSM (BB9001), and Table 3 shows the relevant data. When combined, viscosity did not follow a linear trend. To obtain the desired viscosity for certain samples (Sample 1064-6-4), the OFSM would have to be combined with 4550 wt% high molecular weight OFSM. Note: This combination study was performed using balanced high molecular weight OFSM, not the lower converting high molecular weight OFSM, as discussed in the next section. Table 3
Synthesis of low converting high molecular weight OFSM
[0102]Using the results of the kinetic study and the combination study, an OFSM of high molecular weight and lower conversion was synthesized, with a target of 390 cP at 40°C with a speed of 10 RPM. Using 30 ppm of ruthenium catalyst (C827), and the time estimate determined by the kinetic study, the high molecular weight OFSM was synthesized. During the reaction, samples were extracted and analyzed using dynamic viscosity to determine reaction progress, and their results are listed in Table 4. When the target viscosity was reached, the reaction was stopped by adding B80 clay and heating until 80°C. For the previous OFSM studies, the initial rise in viscosity was slow, and as the conversion increased, the viscosity increased at a more intense rate. The additional time after the desired viscosity is justified by the time needed to measure the dynamic viscosity. Table 4. Dynamic viscosity data for kinetic samples

[0103]The viscosity of the sample removed by drag at 150°C was 855 cP at 40°C, where the target viscosity for this sample was 567 cP. To obtain the desired viscosity, the sample was retro-blended with the OFSM at 24.9% by weight. This produced a sample (BB9014) with a viscosity of 590 cP at 40°C with a speed of 10 RPM. CPG was performed on this combination sample by way of comparison with the LF 2XOFSM @150 °C sample, and the CPG reports showed similar profiles, as shown in Figure 13 (for BB9014) and Figure 14 (for LF 2XOFSM), with the average molecular weights shown in Table 5. The LF2XOFSM sample had a higher concentration of the high molecular weight fraction than the combined sample, and the viscosity of LF2XOFSM was 720 cP. Table 5a. BB9014 Table 5b. LF2XOFSM
[0104]Another sample removed by drag at 200°C also had to be retro-blended due to viscosity beyond that intended. After dragging at 200°C, the sample had a viscosity of 1010 cP at 40°C with a speed of 10 RPM, and 14.4% by weight of the OFSM was retro-combined to the sample to produce a sample (BB9015) with a viscosity of 635 cP at 40°C at 10 RPM, which was close to the target viscosity of 650 cP. CPG was performed on the sample by way of comparison with sample 1064-6-4. The CPG reports had similar profiles and viscosities, as shown in Figure 15 (for BB 9015) and Figure 16 (for 1064-6-4). The average molecular weights for these samples are shown in Table 6. Table 6a. BB9015 Table 6b. 1064-6-4
[0105]Table 7 below gives the reaction conditions for several samples of OFSM with high molecular weight and lower conversion. Table 7



Data Set #5 High Molecular Weight OFSM Synthesis and Kinetic Studies
[0106]Two batches of OFSM were synthesized as described in Data Set No. 4. Then, the OFSM was introduced into a 5 L reactor equipped with nitrogen bubbling tube, mechanical air agitation and nitrogen outlet. OFSM was bubbled while stirring at room temperature for 30 minutes. The reactor was heated to 70°C and the bubbling tube was raised above the oil level to maintain positive nitrogen pressure. Then, 40 ppm of ruthenium catalyst (C827) was added to the reactor. The reaction was held at this temperature until equilibrium, as determined by the stable dynamic viscosity samples obtained at 30-minute intervals, was reached.
[0107]Kinetic samples were removed from the reactor and placed in a freezer to stop the reaction from progressing. When the sample temperature reached less than 40°C, the dynamic viscosity was measured. Once the dynamic viscosity was determined, the sample was returned to the freezer. At the end of the reaction, all kinetic samples were removed from the freezer to prepare the CPG samples.
[0108]The synthesis of high molecular weight OFSM using conventional metathesis conditions produced a product with pre-drag viscosity between 1510-1610 cP at 40°C and 10 RPM. The viscosity of the products was shown to be dependent on the viscosity of the initial OFSM. A lower viscosity starting material will produce a lower viscosity product. A 6.8% percent difference between lots of OFSM led to a 9.5% difference in the pre-drag high molecular weight OFSM. The viscosity difference of OFSM was due to a 0.4 wt% difference in drag removal levels.
[0109]The high molecular weight OFSM drag removal was performed at 150°C and 200°C to show the difference in products due to the level of drag. Dragging at 150°C for 2 hours was enough to remove any benzenes produced during the metathesis reaction. Comparison of removed products was more difficult as high molecular weight OFSM was not removed by the same wt%, and small changes in removal can significantly impact viscosity. The reaction conditions and viscosities of the various OFSM and high molecular weight OFSM products are shown in Table 8 below. Table 8
[0110]Kinetic samples were evaluated using CPG and dynamic viscosity at 40°C. Dynamic viscosity was plotted against time as shown in Figure 10, with the relevant data shown in Table 9. This graph shows a similar rate of reaction, as the two batches of high molecular weight OFSM bear a similar curve. Between standard batch 1 (Figure 12) and standard batch 2 (Figure 11), the columns in the CPG were replaced and better separation was observed. Standard batch 1 was not reprocessed in the new columns as it was at room temperature, and metathesis may have continued slowly, causing data to drift. The best resolution allowed tracking of the OFS as the reaction progressed and was represented with dynamic viscosity measurements, shown in Figure 10. The peak area of the soybean oil was inversely related to the dynamic viscosity and appeared to be in equilibrium therein. moment the viscosity. Table 9

权利要求:
Claims (16)
[0001]
1. Metatized natural oil composition CHARACTERIZED by the fact that it comprises: (i) a mixture of olefins and/or esters, or (ii) a metatized natural oil, wherein the metatized natural oil composition has a number average molecular weight in the a range of 2,000 g/mol to 4,000 g/mol, a weight average molecular weight in the range of 7,000 g/mol to 35,000 g/mol, a z average molecular weight in the range of 10,000 g/mol to 125,000 g/mol, and an index of polydispersity from 2 to 12, a dynamic viscosity at 40 °C of between 200 centipoise and 35,000 centipoise, and a dynamic viscosity at 100 °C of between 75 centipoise and 600 centipoise and in which the metatized natural oil composition is further metatized by at least once.
[0002]
2. Metatized natural oil composition, according to claim 1, CHARACTERIZED by the fact that the metatized natural oil composition has a number average molecular weight in the range of 2,300 g/mol to 3,400 g/mol, a weight average molecular weight in the range of 9,600 g/mol to 31,500 g/mol, and a z-average molecular weight in the range of 28,000 g/mol to 111,000 g/mol and a polydispersion index of 4 to 12.
[0003]
3. Metatized natural oil composition, according to claim 1, CHARACTERIZED by the fact that the metatized natural oil composition has a number average molecular weight in the range of 2600 g/mol to 3,100 g/mol, a weight average molecular weight in the range of 12,000 g/mol to 13,500 g/mol, and a z-average molecular weight in the range of 38,000 g/mol to 46,000 g/mol and a polydispersion index of 4 to 5, and in which still the composition of natural oil metatized is metatized at least twice.
[0004]
4. Metatized natural oil composition, according to claim 1, CHARACTERIZED by the fact that the metatized natural oil composition has a dynamic viscosity at 40 °C between 550 centipoise and 3250 centipoise.
[0005]
5. Metatized natural oil composition according to any one of claims 1 to 4, CHARACTERIZED by the fact that the metatized natural oil is selected from the group consisting of metatized canola oil, metatized rapeseed oil, metatized coconut oil , metatized corn oil, metatized cottonseed oil, metatized olive oil, metatized palm oil, metatized peanut oil, metatized saffron oil, metatized sesame oil, metatized soybean oil, metatized sunflower oil, metatized linseed, metatized palm seed oil, metatized tung oil, metatized jatropha oil, metatized mustard oil, metatized castor oil, metatized camelina oil, metatized thlaspi oil, metatized derivatives of these oils and their mixtures.
[0006]
6. Metatized natural oil composition, according to claim 1, CHARACTERIZED by the fact that the natural oil composition is metatized at least twice.
[0007]
7. Composition of metatized natural oil, according to claim 3, CHARACTERIZED by the fact that the composition of metatized natural oil is subjected to steam distillation at a temperature between 150 °C and 200 °C, and has dynamic viscosity at 40°C between 575 centipoise and 670 centipoise.
[0008]
8. Method for producing the metatized natural oil composition, as defined in any one of claims 1 to 7, CHARACTERIZED by the fact that it comprises the step of reacting a raw material of natural oil in the presence of a metathesis catalyst to form a first metatized natural oil product.
[0009]
9. Method according to claim 8, CHARACTERIZED by the fact that yet the first metatized natural oil product is self-metamatized to form another metatized natural oil product.
[0010]
10. Method according to claim 8, CHARACTERIZED by the fact that yet the first metatized natural oil product undergoes cross-metathesis with a natural oil to form another metatized natural oil product.
[0011]
11. Method, according to any one of claims 8 to 10, CHARACTERIZED by the fact that the composition of metatized natural oil can be subjected to distillation by steam drag at a temperature between 100 °C and 250 °C.
[0012]
12. Method according to any one of claims 8 to 10, CHARACTERIZED by the fact that the metatized natural oil composition can be subjected to reduced pressure conditions to remove C12 or lighter olefins.
[0013]
13. Method according to any one of claims 8 to 12, CHARACTERIZED by the fact that when the metatized natural oil composition comprises a mixture of olefins and esters, and in which the mixture of olefins and esters can be further separated into olefins and esters and, consequently, transesterification of the esters in the presence of an alcohol occurs to form a transesterified product.
[0014]
14. Method according to any one of claims 8 to 12, CHARACTERIZED by the fact that the molecular weight of the metatized natural oil composition can be increased by transesterification of the metatized natural oil composition with diesters.
[0015]
15. Method according to any one of claims 8 to 12, CHARACTERIZED by the fact that the molecular weight of the metatized natural oil composition can be increased by transesterification of the metatized natural oil composition with diacids.
[0016]
16. Use of the metatized natural oil composition, as defined in any one of claims 1 to 4, CHARACTERIZED by the fact that it is independently and/or incorporated in various formulations and as functional ingredients, selected from the group consisting of substitutes from dimethicone, laundry detergents, fabric softeners, emollients, hair fixing polymers, rheology modifiers, special conditioning polymers, surfactants, UV absorbers, solvents, humectants, occlusives, cosmetics, lip balms, lipsticks, hair creams, products for sun care, moisturizer, scented sticks, perfume carriers, skin perception agents, shampoos/conditioners, bar soaps, hand soaps/liquids, bubble baths, body fluids, facial cleansers, shower gels, wipes, products for baby cleaners, creams/lotions, antiperspirants/deodorants, lubricants, functional fluids, fuels and additives for fuel, additives for such lubricants, functional fluids and fuels, plasticizers, asphalt additives, friction reducing agents, antistatic agents in the textile and plastic industries, flotation agents, gelling agents, epoxy curing agents, corrosion inhibitors, pigment wetting, in cleaning compositions, plastics, coatings, adhesives, skin perceiving agents, film formers, rheological modifiers, release agents, conditioning dispersants, hydrotropes, industrial and institutional cleaning products, oilfield applications, gypsum, sealants, agricultural formulations, advanced oil recovery compositions, solvent products, gypsum products, gels, semi-solids, detergents, heavy duty liquid detergents, light duty liquid detergents, liquid detergent softeners, antistatic formulations, dryer softeners, surface cleaners harsh for household items, automatic washers, rinse additives, laundry additives, carpet cleaners, detergent softeners (softergents), one-rinse fabric softeners, stove cleaners, car wash liquids, transport cleaners, drain cleaners , defoamers, defoamers, foam intensifiers, antidust/dust repellents, industrial cleaners, institutional cleaners, service cleaners, glass cleaners, graphite removers, concrete cleaners, metal/machine parts cleaners, pesticides , agricultural formulations and cleaners for food services, plasticizers, asphalt additives and emulsifiers, friction reducing agents, film formers, rheological modifiers, biocides, biocide enhancers, release agents, household cleaning products, including laundry detergents in powder and liquids, liquid and sheet fabric softeners, cleaned soft and hard surface cleaners, antiseptics and disinfectants, and industrial cleaners, emulsion polymerization, including processes for the manufacture of latex and for use as surfactants as wetting agents, formulation inerts in pesticide applications or as adjuvants used in in conjunction with the delivery of pesticides including crop protection, ornamental, home and garden, and professional peat applications, institutional cleaning products, oilfield applications including oil and gas transport, production, drilling chemicals and stimulation and intensification and shaping of reservoirs, organoclays for drilling muds, special foams to control or disperse foam in the gypsum manufacturing process, cement wall board, concrete additives and firefighting foams, paints and coalescing agents, thickeners of ink, or other applications that need to be run with tolerance. cold or chilling (winterization).

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112014032139B1|2021-08-03|COMPOSITION OF METATIZED NATURAL OIL, AS WELL AS ITS USE IN FORMULATION AND METHOD OF PRODUCTION

---

JP2016179989A|2016-10-13|Methods of refining and producing fuel from natural oil feedstocks

---

US9388098B2|2016-07-12|Methods of making high-weight esters, acids, and derivatives thereof

---

BR112015006248B1|2020-10-27|methods to refine a natural oil

---

EP2906664B1|2020-12-09|Methods of making high-weight esters and derivatives thereof

---

US10711096B2|2020-07-14|Aqueous monomer compositions and methods of making and using the same

---

EP3699168A1|2020-08-26|Branched-chain esters and methods of making and using the same

---

US10017447B2|2018-07-10|Processes for making azelaic acid and derivatives thereof

---

CN104080757B|2016-01-13|Suppress the method for the isomerized method of olefin metathesis product, refining natural oil and produce the method for fuel composition

---

US20150368180A1|2015-12-24|Acid catalyzed oligomerization of alkyl esters and carboxylic acids

---

WO2016014287A1|2016-01-28|Conjugated diene acids and derivatives thereof

---

EP3250175A1|2017-12-06|Branched saturated hydrocarbons derived from olefins

同族专利:

---

公开号 | 公开日

---

JP6424242B2|2018-11-14|

---

US20150105566A1|2015-04-16|

---

US9890348B2|2018-02-13|

---

EP2864447A1|2015-04-29|

---

AU2013277107A1|2015-01-22|

---

KR102093707B1|2020-03-26|

---

MX2014015460A|2015-06-23|

---

KR20150132068A|2015-11-25|

---

US20130344012A1|2013-12-26|

---

EA201492139A1|2015-04-30|

---

CN108485698A|2018-09-04|

---

JP2015523440A|2015-08-13|

---

CA2876675A1|2013-12-27|

---

AU2013277107B2|2018-03-08|

---

US20180208873A1|2018-07-26|

---

JP2017115156A|2017-06-29|

---

CN104583369A|2015-04-29|

---

EP2864447B3|2019-07-17|

---

BR112014032139A2|2020-12-22|

---

WO2013192384A1|2013-12-27|

---

ZA201409328B|2016-09-28|

---

CA2876675C|2020-09-15|

---

EP2864447B1|2017-12-06|

---

EA033372B1|2019-10-31|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2619422A|1950-03-23|1952-11-25|Holton W Diamond|Dessert mix and method of making the same|

---

US3150205A|1960-09-07|1964-09-22|Standard Oil Co|Paraffin isomerization process|

---

US3351566A|1963-10-21|1967-11-07|Exxon Research Engineering Co|Stabilized high-activity catalyst|

---

US3448178A|1967-09-22|1969-06-03|Nat Starch Chem Corp|Hot melt adhesives comprising ethylene/vinyl acetate copolymers and alpha-pinene/phenol condensation products|

---

DE2228332B2|1972-06-10|1978-09-28|Basf Ag, 6700 Ludwigshafen|Process for the selective hardening of fats and oils|

---

US4210771A|1978-11-02|1980-07-01|Union Carbide Corporation|Total isomerization process|

---

JPS626700B2|1979-11-29|1987-02-13|Takasago Perfumery Co Ltd|

---

JPS629580B2|1980-01-28|1987-02-28|Takasago Perfumery Co Ltd|

---

US4545941A|1983-06-20|1985-10-08|A. E. Staley Manufacturing Company|Co-metathesis of triglycerides and ethylene|

---

NL190750C|1984-06-21|1994-08-01|Unilever Nv|Nickel aluminate catalyst, its preparation and the hydrogenation of unsaturated organic compounds therewith.|

---

US5095169A|1988-03-30|1992-03-10|Uop|Normal paraffin hydrocarbon isomerization process using activated zeolite beta|

---

SU1565872A1|1988-07-18|1990-05-23|Всесоюзный Заочный Институт Пищевой Промышленности|Method of obtaining oils simulating palm oils|

---

YU46273B|1989-11-20|1993-05-28|Do Helios Kemična Industrija Domžale|OIL HYDROGENATION PROCEDURE|

---

US5142072A|1989-12-19|1992-08-25|The Procter & Gamble Company|Selective esterification of long chain fatty acid monoglycerides with medium chain fatty acid anhydrides|

---

CA2077548A1|1990-03-05|1991-09-06|John H. Grate|Catalytic system for olefin oxidation to carbonyl products|

---

US5312940A|1992-04-03|1994-05-17|California Institute Of Technology|Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization|

---

EP0773948A4|1992-04-03|1998-09-02|California Inst Of Techn|High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof|

---

US5710298A|1992-04-03|1998-01-20|California Institute Of Technology|Method of preparing ruthenium and osmium carbene complexes|

---

WO1994023836A1|1993-04-08|1994-10-27|E.I. Du Pont De Nemours And Company|Catalyst composition and process for the production of unsaturated diesters|

---

AU7365694A|1993-07-22|1995-02-20|S.C. Johnson & Son, Inc.|Repulpable hot melt polymer/wax compositions for fibrous products|

---

US5734070A|1994-02-17|1998-03-31|Degussa Aktiengesellschaft|Hardening of unsaturated fats, fatty acids or fatty acid esters|

---

JPH0914574A|1995-06-30|1997-01-17|Furukawa Electric Co Ltd:The|Anticorrosion protecting method for propeller pipe|

---

US5728785A|1995-07-07|1998-03-17|California Institute Of Technology|Romp polymerization in the presence of peroxide crosslinking agents to form high-density crosslinked polymers|

---

US5831108A|1995-08-03|1998-11-03|California Institute Of Technology|High metathesis activity ruthenium and osmium metal carbene complexes|

---

KR100304416B1|1997-05-28|2002-05-09|나까니시 히로유끼|Preparation of hydrogenated product of cyclic olefin ring-opening metathesis polymer|

---

DE19815275B4|1998-04-06|2009-06-25|Evonik Degussa Gmbh|Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis|

---

US7507854B2|1998-09-01|2009-03-24|Materia, Inc.|Impurity reduction in Olefin metathesis reactions|

---

US6696597B2|1998-09-01|2004-02-24|Tilliechem, Inc.|Metathesis syntheses of pheromones or their components|

---

US6900347B2|1998-09-01|2005-05-31|Tilliechem, Inc.|Impurity inhibition in olefin metathesis reactions|

---

US6211315B1|1998-11-12|2001-04-03|Iowa State University Research Foundation, Inc.|Lewis acid-catalyzed polymerization of biological oils and resulting polymeric materials|

---

US20020095007A1|1998-11-12|2002-07-18|Larock Richard C.|Lewis acid-catalyzed polymerization of biological oils and resulting polymeric materials|

---

US6962729B2|1998-12-11|2005-11-08|Lord Corporation|Contact metathesis polymerization|

---

EP1248764B1|1999-01-26|2012-08-01|California Institute Of Technology|Novel method for cross-metathesis of terminal olefins|

---

US6486264B1|1999-05-31|2002-11-26|Zeon Corporation|Process for producing hydrogenated ring-opening polymerization polymer of cycloolefin|

---

US6214764B1|1999-06-01|2001-04-10|Uop Llc|Paraffin-isomerization catalyst and process|

---

CA2392049C|1999-11-18|2012-01-31|Richard L. Pederson|Metathesis syntheses of pheromones or their components|

---

CA2413852C|2000-06-23|2012-06-05|California Institute Of Technology|Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing metathesis|

---

GB0017839D0|2000-07-21|2000-09-06|Ici Plc|Hydrogenation catalysts|

---

DE60232062D1|2001-03-26|2009-06-04|Dow Global Technologies Inc|METATHESIS REACTION OF UNSATURATED FATTY ACID ESTERS OR FATTY ACIDS WITH LOW-MOLECULAR OLEFINS|

---

JP2002363263A|2001-06-08|2002-12-18|Nippon Zeon Co Ltd|Ring-opened copolymer, hydrogenated product of ring- opened copolymer, method for producing the same and composition thereof|

---

US20050124839A1|2001-06-13|2005-06-09|Gartside Robert J.|Catalyst and process for the metathesis of ethylene and butene to produce propylene|

---

WO2003044060A2|2001-11-15|2003-05-30|Materia, Inc.|Chelating carbene ligand precursors and their use in the synthesis of metathesis catalysts|

---

US6811824B2|2002-01-04|2004-11-02|Marcus Oil And Chemical Corp.|Repulpable wax|

---

US7034096B2|2002-02-19|2006-04-25|California Institute Of Technology|Ring-expansion of cyclic olefins metathesis reactions with an acyclic diene|

---

KR20040111565A|2002-04-29|2004-12-31|다우 글로벌 테크놀로지스 인크.|Integrated chemical processes for industrial utilization of seed oils|

---

US6890982B2|2002-06-11|2005-05-10|Marcus Oil And Chemical-Corp.|Wax for hot melt adhesive applications|

---

DE60310442T2|2002-10-10|2007-04-12|HRD Corp., Houston|ADDITIVE TO MOISTURE RESISTANT TO A PLASTER|

---

US7960599B2|2003-01-13|2011-06-14|Elevance Renewable Sciences, Inc.|Method for making industrial chemicals|

---

US7267743B2|2003-03-17|2007-09-11|Marcus Oil And Chemical|Wax emulsion coating applications|

---

US7314904B2|2003-06-18|2008-01-01|Baker Hughes Incorporated|Functionalized polyalphaolefins|

---

US7585990B2|2003-07-31|2009-09-08|Cargill, Incorporated|Low trans-fatty acid fat compositions; low-temperature hydrogenation, e.g., of edible oils|

---

US7176336B2|2003-10-09|2007-02-13|Dow Global Technologies Inc.|Process for the synthesis of unsaturated alcohols|

---

CA2462011A1|2004-02-23|2005-08-23|Bayer Inc.|Process for the preparation of low molecular weight nitrile rubber|

---

KR101291468B1|2004-06-09|2013-07-30|유티아이 리미티드 파트너쉽|Transition metal carbene complexes containing a cationic substituent as catalysts of olefin metathesis reactions|

---

FR2878246B1|2004-11-23|2007-03-30|Inst Francais Du Petrole|PROCESS FOR CO-PRODUCTION OF OLEFINS AND ESTERS BY ETHENOLYSIS OF UNSATURATED FATTY BODIES IN NON-AQUEOUS IONIC LIQUIDS|

---

WO2006076364A2|2005-01-10|2006-07-20|Cargill, Incorporated|Candle and candle wax containing metathesis and metathesis-like products|

---

JP5437628B2|2005-06-06|2014-03-12|ダウグローバルテクノロジーズエルエルシー|Metathesis process for preparing olefins with α, ω-functional groups|

---

WO2007081987A2|2006-01-10|2007-07-19|Elevance Renewable Sciences, Inc.|Method of making hydrogenated metathesis products|

---

FR2896498B1|2006-01-24|2008-08-29|Inst Francais Du Petrole|PROCESS FOR CO-PRODUCTION OF OLEFINS AND DIESTERS OR DIACIDS FROM UNSATURATED FATTY BODIES|

---

EP1996149B1|2006-03-07|2017-05-10|Elevance Renewable Sciences, Inc.|Compositions comprising metathesized unsaturated polyol esters|

---

WO2007103460A2|2006-03-07|2007-09-13|Elevance Renewable Sciences, Inc.|Colorant compositions comprising metathesized unsaturated polyol esters|

---

CN101563434B|2006-07-12|2012-01-25|埃莱文斯可更新科学公司|Hot melt adhesive compositions comprising metathesized unsaturated polyol ester wax|

---

CN101563315B|2006-07-12|2013-08-14|埃莱文斯可更新科学公司|Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like|

---

WO2008010961A2|2006-07-13|2008-01-24|Elevance Renewable Sciences, Inc.|Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis|

---

US8501973B2|2006-10-13|2013-08-06|Elevance Renewable Sciences, Inc.|Synthesis of terminal alkenes from internal alkenes via olefin metathesis|

---

CN101627001A|2006-10-13|2010-01-13|埃莱文斯可更新科学公司|Methods of making organic compounds by metathesis and hydrocyanation|

---

EP2121546B1|2006-10-13|2017-12-13|Elevance Renewable Sciences, Inc.|Methods of making alpha, omega-dicarboxylic acid alkene derivatives by metathesis|

---

EP2074079B1|2006-10-13|2011-08-10|Elevance Renewable Sciences, Inc.|Metathesis methods involving hydrogenation and compositions relating to same|

---

US20090005624A1|2007-06-27|2009-01-01|Bozzano Andrea G|Integrated Processing of Methanol to Olefins|

---

WO2010062958A1|2008-11-26|2010-06-03|Elevance Renewable Sciences, Inc.|Methods of producing jet fuel from natural oil feedstocks through metathesis reactions|

---

US8957268B2|2009-10-12|2015-02-17|Elevance Renewable Sciences, Inc.|Methods of refining natural oil feedstocks|

---

US9249360B2|2010-07-09|2016-02-02|Elevance Renewable Sciences, Inc.|Compositions derived from metathesized natural oils and amines and methods of making|

---

EP2838615A1|2012-04-20|2015-02-25|The Procter and Gamble Company|Personal cleansing compositions|

---

KR102093707B1|2012-06-20|2020-03-26|엘레반스 리뉴어블 사이언시즈, 인코포레이티드|Natural oil metathesis compositions|US9000246B2|2009-10-12|2015-04-07|Elevance Renewable Sciences, Inc.|Methods of refining and producing dibasic esters and acids from natural oil feedstocks|

---

US9388098B2|2012-10-09|2016-07-12|Elevance Renewable Sciences, Inc.|Methods of making high-weight esters, acids, and derivatives thereof|

---

KR102093707B1|2012-06-20|2020-03-26|엘레반스 리뉴어블 사이언시즈, 인코포레이티드|Natural oil metathesis compositions|

---

US9388097B2|2013-03-14|2016-07-12|Elevance Renewable Sciences, Inc.|Methods for treating substrates prior to metathesis reactions, and methods for metathesizing substrates|

---

US9919299B2|2013-03-14|2018-03-20|Ximo Ag|Metathesis catalysts and reactions using the catalysts|

---

CN105050567B|2013-04-05|2018-04-27|宝洁公司|Include the personal care composition of pre-emulsified preparation|

---

EP3052229B1|2013-10-01|2021-02-24|Verbio Vereinigte BioEnergie AG|Immobilized metathesis tungsten oxo alkylidene catalysts and use thereof in olefin metathesis|

---

CN105939602B|2014-01-30|2020-01-14|巴斯夫欧洲公司|Asymmetric formals and acetals as adjuvants in crop protection|

---

CA2937376A1|2014-02-26|2015-09-03|Elevance Renewable Sciences, Inc.|Low-voc compositions and methods of making and using the same|

---

WO2015143562A1|2014-03-27|2015-10-01|Trent University|Metathesized triacylglycerol green polyols from palm oil for use in polyurethane applications and their related physical properties|

---

US10000601B2|2014-03-27|2018-06-19|Trent University|Metathesized triacylglycerol polyols for use in polyurethane applications and their related properties|

---

US10806688B2|2014-10-03|2020-10-20|The Procter And Gamble Company|Method of achieving improved volume and combability using an anti-dandruff personal care composition comprising a pre-emulsified formulation|

---

EP3217948B1|2014-11-10|2020-09-16|The Procter and Gamble Company|Personal care compositions with two benefit phases|

---

CN107106474B|2014-11-10|2021-06-01|宝洁公司|Personal care composition with two benefit phases|

---

US10966916B2|2014-11-10|2021-04-06|The Procter And Gamble Company|Personal care compositions|

---

US9993404B2|2015-01-15|2018-06-12|The Procter & Gamble Company|Translucent hair conditioning composition|

---

US20160244698A1|2015-02-20|2016-08-25|The Procter & Gamble Company|Fabric care composition comprising metathesized unsaturated polyol esters|

---

MX2017010934A|2015-02-25|2018-01-23|Procter & Gamble|Fibrous structures comprising a surface softening composition.|

---

CN107429953A|2015-03-30|2017-12-01|开利公司|Low oily refrigerant and steam compression system|

---

WO2017011249A1|2015-07-10|2017-01-19|The Procter & Gamble Company|Fabric care composition comprising metathesized unsaturated polyol esters|

---

CA2947599A1|2015-11-04|2017-05-04|Trent University|Biodiesel compositions containing pour point depressants and crystallization modifiers|

---

US10301557B2|2015-11-13|2019-05-28|Exxonmobil Research And Engineering Company|High viscosity base stock compositions|

---

EP3405168A1|2016-01-20|2018-11-28|The Procter and Gamble Company|Hair conditioning composition comprising monoalkyl glyceryl ether|

---

US20180008843A1|2016-07-08|2018-01-11|The Gillette Company Llc|Lubricating member for razor cartridges comprising metathesized unsaturated polyols|

---

BR112019000375A2|2016-07-08|2019-04-24|The Gillette Company Llc|lubricating members for shaver cartridges comprising a metatetised unsaturated polyol ester|

---

EP3481366A1|2016-07-08|2019-05-15|The Gillette Company LLC|Liquid compositions for hair removal devices comprising metathesized unsaturated polyol esters|

---

US20180008484A1|2016-07-11|2018-01-11|The Procter & Gamble Company|Absorbent articles comprising metathesized unsaturated polyol esters|

---

US10285928B2|2016-07-11|2019-05-14|The Procter & Gamble Company|Fibrous structures comprising metathesized unsaturated polyol esters|

---

EP3500656A1|2016-08-18|2019-06-26|The Procter and Gamble Company|Fabric care composition comprising glyceride copolymers|

---

US20180049969A1|2016-08-18|2018-02-22|The Procter & Gamble Company|Hair care compositions comprising metathesized unsaturated polyol esters|

---

US10155833B2|2016-08-18|2018-12-18|Elevance Renewable Sciences, Inc.|High-weight glyceride oligomers and methods of making the same|

---

US20180049970A1|2016-08-18|2018-02-22|The Procter & Gamble Company|Hair care compositions comprising metathesized unsaturated polyol esters|

---

US10894932B2|2016-08-18|2021-01-19|The Procter & Gamble Company|Fabric care composition comprising glyceride copolymers|

---

CN109789068A|2016-09-30|2019-05-21|宝洁公司|Hair care composition comprising gel-type vehicle and glycerol ester copolymer|

---

WO2019006056A2|2017-06-30|2019-01-03|The Procter & Gamble Company|Disposable absorbent article having surface modified topsheet|

---

CN110799162A|2017-06-30|2020-02-14|宝洁公司|Disposable absorbent article with surface modified topsheet|

---

CN110785156A|2017-06-30|2020-02-11|宝洁公司|Disposable absorbent article with surface modified topsheet|

---

CN111212625A|2017-10-20|2020-05-29|宝洁公司|Aerosol foam skin cleaning agent|

---

EP3699354A1|2019-02-21|2020-08-26|The Procter & Gamble Company|Fabric care compositions that include glyceride polymers|

法律状态:
2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-01-26| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

---

2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-06-15| B25A| Requested transfer of rights approved|Owner name: WILMAR TRADING PTE LTD (SG) |

---

2021-08-03| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/06/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201261662318P| true| 2012-06-20|2012-06-20|

---

US61/662,318|2012-06-20|

---

US201361781892P| true| 2013-03-14|2013-03-14|

---

US61/781,892|2013-03-14|

---

PCT/US2013/046735|WO2013192384A1|2012-06-20|2013-06-20|Natural oil metathesis compositions|

---