CA1148537A - Process for preparing molybdenum-containing compositions useful for improved fuel economy of internal combustion engines - Google Patents
Process for preparing molybdenum-containing compositions useful for improved fuel economy of internal combustion enginesInfo
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- CA1148537A CA1148537A CA000369004A CA369004A CA1148537A CA 1148537 A CA1148537 A CA 1148537A CA 000369004 A CA000369004 A CA 000369004A CA 369004 A CA369004 A CA 369004A CA 1148537 A CA1148537 A CA 1148537A
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Abstract
ABSTRACT OF THE DISCLOSURE:
Molybdenum-containing compositions prepared by reacting:
(a) a phosphorus-containing acid represented by the formula:
Molybdenum-containing compositions prepared by reacting:
(a) a phosphorus-containing acid represented by the formula:
Description
1~48537 TITLE: PROCESS FOR PREPARING MOLYBDENUM-CONTAINING
COMPOSITIONS USEFUL FOR IMPROVED FUEL
ECONOMY OF INTERNAL COMBUSTION ENGINES
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to sulfur-, phosphorus- and molybdenum-containing compositions made from phosphorus-containing acids. More specifically this invention relates to processes for preparing these sulfur-, phosphorus- and molybdenum-containing compositions, which are useful as additives in lubricants. Additionally, this invention relates to concentrates of the~e compositions and to lubri-cant composition~ comprising these compositions. This invention also relates to methods for reducing fuel con-sumption by lubricating an internal combustion engine withthese lubricating compositions.
Description of the Prior Art Sulfur-containing molybdenum salts of phosphorus-containing acids and processes for preparing said composi-20 tions have been described in U. S. Patents 3,223,625;
3,256,184; 3,400,140; 3,494,866; 3,840,463, and 4,156,099.
A principal object of the present invention is to provide novel sulfur-, phosphorus- and molybdenum-containing compositions made from phosphorus-containing acids as well as processes for making them.
. ~
Another object is to provide novel sulfur-, phos-phorus- and molybdenum-containing compositions made from phosphorus-containing acids which exhibit friction reducing properties in lubricants.
Still another object is to provide novel sulfur-, phosphorus- and molybdenum-containing compositions made from pho~phorus-containing acids having improved incorporation of molybdenum.
An additional object is to provide novel concen-10 trates comprising theqe novel sulfur-, phosphorus- and molybdenum-containing compositions.
Another additional object is to provide novel lubricant compositions of these novel, friction-reducing, sulfur-, phosphorus- and molybdenum-containing compositions.
A further object is to provide a novel method for reducing fuel consumption by lubricating an internal com-bustion engine with the~e novel, friction-reducing, sulfur-, pho~phorus- and molybdenum-containing compositions.
These and other objects of the invention are 20 accomplished by providing a process for preparing a compo-sition which comprise~ reacting:
~a) A phosphorus-containing acid represented by the formula:
R(X')n X
P-XH
R(X') ~
wherein each X and X' is independently oxygen or sul-fur, each n is zero or one, and each R is independently the same or a different hydrocarbon-based rad~cal;
(b) at least one hexavalent molybdenum oxide compound, and (c) hydrogen sulfide, in the presence of (d) a polar solvent.
Typical phosphorus-containing acids (a) from which the compositions of this invention can be ~ade are known.
Illustrative examples of some preferred phosphorus- and sulfur-containing acids are:
1. Dihydrocarbylphosphinodithioic acids, such as amylphosphinodithioic acid, corresponding to the S formula, (C~H~ Sl ~ -SH;
(CsHl I )~
COMPOSITIONS USEFUL FOR IMPROVED FUEL
ECONOMY OF INTERNAL COMBUSTION ENGINES
BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to sulfur-, phosphorus- and molybdenum-containing compositions made from phosphorus-containing acids. More specifically this invention relates to processes for preparing these sulfur-, phosphorus- and molybdenum-containing compositions, which are useful as additives in lubricants. Additionally, this invention relates to concentrates of the~e compositions and to lubri-cant composition~ comprising these compositions. This invention also relates to methods for reducing fuel con-sumption by lubricating an internal combustion engine withthese lubricating compositions.
Description of the Prior Art Sulfur-containing molybdenum salts of phosphorus-containing acids and processes for preparing said composi-20 tions have been described in U. S. Patents 3,223,625;
3,256,184; 3,400,140; 3,494,866; 3,840,463, and 4,156,099.
A principal object of the present invention is to provide novel sulfur-, phosphorus- and molybdenum-containing compositions made from phosphorus-containing acids as well as processes for making them.
. ~
Another object is to provide novel sulfur-, phos-phorus- and molybdenum-containing compositions made from phosphorus-containing acids which exhibit friction reducing properties in lubricants.
Still another object is to provide novel sulfur-, phosphorus- and molybdenum-containing compositions made from pho~phorus-containing acids having improved incorporation of molybdenum.
An additional object is to provide novel concen-10 trates comprising theqe novel sulfur-, phosphorus- and molybdenum-containing compositions.
Another additional object is to provide novel lubricant compositions of these novel, friction-reducing, sulfur-, phosphorus- and molybdenum-containing compositions.
A further object is to provide a novel method for reducing fuel consumption by lubricating an internal com-bustion engine with the~e novel, friction-reducing, sulfur-, pho~phorus- and molybdenum-containing compositions.
These and other objects of the invention are 20 accomplished by providing a process for preparing a compo-sition which comprise~ reacting:
~a) A phosphorus-containing acid represented by the formula:
R(X')n X
P-XH
R(X') ~
wherein each X and X' is independently oxygen or sul-fur, each n is zero or one, and each R is independently the same or a different hydrocarbon-based rad~cal;
(b) at least one hexavalent molybdenum oxide compound, and (c) hydrogen sulfide, in the presence of (d) a polar solvent.
Typical phosphorus-containing acids (a) from which the compositions of this invention can be ~ade are known.
Illustrative examples of some preferred phosphorus- and sulfur-containing acids are:
1. Dihydrocarbylphosphinodithioic acids, such as amylphosphinodithioic acid, corresponding to the S formula, (C~H~ Sl ~ -SH;
(CsHl I )~
2. S-hydrocarbyl hydrogen hydrocarbylphosphonotri-thioates, such as S-amyl hydrogen amylphosphonotri-thioate, corresponding to the formula, (CsHll).\S
~-SH;
(CsHl 1 )~S
~-SH;
(CsHl 1 )~S
3. O-hydrocarbyl hydrogen hydrocarbylphosphonodi-thioates, ~uch as O-amyl hydrogen amylphosphonodi-thioate, corresponding to the formula, (CsHl 1 )~
~P-SH;
(CsHll)~O
~P-SH;
(CsHll)~O
4. S,S-dihydrocarbyl hydrogen pho~phorotetrathioate~, such as diamyl hydrogen phosphorotetrathioate, corre~-ponding to the formula, (CsHl I )~ S
S\ll P-SH;
S'/
(CsHll)
S\ll P-SH;
S'/
(CsHll)
5. O,S-dihydrocarbyl hydrogen phosphorotrithioates, such as O,S-diamyl hydrogen phosphorotrithioate, corresponding to the formula, ~CsHl~
o\ll P-SH;
(CsHl 1 ) ~,.~
8~7
o\ll P-SH;
(CsHl 1 ) ~,.~
8~7
6. O,O-dihydrocarbyl hydrogen phosphorodithioates, such as O,O-diamyl hydrogen phosphorodithioate, corres-ponding to the formula, (CsHIl) \ S
o\ll P-SH;
~0 (CsHIl) S
Preferred acids of the formula [(RO)2PSH] are readily obtainable from the reaction of phosphorus penta-sulfide (P2S5) and an alcohol or a phenol. The reaction in-volves mixing at a temperature of about 20 to about 200C., 4 moles of the alcohol or a phenol with one mole of phos-10 phorus pentasulfide. Hydrogen sulfide is liberated in this reaction. The oxygen-containing analogs of these acids are conveniently prepared by treating the preferred dithioic acid with water or steam which, in effect, replaces one or both of the sulfur atoms.
Thus, as prev~ously mentioned, the preferred phosphorus-containing acids are phosphorus- and sulfur-containing acids. These preferred acids more preferably include those wherein at least one ~ is sulfur, more pre-ferably both of X are sulfur; at least one X' i8 oxygen or 20 sulfur, more preferably both of X' are oxygen and n is 1.
Mixtures of acids may be employed according to this in-vention.
The terminology of "hydrocarbon-based radical n ag u~ed herein, (nherein" includes the appended claims) is used 25to define a substantially saturated monovalent rad~cal derived from a hydrocarbon by removal of a hydrogen from a carbon atom of the hydrocarbon. This carbon atom is di-rectly connected to the remainder of the molecule. These hydrocarbon-based radicals are derived from aliphatic hydro-30carbons, cyclo-aliphatic hydrocarbons, aromatic hydrocar-bons, mixed aliphatic-cyclo-aliphatic hydrocarbons, mixed aliphatic aromatic hydrocarbons, and mixed cyclo-aliphatic-~1~8537 aromatic hydrocarbons. Therefore, these hydrocarbon-based radicals would be referred to as aliphatic-based radicals, cyclo-aliphatic-based radicals, etc. The base hydrocarbons from which these radicals are derived may contain certain non-reactive or substantially non-reactive polar or non-hydrocarbon substituents.
The terminology "substantially saturated" as used herein is intended to define radicals free from acetylenic unsaturation (-C-C-) in which there is not more than one 10 ethylenic linkage (-C=C-) for every 10 carbon-to-carbon (preferably 20) covalent bonds. The so-called "double bonds" in the aromatic ring (e.g., benzene) are not to be considered as contributing to unsaturation with respect to the terminology "substantially saturated". Usually there 15 will be no more than an average of one ethylenic linkage per ~ubstantially saturated monovalent radical as described herein. Preferably, (with the exception of aromatic rings) all the carbon-to-carbon bonds in a substantially saturated radical will be saturated linkages; that is, the radical 20 will be free from acetylenic and ethylenic linkages.
In general, the hydrocarbon-based radical may con-tain up to about 30 carbon atoms with a preferred range of carbon atoms being from one to about 20. The hydrocarbon-ba~ed radical~ may conta~n certain non-reactive or 8ub-25 ~tantially non-reactive polar or non-hydrocarbon substi-tuents which do not materially interfere with the reactions or compositions herein, as will be recognized by those skilled in the art. Representative non-hydrocarbon or polar substituents include halo substituents, ~uch as chloro, 30 fluoro, bromo and iodo; nitro; lower alkoxy, such as butoxy and hexyloxy; lower alkyl thio, such as pentylthio and O
heptylthio; hydroxy; mercapto; ~O- hydrocarbyl, e.g., -~-lower alkyl; hydrocarbyl O-C- hydrocarbon and the like. As 53~7 a general rule, and particularly when the compositions of this invention are to be used as lubricant additives, the degree of substitution and nature of the substituent of the hydrocarbon-based radical is such that the predominantly hydrocarbon character of the radical is not destroyed.
Thus, in view of this requirement, these radicals normally have no more than four substituents per radical, and usually, not more than one substituent for every 10 carbon atoms in the radical. Preferably, the hydrocarbon-based radical is a 10 purely hydrocarbyl (i.e., a hydrocarbon radical containing only carbon and hydrogen atoms).
The term "lower" when used herein to denote radicals such as lower alkyl is intended to describe a radical containing up to seven carbon atoms.
lS Desirable compositions of this invention include tho~e made from phosphorus-containing acids wherein each R
is hydrocarbyl, particularly, independently alkyl, aryl, alkaryl and arylalkyl of up to about 30 carbon atoms, more preferably from three to about 20 carbon atoms. The pre-20 ferred R groups are alkyl and alkaryl, preferably alkyl.
The hexavalent molybdenum oxide compounds (b)useful for this invention are water-soluble hexavalent molybdenum oxlde compounds which are acidic under aqueous condition~. The aqueou~ chemistry of hexavalent molybdenum 25 oxide compounds ls well known to those of ordinarily skill in the art and further discussion is not necessaryO
These acidic water-soluble hexavalent molybdenum compounds can be obtained from molybdenum trioxide-con-taining compounds or mixtures of two or more of these com-30pounds.
These molybdenum trioxide-containing compounds include molybdenum trioxide (MoO3) and compounds that are made from molybdenum trioxide. The molybdenum trioxiae-containing compounds include MoO3, molybdenum trioxide 35hydrates, molybdic acid, ammonium molybdate, alkali metal ~4~537 molybdates (e.g., sodium or potassium) and heteropolyacid molybdates (e.g., phosphomolybdic acid).
The preferred acidic water-soluble hexavalent molyb-denum oxide compounds are molybdenum trioxide; molybdic acid; the heteropolyacid molybdates, especially the phos-phomolybdates; those generated by acidification of alkali metal molybdates or ammonium molybdates with, e.g., hydro-chloric acid, acetic acid or sulfuric acid; and those generated in an aqueous solution of MoO3 or its hydrates, wherein the solubility in water of the MoO3 or its hydrates has been enhanced by the addition of an acid or base.
Also useful a~ (b) are the hexavalent molybdenum oxyhalides such as MoOC14, MoO2C12, MoO2Br2, Mo203C16, MoOF4 and mixtures thereof which can be hydrolyzed by water to the acidic water-soluble hexavalent molybdenum oxide compounds .
A more detailed discussion of the nature of molybdenum trioxide-containing compounds, particularly concerning the description, preparation, acidity and water solubility of these compounds, can be found in D.H. Killeffer and A. Linz, Molybdenum Compounds, Their Chemistry and Technolo~, Interscience Publishers, New York, 1952, Chapters 4, 6, 7 and 8; and F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, A Com~rehensive Text, 2nd Edition, Interscience Publisher - a division of John Wiley and Sons, New York, London, Sidney, 1966, pages 930 - 960.
Normally the hexavalent molybdenum compound (b) or its precursor is dispersed or dissolved in a polar solvent (d). Alternatively, (a) and (b), or their precursor~, may be first combined followed by the addition of (d). In some situations it may be desirable to generate (a) and/or (b) in situ, preferably in the presence of (d). In the case of (a), for example, a metal salt of the phosphorus-containing :~:14~53~
acid (e.g., alkali metal) could be acidified in the presence of (b) to yield (a). In the case of (b), for example, a molybdenum trioxide-containing compound can be used to generate an acidic water-soluble hexavalent molybdenum compound by acidifying an alkali metal molybdate in the pre~ence of (a) and (d) to generate (b) in situ.
For the purpose of this invention it is necessary that a reaction mixture of (a) and (b) is first prepared, preferably in the presence of ~d), before reaction with 10 hydrogen sulfide (c).
Hydrogen sulfide (c) is commercially available and can be introduced into the reaction chamber either above or below the surface of the reaction mixture of (a) and (b) in the presence of (d~.
Another source can be H2S generated in ~itu. For example, alkali metal sufides, e.g., Na2S, could be aci-dified with HCl to generate in H2S in the presence of (a), (b) and ~d).
The polar solvent (d) useful for this invention 20 includes water, organic polar solvents such as alcohols, ethers, ketones, and mixtures thereof. ~he preferred polar solvent (d) is water and mixtures of water and one or more other organic polar solvents. The preferred organic polar solvents are the lower alkyl alcohols, ethers and ~etones.
In addition to the polar solvents, the reaction may be carried out in the presence of a substantially inert liquid solvent/diluent medium. This solvent/diluent medium desirably serves to maintain contact of the reactants and facilitate control of the reaction temperatures. Examples 30 of suitable solvent/diluent media include aliphatic and aromatic hydrocarbons as benzene, toluene, naphtha, mineral oil, hexane; chlorinated hydrocarbons as dichlorobenzene and heptylchloride.
As used in the specification and the appended 35claims, the term "substantially inert" when used to refer to ~148537 g solvents/diluents, and the like, is intended to mean that the solvent/diluent, etc., is sufficiently inert to chemical or physical change under the conditions in which it is used 80 as not to materially interfere in an adverse manner with the preparation, storage, blending and/or functioning of the compositions, additive, compound, etc., of this invention in the context of its intended use. For example, small amounts of a solvent/diluent, etc. can undergo minimal reaction or degradation without preventing the makin~ and using of the 10 invention as described herein. In other words, such reac-tion or degradation, while technically discernible, would not be sufficient to deter the practical worker of ordinary skill in the art from making and using the invention for its intended purposes. "Substantially inert" as used herein is, 15 thus, readily understood and appreciated by those of or-dinary sklll in the art.
As used in the specification and the appended claims, the term "solvent/diluent medium" is intended to include those solvent/diluent media in which independently 20 each of the reactants are soluble or stably dispersible.
The term "stably dispersible" as used in the specification and the appended claims is intended to mean a composition (e.g., a single compound, a mixture of two or more com-pounds, etc.) i8 capable of being dispersed in a given 25 medium to an extent which allows it to function in its intended manner. Thus, for example, where a composition is prepared by a reaction in an oil, it is sufficient that the reactants be capable of being suspended in the oil in a manner sufficient to allow the reaction to occur and the 30 formation of the composition. Thus, the term ~solvent~
diluent medium" is understood and can be used in a con-ventional manner by those of ordinary skill in the art.
The product of rea~tin~ components (a), (b) and (c) in the presence of (d) may be used as a lubricant addi-35 tive, however, it is preferred that (d) be removed parti-.
~1~L8537 cularly when (d) is water. The compositions made by reac-ting (a), (b) and (c) in the presence of (d) sometimes may be accompanied by the formation of by-products and/or excess solvent/diluent medium which may lessen its commercial appeal. Accordingly, the polar solvent (d), undesirable by-products and/or excess or undesired solvent/diluent medium can be ~eparated from the compositions of this invention by techniques known in the art, e.g., filtration, evaporation ~e.g., stripping), etc., to obtain a more desirable product.
10 Alternatively, if the solvent/diluent medium is, for example, a base suitable for use in the lubricating compositions of this invention, the product can be left in the solvent/
diluent medium and used to form the lubricating compositions as described below.
A reaction mixture of ta) and (b) must first be prepared before reaction with (c) in the presence of (d).
It is preferred that (d) is present when preparing the reaction mixture of (a) and (b); and it is particularly preferred to disperse or dissolve (b) in (d) before contact 20 with (a). This reactlon mixture may be conveniently pre-pared within a temperature range of from about 0 up to about 150C., preferably from about 25C. up to about 100C.
The reaction of (a), (b) and (c) in the presence of (d) may be conveniently carried out at within the temper-25 ature range of about 0-150C. Although it is not necessary, it i9 preferred to control the temperature so that it i9 reasonably constant throughout the course of the reaction, It is particularly preferred to control the temperature within the range of from about 50C. up to about 100C.
The period of time for reaction varies with several factors including nature and amount of reactants, reaction equipment, solvent/diluent medium, degree of mixing, and the like.
For the purposes of this invention, the molecular 35weight of a phosphorus-containing acid (a) is e~ual to its ~1~8~37 equivalent weight and, therefore, one mole of ~a) is equal to its equivalent weight, which is determined by substituting its "acid number" in the following equation:
56,100 milligrams of KOH~equivalent Equ~valent welght =
acid number (milligrams of KOH/gram) The "acld number" is defined as the number of milligrams of KOH used to raise the pH of one gram of sample under aqueous conditions to about 4Ø The pH of about 4.0 can be deter-mined by the use of an indicator that changes color in the range of 3.0 to 4.5 such as bromphenol blue or by electrical 10 means such as a pH-meter.
For the purposes of this invention, the ratio of reactants (a) to (b) is from about 0.5 up to about four moles of the phosphorus-containing acid (a) per mole of molybdenum in (b) (e.g., one mole of Na2MoO4 contains one 15 mole of molybdenum; ammonium paramolybdate, (NH4) ~07024-4H20, contains seven moles of molybdenum). A ratio of at least about 0.5 mole of hydrogen sulfide per mole of molybdenum in the reaction mixture of (a) and (b) is desirable.
Therefore, the range ratios of (a):(b):(c) i8 from 20 about 0.5 up to about four mole~ of (a):one mole of molyb-denum in (b):at least 0.5 mole of H2S. A ratio of about 1:1:1.5 is optimum, although an excess ti.e., 1:1:~1.5) of hydrogen 3ulfide can be used to insure complete reaction. A
ratio of 1:1:4 or more may be used, but a ratio of 1:1:2 25 should be sufficient to insure complete reaction. Excess hydrogen sulfide can be removed by blowing the reaction mixture with an inert gas such as nitrogen.
The polar solvent (d) is essentially a promotor or contact agent. m erefore, minlmum amount of polar solvent 30 (d) iæ that amount necessary for the reaction of (a), (b) and (c) to proceed (i.e., the point at which the hydrogen sulfide will react with (a) and (b) in the presence of (d)).
, Generally, enough (d) is used to disperse or, preferably, dissolve the molybdenum trioxide containing compounds or the molybdenum-oxyhalide compounds previously described.
Usually from about one up to about four parts of (d) will be used for each part by weight of the above-described molyb-denum compound used. Substantial amounts of (d) in excess of this would not b~ uncommon, but would not be advanta-geous.
This invention is exemplified in the following 10 examples. Of course, these examples are not intended as limiting this invention as modification of the examples by ordinary expedients will be readily apparent to those of ordinary skill in the art.
In all examples, unless otherwise stated, all 15 temperatures are in C.; all part~ are parts by weight and all percentages are derived from parts by weight.
Example 1 A reaction mixture is prepared by the addition of 2035 parts t9.17 mole~) of P2Ss to 7335 parts (36.68 moles) 20 of a commercially available Cl2-l4 alcohol at 80C. under a nitrogen blanket. The P2Ss is added over a two-hour perlod and the exotherm lncreases the temperature to 95C. during the addltion period. The hydrogen sulfide formed as a result of the reaction is removed continuously and trapped 25 by caustic soda solution. The reaction mixture is allowed to cool while stirring for two hours under nitrogen. ~he reaction mixture is filtered to yield the de~ired O,O-di-Cl2-l4 phosphorodithioic acid which has an acid number of 96.
30 Example 2 The procedure for Example 1 is repeated except the Cl 2-14 alcohol is replaced on an equimolar basis with 2-ethylhexyl alcohol to yield the desired O,O-di-2-ethylhexyl phosphorodithioic acid which has an acid number of 137.
53~7 Example 3 A reaction mixture is prepared by adding a mixture of 584 parts (1 mole) of the O,Q-di-Cl 2-14 phosphorodithioic acid prepared in Example 1 and 500 parts of toluene to a room temperature (26C.) solution of 40 parts (1 mole) of sodium hydroxide, 190 parts of water and 144 parts (1 mole) of molybdenum trioxide prepared by heating until a clear solution is obtained. After the addition is complete, 100 parts (1 equivalent~ of concentrated hydrochloric acid is 10 added to the reaction mixture. The reaction mixture is heated at 40C. for two hours.
Hydrogen sulfide (90 parts; 2.6 moles) is added to the reaction mixture by subsurface addition over a period of three hours. During the hydrogen sulfide addition, the 15 temperature of the reaction mixture i8 increased to 90C.
The reaction mixture is then purged of excess hydrogen sulfide by blowing with nitrogen, stripped under vacuum at 94C. and filtered to yield the desired sulfur-, phosphorus- and molybdenum-containing composition made from 20 an O,O-di-Cl 2-I 4 phosphorodithioic acid.
Example 4 A reaction mixture iB prepared by the addition of 3,275 parts (8 moles) of the O,O-di-2-ethylhexylphosphoro-dithioic acid prepared in Example 2 to a room temperature 25 slurry of 1,152 parts ~8.0 moles) of molybdenum trioxide in 2,000 parts of water. The reaction mixture is heated to 80C. and 533 parts hydrogen sulfide is added by subsurface addition over a 6.5-hour period. The reaction mixture is maintained at 80-90C. during the hydrogen sulfide addition.
30 The reaction mixture is then purged of excess hydrogen sulfide by blowing with nitrogen and stripped at 95-100C.
under vacuum to yield the residue as the desired sulfur-, phosphorus- and molybdenum-containing composition made from an O,O-di-2-ethylhexylphosphorodithioic acid.
5~37 Example 5 An aqueous solution of phosphomolybdic acid is prepared by heating 360 parts (2.5 moles) of molybdenum trioxide, 24 parts of 85% phosphoric acid and 2,000 parts of water at boiling for three hours, then filtering through filter paper and washing the residue with 150 parts of water. The total volume of the resulting solution is reduced to yield 921 parts of solution containing 19.37%
molybdenum.
10 Example 6 A reaction mixture is prepared by the dropwise addition of 1,475 parts (3.0 moles) of the phosphomolybdic acid prepared in Example 5 to 1,228 parts (3 moles) of the O,O-di-2-ethylhexylphosphorodithioic acid prepared in 15 Example 2 at room temperature over a one-hour period. The reaction mixture is then held at 55C. for 3.5 hours. ~he reaction mixture is heated to reflux while blowing with hydrogen sulfide beneath the surface. The reaction mixture $s held at 90-95C. for three hours during which hydrogen 20 gulfide blowing is continued. A total of 242 parts of hydrogen sulfide is added to the reaction mixture. The reaction mixture is then purged of excess hydrogen sulfide by blowing with nitrogen. Toluene ~1000 parts~ is added to the reaction mixture and water is removed by azeotropic 25 distillation. The reaction mixture is filtered and then stripped of toluene at 95C. under vacuum to yield the desired sulfur-, pho~phorus- and molybdenum-containing composition made from an O,O-di-2-ethylhexylphosphorodi~
thioic acid.
30 Example 7 A reaction mixture is prepared by adding a mixture of 2050 parts (5.0 moles) of the O,O-di-2-ethylhexylphos-phorodithioic acid prepared in Example 2 and 2,500 parts of ~1~85~7 toluene to a room temperature solution prepared by heating parts (5 moles) of sodium hydroxide, 1,000 parts of water and 720 parts t5.0 moles) of molybdenum trioxide until a clear solution is obtained and then adding 39 parts (0.25 mole) of 85~ phosphoric acid to the solution. After addi-tion is complete, 500 parts (5 moles) of concentrated hydro-chloric acid is added to the reaction mixture and then heated at 40C. for two hours. Hydrogen sulfide (31~ parts;
9.35 moles) is added to the reaction mixture by subsurface 10 addition over a period of ten hours. During the hydrogen sulfide addition, the temperature of the reaction mixture is increased to reflux. ~he reaction mixture is then purged of excess hydrogen sulfide by blowing with ni~rogen and strip-ped under vacuum at 90C. Toluene (2,000 parts) is added to 15 the reactlon mixture which i8 filtered and then stripped to yield the desired sulfur-, phosphorus- and molybdenum-containing composition made from O,O-di-2-ethylhexylphos-phorodithioic acid.
Example 8 A reaction mixture of 1,152 parts (8 moles) of molybdenum trioxide, 77 parts (0.67 mole) of 85~ phosphoric acid, 3,000 parts of water and 3,275 parts (8 moles) of O,O-di-2-ethylhexylphosphorodithioic acid prepared in Example 2 is heated to 85C. To the reaction mixture 533 parts of 25 hydrogen sulfide is added by subsurface addition over a 6.5-hour period. The reaction mixture is maintained at 80-90C.
during the hydrogen sulfide addition. The reaction mixture is then purged of excess hydrogen sulfide by blowlng with nitrogen and stripped at 95-100C. under vacuum to yield the 30 residue as the desired sulfur-, phosphorus- and molybdenum-containing composition made from an O,O-di-2-ethylhexyl-phosphorodithioic acid.
As previously indicated, the compositions of this invention are also useful as additives for lubricants, in ~8~37 which they function primarily as oxidation inhibitors, antiwear and/or extreme pressure agents and friction modi-fiers. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including 5 natural and synthetic lubricating oils and mixtures thereof.
These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel 10 engines, and the like. Ihey can also be used in gas en-gines, stationary power engines and turbines and the like.
Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also 15 benefit from the incorporation therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liquid petro-leum oils and solvent-treated or acid-treated mineral 20 lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating visco~ity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and 25 interpolymerized olefins [e.g., polybutylenes, polypro-pylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-aecenes), etc. and mixtures thereof]; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-30 ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and 35 derivatives thereof where the terminal hydroxyl groups have ~1~85~37 been modified by esterification, etherification, etc. con-stitute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through poly-merization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers ~e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-10 1500~ etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C~ fatty acid esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., 15 phthalic acid, succinic acid, alkyl succlnic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic ac~ds, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl al-20 cohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, dilsodecyl 25 azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those made from Cs to Cl 2 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, poly-35 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-853~
cate oils comprise another useful class of synthetic lubri-cants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-s methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly-~methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahy-lOdrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-inabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained 15directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further 20treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more propextie~. Many such purification techniques are known to those of skill in the art such as solvent extraction, 25acid or base extraction, filtration, percolation, etc.
Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are 30additionally processed by techniques directed to removal of spent additives and oil breakdown products.
Generally, the lubricants of the present invention contain an amount of the composition of this invention sufficient to provide it with improved oxidation stability 35and/or antiwear and/or extreme pressure and/or friction reducing properties. Normally this amount will be about 0.05% to about 20%. Preferably about 0.1% to about 10~, more preferably up to about 5% and typically about 0.5% to about 2% of the total weight of the lubricant. In lubri-5 cating oils operated under extremely adverse conditions,such as lubricating oils for marine diesel engines, the reaction products of this invention may be present in amounts of up to about 30% by weight.
The invention also contemplates the use of other lOadditives in combination with the compositions of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers l5and anti-foam agent~.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or Organic phosphorus acids characterized by at least one 20direct carbon-to-phosphorw3 lin~age such as tho~e prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a pho~phorizing agent such a~ phosphorus trichloride, phosphoru~ hepta-sulfide, pho~phoru~ pentasulfide, phosphorus trichloride and 25sulfur, white pho~phorus and a sulfur halide, or phosphoro-thioic chloride. ~he most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal 30salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. ~he commonly employed methods for preparing the basic salts involve heat-ing a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal 350xide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include 5 phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation pro-ducts of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl 10 alcohol: and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol 15 promoter, and carbonating the mixture at an elevated tem-perature such as 60-200C.
Auxiliary ashless detergents and dispersants are so called despite the fact that, depending on its constitu-tion, the dispersant may upon combustion yield a non-vola-20 tile material such as boric oxide or phosphorus pentoxide;however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for u~e in the lubricant~ of this invention. The following are 25 illustrative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and pre-ferably at least about 54 carbon atoms with nitrogen-con-taining compounds such as amine, organic hydroxy compounds 30 such as phenols and alcohols, and/or basic inorganic ma-terials. Examples of these "carboxylic dispersants~ are described in British Patent 1,306,529 and in many U.S.
patents including the following:
3,163,603 3,351,552 3,541,012 3,184,474 3,381,022 3,542,678 3,215,707 3,399,141 3,542,680 1~48S~37 3,219,666 3,415,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,~44,170 3,576,743 3,281,357 3,448,048 3,630,904 3,306,gO8 3,448,049 3,632,510 3,311,558 3,451,933 3,632,511 3,316,177 3,454,607 3,697,428 3,340,281 3,467,668 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,179 (2) Reaction products of relatively high molecu-lar weight aliphatic or alicyclic halides with amines, pre-ferably polyalkylene polyamines. These may be characterized as "amine dispersants" and examples thereof are described 15 for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with 20 aldehydes ~especially formaldehyde) and amines (especially polyalkylene polyamines), which may be characterized as "Mannich dispersants". The materials described in the following U.S. patents are illustrative:
3,413,347 3,725,480 3,~97,574 3,726,882 3,725,277 (4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersant~ with such reagents a~
urea, thiourea, carbon disulfide, aldehydes, ketones, car-30boxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S. patents:
~14~537 3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,g36 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,5gl,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522 (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These may be charac-terized as "polymeric dispersants" and examples thereof are disclosed in the following U. S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 Extreme pressure agents and corrosion-and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)-disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus qulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclo-hexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, X~
8~37 polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phos-phorodithioates such as zinc dicyclohexylphosphorodithioate,zinc dioctylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mix-10 ture of isopropyl alcohol and n-hexyl alcohol.
The compositions of this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or 15 xylene, to form an additive concentrate. These concentrates u8ually contain about 20-90~ by weight of the composition of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove.
The lubricating compositions made according to 20 this invention can be exemplified by a lubricating compo-sition prepared by treating a mineral oil of lubricating viscosity with 1% by weight of the product of Example 8.
o\ll P-SH;
~0 (CsHIl) S
Preferred acids of the formula [(RO)2PSH] are readily obtainable from the reaction of phosphorus penta-sulfide (P2S5) and an alcohol or a phenol. The reaction in-volves mixing at a temperature of about 20 to about 200C., 4 moles of the alcohol or a phenol with one mole of phos-10 phorus pentasulfide. Hydrogen sulfide is liberated in this reaction. The oxygen-containing analogs of these acids are conveniently prepared by treating the preferred dithioic acid with water or steam which, in effect, replaces one or both of the sulfur atoms.
Thus, as prev~ously mentioned, the preferred phosphorus-containing acids are phosphorus- and sulfur-containing acids. These preferred acids more preferably include those wherein at least one ~ is sulfur, more pre-ferably both of X are sulfur; at least one X' i8 oxygen or 20 sulfur, more preferably both of X' are oxygen and n is 1.
Mixtures of acids may be employed according to this in-vention.
The terminology of "hydrocarbon-based radical n ag u~ed herein, (nherein" includes the appended claims) is used 25to define a substantially saturated monovalent rad~cal derived from a hydrocarbon by removal of a hydrogen from a carbon atom of the hydrocarbon. This carbon atom is di-rectly connected to the remainder of the molecule. These hydrocarbon-based radicals are derived from aliphatic hydro-30carbons, cyclo-aliphatic hydrocarbons, aromatic hydrocar-bons, mixed aliphatic-cyclo-aliphatic hydrocarbons, mixed aliphatic aromatic hydrocarbons, and mixed cyclo-aliphatic-~1~8537 aromatic hydrocarbons. Therefore, these hydrocarbon-based radicals would be referred to as aliphatic-based radicals, cyclo-aliphatic-based radicals, etc. The base hydrocarbons from which these radicals are derived may contain certain non-reactive or substantially non-reactive polar or non-hydrocarbon substituents.
The terminology "substantially saturated" as used herein is intended to define radicals free from acetylenic unsaturation (-C-C-) in which there is not more than one 10 ethylenic linkage (-C=C-) for every 10 carbon-to-carbon (preferably 20) covalent bonds. The so-called "double bonds" in the aromatic ring (e.g., benzene) are not to be considered as contributing to unsaturation with respect to the terminology "substantially saturated". Usually there 15 will be no more than an average of one ethylenic linkage per ~ubstantially saturated monovalent radical as described herein. Preferably, (with the exception of aromatic rings) all the carbon-to-carbon bonds in a substantially saturated radical will be saturated linkages; that is, the radical 20 will be free from acetylenic and ethylenic linkages.
In general, the hydrocarbon-based radical may con-tain up to about 30 carbon atoms with a preferred range of carbon atoms being from one to about 20. The hydrocarbon-ba~ed radical~ may conta~n certain non-reactive or 8ub-25 ~tantially non-reactive polar or non-hydrocarbon substi-tuents which do not materially interfere with the reactions or compositions herein, as will be recognized by those skilled in the art. Representative non-hydrocarbon or polar substituents include halo substituents, ~uch as chloro, 30 fluoro, bromo and iodo; nitro; lower alkoxy, such as butoxy and hexyloxy; lower alkyl thio, such as pentylthio and O
heptylthio; hydroxy; mercapto; ~O- hydrocarbyl, e.g., -~-lower alkyl; hydrocarbyl O-C- hydrocarbon and the like. As 53~7 a general rule, and particularly when the compositions of this invention are to be used as lubricant additives, the degree of substitution and nature of the substituent of the hydrocarbon-based radical is such that the predominantly hydrocarbon character of the radical is not destroyed.
Thus, in view of this requirement, these radicals normally have no more than four substituents per radical, and usually, not more than one substituent for every 10 carbon atoms in the radical. Preferably, the hydrocarbon-based radical is a 10 purely hydrocarbyl (i.e., a hydrocarbon radical containing only carbon and hydrogen atoms).
The term "lower" when used herein to denote radicals such as lower alkyl is intended to describe a radical containing up to seven carbon atoms.
lS Desirable compositions of this invention include tho~e made from phosphorus-containing acids wherein each R
is hydrocarbyl, particularly, independently alkyl, aryl, alkaryl and arylalkyl of up to about 30 carbon atoms, more preferably from three to about 20 carbon atoms. The pre-20 ferred R groups are alkyl and alkaryl, preferably alkyl.
The hexavalent molybdenum oxide compounds (b)useful for this invention are water-soluble hexavalent molybdenum oxlde compounds which are acidic under aqueous condition~. The aqueou~ chemistry of hexavalent molybdenum 25 oxide compounds ls well known to those of ordinarily skill in the art and further discussion is not necessaryO
These acidic water-soluble hexavalent molybdenum compounds can be obtained from molybdenum trioxide-con-taining compounds or mixtures of two or more of these com-30pounds.
These molybdenum trioxide-containing compounds include molybdenum trioxide (MoO3) and compounds that are made from molybdenum trioxide. The molybdenum trioxiae-containing compounds include MoO3, molybdenum trioxide 35hydrates, molybdic acid, ammonium molybdate, alkali metal ~4~537 molybdates (e.g., sodium or potassium) and heteropolyacid molybdates (e.g., phosphomolybdic acid).
The preferred acidic water-soluble hexavalent molyb-denum oxide compounds are molybdenum trioxide; molybdic acid; the heteropolyacid molybdates, especially the phos-phomolybdates; those generated by acidification of alkali metal molybdates or ammonium molybdates with, e.g., hydro-chloric acid, acetic acid or sulfuric acid; and those generated in an aqueous solution of MoO3 or its hydrates, wherein the solubility in water of the MoO3 or its hydrates has been enhanced by the addition of an acid or base.
Also useful a~ (b) are the hexavalent molybdenum oxyhalides such as MoOC14, MoO2C12, MoO2Br2, Mo203C16, MoOF4 and mixtures thereof which can be hydrolyzed by water to the acidic water-soluble hexavalent molybdenum oxide compounds .
A more detailed discussion of the nature of molybdenum trioxide-containing compounds, particularly concerning the description, preparation, acidity and water solubility of these compounds, can be found in D.H. Killeffer and A. Linz, Molybdenum Compounds, Their Chemistry and Technolo~, Interscience Publishers, New York, 1952, Chapters 4, 6, 7 and 8; and F.A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, A Com~rehensive Text, 2nd Edition, Interscience Publisher - a division of John Wiley and Sons, New York, London, Sidney, 1966, pages 930 - 960.
Normally the hexavalent molybdenum compound (b) or its precursor is dispersed or dissolved in a polar solvent (d). Alternatively, (a) and (b), or their precursor~, may be first combined followed by the addition of (d). In some situations it may be desirable to generate (a) and/or (b) in situ, preferably in the presence of (d). In the case of (a), for example, a metal salt of the phosphorus-containing :~:14~53~
acid (e.g., alkali metal) could be acidified in the presence of (b) to yield (a). In the case of (b), for example, a molybdenum trioxide-containing compound can be used to generate an acidic water-soluble hexavalent molybdenum compound by acidifying an alkali metal molybdate in the pre~ence of (a) and (d) to generate (b) in situ.
For the purpose of this invention it is necessary that a reaction mixture of (a) and (b) is first prepared, preferably in the presence of ~d), before reaction with 10 hydrogen sulfide (c).
Hydrogen sulfide (c) is commercially available and can be introduced into the reaction chamber either above or below the surface of the reaction mixture of (a) and (b) in the presence of (d~.
Another source can be H2S generated in ~itu. For example, alkali metal sufides, e.g., Na2S, could be aci-dified with HCl to generate in H2S in the presence of (a), (b) and ~d).
The polar solvent (d) useful for this invention 20 includes water, organic polar solvents such as alcohols, ethers, ketones, and mixtures thereof. ~he preferred polar solvent (d) is water and mixtures of water and one or more other organic polar solvents. The preferred organic polar solvents are the lower alkyl alcohols, ethers and ~etones.
In addition to the polar solvents, the reaction may be carried out in the presence of a substantially inert liquid solvent/diluent medium. This solvent/diluent medium desirably serves to maintain contact of the reactants and facilitate control of the reaction temperatures. Examples 30 of suitable solvent/diluent media include aliphatic and aromatic hydrocarbons as benzene, toluene, naphtha, mineral oil, hexane; chlorinated hydrocarbons as dichlorobenzene and heptylchloride.
As used in the specification and the appended 35claims, the term "substantially inert" when used to refer to ~148537 g solvents/diluents, and the like, is intended to mean that the solvent/diluent, etc., is sufficiently inert to chemical or physical change under the conditions in which it is used 80 as not to materially interfere in an adverse manner with the preparation, storage, blending and/or functioning of the compositions, additive, compound, etc., of this invention in the context of its intended use. For example, small amounts of a solvent/diluent, etc. can undergo minimal reaction or degradation without preventing the makin~ and using of the 10 invention as described herein. In other words, such reac-tion or degradation, while technically discernible, would not be sufficient to deter the practical worker of ordinary skill in the art from making and using the invention for its intended purposes. "Substantially inert" as used herein is, 15 thus, readily understood and appreciated by those of or-dinary sklll in the art.
As used in the specification and the appended claims, the term "solvent/diluent medium" is intended to include those solvent/diluent media in which independently 20 each of the reactants are soluble or stably dispersible.
The term "stably dispersible" as used in the specification and the appended claims is intended to mean a composition (e.g., a single compound, a mixture of two or more com-pounds, etc.) i8 capable of being dispersed in a given 25 medium to an extent which allows it to function in its intended manner. Thus, for example, where a composition is prepared by a reaction in an oil, it is sufficient that the reactants be capable of being suspended in the oil in a manner sufficient to allow the reaction to occur and the 30 formation of the composition. Thus, the term ~solvent~
diluent medium" is understood and can be used in a con-ventional manner by those of ordinary skill in the art.
The product of rea~tin~ components (a), (b) and (c) in the presence of (d) may be used as a lubricant addi-35 tive, however, it is preferred that (d) be removed parti-.
~1~L8537 cularly when (d) is water. The compositions made by reac-ting (a), (b) and (c) in the presence of (d) sometimes may be accompanied by the formation of by-products and/or excess solvent/diluent medium which may lessen its commercial appeal. Accordingly, the polar solvent (d), undesirable by-products and/or excess or undesired solvent/diluent medium can be ~eparated from the compositions of this invention by techniques known in the art, e.g., filtration, evaporation ~e.g., stripping), etc., to obtain a more desirable product.
10 Alternatively, if the solvent/diluent medium is, for example, a base suitable for use in the lubricating compositions of this invention, the product can be left in the solvent/
diluent medium and used to form the lubricating compositions as described below.
A reaction mixture of ta) and (b) must first be prepared before reaction with (c) in the presence of (d).
It is preferred that (d) is present when preparing the reaction mixture of (a) and (b); and it is particularly preferred to disperse or dissolve (b) in (d) before contact 20 with (a). This reactlon mixture may be conveniently pre-pared within a temperature range of from about 0 up to about 150C., preferably from about 25C. up to about 100C.
The reaction of (a), (b) and (c) in the presence of (d) may be conveniently carried out at within the temper-25 ature range of about 0-150C. Although it is not necessary, it i9 preferred to control the temperature so that it i9 reasonably constant throughout the course of the reaction, It is particularly preferred to control the temperature within the range of from about 50C. up to about 100C.
The period of time for reaction varies with several factors including nature and amount of reactants, reaction equipment, solvent/diluent medium, degree of mixing, and the like.
For the purposes of this invention, the molecular 35weight of a phosphorus-containing acid (a) is e~ual to its ~1~8~37 equivalent weight and, therefore, one mole of ~a) is equal to its equivalent weight, which is determined by substituting its "acid number" in the following equation:
56,100 milligrams of KOH~equivalent Equ~valent welght =
acid number (milligrams of KOH/gram) The "acld number" is defined as the number of milligrams of KOH used to raise the pH of one gram of sample under aqueous conditions to about 4Ø The pH of about 4.0 can be deter-mined by the use of an indicator that changes color in the range of 3.0 to 4.5 such as bromphenol blue or by electrical 10 means such as a pH-meter.
For the purposes of this invention, the ratio of reactants (a) to (b) is from about 0.5 up to about four moles of the phosphorus-containing acid (a) per mole of molybdenum in (b) (e.g., one mole of Na2MoO4 contains one 15 mole of molybdenum; ammonium paramolybdate, (NH4) ~07024-4H20, contains seven moles of molybdenum). A ratio of at least about 0.5 mole of hydrogen sulfide per mole of molybdenum in the reaction mixture of (a) and (b) is desirable.
Therefore, the range ratios of (a):(b):(c) i8 from 20 about 0.5 up to about four mole~ of (a):one mole of molyb-denum in (b):at least 0.5 mole of H2S. A ratio of about 1:1:1.5 is optimum, although an excess ti.e., 1:1:~1.5) of hydrogen 3ulfide can be used to insure complete reaction. A
ratio of 1:1:4 or more may be used, but a ratio of 1:1:2 25 should be sufficient to insure complete reaction. Excess hydrogen sulfide can be removed by blowing the reaction mixture with an inert gas such as nitrogen.
The polar solvent (d) is essentially a promotor or contact agent. m erefore, minlmum amount of polar solvent 30 (d) iæ that amount necessary for the reaction of (a), (b) and (c) to proceed (i.e., the point at which the hydrogen sulfide will react with (a) and (b) in the presence of (d)).
, Generally, enough (d) is used to disperse or, preferably, dissolve the molybdenum trioxide containing compounds or the molybdenum-oxyhalide compounds previously described.
Usually from about one up to about four parts of (d) will be used for each part by weight of the above-described molyb-denum compound used. Substantial amounts of (d) in excess of this would not b~ uncommon, but would not be advanta-geous.
This invention is exemplified in the following 10 examples. Of course, these examples are not intended as limiting this invention as modification of the examples by ordinary expedients will be readily apparent to those of ordinary skill in the art.
In all examples, unless otherwise stated, all 15 temperatures are in C.; all part~ are parts by weight and all percentages are derived from parts by weight.
Example 1 A reaction mixture is prepared by the addition of 2035 parts t9.17 mole~) of P2Ss to 7335 parts (36.68 moles) 20 of a commercially available Cl2-l4 alcohol at 80C. under a nitrogen blanket. The P2Ss is added over a two-hour perlod and the exotherm lncreases the temperature to 95C. during the addltion period. The hydrogen sulfide formed as a result of the reaction is removed continuously and trapped 25 by caustic soda solution. The reaction mixture is allowed to cool while stirring for two hours under nitrogen. ~he reaction mixture is filtered to yield the de~ired O,O-di-Cl2-l4 phosphorodithioic acid which has an acid number of 96.
30 Example 2 The procedure for Example 1 is repeated except the Cl 2-14 alcohol is replaced on an equimolar basis with 2-ethylhexyl alcohol to yield the desired O,O-di-2-ethylhexyl phosphorodithioic acid which has an acid number of 137.
53~7 Example 3 A reaction mixture is prepared by adding a mixture of 584 parts (1 mole) of the O,Q-di-Cl 2-14 phosphorodithioic acid prepared in Example 1 and 500 parts of toluene to a room temperature (26C.) solution of 40 parts (1 mole) of sodium hydroxide, 190 parts of water and 144 parts (1 mole) of molybdenum trioxide prepared by heating until a clear solution is obtained. After the addition is complete, 100 parts (1 equivalent~ of concentrated hydrochloric acid is 10 added to the reaction mixture. The reaction mixture is heated at 40C. for two hours.
Hydrogen sulfide (90 parts; 2.6 moles) is added to the reaction mixture by subsurface addition over a period of three hours. During the hydrogen sulfide addition, the 15 temperature of the reaction mixture i8 increased to 90C.
The reaction mixture is then purged of excess hydrogen sulfide by blowing with nitrogen, stripped under vacuum at 94C. and filtered to yield the desired sulfur-, phosphorus- and molybdenum-containing composition made from 20 an O,O-di-Cl 2-I 4 phosphorodithioic acid.
Example 4 A reaction mixture iB prepared by the addition of 3,275 parts (8 moles) of the O,O-di-2-ethylhexylphosphoro-dithioic acid prepared in Example 2 to a room temperature 25 slurry of 1,152 parts ~8.0 moles) of molybdenum trioxide in 2,000 parts of water. The reaction mixture is heated to 80C. and 533 parts hydrogen sulfide is added by subsurface addition over a 6.5-hour period. The reaction mixture is maintained at 80-90C. during the hydrogen sulfide addition.
30 The reaction mixture is then purged of excess hydrogen sulfide by blowing with nitrogen and stripped at 95-100C.
under vacuum to yield the residue as the desired sulfur-, phosphorus- and molybdenum-containing composition made from an O,O-di-2-ethylhexylphosphorodithioic acid.
5~37 Example 5 An aqueous solution of phosphomolybdic acid is prepared by heating 360 parts (2.5 moles) of molybdenum trioxide, 24 parts of 85% phosphoric acid and 2,000 parts of water at boiling for three hours, then filtering through filter paper and washing the residue with 150 parts of water. The total volume of the resulting solution is reduced to yield 921 parts of solution containing 19.37%
molybdenum.
10 Example 6 A reaction mixture is prepared by the dropwise addition of 1,475 parts (3.0 moles) of the phosphomolybdic acid prepared in Example 5 to 1,228 parts (3 moles) of the O,O-di-2-ethylhexylphosphorodithioic acid prepared in 15 Example 2 at room temperature over a one-hour period. The reaction mixture is then held at 55C. for 3.5 hours. ~he reaction mixture is heated to reflux while blowing with hydrogen sulfide beneath the surface. The reaction mixture $s held at 90-95C. for three hours during which hydrogen 20 gulfide blowing is continued. A total of 242 parts of hydrogen sulfide is added to the reaction mixture. The reaction mixture is then purged of excess hydrogen sulfide by blowing with nitrogen. Toluene ~1000 parts~ is added to the reaction mixture and water is removed by azeotropic 25 distillation. The reaction mixture is filtered and then stripped of toluene at 95C. under vacuum to yield the desired sulfur-, pho~phorus- and molybdenum-containing composition made from an O,O-di-2-ethylhexylphosphorodi~
thioic acid.
30 Example 7 A reaction mixture is prepared by adding a mixture of 2050 parts (5.0 moles) of the O,O-di-2-ethylhexylphos-phorodithioic acid prepared in Example 2 and 2,500 parts of ~1~85~7 toluene to a room temperature solution prepared by heating parts (5 moles) of sodium hydroxide, 1,000 parts of water and 720 parts t5.0 moles) of molybdenum trioxide until a clear solution is obtained and then adding 39 parts (0.25 mole) of 85~ phosphoric acid to the solution. After addi-tion is complete, 500 parts (5 moles) of concentrated hydro-chloric acid is added to the reaction mixture and then heated at 40C. for two hours. Hydrogen sulfide (31~ parts;
9.35 moles) is added to the reaction mixture by subsurface 10 addition over a period of ten hours. During the hydrogen sulfide addition, the temperature of the reaction mixture is increased to reflux. ~he reaction mixture is then purged of excess hydrogen sulfide by blowing with ni~rogen and strip-ped under vacuum at 90C. Toluene (2,000 parts) is added to 15 the reactlon mixture which i8 filtered and then stripped to yield the desired sulfur-, phosphorus- and molybdenum-containing composition made from O,O-di-2-ethylhexylphos-phorodithioic acid.
Example 8 A reaction mixture of 1,152 parts (8 moles) of molybdenum trioxide, 77 parts (0.67 mole) of 85~ phosphoric acid, 3,000 parts of water and 3,275 parts (8 moles) of O,O-di-2-ethylhexylphosphorodithioic acid prepared in Example 2 is heated to 85C. To the reaction mixture 533 parts of 25 hydrogen sulfide is added by subsurface addition over a 6.5-hour period. The reaction mixture is maintained at 80-90C.
during the hydrogen sulfide addition. The reaction mixture is then purged of excess hydrogen sulfide by blowlng with nitrogen and stripped at 95-100C. under vacuum to yield the 30 residue as the desired sulfur-, phosphorus- and molybdenum-containing composition made from an O,O-di-2-ethylhexyl-phosphorodithioic acid.
As previously indicated, the compositions of this invention are also useful as additives for lubricants, in ~8~37 which they function primarily as oxidation inhibitors, antiwear and/or extreme pressure agents and friction modi-fiers. They can be employed in a variety of lubricants based on diverse oils of lubricating viscosity, including 5 natural and synthetic lubricating oils and mixtures thereof.
These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel 10 engines, and the like. Ihey can also be used in gas en-gines, stationary power engines and turbines and the like.
Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also 15 benefit from the incorporation therein of the compositions of the present invention.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard oil) as well as liquid petro-leum oils and solvent-treated or acid-treated mineral 20 lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Oils of lubricating visco~ity derived from coal or shale are also useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and 25 interpolymerized olefins [e.g., polybutylenes, polypro-pylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l-octenes), poly(l-aecenes), etc. and mixtures thereof]; alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-30 ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyls, alkylated polyphenyls, etc.), alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof and the like.
Alkylene oxide polymers and interpolymers and 35 derivatives thereof where the terminal hydroxyl groups have ~1~85~37 been modified by esterification, etherification, etc. con-stitute another class of known synthetic lubricating oils.
These are exemplified by the oils prepared through poly-merization of ethylene oxide or propylene oxide, the alkyl and aryl ethers of these polyoxyalkylene polymers ~e.g., methyl-polyisopropylene glycol ether having an average molecular weight of 1000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1000-10 1500~ etc.) or mono- and polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-C~ fatty acid esters, or the C~ 3 OXO acid diester of tetraethylene glycol.
Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., 15 phthalic acid, succinic acid, alkyl succlnic acids and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic ac~ds, alkenyl malonic acids, etc.) with a variety of alcohols (e.g., butyl al-20 cohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, dilsodecyl 25 azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid, and the like.
Esters useful as synthetic oils also include those made from Cs to Cl 2 monocarboxylic acids and polyols and polyol ethers such neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.
Silicon-based oils such as the polyalkyl-, poly-35 aryl-, polyalkoxy-, or polyaryloxy-siloxane oils and sili-853~
cate oils comprise another useful class of synthetic lubri-cants (e.g., tetraethyl silicate, tetraisopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-s methyl-2-pentoxy)-disiloxane, poly(methyl)-siloxanes, poly-~methylphenyl)siloxanes, etc.). Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymeric tetrahy-lOdrofurans and the like.
Unrefined, refined and rerefined oils (and mix-tures of each with each other) of the type disclosed here-inabove can be used in the lubricant compositions of the present invention. Unrefined oils are those obtained 15directly from a natural or synthetic source without further purification treatment. For example, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further 20treatment would be an unrefined oil. Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more propextie~. Many such purification techniques are known to those of skill in the art such as solvent extraction, 25acid or base extraction, filtration, percolation, etc.
Rerefined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such rerefined oils are also known as reclaimed or reprocessed oils and often are 30additionally processed by techniques directed to removal of spent additives and oil breakdown products.
Generally, the lubricants of the present invention contain an amount of the composition of this invention sufficient to provide it with improved oxidation stability 35and/or antiwear and/or extreme pressure and/or friction reducing properties. Normally this amount will be about 0.05% to about 20%. Preferably about 0.1% to about 10~, more preferably up to about 5% and typically about 0.5% to about 2% of the total weight of the lubricant. In lubri-5 cating oils operated under extremely adverse conditions,such as lubricating oils for marine diesel engines, the reaction products of this invention may be present in amounts of up to about 30% by weight.
The invention also contemplates the use of other lOadditives in combination with the compositions of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ash-producing or ashless type, corrosion- and oxidation-inhibiting agents, pour point depressing agents, extreme pressure agents, color stabilizers l5and anti-foam agent~.
The ash-producing detergents are exemplified by oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids, or Organic phosphorus acids characterized by at least one 20direct carbon-to-phosphorw3 lin~age such as tho~e prepared by the treatment of an olefin polymer (e.g., polyisobutene having a molecular weight of 1000) with a pho~phorizing agent such a~ phosphorus trichloride, phosphoru~ hepta-sulfide, pho~phoru~ pentasulfide, phosphorus trichloride and 25sulfur, white pho~phorus and a sulfur halide, or phosphoro-thioic chloride. ~he most commonly used salts of such acids are those of sodium, potassium, lithium, calcium, magnesium, strontium and barium.
The term "basic salt" is used to designate metal 30salts wherein the metal is present in stoichiometrically larger amounts than the organic acid radical. ~he commonly employed methods for preparing the basic salts involve heat-ing a mineral oil solution of an acid with a stoichiometric excess of a metal neutralizing agent such as the metal 350xide, hydroxide, carbonate, bicarbonate, or sulfide at a temperature above 50C. and filtering the resulting mass.
The use of a "promoter" in the neutralization step to aid the incorporation of a large excess of metal likewise is known. Examples of compounds useful as the promoter include 5 phenolic substances such as phenol, naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation pro-ducts of formaldehyde with a phenolic substance; alcohols such as methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl 10 alcohol: and amines such as aniline, phenylenediamine, phenothiazine, phenyl-~-naphthylamine, and dodecylamine. A
particularly effective method for preparing the basic salts comprises mixing an acid with an excess of a basic alkaline earth metal neutralizing agent and at least one alcohol 15 promoter, and carbonating the mixture at an elevated tem-perature such as 60-200C.
Auxiliary ashless detergents and dispersants are so called despite the fact that, depending on its constitu-tion, the dispersant may upon combustion yield a non-vola-20 tile material such as boric oxide or phosphorus pentoxide;however, it does not ordinarily contain metal and therefore does not yield a metal-containing ash on combustion. Many types are known in the art, and any of them are suitable for u~e in the lubricant~ of this invention. The following are 25 illustrative:
(1) Reaction products of carboxylic acids (or derivatives thereof) containing at least about 34 and pre-ferably at least about 54 carbon atoms with nitrogen-con-taining compounds such as amine, organic hydroxy compounds 30 such as phenols and alcohols, and/or basic inorganic ma-terials. Examples of these "carboxylic dispersants~ are described in British Patent 1,306,529 and in many U.S.
patents including the following:
3,163,603 3,351,552 3,541,012 3,184,474 3,381,022 3,542,678 3,215,707 3,399,141 3,542,680 1~48S~37 3,219,666 3,415,750 3,567,637 3,271,310 3,433,744 3,574,101 3,272,746 3,~44,170 3,576,743 3,281,357 3,448,048 3,630,904 3,306,gO8 3,448,049 3,632,510 3,311,558 3,451,933 3,632,511 3,316,177 3,454,607 3,697,428 3,340,281 3,467,668 3,725,441 3,341,542 3,501,405 Re 26,433 3,346,493 3,522,179 (2) Reaction products of relatively high molecu-lar weight aliphatic or alicyclic halides with amines, pre-ferably polyalkylene polyamines. These may be characterized as "amine dispersants" and examples thereof are described 15 for example, in the following U.S. patents:
3,275,554 3,454,555 3,438,757 3,565,804 (3) Reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with 20 aldehydes ~especially formaldehyde) and amines (especially polyalkylene polyamines), which may be characterized as "Mannich dispersants". The materials described in the following U.S. patents are illustrative:
3,413,347 3,725,480 3,~97,574 3,726,882 3,725,277 (4) Products obtained by post-treating the car-boxylic, amine or Mannich dispersant~ with such reagents a~
urea, thiourea, carbon disulfide, aldehydes, ketones, car-30boxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds, phosphorus compounds or the like. Exemplary materials of this kind are described in the following U.S. patents:
~14~537 3,036,003 3,282,955 3,493,520 3,639,242 3,087,936 3,312,619 3,502,677 3,649,229 3,200,107 3,366,569 3,513,093 3,649,659 3,216,g36 3,367,943 3,533,945 3,658,836 3,254,025 3,373,111 3,539,633 3,697,574 3,256,185 3,403,102 3,573,010 3,702,757 3,278,550 3,442,808 3,579,450 3,703,536 3,280,234 3,455,831 3,5gl,598 3,704,308 3,281,428 3,455,832 3,600,372 3,708,522 (5) Interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., aminoalkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. These may be charac-terized as "polymeric dispersants" and examples thereof are disclosed in the following U. S. patents:
3,329,658 3,666,730 3,449,250 3,687,849 3,519,565 3,702,300 Extreme pressure agents and corrosion-and oxidation-inhibiting agents are exemplified by chlorinated aliphatic hydrocarbons such as chlorinated wax; organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl)-disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, sulfurized dipentene, and sulfurized terpene; phosphosulfurized hydrocarbons such as the reaction product of a phosphorus qulfide with turpentine or methyl oleate; phosphorus esters including principally dihydrocarbon and trihydrocarbon phosphites such as dibutyl phosphite, diheptyl phosphite, dicyclo-hexyl phosphite, pentylphenyl phosphite, dipentylphenyl phosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthyl phosphite, oleyl 4-pentylphenyl phosphite, X~
8~37 polypropylene (molecular weight 500)-substituted phenyl phosphite, diisobutyl-substituted phenyl phosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate, and barium heptylphenyl dithiocarbamate; Group II metal phos-phorodithioates such as zinc dicyclohexylphosphorodithioate,zinc dioctylphosphorodithioate, barium di(heptylphenyl)-phosphorodithioate, cadmium dinonylphosphorodithioate, and the zinc salt of a phosphorodithioic acid produced by the reaction of phosphorus pentasulfide with an equimolar mix-10 ture of isopropyl alcohol and n-hexyl alcohol.
The compositions of this invention can be added directly to the lubricant. Preferably, however, they are diluted with a substantially inert, normally liquid organic diluent such as mineral oil, naphtha, benzene, toluene or 15 xylene, to form an additive concentrate. These concentrates u8ually contain about 20-90~ by weight of the composition of this invention and may contain, in addition, one or more other additives known in the art or described hereinabove.
The lubricating compositions made according to 20 this invention can be exemplified by a lubricating compo-sition prepared by treating a mineral oil of lubricating viscosity with 1% by weight of the product of Example 8.
Claims (54)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing a composition which comprises reacting:
(a) A phosphorus-containing acid represented by the formula:
wherein each X and X' is independently oxygen or sulfur, each n is zero or one, and each R is independently the same or a different hydrocarbon-based radical;
(b) at least one hexavalent molybdenum oxide compound, and (c) hydrogen sulfide, in the presence of (d) a polar solvent.
(a) A phosphorus-containing acid represented by the formula:
wherein each X and X' is independently oxygen or sulfur, each n is zero or one, and each R is independently the same or a different hydrocarbon-based radical;
(b) at least one hexavalent molybdenum oxide compound, and (c) hydrogen sulfide, in the presence of (d) a polar solvent.
2. A process according to claim 1 wherein the hydrocarbon-based radical is an aliphatic-based radical and contains up to about 30 carbon atoms.
3. A process according to claim 2 wherein the aliphatic-based radical is alkyl and contains from 3 to about 30 carbon atoms.
4. A process according to claim 3 wherein at least one X is sulfur; at least one X' is oxygen; and each n is 1.
5. A process according to claim 4 wherein a reaction mixture of (a) and (b) in the presence of (d) is first prepared, which is then reacted with (c) at a tempera-ture of 0°-150°C.
6. A process according to claim 5 wherein (d) is water, organic polar solvents or mixtures thereof.
7. A process according to claim 1 wherein the hexavalent molybdenum oxide compound (b) is an acidic water-soluble hexavalent molybdenum compound that is obtained from molybdenum-trioxide compounds or mixtures of one or more of these compounds.
8. A process according to claim 7 wherein the molybdenum-trioxide compounds are molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid, ammonium molyb-dates, alkali metal molybdates, or heteropolyacid molybdates.
9. A process accordi.ng to claim 4 wherein the hexavalent molybdenum oxide compound (b) is an acidic water-soluble hexavalent molybdenum compound that is obtained from molybdenum-trioxide compounds or mixtures of one or more of these compounds.
10. A process according to claim 9 wherein the molybdenum-trioxide compounds are molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid, ammonium molyb-dates, alkali metal molybdates, or heteropolyacid molybdates.
11. A process according to claim 6 wherein the hexavalent molybdenum oxide compound (b) is an acidic water-soluble hexavalent molybdenum compound that is obtained from molybdenum-trioxide compounds or mixtures of one or more of these compounds.
12 A process according to claim 11 wherein the molybdenum-trioxide compounds are molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid, ammonium molyb-dates, alkali metal molybdates, or heteropolyacid molybdates.
13. A process according to claim 8 wherein the heteropolyacid molybdates are the phosphomolybdates.
14. A process according to claim 10 wherein the heteropolyacid molybdates are the phosphomolybdates.
15. A process according to claim 12 wherein the heteropolyacid molybdates are the phosphomolybdates.
16. A process according to claim 1 wherein (d) is water.
17. A process according to claim 4 wherein (d) is water.
18. A process according to claim 6 wherein (d) is water.
19. A process according to claim 8 wherein (d) is water.
20. A process according to claim 10 wherein (d) is water.
21. A process according to claim 12 wherein (d) is water.
22. A process according to claim 15 wherein (d) is water.
23. A composition prepared according to the process of claim 1.
24. A composition prepared according to the process of claim 4.
25. A composition prepared according to the process of claim 6.
26. A composition prepared according to the process of claim 10.
27. A composition prepared according to the process of claim 16.
28. A composition prepared according to the process of claim 17.
29. A composition prepared according to the process of claim 18.
30. A composition prepared according to the process of claim 22.
31. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 23.
32. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 24.
33. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 25.
34. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 26.
35. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 27.
36. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 28.
37. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 29.
38. A lubricant composition comprising a major amount of an oil of lubricating viscosity and a minor amount of at least one composition of claim 30.
39. An additive concentrate comprising about 20-90% of at least one composition of claim 23 and a substan-tially inert, normally liquid organic diluent.
40. An additive concentrate comprising about 20-90% of at least one composition of claim 24 and a substan-tially inert, normally liquid organic diluent.
41. An additive concentrate comprising about 20-90% of at least one composition of claim 25 and a substan-tially inert, normally liquid organic diluent.
42. An additive concentrate comprising about 20-90% of at least one composition of claim 26 and a substan-tially inert, normally liquid organic diluent.
43. An additive concentrate comprising about 20-90% of at least one composition of claim 27 and a substan-tially inert, normally liquid organic diluent.
44. An additive concentrate comprising about 20-90% of at least one composition of claim 28 and a substan-tially inert, normally liquid organic diluent.
45. An additive concentrate comprising about 20-90% of at least one composition of claim 29 and a substan-tially inert, normally liquid organic diluent.
46. An additive concentrate comprising about 20-90% of at least one composition of claim 30 and a substan-tially inert, normally liquid organic diluent.
47. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composition of claim 31.
48. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composition of claim 32.
49. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composition of claim 33.
50. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composition of claim 34.
51. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composition of claim 35.
52. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composi-tion of claim 36.
53. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composi-tion of claim 37.
54. A method for reducing the fuel consumption of an internal combustion engine which comprises lubricating said engine during operation with the lubricant composi-tion of claim 38.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11789180A | 1980-02-01 | 1980-02-01 | |
| US117,891 | 1980-02-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148537A true CA1148537A (en) | 1983-06-21 |
Family
ID=22375377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000369004A Expired CA1148537A (en) | 1980-02-01 | 1981-01-21 | Process for preparing molybdenum-containing compositions useful for improved fuel economy of internal combustion engines |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1148537A (en) |
-
1981
- 1981-01-21 CA CA000369004A patent/CA1148537A/en not_active Expired
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