EP2964737A1 - Compositions de graisse à base d'huile naturelle et procédés pour produire ces compositions - Google Patents

Compositions de graisse à base d'huile naturelle et procédés pour produire ces compositions

Info

Publication number
EP2964737A1
EP2964737A1 EP14712534.8A EP14712534A EP2964737A1 EP 2964737 A1 EP2964737 A1 EP 2964737A1 EP 14712534 A EP14712534 A EP 14712534A EP 2964737 A1 EP2964737 A1 EP 2964737A1
Authority
EP
European Patent Office
Prior art keywords
oil
hydrogenated
metathesized
derivatives
natural
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14712534.8A
Other languages
German (de)
English (en)
Inventor
Paul A. Bertin
Zachary Jon HUNT
Syed Q.A. RIZVI
Stephen A. Dibiase
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wilmar Trading Pte Ltd
Original Assignee
Elevance Renewable Sciences Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elevance Renewable Sciences Inc filed Critical Elevance Renewable Sciences Inc
Publication of EP2964737A1 publication Critical patent/EP2964737A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/02—Mixtures of base-materials and thickeners
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M123/00—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential
    • C10M123/02—Lubricating compositions characterised by the thickener being a mixture of two or more compounds covered by more than one of the main groups C10M113/00 - C10M121/00, each of these compounds being essential at least one of them being a non-macromolecular compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/006—Inorganic compounds or elements as ingredients in lubricant compositions used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/14—Synthetic waxes, e.g. polythene waxes
    • C10M2205/146—Synthetic waxes, e.g. polythene waxes used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/18—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras
    • C10M2205/186—Natural waxes, e.g. ceresin, ozocerite, bees wax, carnauba; Degras used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/006—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/123—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic
    • C10M2207/1236—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms polycarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • C10M2207/1265—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C10M2207/1276—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic used as thickening agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
    • C10M2207/1285—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • C10M2207/166—Naphthenic acids used as thickening agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/40—Fatty vegetable or animal oils
    • C10M2207/401—Fatty vegetable or animal oils used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition
    • C10N2060/02—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • a grease composition comprises from 50 to 99 weight percent of a lubricating base oil, and from 1 to 30 weight percent of a thickener component.
  • the thickener component comprises one or more of (i) one or more natural oil derivatives, (ii) one or more hydrogenated metathesized natural oils and/or natural oil derivatives, (iii) one or more amidated metathesized natural oils and/or natural oil derivatives, (iv) one or more carboxylic acids and/or derivatives thereof, and (v) one or more of a metal base compound.
  • the one or more hydrogenated metathesized natural oils and/or natural oil derivatives comprises a hydrogenated metathesized soybean oil based wax.
  • the grease composition may further comprise from 1 to 15 weight percent of one or more optional additives.
  • a process for preparing a simple grease composition comprises adding from 1 to 30 weight percent of a thickener component comprising one or more of (i) one or more natural oil derivatives, (ii) one or more hydrogenated metathesized natural oils and/or natural oil derivatives, (iii) one or more amidated metathesized natural oils and/or natural oil derivatives, (iv) one or more carboxylic acids and/or derivatives thereof, to from 50 to 99 weight percent of a lubricating base oil, and charging this mixture to a kettle, mixer or equivalent vessel.
  • a thickener component comprising one or more of (i) one or more natural oil derivatives, (ii) one or more hydrogenated metathesized natural oils and/or natural oil derivatives, (iii) one or more amidated metathesized natural oils and/or natural oil derivatives, (iv) one or more carboxylic acids and/or derivatives thereof, to from 50 to 99 weight percent of a lubricating base oil, and charging this mixture to a kettle, mixer or equivalent
  • This mixture is then heated to a temperature between about 140° F to 200° F for approximately 30-60 minutes, in order to dissolve the one or more carboxylic acids and/or derivatives thereof into the lubricating base oil.
  • One or more of a metal base compound is then charged to this mixture in an amount slightly in excess of the stoichiometric amount required to neutralize the one or more carboxylic acids and/or derivatives thereof.
  • the mixture is then maintained at a temperature between about 190°F to about 270° F for approximately 30-90 minutes to complete the neutralization and to effect a substantial dehydration of the mixture.
  • This mixture is then heated to about 350° F to about 430° F for up to approximately 60 minutes. Thereafter, the mixture is cooled with the assistance of incorporating an additional amount of the lubricating base oil and the removal of heat, to yield the grease composition.
  • from 1 to 15 weight percent of one or more additives may be added to the grease composition.
  • a process for preparing a complex grease composition comprises adding from 1 to 30 weight percent of a thickener component comprising one or more of (i) one or more natural oil derivatives, (ii) one or more hydrogenated metathesized natural oils and/or natural oil derivatives, (iii) one or more amidated metathesized natural oils and/or natural oil derivatives, (iv) two or more carboxylic acids and/or derivatives thereof, to from 50 to 99 weight percent of a lubricating base oil, and charging this mixture to a kettle, mixer or equivalent vessel.
  • a thickener component comprising one or more of (i) one or more natural oil derivatives, (ii) one or more hydrogenated metathesized natural oils and/or natural oil derivatives, (iii) one or more amidated metathesized natural oils and/or natural oil derivatives, (iv) two or more carboxylic acids and/or derivatives thereof, to from 50 to 99 weight percent of a lubricating base oil, and charging this mixture to a kettle, mixer or equivalent
  • This mixture is then heated to a temperature between about 140° F to 200° F for approximately 30-60 minutes, in order to dissolve the two or more carboxylic acids and/or derivatives thereof into the lubricating base oil.
  • One or more of a metal base compound is then charged to this mixture in an amount slightly in excess of the stoichiometric amount required to neutralize the two or more carboxylic acids and/or derivatives thereof.
  • the mixture is then maintained at a temperature between about 190°F to about 270° F for approximately 30-90 minutes to complete the neutralization and to effect a substantial dehydration of the mixture.
  • This mixture is then heated to about 350° F to about 430° F for up to approximately 60 minutes. Thereafter, the mixture is cooled with the assistance of incorporating an additional amount of the lubricating base oil and the removal of heat, to yield the grease composition.
  • from 1 to 15 weight percent of one or more additives may be added to the grease composition.
  • the present application relates to natural oil based grease compositions and processes for making such compositions.
  • natural oil may refer to oil derived from plants or animal sources.
  • natural oil includes natural oil derivatives, unless otherwise indicated.
  • natural oils include, but are not limited to, vegetable oils, algae oils, animal fats, tall oils, 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 kernel oil, tung oil, jatropha oil, mustard oil, camelina oil, pennycress oil, hemp oil, algal oil, and castor oil.
  • animal fats include lard, tallow, poultry fat, yellow grease, and fish oil.
  • Tall oils are by-products of wood pulp manufacture.
  • the natural oil may be refined, bleached, and/or deodorized.
  • the natural oil may be partially or fully hydrogenated.
  • the natural oil is present individually or as mixtures thereof.
  • natural oil derivatives may refer to the compounds or mixture of compounds derived from the natural oil using any one or combination of methods known in the art. Such methods include metathesis, saponification, transesterification, esterification, interesterification, hydrogenation (partial or full), isomerization, amidation, oxidation, and reduction, individually or in combinations thereof.
  • Representative non-limiting examples of natural oil derivatives include gums, phospholipids, waxes (e.g. non-limiting examples such as hydrogenated metathesized natural oil waxes and amidated hydrogenated metathesized natural oil waxes), soapstock, acidulated soapstock, distillate or distillate sludge, fatty acids and fatty acid alkyl ester (e.g.
  • a feedstock includes canola or soybean oil, as a non-limiting example, refined, bleached, and deodorized soybean oil (i.e., RBD soybean oil).
  • Soybean oil typically comprises about 95% weight or greater (e.g., 99% weight or greater) triglycerides of fatty acids.
  • Major fatty acids in the polyol esters of soybean oil 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, oleic acid (9- octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), and linolenic acid (9, 12, 15-octadecatrienoic acid).
  • one particular natural oil derivative is hydrogenated castor oil, which is the glyceride of 12-hydroxystearic acid.
  • hydrogenation and saponification of castor oil yields 12- hydroxystearic acid, which is then reacted with lithium hydroxide or lithium carbonate to give high performance grease.
  • metalathesis or “metathesizing” refers to the reacting of a feedstock in the presence of a metathesis catalyst to form a metathesized product or "metathesized natural oil” comprising a new olefinic compound. Metathesizing may refer to cross-metathesis (a.k.a.
  • metathesizing may refer to reacting two triglycerides present in a natural oil feedstock (self-metathesis) in the presence of a metathesis catalyst, wherein each triglyceride has an unsaturated carbon-carbon double bond, thereby forming a "natural oil oligomer” having a new mixture of olefins and esters that may comprise one or more of: metathesis monomers, metathesis dimers, metathesis trimers, metathesis tetramers, metathesis pentamers, and higher order metathesis oligomers (e.g., metathesis hexamers).
  • metathesis hexamers refers to the product formed from the metathesis reaction of a natural oil in the presence of a metathesis catalyst to form a mixture of olefins and esters comprising one or more of: metathesis monomers, metathesis dimers, metathesis trimers, metathesis tetramers, metathesis pentamers, and higher order metathesis oligomers (e.g., metathesis hexamers).
  • the metathesized natural oil has been partially to fully hydrogenated, forming a "hydrogenated metathesized natural oil.”
  • the metathesized natural oil is formed from the metathesis reaction of a natural oil comprising more than one source of natural oil (e.g., a mixture of soybean oil and palm oil).
  • the metathesized natural oil is formed from the metathesis reaction of a natural oil comprising a mixture of natural oils and natural oil derivatives.
  • dropping point As used herein, the term “dropping point,” “drop point,” or “melting point” are terms that may refer to the temperature at which the grease begins to melt. The drop point may be measured using ASTM-D 127-08 or the Mettler Drop Point FP80 system, incorporated by reference herein.
  • needle penetration may refer to the relative hardness of the grease composition.
  • the needle penetration may be measured using ASTM-D1321 -02a, incorporated by reference herein.
  • the term "cone penetration” may refer to the measurement of the solidity of the grease. Penetration is the depth, in tenths of millimeters, to which a standard cone sinks into the grease under prescribed conditions. Thus higher penetration numbers indicate softer grease, since the cone has sunk deeper into the sample.
  • the elements of a lubricating grease composition are generally divided among three parts: lubricating base oil, thickener, and additives.
  • lubricating base oil carries out the main role of lubrication
  • the thickener structures the lubricating base oil into a semi-solid
  • the additives impart additional functionality to the lubricating base oil and/or thickener, such as corrosion or oxidation resistance.
  • the lubricating base oil employed in the grease composition can be any of the conventionally used lubricating oils, and is preferably a mineral oil, a synthetic oil or a blend of mineral and synthetic oils, or in some cases, natural oils and natural oil derivatives, all individually or in combinations thereof.
  • Mineral lubricating oil base stocks used in preparing the greases can be any conventionally refined base stocks derived from paraffinic, naphthenic and mixed base crudes.
  • the lubricating base oil may include polyolefin base stocks, of both polyalphaolefin (PAO) and polyinternal olefin (PIO) types. Oils of lubricating viscosity derived from coal or shale are also useful.
  • Examples of synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propyleneisobutylene copolymers); poly(l -hexenes), poly(l -octenes), poly(1 - decenes), and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di-(2-ethylhexyl)-benzenes); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof.
  • hydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,
  • Alkylene oxide polymers and interpolymers and derivatives thereof where the terminal hydroxyl groups have been modified by esterification, and etherification constitute another class of known synthetic lubricating oils that can be used. These are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropylene glycol ether having a number average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000- 1500) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C 3-8 fatty acid esters, or the Ci 3 Oxo acid diester of tetraethylene glycol.
  • the oils prepared through polymerization of ethylene oxide or propylene oxide the alkyl and aryl
  • Another suitable class of synthetic lubricating oils that can be used comprises the esters of dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acids, and alkenyl malonic acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol).
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid
  • esters include dibutyl adipate, di-(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
  • Esters useful as synthetic oils also include those made from C5 to C12 monocarboxylic acids and polyols such as neopentyl glycol, trimethylol propane, and pentaerythritol, or polyol ethers such as dipentaerythritol, and tripentaerythritol.
  • polyols such as neopentyl glycol, trimethylol propane, and pentaerythritol, or polyol ethers such as dipentaerythritol, and tripentaerythritol.
  • Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils comprise another useful class of synthetic lubricants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methylhexyl)silicate, tetra-(p-tert-butylphenyl) silicate, hexyl-(4-methyl-2- pentoxy)disiloxane, poly(methyl)siloxanes, and poly-(methylphenyl)siloxanes).
  • synthetic lubricants e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl)silicate, tetra-(4-methylhexy
  • Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid), and polymeric tetrahydrofurans.
  • liquid esters of phosphorus-containing acids e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid
  • polymeric tetrahydrofurans e.g., tricresyl phosphate, trioctyl phosphate, and the diethyl ester of decane phosphonic acid
  • Unrefined, refined and re-refined oils can be used as the lubricating base oil in the grease composition .
  • Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
  • a shale oil obtained directly from retorting operations a petroleum oil obtained directly from primary distillation or ester oil obtained directly from an esterification process and used without further treatment would be an unrefined oil.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service.
  • Such re- refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Oils of lubricating viscosity can also be defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines.
  • API American Petroleum Institute
  • Group I >0.03 and/or ⁇ 90 80-120
  • PAOs polyalphaolefins
  • Groups I, II, and III are mineral oil base stocks.
  • the oil of lubricating viscosity is a Group I, II, III, IV, or V oil or mixtures thereof.
  • the lubricating base oil is present in a "major amount,” meaning greater than about 50 weight percent of the grease composition, preferably in the range 50 to 99 weight percent of the grease composition, preferably 60 to 95 weight percent of the grease composition, more preferably 70 to 92 weight percent of the grease composition and most preferably 75 to 90 weight percent of the grease composition.
  • these lubricating oils have a viscosity in the range of 15 to 220, preferably 30 to 150 cSt at 40° C, and a viscosity index in the range of 30 to 170, preferably 30 to 140.
  • the thickener generally comprises multiple components, which may include one or more of the following: (i) one or more natural oil derivatives, such as hydrogenated natural oils,
  • amidated metathesized natural oils and/or natural oil derivatives (iii) one or more amidated metathesized natural oils and/or natural oil derivatives, (iv) one or more carboxylic acids, such as 12-hydroxystearic acid (12-HSA) and azelaic acid, and derivatives thereof, and (v) one or more of a metal base compound, such as metal oxide, metal hydroxide, or metal carbonate, or mixtures thereof.
  • carboxylic acids such as 12-hydroxystearic acid (12-HSA) and azelaic acid, and derivatives thereof
  • a metal base compound such as metal oxide, metal hydroxide, or metal carbonate, or mixtures thereof.
  • the thickener may be present in a "minor amount,” meaning less than about 50 weight percent of the grease composition, preferably in the range of 1 to 30 weight percent of the grease composition, and more preferably 5 to 20 weight percent of the grease composition, and most preferably 10 to 20 weight percent of the grease composition.
  • the function of the thickener is to provide a physical matrix which holds the lubricating base oil in a solid structure until operating conditions initiate viscoelastic flow.
  • the natural oil derivatives may include one or more hydrogenated natural oils.
  • Such hydrogenated natural oils may include: hydrogenated vegetable oil, hydrogenated algae oil, hydrogenated animal fat, hydrogenated tall oil, hydrogenated derivatives of these oils, and mixtures thereof.
  • the hydrogenated vegetable oil is hydrogenated canola oil, hydrogenated rapeseed oil, hydrogenated coconut oil, hydrogenated corn oil, hydrogenated cottonseed oil, hydrogenated olive oil, hydrogenated palm oil, hydrogenated peanut oil, hydrogenated safflower oil, hydrogenated sesame oil, hydrogenated soybean oil, hydrogenated sunflower oil, hydrogenated linseed oil, hydrogenated palm kernel oil, hydrogenated tung oil, hydrogenated jatropha oil, hydrogenated mustard oil, hydrogenated camelina oil, hydrogenated pennycress oil, hydrogenated castor oil, hydrogenated derivatives of these oils, and mixtures thereof.
  • the hydrogenated natural oil is a hydrogenated animal fat such as hydrogenated lard, hydrogenated tallow, hydrogenated poultry fat, hydrogenated fish oil, hydrogenated derivatives of these oils, and mixtures thereof.
  • the hydrogenated natural oil is hydrogenated castor oil.
  • the thickener may have a component comprising a hydrogenated metathesized natural oil or a natural oil derivative thereof, such as a hydrogenated metathesized natural oil based wax.
  • the natural oil is metathesized and hydrogenated to modify the physical properties of the natural oil such that it forms a wax.
  • hydrogenated metathesized natural oils include hydrogenated metathesized vegetable oil, hydrogenated metathesized algae oil, hydrogenated metathesized animal fat, hydrogenated metathesized tall oil, hydrogenated metathesized derivatives of these oils, and mixtures thereof.
  • the hydrogenated metathesized vegetable oil is hydrogenated metathesized canola oil, hydrogenated metathesized rapeseed oil, hydrogenated metathesized coconut oil, hydrogenated metathesized corn oil, hydrogenated metathesized cottonseed oil, hydrogenated metathesized olive oil, hydrogenated metathesized palm oil, hydrogenated metathesized peanut oil, hydrogenated metathesized safflower oil, hydrogenated metathesized sesame oil, hydrogenated metathesized soybean oil, hydrogenated metathesized sunflower oil, hydrogenated metathesized linseed oil, hydrogenated metathesized palm kernel oil, hydrogenated metathesized tung oil, hydrogenated metathesized jatropha oil, hydrogenated metathesized mustard oil, hydrogenated metathesized camelina oil, hydrogenated metathesized pennycress oil, hydrogenated metathesized castor oil, hydrogenated metathesized derivatives of these oils, and mixtures thereof.
  • the hydrogenated metathesized natural oil is a hydrogenated metathesized animal fat such as hydrogenated metathesized lard, hydrogenated metathesized tallow, hydrogenated metathesized poultry fat, hydrogenated metathesized fish oil, hydrogenated metathesized derivatives of these oils, and mixtures thereof.
  • the natural oil is a hydrogenated metathesized soybean oil ("HMSBO").
  • S-55 is a hydrogenated metathesized soybean oil available from Elevance Renewable Sciences, Woodridge, IL.
  • the HMSBO has a drop point of about 54°C (129°F), a congeal point of about 52°C (126°F) and a needle penetration of about 13 dmm.
  • the natural oil is a hydrogenated metathesized soybean oil that has been vacuum stripped to remove paraffins.
  • this vacuum stripped version of HMSBO, S-60 is a hydrogenated metathesized soybean oil available from Elevance Renewable Sciences, Woodridge, IL.
  • this vacuum stripped HMSBO has a drop point of about 54°C (129°F) and a needle penetration of about 1 .4 dmm.
  • this vacuum stripped HMSBO shall also be included in the general definition of HMSBO.
  • Metathesis is a catalytic reaction generally known in the art that involves the interchange of alkylidene units among compounds containing one or more double bonds ⁇ e.g., olefinic compounds) via the formation and cleavage of the carbon-carbon double bonds. Metathesis may occur between two like molecules (often referred to as self-metathesis) and/or it may occur between two different molecules (often referred to as cross-metathesis). Self-metathesis may be represented schematically as shown in Equation I.
  • R 1 and R 2 are organic groups.
  • Cross-metathesis may be represented schematically as shown in Equation II.
  • the hydrogenated metathesized natural oil based wax may be produced by the steps of: (a) providing a metathesis composition;(b) providing a metathesis catalyst comprising a transition metal; (c) metathesizing at least a portion of the metathesis composition in the presence of the metathesis catalyst to form a first composition comprising one or more metathesis products and transition metal; (d) hydrogenating at least a portion of the first composition in the presence of a hydrogenation catalyst to form a second composition comprising one or more hydrogenated metathesis products, transition metal, and hydrogenation catalyst; and (e) removing at least a portion of the hydrogenation catalyst from the second composition, wherein the removal of the hydrogenation catalyst removes at least a portion of the transition metal of the metathesis catalyst from the second composition.
  • the metathesis compositions comprise polyol esters of unsaturated fatty acids.
  • the polyol esters typically comprise one or more of monoacylglycerides, diacylglycerides, and triacylglycerides.
  • the polyol esters are derived, for example, from natural oils.
  • the metathesis composition is refined, bleached, and deodorized (i.e., RBD) soybean oil.
  • the metathesis compositions may include esters of the fatty acids provided by the oils and fats and molecules with a single hydroxy site such as fatty acid methyl esters.
  • polyol esters refers to esters produced from polyols.
  • Polyols may include more than two hydroxyl groups. These polyols may comprise from two to about 10 carbon atoms, and may comprise from two to six hydroxyl groups, but other numbers of carbon atoms and/or hydroxyl groups are possible as well.
  • the polyols may contain two to four hydroxyl moieties.
  • Non-limiting examples of polyols include glycerin, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3- butanediol, 2,3-butanediol, 2-ethyl-1 ,3-propanediol, 2-ethyl-2-butyl-1 ,3-propanediol, neopentyl glycol, 2,2,4-trimethyl-1 ,3-pentanediol, trimethylolpropane (TMP), sorbitol and pentaerythritol.
  • the polyol esters employed herein are esters of glycerin, e.g., triacylglycerides, or esters of a mixture of glycerin and one or more other polyols.
  • the polyol ester component may include a partial fatty acid ester of one or more polyols and/or a polyol which is fully esterified with fatty acids ("complete polyol fatty acid ester").
  • complete polyol fatty acid esters include triacylglycerides, propylene glycol diesters and tetra esters of pentaerythritol.
  • suitable polyol partial esters include fatty acid monoglycerides, fatty acid diglycerides and sorbitan partial esters (e.g., diesters and triesters of sorbitan).
  • the polyol may include from 2 to 6 carbon atoms and 2 to 6 hydroxyl groups.
  • suitable polyols include glycerol, trimethylolpropane, ethylene glycol, propylene glycol, pentaerythritol, sorbitan and sorbitol.
  • the polyol esters are metathesized and hydrogenated to form wax compositions.
  • refined, bleached and deodorized (RBD) soybean oil is self-metathesized in the presence of a metathesis catalyst to form a metathesis product.
  • the resulting metathesis product is then hydrogenated without first removing the metathesis catalyst to form a hydrogenated metathesis product in the form of a wax.
  • the metathesis product is steam stripped and/or vacuum stripped in order to remove or reduce hydrocarbon impurities.
  • the metathesis product may be distilled in order to remove or reduce hydrocarbons having a molecular weight of about 200 gram/mole or less or to remove or reduce hydrocarbons having a molecular weight of about 300 grams/mole or less.
  • the stripping may be accomplished by sparging the mixture in a vessel, typically agitated, by contacting the mixture with a gaseous stream in a column that may contain typical distillation packing (e.g., random or structured), or evaporating the lights in an evaporator such as a wiped film evaporator.
  • stripping will be conducted at reduced pressure and at temperatures ranging from about 100° C. to 250° C.
  • the hydrogenated metathesized natural oil is a hydrogenated metathesized soybean oil that is vacuum stripped to remove paraffins.
  • S-60 is a hydrogenated metathesized soybean oil available from Elevance Renewable Sciences, in Woodridge, IL.
  • the hydrogenated metathesized natural oil and/or natural oil derivatives may arise from bottoms streams from a metathesis reactor, or from bottoms streams of downstream separation units from a metathesis reactor.
  • Such bottoms streams may be primarily esters, where such esters may include triglycerides, diglycerides, monoglycerides, or oligomers therefrom, or fatty acid methyl esters ("FAME"), or Ci 0- Ci 5 esters, Ci 5- Ci 8 esters, or Cis+ esters, or diesters therefrom, wherein such esters may occur as free esters or in combinations thereof.
  • esters are preferably monoglycerides and/or fatty acid methyl esters.
  • metathesis catalyst includes any catalyst or catalyst system that catalyzes a metathesis reaction. Any known or future- developed metathesis catalyst may be used, individually or in combination with one or more additional catalysts. Non-limiting exemplary metathesis catalysts and process conditions are described in PCT/US2008/009635, pp. 18-47, incorporated by reference herein. A number of the metathesis catalysts as shown are manufactured by Materia, Inc. (Pasadena, CA). Additional exemplary metathesis catalysts include, without limitation, metal carbene complexes selected from the group consisting of molybdenum, osmium, chromium, rhenium, and tungsten.
  • complex refers to a metal atom, such as a transition metal atom, with at least one ligand or complexing agent coordinated or bound thereto.
  • a ligand typically is a Lewis base in metal carbene complexes useful for alkyne or alkene-metathesis.
  • Typical examples of such ligands include phosphines, halides and stabilized carbenes.
  • Some metathesis catalysts may employ plural metals or metal co-catalysts (e.g., a catalyst comprising a tungsten halide, a tetraalkyl tin compound, and an organoaluminum compound). An immobilized catalyst can be used for the metathesis process.
  • An immobilized catalyst is a system comprising a catalyst and a support, the catalyst associated with the support. Exemplary associations between the catalyst and the support may occur by way of chemical bonds or weak interactions (e.g. hydrogen bonds, donor acceptor interactions) between the catalyst, or any portions thereof, and the support or any portions thereof. Support is intended to include any material suitable to support the catalyst.
  • immobilized catalysts are solid phase catalysts that act on liquid or gas phase reactants and products. Exemplary supports are polymers, silica or alumina. Such an immobilized catalyst may be used in a flow process. An immobilized catalyst can simplify purification of products and recovery of the catalyst so that recycling the catalyst may be more convenient.
  • the metathesis process can be conducted under any conditions adequate to produce the desired metathesis products. For example, stoichiometry, atmosphere, solvent, temperature and pressure can be selected to produce a desired product and to minimize undesirable byproducts.
  • the metathesis process may be conducted under an inert atmosphere.
  • an inert gaseous diluent can be used.
  • the inert atmosphere or inert gaseous diluent typically is an inert gas, meaning that the gas does not interact with the metathesis catalyst to substantially impede catalysis.
  • particular inert gases are selected from the group consisting of helium, neon, argon, nitrogen and combinations thereof.
  • substantially inert solvents include, without limitation, aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.; halogenated aromatic hydrocarbons, such as chlorobenzene and dichlorobenzene; aliphatic solvents, including pentane, hexane, heptane, cyclohexane, etc.; and chlorinated alkanes, such as dichloromethane, chloroform, dichloroethane, etc.
  • aromatic hydrocarbons such as benzene, toluene, xylenes, etc.
  • halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene
  • aliphatic solvents including pentane, hexane, heptane, cyclohexane, etc.
  • chlorinated alkanes such as dichloromethane, chloroform, dichloroethane, etc.
  • a ligand may be added to the metathesis reaction mixture.
  • the ligand is selected to be a molecule that stabilizes the catalyst, and may thus provide an increased turnover number for the catalyst.
  • the ligand can alter reaction selectivity and product distribution.
  • ligands examples include Lewis base ligands, such as, without limitation, trialkylphosphines, for example tricyclohexylphosphine and tributyl phosphine; triarylphosphines, such as triphenylphosphine; diarylalkylphosphines, such as, diphenylcyclohexylphosphine; pyridines, such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine; as well as other Lewis basic ligands, such as phosphine oxides and phosphinites. Additives may also be present during metathesis that increase catalyst lifetime.
  • Lewis base ligands such as, without limitation, trialkylphosphines, for example tricyclohexylphosphine and tributyl phosphine
  • triarylphosphines such as triphenylphosphine
  • diarylalkylphosphines such as, dipheny
  • the molar ratio of the unsaturated polyol ester to catalyst may range from about 5: 1 to about 10,000,000: 1 or from about 50: 1 to 500,000: 1.
  • the metathesis reaction temperature may be a rate-controlling variable where the temperature is selected to provide a desired product at an acceptable rate.
  • the metathesis temperature may be greater than -40° C, may be greater than about -20° C, and is typically greater than about 0° C. or greater than about 20° C.
  • the metathesis reaction temperature is less than about 150° C, typically less than about 120° C.
  • An exemplary temperature range for the metathesis reaction ranges from about 20° C. to about 120° C.
  • the metathesis reaction can be run under any desired pressure.
  • the total pressure may be selected to be greater than about 10 kPa, in some embodiments greater than about 30 kPa, or greater than about 100 kPa.
  • the reaction pressure is no more than about 7000 kPa, in some embodiments no more than about 3000 kPa.
  • An exemplary pressure range for the metathesis reaction is from about 100 kPa to about 3000 kPa.
  • the metathesis reaction is catalyzed by a system containing both a transition and a non-transition metal component.
  • the most active and largest number of catalyst systems are derived from Group VI A transition metals, for example, tungsten and molybdenum.
  • the metathesis composition is thereafter hydrogenated with one or more hydrogenation catalysts.
  • hydrogenation catalysts may comprise, for example, nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, or iridium. Combinations of metals may also be used.
  • Useful catalyst may be heterogeneous or homogeneous.
  • the catalysts are supported nickel or sponge nickel type catalysts.
  • the hydrogenation catalyst comprises nickel that has been chemically reduced with hydrogen to an active state (i.e., reduced nickel) provided on a support.
  • the support comprises porous silica (e.g., kieselguhr, infusorial, diatomaceous, or siliceous earth) or alumina.
  • the catalyst are characterized by a high nickel surface area per gram of nickel.
  • the particles of supported nickel catalyst are dispersed in a protective medium comprising hardened triacylglyceride, edible oil, or tallow.
  • the supported nickel catalyst is dispersed in the protective medium at a level of about 22 wt. % nickel.
  • the supported nickel catalysts are of the type reported in U.S. Pat. No. 3,351 ,566 (Taylor et al.), incorporated herein by reference in its entirety. These catalyst comprise solid nickel-silica having a stabilized high nickel surface area of 45 to 60 sq. meters per gram and a total surface area of 225 to 300 sq. meters per gram.
  • the catalysts are prepared by precipitating the nickel and silicate ions from solution such as nickel hydrosilicate onto porous silica particles in such proportions that the activated catalyst contains 25 to 50 wt. % nickel and a total silica content of 30 to 90 wt %. The particles are activated by calcining in air at 600 to 900 F, then reducing with hydrogen.
  • Useful catalysts having a high nickel content are described in EP 0 168 091 , incorporated herein by reference in its entirety, wherein the catalyst is made by precipitation of a nickel compound. A soluble aluminum compound is added to the slurry of the precipitated nickel compound while the precipitate is maturing. After reduction of the resultant catalyst precursor, the reduced catalyst typically has a nickel surface area of the order of 90 to 150 sq. m per gram of total nickel.
  • the catalysts have a nickel/aluminum atomic ratio in the range of 2 to 10 and have a total nickel content of more than about 66% by weight.
  • nickel/silica hydrogenation catalysts are described in U.S. Pat. No. 6,846,772, incorporated herein by reference in its entirety.
  • the catalysts are produced by heating a slurry of particulate silica (e.g. kieselguhr) in an aqueous nickel amine carbonate solution for a total period of at least 200 minutes at a pH above 7.5, followed by filtration, washing, drying, and optionally calcination.
  • the nickel/silica hydrogenation catalysts are reported to have improved filtration properties.
  • supported nickel hydrogenation catalysts include those available under the trade designations "NYSOFACT”, “NYSOSEL”, and “Nl 5248 D” (from Englehard Corporation, Iselin, N.H.). Additional supported nickel hydrogenation catalysts include those commercially available under the trade designations "PRICAT 9910", “PRICAT 9920”, “PRICAT 9908”, “PRICAT 9936, and "PRICAT 9925” (from Johnson Matthey Catalysts, Ward Hill, Mass.).
  • Hydrogenation may be carried out in a batch or in a continuous process and may be partial hydrogenation or complete hydrogenation.
  • a vacuum is pulled on the headspace of a stirred reaction vessel and the reaction vessel is charged with soybean oil (e.g., RBD soybean oil).
  • the soybean oil may be heated to a desired temperature. Typically, the temperature ranges from about 50° C. to 350° C, for example, about 100° C. to 300° C. or about 150° C. to 250° C.
  • the desired temperature may vary, for example, with hydrogen gas pressure. Typically, a higher gas pressure will require a lower temperature.
  • the hydrogenation catalyst is weighed into a mixing vessel and is slurried with a small amount of soybean oil.
  • the slurry of hydrogenation catalyst is added to the reaction vessel. Hydrogen gas is then pumped into the reaction vessel to achieve a desired pressure of H 2 gas.
  • the H 2 gas pressure ranges from about 15 to 3000 psig, for example, about 40 to about 100 psig. As the gas pressure increases, more specialized high-pressure processing equipment may be required. Under these conditions the hydrogenation reaction begins and the temperature is allowed to increase to the desired hydrogenation temperature, where it is maintained by cooling the reaction mass, for example, with cooling coils.
  • the hydrogenation temperature ranges from about 20° C. to about 250° C, for example, about 100° C. or greater, or about 120° C. to about 220° C.
  • the reaction mass is cooled to the desired filtration temperature.
  • the amount of hydrogenation catalysts is typically selected in view of a number of factors including, for example, the type of hydrogenation catalyst used, the amount of hydrogenation catalyst used, the degree of unsaturation in the metathesis product, the desired rate of hydrogenation, the desired degree of hydrogenation (e.g., as measure by iodine value (IV)), the purity of the reagent, and the H 2 gas pressure.
  • the hydrogenation catalyst is used in an amount of about 10 wt. % or less, for example, about 5 wt. % or less or about 1 wt. % or less.
  • the used hydrogenation catalyst is removed from the hydrogenated metathesized product using known techniques such as filtration.
  • the hydrogenation catalyst is removed using a plate and frame filter such as those commercially available from Sparkle Filters, Inc., Conroe Tex.
  • the filtration is performed with the assistance of pressure or a vacuum.
  • a filter aid may be used.
  • a filter aid may be added to the metathesized product directly or it may be applied to the filter.
  • Representative examples of filtering aids include diatomaceous earth, silica, alumina, and carbon.
  • the filtering aid is used in an amount of about 10 wt. % or less, for example, about 5 wt. % or less or about 1 wt. % or less.
  • Other filtering techniques and filtering aids may also be employed to remove the used hydrogenation catalyst.
  • the hydrogenation catalyst is removed using centrifugation followed by decantation of the product.
  • the hydrogenated metathesis products typically contain less than about 100 ppm of the metathesis catalyst transition metal. In other embodiments, the hydrogenated metathesis products contain less than about 10 ppm of the metathesis catalyst transition metal. In still other embodiments, the hydrogenated metathesis products contain less than about 1 ppm of the metathesis catalyst transition metal, for example, about 0.9 ppm or less, about 0.8 ppm or less, about 0.7 ppm or less, about 0.6 ppm or less, about 0.5 ppm or less, about 0.4 ppm or less, about 0.3 ppm or less, or about 0.1 ppm or less. In exemplary embodiments, the metathesis catalyst is a ruthenium-based catalyst and the hydrogenated metathesis product contains less than about 0.1 ppm ruthenium.
  • hydrogenated metathesized oil is a mixture of compounds of at least two general types: paraffinic compounds and triglycerides of long-chain mono-carboxylic and di-carboxylic acids and oligomers thereof.
  • the paraffinic compounds typically do not react under any fat splitting conditions and exit the reaction unaltered. Depending on the application, the paraffinic compounds can be partly or fully removed (stripped).
  • Triglycerides and oligomers thereof are reacted with water or OH7H + giving mainly free fatty acids corresponding to the hydrogenated metathesized oil fatty acid profile (mono- and di-acids) and glycerol leaving small amounts of partially hydrolyzed hydrogenated metathesized oil composed of diglycerides, monoglycerides, and oligomers thereof.
  • the metathesized natural oil may be epoxidized.
  • the metathesized natural oil may be epoxidized via any suitable peroxyacid.
  • Peroxyacids are acyl hydroperoxides and are most commonly produced by the acid-catalyzed esterification of hydrogen peroxide. Any peroxyacid may be used in the epoxidation reaction.
  • hydroperoxides include, but are not limited to, peracetic acid, performic acid, m-dichloroperbenzoic acid, tert-butylhydroperoxide, triphenylsilylhydroperoxide, cumylhydroperoxide, and hydrogen peroxide.
  • the thickener may have a component comprising an amidated hydrogenated metathesized natural oil or natural oil derivative, such as an amidated hydrogenated metathesized natural oil based wax.
  • a number of valuable amide wax compositions may be prepared by reacting an amine with an ester-functional group of a metathesized natural oil in the presence of a basic catalyst or heat to form an amidated metathesized natural oil. This reaction may generate amidated metathesized natural oil compositions having unique properties over other forms of amide waxes, natural oils, or metathesized natural oils.
  • Such unique properties may include a higher drop point, higher congeal point, improved hardness, improved malleability, improved emulsifiability, improved functionality, improved viscosity, and/or improved compatibility with other materials (such as triglyceride oils and waxes, polyamides, stearic acid, ethylene vinyl acetate copolymers, tackifier resins, and paraffins in low concentration).
  • other materials such as triglyceride oils and waxes, polyamides, stearic acid, ethylene vinyl acetate copolymers, tackifier resins, and paraffins in low concentration.
  • the metathesized natural oil in the amidated metathesized natural oil composition has been "hydrogenated" (i.e., full or partial hydrogenation of the unsaturated carbon-carbon bonds in the metathesized natural oil) in the presence of a hydrogenation catalyst to form a hydrogenated metathesized natural oil.
  • a hydrogenation catalyst to form a hydrogenated metathesized natural oil.
  • the natural oil is partially hydrogenated before it is subjected to the metathesis reaction.
  • the natural oil is metathesized prior to being subjected to partial or full hydrogenation.
  • Any known or future-developed hydrogenation catalysts may be used, alone or in combination with one or more additional catalysts.
  • Non-limiting exemplary hydrogenation catalysts were described previously in this document. Representative examples of hydrogenated metathesized natural oils were described previously in this document.
  • the amine compound(s) selected for the reaction with the metathesized natural oil may be ammonia or a compound containing one or more primary or secondary amino groups.
  • the amine is a mono- substituted amine having one non-hydrogen substituted group (such as an alkyl, aryl group, alkyl-amino group, or aryl-amino group), a di-substituted amine having two non-hydrogen substituted groups, an amino-alcohol, or a combination thereof.
  • the amine is a mono-substituted or di-substituted amine such as: methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, or a mixture thereof.
  • the amine is an amino-alcohol such as: methanolamine, dimethanolamine, ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine, dibutanolamine, pentanolamine, dipentanolamine, hexanolamine, dihexanolamine, heptanolamine, diheptanolamine, octanolamine, dioctanolamine, aniline, or a mixture thereof.
  • amino-alcohol such as: methanolamine, dimethanolamine, ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine, dibutanolamine, pentanolamine, dipentanolamine, hexanolamine, dihexanolamine, heptanolamine, diheptanolamine, octanolamine, dioctanolamine, aniline, or a mixture thereof
  • the amine is a diamine such as: ethylenediamine (1 ,2-ethanediamine), 1 ,3- propanediamine, 1 ,4-butanediamine (putrescine), 1 ,5-pentanediamine, 1 ,6- hexanediamine, 1 ,7-heptanediamine, 1 ,8-octanediamine, 1 ,3- bis(aminomethyl)cyclohexane, meta-xylenediamine, 1 ,8-naphthalenediamine, p- phenylenediamine, N-(2-aminoethyl)-1 ,3-propanediamine, or a mixture thereof.
  • diamine such as: ethylenediamine (1 ,2-ethanediamine), 1 ,3- propanediamine, 1 ,4-butanediamine (putrescine), 1 ,5-pentanediamine, 1 ,6- hexanediamine, 1 ,7-heptanediamine
  • the amine is a triamine or tetramine such as: diethylenetriamine, dipropylenetriamine, dibutylenetriamine, dipentylenetriamine, dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, spermidine, melamine, triethylenetetramine, tripropylenetetramine, tributylenetetramine, tripentylenetetramine, trihexylenetetramine, triheptylenetetramine, trioctylenetetramine, hexamine, or a mixture thereof.
  • the amine is an imidazole or oxazolidine.
  • the amine is selected from the group consisting of: ethanolamine, diethanolamine, diethylamine, ethylenediamine (1 ,2-ethanediamine), hexamethyleneamine, and mixtures thereof.
  • the amine is ethylenediamine.
  • the amine is diethanolamine.
  • HMSBO may be fractionally amidated with diethanol amine to generate an emulsifying amidated wax, A100, available from Elevance Renewable Sciences, in Woodridge, IL.
  • the amine is a polar compound that is useful for forming a hydrous amidated metathesized natural oil composition.
  • the hydrous composition is capable of being water dispersible and improving the viscosity of the wax composition.
  • Non-limiting examples of polar amines include amino-alcohols such as: methanolamine, dimethanolamine, ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine, dibutanolamine, pentanolamine, dipentanolamine, hexanolamine, dihexanolamine, heptanolamine, diheptanolamine, octanolamine, dioctanolamine, aniline, or mixtures thereof.
  • the amine is a non-polar compound that is useful for forming an anhydrous amidated metathesized natural oil composition.
  • anhydrous compositions may be capable of improving the hardness and drop point of the wax composition.
  • the amount of amine present in the amine- metathesized natural oil reaction is between approximately 0.1 percent by weight and 30 percent by weight of the metathesized natural oil present.
  • the amount of basic catalyst is between approximately 0.1 percent by weight and 10 percent by weight of the metathesized natural oil or between approximately 1 percent by weight and 15 percent by weight of the metathesized natural oil.
  • the amount of amine added to the reaction can be expressed in terms of the ratio of amine equivalents in the amine to ester equivalents in the metathesized natural oil. In one embodiment, the ratio of amine equivalents to ester equivalents is between approximately 1 :100 and approximately 10:1 .
  • the ratio of amine equivalents to ester equivalents is between approximately 1 :10 and approximately 5:1 . In other embodiments, the ratio of amine equivalents to ester equivalents is approximately 1 :3, approximately 2:3, approximately 1 :2, or approximately 1 :1 .
  • the basic catalyst that may be used to improve the reaction rate of the amine-metathesized natural oil reaction is a basic compound generally known to a person of skill in the art.
  • the basic catalyst is sodium carbonate, lithium carbonate, sodium methanolate, potassium hydroxide, sodium hydride, potassium butoxide, potassium carbonate, or a mixture thereof.
  • the basic catalyst may be added to the reaction between the amine and metathesized natural oil in dry form or dissolved in water.
  • the reaction rate of the amine-metathesized natural oil reaction is improved by heating the amine-metathesized natural oil mixture (with or without a basic catalyst present) to at least 100°C, at least 120°C, at least 140°C, at least 160°C, or between approximately 100°C and approximately 200°C.
  • the amount of basic catalyst added to the reaction is between approximately 1 percent by weight and 10 percent by weight of the metathesized natural oil present. In other embodiments, the amount of basic catalyst is between approximately 0.1 percent by weight and 1 .0 percent by weight of the metathesized natural oil or between approximately 0.01 percent by weight and 0.1 percent by weight of the metathesized natural oil. In another embodiment, the amount of basic catalyst is approximately 0.5 percent by weight of the metathesized natural oil.
  • the amine-metathesized natural oil reaction is conducted in a nitrogen or other inert atmosphere.
  • the reaction is conducted under atmospheric conditions and the reactor temperature is between approximately 80-250°C, between approximately 120-180°C, or between approximately 120-160°C.
  • the reactor temperature is held for approximately 1 -24 hours, approximately 4-24 hours, approximately 1 hour, approximately 2 hours, approximately 4 hours, or approximately 6 hours.
  • the product mixture is vacuum pumped for at least 30 minutes or at least 1 hour to separate the water, any unreacted amine, and/or glycerol from the amidated metathesized natural oil product.
  • paraffin byproduct from the metathesis and hydrogenation reactions can be separated from the amidated metathesized natural oil product.
  • the ester functionality is replaced by an amine to form an amidated metathesized natural oil comprising molecules having the following structures:
  • Ri is selected from the group consisting of:
  • R 2 , R3, R4, R5, R6, R7, Rs, and Rg are independently selected from the group consisting of hydrogen, alcohols, alkyls, aryls, alkyl-amines, and aryl-amines, wherein R 0 and Rn are independently selected from the group consisting of:
  • X-i , X 2 , X 3 , X4, X 5 , and XQ are independently selected from the group consisting of Cs - C 2 s saturated or unsaturated alkyl chains from either a fatty acid of a natural oil, or a derivative thereof formed by a metathesis reaction.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R7, Re, and R 9 may form at least one amine selected from the group consisting of: methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, methanolamine, dimethanolamine, ethanolamine, diethanolamine, propanolamine, dipropanolamine, butanolamine, dibutanolamine, pentanolamine, dipentanolamine, hexanolamine, dihexanolamine, heptanolamine, diheptanolamine, octanolamine, dioctano
  • the amidated metathesized natural oil contains the diacid functionality and a glycerol backbone of the metathesized natural oil.
  • the reaction between the metathesized natural oil and amine produces a hydroxy-metathesis oligomer co-product having the following structure:
  • R-12 wherein R-12 is:
  • R 3 and Ri 4 are independently selected from the group consisting of:
  • X 7 , Xs, and Xg are independently selected from the group consisting of Cs - C28 saturated or unsaturated alkyl chains from either a fatty acid of a natural oil, or a derivative thereof formed by a metathesis reaction.
  • the carboxylic acid has about 2 to about 36, preferably about 6 to about 24, more preferably about 9 to about 20 carbon atoms, and mono-, di-, tri-, and/or poly- acid variants, hydroxy-substituted variants, aliphatic, cyclic, alicyclic, aromatic, branched, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic groups, saturated and unsaturated variants, and heteroatom substituted variants thereof.
  • the mono- or di-esters or poly-esters of these acids thereof may be used.
  • Non-limiting examples of such carboxylic acids include lauric acid, azelaic acid, myristic acid, palmitic acid, arachic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, capric acid, lignoceric acid, decenoic acid, undecenoic acid, dodecenoic acid, ricinoleic acid, myristoleic acid, palmitoleic acid, gadoleic acid, elaidic acid, cis-eicosenoic acid, erucic acid, nervonic acid, 2,4-hexadienoic acid, linoleic acid, 12-hydroxy tetradecanoic acid, 10-hydroxy tetradeconoic acid, 12- hydroxy hexadecanoic acid, 8-hydroxy hexadecanoic acid, 12-hydroxy icosanic acid, 16-hydroxy icosanic acid 1 1 ,14-e
  • azelaic acid is a preferred carboxylic acid.
  • naphthenic acids and mixtures thereof such as are obtainable from various petroleum sources, may be used.
  • Other non-limiting examples such as hydroxystearic, hydroxy-ricinoleic, hydroxybehenic and hydroxypalmitic acids may be used, preferably hydroxystearic acid or esters of these acids such as 9-hydroxy-, 10-hydroxy- or 12-hydroxy- stearic acid, and most preferably 12-hydroxystearic acid.
  • the metals themselves can be selected from alkali metals or alkaline earth metals, such as, without limitation, beryllium, magnesium, calcium, lithium, sodium, potassium, strontium and barium; transition metals, without limitation, such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, palladium, silver, cadmium, tungsten and mercury; and other metals such as aluminum, gallium, tin, iron, lead, and lanthanoid metals, all individually or in combinations thereof. Said metals are more preferably selected from lithium, sodium, magnesium, aluminum, calcium, zinc and barium.
  • alkali metals or alkaline earth metals such as, without limitation, beryllium, magnesium, calcium, lithium, sodium, potassium, strontium and barium
  • transition metals without limitation, such as titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zircon
  • carboxylic acid metal salts which may be conveniently used in the present invention are metal salts of any combination of a mono- or poly- carboxylic; branched alicyclic, cyclic, cycloalkyl, or linear, saturated or unsaturated, mono- or poly-hydroxy substituted or unsubstituted carboxylic acid, acid chloride or the ester of said carboxylic acid with an alcohol such as an alcohol of about 1 to about 5 carbon atoms.
  • the base compound the alkoxides, oxides, hydroxides, carbonates, chlorides, and mixtures thereof of any of the aforementioned metals are found to be especially useful.
  • hydroxides of these aforementioned metals are preferred, and calcium hydroxide, strontium hydroxide, magnesium hydroxide, sodium hydroxide, and lithium hydroxide are more preferred .
  • the metal hydroxide is a mono- or di- or tri-valent metal or a mixture thereof. In one embodiment the metal hydroxide is lithium hydroxide monohydrate and can be solid or aqueous, although aqueous is preferred.
  • the metal base usually a metal hydroxide, such as lithium hydroxide or in its more commonly available form of lithium hydroxide monohydrate
  • a carboxylic acid usually 12-hydroxystearic acid
  • a carboxylic acid derivative usually 12-hydroxystearate or hydrogenated castor oil
  • This reaction is most often carried out in the lubricating base oil with water also being present.
  • the water is added to act as a reaction solvent if the acid is used.
  • the carboxylic acid derivative is used, the water acts both as reaction solvent and reactant, the latter effect being necessary for the hydrolytic cleavage of the ester linkages in the 12-hydroxystearate or the hydrogenated castor oil.
  • the lithium hydroxide is reacted with two or more carboxylic acids, such as 12-hydroxystearic acid and azelaic acid, to form a metallic (lithium) soap.
  • optional additives may be incorporated into the grease compositions of this invention, for the particular service intended.
  • Such optional additives include: metal deactivators, antioxidants, antiwear agents, rust inhibitors, viscosity modifiers, extreme pressure agents, corrosion inhibitors, and other additives recognized in the art to perform a particular function or functions.
  • Such additives may be present in the range of 1 to 15 weight percent of the grease composition, and more preferably 3 to 10 weight percent of the grease composition.
  • Metal deactivators may include derivatives of benzotriazoles, benzimidazole, 2-alkyldithiobenz-imidazoles, 2-alkyldithiobenzothiazoles, 2-(N,N- dialkyldithiocarbamoyl)-benzothiazoles, 2,5-bis(alkyl-dithio)-1 ,3,4-thiadiazoles, 2,5- bis(N,N-dialkyldithio-carbamoyl)-1 ,3,4-thiadiazoles, 2-alkyldithio-5-mercapto thiadiazoles or mixtures thereof.
  • Antioxidants may include a variety of chemical types including phenate sulfides, phosphosulfurized terpenes, sulfurized esters, aromatic amines, and hindered phenols.
  • Antiwear agents may include a metal thiophosphate, especially a zinc dialkyldithiophosphate; a phosphoric acid ester or salt thereof; a phosphite; and a phosphorus-containing carboxylic ester, ether, or amide.
  • Rust inhibitors may include include metal sulfonates such as calcium sulfonate or magnesium sulfonate, amine salts of carboxylic acids such as octylamine octanoate, condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine, e.g. a polyalkylene polyamine such as triethylenetetramine, and half esters of alkenyl succinic acids in which the alkenyl radical contains 8 to 24 carbon atoms with alcohols such as polyglycols.
  • metal sulfonates such as calcium sulfonate or magnesium sulfonate
  • amine salts of carboxylic acids such as octylamine octanoate
  • condensation products of dodecenyl succinic acid or anhydride and a fatty acid such as oleic acid with a polyamine, e.g.
  • Viscosity modifiers may include polymeric materials including styrene- butadiene rubbers, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated radical isoprene polymers, polymethacrylate acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl conjugated diene copolymers, polyolefins, polyalkylmethacrylates, esters of maleic anhydride-styrene copolymers and mixtures thereof.
  • polymeric materials including styrene- butadiene rubbers, ethylene-propylene copolymers, polyisobutenes, hydrogenated styrene-isoprene polymers, hydrogenated radical isoprene polymers, polymethacrylate acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl
  • EP Agents may include agents that are soluble in the oil include a sulfur or chlorosulfur EP agent, a chlorinated hydrocarbon EP agent, or a phosphorus EP agent, or mixtures thereof.
  • EP agents are chlorinated wax, organic sulfides and polysulfides, such as benzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate, phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphites, i.e., dibutyl phosphite, dih
  • Corrosion inhibitors may include: mercaptobenzothiazole, barium dinonylnaphthalene sulfonate, glycerol monooleate, sodium nitrite, and imidazolines of tetraethylenepentamine, among others.
  • the grease compositions described herein are useful for lubricating, sealing and protecting mechanical components such as gears, axles, bearings, shafts, hinges and the like.
  • mechanical components are found in automobiles, trucks, bicycles, steel mills, mining equipment, railway equipment including rolling stock, aircraft, boats, construction equipment and numerous other types of industrial and consumer machinery.
  • the grease compositions described herein may be used in various applications, including, but not limited to, lubricating surface mining machinery (pins and bushings, open gears in large electric shovels), constant velocity joints (CV joints), ball bearings, journal bearings, high speed low load machinery lubrication, low speed-high load machinery lubrication, conveyor belt bearings lubrication, gears lubrication, open gears lubrication, curve and flange rail lubrication, traction motor gear lubrication, high temperature highly corrosive media lubrication, wheel bearing lubrication of motor vehicles and trucks, journal bearing lubrication of freight and high speed trains, paper machinery lubrication, lawn and garden machinery lubrication, pipe dope anti seize lubrication, automotive tie rod ends, roof, seating and steering mechanism lubrication, jacks and landing gear equipment lubrication, continuous castor and hot mills bearing lubrication, lubrication of garage door mechanisms and oven chain lubrication.
  • Greases can be manufactured in several consistencies as defined by National Lubricating Grease Institute (N. L.G.I.) as described in ASTM Method D-217 for Cone Penetration of Lubricating Greases. Adjusting the lubricating base oil, thickener component, and additive content will permit the manufacture of various grades of greases.
  • NLGI 0 very soft greases sold under the designation NLGI 0 have a cone penetration number from about 355 to 385, those having a cone penetration range of 310 to 340 are designated NLGI 1 and the most widely sold greases have a cone penetration range of 265 to 295 and are designated NLGI 2.
  • Table 1 below shows the various NLGI grades for greases.
  • Batch processing generally comprises the use of one or more large kettles that may be equipped with, for example, paddle agitation, stirring, heating, external recirculation systems capable of pumping the contents from the bottom of the kettle to the top, and combinations thereof.
  • the kettles that may be utilized herein may be of a size generally in a range of from 500 liters to 20,000 liters, preferably in a range of from 2,000 liters to 15,000 liters, and more preferably in a range of from 3,000 liters to 10,000 liters.
  • suitable kettles include open kettles and pressurized kettles.
  • An example grease kettle is equipped with stirring, heating, and an external recirculation system, capable of pumping the contents from the bottom of the kettle to the top.
  • the kettles may have heating means, cooling means, paddle type stirrers, gear-type circulation pumps, circulation line, back pressure shear valve in said circulation line, colloid mill, product filter, and other associated piping, valves, instrumentation, etc. required for the commercial manufacture of grease.
  • the grease may also be passed through a grease mill again to obtain a further improvement in yield and appearance, where such mills may include a Morehouse mill, a Charlotte mill, and a Gaulin homogenizer.
  • Another type of batch processor sometimes used is a Stratco® mixer which has a different internal mixing configuration.
  • the material is circulated by an impeller located at the bottom of the vessel, where it is possible to obtain rapid circulation and thorough mixing.
  • the various thickener components are added to a lubricating base oil, and this mixture is charged to a kettle, mixer, or equivalent vessel.
  • these thickener components are naphthenic acid, 12-hydroxystearic acid, hydrogenated castor oil, and hydrogenated metathesized soybean oil (S60), and the lubricating base oil is a naphthenic pale oil.
  • the metal base usually a metal hydroxide such as lithium hydroxide is then charged to the vessel, usually in an amount slightly in excess of the stoichiometric amount required to neutralize the acid.
  • the temperature at this stage is usually between about 190°F to about 270° F., preferably between about 240° F to about 260° F, for a period of time (approximately 30-90 minutes) sufficient to complete the neutralization and to effect a substantial dehydration of the mixture, i.e., the removal of 70 to 100% of the water, by venting.
  • heating of the mixture is resumed and increased to about 350° to about 430° F, preferably between about 390° F to about 410° F, and maintained at that level for about 15 minutes to about 1 hour to ensure optimum soap crystallization, dispersing of the acid into the mixture, and improved yields.
  • This increase in temperature is effected as rapidly as possible to save time and to minimize oxidation.
  • the mixture is then transferred to a finishing kettle or equivalent vessel for cooling. This cooling is assisted by incorporating additional lubricating base oil into the mixture. Mixing can be continued until the grease reaches ambient temperatures. After about 90 minutes into this cooling phase, the heat is removed, and at about 1 hour thereafter, optional grease additives may be added to the finishing kettle.
  • the grease compositions described herein may also encompass complex greases.
  • Complex greases are formed by reaction of a metal-containing reagent with two or more acids.
  • One of the acids is (i) a hydroxy carboxylic acid or reactive derivative thereof, such as a C9-C24 hydroxystearic acid, preferably 9-hydroxy, 10-hydroxy, or 12-hydroxystearic acid, or the mono- or di- esters or poly-esters thereof, and (ii) a dicarboxylic acid, such as one or more straight or branched chain C 2 -Ci 2 dicarboxylic acids, examples of which may include oxalic, malonic, succinic, glutaric, adipic, suberic, pimelic, azelaic, dodecanedioic and sebacic acids, preferably azelaic acid, or the mono- or di-esters or poly-esters thereof.
  • a hydroxy carboxylic acid or reactive derivative thereof such as a C9-C24 hydroxy
  • an additional hydroxy carboxylic acid may be utilized, where such acid has from 3 to 14 carbon atoms and can be either an aliphatic acid such as lactic acid, 6-hydroxy decanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, etc. or an aromatic acid such as parahydroxybenzoic acid, salicylic acid, 2- hydroxy-4-hexylbenzoic acid, meta hydroxybenzoic acid, 2,5-dihydroxybenzoic acid; 2,6-dihydroxybenzoic acid; 4-hydroxy-3-methoxybenzoic acid, etc. or a hydroxyaromatic aliphatic acid such as orthohydroxyphenyl, metahydroxyphenyl, or parahydroxyphenyl acetic acid.
  • an aliphatic acid such as lactic acid, 6-hydroxy decanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, etc.
  • an aromatic acid such as parahydroxybenzoic acid, salicylic acid, 2- hydroxy-4-hexylbenzoic acid, meta
  • a cycloaliphatic hydroxy acid such as hydroxy cyclopentyl carboxylic acid or hydroxynaphthenic acid could also be used .
  • a cycloaliphatic hydroxy acid such as hydroxy cyclopentyl carboxylic acid or hydroxynaphthenic acid could also be used .
  • the various thickener components are added to a lubricating base oil, and this mixture is charged to a kettle, mixer, or equivalent vessel.
  • these thickener components are naphthenic acid, 12-hydroxystearic acid, azelaic acid, and hydrogenated metathesized soybean oil (S60), and the lubricating base oil is a naphthenic pale oil.
  • the metal base usually a metal hydroxide such as lithium hydroxide is then charged to the vessel, is then added to convert the azelaic acid to its dilithium soap (dilthium azelate) usually in an amount slightly in excess of the stoichiometric amount required to neutralize both acid groups of the azelaic acid.
  • the temperature at this stage is usually between about 190°F to about 270° F, preferably between about 240° F to about 260° F, for a period of time (approximately 30-90 minutes) sufficient to complete the neutralization and to effect a substantial dehydration of the mixture, i.e., the removal of 70 to 100% of the water, by venting.
  • heating of the mixture is resumed and increased to about 350° to about 430° F, preferably between about 390° F to about 410° F, and maintained at that level for about 15 minutes to about 1 hour to ensure optimum soap crystallization, dispersing of the acid into the mixture, and improved yields.
  • This increase in temperature is effected as rapidly as possible to save time and to minimize oxidation.
  • the mixture is then transferred to a finishing kettle or equivalent vessel for cooling.
  • This cooling is assisted by incorporating additional lubricating base oil into the mixture.
  • Mixing can be continued until the grease reaches ambient temperatures.
  • the heat is removed, and at about 1 hour thereafter, optional grease additives may be added to the finishing kettle.
  • the S60 component of the thickener serves to liberate long chain (i.e. C18 and higher) dicarboxylate salts, carboxylate salts, and glycerol upon exposure to metal hydroxides during grease processing, thus serving as a latent grease complexing agent.
  • long chain i.e. C18 and higher
  • dicarboxylate salts carboxylate salts
  • glycerol glycerol
  • simple greases may achieve some complex character under standard processing conditions (3 hours). The inclusion of S60 into simple grease compositions would allow for lower processing temperatures and increased production capacity without compensating simple grease performance.
  • This mixture was then transferred to a finishing kettle, at a period between 60 and 90 minutes from the start of the experiment, an additional amount of lubricating base oil was added dropwise for dilution. At about 90 minutes, the heat was removed, and at about 1 hour thereafter, optional additives were charged to the finishing kettle, and cooling resumed until the end of the experiment at 4 hours.
  • This mixture was then transferred to a finishing kettle, at a period between 60 and 90 minutes from the start of the experiment, an additional amount of lubricating base oil was added dropwise for dilution. At about 90 minutes, the heat was removed, and at about 1 hour thereafter, optional additives were charged to the finishing kettle, and cooling resumed until the end of the experiment at 4 hours.
  • a pilot scale run at 350 °F for experiment 5 yielded at NLGI specification grease (drop point of 378 °F, unworked/worked cone penetration of 326/324 dmm).
  • a pilot scale run at 350 °F for experiment 14 successfully yielded a complex grease at 350 °F.
  • Experiment 9 also showed that a simple grease may be made without the inclusion of hydrogenated castor oil, which produced a grease at NLGI Grade 1 specifications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne une composition de graisse, qui comporte de 50 à 99 pour cent en poids d'une huile de base lubrifiante, de 1 à 30 pour cent en poids d'un composant épaississant comprenant au moins l'un des composants suivants (i) au moins un dérivé d'huile naturelle, (ii) au moins une huile naturelle hydrogénée métathétisée et/ou des dérivés d'huile naturelle, (iii) au moins une huile naturelle amidée métathétisée et/ou des dérivés d'huile naturelle, (iv) au moins un ou au moins deux acides carboxyliques et/ou des dérivés de ceux-ci et (v) au moins un composé à base métallique et de 1 à 15 pour cent en poids d'au moins un additif optionnel. L'invention concerne également des procédés de fabrication de compositions de graisse.
EP14712534.8A 2013-03-08 2014-03-07 Compositions de graisse à base d'huile naturelle et procédés pour produire ces compositions Withdrawn EP2964737A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201361774760P 2013-03-08 2013-03-08
PCT/US2014/021863 WO2014138613A1 (fr) 2013-03-08 2014-03-07 Compositions de graisse à base d'huile naturelle et procédés pour produire ces compositions

Publications (1)

Publication Number Publication Date
EP2964737A1 true EP2964737A1 (fr) 2016-01-13

Family

ID=50349979

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14712534.8A Withdrawn EP2964737A1 (fr) 2013-03-08 2014-03-07 Compositions de graisse à base d'huile naturelle et procédés pour produire ces compositions

Country Status (6)

Country Link
US (2) US20140256605A1 (fr)
EP (1) EP2964737A1 (fr)
CN (1) CN105026533A (fr)
CA (1) CA2899369A1 (fr)
MX (1) MX2015009619A (fr)
WO (1) WO2014138613A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3845622A1 (fr) * 2020-01-03 2021-07-07 Indian Oil Corporation Limited Graisse complexe de zinc à haute température

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9771538B2 (en) * 2013-03-15 2017-09-26 Ethox Chemicals, Llc Bio-based lubricants
SG11201800960XA (en) * 2015-08-31 2018-03-28 Fraunhofer Ges Forschung Lubricating mixture having glycerides
CN105695066A (zh) * 2016-01-19 2016-06-22 张志强 一种新型润滑脂及其制备方法
CN106190461B (zh) * 2016-07-07 2018-11-23 东营国安化工有限公司 一种高性能润滑油
CN106221868B (zh) * 2016-07-07 2018-10-23 蚌埠海明压铸机有限公司 一种节能压铸机专用润滑油
CN106221871B (zh) * 2016-07-13 2018-11-23 东营国安化工有限公司 一种齿轮用润滑油
FR3069864B1 (fr) * 2017-08-03 2019-08-16 Total Marketing Services Composition lubrifiante comprenant un diester
CN107699328A (zh) * 2017-10-20 2018-02-16 安徽中天石化股份有限公司 一种可生物降解型润滑脂
US11697786B2 (en) * 2018-03-06 2023-07-11 Nippon Grease Co., Ltd. Grease composition
CN111849590B (zh) * 2020-06-19 2022-07-19 中国石油化工股份有限公司 一种低噪音混合皂基润滑脂组合物及其制备方法
CN114479999B (zh) * 2022-01-11 2023-03-31 江苏中晟高科环境股份有限公司 一种快速脱水造纸循环系统润滑油

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013009605A1 (fr) * 2011-07-10 2013-01-17 Elevance Renewable Sciences, Inc. Compositions de savon métallique pour diverses applications

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB644395A (en) * 1940-07-25 1950-10-11 Bataafsche Petroleum Lubricating greases containing lead soaps
US3351566A (en) 1963-10-21 1967-11-07 Exxon Research Engineering Co Stabilized high-activity catalyst
NL8201696A (nl) 1982-04-23 1983-11-16 Unilever Nv Werkwijze ter bereiding van methaneringskatalysatoren.
US4435299A (en) * 1982-06-07 1984-03-06 Texaco Inc. Preparation of high dropping point lithium complex soap grease
NL190750C (nl) 1984-06-21 1994-08-01 Unilever Nv Nikkelaluminaat katalysator, de bereiding daarvan en het hydrogeneren van onverzadigde organische verbindingen daarmee.
US5391309A (en) * 1991-12-09 1995-02-21 Exxon Research And Engineering Company Method of preparing high dropping point lithium complex soap greases
GB0017839D0 (en) 2000-07-21 2000-09-06 Ici Plc Hydrogenation catalysts
US20110218128A1 (en) * 2008-10-17 2011-09-08 Nok Kluber Co., Ltd. Lubricating grease composition and method for producing the same
JP5911857B2 (ja) * 2010-07-05 2016-04-27 シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイＳｈｅｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ Ｒｅｓｅａｒｃｈ Ｍａａｔｓｃｈａｐｐｉｊ Ｂｅｓｌｏｔｅｎ Ｖｅｎｎｏｏｔｓｈａｐ グリース組成物の製造方法
US8846587B2 (en) * 2011-03-24 2014-09-30 Elevance Renewable Sciences, Inc. Functionalized monomers and polymers
US9315748B2 (en) * 2011-04-07 2016-04-19 Elevance Renewable Sciences, Inc. Cold flow additives

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013009605A1 (fr) * 2011-07-10 2013-01-17 Elevance Renewable Sciences, Inc. Compositions de savon métallique pour diverses applications

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2014138613A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3845622A1 (fr) * 2020-01-03 2021-07-07 Indian Oil Corporation Limited Graisse complexe de zinc à haute température

Also Published As

Publication number Publication date
WO2014138613A1 (fr) 2014-09-12
CA2899369A1 (fr) 2014-09-12
MX2015009619A (es) 2015-12-11
CN105026533A (zh) 2015-11-04
US20140256605A1 (en) 2014-09-11
US20160040093A1 (en) 2016-02-11

Similar Documents

Publication Publication Date Title
EP2964737A1 (fr) Compositions de graisse à base d'huile naturelle et procédés pour produire ces compositions
US9347013B2 (en) Natural oil derivative based thickener components used in grease compositions and processes for making such compositions
US10150931B2 (en) Grease compositions comprising estolide base oils
JP6826682B2 (ja) ベースストックとして、および潤滑油用途で用いるための、分岐ジエステル
EP2591080B1 (fr) Procédé pour la fabrication d'une composition de graisse
CN106459817B (zh) 润滑剂
EP3692121B1 (fr) Composition de graisse
EP3328971A1 (fr) Composition lubrifiante comprenant des diesters ramifiés et un agent améliorant l'indice de viscosité
WO2017021333A1 (fr) Diesters ramifiés pour utilisation en vue de réduire la consommation de carburant d'un moteur
KR20080066977A (ko) 분산체의 제조방법
US6399801B1 (en) Dry powder lithium carboxylates
KR101305076B1 (ko) 황을 이용한 윤활유용 극압첨가제의 제조방법
CA1148529A (fr) Additifs pour lubrifiants utilises dans l'usinage des metaux
JP6843289B6 (ja) グリース組成物の製造方法およびグリース組成物
WO2024033188A1 (fr) Composition de graisse
WO2024188995A1 (fr) Composition de graisse biodégradable
EP1327621A1 (fr) Poudre sèche de lithium carboxylates

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150904

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HUNT, ZACHARY, JON

Inventor name: RIZVI, SYED, Q.A.

Inventor name: DIBIASE, STEPHEN, A.

Inventor name: BERTIN, PAUL, A.

RIN1 Information on inventor provided before grant (corrected)

Inventor name: RIZVI, SYED, Q.A.

Inventor name: HUNT, ZACHARY, JON

Inventor name: DIBIASE, STEPHEN, A.

Inventor name: BERTIN, PAUL, A.

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180829

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: WILMAR TRADING PTE LTD

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20211001