METHOD FOR CHEMICALLY TREATING A SUBSTRATE MATERIAL OF METATHESIS

专利摘要:
substrate treated materials by metathesis and methods of preparing and using it. a method for treating a substrate prior to a metathesis reaction includes treating the substrate with a first agent configured to mitigate the potentially adverse effects of one or more contaminants on the substrate on a catalyst used to catalyze the metathesis reaction. the treatment reduces to a level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed to a substrate-to-catalyst molar ratio of at least about 7500 to 1. methods for metathesis reaction of the substrates are described here.
公开号:BR112015019827B1
申请号:R112015019827-9
申请日:2014-03-13
公开日:2020-10-06
发明作者:Keith M. Wampler；Steven A. Cohen；Georg E. Frater；Levente Ondi；Jeno Varga
申请人:Elevance Renewable Sciences, Inc.；
IPC主号:

专利说明:

CROSS REFERENCE OF RELATED ORDERS
[001] The present application claims priority benefit for United States Provisional Patent Application US No. 61 / 784,321, filed on March 14, 2013, which is incorporated herein by reference as if completely presented here. BACKGROUND OF THE INVENTION
[002] The olefin metathesis reaction has established itself as one of the most powerful chemical reactions available for the synthetic preparation of alkenes. In recent years, a great deal of research has been directed towards the development of new catalyst systems for use in olefin metathesis, with catalysts that incorporate transition metals, including metals such as ruthenium, molybdenum, and tungsten.
[003] A criterion for assessing the effectiveness of a metathesis catalyst is the turnover number ("TON") that can be achieved before deactivating the catalyst. Often, catalyst systems that show efficacy in catalyzing an olefin metathesis reaction are sensitive to a variety of contaminants that can significantly reduce the TON that might otherwise be achieved.
[004] Natural raw materials, including, but not limited to, natural oils (for example, vegetable oils, algae oils, animal fats, liquid resin, and the like) and derivatives of natural oils (for example, fatty acids and fatty acid esters) can be converted into industrially useful chemicals through metathesis of olefins. But the efficiency of the catalyst and the conversion of the product can vary dramatically depending on the purity of the raw material that is undergoing metathesis. A challenge in using natural raw materials is that they can include impurities that do not exist in petroleum raw materials. These impurities often react (and / or otherwise interact) with the metathesis catalyst and can dramatically affect the efficiency of the catalyst and the metathesis reaction. In addition, the presence and level of various impurities in natural oils can vary from batch to batch, depending, for example, on the geographical location of the harvest, and even on the specific time of harvest, as well as other growing conditions. The presence of such impurities in renewable raw materials presents a significant challenge for the industrial applicability of olefin metathesis.
[005] Therefore, there is a continuing need to develop methods of treating renewable raw materials (for example, natural oils) to reduce impurities that would otherwise limit the effectiveness of the metathesis catalyst. SUMMARY
[006] In a first aspect, the invention provides compositions of metathesis substrates (for example, treated compositions of natural oils) with low concentrations of impurities that can serve as a poison for certain olefin metathesis catalysts.
[007] In a second aspect, the description provides methods for chemically treating a metathesis substrate material, including: providing a metathesis substrate material comprising one or more contaminants from the catalyst poisoning; and treating the metathesis substrate material to reduce the concentration of at least one of the one or more catalyst poisoning contaminants in the metathesis raw material; in which the treatment comprises contacting the metathesis raw material with an alkyl metal compound. In some embodiments, the metathesis substrate material is a natural oil.
[008] In a third aspect, the invention provides methods for chemically treating a metathesis substrate material, including: providing a metathesis substrate material comprising one or more contaminants from the catalyst poisoning; and treating the metathesis substrate material to reduce the concentration of at least one of the one or more poisoning contaminants of the catalyst in the metathesis raw material; in which the treatment involves contacting the raw material of metathesis with activated copper. In some embodiments, the metathesis substrate material is a natural oil.
[009] In a fourth aspect, the description provides methods for chemically treating a metathesis substrate material, including: providing a metathesis substrate material comprising one or more contaminants from the catalyst poisoning; and treating the metathesis substrate material to reduce the concentration of at least one of the one or more poisoning contaminants of the catalyst in the metathesis raw material; in which the treatment involves contacting the raw material of metathesis with activated magnesium. In some embodiments, the metathesis substrate material is a natural oil.
[010] In a fifth aspect, the invention provides methods for chemically treating a metathesis substrate material, including: providing a metathesis substrate material comprising one or more contaminants from the catalyst poisoning; and treating the metathesis substrate material to reduce the concentration of at least one of the one or more poisoning contaminants of the catalyst in the metathesis raw material; in which the treatment comprises contacting the metathesis raw material with acetic anhydride. In some embodiments, the metathesis substrate material is a natural oil.
[011] In a sixth aspect, the invention provides methods for metathesis a substrate material, including: treating a metathesis substrate material according to the method of the second, third, fourth, fifth aspects, or any of its modalities; undergo metathesis and the substrate material treated in the presence of a metathesis catalyst to form a metathesis product. In some embodiments, the metathesis substrate material is a natural oil.
[012] In some modalities, treatment methods include treating a metathesis substrate before a metathesis reaction. In some of these modalities, the substrate is treated with metathesis with a first agent that is configured to mitigate the potentially adverse effects of one or more contaminants on the substrate on a catalyst used to catalyze the metathesis reaction (for example, it was designed to remove the poisoning of the catalyst from the composition of the substrate to chemically convert the poisons to chemical species that are not poisons or that are not less potent poisons In some embodiments, the treatment reduces a level of one or more contaminants in the composition of the substrate metathesis by an amount sufficient to allow the metathesis reaction to proceed at a molar ratio of substrate to catalyst at least about 7500 to 1.
[013] In some embodiments, treatment methods include treating the substrate with a first agent, and reacting the substrate, following its treatment with the first agent, in a metathesis reaction in the presence of a metathesis catalyst. In some of these embodiments, the substrate includes a natural oil and / or a derivative thereof; and the first agent is configured to mitigate the potentially adverse effects of one or more contaminants on the substrate on the metathesis catalyst. In some embodiments, the treatment reduces a level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 7500 to 1. BRIEF DESCRIPTION OF THE DRAWINGS
[014] FIG. 1 is a graph showing the effect of a triethyl aluminum treatment (here "TEAL") on the purification of 9-DAME.
[015] FIG. 2 is a graph showing the effect of an alumina aftertreatment following an initial TEAL treatment on the purification of 9-DAME.
[016] FIG. 3 is a graph showing the effect of varying the amount of alumina used for the post-treatment after an initial TEAL treatment on the 9-DAME purification.
[017] FIG. 4 is a graph showing the effect of various amounts of OcsAI on the performance of the Mo X052 catalyst for "crude" and "pre-dried" 9-DAME. The determination of the optimal amount of OcsAI for both substrates.
[018] FIG. 5 is a graph showing the effect of various amounts of OcsAI on the performance of the W X123 catalyst for "crude" and "pre-dried" 9-DAME. The determination of the optimal amount of OcsAI for both substrates.
[019] FIG. 6 is a graph showing the effect of 3% by weight of post-treatment alumina after an initial treatment of OcsAI on the purification of "crude" 9-DAME in several Mo X051 catalyst loads.
[020] FIG. 7 is a graph showing the effect of 3% by weight of alumina aftertreatment following an initial treatment of OcsAI on the purification of "crude" 9-DAME in various W x154 catalyst loads.
[021] FIG. 8 is a graph showing the% conversion as a function of the substrate-to-catalyst ratio using Mo X052 catalyst in the case of 9-DAME "crude" and "pre-dried".
[022] FIG. 9 is a graph showing the% conversion as a function of the substrate to catalyst ratio using W x123 catalyst in the case of "crude" and "pre-dry" 9-DAME.
[023] FIG. 10 is a graph showing the% conversion of auto-metathesis to soybean oil as a function of the catalyst load and TEAL treatment. DETAILED DESCRIPTION
[024] The methods for pretreating substrates to be used in metathesis reactions have been discovered and are described here below. These pretreatment methods mitigate the potentially adverse effects that one or more contaminants on the substrate may have on metathesis catalysts used to catalyze the metathesis reaction, such that the efficiency of the catalyst (for example, as quantified by its TON ) can be increased. Since different raw materials typically contain different types of impurities, the methods according to the present teachings, as explained below, use different methodologies and, in some modalities, methodological combinations in order to neutralize adverse effects specific contaminants.
[025] Throughout this description and the appended claims, the following definitions must be understood:
[026] The term "olefin" refers to a hydrocarbon compound that contains at least one carbon-carbon double bond. As used herein, the term "olefin" encompasses hydrocarbons having more than one carbon-carbon double bond (e.g., di-olefins, tri-olefins, etc.). In some embodiments, the term "olefin" refers to a group of compounds that contain carbon-carbon double bonds with different chain lengths. In some embodiments, the term "olefin" refers to poly-olefins, linear, branched and / or cyclic olefins.
[027] The term "functionalized" and the phrase "functional group" refer to the presence of a molecule of one or more hetero atoms in a terminal and / or internal position, where the one or more hetero atoms is an atom other than carbon and hydrogen. In some embodiments, the heteroatom is an atom of a polyatomic functional group. Representative functional groups including, but not limited to halides, alcohols, amines, carboxylic acids, carboxylic esters, ketones, aldehydes, anhydrides, ether groups, cyano groups, nitro groups, sulfur-containing groups, phosphorus-containing groups, amides, imides, heterocycles containing N, heterocycles containing aromatic N, their salts, and the like, and combinations thereof.
[028] The term "metathesis reaction" refers to a chemical reaction involving a single type of olefin or a plurality of different types of olefin, which is conducted in the presence of a metathesis catalyst, and which results in the formation of hair least one new olefin product. The term "metathesis reaction" encompasses auto-metathesis, cross-metathesis (ie co-metathesis; CM), open ring metathesis (ROM), open ring metastasis polymerizations (ROMP), closed ring metathesis (RCM ), acyclic diene metathesis (ADMET), and the like, and combinations thereof. In some embodiments, the phrase "metathesis reaction" refers to a chemical reaction involving a natural oil feed.
[029] The term "mitigate" as used in reference to the adverse effects of a particular contaminant on a metathesis catalyst refers to a decrease in the severity of such effects. It is to be understood that the term "mitigate" includes, but does not necessarily imply, 100% elimination of adverse effects associated with a particular contaminant.
[030] The term "contaminant" refers widely and without limitation to any impurity, regardless of the amount in which it is present, mixed with a substrate to be used in the metathesis of olefins.
[031] The phrase "protic material" refers to a material that contains a dissociable proton.
[032] The phrase "polar material" refers to a material that has an uneven distribution of electrons and thus a permanent dipole moment.
[033] The phrase "Lewis base catalyst poison" generally refers to a material containing a heteroatom that can function as an electron pair donor.
[034] Phrases such as "natural oils", "natural raw materials", or "raw materials for natural oil" can refer to oils derived from plant or animal sources. The phrase "natural oil" includes derivatives of natural oil, unless otherwise specified. The phrases also include modified plant or animal sources (for example, genetically modified plant or animal sources), unless otherwise specified. Examples of natural oils include, but are not limited to, vegetable oils, seaweed oils, fish oils, animal fats, liquid resins, derivatives of these oils, combinations of any of these 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, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm oil, tung oil, jatropha oil, mustard oil, pennycress oil, cameline oil and castor oil. Representative non-limiting examples of animal fats include lard, tallow, poultry fats, recycled vegetable oil, and fish oil. Liquid resins are by-products of wood pulp production.
[035] The term "derived from natural oil" can refer to compounds or a mixture of compounds derived from natural oil, using any one or combination of methods known in the art. Such methods include, but are not limited to, saponification, fat separation, transesterification, esterification, hydrogenation (partial or total), isomerization, oxidation and reduction. Representative non-limiting examples of natural oil derivatives include gums, phospholipids, sludge, acidified sludge, distillate or distillate slurries, fatty acids and fatty acid alkyl ester (eg non-limiting examples such as 2-ethylhexyl ester), variations in hydroxy substituted natural oil. For example, the natural oil derivative may be a fatty acid methyl ester ("FAME") derived from the natural oil glyceride. In some embodiments, a raw material includes canola or soy oil, as a non-limiting, refined, bleached and deodorized soy oil (ie, RBD soy oil) example. Soybean oil typically comprises about 95% by weight or greater (e.g. 99% by weight, or greater) of fatty acid triglycerides. The major fatty acids in the soybean oil polyol include saturated fatty acids, as a non-limiting example, palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid), and unsaturated fatty acids, as a non-limiting example, acid oleic (9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid) and linolenic acid (9,12,15-octadecatrienoic acid).
[036] The phrase "low molecular weight olefin" refers to any linear, branched or cyclic olefin in the range of C2 to C30 and / or any combination of such olefins. The phrase "low molecular weight olefin" includes mono-olefins, including, but not limited to, internal olefins, terminal olefins, and combinations thereof, as well as polyolefins, including, but not limited to dienes, triennes, and the like, and combinations thereof. In some embodiments, the low molecular weight olefin is functionalized.
[037] The term "ester" refers to compounds having the general formula R-COO-R ', where R and R' denote any alkyl, alkenyl, alkynyl group, or a substituted or unsubstituted aryl group. In some embodiments, the term "ester" refers to a group of compounds having a general formula as described above, wherein the compounds have different chain lengths.
[038] The term "alkyl" refers to the straight, branched, cyclic chain and / or groups of polycyclic aliphatic hydrocarbons, which, optionally, can incorporate one or more hetero atoms within their carbon-carbon structures (for example, example, to form ethers, heterocycles, and the like), and which, optionally, can be functionalized.
[039] The phrase "an amount sufficient to allow [a] metathesis reaction to proceed to a [specified] molar ratio of substrate-to-catalyst" refers to a degree of reduction in the concentration of a given contaminant. The determination of the amount of reduction required to achieve a desired molar ratio of substrate to catalyst is within the skill of the person skilled in the art taking into account the guiding principles described herein, and will vary according to the nature of the particular contaminant and / or your initial concentration. Conditions that may affect the level of reduction include, but are not limited to, experimental parameters, such as reactivity and / or concentrations of reagents, the type of mixture and / or agitation provided (eg, high shear, low intensity, etc. .), reaction temperature, residence time, reaction pressure, reaction atmosphere (for example, exposure to the atmosphere versus an inert gas, etc.), and the like, and combinations thereof.
[040] The term "bonded", as used in reference to a solid support and an agent used for the treatment of a substrate before a metathesis reaction is to be understood broadly and without limitation to cover a range of forces of the associative types, but not including limited to covalent bonds, ionic bonds, physical and / or electrostatic forces of attraction (eg, hydrogen bonds, Van der Waals forces, etc.), and the like, and combinations thereof.
[041] The terms "slow addition" or "added slowly" may refer to fractional additions of the complete catalyst load over an extended period of time, in contrast to a single full batch load at once. In some embodiments, the slow addition of the catalyst may refer to catalyst that is added fractionally to a substrate or raw material at a rate of approximately 10 ppm weight of catalyst per hour (ppm weight / h), 5 ppm weight / h , 1 ppm weight / h, 0.5 ppm weight / h, 0.1 ppm weight / h, 0.05 ppm weight / h, or 0.01 ppm weight / h. In other embodiments, the catalyst is added slowly at a rate of between about 0.01-10 ppm weight / h 0.05-5 ppm weight / h, or 0.1-1 ppm weight / h.
[042] The phrase "continuous addition" or "continuously added" can also refer to the addition of a percentage of a catalyst load over an extended period of time, in contrast to a batch load of the entire catalyst load at once. In a continuous addition, the catalyst is being added to a substrate or raw material at a continuous or practically continuous frequency (that is, at least once a minute), as opposed to a batch load, or several fractional batch loads in longer intervals, such as once an hour.
[043] It is to be understood that the elements and characteristics of the various representative modalities described below can be combined in different ways to produce new modalities that are also within the scope of the present teachings.
[044] As a general introduction, a method in accordance with the present teachings for the treatment of a substrate before a metathesis reaction includes treating the substrate with a first agent configured to mitigate the potentially adverse effects of one or more contaminants on the substrate in a catalyst used to catalyze the metathesis reaction. In some embodiments, the treatment reduces a level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 7,500 to 1.
[045] In some embodiments, the substrate comprises one or a plurality of functional groups. In some embodiments, the substrate comprises a heteroatom which, in some embodiments, comprises oxygen. In some embodiments, the substrate comprises a natural oil and / or a derivative thereof, or both of which, in some embodiments, is optionally functionalized. Representative examples of natural oils for use in accordance with the present teachings include, but are not limited to, vegetable oils, algae oils, animal fats, liquid resin (for example, by-products from the manufacture of wood pulp), derived from these oils, and the like, and their combinations. Representative examples of vegetable oils for use in accordance with the present teachings include, but are not limited to, canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesame oil, soybean oil, sunflower oil, highly oleic sunflower oil, linseed oil, palm oil, tung oil, jatropha oil, mustard oil, pennycress oil, oil camelina, hemp oil, castor oil, and the like, and combinations thereof. Representative examples of animal fats for use in accordance with the present teachings include, but are not limited to lard, tallow, poultry fat, recycled vegetable oil, brown fat, fish oil, and the like, and combinations thereof. In some embodiments, natural oil can be refined, bleached, and / or deodorized. In some embodiments, natural oil is selected from the group consisting of canola oil, rapeseed oil, corn oil, cottonseed oil, peanut oil, sesame oil, soybean oil, sunflower oil, linseed oil, palm oil, tung oil, and their combinations.
[046] Representative examples of natural oil derivatives for use in accordance with the present teachings include, but are not limited to, gums, phospholipids, sludge, acidified sludge, distillates or distillate sludges, fatty acids, fatty acid esters (for example , non-limiting examples such as 2-ethylhexyl ester, etc., the hydroxy-substituted variations thereof, and the like, and combinations thereof. In some embodiments, the natural oil derivative comprises an ester. In some embodiments, the derivative is selected from the group consisting of a monoacylglyceride (MAG), a diacylglyceride (DAG), a triacylglyceride (TAG), and their combinations In some embodiments, the natural oil derivative comprises a fatty acid methyl ester (FAME) derived of glyceride from natural oil.
[047] In some modalities, the metathesis reaction comprises auto-metathesis of a natural oil and / or a derivative thereof. In some embodiments, the metathesis reaction comprises cross-metathesis between a natural oil and / or a derivative thereof, and a low molecular weight olefin and / or a high molecular weight olefin. In some embodiments, the metathesis reaction comprises cross-metathesis between a natural oil and / or a derivative thereof, and a low molecular weight olefin. In some embodiments, the metathesis reaction comprises cross-metathesis between a natural oil and / or a derivative thereof, and a high molecular weight olefin.
[048] All types of metathesis reactions are contemplated for use in accordance with the present teachings. Representative types of metathesis reactions include, but are not limited to, auto metathesis, CM, ROM, ROMP, RCM, ADMET, and the like, and combinations thereof. In some embodiments, the metathesis reaction is catalyzed by an alkylidene ruthenium complex. In some embodiments, the metathesis reaction is catalyzed by a complex of molybdenum and alkylidene. In some embodiments, the metathesis reaction is catalyzed by a complex of tungsten and alkylidene. In some embodiments, the metathesis reaction comprises closed ring metathesis. In some embodiments, the metathesis reaction comprises auto-metathesis of an optionally functionalized olefin reagent. In some embodiments, the optionally functionalized olefin reagent comprises a natural oil. In some embodiments, the metathesis reaction comprises cross-metathesis between an optionally functionalized olefin reagent and an optionally functionalized olefin co-reagent. In some embodiments, the optionally functionalized olefin reagent comprises a natural oil, and the optionally functionalized olefin co-reagent comprises a low molecular weight olefin. In some embodiments, the optionally functionalized olefin reagent comprises a natural oil, and the optionally functionalized olefin co-reagent comprises a fatty acid methyl ester with representative FAMEs including, but not limited to, decenoic acid methyl esters (eg 9-DAME), methyl esters of undecenoic acid esters (eg 9-UDAME), methyl esters of dodecenoic acids (eg 9-DDAME), dimethyl esters of octadecene dicarboxylic acid (eg 9- ODDAME), and the like, and their combinations.
[049] In some embodiments, the low molecular weight olefin is a "cc-olefin" (or "terminal olefin"), in which the unsaturated carbon-carbon bond is present at one end of the compound. In some embodiments, low molecular weight olefin is an internal olefin. In some embodiments, the low molecular weight olefin is functionalized. In some embodiments, the low molecular weight olefin is a polyolefin. In some embodiments, the low molecular weight olefin comprises one or a plurality of substructures having a formula -CH = CH- CH2-CH = CH-. In some embodiments, the low molecular weight olefin is a C2-C30 olefin. In some embodiments, the low molecular weight olefin is a C2-C30 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C25 olefin. In some embodiments, the low molecular weight olefin is a C2-C25 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C20 olefin. In some embodiments, the low molecular weight olefin is a C2-C20 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C15 olefin. In some embodiments, the low molecular weight olefin is a C2-C15 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C14 olefin. In some embodiments, the low molecular weight olefin is a C2-C14 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C10 olefin. In some embodiments, the low molecular weight olefin is a C2-C10 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C8 olefin. In some embodiments, the low molecular weight olefin is a C2-C8 ocoolefin. In some embodiments, the low molecular weight olefin is a C2-C6 olefin. In some embodiments, the low molecular weight olefin is a C2-C6 ocoolefin. Representative low molecular weight olefins include, but are not limited to, 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, cyclobutene, 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, 1-hexene, 2-hexene, 3- hexene, cyclohexene, 1,4-pentadiene, 1,4-hexadiene, 1,4-heptadiene, 1,4-octadiene, 1,4-nonadiene, 1,4-decadiene, 2,5-heptadiene, 2, 5-octadiene, 2,5-nonadiene, 2,5-decadiene, 3,6-nonadiene, 3,6-decadiene, 1,4,6-octatriene, 1,4,7-octatriene, 1,4,6- nonatriene, 1,4,7-nonatriene, 1,4,6-decathriene, 1,4,7-decathriene, 2,5,8-decathriene, and the like, and combinations thereof. In some embodiments, the low molecular weight olefin is an ocoolefin selected from the group consisting of styrene, vinyl cyclohexane, and a combination of these. In some embodiments, the low molecular weight olefin is a mixture of linear and / or branched olefins in the C4-C10 range. In some embodiments, the low molecular weight olefin is a mixture of linear and / or branched C4 olefins (for example, combinations of 1-butene, 2-butene, and / or iso-butene). In some embodiments, low molecular weight olefin is a mixture of linear and / or branched olefins in the largest C11-C14 range.
[050] In some modalities, the metathesis reaction comprises the reaction of two triglycerides present in the natural raw material in the presence of a metathesis catalyst (auto-metathesis), in which each triglyceride comprises at least one carbon-carbon double bond thus forming a new mixture of olefins and esters which, in some modalities, comprises a triglyceride dimer. In some embodiments, the triglyceride dimer comprises more than one carbon-carbon double bond, such that larger oligomers can also be formed. In some embodiments, the metathesis reaction comprises the reaction of an olefin (for example, a low molecular weight olefin) and a triglyceride of a natural raw material that comprises at least one carbon-carbon double bond, thereby forming new olefinic molecules, as well as new ester molecules (crossed metathesis).
[051] In some embodiments, the metathesis catalyst comprises a transition metal. In some embodiments, the metathesis catalyst comprises ruthenium. In some embodiments, the metathesis catalyst comprises rhenium. In some embodiments, the metathesis catalyst comprises tantalum. In some embodiments, the metathesis catalyst comprises tungsten. In some embodiments, the metathesis catalyst comprises molybdenum.
[052] In some embodiments, the metathesis catalyst comprises a ruthenium carbene complex and / or an entity derived from such a complex. In some embodiments, the metathesis catalyst comprises a material selected from the group consisting of a ruthenium and vinylidene complex, a ruthenium and alkylidene complex, a ruthenium and methylidene complex, a ruthenium and benzylidene complex, and combinations of themselves, and / or an entity derived from any complex or a combination of such complexes. In some embodiments, the metathesis catalyst comprises a ruthenium carbene complex that comprises at least one phosphine binder and / or an entity derived from such a complex. In some embodiments, the metathesis catalyst comprises a ruthenium carbene complex that comprises at least one tricyclohexylphosphine binder and / or an entity derived from such a complex. In some embodiments, the metathesis catalyst comprises a ruthenium carbene complex comprising at least two tricyclohexylphosphine ligands [eg (PCy3) 2Cl2Ru = CH-CH = C (CH3) 2, etc.] and / or an entity derived from such a complex. In some embodiments, the metathesis catalyst comprises a ruthenium and carbene complex that comprises at least one imidazolidine ligand and / or an entity derived from such a complex. In some embodiments, the metathesis catalyst comprises a ruthenium and carbene complex comprising an isopropyloxy group attached to a benzene ring and / or an entity derived from such a complex.
[053] Non-limiting examples of metathesis catalysts and process conditions are described in PCT / US2008 / 009635, hereby incorporated by reference in their entirety. In some embodiments, the metathesis catalyst comprises an olefin metathesis catalyst of the Grubbs type and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a first generation Grubbs type olefin catalyst and / or an entity derived from it. In some embodiments, the metathesis catalyst comprises a second generation Grubbs type olefin catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises a first generation Hoveda-Grubbs type olefin catalyst and / or an entity derived from it. In some embodiments, the metathesis catalyst comprises a second generation Hoveda-Grubbs type olefin catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises one or a plurality of ruthenium carbene metathesis catalysts sold by Materia, Inc. of Pasadena, California, and / or one or more entities derived from such catalysts. Representative metathesis catalysts from Materia, Inc. for use in accordance with the present teachings include, but are not limited to, those sold under the following product numbers, as well as their combinations: product no. C823 (CAS No. 172222-30-9), product no. C848 (CAS No. 246047-72-3), product no. C601 (CAS No. 203714-71-0), product no. C627 (CAS No. 301224-40-8), product no. C571 (CAS No. 927429-61-6), product no. C598 (CAS No. 802912-44-3), product no. C793 (CAS No. 927429-60-5), product no. C801 (CAS No. 194659-03-9), product no. C827 (CAS No. 253688-91-4), product no. C884 (CAS No. 900169-53-1), product no. C833 (CAS No. 1020085-61-3), product no. C859 (CAS No. 832146-68-6), product no. C711 (CAS No. 635679-24-2), product no. C933 (CAS No. 373640-75-6).
[054] In some embodiments, the metathesis catalyst comprises a complex of molybdenum and / or carbene tungsten and / or an entity derived from such a complex. In some embodiments, the metathesis catalyst comprises a Schrock type olefin metathesis catalyst and / or an entity derived therefrom. In some embodiments, the metathesis catalyst comprises an alkylidene complex with a high oxidation state of molybdenum and / or an entity derived from it. In some embodiments, the catalyst comprises a metathesis and alkylidene complex with a high oxidation state of tungsten and / or an entity derived from it. In some embodiments, the metathesis catalyst is composed of molybdenum (VI). In some embodiments, the metathesis catalyst comprises tungsten (VI). In some embodiments, the metathesis catalyst comprises an alkylidene complex containing molybdenum and / or tungsten of a type described in one or more of (a) Angew. Chem. Int. Ed. Engl. 2003, 42, 4592- 4633; (B) Chem. Rev. 2002, 102, 145-179; (c) Chem. Rev. 2009, 109, 3211-3226, (d) Nature 2011, 479, 88-93, and / or Angew. Chem. Int. Ed. Engl. 2013, 52, 1939-1943, each of which is incorporated herein by reference in its entirety, except that in the case of any inconsistent disclosure or definition in this specification, the disclosure or definition here must be considered to prevail. In other embodiments, the catalyst can be any of those described in US patent application No. 14 / 209,313, filed on March 13, 2014, the disclosure of which is thus incorporated by reference in its entirety. In some embodiments, the metathesis catalyst is selected from the group consisting of: • Mo (N-2,6- / PR2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (0-2,6-Ph2C6H3) (in this "X004"); • Mo (N-2,6- / Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(/ : ) - 3,3'-dibromo-2'- (tert-buí / 7c // met / 7s / 7 / 7ox /) - 5,5 ', 6,6', 7,7 ', 8,8'-octahydro-1,1' -binaft-2-olate)] (in this “X007”); • Mo (N-2,6- / Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(/ : ) - 3,3'-dibromo-2'- methoxy / -5,5 ', 6 , 6 ', 7,7', 8,8'-octahidro-1,1'-binaft-2-olato)] (in this "X008"); and • W (N-2,6-Cl2-C6H3) (CHCMe3) (2,5-dimethylpyrrolid) [(/ : ) - 3,3'-dibromo-2 '- (tert-bt / t / 7c / / met / 7s / 7 / 7ox /) - 5.5 ', 6.6', 7.7 ', 8.8'-octahydro-1,1' -binaft-2-olate)] (in this “X022” ); • W (N-2,6-Cl2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(/ : ) - 3,3'-dibromo-2'- (7erc-but / 7d / 7 et / 7s / 7 / 7ox /) - 5,5 ', 6,6', 7,7 ', 8,8'-octahidro-1,1' -binaft-2-olato)] (in this “X207”) ; • Mo (N-2,6-'Pr2-C6H3) (CHCMe2Ph) (pyrrolid) (0-2,6-fBu2C6H3) (in this “X027”); • Mo (N-2,6-Me2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(S) -3,3'-dibromo-2'- (7erc-but / 7d / 7 et / 7s / 7 / 7ox /) - 5.5 ', 6.6', 7.7 ', 8.8'-octahydro-1,1' -binaft-2-olate)] (in this “X030”); • W (N-2,6-Cl2-C6H3) (CHCMe3) (pyrrolid) [2,6-bis (2 ', 4', 6'-tri-isopropyl-phenyl) - phenoxide] (in this “X038”) ; • Mo (N-1-adamantyl) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(/ : ) - 3,3'-dibromo-2'- (7erc-but / 7d / 7 et / 7s / 7 / 7ox /) - 5.5 ', 6.6', 7.7 ', 8.8'-octahydro-1,1' -binaft-2-olate)] (in this "X048"); • Mo (N-2,6- / Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (0-2,3,5,6-Ph4C6Hi) (in this “X051”); • Mo (N-2,6- / Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (0-2,3,5,6-Ph4-4-Br-CΘ) (in this “X052”); • W (N-2,6-Ol2-C6H3) (CHCMe3) (2,5-dimethyl-pyrrolide) (O-2,3,5,6-Ph4-4-Br-C6) (in this “X123”) ; • W (N-2,6-Cl2-C6H3) (CHCMe3) (2,5-dimethyl-pyrrolide) (O-2,3,5,6-Ph4-C6Hi) (in this “X154”); • Mo (N-2,6-'Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (4-F-2,6- (2 ', 4', 6'-trimethylphen-1-yl) 2 -phenolate) (in this “X085”); • W (N-2,6-'Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(/ : ) - 3,3'-dibromo-2'- (erc-di7í / 7c // met / 7s / 7 / 7ox /) - 5,5 ', 6,6', 7,7 ', 8,8'-octahidro-1,1' -binaft-2-olato)] (in this “X106”); • Mo (N-2,6-Me2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (4-F-2,6- (2 ', 4', 6'-trimethylphen-1-yl) 2- phenolato) (in this “X122”); • W (N-2,6-Cl2-C6H3) (CHCMe3) (2,5-dimethylpyrrolid) (4-F-2,6- (2 ', 4', 6'-trimethylphen-1-yl) 2- phenolate) (in this “X131”); • W (N-2,6-'Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (4-F-2,6- (2 ', 4', 6'-trimethylphen-1-yl) 2 -phenolate) (in this “X135”); • W (N-2,6-Cl2-C6H3) (CHCMe3) (2,5-dimethylpyrrolid) (0-Si'Pr3) (in this “X137”); • Mo (N-2,6- / Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (0-Si'Pr3) (in this “X138”); • W (N-2,6-Cl2-C6H3) (CHCMe3) (2,5-dimethylpyrrolid) (8 '- (tert-butyldimethylsilyloxy) - 1,1'-binafil-8-olatol) (in this “X214”) ; • W (N-2,6-Cl2-C6H3) (CHCMe3) (2,5-dimethyl-pyrrolide) (8-phenylnaphthalen-1-olate) (in this “X216”); • Mo (N-2,6- 'Pr2-C6H3) (CHCMe2Ph) (2,5-dimethyl-pyrrolide) (8' - (tert-butyldimethylsilyloxy) -1,1 '-binafil-8-olatol) (in this “ X217 "); • Mo (N-2,6- 'Pr2-C6H3) (CHCMe2Ph) (2,5-dimethyl-pyrrolide) (8-phenylnaphthalene-1-olate) (in this “X218”);
[055] In some embodiments, the metathesis catalyst is selected from the group consisting of the following molybdenum-based complexes, available from XiMo AG (Lucerne, Switzerland):
[056] As presently contemplated, all types of contaminants with the potential to adversely affect the performance of a metathesis catalyst can be treated in accordance with the present teachings. For example, representative contaminants include, but are not limited to, water, peroxides, peroxide decomposition products, hydroperoxides, prosthetic materials, polar materials, Lewis base catalyst poisons, and the like, and combinations thereof . It is to be understood that some contaminants can be properly classified into several categories (for example, an alcohol can be considered both a protic material and a polar material). It should also be understood that different catalysts may have different susceptibilities to a particular contaminant, and that a contaminant that adversely affects the performance of a catalyst (eg, a ruthenium-based catalyst) may or may not affect (at a similar level or to any extent) a different catalyst (for example, a molybdenum based catalyst). By way of illustration, while neither wishing to be limited by any particular theory, nor with the intention of limiting to any extent, the scope of the appended claims or their equivalents, it is currently believed that ruthenium catalysts are generally more sensitive to peroxides than molybdenum catalysts are. In addition, while not wishing to be limited by any particular theory, nor with the intention of limiting to any extent, the scope of the attached claims or their equivalents, it is currently believed that moisture (and / or prosthetic materials in general) it poses a greater problem in high valence olefin metathesis catalysts (eg molybdenum catalysts) than the peroxides that are so harmful to ruthenium catalysts. Thus, it is currently believed that removing peroxides from raw materials used with molybdenum catalysts, while improving the performance of molybdenum catalysts, is necessary, but it may not be sufficient to make a suitable raw material for molybdenum catalyzed metathesis . Furthermore, it is currently believed that the slow addition of catalyst to a substrate, with or without the removal of contaminants from the substrate, can improve the performance of the metathesis catalyst.
[057] Representative protic materials that can be found as contaminants on a substrate that is to be reacted in a metathesis reaction include, but are not limited to materials that have an oxygen-bonded hydrogen atom (e.g., carboxylic acids, alcohols, and the like) and / or a hydrogen atom bound to nitrogen (for example, primary amines, secondary amines, and the like). In some embodiments, particularly, but not exclusively on natural oil substrates, a protic material contaminant may comprise a carboxylic acid functional group, a hydroxyl functional group, or a combination thereof. In some embodiments, the protic material is selected from the group consisting of free fatty acids, materials containing hydroxyl, MAGs, DAGs, and the like, and their combinations.
[058] Representative polar materials that can be found as contaminants on a substrate that is reacted in a metathesis reaction include, but are not limited to, the heteroatom containing materials such as oxygenates. In some embodiments, the polar material is selected from the group consisting of alcohols, aldehydes, ethers, and the like, and their combinations. In some embodiments, the polar material comprises an aldehyde.
[059] Representative Lewis base catalyst poisons that can be found as contaminants on a substrate that is reacted in a metathesis reaction include, but are not limited to, heteroatom-containing materials. In some embodiments, the Lewis base catalyst poisons are selected from the group consisting of materials containing N, materials containing P, materials containing S, and the like, and combinations thereof.
[060] In some embodiments, a substrate to be reacted in a metathesis reaction comprises a contaminant with the potential to adversely affect the performance of a metathesis catalyst. As is recognized in the art, such contaminants can be referred to as "catalyst poisons" or "catalyst poisoning contaminants". In other embodiments, a substrate to be reacted in a metathesis reaction comprises a plurality of contaminants with the potential to adversely affect the performance of a metathesis catalyst. In some embodiments, the substrate comprises a plurality of contaminants and the method comprises reducing levels of two or more of the contaminants. In some embodiments, the substrate comprises a plurality of contaminants and the method comprises reducing levels of three or more of the contaminants. In some embodiments, the substrate comprises a plurality of contaminants and the method comprises reducing levels of four or more of the contaminants. In some embodiments, the substrate comprises a plurality of contaminants and the method comprises reducing levels of five or more of the contaminants.
[061] In certain embodiments, the effectiveness of the metathesis catalyst can be improved (for example, TON can be increased or the total catalyst load can be reduced), by slowly adding the catalyst to a substrate. In some embodiments, the total catalyst load can be reduced by at least 10%, at least 20%, or at least 30% compared to the same TON as a single, complete batch load. The slow addition of the general catalyst load may comprise adding fractional catalyst loads to the substrate at an average rate of approximately 10 ppm weight / h of the catalyst per hour (ppm weight / h), 5 ppm weight / h, 1 ppm weight / h , 0.5 ppm weight / h, 0.1 ppm weight / h, 0.05 ppm weight / h, or 0.01 ppm weight / h. In other embodiments, the catalyst is added slowly at a rate of between about 0.01-10 ppm weight / h, 0.05-5 ppm weight / h, or 0.1-1 ppm weight / h. The slow addition of the catalyst can be conducted in batch loads at frequencies every 5 minutes, 15 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 12 hours or one day. In other embodiments, the slow addition is conducted in a continuous addition process.
[062] In some embodiments, the substrate is treated with at least one agent (as described in detail below) before the slow addition of the catalyst. In other embodiments, the slow addition of the catalyst improves the effectiveness of the catalyst regardless of any substrate treatment.
[063] In some embodiments, the first agent used to treat the substrate before the metathesis reaction is configured to mitigate the potentially adverse effects of two or more of the contaminants. In some embodiments, the first agent is configured to mitigate the potentially adverse effects of three or more of the contaminants. In some embodiments, the first agent is configured to mitigate the potentially adverse effects of four or more of the contaminants. In some embodiments, the first agent is configured to mitigate the potentially adverse effects of five or more of the contaminants. In some embodiments, the first agent is configured to mitigate the potentially negative effects of water on the catalyst. In some embodiments, the first agent is configured to mitigate the potentially negative effects of peroxides, hydroperoxides, and / or peroxide decomposition products on the catalyst. In some embodiments, the first agent is configured to mitigate the potentially adverse effects of protic materials on the catalyst. In some embodiments, the first agent is configured to mitigate the potentially adverse effects of polar materials on the catalyst. In some embodiments, the first agent is configured to mitigate the potentially negative effects of water, peroxides, hydroperoxides, and / or peroxide decomposition products, protic materials, and / or polar materials on the catalyst.
[064] In some embodiments, the methods according to the present teachings still comprise the treatment of the substrate, simultaneously and / or successively, with a second agent that is configured to mitigate the potentially adverse effects of one or more of the contaminants. In some embodiments, the methods according to the present teachings still comprise treating the substrate, simultaneously and / or successively, with a second agent and, simultaneously and / or successively, with a third agent, each of which is individually configured to potentially mitigate the adverse effects of one or more of the contaminants. In some embodiments, the methods according to the present teachings still comprise the treatment of the substrate, simultaneously and / or successively, with a plurality of additional agents, each of which is individually configured to mitigate the potentially adverse effects of one or more of the contaminants.
[065] The nature of the first agent, second agent, third agent and any additional agents used to treat a substrate in accordance with the present teachings, is determined taking into account the nature of the particular substrate or substrates, taking into account the nature of the particular contaminant (or contaminants), and / or because of the known sensitivities of a particular metathesis catalyst. Some agents are incompatible with (for example, reactive with) certain functional groups and, in such modalities, it may be less desirable to use these agents for the treatment of substrates containing incompatible functional groups (for example, using LÍAIH4 in large quantities for treating a natural oil containing ester) or one skilled in the art may choose to employ such agents, but limit the amount or conditions for treatment. Similarly, some agents are extremely reactive (for example, dangerously exothermic) towards some contaminants, so that it may be advisable for safety reasons (a) not to use highly reactive agents in the known presence of the contaminant, (b ) first check that the contaminant is present only in residual amounts below the safety limit level before attempting treatment (for example, using an organometallic reagent to reduce the moisture level in a substrate), and / or (c) performing a large removal of contaminant quantities starting with a less reactive agent before removing residual amounts of residual contaminants using the agent with greater reactivity.
[066] In some embodiments, the first agent, the second agent, the third agent, and any additional agents can be a Group I, II, or III alkyl metal compound. In some embodiments, the Group I, II, and 11IA metal alkyl compounds are compounds of the formula MRm, in which, in some embodiments, M is a Group II metal, or IIIA, each R is, independently, an alkyl radical from 1 to about 20 carbon atoms, in corresponds to the valence of M. In some other modalities, the metal, M, can be lithium, sodium, potassium, magnesium, calcium, zinc, cadmium, aluminum, or gallium. Examples of suitable alkyl radicals, R, include, but are not limited to, methyl, ethyl, butyl, hexyl, decyl, tetradecyl, and eicosyl. Specific examples of such compounds include Mg (CH3) 2, Mg (C2H5) 2, Mg (C2H5) (C4H9), Mg (C4H9) 2, Mg (C6Hi3) 2, Mg (Ci2H25) 2, Zn (CH3) 2, Zn (C2H5) 2, Zn (C4H9) 2, Zn (C4H9) (CsHπ), Zn (C6Hi3) 2, Zn (C6Hi3) 2, AI (C2H5) 3, AI (CH3) 3, AI (n-C4H9) 3, AI (CδHi7) 3, AI (iso-C4H9) 3, AI (Ci2H2s) 3, and their combinations. If desired, alkyl metal compounds having one or more halogen groups or hydride groups can be employed, such as ethyl aluminum dichloride, diethyl aluminum chloride, diethyl aluminum hydride, Grignard reagents, diisobutyl aluminum hydride, and the like.
[067] In some embodiments, the first agent, the second agent, the third agent, and / or any additional agents used in accordance with the present teachings are each individually selected from the group consisting of heat, molecular sieves, alumina (oxide aluminum), silica gel, montmorillonite clay, flooring clay, bleaching clay, diatomaceous earth, zeolites, kaolin, activated metals (eg Cu, Mg, and the like), acid anhydrides (eg acetic anhydride " AcsO "and the like) activated carbon (also known as activated charcoal), sodium carbonate, metal hydrides (for example, alkaline earth metal hydrides, such as CaH2 and the like), metal sulfates (for example, metal sulfates alkaline earth, such as calcium sulfate, magnesium sulfate, and the like; alkali metal sulfates, such as potassium sulfate, sodium sulfate, and the like; and other m etal, such as aluminum sulfate, magnesium potassium sulfate, and the like), metal halides (e.g., alkaline earth metal halides, such as potassium chloride and the like), metal carbonates (e.g., calcium carbonate, sodium carbonate, and the like), metal silicates (for example, magnesium silicate and the like), phosphorus pentoxide, aluminum metal hydrides (for example, aluminum and alkali metal hydrides, such as LÍAIH4, NaAIH4 and the like ), alkyl aluminum hydrides (for example, ÍBU2AIH also known as DIBALH), metal borohydrides (for example, alkali metal borohydrides, such as LÍBH4, NaBH4, and the like), organometallic reagents (for example, Grignard reagents; organolytic reagents, such as n-butyl lithium, f-butyl lithium, sec-butyl lithium; trialkyl aluminum, such as triethyl aluminum ("EtsAI"), tributyl aluminum, triisobutyl aluminum, tri isopropyl aluminum, trioctyl aluminum ("OcsAI"), and the like, metal amides (eg, lithium diisopropylamide, LDA also known as metal bis (trimethylsilyl) amides, such as KHMDS, and the like), palladium on carbon (Pd / C) catalysts, and combinations thereof.
[068] In some embodiments, the treatment of the metathesis substrate material (for example, a natural oil) may include contacting the metathesis substrate with a metallic alkyl compound (according to any of the above modalities) and , or simultaneously or separately, contacting the metathesis substrate material with a hydride-containing compound. In some embodiments, where the metathesis substrate material is brought into contact simultaneously with the alkyl metal compound and the hydride containing compound, the hydride containing compounds can be included in the alkyl metal compound. For example, in some cases, the processes used to make certain alkyl metal compounds, such as trialkyl aluminum compounds, can lead to the formation of a certain concentration of hydride-containing compounds. In other embodiments, however, the alkyl metal compounds can be combined with one or more hydride-containing compounds. Or, in some embodiments, the metathesis substrate material can be treated with the hydride-containing compounds in a separate treatment step, which can be carried out before, after, both before and after treating the metathesis substrate material with the compounds of alkyl metal.
[069] Any compounds containing suitable hydride can be used. In some embodiments, hydride-containing compounds are selected from the group consisting of aluminum metal hydrides (for example, aluminum hydrides and alkali metal, such as UAIH4, NaAIH4 and the like), alkyl aluminum hydrides (eg, ÍBU2AIH, also known as DIBALH), and any combinations thereof. In some embodiments, the hydride-containing compound is an alkyl aluminum hydride, such as DIBALH.
[070] In the embodiments, where the metathesis substrate material is treated with an alkyl metal compound and a hydride-containing compound, any suitable combination of materials can be used. In some of such embodiments, the alkyl metal compound is an alkyl aluminum compound, such as aluminum triethyl, aluminum trioctyl, and the like. In some embodiments, the hydride-containing compound is an alkyl aluminum hydride, such as DIBALH. As noted above, such treatments can be carried out in the same step and / or in separate steps.
[071] In some embodiments, the contact of the metathesis substrate material with the hydride-containing compound occurs in the same step as the contact of the metathesis substrate material with the alkyl metal compound. In some of such embodiments, the alkyl metal compound and the hydride-containing compound are disoised in a common treatment composition. In some embodiments, the weight to weight ratio of the alkyl metal compound to the hydride-containing compound in the treatment composition is from 2: 1, or from 5: 1, or from 10: 1, or from 15 : 1, or from 20: 1, 1000: 1. In some embodiments, the weight to weight ratio of alkyl metal compound to hydride-containing compound in the treatment composition is at least 2: 1 or at least 5: 1 or at least 10: 1 or at least 15 : 1 or at least 20: 1.
[072] An additional description on the use of heat as an agent to treat a substrate prior to a metathesis reaction is provided in United States Patent Application Publication No. US 2011/0313180, which is assigned to the applicant of the present invention . An additional description of the use of reducing agents and compositions based on inorganic cations, such as agents for treating a substrate before a metathesis reaction is provided in United States Patent Application Publication No. US 2011 / 0160472, which is attributed to the applicant for this disclosure. The entire contents of each of the three documents identified above are incorporated herein in their entirety, except that in the case of any disclosure or inconsistency in the definition of this report, the disclosure or definition here must be considered to prevail.
[073] In some embodiments, the first agent, second agent, third agent, and / or any additional agents used in accordance with the present teachings are each individually selected from the group consisting of heat, molecular sieves optionally heat treated, optionally heat-treated alumina (for example, activated, acidic, basic and neutral), optionally heat-treated silica gel, montmorillonite clay, flooring clay, bleaching clay, diatomaceous earth (for example, as sold under the trade name CELITE), zeolites, kaolin, activated metals, acid anhydrides, activated carbon, sodium carbonate, metal hydrides, metal sulfates, metal halides, metal carbonates, metal silicates, phosphorus pentoxide, aluminum metal hydrides, aluminum alkyl hydrides , metal borohydrides, organometallic reagents, metal amides, and the like, and combinations thereof.
[074] In some embodiments, the first agent, second agent, third agent, and / or any additional agents used in accordance with the present teachings are each individually selected from the group consisting of activated molecular sieves optionally treated with heat, alumina optionally activated heat treated, acid activated optionally treated with heat, optionally activated neutral alumina treated with heat, optionally activated basic alumina treated with heat, alkaline earth metal hydrides, alkaline earth metal sulphates, alkali metal sulphates, metal halides alkaline earth, alkali metal aluminum hydrides, alkali metal borohydrides, Grignard reagents; organolithium reagents, trialkylaluminiums, metal bis (trimethylsilyl) amides, and the like, and combinations thereof.
[075] In some embodiments, the first agent, second agent, third agent, and / or any additional agents used in accordance with the present teachings are each individually selected from the group consisting of CaH2, activated Cu, activated Mg, acetic anhydride, calcium sulfate, magnesium sulfate, potassium sulphate, aluminum sulphate, magnesium potassium sulphate, sodium carbonate, calcium carbonate, sodium carbonate, magnesium silicate, potassium chloride, LÍAIH4, NaAIH4, ÍBU2AIH, metal methoxide, metal ethoxide, metal n-propoxide, metal isopropoxide, metal butoxide, metal 2-methylpropoxide, metal tert-butoxide, titanium isopropoxide, aluminum ethoxide, aluminum isopropoxide, zirconium ethoxide and combinations thereof, n-butyl lithium, t-butyl lithium, sec-butyl lithium, triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, lithium diisopropyl amide, KHMDS, and the like, and the like their combinations.
[076] In some embodiments, the first agent, the second agent, the third agent, and / or any additional agents used in accordance with the present teachings are each individually and optionally attached to a solid support. Representative solid supports for use in accordance with the present teachings include, but are not limited to, carbon, silica, silica-alumina, alumina, clay, magnesium silicates (eg, Magnesols), the synthetic silica adsorbent sold under the trade name TRISYL by WR Grace & Co., diatomaceous earth, polystyrene, macroporous resins (MP), and the like, and their combinations.
[077] Usually, there are several options of different and often complementary agents from these to choose from when preparing to treat a contaminated substrate (for example, natural oil raw materials and the like) before a metathesis reaction. While not wishing to be limited by any particular theory, nor with the intention of limiting the scope of the appended claims or their equivalents to any extent, it is currently believed that the following non-exhaustive and non-limiting list of representative treatment methodologies may be useful in the treatment of substrates that contain the specified contaminants (provided that the agents are compatible with any functional groups on the substrate and / or with the contaminants themselves, etc.): (a) a heat treatment - for example, heating (and / or distill) a substrate (for example, between about 100QC and about 250QC, or around 200QC, in some embodiments - depending on the substrate's boiling point, optionally with an inert gas purge, such as N2, and / or similar) and / or treatment with an adsorbent (for example, alumina and the like) can be useful in the decomposition of contaminants peroxide and / or their decomposition products; (b) treatment with an acid anhydride (eg, acetic anhydride, AC2O) can be useful in removing moisture, materials containing active hydroxyls (eg, alcohols) and hydroperoxides (via acetylation); (c) treatment with a desiccant (for example, silica gel, alumina, molecular sieves, magnesium sulfate, calcium sulfate, and the like, and combinations thereof) and / or an organometallic reagent (for example, t-butyl lithium, triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof) and / or metal hydrides (e.g., CaH2 and the like) and / or acid anhydrides (e.g. , acetic anhydride and the like) can be useful in removing moisture; (d) treatment with an adsorbent (for example, alumina, silica gel, activated charcoal, and the like, and combinations thereof) and / or an organometallic reagent (for example, t-butyl lithium, triethyl aluminum, tributyl aluminum, tri-aluminum) isobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof) and / or a metal amide (e.g., LDA, KHMDA, and the like) may be useful in removing prosthetic materials; (e) treatment with an adsorbent (for example, alumina, silica gel, activated charcoal, and the like, and combinations thereof) can be useful in removing polar materials; and / or (f) treatment with an organometallic reagent (for example, t-butyl lithium, triethyl aluminum, tributyl aluminum, tri-isobutyl aluminum, tri-isopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof) useful in removing poisons from the Lewis base catalyst; etc.
[078] In some embodiments, the first agent used to treat a substrate before a metathesis reaction comprises an adsorbent which, in some embodiments, is selected from the group consisting of silica gel, alumina, bleaching clay, activated carbon , molecular sieves, zeolites, paver soil, diatomaceous earth, and the like, and combinations thereof. In some embodiments, the first agent is selected from the group consisting of molecular sieves optionally heat treated, alumina optionally treated with heat, and a combination of these. In some embodiments, the adsorbent comprises optionally activated heat treated alumina which, in some embodiments, is selected from the group consisting of heat treated optionally activated acid alumina, heat treated optionally activated neutral alumina, optionally treated basic alumina activated with heat. heat, and their combinations. In some embodiments, the absorber comprises neutrally activated, optionally heat treated alumina, which can be useful in the treatment of substrates (for example, olefins), which are susceptible to isomerization and / or acid-catalyzed rearrangement.
[079] For modalities in which the first agent, the second agent, the third agent, and / or any additional agents used in accordance with the present teachings comprise an adsorbent (for example, molecular sieves, aluminum oxide, etc.), believe it is now known that the treatment of the substrate with the adsorbent is most effectively carried out by flowing the substrate through the first agent using a percolation or flow type system (for example, column chromatography), as opposed to the simple addition of the adsorbent to the substrate in a container. In some embodiments, about 20% by weight of alumina is used in a column. While not wishing to be limited by any particular theory, nor with the intention of limiting the scope of the appended claims or their equivalents to any extent, it is currently believed that the treatment of a raw material with alumina by about a weight basis by weight to 5 to 1 is effective for some modalities. However, it is to be understood that the amount of alumina used is not restricted and will be both the raw material and the impurity dependent on the addition to be influenced by the shape of the alumina, its activation process, and the precise treatment method ( for example, flow through a column vs. direct addition to the container).
[080] In some embodiments, the first agent, second agent, third agent, and / or any additional agents used to treat a substrate before a metathesis reaction comprises a trialkyl aluminum which, in some embodiments, is selected from the group consisting of triethyl aluminum, tributyl aluminum, tri-isobutyl aluminum, tri-isopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof. While not wishing to be bound by any particular theory, nor with the intention of limiting the scope of the attached claims or their equivalents to any extent, it is currently believed that treating a substrate with a trialkyl aluminum significantly improves the conversions of the raw material press at low concentrations of the metathesis catalyst, but that, in the presence of excess trialkyl aluminum, the catalyst performance is negatively affected. Thus, in some embodiments (for example, when a trialkyl aluminum is used as a first agent and / or an excess of trialkyl aluminum is used), a successive agent used to treat the substrate may comprise an adsorbent, which can remove the excess of trialquil aluminum. In other embodiments, the amount of trialkyl aluminum used for treating the substrate can be reduced first by treating the substrate with an agent other than the type described herein (for example, an adsorbent, including, but not limited to, alumina, molecular sieves, and / or the like), and then introducing trialkyl aluminum as a second (or subsequent) agent to remove residual contaminants. In any case, while not wishing to be limited by any particular theory, nor with the intention of limiting to any extent, the scope of the attached claims or their equivalents, it is currently believed that the removal of excess trialkyl aluminum from Organic products must be carried out with great care, as the use of the wrong adsorbent may not be safe. In some embodiments, the trialquil aluminum is attached to a solid support to facilitate its removal.
[081] In some embodiments, molecular sieves can be used as a first agent for bulk drying a substrate, alumina "treated with high heat" can then be used as a second agent to remove additional moisture and finally , molecular sieves can be used at the end as a third agent to further remove residual moisture. In other embodiments, molecular sieves can be used as a first bulk drying agent for a substrate, alumina "treated with high heat" can then be used as a second agent to remove additional moisture, and finally a trialkyl aluminum (e.g., triethyl aluminum, tributyl aluminum, triisobutyl aluminum, triisopropyl aluminum, trioctyl aluminum, and the like, and combinations thereof) can be used as a third agent for removing any residual moisture.
[082] In a particular embodiment, activated copper powder is used alone or in combination with another treatment. For example, in some embodiments, activated copper powder is used in combination with heat (eg 200 ° C for at least 2 hours, under nitrogen gas), molecular sieves, and / or a trialkyl aluminum treatment. In another embodiment, activated magnesium chips are used alone or in combination with another treatment. For example, in some embodiments, activated magnesium chips are used in combination with heat (eg 200 ° C for at least 2 hours, under nitrogen gas), molecular sieves, and / or a trialkyl aluminum treatment.
[083] In another particular embodiment, acetic anhydride is used alone or in combination with another treatment / agent. For example, in some embodiments, acetic anhydride is used in combination with alumina (aluminum oxide) and / or a trialkyl aluminum treatment. In other embodiments, acetic anhydride is used in combination with alumina, distillation, molecular sieves, and / or a trialkyl aluminum treatment. In addition, percolation over activated alumina or molecular filters can be applied before or instead of trialkyl aluminum treatment.
[084] In another embodiment, alumina is used alone or in combination with another treatment / agent. In one embodiment, alumina is used in combination with a palladium on carbon (Pd / C) catalyst and / or a trialkyl aluminum treatment.
[085] In some embodiments, treatment of a substrate with a first agent reduces the level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 1000 to 1, in some modalities, at least about 2500 to 1, in some modalities, at least about 5000 to 1, in some modalities, at least about 7500 to 1, in some modalities, at least about 10,000 to 1 , in some modalities, at least about 15000 to 1, in some modalities, at least about 20000 to 1, in some modalities, at least about 25000 to 1, in some modalities, at least about 30,000 to 1, in some modalities, at least about 35,000 to 1, in some modalities, at least about 40,000 to 1, in some modalities, at least about 45,000 to 1, and in some modalities, at least about 50,000 to 1.
[086] In other embodiments, treatment of a substrate with a first agent reduces the level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate to catalyst molar ratio as high as about 100000 to 1, in some modalities, as high as about 500000 to 1, in some modalities, as high as about 1000000 to 1, in some modalities, as high as about 2.000000 to 1, in some modalities, as high as about from 1 to 3000000, and, in some modalities, as high as 1 to 4000000.
[087] In some embodiments, the metathesis reaction proceeds from a molar ratio of substrate to catalyst between about 4000000: 1 and 1000: 1, or between about 3000000: 1 and 5000: 1, or between about 2000000: 1 and 7500: 1, or between about 1000000: 1 and 10000: 1, or between about 500000: 1 and 20000: 1, or between about 100000: 1 and 50000: 1.
[088] In one embodiment, substrate treatment reduces the level of at least one contaminant in an amount sufficient to allow the metathesis reaction to proceed at a substrate-to-catalyst molar ratio of at least 1000: 1, 2500: 1, 5000 : 1, 7500: 1, 10000: 1, 15000: 1, 20000: 1, 25000: 1, 30000: 1, 35000: 1, 40000: 1, 45000: 1, 50000: 1, 100000: 1, 500000: 1 , 1000000: 1, or 2000000: 1, and the corresponding conversion is at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80% , or at least 90%.
[089] In other embodiments, substrate treatment reduces the level of at least one contaminant in an amount sufficient to allow the metathesis reaction to proceed from substrate to catalyst molar ratio between 50000: 1 and 1000: 1, or between 40000 : 1 and 2500: 1, or between 30000: 1 and 5000: 1, or between 25000: 1 and 7500: 1, or between 30000: 1 and 10000: 1, or between 30000: 1 and 15000: 1, and the conversion correspondent is between 30% and 100%, or between 50% and 100%, or between 60% and 100%.
[090] In some embodiments, treating a substrate before a metathesis reaction with a first agent, second agent, third agent, and / or any additional agents in accordance with the present teachings reduces the moisture contamination on the substrate to a level that is less than about 10 ppm, in some modalities, less than about 7 ppm, in some modalities, less than about 5 ppm, in some modalities, less than about 3 ppm, in some modalities , less than about 2 ppm, and in some embodiments less than about 1 ppm. In addition, or alternatively, in some embodiments, treating a substrate prior to a metathesis reaction with a first agent, second agent, third agent, and / or any additional agents in accordance with the present teachings reduces peroxides to a level that is less than about 10 milliequivalents per kilogram, in some modalities, less than about 7 milliequivalents per kilogram, in some modalities, less than about 5 milliequivalents per kilogram, in some modalities, less than about 3 milliequivalents per kilogram, in some modalities, less than about 2 milliequivalents per kilogram, and in some modalities, less than about 1 milliequivalents per kilogram.
[091] A method for metathetically reacting a substrate incorporating the characteristics of the present invention includes treating the substrate with a first agent; and react the substrate, after its treatment with the first agent, in a metathesis reaction, in the presence of a metathesis catalyst. The first agent is configured to mitigate the potentially adverse effects of one or more contaminants on the substrate on the metathesis catalyst. In some embodiments, the substrate comprises a natural oil and / or a derivative thereof. In some embodiments, the treatment reduces a level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 7500 to 1 and, in some embodiments, as high like about 2000000 to 1.
[092] The following examples illustrate representative procedures and features in accordance with the present teachings, and are provided by way of illustration only. They are not intended to limit the scope of the attached claims or their equivalents. EXAMPLES Examples 1 - 15 - Study of various substrate treatments before the ethenolysis of natural triglycerides Materials and methods
[093] Edible grade soybean oil (Master Chef, called ‘SBO-1’) and rapeseed oil (Canola oil, Cargill Solo, ‘CO-1’) were purchased at the supermarket. Unless otherwise indicated, the natural triglyceride used in the examples below was canola oil.
[094] Compounds X007, X008, and X022 refer to molybdenum and tungsten catalysts with the structures described in the detailed description part above.
[095] Ethylene gas (5.0, impurities: methane, ethane) was obtained in cylinders from Messer Hungarogas Ltd. and was used without any further purification. Triethyl aluminum (25% in toluene; Cat. # 192708), trioctyl aluminum (25% in n-hexane; Cat. # 386553), acetic anhydride (ACS reagent, Cat # 242845), Cu powder (Cat # 12806) and shavings Mg (Cat. # 403148) were purchased from Sigma-Aldrich. The copper powder surface was activated, following the procedure described in Organic Reactions vol. 63 .: Cu, Ni and Pd Mediated Homocoupling reactions in biaryl syntheses: The Ullmann Reaction (Viley, DOI: 10.1002 / 0471264180). To activate the surface of magnesium chips, Grignard's reaction in diethyl ether with 1,2-dibromoethane was initiated, then the activated magnesium chips were isolated by filtration, washing with dry diethyl ether and drying under a dry nitrogen atmosphere. Molecular sieves (3Â, granules, ~ 2 mm; Cat. # 1.05704.1000), molecular sieves (3Â, powder; Cat. # 1.05706.0250), aluminum oxide (basic, 0.063-0.200 mm; Cat. # 1.01076 .2000) were purchased from Merck. For the activation of molecular sieves and alumina, they were heated at 300 ° C under 1 mbar (0.1 KPa) for 24 hours and allowed to cool and store under a dry nitrogen atmosphere. Pd / C (10%, Selkat-Q-6) was purchased from Szilor Kft., Hungary. Peroxide value [milliequivalent peroxide / kg of sample (meq / kg)] was determined by titration using an autotiter (Metrohm 888 Titrando). The moisture content was determined by a Metrohm 899 Coulometer Karl Fischer titration device. Para-Anisidine (pAV) value was determined according to AOCS Official Method Cd 18-90.
[096] The studies were conducted on samples of natural triglycerides (eg, canola oil or soybean oil) by various substrate treatment methods to create an appropriate classification system for comparing their performance. The performance of the treatment method was described by the result of the ethenolysis reaction performed on the treated oil samples. The values of% conversion and% yield MD9 were compared, together with the% selectivity and% yield of 9ODDAME.
1 O óleo de soja utilizado como o substrato 2 * Não realizada devido à falta de substrato Tabela 1. Visão geral das condições de teste para os Exemplos 1 -15 Exemplos 1 (a) e 1 (b)[097] In certain tests (designated "A"), the substrate samples were treated and then subjected to ethenolysis using different amounts of molybdenum- or tungsten-based catalysts (ie X007, X008, and X022 ). In comparable tests (designated "B"), the samples were treated with the substrate and then subjected to treatment with different amounts of a trialkyl aluminum (eg, triethyl aluminum, trioctyl aluminum) and then subjected to ethenolysis (at 250 ppm by weight of X022) to determine how the demand for trialkyl aluminum decreases. In these tests, trialquil aluminum treatment was carried out for four hours and without time dependence was examined. However, in later examples it is shown that the success of the trialkyl aluminum treatment depends on the reaction time. In addition, additional tests from experiment 'B' were carried out using other treatments before or replacing a trialkyl aluminum substrate treatment. Table 1, below, describes the various tests conducted in Examples 1-15. Unless otherwise indicated, canola oil was used as the substrate. 1 The soybean oil used as the substrate 2 * Not performed due to lack of substrate Table 1. Overview of test conditions for Examples 1 -15 Examples 1 (a) and 1 (b)
[098] Example 1 (a): samples of canola oil (CO-1) were placed in glass flasks in an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of gas ethylene at 50 ° C for 18 hours using the given amounts of catalyst X008 or X022. After ethenolysis, the reaction mixtures were subjected to Zemplen transesterification (NaOMe / MeOH; ta, 3h), and were analyzed by GCMS using pentadecane as an internal standard. The tests are described in Table 2, shown below.
Exemplos 2 (a) e 2 (b)[099] Example 1 (b): The samples of canola oil (CO-1) were shaken in glass flasks with the given amounts of aluminum trialkyl under a dry nitrogen atmosphere at room temperature for 4 hours. The flasks with the reaction mixtures were placed in a 850 ml stainless steel autoclave and the mixtures were subjected to ethylene under 10 atm (1013.25 Kpa) ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After ethenolysis, the reaction mixtures were subjected to Zemplen transesterification (NaOMe / MeOH; ta, 3h), having been analyzed by GCMS using pentadecane as an internal standard. The tests are described in Table 3, shown below. Examples 2 (a) and 2 (b)
[0100] Example 2 (a): In a glove chamber loaded with nitrogen, commercial-grade rapeseed oil (canola oil CO-1,200 ml, 180.24 g, water content: 9 ppm) was stirred with molecular sieves (granules, 3Â, activated, 25.4 g) at room temperature for 6 days. The substrate was filtered over an activated celite pad giving batch E01JVA640. Water content: 3 ppm. The treated substrate samples were then placed in glass flasks in an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of the catalyst X008. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are shown in Table 4, shown below.
Exemplos 3 (a) e 3 (b)[0101] Example 2 (b): In a glove chamber loaded with nitrogen, commercial-grade rapeseed oil (Canola oil CO-1,200 ml, 180.24 g, water content: 9 ppm) was stirred with molecular sieves (granules, 3Â, activated, 25.4 g) at room temperature for 6 days. The substrate was filtered over an activated celite pad giving batch E01JVA640. Water content: 3 ppm. Samples of E01JVA640 were placed in glass flasks and stirred with the given amounts of triethyl aluminum under a dry nitrogen atmosphere at room temperature for 4 hours. The flasks with the reaction mixtures were placed in an 850 ml stainless steel autoclave and the mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas in 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After ethenolysis, the reaction mixtures were subjected to Zemplen transesterification (NaOMe / MeOH; ta, 3h), and were analyzed by GCMS using pentadecane as an internal standard. The tests are described in Table 5, shown below. Examples 3 (a) and 3 (b)
[0102] Example 3 (a): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1, 1.3 ml) was stirred at 200 ° C for 2 hours. Cooling to room temperature provided E01JVA752. Samples of E01JVA752 were then placed in glass flasks into an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of catalyst X008. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in
Exemplos 4(a) e 4(b)[0103] Example 3 (b): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1, 1.3 ml) was stirred at 200 ° C for 2 hours. Cooling to room temperature provided E01JVA752. Then, in a glove chamber loaded with gaseous nitrogen, samples from E01JVA752 were stirred in glass flasks with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in Table 7, shown below. Examples 4 (a) and 4 (b) Examples 4 (a) and 4 (b)
[0104] Example 4 (a): Commercial grade canola oil (CO-1) was subjected to vacuum distillation in a short path distillation apparatus in an 280 ° C oil bath under 0.5 mbar (0, 05 Kpa), for 5 hours, while a slow continuous flow of nitrogen was allowed to pass through the oil to purge the volatile components. The residue from the treatment distillation (E01JVA721) was transferred to a glove chamber loaded with gaseous nitrogen. Samples of E01JVA721 in glass flasks were placed in a 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given quantities of catalyst X008. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in Table 8, shown below.
Exemplos 5 (a) e 5 (b)[0105] Example 4 (b): Commercial grade canola oil (CO-1) was subjected to vacuum distillation in a short path distillation apparatus in an 2809C oil bath under 0.5 mbar (0, 05 Kpa) of vacuum for 5 hours, while a slow continuous flow of nitrogen was allowed to pass the oil to purge the volatile components. The residue from the distillation treatment was transferred to a glove chamber loaded with nitrogen gas (E01JVA721). The E01JVA721 samples were shaken in glass flasks with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 9, shown below. Examples 5 (a) and 5 (b)
[0106] Example 5 (a): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1.21 ml) was stirred with activated copper powder (3.35 g) at room temperature for 114 hours. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction provided E01JVA630. Samples of E01JVA630 were placed in glass flasks for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50eC for 18 hours using the given quantities of catalyst X008 or X022 . After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 10, shown below.
Exemplos 6 (a) e 6 (b)[0107] Example 5 (b): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1.21 ml) was stirred with activated copper powder (3.35 g) at room temperature for 114 hours. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA630. Samples of E01JVA630 were placed in glass flasks and were stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in Table 11, shown below. Examples 6 (a) and 6 (b)
[0108] Example 6 (a): In a glove chamber loaded with nitrogen, commercial canola oil (CO-1.21 g, 24 mmols) was stirred with activated copper powder (3.3 g, 52 mmols ) at 200 ° C for 2 hours. After cooling to room temperature again, filtration through Whatman AutoCup filters (0.45pm PTFE) by suction gave E01JVA701B. Samples of E01JVA701B were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 or X022 catalyst . After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 12, shown below.
Exemplos 7 (a) e 7 (b)[0109] Example 6 (b): In a glove chamber loaded with nitrogen, commercial canola oil (CO-1.21 g, 24 mmols) was stirred with activated copper powder (3.3 g, 52 mmols ) at 200 ° C for 2 hours. After cooling to room temperature again, by filtration on Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA701B. Samples of E01JVA701B were placed in glass flasks and stirred with the given amount of OcsAI (25 wt.% Hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), the GCMS analysis was performed. The tests are described in Table 13, shown below. Examples 7 (a) and 7 (b)
[0110] Example 7 (a): In a glove chamber loaded with gaseous nitrogen, sample CO-1 treated with Cu / 200QC (E01JVA701B from Examples 6 (a) and (b), 9.909 g) was stirred with sieve granules molecular molecules (3 Â, 5.927 g) at room temperature for 18 hours. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA701C. Samples of E01JVA701C were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 catalyst. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in Table 14, shown below.
Exemplos 8 (a) e 8 (b)[0111] Example 7 (b): In a glove chamber loaded with gaseous nitrogen, sample CO-1 treated with Cu / 200sC (Examples E01JVA701B from Examples 6 (a) and (b), 9.909 g) was sieved with sieve granules molecular molecules (3 Â, 5.927 g) at room temperature for 18 hours. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA701C. Samples of E01JVA701C were placed in glass flasks and stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas in 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 15, below. Examples 8 (a) and 8 (b)
[0112] Example 8 (a): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1, 21 ml) was stirred with activated magnesium chips (4.49 g) at room temperature 14 days. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA632. Samples of E01JVA632 were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 or X022 catalyst . After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 16, shown below.
Exemplos 9 (a) e 9 (b)[0113] Example 8 (b): In a glove chamber loaded with gaseous nitrogen, commercial-grade canola oil (CO-1, 21 ml) was stirred with activated magnesium chips (4.49 g) at room temperature for 14 days. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA632. Samples of E01JVA632 were placed in glass flasks and stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of X022 catalyst. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in Table 17, shown below. Examples 9 (a) and 9 (b)
[0114] Example 9 (a): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1, 21 ml) was stirred with activated magnesium chips (4.49 g) at room temperature for 14 days. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA777. Samples of E01JVA777 were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 catalyst. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 18, shown below.
Exemplos 10 (a) e 10 (b)[0115] Example 9 (b): In a glove chamber loaded with gaseous nitrogen, commercial canola oil (CO-1, 21 ml) was stirred with activated magnesium chips (4.49 g) at room temperature for 14 days. Filtration over Whatman AutoCup filters (0.45 pm PTFE) by suction gave E01JVA777. Samples of E01JVA777 were placed in glass flasks and stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 19, shown below. Examples 10 (a) and 10 (b)
[0116] Example 10 (a): In a charged glove chamber, canola nitrogen gas oil (CO-1, 500 ml) was stirred with acetic anhydride (15 ml, 30 mol%) at 110 ° C internal temperature, for 18 hours. Excess AC2O and volatile products were removed by distillation at the same internal temperature for the purpose of a membrane pump (17 mbar - 1.7 KPa), while a steady slow flow of nitrogen was bubbled through the oil for 5 hours. PV was below the detection limit. E01JVA808 was isolated by suction of the distillation residue from the distillation flask through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. Samples of E01JVA808 were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 catalyst. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 20, shown below.
[0117] Example 10 (b): In a charged glove chamber, canola nitrogen gas oil (CO-1,500 ml) was stirred with acetic anhydride (15 ml, 30 mol%) at 110 ° C internal temperature for 18 hours. Excess AC2O and volatile products were removed by distillation at the same internal temperature, with the objective of a membrane pump (17 mbar - 1.7 KPa), while a constant slow flow of nitrogen was bubbled through the oil during 5 hours. PV was below the detection limit. E01JVA808 was isolated by suction of the distillation residue from the distillation flask through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. Samples of E01JVA808 were placed in glass flasks and stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 21, shown below.
[0118] Example 11 (a): In a glove chamber loaded with gaseous nitrogen, soybean oil (SBO-1, 150 ml) was mixed with 30 mol% of acetic anhydride ('AC2O', 5 ml) and the mixture it was stirred at 110 ° C of internal temperature, under nitrogen atmosphere for 18 hours. The initial PV = 0.73 dropped below the detection limit. Excess AC2O and volatile by-products were removed by distillation under reduced pressure (17 mbar - 1.7 KPa), while a steady slow flow of nitrogen was bubbled through the oil to help remove the volatile components for 5 hours. E01JVA168A was isolated by suction of the distillation residue from the distillation flask through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. E01JVA168A (140 ml) was mixed with activated gamma aluminum oxide (Brockman I., 5 g / 100 ml) and the mixture was stirred under nitrogen at room temperature for 96 hours. Filtration over celite pad gave E01JVA168B. Samples of E01JVA168B were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given quantities of X008 or X007 catalyst . After Zemplen transesterification (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 22, shown below.
[0119] Example 11 (b): In a glove chamber loaded with gaseous nitrogen, soybean oil (SBO-1, 150 ml) was mixed with 30 mol% of acetic anhydride ('AC2O', 5 ml) and the mixture it was stirred at 110 ° C of internal temperature, under nitrogen atmosphere for 18 hours. The initial PV = 0.73 dropped below the detection limit. Excess AC2O and volatile by-products were removed by distillation under reduced pressure (17 mbar - 1.7 KPa), while a steady slow flow of nitrogen was bubbled through the oil to help remove the volatile components for 5 hours. E01JVA168A was isolated by suction of the distillation residue from the distillation flask through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. E01JVA168A (140 ml) was mixed with activated gamma aluminum oxide (Brockman I., 5 g / 100 ml) and the mixture was stirred under nitrogen at room temperature for 96 hours. Filtration over celite pad gave E01JVA168B. Samples of E01JVA168B were placed in glass flasks and stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 23, shown below.
[0120] Example 12 (a): In a glove chamber loaded with gaseous nitrogen, SBO-1 (500 ml) was mixed with activated gamma aluminum oxide (Brockman I., 5 g / 100 ml) and the mixture was stirred at room temperature for 21 hours. Filtration gave E01JVA161A. (The initial PV = 0.73 dropped to PV = 0.09). E01JVA161A was mixed with Selcat-Q 6 10% Pd / C (0.25 g / 100 ml) and charcoal (1 g / 100 ml) and was stirred at 110 ° C (internal temperature) while the nitrogen atmosphere of the chamber glove was bubbled through it. After 2h, PV was below the detection limit. After 13 h, filtration on Whatman filters (0.45 pm AutoCup PTFE) with suction gave E01JVA161C. E01JVA161C was mixed with AC2O (30 mol%) under a nitrogen atmosphere at room temperature. The mixture was stirred at 110 ° C (internal temperature) for 18 hours, then the excess reagent and the by-products were removed by distillation under reduced pressure (17 mbar - 1.7 KPa), while a constant flow of nitrogen was bubbled slowly through the oil to help remove volatile compounds. After 5 hours of distillation, E01JVA161H was isolated by suction of the distillation residue through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. Samples of E01JVA161H were placed in glass flasks in an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 catalyst. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 24, shown below.
Exemplo 13[0121] Example 12 (b): In a glove chamber loaded with gaseous nitrogen, SBO-1 (500 ml) was mixed with activated gamma aluminum oxide (Brockman I., 5 g / 100 ml) and the mixture was stirred at room temperature for 21 hours. Filtration gave E01JVA161A. (The initial PV = 0.73 dropped to PV = 0.09). E01JVA161A was mixed with Selcat-Q 6 10% Pd / C (0.25 g / 100 ml) and charcoal (1 g / 100 ml) and was stirred at 110 ° C (internal temperature), while the nitrogen atmosphere of The gloved chamber was bubbled through. After 2h, PV was below the detection limit. After 13 h, filtration on Whatman AutoCup filters (0.45 pm PTFE) with suction gave E01JVA161C. E01JVA161C was mixed with AC2O (30 mol%) under a nitrogen atmosphere at room temperature. The mixture was stirred at 110 ° C (internal temperature) for 18 hours, then the excess reagent and the by-products were removed by distillation under reduced pressure (17 mbar - 1.7 KPa), while a constant flow of nitrogen was bubbled slowly through the oil to help remove volatile compounds. After 5 hours of distillation, E01JVA161H was isolated by suction of the distillation residue through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. Samples of E01JVA161H were placed in glass flasks and stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 25, shown below. Example 13
[0122] Canola oil (CO-1, 500 ml) was subjected to the short distillation form of 250 ° C, 0.25 mbar (0.025 KPa) for 1 hour. The residue (heated E01JVA327) was compartmentalized in a glove chamber loaded with gaseous nitrogen (PV: below the detection limit) and stirred at room temperature with AC2O (15 ml, 10 mol%) for 67 hours and then at 105 ° C for two hours. Excess reagent and by-products were removed by distillation under reduced pressure (pressure was gradually decreased from 650 mbar (65 KPa) to 4 mbar (0.4 KPa) over 30 min, then the distillation continued to 4 mbar ( 0.4 KPa)) at 110 ° C internal temperature, while a steady slow flow of nitrogen was bubbled through the oil through a stainless steel needle for 5 hours. After cooling to room temperature, E01 JVA327Ac2O was isolated by suctioning the oil from the flask through a stainless steel needle taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask. E01 JVA327Ac2O was stirred at rt with activated y-aluminum oxide (Brockman I., 5 g / 100 ml) for 18 hours. Filtration on a pad of activated celite (d = 5 cm, I = 3 mm) and activated oxide y-aluminum (Brockman I, 1.5 cm) gave E01JVA327A. A sample of E01JVA327A was placed in a 250 ml stainless steel autoclave and was subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using the given amounts of X008 catalyst. After Zemplen transesterification (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The assay is described in Table 26, shown below.
[0123] Example 14 (a): Canola oil (CO-1, 500 ml) was subjected to short path distillation first at room temperature until the vacuum decreased to 0.044 mbar (0.0044 KPa), then to temperature was increased to 250 ° C and distillation continued until the initially rising pressure dropped to 0.044 mbar - 0.0044 KPa (about 60-70 min). The residue (E01 JVA335res) was compartmentalized in nitrogen as a loaded glove chamber and AC2O was added (3 ml, 30 mol% to 100 ml of oil) and the mixture was stirred at 105 ° C of internal temperature for 24 hours. The volatiles were removed by distillation under reduced pressure (pressure was gradually decreased from 700 mbar (70 KPa) to 7 mbar (0.7KPa)), increasing the internal temperature to 1109C and a slow flow of nitrogen was bubbled through the oil through a stainless steel needle for 4 hours, then the oil was allowed to cool to room temperature, transferred to an Erlenmeyer flask with a hypodermic syringe taking care to avoid mixing the oil with the small drops on the inner wall of the distillation flask (to give E01JVA335A). E01JVA335A was stirred with activated molecular sieves (Á granules, 25 g) at room temperature for 96 hours. Then, the substrate was filtered over a pad of activated molecular sieves (3Å, powder) to give E01JVA335B. E01JVA335B was stirred with activated alumina (Brockman I., 5 g / 100 ml) at room temperature for 24 hours, then the oil was filtered through an activated celite pad giving E01JVA335C. Samples of E01JVA335C were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 catalyst. After Zemplen transesterification (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 27, shown below.
Exemplos 15 (a) e 15 (b)[0124] Example 14 (b): Canola oil (CO-1, 500 ml) was subjected to short path distillation, first at room temperature until the vacuum decreased to 0.044 mbar (0.0044 KPa), then the temperature was increased to 250 ° C and distillation continued until the initially increasing pressure dropped to 0.044 mbar - 0.0044 KPa (about 60-70 min). The residue (E01 JVA335res) was partitioned into nitrogen as a loaded glove chamber and AC2O (3 ml, 30 mol% to 100 ml of oil) was added and the mixture was stirred at 105 ° C of internal temperature for 24 hours. The volatiles were removed by distillation under reduced pressure (pressure was gradually decreased from 700 mbar (70 KPa) to 7 mbar (0.07 KPa)) by increasing the internal temperature to 110 ° C and a slow flow of nitrogen was bubbled through the oil through a stainless steel needle for 4 hours, then the oil was allowed to cool to room temperature, transferred to an Erlenmeyer flask with a hypodermic syringe taking care to avoid mixing the oil with the small drops on the inner wall distillation flask (to give E01JVA335A). E01JVA335A was stirred with activated molecular sieves (3Â, granules, 25 g) at room temperature for 96 hours. Then, the substrate was filtered over a pad of activated molecular sieves (3Å, powder) to give E01JVA335B. E01JVA335B was stirred with activated alumina (Brockman I., 5 g / 100 ml) at room temperature for 24 hours, then the oil was filtered through a pad of celite giving activated E01JVA335C. Samples of E01JVA335C were placed in glass flasks and were stirred with the given amounts of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After Zemplen transesterification (NaOMe / MeOH; ta, 3h) GCMS analysis was performed. The tests are described in Table 28, shown below. Examples 15 (a) and 15 (b)
[0125] Example 15 (a): E01JVA327A (see Example 13; 400 ml) was percolated through a column (diameter = 55 mm) packed with activated celite (height: 5 mm), activated molecular sieves (powder form, 0.3 nm, height: 22 mm), activated molecular sieves (granules, 3 Â, height: 70 mm) and activated alumina on top of them (height: 20 mm) by suction (membrane pump) giving E01JVA327C (pAV was below detection limit). Samples of E01JVA327C were placed in glass vials for an 850 ml stainless steel autoclave and were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours using the given amounts of X008 catalyst. After transesterification of Zemplen (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 29, shown below.
Resumo dos resultados dos Exemplos 1-15[0126] Example 15 (b): E01JVA327A (see Example 13; 400 ml) was percolated through a column (diameter = 55 mm) packed with activated celite (height: 5 mm), activated molecular sieves (powder form, 0.3 nm, height: 22 mm), activated molecular sieves (granules, 3 Â, height: 70 mm) and activated alumina on top of them (height: 20 mm) by suction (membrane pump) giving E01JVA327C (pAV was below detection limit). Samples of E01JVA327C were placed in glass flasks and were stirred with the given amount of OcsAI (25% by weight in hexane) at room temperature for 4 hours. The flasks were then placed in an 850 ml stainless steel autoclave and the reaction mixtures were subjected to ethenolysis under 10 atm (1013.25 Kpa) of ethylene gas at 50 ° C for 18 hours, using 250 ppm by weight of catalyst X022. After Zemplen transesterification (NaOMe / MeOH; ta, 3h), GCMS analysis was performed. The tests are described in Table 30, shown below. Summary of Results from Examples 1-15
Tabela 31 Comparação dos tratamentos nos Exemplos 1-15:[0127] Sample analyzes (calculated on pentadecane) for Examples 1 -15 are provided in Table 31, shown below, where: • C [%] refers to the conversion: Conversion = 100 - 100 x [(moles end of decenoate precursors) / (initial moles of decenoate precursors in triglycerides)]; Decenoate precursors: oleate, linoleate, linolenate and palmitoleate chains. • S [%] refers to selectivity: Selectivity = 100 x (moles of M9D) / (total moles of all ester compounds in the product mixture, except for the precursor esters of deceonate and saturated esters); In the calculation, the dimethyl ester moles of the oc, co-dicarboxylic acid are multiplied by two, as these compounds are made of two chains from carboxylic acids by the catalyst. • M9D Y [%] refers to the yield of 9-methyl decenoate: Yield of methyl 9-decenoate (M9D) = (moles of M9D) x 100 / (initial moles of the decenoate precursor chains); • TON refers to the number of turnover; TON = M9D Y [%] * moles of substrate I moles of catalyst. • P [%] refers to the purity of the ester: Purity of the ester = 100 x (moles of M9D) / (total moles of all ester compounds in the product mixture); • 9-ODDAME Y [%] refers to the yield of dimethyl octadec-9-en-dicarboxylate: Yield dimethyl octadec-9-en-dicarboxylate (9) ODDAME = 100 x (moles of 9-ODDAME) / [(moles initial values of decenoate precursors in the triglyceride) / Table 31 Comparison of treatments in Examples 1-15:
Tabela 32. *óleo de soja usado como o substrato **não realizado devido à falta de substrato[0128] Table 32, below, provides an overview of the various treatments performed in Examples 1-15, as well as their% MD9 yield and selectivity%.Table 32. * soybean oil used as substrate ** not realized due to lack of substrate
[0129] Based on the results of Examples 1-15, it was observed that almost complete conversion could be achieved in commercial grade ethnolysis of edible rapeseed oil (canola oil), without any pretreatment by 7 mol% of X008. However, M9D yield and selectivity were low. The slightly worse results were observed by catalyst X022, however, after the application of AlksAI, the use of X022 was improved.
[0130] Among the pretreatment methods, it was observed that the catalyst load can be reduced more effectively by drying.
[0131] The worst results were seen more with the treatment of Mg at high temperature than with room temperature, which suggests that some type of decomposition side reaction was taking place.
[0132] It was also observed that the most effective initial pretreatment method was AC2O treatment. The demand for AlksAI could also be reduced considerably by treatment with AC2O. The success of AC2O treatment and vacuum distillation strongly depends on the quality of the separation of the volatile components. In the case of most treatments and combinations of treatments the conversion was not considerably reduced by applying a slight excess of AIsAI than the optimum amount. The only exception is observed when the AC2O treatment was applied alone. In this case, the observed conversion is reduced considerably by increasing the amount of AlksAI applied above the optimum value. In general, the maximum values of M9D yield and selectivity were generally not reached (esters C12: 1, C13: 2 and C16: 3 Me in the product mixture).
[0133] It was also observed that the best method of combining pre-treatment before the ethenolysis of natural triglycerides was the AC2O treatment, followed by the AlksAI treatment. Percolation through activated alumina or molecular sieves can be applied before or instead of the AlksAI treatment.
[0134] Regarding the catalyst, X008 was found to be the best choice if the AlksAI treatment is not used. X022 was found to be the best choice of catalyst when the AlksAI treatment was applied. Example 16 - Study of catalyst addition in ethenolysis of pretreated natural triglycerides
[0135] In an experiment using canola oil treated with EtsAI as a substrate, the catalyst was added in small portions to the reaction mixture during the course of the ethenolysis reaction. The samples were taken from the reaction mixture that were analyzed to follow the progress of the ethenolysis reaction.
[0136] In a glove chamber loaded with nitrogen, Canola oil (CO-1, 1000 ml) was mixed with triethyl aluminum (25% by weight in toluene, 35.5 ml; 6.5 mol%) and the mixture was stirred at room temperature for 5 days, giving E01JVA399.
[0137] In a glove chamber loaded with nitrogen, Canola rapeseed oil treated with EtsAI (E01JVA399, 511.19 g; 579.45 mmol; Medium PM: 882.19) was placed in a stainless steel autoclave and stirred at 50QC. The gas space was charged with ethylene, then the standard solution (0.01 M in benzene) of catalyst X022 (X01JVA036) was injected into the autoclave over time and the stirring under 10 bar (1KPa) of ethylene gas 50 ° C continued. At the time of catalyst injections, the excess pressure of ethylene in the autoclave was reduced by leaving out excess ethylene without opening the autoclave and samples were collected for analysis by GCMS at the same time. The addition of catalyst and the sample taken were made by a hypodermic syringe through a stainless steel needle, which was guided through a precision rubber septum placed over the opening of a ball valve connected to the upper part of the autoclave. The valve was opened only during injection - sample taking operations. The samples were analyzed by GCMS-FID after Zemplen transesterification. Addition sequence: • 50 x 1 ppm of X022 catalyst; ethylene under 10 bar (1KPa) of ethylene at 50 ° C for different periods of time. • 1 x 50 ppm of X022 catalyst; ethylene under 10 bar (1KPa) of ethylene at 50 ° C for 22 hours. • EtsAI (molar quantity equal to 100 ppm of X022); 50 ° C for 2 hours. • 2 x 1 ppm of X022 catalyst; ethylene under 10 bar (1KPa) of ethylene at 50 ° C for 2 x 1 hour. • Finally, 5 ppm of X022 catalyst; ethylene under 10 bar of ethylene at 50 ° C for 18 hours.
Tabela 33.[0138] Sample analyzes (calculated on pentadecan) for Example 16 are shown in Table 33, shown below, where: • C [%] refers to the conversion: Conversion = 100 - 100 x [(final moles of decenoate precursors) / (initial moles of decenoate precursors in triglycerides)]; Decenoate precursors: oleate, linoleate, linolenate and palmitoleate chains. • S [%] refers to selectivity: Selectivity = 100 x (moles of M9D) / (total moles of all ester compounds in the product mixture, except for the precursor esters of deceonate and saturated esters); In the calculation, moles of dimethyl ester of the oc, co-dicarboxylic acid are multiplied by two, as these compounds are made up of two chains from carboxylic acids by the catalyst. • M9D Y [%] refers to the yield of methyl 9-decenoate: Yield of methyl 9-decenoate (M9D) = (m9D moles) x 100 / (initial moles of decenoate precursor chains); • TON refers to the number of turnover; TON = M9D Y [%] * moles of substrate / moles of catalyst. • P [%] refers to ester purity: Ester purity = 100 x (moles of M9D) / (total moles of all ester compounds in the product mixture); • 9-ODDAME Y [%] refers to the yield of dimethyl octadec-9-en-dicarboxylate: Dimethyl yield octadec-9-en-dicarboxylate (9-ODDAME) = 100 x (moles of 9-ODDAME) / [(initial moles of decenoate precursors in the triglyceride) / 4. Table 33.
[0139] Based on the results of Example 16, it was observed that the catalyst load can be further reduced in the case of triglyceride ethenolysis treated with AlkaAI by catalyst X022 by slowly adding the catalyst to the reaction mixture during the course of the reaction. Examples 17-34 Materials and methods
[0140] Methyl 9,12-tridecadienoate and 1-decene (91,4%) were obtained from Materia. The 9-DAME samples were obtained from raw materials of natural oils under conditions similar to those described in US Patent Application Publication No. 2011/0113679, hereby incorporated by reference in their entirety, and depending on the source and the handling, contained different types and amounts of impurities. Unless otherwise indicated, the 9-DAME used in the examples below was material from Materia, Inc. (Pasadena, California, USA).
[0141] 1-octene was obtained from Alpha-Aesar. Molecular sieves (4Â, granules, 8-12 mesh) and alumina (activated, neutral, Brockmann I, ~ 150 mesh, 58 Â pore size) were obtained from Sigma-Aldrich. The molecular sieves were activated by heating in one of two ways: (a) 250 ° C to 0.05 torr (6.7 Pa) or (b) 150 ° C in air. Activated alumina was dried either at 250 ° C under vacuum (<0.1 torr - 13.3Pa) or at 375 ° C under a flow of nitrogen (0.5-2 liters / minute). Substrates (eg, decenoate ester) can be stored on activated molecular sieves before use and monitored by Karl Fischer titration until the moisture value is <10 ppm. In some embodiments, stirring and moving to a new sieve bed can be useful in accelerating the time required to reach the desired moisture value. In addition, in some embodiments, the flocculation powder and / or filtering sieve can sometimes affect. The columns were prepared and operated using vacuum or pressure to percolate substrate through the adsorbent. Peroxide value [milliequivalents of peroxide / kg of sample (meq / kg)] was determined by means of titration using an autotiter (Metrohm 888 Titrando). The moisture content was determined by Karl Fischer coulometric titration using Metrohm 756 KF Coulometer. Unless otherwise indicated, all metathesis reactions were conducted on a 1 gram scale inside a glove chamber at room temperature. Example 17 - Large scale self-metathesis from 9-DAME to 9-ODDAME
[0142] The purification of 9-DAME: 9-DAME was stored more than 10% by weight of 4Â ° non-activated molecular sieves for 24 hours. This procedure reduced the residual moisture content from 212 ppm to 31 ppm. The material was then transferred to a solvent bulb style flask and degassed for three purge pump cycles and brought into a glove chamber. The material was percolated three times through an activated alumina column (20% by weight). This procedure reduced the moisture content to 5 ppm and the peroxide index was found to be equal to or less than that of a blank sample. The material was left more than 10% by weight of the activated 4Â ° molecular sieves inside the glove chamber. The molecular sieves were dried at 250 ° C under vacuum (<0.1 torr-13.33 Pa). Activated alumina was dried at 250 ° C under vacuum (<0.1 torr - 13.33 Pa).
[0143] Synthesis of 9-ODDAME: In a glove chamber loaded with N2, in a 1 L round-bottom flask equipped with a magnetic stir bar, it was loaded with 250 g of 9-DAME which had been dried by means of passage through a column of activated alumina and then stored on activated molecular sieves 4Â. A solution of X004 was prepared by combining 40.1 mg of Mo (NaAr) (CHCMe2Ph) (Me2pyr) 2 and 16.7 mg of 2,6-diphenylphenol in 1 ml of toluene followed by stirring the solution at room temperature for 30 minutes. The catalyst solution was added to the ester and the mixture was stirred open into the glove chamber atmosphere for 6 hours, after which time the mixture was placed under dynamic vacuum for 2 hours, during which time the gas evolution was observed . After standing overnight, the balloon was removed from the glove chamber after a needle valve inlet adapter was fitted. The mixture was melted in a 50 ° C silicone oil bath and placed under dynamic vacuum for 1 hour, during which time more gas evolution was observed. The observed GC conversion was 92% (18400 TON). Neutral activated alumina (12.5 g) was added and the mixture was stirred for 30 minutes and then the alumina was removed by filtration. The light components of the mixture were removed by vacuum distillation (120 ° C at 0.3 mm Hg) and then the bottoms were again treated with 12.5 g of neutral activated alumina to remove a green colored impurity. The isolated yield was 186.91 g (80.9% yield). Example 18
[0144] It had previously been found that 0.04 mol% of the X027 molybdenum catalyst [Mo (N-2,6-iPR2-C6H3) (CHCMe2Ph) (pyrrolid) (0-2,6-tBu2C6H3)] would only convert 9 -DAME, purified by a thermal method (heat treated at 200 ° C, followed by stirring over dry alumina at 250 ° C in vacuum; PV reduced from 0.56 to <0.06 (blank)), at 9-ODDAME 0, 2% (5 TON). In addition, it was found that 0.04 mol% of X007 [Mo (N-2,6-'Pr2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) [(/ = ) - 3,3'- dibromo-2 '- (ich-butyldimethylsilyloxy) - 5.5', 6.6 ', 7.7', 8.8'-octahidro-1,1 '-binaft-2-olato)] would be similar to provide low conversion (3.5%; 88 TON) with the same substrate. It was found that the addition of 10% by weight of the 4Â molecular sieve that had been activated in vacuum at 275 ° C reduced the moisture content from 76 ppm to 12 ppm. After drying, 0.04 mol% of X027 would convert 91.9% (2298 TON) and 0.04 mol% X007 would convert 88.0% (2200 TON). Example 19
[0145] The elimination of the thermal pretreatment step in the purification of 9-DAME was investigated. The agitation of 9-DAME more than 20% by weight of dry alumina (250 ° C, vacuum), followed by the addition of 20% by weight of activated 4Á molecular sieves reduced the peroxide value from 0.64 to 0, 16 milliequivalents / kg of sample peroxide (meq / kg) and the moisture content from 194 ppm to 3 ppm. Example 20
[0146] The reaction of 9-DAME prepared without thermal pretreatment with 0.02 mol% of X027 resulted in the conversion of 87.4% (4368 TON). With feed that was pre-heat treated (see Example 18 above), 77.6% conversion was observed (3880 TON). At a catalyst load of 0.01 mol%, 47.3% conversion (4726 TON) could be achieved with the non-heat treated feed, while only 22.8% conversion (2277 TON) with feed that had been pre-heat treated. Example 21
[0147] Methyl 9,12-tridecadienoate was purified by percolation through an alumina column and storage on molecular sieves. This procedure reduced the peroxide index from 12.75 to 0.06 and the moisture content from 166 ppm to 5 ppm. Example 22
[0148] Repeated percolation of 9-DAME through a 20 wt.% Dry alumina column was found to reduce the peroxide value from 0.56 to <0.06 (blank). The addition of 20% by weight of 4Â molecular sieves reduced the moisture content from 194 ppm to 7 ppm. Example 23
[0149] 0.004 molar X004 [Mo (N-2,6-iPR2-C6H3) (CHCMe2Ph) (2,5-dimethylpyrrolid) (0-2,6-Ph2C6H3)] was found to obtain 25.4% conversion (6350 TON) of 9-DAME percolated through alumina and dried over molecular sieves. Example 24
[0150] Decanting the purified 9-DAME from the molecular sieve bed and placing it over a fresh 10 wt% molecular sieve bed allowed 0.004 mol% of X004 to achieve a 46.8% conversion (11693 TON). Example 25
[0151] 1-decene (91.4%), which had a peroxide value of 35.89 meq / kg and a moisture content of 259 ppm was purified by passing through a dry alumina column (150 ° C in air ) and storage under activated molecular sieves of 4Â in the glove chamber. This procedure reduced the peroxide value to 0.16 meq / kg and the humidity to 5 ppm. Example 26
[0152] It was found that 0.001 molar% of X004 would react with purified 1-decene (see supra) converting 63.1% to 9-octadecene. Example 27
[0153] The addition of 5 wt% dry molecular sieves from 4Â ° in 150Â ° C in air to 1-octene reduced the moisture content from 42 ppm to 3 ppm. It was found on a 10 kg scale that 0.00225 mol% of X004 (150 ppm by weight) would convert this dry 1-octene to 7-tetradecene in 86.9% conversion. Example 28
[0154] 9-DAME was dried with 2.5% by weight of 4Â ° molecular sieves. This reduced the moisture content from 68 ppm to 15 ppm. Attempting to self-metastasize this material with 0.01 mol% of X004 resulted in conversion <0.1% in 9-ODDAME. Example 29
[0155] 9-DAME pre-dried with molecular sieves was percolated through a stainless steel filled with alumina (activated at 375 ° C with a nitrogen purge) by nitrogen pressure column. The material was then collected and stored on a bed of activated molecular sieves of 4Â ° (275 ° C, vacuum). The moisture content was then found to be 5 ppm. Metathesis with 0.01 mol% of X004 converted to 20.1% from 9-DAME to 9-ODDAME, above the residual conversion before the alumina treatment. This 9-DAME was later used for an 8 kg scale reaction where it was found that 0.0149 mol% (600 ppm by weight) of X004 would give 91.2% conversion from 9-DAME to 9-ODDAME. Example 30
[0156] Auto-metathesis catalyzed with 8 kg Mo 9-DAME derived from Elevance to 9-ODDAME was completed using the procedure described in Example 17. The reaction proceeded to 91.2% conversion with an initial catalyst load 600 ppm by weight of X004. An additional cost of 100 ppm by weight of X004 resulted in a final conversion of 95.4%. Previous work had indicated that a catalyst load of 200 ppm by weight was sufficient to achieve> 90% conversion of a sample other than 9-DAME to 9-ODDAME with the same catalyst with an approximate moisture content of the feed that was < 5 ppm. It was determined that there was no protic or phosphorus containing impurities in the material. Example 31
[0157] The experiments were carried out to analyze whether the application of TEAL to dry Elevance-derived 9-DAME would allow the use of lower catalyst loads. The initial results, as shown in FIG. 1, indicated that TEAL had a beneficial effect, although a large excess of TEAL negatively affected the conversion. The removal of excess TEAL by adsorption on AI2O3 was then explored.
[0158] FIG. 2 displays the screening data for treatment of 9-DAME TEAL derived from dry Elevance with and without alumina post-treatment. The process for these experiments was to treat 9-DAME with the specified amount of TEAL (as a 1.0 M solution in hexanes) for 30 minutes and then add 5% dry weight of neutral activated alumina and stir for more 30 minutes. The alumina was removed by filtration through a glass fiber filter. Two loads of different TEALs were tested -620 and 310 ppm by weight- as well as a control by which no TEAL was added. The control reactions indicated that there was no beneficial effect associated with treating the material with only alumina (the material had already been treated on a heat-treated alumina column). Example 32
[0159] FIG. 3 shows the effect of varying the amount of alumina used for the post-treatment of 9-Dame treated with TEAL. The process for these experiments was to treat 9-DAME with the specified amount of TEAL (as a 1.0 M solution in hexanes) for 30 minutes and then add either 0% by weight, 1% by weight, or 5 Dry weight% of activated neutral alumina and stir for another 30 minutes. The alumina was removed by filtration through a glass fiber filter. The samples were then metathetically reacted with either 403 or 202 ppm by weight of X004. It has been found that an alumina treatment to remove unreacted TEAL (and / or possibly TEAL reaction products with impurities) can be beneficial for the efficiency of the catalyst. Example 33 - Treatment of 9-DAME TEAL on a 0.5 kg scale
[0160] Purification of TEAL on the 0.5 kg scale of 9-DAME was performed. After the material was treated as described below, a 0.25 kg auto-metathesis employing 200 ppm X004 was conducted as described in Example 18. After 4 hours, the conversion had reached 91.6%.
[0161] Treatment of dry 9-DAME (<10 ppm H2O) with 310 ppm TEAL results in a three-fold reduction in the required molybdenum catalyst (X004) required to achieve> 90% conversion to 9-ODDAME (from from 600 ppm to 200 ppm). It was found that an excess of TEAL (> 10 molar equivalents) reduces the efficiency of the catalyst and, consequently, passivation by adsorption on alumina is necessary. Pretreatment was reduced to 0.5 kg, as described below.
[0162] In the glove compartment, 500 g of 9-DAME (2,713 moles), which had previously been treated with heat treated alumina (375 ° C) and 4 ° molecular sieves (PV «0; H2O = 4.9 ppm), were weighed into a 1 L round bottom flask equipped with a magnetic stir bar. To the stirring ester, 1.36 ml of a 1.0 M solution of TEAL in hexanes (1.36 mmol; 0.05 mol%; 310 ppm by weight) was added. Stirring was continued for 1 hour and then 5 g (1% by weight) of neutral, activated alumina that had been dried at 250 ° C in vacuo was added causing a small amount of gas to evolve. The mixture was stirred for an additional hour. The alumina was removed by filtration through a sintered glass frit of medium porosity and then the purified ester was stored in a glass bottle. Example 34
[0163] The auto-metathesis of 9-DAME treated with TEAL / AI2O3 for 200 ppm by weight of X004 on a 0.25 kg scale: In a glove chamber loaded with N2, 0.25 kg 9-Dame (see supra) was weighed and transferred to a 1-L in a Schlenk flask equipped with a magnetic stir bar and an adapter for entering a Teflon valve. A solution of 50.0 mg of X004 in 1.5 ml of toluene was prepared and transferred to a gas-impermeable syringe. The flask was removed from the glove compartment and then connected to the Schlenk line and brought to 50 ° C by immersion in a bath of silicone oil. The X004 catalyst solution was then added to the ester under a stream of nitrogen. The mixture was then stirred at 50 ° C open to the Schlenk line silicon oil bubbler. Evolution of ethylene was observed immediately and continued for ~ 15 minutes. After reducing the evolution of gas, the inlet adapter connected to the Schlenk line nitrogen trail was closed and the top pressure was regulated at 200 torr (26.7 KPa), by means of a digital vacuum regulator connected to the line Schlenk. The digital vacuum regulator was equipped with a 1/3 PSI relief valve that was vented to a silicone oil bubbler. After 2 hours, the gas release was reduced again and the top pressure was set at 100 torr (13.3 Kpa). After another hour (3 hours of reaction time), the flask was then opened to full vacuum and the pressure slowly reduced from 5 torr (0.6 Kpa) to 0.5 torr (0.06 Kpa) over over an hour. After a total of 4 hours, the flask was opened in the air to extinguish the catalyst. Analysis of the mixture by GC-FID was found to be 91.6% 9-ODDAME. Example 35
[0164] According to analytical measurements, 9-DAME derived from a natural oil (here 9-DAME "crude") was found to contain 268.9 water ppm by weight, which corresponds to 0.275% in moles having a peroxide value (PV, see above) as high as 3.0 mEq / kg and the para-anisidine value (pAV, see above) 9.6 mEq / kg.
[0165] In order to reduce the original water content of "crude" 9-DAME, it was treated with activated molecular sieves (10% by weight) for 24 hours, in which the water content decreased to 40 ppm by weight. The drying process was repeated with an additional 10% by weight of activated fresh molecular sieves. This procedure led to a 9-DAME (here 9-DAME "pre-dried") having a water content of 28 ppm by weight and having PV below the detection limit (<0.001 mol%).
[0166] Compounds X051, X052, x123, and x154 refer to the molybdenum and tungsten catalyst having the structures described in the detailed description at the top.
[0167] Trioctyl aluminum (25% in n-hexane; Cat. # 386553) (OcsAI), acetic anhydride (ACS reagent, Cat # 242845) Cu powder (Cat. # 12806) and Mg shavings (Cat # 403148 ) were purchased from Sigma-Aldrich.
[0168] Molecular sieves (3Â, granules, ~ 2 mm; Cat. # 1.05704.1000), molecular sieves (3Â, powder; Cat. # 1.05706.0250) and aluminum oxide (basic, 0.063-0.200 mm; Cat. # 1.01076.2000) were purchased from Merck. For activation, molecular sieves and alumina were heated to 300 ° C under 1 mbar (0.1 Kpa) for 24 hours and allowed to cool and stored under a dry nitrogen atmosphere.
[0169] The studies were conducted on 9-DAME "crude" and "pre-dry" samples, respectively, in order to determine the optimally necessary amount of trioctyl aluminum used to compensate for the negative effects of various impurities, such as water, organic hydroperoxides, etc., in which the greatest conversion can be achieved in the metathesis reaction of these substrates. The results are shown in Table 34 and in FIG. 4 for X052 Mo-based catalyst and in Table 35 and FIG. 5 for complexes based on W x123. For "crude" 9-DAME, the use of 1.0 mol% of OcsAI gave the highest conversion achievable, no matter if the Mo or W catalyst was applied, while for the "pre-dry" substrate required only 0.1 mol % of trioctyl aluminum for optimal conversion, again, in the case for each catalyst complex. Two more observations deserve attention: (1) the "pre-dried" substrates provided better conversion, and (2) the W-based X123 catalyst gave greater conversion than the Mo-based X052 catalyst.
[0170] 0.0-5.0 mol% of OcsAI: All manipulations were performed under an inert atmosphere of a glove chamber loaded with nitrogen. In a 10 mL flask vented for "crude" 9-DAME (ERS 345-103) or "pre-dried" 9-Dame (E01GBE387_2), the required amount of OcsAI was added at 25 ° C and the reaction mixture was stirred for 20 h before the standard 10 pL (0.1 M) solution of the catalyst (X052, X01ABI331) was added and the reaction mixture was stirred at 25 ° C and 1 atm (101.3 KPa) for an additional 4 h. Then, the mixture was quenched and partitioned out and quenched with EtOAc. Internal standards of 1.0 mL of pentadecane in EtOAc (c = 60.40 mg / mL) and 1.0 mL of mesitylene in EtOAc (c = 60.20 mg / mL) were added and the reaction mixture was completed until 10 mL with ethyl acetate. From the standard solution obtained from the reaction, 1.0 mL was poured on top of a silica column (1.0 mL) and eluted with ethyl acetate (10 mL). From the collected eluted fraction, 100 pL was diluted to 1.0 mL, from which 1.0 mL is injected and analyzed by GCMS-GCFID. The results are shown in Table 34 and in FIG. 4.
Tabela 35 Exemplo 36[0171] Table 34 Í017110,0-5,0 mol% OcsAI: All manipulations were performed under an inert atmosphere of a glove chamber loaded with nitrogen. In a 10 mL vial vented for "crude" 9-DAME (ERS 345-103) or "pre-dried" 9-DAME (E01 GBE387_2), the required amount of OcsAI was added at 25 ° C and the reaction mixture was stirred for 20 h before 10 pL of the standard solution (0.1 M) of the catalyst (X123, X01FTH333) was added and the reaction mixture was stirred at 25 ° C and 1 atm (101.3 KPa) for an additional 4 h. Then, the mixture was compartmentalized and quenched with wet EtOAc. Internal standards of 1.0 mL of pentadecane in EtOAc (c = 60.44 mg / mL) and 1.0 mL of mesitylene in EtOAc (c = 60.48 mg / mL) were added and the reaction mixture was completed until 10 mL with ethyl acetate. From the standard solution obtained from the reaction, 1.0 mL was poured on top of a silica column (1.0 mL) and eluted with ethyl acetate (10 mL). From the eluted fraction collected, 100 pL was diluted to 1.0 mL, from which 1.0 mL is injected and analyzed by GCMS-GCFID. The results are shown in Table 35 and in FIG. 5. Table 35 Example 36
[0172] The experiments were carried out to find out whether the application of 3.0 wt% activated alumina (AI2O3) after the initial 1.0 wt% treatment of "crude" 9-DAME OcsAI would be beneficial and would result in greater conversion using X051 catalyst based on Mo or X154 catalyst based on W in the substrate metathesis reaction. The results obtained were compared with a similar experiment in which 1.0 mol% of OcsAI was used alone as a pretreatment agent. The results are shown in Table 36 and in FIG. 6 for X051 catalyst and in Table 37 and FIG. 7 for X154 catalyst.
[0173] mole% of OcsAI: All manipulations were performed under an inert atmosphere of a glove chamber loaded with nitrogen. In a 10 mL vial vented to "crude" 9-DAME (ERS: 345-103) in 25 ° C, 1.0 mol% of OcsAI was added and the reaction mixture was stirred at room temperature for 20 h before 10 pL (0.1 M) of standard catalyst solution (X051 or X154) is added and the reaction mixture is stirred at 25 ° C and 1 atm (101.3 KPa) for an additional 4 h. Then, the mixture was compartmentalized and quenched with wet EtOAc. Internal standards of 1.0 mL of pentadecane in EtOAc (c = 60.08 mg / mL) and 1.0 mL of mesitylene in EtOAc (c = 61.84 mg / mL) were added and the reaction mixture was completed until 10 ml with ethyl acetate from which 1.0 ml was poured over the top of a column of silica (1.0 ml) and eluted with ethyl acetate (10 ml). From the collected fraction, 100 pL was diluted to 1.0 ml, from which 1.0 pl was injected and analyzed by GCMS-GCFID. The results are shown in Tables 36 and 37 (Figs. 6 and 7).
Tabela 37 Exemplo 37[0174] 0 mol% of OcsAI + 3% by weight of AI2O3: All manipulations were performed under an inert atmosphere of the nitrogen-filled glove chamber. For "crude" 9-DAME (ERS: 345-103) at 25 ° C 1.0 mol%, OcsAI was added and the reaction mixture was stirred at room temperature for 20 h. Then 3.0 wt% activated alumina was added and the reaction mixture was stirred for 2 h before the alumina was removed by filtration. In a 10 mL flask vented to the filtrate aliquot amount, 10 µl of the standard solution (0.1 M) of the catalyst (X051, X01ERE220) was added and the reaction mixture was stirred at 25 ° C and 1 atm (101, 3 KPa) for an additional 4 h. Then, the mixture was compartmentalized and quenched with wet EtOAc. Internal standards of 1.0 mL of pentadecane in EtOAc (c = 60.08 mg / mL) and 1.0 mL of mesitylene in EtOAc (c = 61.84 mg / mL) were added and the reaction mixture was completed until 10 ml with ethyl acetate from which 1.0 ml was poured over the top of a silica column (1.0 ml) and eluted with ethyl acetate (10 ml). From the collected fraction, 100 pL was diluted to 1.0 ml, from which 1.0 pl was injected and analyzed by GCMS-GCFID. The results are shown in Tables 36 and 37 (Figs. 6 and 7). Table 37 Example 37
[0175] In this example, the effect of the amount of a catalyst loading was studied for X052 metathesis catalysts based on Mo and X123 based on W. As described in detail below, the metathesis reactions were conducted at 25 ° C for 4 hours at atmospheric pressure. The results are shown in FIG. 8 in the case of catalyst X052 and in FIG. 9 in the case of the X123 catalyst. The results show that the catalyst loading may have been reduced to as low as 20 ppm by weight, while still having considerable conversion detected. The results show that the use of "pre-dried" 9-DAME was more favorable compared to "crude" 9-DAME, and the W-based X123 catalyst provided a higher conversion than its analog X052 Mo- focused on all cases.
Tabela 38[0176] 1.0 mol% v 0.1 mol OcsAI with X052: All manipulations were performed under the inert atmosphere of a glove chamber loaded with nitrogen. In a 10 mL vial vented for "crude" 9-DAME (ERS: 345-103 or E01 GBE387_2) in 25 ° C, 1.0 mol% or 0.1 mol% of OcsAI was added and the reaction mixture was stirred at 25 ° C for 20 h before 10 µl of the standard solution (1.0 M) of the catalyst (X052, X01ABI385) was added and the reaction mixture was stirred at 25 ° C and 1 atm (101.3 KPa) for an additional 4 h. Then, the mixture was compartmentalized and quenched with wet EtOAc. Internal standards of 1.0 mL of pentadecane in EtOAc (c = 60.08 mg / mL) and 1.0 mL of mesitylene in EtOAc (c = 60.48 mg / mL) were added and the reaction mixture was completed until 10 ml with ethyl acetate from which 1.0 ml was poured over the top of a column of silica (1.0 ml) and eluted with ethyl acetate (10 ml). From the collected fraction, 100 pL was diluted to 1.0 ml, from which 1.0 pl was injected and analyzed by GCMS-GCFID. The results are shown in Table 38 and FIG. 8. Table 38
Exemplo 38[0177] 1.0 mol% v 0.1 mol% OcsAI with x123: All manipulations were performed under an inert atmosphere of the nitrogen-filled glove chamber. In a 10 mL vial vented for "crude" 9-DAME (ERS: 345-103 or E01GBE387_2) at 25 ° C, 1.0 mol% or 0.1 mol% OcsAI was added and the reaction mixture was stirred at 25 ° C for 20 h before 10 pL of the standard solution (1.0 M) of the catalyst (X123, X01FTH344) was added and the reaction mixture was stirred at 25 ° C and 1 atm (101.3 KPa) for an additional 4 h. Then, the mixture was compartmentalized and quenched with wet EtOAc. Manipulations: Internal standards of 1.0 mL of pentadecane in EtOAc (c = 60.08 mg / mL) and 1.0 mL of mesitylene in EtOAc (c = 60.48 mg / mL) were added and the reaction mixture was made up to 10 ml with ethyl acetate from which 1.0 ml was poured on top of a silica column (1.0 ml) and eluted with ethyl acetate (10 ml). From the fraction collected, 100 pL was diluted to 1.0 ml from which 1.0 pL was injected and analyzed by GCMS-GCFID. The results are shown in Table 39 and FIG. 9. Example 38
[0178] The soybean auto-metathesis experiments (Costco) were performed using 40, 30, 20, or 10 ppm by weight of the Ru [1,3-bis- (2,4,6-trimethylphenyl) - catalyst - 2-imidazolidinylidene] dichloro ruthenium (3-methyl-2-butenylidene) (tricyclohexylphosphine) (C827, Materia) after treating the oil samples with between 0 and 2000 ppm by weight of TEAL at 60 ° C for approximately 20 minutes. The TEAL treatment took place after the oil was sparged with nitrogen and heated for 2 hours at 200 ° C. After the metathesis reactions were allowed to proceed for 3 hours, the aliquots of the product mixtures were analyzed by gas chromatography analysis (according to transesterification with 1% w / w NaOMe in methanol at 60 ° C) to determine the extent of conversion of oleate + linoleate + linolinate. FIG. 10 shows that the improved conversions were performed at 40, 30, 20, and 10 ppm by weight C827 when the oil was treated with between 50 and 2000 ppm by weight of TEAL against conversions achieved with the same levels of catalyst C827 when TEAL did not. was employed.
[0179] The products were characterized by comparing the peaks with known patterns. Fatty acid ethyl ester (FAME) analyzes were analyzed using an Agilent 6850 instrument and the following conditions: • Column: J & W Scientific, DB-Wax, 30m x 0.32 mm (ID) x film thickness 0.5 pm • Injector temperature: 250QC • Detector temperature: 300QC • Oven temperature: Starting temperature 70QC, waiting time 1 minute, ramp rate from 20QC / min to 180QC, ramp rate of 3QC / min up to 2209C, waiting time 10 minutes • Carrier gas: hydrogen • Flow rate: 1.0 mL / min
[0180] The entire contents of each and all patent and non-patent publications cited herein are hereby incorporated by reference, except that in the case of any inconsistent disclosure or definition as of this report, the disclosure or definition here should be considered to prevail.
[0181] The previous detailed description and accompanying drawings have been provided by way of explanation and illustration, and are not intended to limit the scope of the attached claims. Many variations of the currently preferred embodiments illustrated herein will be apparent to one of ordinary skill in the art, and remain within the scope of the appended claims and their equivalents.
[0182] The above modalities and examples provide illustrations of various modalities of the methods described here. A non-limiting summary of certain useful modalities is described below.
[0183] Mode 1: A method for the treatment of a substrate before a metathesis reaction, the method comprising: treatment of the substrate with a first agent configured to mitigate the potentially adverse effects of one or more contaminants on the substrate on a used catalyst to catalyze the metathesis reaction; wherein the treatment reduces to a level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 7,500 to 1.
[0184] Mode 2: The Mode 1 method, in which contaminants are selected from the group consisting of water, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis base catalyst poisons , and their combinations.
[0185] Mode 3: The method of Mode 1, in which the substrate comprises a heteroatom.
[0186] Mode 4: The method of Mode 3, in which the heteroatom comprises oxygen.
[0187] Mode 5: The method of Mode 1, in which the substrate comprises a natural oil and / or a derivative thereof.
[0188] Mode 6: The method of Mode 5, in which natural oil is selected from the group consisting of canola oil, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive, palm oil, peanut oil, safflower oil, sesame oil, soy oil, sunflower oil, linseed oil, palm oil, tung oil, jatropha oil, mustard oil, cameline oil, oil of pennycress, hemp oil, seaweed oil, castor oil, lard, tallow, poultry fat, recycled vegetable oil, fish oil, liquid resins, and their combinations.
[0189] Mode 7: The method of Mode 5, in which the derivative comprises an ester.
[0190] Mode 8: The method of Mode 5, in which the derivative is selected from the group consisting of a monoacylglyceride, a diacylglyceride, a triacylglyceride, and their combinations.
[0191] Mode 9: The method of Mode 5, in which the derivative comprises a triacylglyceride.
[0192] Mode 10: The method of Mode 1, in which the substrate comprises a natural oil and in which the protic materials comprise a functional group of carboxylic acid, a functional group of hydroxyl, or a combination thereof.
[0193] Mode 11: The method of Mode 10, in which the prosthetic materials comprise a free fatty acid.
[0194] Mode 12: The method of Mode 1, in which the substrate comprises a plurality of contaminants and, in which the method comprises the reduction of levels of two or more of the contaminants.
[0195] Mode 13: The method of Mode 1, in which the substrate comprises a plurality of contaminants and, in which the method comprises the reduction of levels of three or more of the contaminants.
[0196] Mode 14: The method of Mode 1, in which the substrate comprises a plurality of contaminants and, in which the method comprises the reduction of levels of four or more of the contaminants.
[0197] Mode 15: The method of Mode 1, in which the substrate comprises a plurality of contaminants and, in which the method comprises the reduction of levels of five or more of the contaminants.
[0198] Mode 16: The Mode 1 method, in which the first agent is configured to mitigate the potentially adverse effects of two or more of the contaminants.
[0199] Mode 17: The Mode 1 method, in which the first agent is configured to mitigate the potentially adverse effects of three or more of the contaminants.
[0200] Mode 18: The method of Mode 1, in which the first agent is configured to mitigate the potentially adverse effects of four or more of the contaminants.
[0201] Mode 19: The method of Mode 1, in which the first agent is configured to mitigate the potentially negative effects of water on the catalyst.
[0202] Mode 20: The method of Mode 1, in which the first agent is configured to mitigate the potentially negative effects of peroxides, hydroperoxides, and / or peroxide decomposition products on the catalyst.
[0203] Mode 21: The Mode 1 method, in which the first agent is configured to mitigate the potentially adverse effects of practical materials on the catalyst.
[0204] Mode 22: The Mode 1 method, in which the first agent is configured to mitigate the potentially adverse effects of polar materials on the catalyst.
[0205] Mode 23: The Mode 1 method, in which the first agent is configured to mitigate the potentially negative effects of water, peroxides, hydroperoxides, peroxide decomposition products, practical materials, and / or polar materials on the catalyst.
[0206] Mode 24: The method of Mode 1, in which the first agent is selected from the group consisting of heat, molecular sieves, alumina, silica gel, montmorillonite clay, floor soil, bleaching clay, diatomaceous earth , zeolites, kaolin, activated metals, acid anhydrides, activated carbon, sodium carbonate, metal hydrides, metal sulfates, metal halides, metal carbonates, metal silicates, phosphorus pentoxide, aluminum metal hydrides, aluminum alkyl hydrides, metal borohydrides, organometallic reagents, metal amides, and combinations thereof.
[0207] Mode 25: The method of Mode 1, in which the first agent is selected from the group consisting of molecular sieves optionally heat treated, activated alumina optionally treated with heat, acid activated alumina optionally treated with heat, neutral activated alumina optionally heat treated, activated basic alumina optionally treated with heat, alkaline earth metal hydrides, alkaline earth metal sulphates, alkali metal sulides, alkali earth metal halides, alkali metal hydrides, alkali metal borohydrides, alkali metal reagents Grignard; organolithium reagents, trialkyl aluminum, metal bis (trimethylsilyl) amides, and combinations thereof.
[0208] Mode 26: The Mode 1 method, in which the first agent is selected from the group consisting of CaH2, activated Cu, activated Mg, acetic anhydride, calcium sulfate, magnesium sulphate, potassium sulphate, sulphate aluminum, magnesium and potassium sulfate, sodium sulfate, calcium carbonate, sodium carbonate, magnesium silicate, potassium chloride, LÍAIH4, NaAIH4, ÍBU2AIH, n-butyl lithium, t-butyl lithium, sec-butyl lithium, aluminum triethyl, aluminum tributyl, aluminum tripropyl, aluminum trioctyl, lithium diisopropyl amide, KHMDS, and combinations thereof.
[0209] Mode 27: The method of Mode 1, in which the substrate comprises a natural oil and in which the first agent comprises an adsorbent.
[0210] Mode 28: The method of Mode 1, in which the first agent comprises an adsorbent.
[0211] Mode 29: The method of Mode 28, wherein the treatment of the substrate with the first agent comprises the substrate that flows through the first agent.
[0212] Mode 30: The method of Mode 28, in which the adsorbent is selected from the group consisting of silica gel, bleaching clay, activated carbon, molecular sieves, zeolites, flooring soil, activated alumina optionally treated with heat , activated acid alumina optionally treated with heat, neutral activated alumina optionally treated with heat, activated basic alumina optionally treated with heat, diatomaceous earth, and their combinations.
[0213] Mode 31: The method of Mode 1, in which the first agent is selected from the group consisting of molecular sieves, alumina, and a combination of these.
[0214] Mode 32: The Mode 1 method, in which the first agent comprises alumina.
[0215] Mode 33: The method of Mode 1, further comprising the treatment of the substrate with a second agent that is configured to mitigate the potentially adverse effects of one or more of the contaminants.
[0216] Mode 34: The method of Mode 33, in which the second agent is selected from the group consisting of heat, molecular sieves, alumina, silica gel, montmorillonite clay, floor soil, bleaching clay, diatomaceous earth , zeolites, kaolin, activated metals, acid anhydrides, activated carbon, sodium carbonate, metal hydrides, metal sulfates, metal halides, metal carbonates, metal silicates, phosphorus pentoxide, aluminum metal hydrides, aluminum alkyl hydrides, metal borohydrides, organometallic reagents, metal amides, and combinations thereof.
[0217] Mode 35: The method of Mode 33, in which the second agent is selected from the group consisting of activated molecular sieves, activated alumina, acidic alumina, neutral alumina, basic alumina, alkaline earth metal hydrides, metal sulphates alkaline earth, alkali metal sulphates, alkaline earth metal halides, aluminum and alkali metal hydrides, alkali metal borohydrides, Grignard reagents; organolithium reagents, trialkylaluminiums, metal bis (trimethylsilyl) amides, and combinations thereof.
[0218] Mode 36: The method of Mode 33, in which the second agent is selected from the group consisting of CaH2, activated Cu, activated Mg, acetic anhydride, calcium sulfate, magnesium sulfate, potassium sulfate, sulfate aluminum, magnesium and potassium sulfate, sodium sulfate, calcium carbonate, sodium carbonate, magnesium silicate, potassium chloride, LÍAIH4, NaAIH4, ÍBU2AIH, n-butyl lithium, f-butyl lithium, sec-butyl lithium, aluminum triethyl, aluminum tributyl, aluminum tripropyl, trioctyl aluminum, lithium diisopropylamide, KHMDS, and combinations thereof.
[0219] Mode 37: The Mode 33 method, in which the substrate comprises a natural oil and in which the second agent comprises a trialkyl aluminum.
[0220] Mode 38: The method of Mode 33, in which the second agent comprises a trialkyl aluminum.
[0221] Mode 39: The method of Mode 33, in which the second agent is selected from the group consisting of triethyl aluminum, trioctyl aluminum, tributyl aluminum, triisopropyl aluminum, triisopropyl aluminum, and their combinations.
[0222] Mode 40: The method of Mode 33, which further comprises the treatment of the substrate with a third agent that is configured to mitigate the potentially adverse effects of one or more of the contaminants.
[0223] Mode 41: The Mode 1 method, in which the Lewis base catalyst poisons are selected from the group consisting of materials containing N, materials containing S, materials containing P, and combinations thereof.
[0224] Mode 42: The method of Mode 1, in which the catalyst comprises a transition metal selected from the group consisting of ruthenium, rhenium, tantalum, tungsten, molybdenum, and their combinations.
[0225] Mode 43: The Mode 1 method, in which the catalyst comprises ruthenium.
[0226] Mode 44: The Mode 1 method, in which the catalyst comprises molybdenum catalyst.
[0227] Mode 45: The Method 1 method, wherein the catalyst comprises tungsten catalyst.
[0228] Mode 46: The Mode 1 method, in which the treatment reduces the level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 10,000 to 1.
[0229] Mode 47: The Mode 1 method, in which the treatment reduces the level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate to catalyst molar ratio of at least about 20000 to 1.
[0230] Mode 48: The Mode 1 method, in which the treatment reduces the level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate to catalyst molar ratio of at least about 25000 to 1.
[0231] Mode 49: The method of Mode 1, in which the catalyst is added slowly to the substrate.
[0232] Mode 50: The Mode 1 method, in which the catalyst is added slowly to the substrate at a rate of between 0.01-10 ppm by weight of the catalyst per hour.
[0233] Mode 51: A method for metastasizing a substrate that comprises: treating the substrate with a first agent; and react the substrate, following its treatment with the first agent, in a metathesis reaction, in the presence of a metathesis catalyst; wherein the substrate comprises a natural oil and / or a derivative thereof; wherein the first agent is configured to mitigate the potentially adverse effects of one or more contaminants on the substrate in the metathesis catalyst; wherein the treatment reduces to a level of one or more contaminants by an amount sufficient to allow the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 7,500 to 1.
[0234] Mode 52: The Mode 51 method in which contaminants are selected from the group consisting of water, peroxides, hydroperoxides, peroxide decomposition products, protic materials, polar materials, Lewis-based catalyst poisons, and their combinations.
[0235] Mode 53: The method of Mode 51, which further comprises the treatment of the substrate with a second agent that is configured to mitigate the potentially adverse effects of one or more of the contaminants.
[0236] Mode 54: A method for metastasizing a substrate which comprises: providing a metathesis catalyst; providing a substrate; and slowly adding the catalyst to the substrate to metastasize the substrate; wherein the substrate comprises a natural oil and / or a derivative thereof; wherein the step of slowly adding the catalyst to the substrate allows the metathesis reaction to proceed with a substrate-to-catalyst molar ratio of at least about 7,500 to 1.
[0237] Mode 55: The Mode 54 method, in which the catalyst is added slowly to the substrate at a rate of between 0.01-10 ppm by weight of the catalyst per hour.
[0238] The disclosure contains a variety of modalities in addition to those described above. In addition, the following claims are incorporated herein by reference to the disclosure, as if fully established in this document.
[0239] It is to be understood that the elements and features listed in the attached claims can be combined in different ways to produce new claims that are also within the scope of the present invention. Thus, while the dependent claims attached below depend on only a single independent or dependent claim, it is to be understood that these dependent claims may alternatively be made dependent, alternatively from any preceding independent or dependent claim and that such new combinations are to be understood as forming part of this specification.

权利要求:
Claims (20)
[0001]
1. Method of chemically treating a metathesis substrate material, CHARACTERIZED by the fact that it comprises: providing a metathesis substrate material comprising one or more catalyst poisoning contaminants; and treating the metathesis substrate material to reduce the concentration of at least one of the one or more catalyst poisoning contaminants; wherein the treatment comprises contacting the metastatic substrate material with an alkyl metal compound, wherein the metathesis substrate material comprises a natural oil.
[0002]
2. Method according to claim 1, CHARACTERIZED by the fact that the metathesis substrate comprises a fatty acid monoacylglyceride, a fatty acid diacylglyceride, a fatty acid triacylglyceride, or a combination thereof.
[0003]
3. Method, according to claim 1, CHARACTERIZED by the fact that the metathesis substrate comprises a fatty acid methyl ester.
[0004]
4. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the catalyst poisoning contaminants are peroxides, peroxide decomposition products, protic materials, polar materials, base catalyst poisons Lewis, or combinations thereof, where the practical material refers to a material that contains a dissociable proton, the polar material refers to a material that has an unequal distribution of electrons and thus a permanent dipole moment, the poison Lewis base catalyst refers to a material containing a heteroatom that can function as an electron pair donor.
[0005]
5. Method according to claim 4, CHARACTERIZED by the fact that catalyst poisoning contaminants are peroxides.
[0006]
6. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the alkyl metal compound is selected from the group consisting of: Group I alkyl metal compounds, Group I alkyl metal compounds II, alkyl metal compounds of the IHA Group, and any combinations thereof.
[0007]
7. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the alkyl metal compound is selected from the group consisting of: Mg (CH3) 2, Mg (C2Hs) 2, Mg ( C2H5) (C4H9), Mg (C4H9) 2, Mg (C6Hi3) 2, Mg (C2H25) 2, Zn (CH3) 2, Zn (C2H5) 2, Zn (C4H9) 2, Zn (C4H9) (C8Hi7), Zn (C6Hi3) 2, Zn (C6Hi3) 2, AI (C2H5) 3, AI (CH3) 3, AI (n-C4H9) 3, AI (C8Hi7) 3, AI (iso-C4H9) 3, AI (Ci2H25) 3, and combinations thereof.
[0008]
8. Method, according to claim 7, CHARACTERIZED by the fact that the alkyl metal compound is selected from the group consisting of: AI (C2H5) 3, AI (CeHi7) 3, and combinations thereof.
[0009]
Method according to any one of claims 1 to 3, characterized in that the alkyl metal compound is a trialkyl aluminum compound, and in which the treatment further comprises contacting the metathesis substrate material with one or more of the materials selected from the group consisting of: a molecular sieve, alumina, silica gel, montmorillonite clay, flooring soil, bleaching clay, diatomaceous earth, an activated metal, an acid anhydride, activated carbon, sodium carbonate , a metal sulfate, a metal halide, a metal carbonate, a metal silicate, phosphorus pentoxide, a metal hydrochloride, an organometallic reagent, and a palladium on carbon catalyst.
[0010]
10. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that it further comprises contacting the metathesis substrate material with a hydride-containing compound.
[0011]
11. Method according to claim 10, CHARACTERIZED by the fact that the alkyl metal compound is a trialkyl aluminum compound.
[0012]
12. Method according to claim 11, CHARACTERIZED by the fact that the trialkyl aluminum compound is triethyl aluminum, trioctyl aluminum, or a combination thereof.
[0013]
13. Method according to claim 10, CHARACTERIZED by the fact that the hydride-containing compound is an alkyl aluminum hydride.
[0014]
14. Method according to claim 13, CHARACTERIZED by the fact that the alkyl aluminum hydride is diisobutyl aluminum hydride.
[0015]
15. Method, according to claim 4, CHARACTERIZED by the fact that the polar material is water.
[0016]
16. Method, according to claim 4, CHARACTERIZED by the fact that the peroxide is hydroperoxide.
[0017]
17. Method according to any one of claims 1 to 3, CHARACTERIZED by the fact that the alkyl metal compound is a trialkyl aluminum compound, and wherein the treatment further comprises contacting the metathesis substrate material with one or more of the materials selected from the group consisting of: a zeolite, kaolin.
[0018]
18. Method, according to claim 9, CHARACTERIZED by the fact that the anhydride is a metal anhydride.
[0019]
19. Method according to claim 9, CHARACTERIZED by the fact that the metal halide is an aluminum metal halide.
[0020]
20. Method according to claim 9, CHARACTERIZED by the fact that the organometallic reagent is an alkyl aluminum hydride.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112015019827B1|2020-10-06|METHOD FOR CHEMICALLY TREATING A SUBSTRATE MATERIAL OF METATHESIS

---

US8642824B2|2014-02-04|Chemical methods for treating a metathesis feedstock

---

US9944860B2|2018-04-17|Methods for treating a metathesis feedstock with metal alkoxides

---

US8692006B2|2014-04-08|Thermal methods for treating a metathesis feedstock

---

KR20110103981A|2011-09-21|Methods of producing jet fuel from natural oil feedstocks through metathesis reactions

---

JP2018109006A|2018-07-12|Methods of refining and producing dibasic esters and acids from natural oil feedstocks

---

KR20190062510A|2019-06-05|&amp;Lt; RTI ID = 0.0 &amp;gt; polyamides &amp;lt; / RTI &amp;gt;

---

CA3033679A1|2018-02-22|High-weight glyceride oligomers and methods of making the same

---

Zhu et al.2006|Preparation of terminal oxygenates from renewable natural oils by a one-pot metathesis–isomerisation–methoxycarbonylation–transesterification reaction sequence

---

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

---

US9518002B2|2016-12-13|Terminal selective metathesis of polyenes derived from natural oil

---

US9234156B2|2016-01-12|Low-color ester compositions and methods of making and using the same

---

US9139493B2|2015-09-22|Methods for suppressing isomerization of olefin metathesis products

---

BRPI0814997B1|2017-08-15|Methods for pre-treatment of a metathesis process raw material

---

US20130165708A1|2013-06-27|Methods for suppressing isomerization of olefin metathesis products

---

CS197143B1|1980-04-30|Process for the hydrogenation of higher unsaturated carboxylic acids esters

同族专利:

---

公开号 | 公开日

---

EP2970774A1|2016-01-20|

---

WO2014160417A1|2014-10-02|

---

AU2014243795A1|2015-08-13|

---

BR112015019827A2|2017-07-18|

---

KR20150129681A|2015-11-20|

---

US9388097B2|2016-07-12|

---

MX2015009621A|2015-11-25|

---

CN105189705B|2018-11-20|

---

CN105189705A|2015-12-23|

---

US20170066993A1|2017-03-09|

---

KR102202927B1|2021-01-14|

---

AU2014243795B2|2018-03-29|

---

JP2016516039A|2016-06-02|

---

US20140275595A1|2014-09-18|

---

CA2899451A1|2014-10-02|

---

CA2899451C|2021-03-23|

---

JP6431034B2|2018-11-28|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

IN160358B|1983-01-10|1987-07-11|Thiokol Corp|

---

JPH0428714A|1990-05-23|1992-01-31|Nippon Zeon Co Ltd|Production of dicyclopentadiene having high polymerization activity and its polymerization|

---

US5264606A|1990-10-09|1993-11-23|Union Carbide Chemicals & Plastics Technology Corporation|Process for the preparation of polyvinyl compounds|

---

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

---

EP1910431B1|2005-07-19|2013-11-27|ExxonMobil Chemical Patents Inc.|Polyalpha-olefin compositions and processes to produce the same|

---

US8513478B2|2007-08-01|2013-08-20|Exxonmobil Chemical Patents Inc.|Process to produce polyalphaolefins|

---

CA2695903C|2007-08-09|2015-11-03|Daniel W. Lemke|Chemical methods for treating a metathesis feedstock|

---

CA2695865C|2007-08-09|2015-12-01|Elevance Renewable Sciences, Inc.|Thermal methods for treating a metathesis feedstock|

---

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

---

US9222056B2|2009-10-12|2015-12-29|Elevance Renewable Sciences, Inc.|Methods of refining natural oils, and methods of producing fuel compositions|

---

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

---

US8735640B2|2009-10-12|2014-05-27|Elevance Renewable Sciences, Inc.|Methods of refining and producing fuel and specialty chemicals from natural oil feedstocks|

---

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

---

DE102013004339A1|2013-03-14|2014-09-18|Wilo Se|Pump unit with a one-piece bearing unit|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|

---

WO2015003814A1|2013-07-12|2015-01-15|Ximo Ag|Use of immobilized molybden- und tungsten-containing catalysts in olefin cross metathesis|

---

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

---

DE102014220186B4|2013-12-12|2017-06-22|Technische Universität Dresden|Yeast strains and processes for the production of omega-hydroxy fatty acids and dicarboxylic acids|

---

EP3699168A1|2014-02-18|2020-08-26|Elevance Renewable Sciences, Inc.|Branched-chain esters and methods of making and using the same|

---

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|

---

US9518002B2|2014-10-31|2016-12-13|Elevance Renewable Sciences, Inc.|Terminal selective metathesis of polyenes derived from natural oil|

---

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

---

WO2016154100A1|2015-03-24|2016-09-29|Elevance Renewable Sciences, Inc.|Polyol esters of metathesized fatty acids and uses thereof|

---

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

---

WO2017010983A1|2015-07-13|2017-01-19|Elevance Renewable Sciences, Inc.|Natural oil-derived wellbore compositions and methods of use|

---

US9957356B2|2015-08-17|2018-05-01|Elevance Renewable Sciences, Inc.|Non-isocyanate polyurethanes and methods of making and using the same|

---

CA3005562A1|2015-11-18|2017-05-26|Provivi, Inc.|Production of fatty olefin derivatives via olefin metathesis|

---

ES2757577T3|2015-12-23|2020-04-29|Verbio Ver Bioenergie Ag|Immobilized metal alkylidene catalysts and their use in olefin metathesis|

---

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

---

WO2017136264A1|2016-02-03|2017-08-10|Elevance Renewable Sciences, Inc.|Alkoxylated unsaturated fatty acids and uses thereof|

---

US10280254B2|2016-04-20|2019-05-07|Elevance Renewable Sciences, Inc.|Renewably derived polyesters and methods of making and using the same|

---

US10077333B2|2016-04-20|2018-09-18|Elevance Renewable Sciences, Inc.|Renewably derived polyesters and methods of making and using the same|

---

US10280256B2|2016-04-20|2019-05-07|Elevance Renewable Sciences, Inc.|Renewably derived polyesters and methods of making and using the same|

---

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

---

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

---

US10265249B2|2016-09-29|2019-04-23|The Procter & Gamble Company|Fibrous structures comprising glyceride copolymers|

---

US10265434B2|2016-09-29|2019-04-23|The Procter & Gamble Company|Absorbent articles 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|

---

MX2019003669A|2016-09-30|2019-07-01|Procter & Gamble|Hair care compositions comprising glyceride copolymers.|

---

JP2020507614A|2017-02-17|2020-03-12|プロビビ インコーポレイテッド|Method for synthesizing pheromones and related materials by olefin metathesis|

---

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

---

FI128952B|2019-09-26|2021-03-31|Neste Oyj|Renewable alkene production engaging metathesis|

---

FI128954B|2019-09-26|2021-03-31|Neste Oyj|Renewable base oil production engaging metathesis|

---

WO2021188332A1|2020-03-19|2021-09-23|The Board Of Trustees Of The University Of Illinois|Elastomer with tunable properties and method of rapidly forming the elastomer|

法律状态:
2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-04-22| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2020-10-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

---

2021-06-22| B25A| Requested transfer of rights approved|Owner name: WILMAR TRADING PTE LTD (SG) |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201361784321P| true| 2013-03-14|2013-03-14|

---

US61/784,321|2013-03-14|

---

PCT/US2014/026535|WO2014160417A1|2013-03-14|2014-03-13|Treated metathesis substrate materials and methods of making and using the same|

---