Classifications

• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B31/00—Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
  • G04B31/08—Lubrication
• • 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
• • 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
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  • 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
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
• • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
• • 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
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
  • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
  • C10M2215/064—Di- and triaryl amines
  • C10M2215/065—Phenyl-Naphthyl amines
• • 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
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
  • C10M2229/0415—Siloxanes with specific structure containing aliphatic substituents 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
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/042—Siloxanes with specific structure containing aromatic substituents
  • C10M2229/0425—Siloxanes with specific structure containing aromatic substituents 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
  • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
  • C10M2229/04—Siloxanes with specific structure
  • C10M2229/05—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon
  • C10M2229/051—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen
  • C10M2229/0515—Siloxanes with specific structure containing atoms other than silicon, hydrogen, oxygen or carbon containing halogen 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • 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
  • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• • 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
  • C10N2030/26—Waterproofing or water resistance
• • 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
  • C10N2050/015—Dispersions of solid lubricants
  • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating
• • 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
  • C10N2050/04—Aerosols
• • 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

Definitions

• the presence of the zinc naphthenate in the grease provides corrosion resistance to iron and iron alloy metal surfaces to which the grease is applied.
• the composition may be prepared by heating the polysiloxane and the thickener together at a temperature of about 240 C with mixing, cooling the mixture partially, adding the zinc naphthenate during the remainder of the cooling period, and then milling the resulting material.
• the grease composition was used to lubricate door hinges on houses and automobiles.
• This invention relates to improved polymethyl-alkylsiloxane grease compositions. More particularly, the present invention is concerned with zinc naphthenate containing polyorganosiloxane grease compositions, 25 per cent to 50 per cent of the organic substituents of which are alkyl radicals having six to 20 carbon atoms.
• Organopolysiloxane greases and grease compositions are well known in the art and have been used as lubricants, dielectric compounds, sealing compounds and high vacuum greases. These organopolysiloxane greases have been particularly valuable because of their high degree of heat stability, their water repellency, their low temperature viscosity characteristics and dielectric properties.
• the present invention is based upon the discovery that when from 25 to 50 percent of the organic groups present on the polysiloxane component of the grease contained from six to 20 carbon atoms and zinc naphthenate is present in the grease composition, that the problem of grease film rupture and corrosion of iron containing surfaces is alleviated.
• a thickener preferably a lithium soap of a higher fatty acid having from l2 to 22 carbon atoms such as a lithium soap of lauric, myristic, palmitic or stearic acid, preferably myristic or stearic acid;
• a base such as lithium hydroxide in an amount sufficient to maintain the grease on the alkaline side.
• thickeners which are fatty acid soaps which are employed in the manufacture of greases of the present invention are alkaline, the addition of additional alkaline material such as lithium hydroxide is often not recommended.
• R is an alkyl radical containing from six to 20 carbon atoms, e.g., hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl radicals; R is a t-butyl-substituted hydroxyaryl radical and has the formula:
• Y is a member selected from the class consisting of hydrogen, monovalent hydrocarbon radicals, hydroxyaryl radicals, hydroxyaryl-substituted monovalent hydrocarbon radicals, hydroxyaryl ethers joined to the t-butyl-substituted hydroxyaryl radical through the ether linkage, hydroxyarylthioethers joined to the t-butyl-substituted hydroxyaryl radical through the thioether linkage and hydroxyaryl-methylene ethers joined to the t-butyl-substituted hydroxyaryl radical through the methylene ether linkage;
• R" is selected from the class consisting of lower alkyl radicals having one to five carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, etc.
• radicals ; cycloalkyl radicals having five to seven carbon atoms in the ring, e.g., cyclopentyl, cyclohexyl, cycloheptyl, etc. radicals; mono-nuclear and binuclear aryl radicals, e.g., phenyl, naphthyl, biphenyl, etc. radicals; mononuclear aryl lower alkyl radicals, e.g., benzyl, tolyl, xylyl, phenylethyl, etc. radicals and halogenated derivatives of the above radicals.
• methylalkylpolysiloxane fluid within the scope of formula l is applicable in the process of the present invention, it is preferred that the fluid have a viscosity of from about 10 centistokes to about 100,000 centistokes when measured at 25 C.
• the methylalkylpolysiloxane fluids of formula l can include siloxane units of varied types and formulation such as trimethylsiloxane units and methylalkylsiloxane units alone or in combination with units such as monomethylsiloxane units, monoalkyl-siloxane units, dialkylsiloxane units, trialkylsiloxane units, etc.
• the only requirement is that the ratio of the various siloxane units employed be selected so that the average composition of the copolyrneric fluid is within the scope of formula l
• One component of the grease compositions of the present invention are the grease thickening agents which are well known in the art.
• This invention contemplates the use of any of these well known thickening agents to form a grease composition of the desired consistency.
• the term grease as employed in the present application is intended to refer to greaselike materials which may have consistencies varying from readily flowable materials to materials which exhibit almost no flow.
• the consistence of the greases of the present invention depend on the amount of thickening agent employed, the type of thickening agent employed and the particular polysiloxane fluids in the grease.
• suitable thickening agents include the metallic soaps of fatty acids of at least eight carbon atoms where the metals in such soaps include aluminum, lead, zinc, manganese, lithium, sodium, potassium, calcium, barium, strontium, copper, mercury, bismuth, chromium, iron, cobalt, nickel, etc.
• the metal soap usually used as a thickener in the composition of the present invention is basic and maintains the grease on the alkaline side, so that no additional base is necessary.
• compositions of the present invention may employ as grease thickening agents finely divided inert oxides of metallic and quasi-metallic materials such as silica, alumina, iron oxide, titania, zinc oxides, glass fibers and clays.
• Silica when used as a thickening agent, is preferably employed as an aerogel, but may also be employed as fumed silica, precipitated silica, or silica derived from natural deposits such as diatomaceous earth.
• the invention of the present application contemplates the use of complex metal soaps such as aluminum benzoate stearate as described in US. Pat. No. 2,599,553, acyl ureas such as octadecanoyl urea as described in US. Pat. No. 2,698,300 and the phenylenediamides such as N,N-acetylstearoyl-p-phenylenediamides as described in U.S. Pat. No. 2,709,157.
• a particularly useful group of thickening agents are the aromatic substituted ureas which are commonly referred to as ASU thickeners.
• the most useful thickeners are the lithium soaps of any of the higher fatty acids having from l2 to 22 nomcarboxyl carbon atoms.
• Another suitable thickening agent is phthalocyanine, finely divided inert oxides of metallic and quasi-metallic materials, carbon black, graphite, polyethylene, and phthalocyanine acyl ureas.
• grease as employed in the present application is intended to refer to grease-like materials which may have consistencies varying from readily flowable materials to materials which exhibit essentially no flow.
• the consistency of the greases of the present invention depend on the amount of thickening agent employed, the particular thickening agent employed and the particular polysiloxane fluids in the grease.
• the most useful thickening agents are the lithium soaps of higher fatty acids of l2 to 22 non-carboxyl carbon atoms such as lauric, palmitic, and most preferably the lithium soaps of myristic and stearic acids.
• the amounts of thickening agent employed in the grease compositions of the present invention are not critical and may vary within wide limits depending on the particular consistency desired in the final product, it has been found that the amount of thickening agent usually varies from about 2 per cent to 35 per cent and preferably from about 5 per cent to 25 per cent by weight based on the weight of the polysiloxane in the grease composition.
• zinc naphthanate is added as a corrosion inhibitor.
• zinc naphthanate based upon the weight of the grease composition is added.
• the preferred range is from about 0.02 to about 1 percent zinc as zinc naphthanate.
• a polyether may also be optionally present as a stabilin'ng agent.
• the polyether is preferably that it be present in an amount equal to from about 0.0l to about 5 per cent by weight based upon the weight of the polysiloxane fluid in the composition and preferably from about 0.] to about 2 percent by weight.
• the amount of polyether in the grease composition is in excess of 5.0 percent by weight, it is found that the weight loss of the grease at temperatures in excess of 300 F is so excessive that the grease is unsuitable for use in many high temperature applications.
• polyether is not a necessary stabilizing agent, however, as any number of other known stabilizing agents may be used or the stabilizing agent may be omitted entirely. Trimethoxyboroxine is an excellent stabilizing agent.
• polyethers are added to the oxidation inhibited higher alkyl containing grease compositions to impart a royal purple or brown color to the grease. This is its primary function. Without the polyether in the oxidation inhibited higher alkyl containing greases, they have a lack-luster pinkish tinge.
• polyethers which are used herein in combination with the polysiloxane oils according to this invention are polymeric alkylene oxides and/or polymeric alkylene glycols and may be represented by the following formulas:
• a and B represent radicals selected from the class comprising hydrogen, alkyl radicals containing from one to 12 carbon atoms, cycloalkyl radicals containing five to seven carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuciear aryl lower alkyl radicals wherein the alkyl groups attached to the aromatic nucleus contain a total of no more than five carbon atoms; A and 8 also represent ester forming groups containing from two to 12 carbon atoms; A and B may or may not be alike. When there is more than one A radical per molecule, the A radicals may or may not be the same.
• 0 is a residue of a polyhydn'c initiator radical containing at least two hydroxyl radicals such as ethylene glycol, glycerol, trimethylolpropane, and other polyhydric alcohols having from 2 to 6 hydroxyl groups;
• x is a number having a value of2 to 4;
• n is a number having a value offrom 4 to 2,000 andyhasavalue offrom2to6andzhasa value ofone to S.
• a and B represent radicals selected from the clas comprising hydrogen; alkyl radicals having from one to l2 carbon atoms, e.g., mefllyl, ethyl, propyl, butyl, octyl, etc. radicals; cycloalkyl radicals having five to seven carbon atoms in the ring, e.g., cyclopentyl, cyclohexyl, cycloheptyl, etc. radicals; mononuclear and binuclear aryl radicals, e.g., phenyl, naphthyl, biphenyl, etc.
• radicals mononuclear aryl lower alkyl radicals wherein the alkyl groups attached to the aromatic nucleus contain a total of no more than five carbon atoms, e.g., benzyl, phenylethyl, phenylpropyl, etc.; and ester groups having from one to 12 non-carboxyl carbon atoms such as the residues formed by the removal of a carboxy hydrogen from a fatty acid, e.g., an acetate, propionate, octoate, etc.; hydroxy-ether groups derived from glycols such as butylene glycol, octylene glycol, etc.; and groups formed by esterification with a hydroxyl group of a non-fatty acid, e.g., propyl phosphate, octyl sulfonate, butyl sulfate, etc.
• ester groups having from one to 12 non-carboxyl carbon atoms such as the residues
• the polyethers may be prepared from the various alkylene oxides (e.g., ethylene oxide), the higher l,2-epoxides (such as l,2-propylene oxide), the alkylene glycols (e.g., ethylene glycol) and mixtures of these.
• the resulting products may be polyoxyalkylene diols or polyalkylene glycol derivatives; that is, the terminal hydroxyl groups can remain as such, or one or both of the terminal hydroxyl groups can be removed during the polymerization reaction or subsequent thereto, as by ethenfication or esterification to yield monoor di-ether or monoor di-ester groups or a combination of such terminal groups whereby certain desirable properties are imparted to the final polymeric mistures.
• a and/or B may be: alkyl radicals, forming a di-alkyl polyether (e.g., dibutylheptaoxypropylene di-ether); ester forming radicals, forming alkyl oxyalkylene esters (e.g., butylpentaoxypropylene acetate); hydrogen, forming polyglycols (e.g., polyethylene glycol), etc.
• alkyl radicals forming a di-alkyl polyether (e.g., dibutylheptaoxypropylene di-ether); ester forming radicals, forming alkyl oxyalkylene esters (e.g., butylpentaoxypropylene acetate); hydrogen, forming polyglycols (e.g., polyethylene glycol), etc.
• the polyether oil that is, the (C,H, ,O), section of the above formula can be derived from such basic units as the following oxides:
• a composition containing two different alkylene oxide groups can be prepared, for example, by reacting a polypropylene glycol with ethylene oxide in the presence of boron trit'luoride. This mixed polyalkylene glycol, if desired, can then be reacted with an alkanol such as butanol to form the monobutoxy-ether of the mixed polyalkylene glycol.
• alkanol such as butanol
• a number of these polyalkylene oxide materials are commercially available including the materials sold under the tradename Ucon by Union Carbide Corporation, and the materials sold under the name of "Pluracol" by the Wyandotte Chemicals Corporation.
• the molecular weight of the polyether oils used according to this invention can range from 300 to 200,000, from 400 to 20,000 being preferred.
• an antioxidant which is built into the polysiloxane molecule is used.
• This antioxidant is represented by the R' radical of formula (I) which is a t-butyl-substituted hydroxy-aryl radical and has the formula:
• Y is a member selected from the class consisting of hydrogen, monovalent hydrocarbon radicals, hydroxyaryl radicals, hydroxyaryl-substituted monovalent hydrocarbon radicals, hydroxyaryl ethers joined to the t-butyl-substituted hydroxyaryl radical through the ether linkage, hydroxyarylthioethers joined to the t-butyl-substituted hydroxyaryl radical through the thioether linkage and hydroxarylmethylene ethers joined to the t-butyl-substituted hydroxyaryl radical through the methylene ether linkage.
• the R radical has a valence bond attached to the aromatic nucleus and to a divalent propylene radical which, in turn, is attached to a silicon atom of the polysiloxane.
• a hydroxy radical In the ortho position with respect to this valence bond is a hydroxy radical and in the meta position is a tertiary butyl radical. in the other meta position is the Y radical previously described.
• the t-butyl group is adjacent to the hydroxyl group and hinders its reactivity.
• the hydroxyaryl radical is a hindered hydroxyaryl radical.
• monovalent hydrocarbon radicals free of aliphatic unsaturation represented by Y in formula (2) are, for example, alkyl radicals, e.g., methyl, ethyl, propyl, butyl, octyl, etc. radicals; aryl radicals, e.g., phenyl, naphthyl, etc. radicals; aryl lower alkyl radicals, e.g., benzyl, phenylethyl, etc. radicals.
• hydroxyaryl radicals represented by Y of formula (2) are, for example p-hydroxyphenyl, o,o-di(t-butyl )-p-hydroxy-phenyl, o-( t-butyl )-o-allyl-p-hydroxyphenyl, etc. radicals.
• Illustrative of the hydroxyaryl-substituted monovalent hydrocarbon radicals within the definition of Y of formula (2) are, for example, p-hydroxyphenylmethyl radicals, o,o-di(t-butyl)-p-hydroxyphenylethyl radicals.
• hydroxyarylether radicals are o,o-di(t-butyl)-phydroxyphenylether radicals and o,o-di(t-butyl)-p-hydroxyphenylmethylene ether radicals.
• hydroxyarylthioether radicals is the o,o-di(t-butyl)-phydroxyphenylether radical, etcv
• R" of formula (l) is, for example:
• compositions within the scope of the present invention is best understood by reference to the preparation of the compositions which contain the siliconbonded t-butyl-substituted hydroxyarylpropyl radical.
• the general method of preparation involves a starting material which contains a phenyl nucleus containing a nuclear carbonbonded hydroxyl group and tertiary butyl radical in both of the meta positions of such phenolic compound.
• One or more of the nuclear-bonded t-butyl radicals is replaced by an allyl radical to produce an allyl-substituted material having the formula:
• additives normally present in silicone greases can be present in the composition of the present invention.
• additives include antioxidants such as the amines, e.g., N-phenyl-alphanaphthylamine; extreme pressure additives such as selenium disulfide, molybdenum disulfide, etc.; acids or bases to control pH; and antioxidants is within the scope of this invention. The addition of many of such materials is described in the art.
• the preparation of the polysiloitanes within the scope of formula l) involves an SiH-olefin addition reaction.
• This reaction simply involves the addition ofan alpha-olefin having 2 where n, m, p, q and R" are as above defined, and an alphaolefin.
• the reaction of the alpha-olefin and the polysiloxane of formula (3) can take place in the presence of one of the elemental platinum or platinum compound catalysts.
• the platinum compound catalyst can be selected from that group of platinum compound catalysts which are operative to catalyze the addition of silicon-hydrogen bonds across olefinie bonds.
• chloroplatinic acid as described in US. Pat. No. 2,823,2 l 8 Speier et al.
• the reaction product of chloroplatinic acid with either an alcohol, an ether or an aldehyde as described in U.S. Pat. No. 3,220,972 Lamoreaux
• trimethyl platinum iodide and hexamethyldiplatinum as described in U.S. Pat. No. 3,313,773 Lamoreaux
• the platinum olefin complex catalysts as described in U.S. Pat. No. 3,159,601 of Ashby and the platinum cyclopropane complex catalyst as described in U.S. Pat. No. 3,l59,622 of Ashby.
• the SiH-olefin addition reaction may be run at room temperature or at temperatures up to 200 C, depending upon catalyst concentration.
• the catalyst concentration can vary from 10" to l" and preferably to 10 moles of platinum as metal per mole of olefin containing molecules present.
• the methylhydrogenpoly-siloxane is mixed with a portion of the alpha-olefin, all of the catalyst is added, and then the remaining alpha-olefin is added at a rate sufficient to maintain the reaction temperature in the neighborhood of from about 50 to I C and, at the end of the addition of the alpha-olefin, the reaction is completed.
• the addition reaction is effected by adding to the methylhydrogen polysiloxane a platinum catalyst of one of the types previously described and then one of the allylated materials previously described is slowly added to the reaction mixture at a rate sufficient to maintain the reaction mixture at the desired reaction temperature, which is usually of the order of 50 to 120 C.
• the amount of the allylated material added to the reaction mixture is the amount which it is desired to react with the SiH-containing polysiloxane.
• the allylated aromatic compound is sdded in the ratio of from 0 to 0.5 molecule for every silicon-bonded hydrogen atom of the methylhydrogenpolysiloxane.
• the general procedure as described earlier is followed.
• the polymethylhydrogensiloxane is first reacted with the appropriate amount of the allylated material and then the appropriate amount of alpha-olefin is added.
• the starting material can be a trimethylsilyl chain-stopped polymethyl-hydrogensiloxane containing an average of 38 methylhydrogen-siloxane units per molecule.
• One mole of this polymethyl-hydrogensiloxane is reacted with 1 mole of an allylated t-butyl-substituted phenol, such as the product shown in the formula:
• the grease of the present invention is quite adaptable to aerosol type packaging. This involves dissolving the grease in a volatile solvent, adding an organic aerosol propellant and packaging the mixture in a pressurized type dispenser, such as the usual low pressure aerosol can. if desired, the organic aerosol propellant can also be employed as the solvent.
• Propellants which can be employed come from three classes; compressed inert gasses, hydrocarbons and halogenated hydrocarbons.
• An additional requirement for the halogenated hydrocarbon or hydrocarbon used as the propellant is that it have a vapor pressure greater than atmospheric pressure at a temperature of l05 F and that it be a liquified as.
• the compressed gasses which may be employed include the non-liquifiable gasses, such as air, nitrogen, carbon dioxide, nitrous oxide and other materials which were used in the gaseone state or which are dissolved in the aerosol mixture instead of being added as liquified gasses.
• halogenated hydrocarbons which may be employed as propellants, include monofluorotrichloromethane, dichlorodifluoromethane, dichlorofluoromethane,
• difluorochloromethane dichloromethane, l-chloro-l, l-difluoro-Z-chloro-Z, Z-difluoroethane, l-fluoro-l, l-dichloro- 2,2,2-trifluoroethane, l-chloro-l, l-difluoroethane, l,ldifluoroethane, monochloroethane, l,l-difluoro-2, 2-difluoro-3,3-difluoro-4,4-difluorocyclobutane, l, l l -tri-fluoro- 2, 2-difluoro-3, 3-difluoro-4,4,4-trifluorobutane.
• hydrocarbon propellants examples include propane, isobutane, and butane.
• the gas When a gas is used as the aerosol propellant, the gas must be inert to the other components of the mixture and is preferably present in a quantity to provide a pressure of l5 to I00 pounds per square inch at I00 F in the interior of the aerosol container.
• solvents which may be employed include hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons and halogenated derivatives of aromatic and aliphatic hydrocarbons.
• the solvents are preferably volatile to the extent that they will evaporate from the grease upon prolonged exposure, i.e., 24 hours when exposed to the atmosphere.
• the solvents have melting points below 0
• solvents which may be employed include benzene, toluene, xylene, l,l,l-trichloroethane, carbon tetrachloride, chlorofonn and a host of other aromatic hydrocarbon, aliphatic hydrocarbon and halogenated aliphatic or aromatic hydrocarbons which are well known in the art as solvents.
• the volatile solvent be present, as the aerosol propellant acts as a solvent in the present composition.
• a solvent other than the aerosol propellant it may be present in an amount up to about 98,95 parts of volatile solvent per part of grease.
• an organic aerosol propellant may also be present per part of grease.
• the preferred range of organic aerosol propellant per part of grease is from 0.l to 0.8 parts of the propellant. It is also preferred to have from about 0.22 to about L0 percent zinc by weight based upon the weight of the grease of due naphthenate present in the aerosol mixture.
• Grease compositions of the present invention have been found to be useful for lubricating zippers, nuts and bolts, water closet linkages, hinges on automobiles, homes and other buildings, clothes pulleys, sticking valves on brass instruments, automobile engine exhaust pipe bypass valves, garage door tracks, body jacks, ball connector hitches used in pulling trailers, steel bearings in bench type gliders, roller chains on machinery and trunk locks.
• the catalyst which was used in the following examples was prepared by dissolving one part by weight of chloroplatinic acid hexahydrate in ten parts of octyl alcohol and heating the solution at 70 to 75 C at 25 millimeters for 16 hours during which time all water and hydrogen chloride was removed. The pressure was then reduced to millimeters to remove all unreacted octyl alcohol. At the end of this time a product was obtained which was a dark, reddish-brown liquid soluble in alcohols, acetone, benzene, hexane, xylene, toluene and other common solvents. Chemical analysis of this mixture showed it to contain 3.5 atoms of chlorine per atom of platinum and 0.035 gram platinum per gram of the mixture.
• One thousand grams of a solution containing l l2 g. of potassium hydroxide in ethyl alcohol was made and slowly added to the phenol to provide the stoichiometric equivalent of the phenolic hydroxyl groups.
• a brilliant purple solution resulted which, when dried, showed no evidence of phenol and tested completely for complete conversion to the potassium phenylate.
• the decene-l feed was ad justed at such a rate so as to feed the entire 7 l .4 parts over a 2- hour period.
• a 5 C rise in batch temperature was noted after 10 minutes and the air flow was reduced to lll0th of the initial rate.
• the reaction mixture was cooled so as to maintain a batch temperature of I05 C. Reduced air flow was maintained for I00 minutes and then stopped. At this point, an additional 0.008 parts of catalyst was added.
• an additional 0.008 parts of catalyst was added and agitation was continued for an additional 2 hours. The system pressure ww then reduced to mm Hg.
• a series of greases were prepared containing 0, is, l, 2, 3 and 5 percent zinc naphthanate by the following procedure.
• the base grease was stirred and heated and the zinc naphthanate was added at 70 C.
• the zinc naphthenate was then melted and dispersed in the base grease.
• the grease was cooled and milled through an homogenizer.
• the zinc naphthenate used contained 14.5 percent Zll'lC.
• the composition was stirred and heated to 70 C to insure that the zinc naphthenate was melted and dispersed.
• the composition was then cooled and milled through a homogenizer mill.
• the product will be referred to in the remainder of this example as the bme grease.
• composition described by the above average unit formula comprises a blend of products within the scope of formula 1, in which the majority of the polysiloxane molecules contain one R radical and a minor amount of the polysiloxane molecules do not contain an R radical.
• the zinc naphthanate containing grease was prepared by stirring and heating the base grease to 70 C at which temperature the zinc naphthanate was added, melted and dispersed in the grease. The grease was then cooled and milled through a homogenizer. The corrosion resistance imparted by the grease was then measured using the test described in Example 1. For the steel panel with no grease at all applied, 125 seconds elapsed before rust appeared; when the grease without the zinc naphthanate was applied to the steel panel, it required 630 seconds for rust to appear and when the grease containing 0.145 percent zinc as zinc naphthanate was applied to the steel panel, 1,200 seconds elapsed before rust began to appear on the steel panel.
• a silicone grease comprising on a weight basis:
• n +p+ q has a value of from 2.002 to 3.0
• n has a value of from 0.50 to 1.95
• in has a value of from 0.5 to L0
• p has a value of from 0 to 0.5
• q has a value of from 0 to V4 (m n +P).
• R is an alkyl radical containing from six to 20 carbon atoms;
• R' is a t-butyl-substituted hindered hydroxyaryl radical;
• R is selected from the class consisting of lower alkyl radicals, cycle-alkyl radicals having live to seven carbon atoms in the ring, mononuclear and binuclear aryl radicals, mononuclear aryl lower alkyl radicals, and halogenated derivatives of the above radicals;
• composition of claim I further characterized by from about 0.02 to about I percent of zinc being present as zinc naphthenate.
• composition of claim 2 further characterized by the R radical of the polysiloxane fluid containing from about eight to about l2 carbon atoms.
• composition of claim 3 further characterized by the thickener being selected from the class consisting of lithium myristate and lithium stearate.
• composition of claim 1 further characterized by the grease being aerosol dispensable and containing an aerosol propellant.
• composition of claim 1 further characterized by the grease being aerosol dispensable and being dissolved in a volatile solvent and containing an organic aerosol propellant.
• composition of claim 1 further characterized by the grease being aerosol dispensable and being dissolved in from about 0 to about 98.95 parts of volatile solvent and containing from about 0.05 to about 99 parts of an organic aerosol propellant per part of grease.
• composition of claim 7 further characterized by the grease containing from 0.1 to 0.8 parts of an organic aerosol propellant per part of grease.
• composition of claim 8 further characterized by the grease containing from about 0.02 to about l.0 percent, by weight based upon the weight of the grease of zinc as zinc naphthenate.
• composition of claim 1 further characterized by the grease being aerosol dispensable and being dissolved in from about l to 99 parts ofa volatile solvent, placed in a container and pressurized to l5 to lOO pounds per square inch gauge pressure with an inert gas.
• composition of claim 7 further characterized by the grease constituting from i to 10 percent of the total mixture of grease, solvent and organic aerosol propellant.
• composition of claim 7 further characterized by the grease constituting from 2 to 5 percent of the total mixture of grease, solvent and organic aerosol propellant.

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• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Lubricants (AREA)

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• 1970
  • 1970-06-29 US US50890A patent/US3669884A/en not_active Expired - Lifetime
• 1971
  • 1971-06-08 GB GB1937671*[A patent/GB1352174A/en not_active Expired
  • 1971-06-28 DE DE2132058A patent/DE2132058C2/de not_active Expired
  • 1971-06-28 FR FR7123485A patent/FR2096561B1/fr not_active Expired
  • 1971-06-29 JP JP4691671A patent/JPS5517064B1/ja active Pending

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