EP0531000B1 - Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten - Google Patents

Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten Download PDF

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Publication number
EP0531000B1
EP0531000B1 EP92307448A EP92307448A EP0531000B1 EP 0531000 B1 EP0531000 B1 EP 0531000B1 EP 92307448 A EP92307448 A EP 92307448A EP 92307448 A EP92307448 A EP 92307448A EP 0531000 B1 EP0531000 B1 EP 0531000B1
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Prior art keywords
oil
parts
acid
boron
soluble
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EP92307448A
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English (en)
French (fr)
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EP0531000A1 (de
Inventor
Andrew George Papay
Rolfe John Hartley
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Afton Chemical Corp
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Afton Chemical Corp
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    • C10N2070/02—Concentrating of additives

Definitions

  • This invention relates to additive concentrates and oleaginous compositions (i.e., lubricating oils and functional fluids) having enhanced performance properties.
  • additive concentrates containing, inter alia, sulfur-containing antiwear and/or extreme pressure additives, phosphorus-containing antiwear and/or extreme pressure additives, and other additive components have been proposed and used.
  • other additive components include acidic components such as carboxylic acids, hydrocarbyl phosphoric acids, and hydrocarbyl thiophosphoric acids; basic components such as amines; and ashless dispersants such as boronated succinimides.
  • the finished lubricating oil composition and additive concentrate from which it is made must be formulated to meet the American Petroleum Institute GL-5 requirements. This involves passing a battery of standard tests.
  • the provision of clean gears in the L-60 test is an important consideration in the marketplace. So far as is known, only a very limited number of lubricant additive packages have received GL-5 approval. Thus there is a need for additional automotive gear oil packages which give good performance in the GL-5 qualification tests, and especially for packages capable of satisfying the GL-5 requirements.
  • Still another need is for an ashless or low-ash lubricant additive package affording high dispersancy and high wear resistance to lubricants, such as crankcase lubricants, gear lubricants, manual and automatic transmission fluids, oil-based hydraulic fluids, wet brake fluids, and similar lubricants and functional fluids.
  • lubricants such as crankcase lubricants, gear lubricants, manual and automatic transmission fluids, oil-based hydraulic fluids, wet brake fluids, and similar lubricants and functional fluids.
  • an additive concentrate which comprises a minor proportion of diluent oil and a major proportion of additive components, said additive components comprising:
  • component a) refers collectively to the above components a-1), a-2), a-3) and a-4).
  • components a) and b) of such compositions makes it possible to achieve performance levels (reduction in sludge formation and/or deposition and reduction in wear in gears and/or other relatively moveable metal surfaces in contact with each other) normally achieved, if at all, by higher concentrations of component b).
  • components a) and b) are proportioned such that the mass ratio (wt:wt) of sulfur in component b) to phosphorus in component a) is in the range of 8:1 to 30:1, more preferably in the range of 10:1 to 20:1, and most preferably in the range of 14:1 to 20:1.
  • the finished lubricating oils of this invention will usually contain at least about 05 wt % of sulfur as component b) and preferably will contain an amount of component b) to provide a sulfur content in the finished lubricant in the range of 1 to 3 wt %, and more preferably in the range of 1.5 to 3 wt %, of the total weight of the composition.
  • the foregoing additive concentrates further comprise one or more of the following additive components:
  • lubricant compositions which comprise a major proportion of at least one oil of lubricating viscosity and a minor amount of the various additive combinations referred to hereinabove.
  • compositions of this invention are ashless compositions (i.e., they contain no metal-containing additive components) or are low-ash compositions (i.e., base oil containing an additive concentrate or a combination of additives pursuant to this invention at a total concentration of 10% by weight will contain no more than 100 parts by weight, and more preferably no more than 50 parts by weight, of added metal per million parts by weight of the total composition.
  • Component a) -- i.e., a-1), a-2), a-3) or a-4) -- is one indispensable additive ingredient of the compositions of this invention.
  • the ashless dispersant which is heated concurrently or in any sequence with components (i) and (ii) is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable ashless dispersant formed in the customary manner can be heated with one or more boron compounds to cause boronation to occur and the resultant product mixture can then be heated with one or more inorganic phosphorus compounds such that a liquid phosphorus- and boron-containing composition [component a-1)] is formed.
  • a preformed ashless dispersant can be heated with one or more inorganic phosphorus compounds and thereafter the product mixture can be heated with one or more boron compounds so that a liquid phosphorus- and boron-containing composition is formed.
  • the preferred way of forming component a-1) is to heat a preformed ashless dispersant with a combination of one or more inorganic phosphorus compounds and one or more boron compounds to form a liquid phosphorus- and boron-containing composition.
  • the preformed ashless dispersant is concurrently heated with one or more inorganic phosphorus compounds and one or more boron compounds.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of both phosphorus and boron.
  • component a-1 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-1) by:
  • the ashless dispersant which is used in the process is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable boron-free ashless dispersant formed in the customary manner can be heated with one or more inorganic phosphorus acids to cause phosphorylation to occur.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of phosphorus.
  • component a-2 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-2) by:
  • the ashless dispersant which is heated concurrently or in any sequence with components (i) and (ii) is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable ashless dispersant formed in the customary manner can be heated with one or more boron compounds to cause boronation to occur and the resultant product mixture can then be heated with water and one or more water-hydrolyzable organic phosphorus compounds such that a liquid phosphorus- and boron-containing composition [component a-3)] is formed.
  • a preformed ashless dispersant can be heated with water and one or more water-hydrolyzable organic phosphorus compounds and thereafter the product mixture can be heated with one or more boron compounds so that a liquid phosphorus- and boron-containing composition is formed.
  • the preferred way of forming component a-3) is to heat a preformed ashless dispersant with a combination of water, one or more water-hydrolyzable organic phosphorus compounds and one or more boron compounds to form a liquid phosphorus- and boron-containing composition.
  • component a-3 in the preferred manner, the preformed ashless dispersant is concurrently heated with water, one or more water-hydrolyzable organic phosphorus compounds and one or more boron compounds.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of both phosphorus and boron.
  • water is removed at least during or after the heating with (i) and (ii) (if conducted concurrently) or at least during or after the heating with (i) (if conducted sequentially).
  • Such heating is conducted under conditions such that partial or total hydrolysis of the water-hydrolyzable organic phosphorus compound occurs.
  • component a-3 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-3) by:
  • the ashless dispersant which is used in the process is preferably a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group.
  • any suitable boron-free ashless dispersant formed in the customary manner can be heated with water and one or more water-hydrolyzable organic phosphorus compounds to cause phosphorylation to occur.
  • the resulting liquid product composition when subjected to chemical analysis reveals the presence of phosphorus.
  • component a-4 Rather than utilizing a preformed ashless dispersant containing basic nitrogen and/or at least one hydroxyl group, it is possible to produce component a-4) by:
  • Various methods can be used for removing water from component a-3) or a-4) during or after its formation.
  • the preferred method involves applying a suitable vacuum to the reaction system while heating the water-containing mixture to a suitably elevated temperature. In this way the water is readily stripped off.
  • a suitable vacuum to the reaction system while heating the water-containing mixture to a suitably elevated temperature. In this way the water is readily stripped off.
  • a phosphorus ester made from a lower alcohol such as methanol, ethanol, propanol, 2-propanol, butanol, or isobutyl alcohol
  • both lower alcohol liberated in the process and water can be stripped off from the product mixture during or on completion of the heating operation.
  • an ashless dispersant used in forming component a) is not a liquid but rather is in whole or in part in the solid state of aggregation at room temperature (e.g., 25°C)
  • a suitable solvent or diluent polar or non-polar, as may be required to dissolve the dispersant
  • phosphorylation and/or boronation as the case may be
  • component a including such solvent or diluent, is in the liquid state of aggregation at room temperature (e.g., 25 25°C), even though at a lower temperature the dispersant may revert in whole or in part to the solid state.
  • room temperature e.g. 25 25°C
  • component a-1 must be oil-soluble within the meaning of such term as set forth hereinafter.
  • component a in any instance wherein macro (i.e., non-dispersible) solids are formed or remain in the liquid composition after it has been formed, such solids should be removed, and can be readily removed, by any of a variety of conventional separation techniques such as filtration, centrifugation, or decantation.
  • macro i.e., non-dispersible
  • component a) is in whole or in part a micellar structure containing phosphorus- and/or boron-containing species or moieties.
  • this invention is not limited to, and should not be construed as being limited to, any specific structural configurations with respect to component a).
  • component a) is a liquid that is oil soluble and that if subjected to analysis reveals the presence of phosphorus and, in the case of a-1) and 1-3), boron.
  • component a) should possess dispersant properties.
  • Component a) may contain chemical species and/or moieties besides the phosphorus- and boron-containing species or moieties of a-1) or a-3) or the phosphorus-containing species and/or moieties of a-2) or a-4), such as, for example, nitrogen- and/or oxygen- and/or sulfur-containing species or moieties over and above the basic nitrogen and/or hydroxyl group(s) forming an essential part of the initial ashless dispersant itself.
  • organic phosphorus-containing compounds may be used along with inorganic phosphorus compounds in making component a-1) or a-2) and that inorganic phosphorus-containing compounds may be used along with water and one or more water-hydrolyzable organic phosphorus compounds in making component a-3) or a-4).
  • the inorganic phosphorus compound or compounds can be formed in situ, as, for example, by heating a mixture of phosphorus and sulfur to form a phosphorus sulfide, or by treating one or more organic phosphorus compounds to convert the same in whole or in part into one or more inorganic phosphorus compounds.
  • the water-hydrolyzable organic phosphorus compound or compounds can also be formed in situ, as, for example, by heating a mixture of one or more alcohols or phenols with one or more phosphorus halides (e.g., PCl 3 , POCl 3 , PSCl 3 , RPCl 2 , ROPCl 2 , RSPCl 2 , RPOCl 2 , ROPOCl 2 , RSPOCl 2 , RPSCl 2 , ROPSCl 2 , RSPSCl 2 , R 2 PCl, (RO) 2 PCl, (RS) 2 PCl, (RO)(RS)PCl, R 2 POCl, (RO) 2 POCl, (RS) 2 POCl, (RO)(RS)POCl, R 2 PSCl, (RO) 2 PSCl, (RS) 2 PSCl, where each R is, independently, a hydrocarbyl group) and introducing water into the system in order to hydrolyze the water-hydrolyzable
  • the term phosphorylated means that the ashless dispersant has been heated with one or more inorganic phosphorus compounds [components a-1) and a-2)] or with one or more water-hydrolyzable organic phosphorus compounds and water [components a-3) and a-4)] such that the resultant product, on analysis, reveals the presence of phosphorus.
  • the term "boronated” means that the ashless dispersant has been heated with one or more boron compounds such that the resultant product, on analysis, reveals the presence of boron.
  • the terms "phosphorylated” and “boronated” are not to be construed as requiring that the resultant composition contain chemically bound phosphorus or boron.
  • any of avariety of ashless dispersants can be utilized in forming component a) of the compositions of this invention. These include the following types:
  • Type A - Carboxylic Ashless Dispersants These are reaction products of (i) an acylating agent such as a monocarboxylic acid, or a dicarboxylic or other polycarboxylic acid, or a derivative thereof, with (ii) one or more compounds which contain amine groups and/or hydroxyl groups, such that the acylated reaction product contains basic nitrogen and/or at least one hydroxyl group.
  • an acylating agent such as a monocarboxylic acid, or a dicarboxylic or other polycarboxylic acid, or a derivative thereof
  • one or more compounds which contain amine groups and/or hydroxyl groups such that the acylated reaction product contains basic nitrogen and/or at least one hydroxyl group.
  • component a there are a number of sub-categories of carboxylic ashless dispersants.
  • One such sub-category which constitutes a preferred type for use in the formation of component a) is composed of the polyamine succinamides and more preferably the polyamine succinimides in which the succinic group contains a hydrocarbyl substituent containing at least 30 carbon atoms.
  • the polyamine used in forming such compounds contains at least one primary amino group capable of forming an imide group on reaction with a hydrocarbon-substituted succinic acid or acid derivative thereof such an anhydride, lower alkyl ester, acid halide, or acid-ester.
  • the alkenyl succinimides may be formed by conventional methods such as by heating an alkenyl succinic anhydride, acid, acid-ester, acid halide, or lower alkyl ester with a polyamine containing at least one primary amino group.
  • the alkenyl succinic anhydride may be made readily by heating a mixture of olefin and maleic anhydride to 180°-220°C.
  • the olefin is preferably a polymer or copolymer of a lower monoolefin such as ethylene, propylene, 1-butene, and isobutene.
  • the more preferred source of alkenyl group is from polyisobutene having a number average molecular weight of up to 100,000 or higher.
  • the alkenyl group is a polyisobutenyl group having a number average molecular weight (determined using the method described in detail hereinafter) of 500-5,000, and preferably 700-2,500, more preferably 700-1,400, and especially 800-1,300.
  • the isobutene used in making the polyisobutene is usually (but not necessarily) a mixture of isobutene and other C 4 isomers such as 1-butene.
  • the acylating agent formed from maleic anhydride and "polyisobutene” made from such mixtures of isobutene and other C 4 isomers such as 1-butene can be termed a “polybutenyl succinic anhydride” and a succinimide made therewith can be termed a “polybutenyl succinimide”.
  • a polybutenyl succinic anhydride and a succinimide made therewith
  • polyisobutenyl is used to denote the alkenyl moiety whether made from a highly pure isobutene or a more impure mixture of isobutene and other C 4 isomers such as 1-butene.
  • Polyamines which may be employed in forming the ashless dispersant include any that have at least one primary amino group which can react to form an imide group.
  • a few representative examples include branched-chain alkanes containing two or more primary amino groups such as tetraamino-neopentane polyaminoalkanols such as 2-(2-aminoethylamino)-ethanol and 2-[2-(2-aminoethylamino)-ethylamino]-ethanol; heterocyclic compounds containing two or more amino groups at least one of which is a primary amino group such as 1-( ⁇ -aminoethyl)-2-imidazolidone, 2-(2-aminoethylamino)-5-nitropyridine, 3-amino-N-ethylpiperidine, 2-(2-aminoethyl)-pyridine, 5-aminoindole, 3-amino-5-mercapto-1,2,4-triazole, and 4-(amino
  • the most preferred amines are the ethylene polyamines which can be depicted by the formula H 2 N(CH 2 CH 2 NH) n H wherein n is an integer from one to ten. These include: ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, including mixtures thereof in which case n is the average value of the mixture.
  • the ethylene polyamines which have a primary amine group at each end can form mono-alkenylsuccinimides and bis-alkenylsuccinimides.
  • ethylene polyamine mixtures usually contain minor amounts of branched species and cyclic species such as N-aminoethyl piperazine, N,N'-bis(aminoethyl)piperazine, N,N'-bis(piperazinyl)ethane, and like compounds.
  • the preferred commercial mixtures have approximate overall compositions falling in the range corresponding to diethylene triamine to pentaethylene hexamine, mixtures generally corresponding in overall makeup to tetraethylene pentamine being most preferred.
  • Methods for the production of polyalkylene polyamines are known.
  • especially preferred ashless dispersants for use in the present invention are the products of reaction of a polyethylene polyamine, e.g., mixture known in the trade as "triethylene tetramine” or “tetraethylene pentamine", with a hydrocarbon-substituted carboxylic acid or anhydride (or other suitable acid derivative) made by reaction of a polyolefin, preferably polyisobutene, having a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400 and especially 800 to 1,300, with an unsaturated polycarboxylic acid or anhydride, e.g., maleic anhydride, maleic acid, or fumaric acid, including mixtures of two or more such substances.
  • a polyethylene polyamine e.g., mixture known in the trade as "triethylene tetramine” or “tetraethylene pentamine
  • a hydrocarbon-substituted carboxylic acid or anhydride or other suitable acid derivative
  • uccinimide is meant to encompass the completed reaction product from reaction between the amine reactant(s) and the hydrocarbon-substituted carboxylic acid or anhydride (or like acid derivative) reactant(s), and is intended to encompass compounds wherein the product may have amide, amidine, and/or salt linkages in addition to the imide linkage of the type that results from the reaction of a primary amino group and an anhydride moiety.
  • Residual unsaturation in the alkenyl group of the alkenyl succinimide may be used as a reaction site, if desired.
  • the alkenyl substituent may be hydrogenated to form an alkyl substituent.
  • the olefinic bond(s) in the alkenyl substituent may be sulfurized, halogenated, or hydrohalogenated.
  • component a Another sub-category of carboxylic ashless dispersants which can be used in forming component a) includes alkenyl succinic acid esters and diesters of polyhydric alcohols containing 2-20 carbon atoms and 2-6 hydroxyl groups.
  • the alkenyl succinic portion of these esters corresponds to the alkenyl succinic portion of the succinimides described above including the same preferred and most preferred subgenus, e.g., alkenyl succinic acids and anhydrides, where the alkenyl group contains at least 30 carbon atoms and notably, polyisobutenyl succinic acids and anhydrides wherein the polyisobutenyl group has a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400, and especially 800 to 1,300.
  • the alkenyl group can be hydrogenated or subjected to other reactions involving olefinic double bonds.
  • Alcohols useful in preparing the esters include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, tripropylene glycol, glycerol, sorbitol, 1,1,1-trimethylol ethane, 1,1,1-trimethylol propane, 1,1,1-trimethylol butane, pentaerythritol, and dipentaerythritol.
  • the succinic esters are readily made by merely heating a mixture of alkenyl succinic acid, anhydrides or lower alkyl (e.g., C 1 -C 4 ) ester with the alcohol while distilling out water or lower alkanol. In the case of acid-esters less alcohol is used. In fact, acid-esters made from alkenyl succinic anhydrides do not evolve water.
  • Still another sub-category of carboxylic ashless dispersants useful in forming component a) comprises an alkenyl succinic ester-amide mixture. These may be made by heating the above-described alkenyl succinic acids, anhydrides or lower alkyl esters with an alcohol and an amine either sequentially or in a mixture. Alcohols and amines such as those described above are also useful in this embodiment.
  • linear and/or branched chain monohydric alcohols such as 1-butanol, 2-butanol, 2-methyl-1-propanol, pentanol, hexanol, octanol, decanol, lauryl alcohol, oleyl alcohol, eicosanol, or ethylene glycol monomethyl ether, can be used provided they are used with one or more polyamines.
  • amino alcohols can be used alone or with the alcohol and/or amine to form the ester-amine mixtures.
  • the amino alcohol can contain 2-20 carbon atoms, 1-6 hydroxy groups and 1-4 amine nitrogen atoms. Examples are ethanolamine, diethanolamine, N-ethanol-diethylene triamine, and trimethylol aminomethane.
  • alkenyl group of the succinic ester-amide can be hydrogenated or subjected to other reactions involving olefinic double bonds.
  • Yet another sub-category of carboxylic ashless dispersants useful in forming component a) comprises the Mannich-based derivatives of hydroxyaryl succinimides.
  • Such compounds can be made by reacting a polyalkenyl succinic anhydride with an aminophenol to produce an N-(hydroxyaryl) hydrocarbyl succinimide which is then reacted with an alkylene diamine or polyalkylene polyamine and an aldehyde (e.g., formaldehyde), in a Mannich-base reaction. Details of such synthesis are set forth in U.S. Pat. No. 4,354,950.
  • the alkenyl succinic anhydride or like acylating agent is derived from a polyolefin, preferably a polyisobutene, having a number average molecular weight of 500 to 5,000, preferably 700 to 2,500, more preferably 700 to 1,400, and especially 800 to 1,200.
  • a polyolefin preferably a polyisobutene
  • residual unsaturation in the polyalkenyl substituent group can be used as a reaction site as for example, by hydrogenation or sulfurization.
  • Type B - Hydrocarbyl Polyamine Dispersants This category of ashless dispersants which can be used in forming component a) is likewise well known to those skilled in the art and fully described in the literature.
  • the hydrocarbyl polyamine dispersants are generally produced by reacting an aliphatic or alicyclic halide (or mixture thereof) containing an average of at least about 40 carbon atoms with one or more amines, preferably polyalkylene polyamines.
  • hydrocarbyl-substituted polyamines are high molecular weight hydrocarbyl-N-substituted polyamines containing basic nitrogen in the molecule.
  • the hydrocarbyl group typically has a number average molecular weight in the range of 750-10,000, more usually in the range of 1,000-5,000.
  • the hydrocarbyl radical may be aliphatic or alicyclic and, except for adventitious amounts of aromatic components in petroleum mineral oils, will be free of aromatic unsaturation.
  • the hydrocarbyl groups will normally be branched-chain aliphatic, having 0-2 sites of unsaturation, and preferably from 0-1 site of ethylene unsaturation.
  • the hydrocarbyl groups are preferably derived from petroleum mineral oil, or polyolefins, either homo-polymers or higher-order polymers, or 1-olefins of from 2-6 carbon atoms. Ethylene is preferably copolymerized with a higher olefin to insure oil solubility.
  • Illustrative polymers include polypropylene, polyisobutylene, or poly-1-butene.
  • the polyolefin group will normally have at least one branch per six carbon atoms along the chain, preferably at least one branch per four carbon atoms along the chain.
  • These branched-chain hydrocarbons are readily prepared by the polymerization of olefins of from 3-6 carbon atoms and preferably from olefins of from 3-4 carbon atoms.
  • the composition is a mixture of materials having various structures and molecular weights. Therefore, in referring to molecular weight, number average molecular weights are intended. Furthermore, when speaking of a particular hydrocarbon group, it is intended that the group include the mixture that is normally contained within materials which are commercially available. For example, polyisobutylene is known to have a range of molecular weights and may include small amounts of very high molecular weight materials.
  • Particularly preferred hydrocarbyl-substituted amines or polyamines are prepared from polyisobutenyl chloride.
  • the polyamine employed to prepare the hydrocarbyl-substituted polyamine is preferably a polyamine having from 2 to 12 amine nitrogen atoms and from 2 to 40 carbon atoms.
  • the polyamine is reacted with a hydrocarbyl halide (e.g., chloride) to produce the hydrocarbyl-substituted polyamine.
  • the polyamine preferably has a carbon-to-nitrogen ratio of from 1:1 to 10:1.
  • the amine portion of the hydrocarbyl-substituted amine may be substituted with substituents selected from (A) hydrogen and (B) hydrocarbyl groups of from 1 to 10 carbon atoms.
  • the polyamine portion of the hydrocarbyl-substituted polyamine may be substituted with substituents selected from (A) hydrogen, (B) hydrocarbyl groups of from 1 to 10 carbon atoms, (C) acyl groups of from 2 to 10 carbon atoms, and (D) monoketo, monohydroxy, mononitro, monocyano, lower alkyl and lower alkoxy derivatives of (B) and (C).
  • At least one of the nitrogens in the hydrocarbyl-substituted amine or polyamine is a basic nitrogen atom, i.e., one titratable by a strong acid.
  • Hydrocarbyl as used in describing the substituents in the amine or polyamine used in forming the dispersants, denotes an organic radical composed of carbon and hydrogen which may be aliphatic, alicyclic, aromatic or combinations thereof, e.g., aralkyl.
  • the hydrocarbyl group will be relatively free of aliphatic unsaturation, i.e., ethylenic and acetylenic, particularly acetylenic unsaturation.
  • the hydrocarbyl substituted polyamines used in forming the dispersants are generally, but not necessarily, N-substituted polyamines.
  • hydrocarbyl groups and substituted hydrocarbyl groups which may be present in the amine portion of the dispersant include alkyls such as methyl, ethyl, propyl butyl, isobutyl, pentyl, hexyl, octyl, etc., alkenyls such as propenyl isobutenyl, hexenyl, octenyl, etc., hydroxyalkyls, such as 2-hydroxyethyl, 3-hydroxypropyl, hydroxyisopropyl, 4-hydroxybutyl, etc., ketoalkyls, such as 2-ketopropyl, 6-ketooctyl, etc., alkoxy and lower alkenoxy alkyls, such as ethoxyethyl, ethoxypropyl, propoxyethyl, propoxypropyl, 2-(2-ethoxyethoxy)ethyl, 2-(2-(2-ethoxyethoxy)ethoxy
  • Typical amines useful in preparing the hydrocarbyl-substituted amines include methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, etc. Such amines are either commercially available or are prepared by art recognized procedures.
  • the polyamine component may also contain heterocyclic polyamines, heterocyclic substituted amines and substituted heterocyclic compounds, wherein the heterocyclic comprises one or more 5-6 membered rings containing oxygen and/or nitrogen.
  • heterocyclics may be saturated or unsaturated and substituted with groups selected from the aforementioned (A), (B), (C), and (D).
  • the heterocyclics are exemplified by piperazines, such as 2-methylpiperazine, 1,2-bis(N-piperazinyl-ethane), and N,N'-bis(N-piperazinyl)piperazine, 2-methylimidazoline, 3-aminopiperidine, 2-aminopyridine, 2-( ⁇ -aminoethyl)-3-pyrroline, 3-aminopyrrolidine, N(3-aminopropyl)morpholine, etc.
  • the piperazines are preferred.
  • Typical polyamines that can be used to form the hydrocarbyl polyamine dispersants include the following: ethylene diamine, 1,2-propylene diamine, 1,3-propylene diamine, diethylene triamine, triethylene tetramine, hexamethylene diamine, tetraethylene pentamine, methylaminopropylene diamine, N-( ⁇ -aminoethyl)piperazine, N,N'-di( ⁇ -aminoethyl)piperazine, N,N'-di( ⁇ -aminoethyl)imidazolidone-2, N-( ⁇ -cyanoethyl)ethane-1,2-diamine, 1,3,6,9-tetraaminooctadecane, 1,3,6-triamino-9-oxadecane, N-methyl-1,2-propanediamine, and 2-(2-aminoethylamino)ethanol.
  • polyalkylene amines in which the alkylene groups differ in carbon content, such as for example bis(aminopropyl)ethylenediamine.
  • Such compounds are prepared by the reaction of acrylonitrile with an ethyleneamine, for example, an ethyleneamine having the formula H 2 H(CH 2 CH 2 NH) n H wherein n is an integer from 1 to 5, followed by hydrogenation of the resultant intermediate.
  • the product prepared from ethylene diamine and acrylonitrile has the formula H 2 N-(CH 2 ) 3 NH(CH 2 ) 2 NH(CH 2 ) 3 NH 2 .
  • the polyamine used as a reactant in the production of the hydrocarbyl-substituted polyamine is not a single compound but a mixture in which one or several compounds predominate with the average composition indicated.
  • tetraethylene pentamine prepared by the polymerization of aziridine or the reaction of 1,2-dichloroethane and ammonia will have both lower and higher amine members, e.g., triethylene tetramine, substituted piperazines and pentaethylene hexamine, but the composition will be largely tetraethylene pentamine and the empirical formula of the total amine composition will closely approximate that of tetraethylene pentamine.
  • the preferred hydrocarbyl-substituted polyalkylene polyamines for use in this invention may be represented by the formula R 1 NH(-R 2 NH-) ⁇ -H wherein R 1 is hydrocarbyl having an average molecular weight of from 750 to 10,000; R 2 is alkylene of from 2 to 6 carbon atoms; and ⁇ is an integer of from 0 to 10.
  • R 1 is hydrocarbyl having an average molecular weight of from 1,000 to 10,000.
  • R 2 is alkylene of from 2 to 3 carbon atoms and ⁇ is preferably an integer of from 1 to 6.
  • Type C - Mannich polyamine dispersants This category of ashless dispersant which can be utilized in the formation of component a) is comprised of reaction products of an alkyl phenol, with one or more aliphatic aldehydes containing from 1 to 7 carbon atoms (especially formaldehyde and derivatives thereof), and polyamines (especially polyalkylene polyamines of the type described hereinabove).
  • the polyamine group of the Mannich polyamine dispersants is derived from polyamine compounds characterized by containing a group of the structure -NH- wherein the two remaining valances of the nitrogen are satisfied by hydrogen, amino, or organic radicals bonded to said nitrogen atom. These compounds include aliphatic, aromatic, heterocyclic and carbocyclic polyamines.
  • the source of the oil-soluble hydrocarbyl group in the Mannich polyamine dispersant is a hydrocarbyl-substituted hydroxy aromatic compound comprising the reaction product of a hydroxy aromatic compound, according to well known procedures, with a hydrocarbyl donating agent or hydrocarbon source.
  • the hydrocarbyl substituent provides substantial oil solubility to the hydroxy aromatic compound and, preferably, is substantially aliphatic in character.
  • the hydrocarbyl substituent is derived from a polyolefin having at least about 40 carbon atoms.
  • the hydrocarbon source should be substantially free from pendant groups which render the hydrocarbyl group oil insoluble. Examples of acceptable substituent groups are halide, hydroxy, ether, carboxy, ester, amide, nitro and cyano. However, these substituent groups preferably comprise no more than about 10 weight percent of the hydrocarbon source.
  • the preferred hydrocarbon sources for preparation of the Mannich polyamine dispersants are those derived from substantially saturated petroleum fractions and olefin polymers, preferably polymers of mono-olefins having from 2 to 30 carbon atoms.
  • the hydrocarbon course can be derived, for example, from polymers of olefins such as ethylene, propene, 1-butene, isobutene, 1-octene, 1-methylcyclohexene, 2-butene and 3-pentene. Also useful are copolymers of such olefins with other polymerizable olefinic substances such as styrene.
  • these copolymers should contain at least 80 percent and preferably 95 percent, on a weight basis, of units derived from the aliphatic mono-olefins to preserve oil solubility.
  • the hydrocarbon source generally contains at least 40 and preferably at least 50 carbon atoms to provide substantial oil solubility to the dispersant.
  • the olefin polymers having a number average molecular weight between 600 and 5,000 are preferred for reasons of easy reactivity and low cost However, polymers of higher molecular weight can also be used.
  • Especially suitable hydrocarbon sources are isobutylene polymers.
  • the Mannich polyamine dispersants are generally prepared by reacting a hydrocarbyl-substituted hydroxy aromatic compound with an aldehyde and a polyamine.
  • the aldehyde is typically an aliphatic aldehyde containing 1 to 7 carbon atoms, and in most cases is formaldehyde or a compound such as formalin or a polyformaldehyde from which formaldehyde is derived during the reaction.
  • the substituted hydroxy aromatic compound is contacted with from 0.1 to 10 moles of polyamine and 0.1 to 10 moles of aldehyde per mole of substituted hydroxy aromatic compound.
  • the reactants are mixed and heated to a temperature above about 80°C. to initiate the reaction.
  • the reaction is carried out at a temperature from 100° to 250°C.
  • the resulting Mannich product has a predominantly benzylamine linkage between the aromatic compound and the polyamine.
  • the reaction can be carried out in an inert diluent such as mineral oil, benzene, toluene, naphtha, ligroin, or other inert solvents to facilitate control of viscosity, temperature, and reaction rate.
  • polyamines are preferred for use in preparing the Mannich polyamine dispersants, and suitable polyamines include, but are not limited to, alkylene diamines and polyalkylene polyamines (and mixtures thereof) of the formula: wherein n is an integer from 1 to 10, R is a divalent hydrocarbyl group of from 1 to 18 carbon atoms, and each A is independently selected from the group consisting of hydrogen and monovalent aliphatic groups containing up to 10 carbon atoms which can be substituted with one or two hydroxyl groups. Most preferably, R is a lower alkylene group of from 2 to 6 carbon atoms and A is hydrogen.
  • Suitable polyamines for use in preparation of the Mannich polyamine dispersants include, but are not limited to, methylene polyamines, ethylene polyamines, butylene polyamines, propylene polyamines, pentylene polyamines, hexylene polyamines and heptylene polyamines. The higher homologs of such amines and related aminoalkyl-substituted piperazines are also included.
  • polyamines include ethylene diamine, triethylene tetramine, tris(2-aminoethyl)amine, propylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, decamethylene diamine, di(heptamethylene) triamine, pentaethylene hexamine, di(trimethylene) triamine, 2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-aminoethyl)imidazoline, 1-(2-aminopropyl)piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1(2-aminobutyl)piperazine. Higher homologs, obtained by condensing two or more of the above mentioned amines, are also useful, as are the polyoxyalkylene polyamines.
  • the polyalkylene polyamines are especially useful in preparing the Mannich polyamine dispersants for reasons of cost and effectiveness.
  • Such polyamines are described in detail under the heading "Diamines and Higher Amines" in Kirk-Othmer, Encyclopedia of Chemical Technology , Second Edition, Vol. 7, pp. 22-39. They are prepared most conveniently by the reaction of an ethylene imine with a ring-opening reagent such as ammonia. These reactions result in the production of somewhat complex mixtures of polyalkylene polyamines which include cyclic condensation products such as piperazines. Because of their availability, these mixtures are particularly useful in preparing the Mannich polyamine dispersants. However, it will be appreciated that satisfactory dispersants can also be obtained by use of pure polyalkylene polyamines.
  • Alkylene diamines and polyalkylene polyamines having one or more hydroxyalkyl substituents on the nitrogen atom are also useful in preparing the Mannich polyamine dispersants. These materials are typically obtained by reaction of the corresponding polyamine with an epoxide such as ethylene oxide or propylene oxide.
  • Preferred hydroxyalkyl-substituted diamines and polyamines are those in which the hydroxyalkyl groups have less than about 10 carbon atoms.
  • Suitable hydroxyalkyl-substituted diamines and polyamines include, but are not limited to, N-(2-hydroxyethyl)ethylenediamine, N,N'-bis(2-hydroxyethyl)ethylenediamine, mono(hydroxypropyl)diethlenetriamine, (di(hydroxypropyl)tetraethylenepentamine and N-(3-hydroxybutyl)tetramethylenediamine. Higher homologs obtained by condensation of the above mentioned hydroxyalkyl-substituted diamines and polyamines through amine groups or through ether groups are also useful.
  • Any conventional formaldehyde yielding reagent is useful for the preparation of the Mannich polyamine dispersants.
  • formaldehyde yielding reagents are trioxane, paraformaldehyde, trioxymethylene, aqueous formalin and gaseous formaldehyde.
  • Other aldehydes which can be used include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexanal, heptanal, and mixtures of two or more of these.
  • Mannich base dispersants for use in this invention are Mannich base ashless dispersants formed by condensing about one molar proportion of long chain hydrocarbon-substituted phenol with from 1 to 2.5 moles of formaldehyde and from 0.5 to 2 moles of polyalkylene polyamine.
  • Type D - Polymeric polyamine dispersants are also suitable for preparing component a) of the compositions of this invention.
  • polymers containing basic amine groups and oil solubilizing groups for example, pendant alkyl groups having at least about 8 carbon atoms.
  • Such polymeric dispersants are herein referred to as polymeric polyamine dispersants.
  • Such materials include, but are not limited to, interpolymers of decyl methacrylate, vinyl decyl ether or a relatively high molecular weight olefin with aminoalkyl acrylates and aminoalkyl acrylamides.
  • Type E Post-treated basic nitrogen-containing and/or hydroxyl-containing ashless dispersants .
  • any of the ashless dispersants referred to above as types A-D can be subjected to post-treatment with one or more suitable reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, anhydrides of low molecular weight dibasic acids, nitriles, and epoxides.
  • suitable reagents such as urea, thiourea, carbon disulfide, aldehydes, ketones, carboxylic acids, anhydrides of low molecular weight dibasic acids, nitriles, and epoxides.
  • Such post-treated ashless dispersants can be used in forming component a) of the compositions of this invention provided that the post-treated dispersant contains residual basic nitrogen and/or one or more residual hydroxyl groups.
  • the phosphorylated or the phosphorylated and boronated dispersant can be subjected to post-treatment with such reagents.
  • the post-treatment can be conducted in between the phosphorylation and boronation or conversely, between the boronation and the phosphorylation.
  • Mannich-based derivatives of hydroxyaryl succinimides that have been post-treated with C 5 -C 9 lactones such as ⁇ -caprolactone and optionally with other post-treating agents as described for example in U.S. Pat. No. 4,971,711 can also be utilized in forming component a) for use in the practice of this invention, provided that such post-treated Mannich-based derivatives of hydroxyaryl succinimides contain basic nitrogen, and/or at least one hydroxyl group.
  • post-treated ashless dispersants is comprised of basic nitrogen-containing and/or hydroxyl group-containing ashless dispersants which have been heated with (1) a phosphorus compound such that they contain phosphorus, or (2) a boron compound such that they contain boron, all with the proviso that such post-treated products contain residual basic nitrogen and/or one or more residual hydroxyl groups.
  • a phosphorus compound such that they contain phosphorus
  • a boron compound such that they contain boron
  • Numerous examples of such dispersants and methods for their production are described in the patent literature.
  • the boron-containing post-treated ashless dispersants of the prior art type can be converted into a material suitable for use as component a-1) or a-3) simply by conducting a phosphorylation in the manner described herein.
  • additional boron can also be incorporated into a prior art type post-treated boron-containing ashless dispersant by conducting a boronation in the manner described herein either before, during or after the phosphorylation. It is also possible by using the phosphorylation and/or boronation procedures described herein to phosphorylate and/or boronate a post-treated ashless dispersant that already contains phosphorus and/or boron, provided that such initial post-treated ashless dispersant contains at least some residual basic nitrogen and/or at least some residual hydroxyl substitution.
  • the ashless dispersant(s) used in forming component a) can be any mixture containing any two or more ashless dispersants containing basic nitrogen and/or at least one hydroxyl group.
  • ashless dispersants which contain little, if any, halogen atoms such as chlorine atoms.
  • additive concentrates which, when dissolved in a halogen-free base oil, at a concentration of 10% by weight, yield an oleaginous composition in which the total halogen content, if any, is 100 ppm or less.
  • Typical procedures for producing component a-1) phosphorylated and boronated ashless dispersants involve concurrently or sequentially heating one or more ashless dispersants of the types described above with at least one inorganic phosphorus compound and at least one boron compound under conditions yielding a liquid phosphorus- and boron-containing composition.
  • inorganic phosphorus compounds which are useful in forming such products include phosphorous acid (H 3 PO 3 , sometimes depicted as H 2 (HPO 3 ), and sometimes called ortho-phosphorous acid or phosphonic acid), phosphoric acid (H 3 PO 4 , sometimes called orthophosphoric acid), hypophosphoric acid (H 4 P 2 O 6 ), metaphosphoric acid (HPO 3 ), pyrophosphoric acid (H 4 P 2 O 7 ), hypophosphorous acid (H 3 PO 2 , sometimes called phosphinic acid), pyrophosphorous add (H 4 P 2 O 5 , sometimes called pyrophosphonic acid), phosphinous acid (H 3 PO), tripolyphosphoric acid (H 5 P 3 O 10 ), tetrapolyphosphoric acid (H 6 P 4 O 13 ), trimetaphosphoric acid (H 3 P 3 O 9 ), phosphorus trioxide, phosphorus tetraoxide, and phosphorus pentoxide.
  • H 3 PO 3 sometimes depicted as H 2 (
  • Partial or total sulfur analogs such as phosphorotetrathioic acid (H 3 PS 4 ), phosphoromonothioic acid (H 3 PO 3 S), phosphorodithioic acid (H 3 PO 2 S 2 ), phosphorotrithioic acid (H 3 POS 3 ), phosphorus sesquisulfide, phosphorus heptasulfide, and phosphorus pentasulfide (P 2 S 5 , sometimes referred to as P 4 S 10 ) can also be used in forming products suitable for use as component a-1) in the practice of this invention.
  • inorganic phosphorus halide compounds such as PCl 3 , PBr 3 , POCl 3 , PSCl 3 , etc.
  • the preferred phosphorus reagent is phosphorous acid, (H 3 PO 3 ).
  • the form or composition of the inorganic compound(s) as charged into the mixture to be heated or being heated may be altered in situ.
  • the action of heat and/or water can transform certain inorganic phosphorus compounds into other inorganic phosphorus compounds or species. Any such in situ transformations that may occur are within the purview of this invention provided that the liquid phosphorylated ashless dispersant reveals on analysis the presence therein of phosphorus (as well as boron).
  • Suitable compounds of boron useful in forming the phosphorylated and boronated ashless dispersants for use as component a-1) include, for example, boron acids, boron oxides, boron esters, and amine or ammonium salts of boron acids.
  • Illustrative compounds include boric acid (sometimes referred to as orthoboric acid), boronic acid, tetraboric acid, metaboric acid, pyroboric acid, esters of such acids, such as mono-, di-, and tri-organic esters with alcohols or polyols having up to 20 or more carbon atoms (e.g., methanol, ethanol, 2-propanol, propanol, butanols, pentanols, hexanols, ethylene glycol, propylene glycol, trimethylol propane, diethanol amine, etc.), boron oxides such as boric oxide and boron oxide hydrate, and ammonium salts such as ammonium borate, ammonium pyroborate, etc.
  • boric acid sometimes referred to as orthoboric acid
  • boronic acid such as tetraboric acid, metaboric acid, pyroboric acid
  • esters of such acids such as mono-, di-, and
  • boron halides such as boron trifluoride, and boron trichloride
  • Amine borane addition compounds and hydrocarbyl boranes can also be used, although they tend to be relatively expensive.
  • the preferred boron reagent is boric acid, H 3 BO 3 .
  • auxiliary nitrogen compounds are long chain primary, secondary and tertiary alkyl amines containing from 12 to 24 carbon atoms, including their hydroxyalkyl and aminoalkyl derivatives.
  • the long chain alkyl group may optionally contain one or more ether groups. Examples of suitable compounds are oleyl amine, N-oleyltrimethylene diamine, N-tallow diethanolamine, N,N-dimethyl oleylamine, and myristyloxapropyl amine.
  • benzotriazole including lower (C 1 -C 4 ) alkyl-substituted benzotriazoles, which function to protect copper surfaces.
  • the concurrent heating step or the combination of sequential heating steps is conducted at temperatures sufficient to produce a final liquid composition which contains both phosphorus and boron.
  • the heating can be carried out in the absence of a solvent by heating a mixture of the ashless dispersant and one or more suitable inorganic phosphorus compounds, or one or more suitable boron compounds, or, preferably, a combination of one or more suitable inorganic phosphorus compounds and one or more suitable boron compounds.
  • the temperatures used will vary somewhat depending upon the nature of the ashless dispersant and the inorganic phosphorus and/or boron reagent being utilized. Generally speaking however, the temperature will usually fall within the range of 40 to 200°C.
  • the duration of the heating is likewise susceptible to variation, but ordinarily will fall in the range of 1 to 3 hours.
  • it is important to thoroughly agitate the components to insure intimate contact therebetween.
  • the phosphorous acid may be utilized in the form of an aqueous solution thereby introducing water into the system to facilitate dissolution of the boric acid.
  • Water (and when using boron esters, alcohol) formed in the process and any added water is preferably removed from the heated mixture by vacuum distillation at temperatures of from 100 to 140°C.
  • the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, etc.
  • the amount of phosphorus compound employed in the heating process ranges from 0.001 mole to 0.999 mole per mole of basic nitrogen and free hydroxyl in the mixture being heated, up to one half of which may be contributed by an auxiliary nitrogen compound.
  • the amount of boron compound employed ranges from 0.001 mole to 1 mole per mole of basic nitrogen and/or hydroxyl in the mixture which is in excess of the molar amount of inorganic phosphorus compound.
  • the last-to-be-used reagent(s) -- inorganic phosphorus compound(s) or boron compound(s), as the case may be -- can be used in an amount equivalent to (or even in excess of) the amount of basic nitrogen and/or hydroxyl groups in the dispersant being heated with such last-to-be-used reagent(s).
  • the amount of added water is not particularly critical as it is removed by distillation during the course of, or at the end of, the heating step. Amounts of up to 1% by weight of the mixture being heated are preferred. When used, the amount of diluent usually ranges from 10 to 50% by weight of the mixture being subjected to heating.
  • the phosphorylated and boronated dispersants utilized as component a-1) in the compositions of this invention when in their undiluted state should have on a weight basis a phosphorus content of at least 100 parts per million (ppm) (preferably at least 500 ppm and more preferably at least 1,000 ppm) and a boron content of at least 100 ppm (preferably at least 500 ppm and more preferably at least 1,000 ppm).
  • component a-1 in part by use of one or more organic phosphorus compounds such as one or more organic phosphates (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid phosphates, monohydrocarbyl diacid phosphates, or mixtures thereof), phosphites (e.g., trihydrocarbyl phosphites, dihydrocarbyl hydrogen phosphites, hydrocarbyl diacid phosphites, or mixtures thereof), phosphonates (e.g., hydrocarbyl phosphonic acids, mono- and/or dihydrocarbyl esters of phosphonic acids, or mixtures thereof), phosphonites (e.g., hydrocarbyl phosphinic acids, mono- and/or dihydrocarbyl esters of phosphinic acids, or mixtures thereof), etc., or the partial or total sulfur analogs thereof, and in part by use of one or more inorganic phosphorus compounds,
  • a mixture is formed from 260 parts of a commercial succinimide ashless dispersant (HiTEC® 644 dispersant; Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Limited), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 8 parts of phosphorous acid, 3.5 parts of tolutriazole, 8 parts of boric acid, and 3.0 parts of water.
  • the mixture is heated at 100°C for two hours until all of the solid materials are dissolved.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove the water while the temperature is slowly raised to 100°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-1).
  • Example 1 The procedure of Example 1 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a Mannich polyamine dispersant (AMOCO® 9250 dispersant; Amoco Corporation).
  • AMOCO® 9250 dispersant as supplied by the manufacturer is believed to be a boronated dispersant and in such case, another material suitable for use as component a-1) can be formed by eliminating the boric acid and water from the procedure used in this example and thereby conducting phosphorylation on an already boronated dispersant.
  • Typical procedures for producing component a-2) phosphorylated ashless dispersants involve heating one or more ashless dispersants of the types described above with at least one inorganic phosphorus acid under conditions yielding a liquid phosphorus-containing composition.
  • inorganic phosphorus acid which are useful in forming such products include those described above in connection with component a-1). Partial or total sulfur analogs such as phosphorotetrathioic acid (H 3 PS 4 ), phosphoromonothioic acid (H 3 PO 3 S), phosphorodithioic acid (H 3 PO 2 S 2 ), phosphorotrithioic acid (H 3 POS 3 ), can also be used in forming products suitable for use as component a-2).
  • the preferred phosphorus reagent is phosphorous acid, (H 3 PO 3 ).
  • auxilary nitrogen compounds are as described above inconnection with component a-1).
  • benzotriazole including lower (C 1 -C 4 ) alkyl-substituted benzotriazoles, which function to protect copper surfaces.
  • the heating step is conducted at temperatures sufficient to produce a liquid composition which contains phosphorus and is as described above in connection with component a-1).
  • a liquid composition which contains phosphorus and is as described above in connection with component a-1).
  • the preferred phosphorus reagent solid phosphorous acid
  • the phosphorous add may be utilized in the form of an aqueous solution. Water formed in the process and any added water is preferably removed from the heated mixture by vacuum distillation at temperatures of from 100 to 140°C.
  • the heating may be conducted in more than one stage if desired.
  • the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, and the like.
  • the amount of inorganic phosphorus acid employed in the heating process is preferably as described above in connection with component a-1)
  • the amount of diluent usually ranges from 10 to 50% by weight of the mixture being subjected to heating. Water can be added to the mixture, before and/or during the heating, if desired.
  • the phosphorylated dispersants utilized as component a-2) in the compositions of this invention when in their undiluted state will have on a weight basis a phosphorus content of at least 5,000 parts per million (ppm) (preferably at least 6,000 ppm and more preferably at least 7,000 ppm).
  • organic phosphorus compounds such as one or more organic phosphates (e.g., trihydrocarbyl phosphates, dihydrocarbyl monoacid phosphates, monohydrocarbyl diacid phosphates, or mixtures thereof), phosphites (e.g., trihydrocarbyl phosphites, dihydrocarbyl hydrogen phosphites, hydrocarbyl diacid phosphites, or mixtures thereof), phosphonates (e.g., hydrocarbyl phosphonic acids, mono- and/or dihydrocarbyl esters of phosphonic acids, or mixtures thereof), phosphonites (e.g, hydrocarbyl phosphinic acids, mono- and/or dihydrocarbyl esters of phosphinic acids, or mixtures thereof), etc, or the partial or total sulfur analogs thereof, and in part by use of one or more inorganic phosphorus acids, the latter
  • organic phosphates e.g., trihydr
  • a mixture is formed from 260 parts of a polyisobutenyl succinimide ashless dispersant (derived from polybutene having a number average molecular weight of 950 and a mixture of a polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 8 parts of solid phosphorous acid, and 3.5 parts of tolutriazole.
  • the mixture is heated at 110°C for two hours.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove traces of water while the temperature is maintained at 110°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-2).
  • Example 5 The procedure of Example 5 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%
  • a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%
  • a mixture of 7300 parts of a polyisobutenyl succinimide (derived from polybutene having a number average molecular weight of about 1,300 and a mixture of polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), and 2500 parts of 100 Solvent Neutral mineral oil is heated to 90-100°C. To this mixture is added 200 parts of phosphorous acid and the resultant mixture is heated at 90-100°C for 2 hours. The resultant homogeneous liquid composition is suitable for use as component a-2).
  • Typical procedures for producing component a-3) phosphorylated and boronated ashless dispersants involve concurrently or sequentially heating one or more ashless dispersants of the types described above with (i) water and at least one water-hydrolyzable organic phosphorus compound and (ii) at least one boron compound under conditions yielding a liquid phosphorus- and boron-containing composition.
  • halophosphine halides e.g., hydrocarbyl phosphorus tetra-halides, dihydrocarbyl phosphorus trihalides, and trihydrocarbyl phosphorus dihalides
  • halophosphines monohalophosphines and dihalophosphines
  • water-hydrolyzable is meant that the organic phosphorus compound when boiled at atmospheric pressure for a period of 5 hours with either (a) distilled water, or (a) water adjusted to at least one pH between 1 and 7 by use of H 2 SO 4 , or (c) water adjusted to at least one pH between 7 and 13 with KOH, is hydrolyzed to the extent of at least 50 mole %.
  • hydrolysis of certain types of organophosphorus compounds results in concomitant oxidation, and compounds which undergo both hydrolysis and oxidation under the foregoing conditions are usable in forming the phosphorylated dispersants for use in this invention.
  • sulfur-containing organophosphorus compounds undergo loss of sulfur under hydrolysis conditions.
  • the preferred water-hydrolysable organic phosphorus compounds are the water-hydrolysable phosphate esters, and the water-hydrolysable phosphite esters, especially the dihydrocarbyl hydrogen phosphites.
  • Suitable compounds of boron useful in forming the phophorylated and boronated ashless dispersants for use as component a-3) include, for example those described above in connection with component a-1). While usable, boron halides such as boron trifluoride, boron trichloride, and the like, are undesirable as they tend to introduce halogen atoms into the boronated dispersant, a feature which detrimental from the environmental, toxicological and conservational standpoints.
  • the preferred boron reagent is boric acid, H 3 BO 3 .
  • additional sources of basic nitrogen can be included in the organic phosphorus compound-ashless dispersant-boron compound-water mixture so as to provide a molar amount (atomic proportion) of basic nitrogen up to that equal to the molar amount of basic nitrogen contributed by the ashless as described above in connection with component a-1).
  • benzotriazole including lower (C 1 -C 4 ) alkyl-substituted benzotriazoles, which function to protect copper surfaces.
  • the concurrent heating step or the combination of sequential heating steps is conducted at temperatures sufficient to produce a final liquid composition which contains both phosphorus and boron and is as described above in connection with component a-1).
  • boron reagent boric acid
  • Water and relatively volatile alcohols formed in the hydrolysis process and the added water are preferably removed from the heated mixture by vacuum distillation at temperatures of from 100 to 140°C.
  • the heating step or steps will be conducted in a diluent oil or other inert liquid medium such as light mineral oils, and the like.
  • the amount of phosphorus compound and boron compound is as described above in connection with component a-1).
  • the last-to-be-used reagent(s) -- water and organic phosphorus compound(s) or boron compound (s), as the case may be -- can be used in an amount equivalent to (or even in excess of) the amount of basic nitrogen and/or hydroxyl groups in the dispersant being heated with such last-to-be-used reagent(s).
  • the ashless dispersant As noted above, insotar as the phosphorylation is concerned, it is preferable to heat the ashless dispersant with one or more water-hydrolyzable organic phosphorus compounds in the presence of water.
  • the water can be added before and/or during the heating step, and before, after, or at the same time one or more phosphorus compounds are introduced into the vessel in which the heating is taking place or is to take place. It is also possible to heat the ashless dispersant with the organic phosphorus compound and then subsequently heat the resultant composition with water, although this procedure is less preferred.
  • the amount of added water is not particularly critical as long as a sufficient amount is present to effect hydrolysis of the water-hydrolyzable organic phospnorus compound.
  • Water present in the system can be removed by distillation (preferably at reduced pressure) during the course of, and preferably is removed at the end of, the heating step. Amounts of water up to 15% by weight of the mixture being heated are preferred, and amounts of water of up to 5% by weight are particularly preferred. When used, the amount of diluent usually ranges from 10 to 50% by weight of the mixture being subjected to heating.
  • the hydrolysis of the water-hydrolyzable organic phosphorus compound(s) employed in the phosphorylation operation can be effected in any of a variety of ways.
  • the dispersant to be phosphorylated, one or more water-hydrolyzable organic phosphorus compounds, and water may be mixed together and heated either in an open system at atmospheric pressure or in a closed system at superatmospheric pressure. If conducted with an open system, the temperature may be kept below the boiling point of water and the mixture subjected to stirring of sufficient intensity to cause and maintain intimate contact among the components within the hydrolysis reaction mixture.
  • the system When conducting the hydrolysis in a closed system, the system may be kept at one or more selected autogenous pressures by suitable adjustment and regulation of the temperature. And, still higher pressures may be imposed upon the system, as for example by injecting high pressure steam into a sealed autoclave containing the hydrolysis reaction mixture.
  • the water itself may be charged to the system in any suitable form, such as in the form of liquid water, steam, or even ice. Similarly, the water may be introduced in the form of hydrated solids so that the water is released by the application of heat during the course of the hydrolysis operation. Injection of wet steam into a well-agitated hydrolysis system is one preferred way of conducting the operation.
  • the hydrolysis operation should be conducted under any given set or sequence of hydrolysis conditions for a period of time long enough that at least 10%, preferably at least 50%, and most preferably at least 75%, of the organic phosphorus compound(s) present in the hydrolysis mixture has been hydrolyzed.
  • hydrolysis products can be expected to vary in relation to the type of phosphorus compound(s) used and the severity of the hydrolysis conditions imposed upon the hydrolysis system
  • inorganic and organic hydrolysis products can be formed in the system, and these in turn can be expected to be taken up by the ashless dispersant(s) present in the system substantially as they are formed
  • the chemical structure(s) of the phosphorylated dispersant(s) are not known with absolute certainty, it is reasonable to conclude that at least some interaction occurs between the dispersant(s) and organic and/or inorganic phosphorus-containing species formed in the hydrolysis reactions taking place in the system. It is also conceivable that such interacted components may undergo displacements and/or other forms of interactions with components present in the hydrolysis system as the hydrolysis operation proceeds.
  • the phosphorylation may be conducted apart from the boronation, or it may be conducted concurrently with the boronation.
  • any of the foregoing hydrolysis procedures can be utilized, the principal difference being that one or more boron compounds are used in combination with one or more water-hydrolyzable organic phosphorus compounds.
  • small amounts of one or more acids e.g., sulfuric acid, phosphoric acid phosphorous acid, etc.
  • bases e.g., NaOH, KOH, ammonium hydroxide, etc.
  • the phosphorylated and boronated dispersants utilized as component a-3) in the compositions of this invention when in their undiluted state should have on a weight basis a phosphorus content of at least 100 parts per million (ppm) (preferably at least 500 ppm and more preferably at least 1000 ppm) and a boron content of at least 100 ppm (preferably at least 500 ppm and more preferably at least 1000 ppm).
  • ppm parts per million
  • boron content of at least 100 ppm preferably at least 500 ppm and more preferably at least 1000 ppm
  • component a-3 in part by use of one or more inorganic phosphorus compounds such as those described above in connection with component a-1), trimetaphosphoric acid (H 3 P 3 O 9 ), phosphorus trioxide, phosphorus tetroxide, phosphorus pentoxide, and/or partial or total sulfur analogs as described above in connection with component a-1), and in part by use of one or more water-hydrolyzable organic phosphorus compounds, the latter should be used in an amount sufficient to provide at least 10% (preferably at least 50% and more preferably at least 75%) of the total phosphorus content of the phosphorylated and boronated dispersant.
  • inorganic phosphorus compounds such as those described above in connection with component a-1
  • trimetaphosphoric acid H 3 P 3 O 9
  • phosphorus trioxide phosphorus tetroxide
  • phosphorus pentoxide and/or partial or total sulfur analogs as described above in connection with component a-1
  • component a-3 when in the undiluted state preferably contains at least 3000 ppm (more preferably at least 5000 ppm and most preferably at least 7000 ppm) of phosphorus and at least 1500 ppm (more preferably at least 2500 ppm and most preferably at least 3500 ppm) of boron.
  • Typical procedures for producing component a4) phosphorylated ashless dispersants involve heating one or more ashless dispersants of the types described above with at least one water-hydrolyzable organic phosphorus compound and water under conditions yielding a liquid phosphorus-containing composition.
  • the water-hydrolyzable organic phosphorus compounds used and the conditions under which they are used are the same as described above in connection with production of component a-3), except of course no boron compound is employed in the process.
  • the phosphorylated dispersants utilized as component a-4) in the compositions of this invention when in their undiluted state will have on a weight basis a phosphorus content of at least 5,000 parts per million (ppm) (preferably at least 6,000 ppm and more preferably at least 7,000 ppm).
  • ppm parts per million
  • the preparation of phosphorylated ashless dispersants suitable for use component a-4) in the compositions of this invention is illustrated by the Examples 12-15 in which all parts and percentages are by weight unless otherwise clearly specified.
  • a mixture is formed from 260 parts of a polyisobutenyl succinimide ashless dispersant (derived from polybutene having a number average molecular weight of about 950 and a mixture of a polyethylene polyamines having an average overall composition approximating that of tetraethylene pentamine), 100 parts of a 100 Solvent Neutral refined mineral oil diluent, 26 parts of dibutyl hydrogen phosphite, 35 parts of tolutriazole and 8 parts of water.
  • the mixture is heated at 110°C for two hours.
  • a vacuum of 40 mm Hg is gradually drawn on the product to remove water and butanol while the temperature is maintained at 110°C.
  • a clear solution or composition is obtained which is soluble in oil and suitable for use as component a-4).
  • Example 12 The procedure of Example 12 is repeated except that the succinimide ashless dispersant is replaced by an equal amount of a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%.
  • a boron-free Mannich polyamine dispersant made from tetraethylene pentamine, polyisobutenyl phenol (made from polyisobutene having a number average molecular weight of about 1710 and formalin) having a nitrogen content of 1.1%.
  • a mixture of 260 parts of a commercial succinimide (HiTEC® 644 dispersant), 3 parts of water, 13 parts of tributyl phosphate, and 4 parts of phosphorous acid is heated to 100°C for 2 hours. Then a vacuum of 40 mm of Hg is applied to the system and the temperature is gradually raised to 110°C.
  • a particularly preferred embodiment of this invention involves using as component a-1) and a-3) a phosphorylated and boronated alkenyl succinimide of a polyethylene polyamine or mixture of polyethylene polyamines, wherein the succinimide is formed from (i) an alkenyl succinic acylating agent having a succination ratio (i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acylating agent) in the range of 1 to 1.3, the alkenyl group being derived from a polyolefin (most preferably a polyisobutene) having a number average molecular weight in the range of 600 to 1,300 (more preferably in the range of 700 to 1,250 and most preferably in the range of 800 to 1,200).
  • a succination ratio i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the
  • Another particularly preferred embodiment of this invention involves using as component a-2) and a4) a phosphorylated alkenyl succinimide of a polyethylene polyamine or mixture of polyethylene polyamines, wherein the succinimide is formed from (i) an alkenyl succinic acylating agent having a succination ratio (i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acylating agent) in the range of 1 to 13, the alkenyl group being derived from a polyolefin (most preferably a polyisobutene) having a number average molecular weight in the range of 600 to 1,300 (more preferably in the range of 700 to 1,250 and most preferably in the range of 800 to 1,200).
  • a succination ratio i.e., the ratio of the average number of chemically bound succinic groups per alkenyl group in the molecular structure of the succinic acylating agent
  • a variety of oil-soluble metal-free sulfur-containing antiwear and/or extreme pressure additives can be used as the other indispensable component in the practice of this invention, provided they have the requisite minimum sulfur content of at least 20 wt %. Examples are included within the categories of dihydrocarbyl polysulfides; sulfurized olefins; trithiones; sulfurized thienyl derivatives; sulfurized terpenes; sulfurized oligomers of C 2 -C 8 monoolefins; xanthates; hydrocarbyl trithiocarbonates; and sulfurized Diels-Alder adducts such as those disclosed in U.S. reissue patent Re 27,331.
  • sulfurized polyisobutene of M ⁇ n 1,100 sulfurized isobutylene, sulfurized diisobutylene, sulfurized triisobutylene, dicyclohexyl polysulfide, diphenyl polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and mixtures of di-tert-butyl polysulfide such as mixtures of di-tert-butyl trisulfide, di-tert-butyl tetrasulfide and di-tert-butyl pentasulfide, among others.
  • Combinations of such categories of sulfur-containing antiwear and/or extreme pressure agents can also be used, such as a combination of sulfurized isobutylene and di-tert-butyl trisulfide, a combination of sulfurized isobutylene and dinonyl trisulfide, a combination of sulfurized triisobutylene and dibenzyl polysulfide.
  • the preferred sulfur-containing antiwear and/or extreme pressure agents are the oil-soluble active sulfur-containing antiwear and/or extreme pressure agents.
  • these are substances which possess a linkage of two or more sulfur atoms (e.g., -S-S-, -S-S-S-, -S-S-S-S-, -S-S-S-S-S-, etc.).
  • a sulfur-containing material is an active sulfur-containing material
  • the dried coupon is then rubbed with a paper towel moistened with acetone to remove any surface flakes formed by copper corrosion.
  • the coupon is then air-dried and weighed to the nearest 0.1 mg,
  • the difference in weight between the initial copper coupon and the coupon after the test represents the extent to which the copper was corroded under the test conditions. Therefore the larger the weight difference, the greater the copper corrosion, and thus the more active the sulfur compound.
  • the sulfur-containing agent is considered "active". Oil-soluble sulfur-containing antiwear and/or extreme pressure agents yielding a weight loss of above 50 mg in the above test are more preferred.
  • oil-soluble sulfur-containing antiwear and/or extreme pressure agents and more preferably oil-soluble active sulfur-containing antiwear and/or extreme pressure agents, that yield less than 25 ppm, and more preferably less than 10 ppm, and most preferably no detectable amounts, of vapor space H 2 S when heated in the concentrated state for one week at 65°C.
  • HiTEC® 309 and 312 sulfurized isobutylene additives are especially desirable in this respect.
  • the most preferred oil-soluble metal-free sulfur-containing antiwear and/or extreme pressure agents from the cost-effectiveness standpoint are the sulfurized olefins containing at least 30% by weight of sulfur, the dihydrocarbyl polysulfides containing at least 25% by weight of sulfur, and mixtures of such sulfurized olefins and polysulfides.
  • di-tert-alkyl polysulfides having a sulfur content of at least 35% by weight are particularly desirable.
  • Sulfurized isobutylene having a sulfur content of at least 40% and as much as 50% by weight or more and a chlorine content of less than 1% by weight is the most especially preferred material.
  • This optional but preferred component is composed of one or more oil-soluble amine salts of one or more partial esters of one or more phosphoric acids and/or thiophosphoric acids.
  • Such compounds may be collectively represented by the formulae or mixtures thereof.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ,and R 7 is, independently, a hydrocarbyl group and each of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , and X 12 is, independently, an oxygen atom or a sulfur atom.
  • the amine salts are formed with one or more partially esterified monothiophosphoric acids.
  • These are compounds of Formulae (I), (II), and (III) above wherein only one of X 1 , X 2 , X 3 , and X 4 , only one of X 5 , X 6 , X 7 , and X 8 , and only one of X 9 , X 10 , X 11 , and X 12 is a sulfur atom.
  • the amine salts are formed with one or more partially esterified phosphoric acids.
  • These are compounds of Formulae (I), (II), and (III) above wherein all of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 , and X 12 are oxygen atoms.
  • Another preferred sub-category of amine salts are those formed with one or more partially esterified dithiophosphoric acids. These are compounds of Formulae (I), (II), and (III) above wherein two of X 1 , X 2 , X 3 , and X 4 , two of X 5 , X 6 , X 7 , and X 8 , and two of X 9 , X 10 , X 11 , and X 12 are sulfur atoms.
  • amine salts of Formulae (I), (II), and (III) above wherein three or four of X 1 , X 2 , X 3 , and X 4 , three or four of X 5 , X 6 , X 7 , and X 8 , and three or four of X 9 , X 10 , X 11 , and X 12 are sulfur atoms.
  • oil-soluble amine salts are useful as components in the compositions of this invention, it is most preferred to include at least one oil-soluble amine salt of a dihydrocarbyl monothiophosphoric acid (one sulfur atom per molecule), either alone or in combination with at least one oil-soluble amine salt of a dihydrocarbyl phosphoric acid (no sulfur atom in the molecule).
  • Use can be made of the octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, cyclohexylamine, phenylamine, mesitylamine, oleylamine, cocoamine, soyamine, C 12-14 tertiary alkyl primary amine, C 22-24 tertiary alkyl primary amine, and phenethylamine salts or adducts of the above and similar partially esterified acids of monothiophosphoric acid, including mixtures of any such compounds.
  • the preferred amine salts are salts of aliphatic amines, especially the saturated or olefinically unsaturated aliphatic primary amines, such as n-octylamine, 2-ethylhexylamine, tert-octylamine, n-decylamine, the C 10 , C 12 , C 14 and C 16 tertiary alkyl primary amines (either singly or in any combinations thereof, such as a mixture of the C 12 and C 14 tertiary alkyl primary amines), n-undecylamine, lauryl amine, hexadecylamine, heptadecylamine, octadecylamine, the C 22 and C 24 tertiary alkyl primary amines (either singly or in combination), decenylamine, dodecenylamine, palmitoleylamine, oleylamine, lino
  • Secondary hydrocarbyl amines and teniary hydrocarbyl amines can also be used either alone or in combination with each other or in combination with primary amines.
  • any combination of primary, secondary and/or tertiary amines, whether monoamine or polyamine, can be used in forming the salts or adducts.
  • Use of primary amines is preferred.
  • Especially preferred amines are alkyl monoamines and alkenyl monoamines having from 8 to 24 carbon atoms in the molecule.
  • Amine salts of partially esterified monothiophosphoric acids are usually made by reacting a mono- and/or dihydrocarbyl phosphite with sulfur or an active sulfur-containing compound such as are referred to above under the caption "Sulfur-Containing Antiwear and/or Extreme Pressure Agents" and one or more primary or secondary amines. Such reactions tend to be highly exothermic reactions which can become uncontrollable, if not conducted properly.
  • One preferred method of forming these amine salts involves a process which comprises (i) introducing, at a rate such that the temperature does not exceed about 60°C, one or more dihydrocarbyl hydrogen phosphites, such as a dialkyl hydrogen phosphite, into an excess quantity of one or more active sulfur-containing materials, such as sulfurized branched-chain olefin (e.g., isobutylene, diisobutylene, triisobutylene, etc.), while agitating the mixture so formed, (ii) introducing into this mixture, at a rate such that the temperature does not exceed about 60°C, one or more aliphatic primary or secondary amines, preferably one or more aliphatic primary monoamines having in the range of 8 to 24 carbon atoms per molecule while agitating the mixture so formed, and (iii) maintaining the temperature of the resultant agitated reaction mixture at between 55 and 60°C until reaction is substantially complete.
  • This group of optional but preferred compounds is composed of O,O-dihydrocarbyl-S-hydrocarbyl thiothionophosphates (also known as O,O-dihydrocarbyl-S-hydrocarbyl phosphorothiothionates) which can be represented by the general formula: wherein each of R 1 , R 2 and R 3 is independently a hydrocarbyl group, especially where R 3 is an alicyclic hydrocarbyl group.
  • R 3 is an alicyclic group
  • R 1 and R 2 are alkyl groups each having up to 18 carbon atoms and most preferably up to 12 carbon atoms.
  • Exemplary compounds suitable for use in the compositions of this invention include such compounds as trioctylphosphorothiothionate, tridecylphosphorothiothionate, trilaurylphosphorothiothionate, O,O-diethyl bicyclo(2.2.1)-hepten-2-yl phosphorothiothionate, O,O-diethyl 7,7-dimethylbicyclo(2.2.1)-5-hepten-2-yl phosphorothiothionate, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dimethyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dimethyl ester with cis-endomethylene-tetrahydrophthalic acid dibutyl ester, the product formed by reaction of dithiophosphoric acid-O,O-dibutyl ester with cis-endomethylene-
  • Another component which can be and preferably is used in the compositions of this invention is one or more amine salts of one or more long chain carboxylic acids.
  • the acids can be monocarboxylic acids or polycarboxylic acids. Generally speaking, these acids contain from 8 to 50 carbon atoms in the molecule and thus the salts are oil-soluble.
  • a variety of amines can be used in forming such salts, including primary, secondary and tertiary amines, and the amines can be monoamines, or polyamines. Further, the amines may be cyclic or acyclic aliphatic amines, aromatic amines, heterocyclic amines, or amines containing various mixtures of acyclic and cyclic groups.
  • Preferred amine salts include the alkyl amine salts of alkanoic acid and the alkyl amines salts of alkanedioic acids.
  • the amine salts are formed by classical chemical reactions, namely, the reaction of an amine or mixture of amines, with the appropriate acid or mixture of acids. Accordingly, further discussion concerning methods for the preparation of such materials would be redundant.
  • lauryl ammonium laurate i.e., the lauryl amine salt of lauric acid
  • stearyl ammonium laurate i.e., the lauryl amine salt of lauric acid
  • stearyl ammonium laurate cyclohexyl ammonium laurate
  • octyl ammonium laurate pyridine laurate
  • aniline laurate lauryl ammonium stearate
  • stearyl ammonium stearate cyclohexyl ammonium stearate, octylammonium stearate
  • pyridine stearate aniline stearate
  • lauryl ammonium octanoate stearyl ammonium octanoate
  • cyclohexyl ammonium octanoate octyl ammonium octanoate
  • aniline octanoate nonyl am
  • the preferred amine salts are the primary amine salts of long chain monocarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH 2 ; the secondary amine salts of long chain monocarboxylic acids in which the amine thereof is a dialkyl monoamine, R 2 NH; the tertiary amine salts of long chain monocarboxylic acids in which the amine thereof is a trialkyl monoamine, R 3 N; the bis primary amine salts of long chain dicarboxylic acids in which the amine thereof is a monoalkyl monoamine, RNH 2 ; the bis secondary amine salts of long chain dicarboxylic acids in which the amine thereof is a dialkyl monoamine, R 2 NH; the bis tertiary amine salts of long chain dicarboxylic acids in which the amine thereof is a trialkyl monoamine, R 3 N; and mixtures thereof.
  • R is an alkyl group which contains up to 30
  • Typical additives which may be employed as demulsifiers include alkyl benzene sulfonates, polyethylene oxides, polypropylene oxides, block copolymers of ethylene oxide and propylene oxide, and salts and esters or oil soluble acids.
  • One type of copper corrosion inhibitor additives is comprised of thiazoles, triazoles and thiadiazoles.
  • examples of such compounds include benzotriazole, tolyltriazole, octyltriazole, decyl triazole, dodecyltriazole, 2-mercaptobenzothiazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles, 2-mercapto-5-hydrocarbyldithio-1,3,4- thiadiazoles, 2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and 2,5-(bis)hydrocarbyldithio)-1,3,4-thiadiazoles.
  • the preferred compounds are the 1,3,4-thiadiazoles, especially the 2-hydrocarbyldithio-5-mercapto-1,3,4-thiadiazoles and the 2,5-bis(hydrocarbylthio)1,3,4-thiadiazoles, a number of which are available as articles of commerce.
  • Such compounds are generally synthesized from hydrazine and carbon disulfide by known procedures.
  • Suitable inhibitors of copper corrosion include ether amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; and imidazolines. Materials of these types are well known to those skilled in the art and a number of such materials are available as articles of commerce.
  • the boron-containing additive components are preferably oil-soluble additive components, but effective use can be made of boron-containing components which are sufficiently finely divided as to form stable dispersions in the base oil.
  • boron-containing components include the finely-divided inorganic orthoborate salts such as lithium borate, sodium borate, potassium borate, magnesium borate, calcium borate, ammonium borate and the like.
  • the oil-soluble boron-containing components include boronated ashless dispersants (often referred to as borated ashless dispersants) and esters of acids of boron.
  • borated ashless dispersants examples include boronated ashless dispersants and descriptions of methods by which they can be prepared.
  • examples of boronated ashless dispersants and descriptions of methods by which they can be prepared are well-documented in the literature. Likewise the literature is replete with examples of oil-soluble esters of boron acids and methods for their production.
  • the oleaginous fluids and additive concentrates of this invention can and preferably will contain additional components in order to partake of the properties which can be conferred to the overall composition by such additional components.
  • additional components will, to a large extent, be governed by the particular use to which the ultimate oleaginous composition (lubricant or functional fluid) is to be subjected.
  • methylene-bridged alkylphenols are also useful.
  • these can be used singly or in combinations with each other, or in combinations with sterically-hindered unbridged phenolic compounds.
  • Preferred are mixtures of methylene-bridged alkylphenols such as are described in U.S. Pat. No. 3,211,652.
  • Amine antioxidants especially oil-soluble aromatic secondary amines can also be used.
  • aromatic secondary monoamines are preferred, aromatic secondary polyamines are also suitable.
  • a preferred type of aromatic amine antioxidant is an alkylated diphenylamine of the general formula wherein R 1 is an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms) and R 2 is a hydrogen atom or an alkyl group (preferably a branched alkyl group) having 8 to 12 carbon atoms, (more preferably 8 or 9 carbon atoms). Most preferably, R 1 and R 2 are the same.
  • Naugalube 438L a material which is understood to be predominately a 4,4'-dinonyldiphenylamine (i.e., bis(4-nonylphenyl)amine) wherein the nonyl groups are branched.
  • antioxidants for inclusion in the compositions of this invention is comprised to one or more liquid, partially sulfurized phenolic compounds such as are prepared by reacting sulfur monochloride with a liquid mixture of phenols - at least about 50 weight percent of which mixture of phenols is composed of one or more reactive, hindered phenols - in proportions to provide from 03 to 0.7 gram atoms of sulfur monochloride per mole of reactive, hindered phenol so as to produce a liquid product.
  • One suitable mixture is comprised of a combination of (i) an oil-soluble mixture of at least three different sterically-hindered tertiary butylated monohydric phenols which is in the liquid state at 25°C, (ii) an oil-soluble mixture of at least three different sterically-hindered tertiary butylated methylene-bridged polyphenols, and (iii) at least one bis(4-alkylphenyl)amine wherein the alkyl group is a branched alkyl group having 8 to 12 carbon atoms, the proportions of (i), (ii) and (iii) on a weight basis falling in the range of 3.5 to 5.0 parts of component (i) and 0.9 to 12 parts of component (ii) per part by weight of component (iii).
  • the compositions of this invention may also contain a suitable quantity of a rust inhibitor.
  • a rust inhibitor This may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces. Products of this type are currently available from various commercial sources, such as, for example, the dimer and trimer acids sold under the HYSTRENE trademark by the Humco Chemical Division of Witco Chemical Corporation and under the EMPOL trademark by Emery Chemicals.
  • Another useful type of acidic corrosion inhibitors are the half esters of alkenyl succinic acids having 8 to 24 carbon atoms in the alkenyl group with alcohols such as the polyglycols.
  • the corresponding half amides of such alkenyl succinic acids are also usefuL
  • carboxylic groups of these carboxylic acid type corrosion inhibitors may be neutralized by excess amine present in the compositions.
  • suitable corrosion inhibitors include ether amines; acid phosphates; amines; polyethoxylated compounds such as ethoxylated amines, ethoxylated phenols, and ethoxylated alcohols; and imidazolines. Materials of these types are well known to those skilled in the art and a number of such materials are available as articles of commerce.
  • R 1 , R 2 , R 5 , R 6 and R 7 are aminosuccinic acids or derivatives thereof represented by the formula: wherein each of R 1 , R 2 , R 5 , R 6 and R 7 is, independently, a hydrogen atom or a hydrocarbyl group containing 1 to 30 carbon atoms, and wherein each of R 3 and R 4 is, independently, a hydrogen atom, a hydrocarbyl group containing 1 to 30 carbon atoms, or an acyl group containing from 1 to 30 carbon atoms.
  • the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 when in the form of hydrocarbyl groups, can be, for example, alkyl, cycloalkyl or aromatic containing groups.
  • R 1 and R 5 are the same or different straight-chain or branched-chain hydrocarbon radicals containing 1-20 carbon atoms. Most preferably, R 1 and R 5 are saturated hydrocarbon radicals containing 3-6 carbon atoms.
  • R 2 , either R 3 or R 4 , R 6 and R 7 , when in the form of hydrocarbyl groups, are preferably the same or different straight-chain or branched-chain saturated hydrocarbon radicals.
  • a dialkyl ester of an aminosuccinic acid is used in which R 1 and R 5 are the same or different alkyl groups containing 3-6 carbon atoms, R 2 is a hydrogen atom, and either R 3 or R 4 is an alkyl group containing 15-20 carbon atoms or an acyl group which is derived from a saturated or unsaturated carboxylic acid containing 2-10 carbon atoms.
  • aminosuccinic acid derivatives is a dialkylester of an aminosuccinic acid of the above formula wherein R 1 and R 5 are isobutyl, R 2 is a hydrogen atom, R 3 is octadecyl and/or octadecenyl and R 4 is 3-carboxy-1-oxo-2-propenyl.
  • R 6 and R 7 are most preferably hydrogen atoms.
  • Suitable friction modifiers include aliphatic amines or ethoxylated aliphatic amines, aliphatic fatty acid amides, aliphatic carboxylic acids, aliphatic carboxylic esters, aliphatic carboxylic ester-amides, aliphatic phosphates, aliphatic thiophosphonates, aliphatic thiophosphates, etc., wherein the aliphatic group usually contains above about eight carbon atoms so as to render the compound suitably oil soluble.
  • a desirable friction modifier additive combination which may be used in the practice of this invention is described in European Patent Publication No. 389,237. This combination involves use of a long chain succinimide derivative and a long chain amide.
  • Dispersant viscosity index improvers which combine the activity of dispersants and viscosity index improvers, suitable for use in the compositions of this invention are described, for example, in U.S. Pat Nos. 3,702,300; 4,068,056; 4,068,058; 4,089,794; 4,137,185; 4,146,489; 4,149,984; 4,160,739; and 4,519,929.
  • the above description of other additives which can be used in the compositions of this invention is not to be construed as limitive, as many other types of additives can be used in such compositions. The only requirements are that such other additives not excessively interfere with the performance of the compositions of this invention and that they exhibit suitable compatibility with the additives otherwise being employed therein.
  • K) Free Amine The free amines which can be employed in the compositions of this invention can be any of the amines referred to above in connection with the amine salts of partial esters of phosphoric acid or thiophosphoric acids or in connection with the amine salts of carboxylic acids, provided that the amines are oil-soluble.
  • the preferred type is composed of alkyl primary monoamines, and alkenyl primary monoamines, especially those containing from 6 to 24 carbon atoms.
  • alkyl primary monoamines and alkenyl primary monoamines, especially those containing from 6 to 24 carbon atoms.
  • examples of such amines include hexylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, eicosylamine, docosylamine, tetracosylamine, oleylamine, cocoamine, soyamine, C 12-14 tertiary alkyl primary amine, and C 22-24 tertiary alkyl primary amine.
  • the free amine used in the compositions will correspond to the amine used in forming either the amine salt of the phosphorus acid or the amine salt of the carboxylic acid, or both.
  • free amine refers to the form of the amine as it is charged into the blender or mixing vessel in which the additive concentrate or the lubricating oil or functional fluid composition is being formed. Some or all of the free amine may complex with or react with other components being used in the product being formed, such as acidic additive components. Thus the term “free amine” does not signify or imply that the amine must remain free -- all or part of it may remain uncomplexed and unreacted, but this is not a requirement
  • the additive combinations of this invention can be incorporated in a wide variety of lubricants and functional fluids in effective amounts to provide suitable active ingredient concentrations.
  • the base oils not only can be hydrocarbon oils of lubricating viscosity derived from petroleum (or tar sands, coal, shale, etc.), but also can be natural oils of suitable viscosities such as rapeseed oil, etc., and synthetic oils such as hydrogenated polyolefin oils; poly- ⁇ -olefins (e.g., hydrogenated or unhydrogenated ⁇ -olefin oligomers such as hydrogenated poly-1-decene); alkyl esters of dicarboxylic acids; complex esters of dicarboxylic acid, polyglycol and alcohol; alkyl esters of carbonic or phosphoric acids; polysilicones; fluorohydrocarbon oils; and mixtures of mineral natural and/or synthetic oils in any proportion, etc.
  • base oil for this disclosure includes all the foregoing.
  • the additive combinations of this invention can thus be used in lubricating oil and functional fluid compositions, such as automotive crankcase lubricating oils, automatic transmission fluids, gear oils, hydraulic oils, cutting oils, etc., in which the base oil of lubricating viscosity is a mineral oil, a synthetic oil, a natural oil such as a vegetable oil, or a mixture thereof, e.g., a mixture of a mineral oil and a synthetic oil. Examples of such are known in the art.
  • the base oils used in the compositions of this invention may be composed of (i) one or more mineral oils, (ii) one or more synthetic oils, (iii) one or more natural oils, or (iv) a blend of (i) and (ii), or (i) and (iii), or (ii) and (iii), or (i), (ii) and (iii) does not mean that these various types of oils are necessarily equivalents of each other.
  • Certain types of base oils may be used in certain compositions for the specific properties they possess such as high temperature stability, non-flammability or lack of corrosivity towards specific metals (e.g., silver or cadmium). In other compositions, other types of base oils may be preferred for reasons of availability or low cost
  • the skilled artisan will recognize that while the various types of base oils discussed above may be used in the compositions of this invention, they are not necessarily functional equivalents of each other in every instance.
  • the components of the additive compositions of this invention are employed in the oleaginous liquids (e.g., lubricating oils and functional fluids) in minor amounts sufficient to improve the performance characteristics and properties of the base oil or fluid.
  • the amount employed is most preferably the amount sufficient to render the pH (determined as described hereinafter) of the finished additive concentrate as formed within the range of 4 to 9.
  • the amounts of the other components will vary in accordance with such factors as the viscosity characteristics of the base oil or fluid employed, the viscosity characteristics desired in the finished product, the service conditions for which the finished product is intended, and the performance characteristics desired in the finished product.
  • the individual components can be separately blended into the base oil or fluid or can be blended therein in various subcombinations, if desired. Moreover, such components can be blended in the form of separate solutions in a diluent Except for viscosity index improvers and/or pour point depressants (which in many instances are blended apart from other components), it is preferable to blend the other selected components into the base oil by use of an additive concentrate of this invention, as this simplifies the blending operations, reduces the likelihood of blending errors, and takes advantage of the compatibility and solubility characteristics afforded by the overall concentrate.
  • the additive concentrates of this invention will contain the individual components in amounts proportioned to yield finished oil or fluid blends consistent with the concentrations tabulated above.
  • the additive concentrate will contain one or more diluents such as light mineral oils, to facilitate handling and blending of the concentrate.
  • concentrates containing up to 50% by weight of one or more diluents or solvents can be used.
  • the oleaginous liquids provided by this invention can be used in a variety of applications.
  • they can be employed as crankcase lubricants, gear oils, hydraulic fluids, manual transmission fluids, automatic transmission fluids, cutting and machining fluids, brake fluids, shock absorber fluids, heat transfer fluids, quenching oils, and transformer oils.
  • the compositions are particularly suitable for use as automotive and industrial gear oils.
  • the formulation or blending operations are relatively simple and involve mixing together in a suitable container or vessel, using a dry, inert atmosphere where necessary or desirable, appropriate proportions of the selected ingredients.
  • Those skilled in the art are cognizant of and familiar with the procedures suitable for formulating and blending additive concentrates and lubricant compositions.
  • the order of addition of components to the blending tank or vessel is not critical provided of course, that the components being blended at any given time are not incompatible or excessively reactive with each other. Agitation such as with mechanical stirring equipment is desirable to facilitate the blending operation.
  • the additive ingredients When forming the lubricant compositions of this invention, it is usually desirable to introduce the additive ingredients into the base oil with stirring and application of mildly elevated temperatures, as this facilitates the dissolution of the components in the oil and achievement of product uniformity.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 383 parts of sulfurized isobutylene, 143 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.3 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl add phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 383 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 38.0 parts of sulfurized isobutylene, 14.0 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, 4.76 parts of dibutyl hydrogen phosphite, and 1.75 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 383 parts of sulfurized isobutylene, 14.3 parts of di-tert-nonyl polysulfide, 5.7 parts of dibutyl hydrogen phosphite, 0.1 part of tolyltriazole, and 2.9 parts of amyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.8 parts of sulfurized isobutylene, 3.6 parts of dibutyl hydrogen phosphite, 18.9 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.7 parts of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • reaction vessel To a reaction vessel are charged 35.1 parts of sulfurized isobutylene, 3.8 parts of dibutyl hydrogen phosphite, 16.6 parts of a product formed by reaction of dicyclopentadiene with dithiophosphoric acid-0,0-dialkyl ester in which on a molar basis 40% of the alkyl groups are isopropyl, 40% are isobutyl and 20% are 2-ethylhexyl, and 1.0 part of 2-ethylhexyl acid phosphate. Throughout this addition, the components of the reaction vessel are agitated and maintained at 30°C for 10 minutes.
  • compositions of this invention were illustrated in several standard L-37 and L42 tests.
  • the composition was prepared by blending together the following components in which the proportions are by weight: Phosphorylated ashless dispersant 4.00% Sulfurized isobutylene 3.50% Exxon 1365 mineral oil 28.68% Exxon 2507 mineral oil (Bright Stock) 63.82%
  • the phosphorylated ashless dispersant was formed from a polyisobutenyl succinimide, viz., HiTEC® 646 additive (Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.).
  • Example 5 Phosphorylation was accomplished in the manner of Example 5 using 2.7 parts by weight of HiTEC® 646 additive, 0.3 parts by weight of solid phosphorous acid (H 3 PO 3 ), and 1 part by weight of process oil diluent
  • the sulfurized isobutylene was HiTEC® 309 sulfurized isobutylene additive; (Ethyl Petroleum Additives, Inc.; Ethyl Petroleum Additives, Ltd.; Ethyl S.A.; Ethyl Canada Ltd.).
  • This oil blend had kinematic viscosity at of 153.98 cSt at 40°C, and 16.63 cSt at 100°C.
  • the procedure used in determining pH of preferred additive concentrates of this invention involves diluting the sample of the composition in a mixture of methanol and toluene and then assaying "non-aqueous" pH with a conventional pH probe as used in aqueous systems.
  • Copper corrosion ratings for the purposes of this invention are conducted using the standard ASTM D-130 procedure modified to the extent that the additive concentrate to be tested is first stored in an oven for 120 hours at 65°C. Then the concentrate is blended into the test oil to the selected test concentration and the test is conducted at 121°C.
  • oil-soluble is used in the sense that the component in question has sufficient solubility in the selected base oil in order to dissolve therein at ordinary temperatures to a concentration at least equivalent to the minimum concentration specified herein for use of such component
  • solubility of such component in the selected base oil will be in excess of such minimum concentration, although there is no requirement that the component be soluble in the base oil in all proportions.
  • certain useful additives do not completely dissolve in base oils but rather are used in the form of stable suspensions or dispersions. Additives of this type can be employed in the compositions of this invention, provided they do not significantly interfere with the performance or usefulness of the composition in which they are employed.
  • EP-A- 053100 Reference may also be made to EP-A- 053100.

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  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Claims (14)

  1. Additivkonzentrat, das einen kleineren Anteil Verdünneröl und einen größeren Anteil Additivkomponenten mit folgenden Bestandteilen enthält:
    a-1) mindestens einer öllöslichen Additivzusammensetzung, die dadurch hergestellt wird, daß man gleichzeitig oder in beliebiger Reihenfolge mindestens ein basischen Stickstoff und/oder mindestens eine Hydroxylgruppe enthaltendes aschefreies Dispergiermittel mit (i) mindestens einer anorganischen Phosphorsäure oder einem anorganischen Phosphorsäureanhydrid oder mindestens einem teilweisen oder vollständigen Schwefelanalog davon oder einer beliebigen Kombination der vorstehenden Substanzen und (ii) mindestens einer Borverbindung erhitzt, so daß eine flüssige Zusammensetzung gebildet wird; oder
    a-2) mindestens einer öllöslichen borfreien Additivzusammensetzung, die dadurch hergestellt wird, daß man (i) mindestens ein basischen Stickstoff und/oder mindestens eine Hydroxylgruppe enthaltendes borfreies öllösliches aschefreies Dispergiermittel mit (ii) mindestens einer anorganischen Phosphorsäure erhitzt, so daß eine flüssige borfreie phosphorhaltige Zusammensetzung entsteht, oder
    a-3) einer oder mehreren öllöslichen Additivzusammensetzungen, die dadurch hergestellt werden, daß man gleichzeitig oder in beliebiger Reihenfolge mindestens ein basischen Stickstoff und/oder mindestens eine Hydroxylgruppe enthaltendes aschefreies Dispergiermittel mit (i) mindestens einer durch Wasser hydrolysierbaren organischen Phosphorverbindung und Wasser und (ii) mindestens einer Borverbindung erhitzt, so daß eine flüssige Phosphor und Bor enthaltende Zusammensetzung gebildet wird, oder
    a-4) einer oder mehreren öllöslichen borfreien Additivzusammensetzungen, die dadurch hergestellt werden, daß man gleichzeitig oder in beliebiger Reihenfolge (i) mindestens ein basischen Stickstoff und/oder mindestens eine Hydroxylgruppe enthaltendes borfreies öllösliches aschefreies Dispergiermittel mit (ii) mindestens einer durch Wasser hydrolysierbaren organischen Phosphorverbindung und Wasser erhitzt, so daß eine flüssige borfreie phosphorhaltige Zusammensetzung gebildet wird und
    b) mindestens einem öllöslichen metallfreien schwefelhaltigen Mittel gegen Verschleiß oder zur Verwendung bei extremem Druck mit einem Schwefelgehalt von mindestens 20 Gew.-%,
    wobei die Komponenten a-1), a-2), a-3) oder a-4) und b) in solchen Anteilen vorliegen, daß das Massenverhältnis (nach Gewicht) des Schwefels in Komponente b) zum Phosphor in Komponente a-1), a-2), a-3) oder a-4) im Bereich von 8 : 1 bis 30 : 1 liegt.
  2. Zusammensetzung nach Anspruch 1, in der das Massenverhältnis im Bereich von 10 : 1 bis 20 : 1 liegt.
  3. Zusammensetzung nach Anspruch 1, in der das Massenverhältnis im Bereich von 14 : 1 bis 20 : 1 liegt.
  4. Zusammensetzung nach einem der Ansprüche 1 bis 3, in der die Komponente a-1) verwendet wird.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 3, in der die Komponente a-2) verwendet wird.
  6. Zusammensetzung nach einem der Ansprüche 1 bis 3, in der die Komponente a-3) verwendet wird.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 3, in der die Komponente a-4) verwendet wird.
  8. Zusammensetzung nach einem der Ansprüche 1 bis 7, in der die Additivkomponenten des Additivkonzentrats außerdem folgende Additivkomponenten enthalten:
    c) mindestens ein öllösliches Aminsalz eines Mono- oder Dihydrocarbylesters einer monomeren fünfwertigen Phosphorsäure;
    d) mindestens einen öllöslichen Trihydrocarbylester einer Dithiophosphorsäure;
    e) mindestens ein öllösliches Aminsalz einer Carbonsäure;
    f) mindestens einen öllöslichen Demulgator oder
    g) mindestens ein öllösliches Mittel zur Hemmung der Kupferkorrosion
    oder eine Kombination aus je zwei, drei, vier beliebigen oder allen fünf der Komponenten c), d), e), f) und g).
  9. Zusammensetzung nach Anspruch 5 oder 7, in der die Additivkomponenten des Additivkonzentrats außerdem folgende Additivkomponenten enthalten:
    c) mindestens ein öllösliches Aminsalz eines Mono- oder Dihydrocarbylesters einer monomeren fünfwertigen Phosphorsäure;
    d) mindestens einen öllöslichen Trihydrocarbylester einer Dithiophosphorsäure;
    e) mindestens ein öllösliches Aminsalz einer Carbonsäure;
    f) mindestens einen öllöslichen Demulgator;
    g) mindestens ein öllösliches Mittel zur Hemmung der Kupferkorrosion oder
    h) mindestens eine öllösliche oder in Öl dispergierbare borhaltige Verbindung
    oder eine Kombination aus je zwei, drei, vier, fünf beliebigen oder allen sechs der Komponenten c), d), e), f) g) und h).
  10. Ölhaltige Zusammensetzung, die einen größeren Anteil mindestens eines Basisöls von Schmierviskosität und eine kleinere Menge Additivkomponenten nach einem der Ansprüche 1 bis 9 enthält.
  11. Zusammensetzung nach Anspruch 10, in der die Komponente b) in einer Menge vorhanden ist, die ausreicht, um bezogen auf das Gesamtgewicht der ölhaltigen Zusammensetzung einen Schwefelgehalt im Basisöl von mindestens etwa 1,0 Gew.-% zur Verfügung zu stellen.
  12. Verfahren zum Schmieren relativ beweglicher, nahe beieinander befindlicher Metalloberflächen, bei dem man als Schmiermittel für diese Oberflächen eine ölhaltige Zusammensetzung nach Anspruch 10 oder 11 für die Verwendung bereitstellt oder verwendet.
  13. Verfahren nach Anspruch 12, bei dem die relativ beweglichen Metalloberflächen aus nahe beieinanderliegenden, mechanische Energie übertragenden Oberflächen bestehen.
  14. Mechanischer Apparat, der relativ bewegliche, nahe beieinander befindliche Metalloberflächen umfaßt, die geschmiert werden müssen oder ein Schmiermittel benötigen, wobei das Schmiermittel eine ölhaltige Zusammensetzung nach Anspruch 10 oder 11 ist.
EP92307448A 1991-08-21 1992-08-14 Ölzusatzkonzentrate und Schmieröle mit erhöhten Leistungsfähigkeiten Expired - Lifetime EP0531000B1 (de)

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US747956 1976-12-06
US74801991A 1991-08-21 1991-08-21
US74793991A 1991-08-21 1991-08-21
US74794291A 1991-08-21 1991-08-21
US74795691A 1991-08-21 1991-08-21
US747942 1991-08-21
US747939 1991-08-21
US748019 1991-08-21

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EP0531000A1 (de) 1993-03-10
AU2111492A (en) 1993-02-25
CA2076140A1 (en) 1993-02-22
JPH05263090A (ja) 1993-10-12
CA2076140C (en) 2002-02-26
DE69217299D1 (de) 1997-03-20

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