US3374291A - Trithiophosphites of mercapto acid esters - Google Patents

Trithiophosphites of mercapto acid esters Download PDF

Info

Publication number
US3374291A
US3374291A US370112A US37011264A US3374291A US 3374291 A US3374291 A US 3374291A US 370112 A US370112 A US 370112A US 37011264 A US37011264 A US 37011264A US 3374291 A US3374291 A US 3374291A
Authority
US
United States
Prior art keywords
trithiophosphites
acid esters
mercapto acid
mercapto
trithiophosphite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US370112A
Inventor
Myers Herbert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil Corp filed Critical Mobil Oil Corp
Priority to US370112A priority Critical patent/US3374291A/en
Application granted granted Critical
Publication of US3374291A publication Critical patent/US3374291A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/201—Esters of thiophosphorus acids
    • C07F9/205—Esters of thiophosphorus acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/201—Esters of thiophosphorus acids

Definitions

  • This invention relates to improved lubricating composi tions. More particularly, it relates to a new type of multifunctional additive for such lubricants and a method for their preparation.
  • lubricating compositions are susceptible to oxidation under various conditions of use. For example, oxidation is particularly severe under the high temperature and pressure conditions encountered in internal combustion engines. Such oxidation produces acidic bodies in the lubricating oil which are corrosive to the metal parts of the engine and further results in the deposition of carbonaceous sludge, lacquer and resinous materials whose accumulation impairs the operating efficiency of the engine. In an effort to overcome, insofar as possible, these and other deleterious effects of oxidation it has become the practice to add to the lubricants minor amounts of chemical agents which are commonly known as antioxidants.
  • the present invention provides a new class of addition agents which are multi-functional in their activity, i.e., they are capable of improving lubricants in several respects and particularly with regard to oxidation stability and extreme pressure characteristics.
  • the additives of this invention may be characterized as trithiophosphites of mercapto acid esters. As far as is known, these additive compounds have not been prepared heretofore and they are therefore considered to be new compositions of matter.
  • a further object is to provide improved lubricating compositions containing these trithiophosphites.
  • Another object is to improve the characteristics, particularly the oxidation stability and BF. qualities of lubricants by the addition thereto of such trithiophosphites.
  • trithiophosphites of mercapto acid esters of the present invention may be represented by the general formula,
  • R is a saturated or unsaturated aliphatic group, aryl group, substituted aliphatic or substituted aryl group containing substituents such as halogens, nitro, cyano, alkyl groups etc.; R is a saturated or unsaturated aliphatic or cycloaliphatic group, an aryl group, or substituted aliphatic, cycloaliphatic or aryl group containing suitable substituents, e.g., halogens, nitro, cyano, alkyl etc.; and n is an integer from 1 to 3 inclusive.
  • R groups include alkylene groups, such as methylene, ethylene, propylene, butylene, etc.; halogenated alkylene groups, such as chloroethylene; arylene groups or substituted arylene groups, such as phenylene, naphthalene, or phenylene or naphthalene substituted by one or more substituents.
  • R groups include aliphatic groups, such as methyl, ethyl, propyl, butyl, octyl, oleyl, octadecyl, etc.; substituted aliphatics such as monoand poly-halogenated alkyls; aryl groups, such as phenyl and naphthyl; and substituted .aryls such as phenyl or naphthyls substituted with one or more suitable substituents.
  • R may be a cycloaliphatic group, either unsubstituted or substituted, such as cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • R preferably contains from 1 to about 40 carbon atoms, the greater number of carbons being generally present when n is more than one; while R' may possess preferably from 1 to about 18 carbon atoms. It will be noted from the general formula that the phosphites may contain from one to three carboxylic acid ester groups depending on the value of n. Compounds containing one or two carboxylic acid ester groups are preferred.
  • the trithiophosphites of the invention may, in general, be prepared by reacting phosphorus trihalide (PX with a selected mercapto acid ester in the presence of a suitable base such as tertiary amines, aqueous sodium hydroxide, aqueous sodium carbonate, etc.
  • PX phosphorus trihalide
  • a suitable base such as tertiary amines, aqueous sodium hydroxide, aqueous sodium carbonate, etc.
  • the reaction may be illustrated as follows:
  • the reaction is desirably carried out in a non-polar solvent, such as benzene, toluene, isooctane, etc.
  • a non-polar solvent such as benzene, toluene, isooctane, etc.
  • the reaction may be conducted at ambient temperatures, reaction temperatures in the range from about 15 to 50 C. and reaction periods of from about 5 to 15 hours are preferred.
  • the products may be recovered by removing the precipitated base-hydrochloride, such as by filtration, washing the filtrate with 15% hydrochloric acid and water to remove unreacted base, and then topping off the non-polar solvent and unreac-ted mercapto acid ester.
  • Exemplary of the t-rithiophosphites of the invention are those obtained from (a) aliphatic mono-carboxylic mercapto acid esters, and (b) aliphatic polycarboxylic mercapto acid esters and (c) aromatic carboxylic mercapto esters according to the above reaction, and possessing the formula:
  • the sulfur of the trithiophosphites of the aromatic mercapto esters may be either ortho, meta or para to the ca'rb-oxylic ester group.
  • the aromatic ring of these trithiophosphites may also possess other groups, such as .a-lkyl, halogen, nit-r0, cyano, e-tc., attached thereto.
  • Phosphorus trichloride (137 g., 1.0 mole) was added over a period of /2 hour to a solution of butyl thioglycolate (450 g., 3.1 moles) and triethylamine (312 g., 3.1 moles) in 3.0 liters of benzene while maintaining the reaction temperature at around C. Immediate precipitation of triethyla-mine hydrochloride occurred. Nitrogen was then introduced and the slurry stirred at 15 to C. for 2 hours and at 50 C. for an additional 3 hours.
  • the precipitated triethylamine hydrochloride was filtered off and washed with one liter of benzene. Unreac'ted triethylamine was removed by washing the filtrate with 250 ml. cold 15% hydrochloric acid and 4-500 ml. portions of cold water. After drying the benzene solution over anhydrous potassium carbonate and sodium sulfate, the product was isolated by topping to a pot temperature of 110 C. with nitrogen; to 130 C. under 0.2 mm. pressure and finally filtering through diatomaceous earth.
  • the resulting product was a clear, pale yellow, viscous liquid which analyzed as follows Actual: P, 6.4%; S, 20.8%; C1, nil. Theoretical: P, 6.5%; S, 20.3%; C1, nil.
  • Example 2 Trithiophosphite 0] octyl thi0glyc0late
  • phosphorus trichloride 68 g., 0.5 mole
  • octyl thioglycolate 350 g., 16 moles
  • triethylamine 162 g., 1.6 moles
  • the product was a viscous, clear pale yellow liquid which analyzed as follows' Actual: P, 4.6%; S, 15.0%; C1, nil. Theoretical: P, 4.5%; S, 14.1%; Cl, nil.
  • Example 3 Trithiophosphife of Z-chloroethyl thiaglyc0la1te 0 ll rtsotnooontomona
  • phosphorus trichloride 48 g., 0.35 mole
  • 2-chloroethyl thioglycolate 180 g., 1.13 moles
  • triethylamine 115 g., 1.13 moles
  • the product was a very viscous, clear, pale yellow liquid which analyzed as follows Actual: P, 6.0%; S, 21.1%; C1, 21.0%.
  • Example 4 Trithi0ph0sphite of butyl thipropionateo P[SCH2CH2(JOC4H9]3
  • phosphorus trichloride 137 g., 1.0 mole
  • butyl thiopropionate 510 g., 3.15 moles
  • triethylamine 318 g., 3.15 moles
  • the product was a pale yellow, clear, viscous liquid that had the following analysis Actual: P, 5.8%; S, 19.3%; C1, nil.
  • Example 5 Tr1'thi0ph0sphite of butyl thi0salzlcylate- Following the procedure of Example 1, phosphorus trichloride (14 g., 0.10 mole) was reacted with butyl thiosalicylate (69 g., 0.31 mole) and triethylamine (33 g., 0.33 mole) in 500 ml. benzene.
  • the product was a pale yellow, waxy solid that had the following analysis Actual: P, 4.2%; S, 14.1%; Cl, nil. Theoretical: P, 4.7%; S, 14.6%; C1, nil.
  • phosphorus trichloride 89 g., 0.65 mole
  • dibutylthiomalonate 521 g., 2.0 moles
  • triethyla'mine 202 g., 2.0 moles
  • the product was a pale yellow, clear viscous liquid that gave the following analysis- Actual: P, 4.2%; S, 14.1%; C1, nil.
  • Trithiophosphite Minimum percent of Example Number Phosphorus l
  • the base oil used was a SAE 10, solvent refined Mid-Continent oil SAE LOAD TEST in the same direction while a gradually increasing load is mechanically applied.
  • the machine is operated at a TABLE IL-SAE LOAD TEST Trithiophosphite Phosphorus Cont.
  • Example N o. (Wt. percent) SAE Load Test, 500 r.p.m. Seizure Load 1 o. 5 460+, 460+ 2 0.5 460+, 460+ 3 o. 5 410, 460+ 4 o. 5 400, 415 5 0. 5 390, 390
  • the base oil used was a SAE 00, solvent refined, Mid-Continent Oil.
  • the trithiophosphites of this invention are effective in improving the characteristics particularly the oxidation stability and ER characteristics of a variety of lubricants including lubricating oils, greases, hydraulic fluids etc. These lubricants may contain either mineral or synthetic base oils.
  • the amount of trithiophosphite added to the lubricant Will depend on various factors, including the type of the lubricant the presence or absence of other ingredients, the extent of oxidation stability desired, etc.
  • the trithiophosphites are employed in amounts from about 0.1 to about 10, preferably from about 0.5 to about 5 weight percent.
  • the lubricating compositions of the present invention may, of course, also contain efiective quantities of various other materials which are normally used therein such as detergents, inhibitors, V.I. improvers, thickening agents, defoamants, supplemental antioxidants or E.P. agents, etc.
  • a mercapto acid ester trithiophosphite of the formula 1? [(RO OhRSlaP wherein R is selected from the class consisting of alkylene, alkenylene, arylene, alkarylene and aralkylene having from 1 to about 40 carbon atoms; R is selected from the class consisting of alkyl, cycloalkyl, alkeny-l, aryl, alkaryl, aralkyl, and monochloroalkyl and having from 1 to about 18 carbon atoms; and n is an integer of from 1 to 3, and when R is alkyl, R is selected from the class consisting of alkenylene, arylene, alkary-lene and aralkylene.
  • a trithiophosphite of 2-chloroethyl thioglycolate 6.
  • a trithiophosphite of butyl thiosalicylate 6.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Lubricants (AREA)

Description

United States Patent 3,374,291 TRITHIOPHOSPHITES F MERCAPTO AQID ESTERS Herbert Myers, Cherry Hill, N.J., assignor to Mobil Oil Corporation, a corporation of New York No Drawing. Filed May 25, 1964, Ser. No. 370,112 6 Claims. (Cl. 260942) This invention relates to improved lubricating composi tions. More particularly, it relates to a new type of multifunctional additive for such lubricants and a method for their preparation.
It is well known that lubricating compositions are susceptible to oxidation under various conditions of use. For example, oxidation is particularly severe under the high temperature and pressure conditions encountered in internal combustion engines. Such oxidation produces acidic bodies in the lubricating oil which are corrosive to the metal parts of the engine and further results in the deposition of carbonaceous sludge, lacquer and resinous materials whose accumulation impairs the operating efficiency of the engine. In an effort to overcome, insofar as possible, these and other deleterious effects of oxidation it has become the practice to add to the lubricants minor amounts of chemical agents which are commonly known as antioxidants.
It is also the practice to add ingredients to lubricating compositions for the purpose of improving their extreme pressure characteristics, particularly when these compositions are used for lubricating metal surfaces which are subjected to extremely high pressures and high rubbing speeds such as exist in hypoid gears. Such high pressure conditions tend to disrupt the lubricating film with resulting damage to the metal parts to be lubricated. Numerous additives commonly referred to as extreme pressure (E.P.) agents which act to improve the properties of the lubricant under these conditions, are known.
Ordinarily, a combination of antioxidants and BF. agents must be utilized in lubricating compositions in order to provide the desired effects.
The present invention, however, provides a new class of addition agents which are multi-functional in their activity, i.e., they are capable of improving lubricants in several respects and particularly with regard to oxidation stability and extreme pressure characteristics.
The additives of this invention may be characterized as trithiophosphites of mercapto acid esters. As far as is known, these additive compounds have not been prepared heretofore and they are therefore considered to be new compositions of matter.
It is therefore an object of the present invention to provide certain novel trithiophosphites of mercapto acid esters. A further object is to provide improved lubricating compositions containing these trithiophosphites. Another object is to improve the characteristics, particularly the oxidation stability and BF. qualities of lubricants by the addition thereto of such trithiophosphites. Other objects of the invention and further advantages thereof will become apparent from the following detailed description.
The trithiophosphites of mercapto acid esters of the present invention may be represented by the general formula,
R O (1)11RS]3 wherein R is a saturated or unsaturated aliphatic group, aryl group, substituted aliphatic or substituted aryl group containing substituents such as halogens, nitro, cyano, alkyl groups etc.; R is a saturated or unsaturated aliphatic or cycloaliphatic group, an aryl group, or substituted aliphatic, cycloaliphatic or aryl group containing suitable substituents, e.g., halogens, nitro, cyano, alkyl etc.; and n is an integer from 1 to 3 inclusive.
Some examples of suitable R groups include alkylene groups, such as methylene, ethylene, propylene, butylene, etc.; halogenated alkylene groups, such as chloroethylene; arylene groups or substituted arylene groups, such as phenylene, naphthalene, or phenylene or naphthalene substituted by one or more substituents.
Some examples of suitable R groups include aliphatic groups, such as methyl, ethyl, propyl, butyl, octyl, oleyl, octadecyl, etc.; substituted aliphatics such as monoand poly-halogenated alkyls; aryl groups, such as phenyl and naphthyl; and substituted .aryls such as phenyl or naphthyls substituted with one or more suitable substituents. In addition, R may be a cycloaliphatic group, either unsubstituted or substituted, such as cyclobutyl, cyclopentyl, cyclohexyl, etc.
R preferably contains from 1 to about 40 carbon atoms, the greater number of carbons being generally present when n is more than one; while R' may possess preferably from 1 to about 18 carbon atoms. It will be noted from the general formula that the phosphites may contain from one to three carboxylic acid ester groups depending on the value of n. Compounds containing one or two carboxylic acid ester groups are preferred.
The trithiophosphites of the invention may, in general, be prepared by reacting phosphorus trihalide (PX with a selected mercapto acid ester in the presence of a suitable base such as tertiary amines, aqueous sodium hydroxide, aqueous sodium carbonate, etc.
The reaction may be illustrated as follows:
0 3(R O )uRSH PXa -I- 3 Base wherein R, R and n have the meanings given above. Various amounts of mercapto acid ester and base may be employed. In general, however, the relative proportions are selected so as to supply at least about 3 mols of base per mol of the phosphorus trihalide.
The reaction is desirably carried out in a non-polar solvent, such as benzene, toluene, isooctane, etc. Although the reaction may be conducted at ambient temperatures, reaction temperatures in the range from about 15 to 50 C. and reaction periods of from about 5 to 15 hours are preferred. The products may be recovered by removing the precipitated base-hydrochloride, such as by filtration, washing the filtrate with 15% hydrochloric acid and water to remove unreacted base, and then topping off the non-polar solvent and unreac-ted mercapto acid ester.
Exemplary of the t-rithiophosphites of the invention are those obtained from (a) aliphatic mono-carboxylic mercapto acid esters, and (b) aliphatic polycarboxylic mercapto acid esters and (c) aromatic carboxylic mercapto esters according to the above reaction, and possessing the formula:
[RO h (OHilxShP R'O(%(CH2)1 OHS P RO o oi-n)y 3 and where x and y represent integers from 1-18. As will be seen from Formula c, the sulfur of the trithiophosphites of the aromatic mercapto esters may be either ortho, meta or para to the ca'rb-oxylic ester group. In addition, as indicated in the general formula, the aromatic ring of these trithiophosphites may also possess other groups, such as .a-lkyl, halogen, nit-r0, cyano, e-tc., attached thereto.
The following examples illustrate the preparation of some typical trit-hiophosphites of mercapto acid esters.
Example 1.Tritlziphosphite of butyl thi0glyc0latell P[SCH2C O Odin]:
Phosphorus trichloride (137 g., 1.0 mole) was added over a period of /2 hour to a solution of butyl thioglycolate (450 g., 3.1 moles) and triethylamine (312 g., 3.1 moles) in 3.0 liters of benzene while maintaining the reaction temperature at around C. Immediate precipitation of triethyla-mine hydrochloride occurred. Nitrogen was then introduced and the slurry stirred at 15 to C. for 2 hours and at 50 C. for an additional 3 hours.
The precipitated triethylamine hydrochloride was filtered off and washed with one liter of benzene. Unreac'ted triethylamine was removed by washing the filtrate with 250 ml. cold 15% hydrochloric acid and 4-500 ml. portions of cold water. After drying the benzene solution over anhydrous potassium carbonate and sodium sulfate, the product was isolated by topping to a pot temperature of 110 C. with nitrogen; to 130 C. under 0.2 mm. pressure and finally filtering through diatomaceous earth.
The resulting product was a clear, pale yellow, viscous liquid which analyzed as follows Actual: P, 6.4%; S, 20.8%; C1, nil. Theoretical: P, 6.5%; S, 20.3%; C1, nil.
Example 2.Trithiophosphite 0] octyl thi0glyc0late Following the procedure of Example 1, phosphorus trichloride (68 g., 0.5 mole) was reacted with octyl thioglycolate (350 g., 16 moles) and triethylamine (162 g., 1.6 moles) in 2.0 liters of benzene. The product was a viscous, clear pale yellow liquid which analyzed as follows' Actual: P, 4.6%; S, 15.0%; C1, nil. Theoretical: P, 4.5%; S, 14.1%; Cl, nil.
Example 3.Trithiophosphife of Z-chloroethyl thiaglyc0la1te 0 ll rtsotnooontomona Following the procedure of Example 1, phosphorus trichloride (48 g., 0.35 mole) was reacted with 2-chloroethyl thioglycolate (180 g., 1.13 moles) and triethylamine (115 g., 1.13 moles) in 2.0 liters of benzene. The product was a very viscous, clear, pale yellow liquid which analyzed as follows Actual: P, 6.0%; S, 21.1%; C1, 21.0%. Theoretical: P, 6.3%; S, 19.6%; C1, 21.7%.
Example 4.Trithi0ph0sphite of butyl thipropionateo P[SCH2CH2(JOC4H9]3 Following the procedure of Example 1, phosphorus trichloride (137 g., 1.0 mole) was reacted with butyl thiopropionate (510 g., 3.15 moles) and triethylamine (318 g., 3.15 moles) in 3.0 liters benzene. The product was a pale yellow, clear, viscous liquid that had the following analysis Actual: P, 5.8%; S, 19.3%; C1, nil. Theoretical: P, 6.0%; S, 18.7%; Cl, nil.
Example 5.Tr1'thi0ph0sphite of butyl thi0salzlcylate- Following the procedure of Example 1, phosphorus trichloride (14 g., 0.10 mole) was reacted with butyl thiosalicylate (69 g., 0.31 mole) and triethylamine (33 g., 0.33 mole) in 500 ml. benzene. The product was a pale yellow, waxy solid that had the following analysis Actual: P, 4.2%; S, 14.1%; Cl, nil. Theoretical: P, 4.7%; S, 14.6%; C1, nil.
Example 6.-Trithi0ph0sphite of dibutylthiomalonate o SCIIOC4H9 CH(3OC4Hq Following the procedure of Example 1, phosphorus trichloride (89 g., 0.65 mole) was reacted with dibutylthiomalonate (521 g., 2.0 moles) and triethyla'mine (202 g., 2.0 moles) in 2.0 liters benzene. The product was a pale yellow, clear viscous liquid that gave the following analysis- Actual: P, 4.2%; S, 14.1%; C1, nil. Theoretical: P, 4.7%; S, 14.6%; C1, nil.
CATALYTIC OXIDATION TEST In order to demonstrate the effectiveness of the compounds of this invention in inhibiting the catalytic oxidation of oils, the trithiophosphites of the working examples were subjected to a Catalytic Oxidation Test. This test is based on the fact that the oxidized products which form in the oil are known to be acidic in character. Thus, the higher the neutralization number (N.N.), the greater the extent of oxidation. The ability of a compound to maintain the N.N. of an oil composition at a low level is a measure of its antioxidant ability.
According to the test procedure, 25 ccs. of the test oil is placed in a 200 x 25 mm. test tube with 15.6 sq. in. of sand-blasted iron wire, 0.78 sq. in. of polished copper wire, 0.87 sq. in. of polished aluminum wire and 0.167 sq. in. of a polished lead surface. Dry air is passed through the sample at the rate of 10 liters per hour while heating in an aluminum block bath for a period of 24 hours at a temperature of 325 F. The minimum concentration of phosphorus necessary to maintain the acidity of the oxidized oil below a neutralization number of 2 is determined and reported in the following Table I.
It will be seen from Table I that by employing the trithiophosphites of the invention less than 0.10% of phosphorus is required to maintain the neutralization number of the oil below 2.
TABLE L-GATALYTIC OXIDATION TEST Trithiophosphite Minimum percent of Example Number Phosphorus l The base oil used was a SAE 10, solvent refined Mid-Continent oil SAE LOAD TEST in the same direction while a gradually increasing load is mechanically applied. The machine is operated at a TABLE IL-SAE LOAD TEST Trithiophosphite Phosphorus Cont.
of Example N o. (Wt. percent) SAE Load Test, 500 r.p.m. Seizure Load 1 o. 5 460+, 460+ 2 0.5 460+, 460+ 3 o. 5 410, 460+ 4 o. 5 400, 415 5 0. 5 390, 390
I The base oil used was a SAE 00, solvent refined, Mid-Continent Oil.
2 Fails break in. Break ln=20 pounds.
The trithiophosphites of this invention are effective in improving the characteristics particularly the oxidation stability and ER characteristics of a variety of lubricants including lubricating oils, greases, hydraulic fluids etc. These lubricants may contain either mineral or synthetic base oils. Thus, mineral oils from various crudes, both solvent and acid refined, hydrocracked, etc., as well as synthetic hydrocarbons, including olefin polymers, hydrogenated olefin polymers, alkyl benzenes, etc., synthetic esters, such as di-Z-ethylhexyl sebacate, dialkyl adipate, trirnethylol propane dioctanoate, etc., silicone fluids and the like may have their characteristics improved by the addition of the trithiophosphites described herein.
The amount of trithiophosphite added to the lubricant Will depend on various factors, including the type of the lubricant the presence or absence of other ingredients, the extent of oxidation stability desired, etc. In general, the trithiophosphites are employed in amounts from about 0.1 to about 10, preferably from about 0.5 to about 5 weight percent.
The lubricating compositions of the present invention may, of course, also contain efiective quantities of various other materials which are normally used therein such as detergents, inhibitors, V.I. improvers, thickening agents, defoamants, supplemental antioxidants or E.P. agents, etc.
It will, of course, be appreciated that many variations and modifications may be practiced without departing from the scope and spirit of the present invention.
6 Having thus described the invention, what I desire to obtain and secure by Letters Patent is:
1. A mercapto acid ester trithiophosphite of the formula 1? [(RO OhRSlaP wherein R is selected from the class consisting of alkylene, alkenylene, arylene, alkarylene and aralkylene having from 1 to about 40 carbon atoms; R is selected from the class consisting of alkyl, cycloalkyl, alkeny-l, aryl, alkaryl, aralkyl, and monochloroalkyl and having from 1 to about 18 carbon atoms; and n is an integer of from 1 to 3, and when R is alkyl, R is selected from the class consisting of alkenylene, arylene, alkary-lene and aralkylene.
2. A trithiophosphite according to claim 1 of the formula:
5 [RO k? (CH2) xSlaP where x is an integer from 1 to about 18 wherein R is se lected from the class consisting of alkenyl, aryl, alkaryl, aralkyl and monochloro alkyl.
3. A trithiophosphite according to claim 1 of the formula:
R'OC S P 4. A trithiophosphite according to claim 1 of the formula:
0 R 0 g (0 H2) x 0 OHS R 0 A l (43112) y 3 where x and y are integers from 1 to about 18.
5. A trithiophosphite of 2-chloroethyl thioglycolate. 6. A trithiophosphite of butyl thiosalicylate.
References Cited UNITED STATES PATENTS 2,824,847 2/1958 Fath 260-942 X CHARLES B. PARKER, Primary Examiner.
F. M. SIKORA, A. H. SUTTO, Assistant Examiners.

Claims (1)

1. A MERCAPTO ACID ESTER TRITHIOPHOSPHITE OF THE FORMULA
US370112A 1964-05-25 1964-05-25 Trithiophosphites of mercapto acid esters Expired - Lifetime US3374291A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US370112A US3374291A (en) 1964-05-25 1964-05-25 Trithiophosphites of mercapto acid esters

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US370112A US3374291A (en) 1964-05-25 1964-05-25 Trithiophosphites of mercapto acid esters

Publications (1)

Publication Number Publication Date
US3374291A true US3374291A (en) 1968-03-19

Family

ID=23458271

Family Applications (1)

Application Number Title Priority Date Filing Date
US370112A Expired - Lifetime US3374291A (en) 1964-05-25 1964-05-25 Trithiophosphites of mercapto acid esters

Country Status (1)

Country Link
US (1) US3374291A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE29523E (en) * 1972-08-22 1978-01-24 Borg-Warner Corporation Olefinic polymers stabilized with thioacyl trivalent phosphorus compounds
JPS53112819A (en) * 1977-03-10 1978-10-02 Ciba Geigy Ag Trithioo and tetrathio phosphoric triester process for preparing same and lubricant composition containing same
EP0337084A1 (en) * 1988-04-11 1989-10-18 Hüls Aktiengesellschaft Stabilizer mixtures, their use and moulding compositions and moulded parts stabilized therewith
US6534452B1 (en) * 2001-03-27 2003-03-18 Exxonmobil Research And Engineering Company Long-life lubricating oil with wear prevention capability

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824847A (en) * 1954-08-25 1958-02-25 Heyden Newport Chemical Corp Vinyl chloride polymer stabilized with thiophosphite and polyvalent metal soap

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2824847A (en) * 1954-08-25 1958-02-25 Heyden Newport Chemical Corp Vinyl chloride polymer stabilized with thiophosphite and polyvalent metal soap

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE29523E (en) * 1972-08-22 1978-01-24 Borg-Warner Corporation Olefinic polymers stabilized with thioacyl trivalent phosphorus compounds
JPS53112819A (en) * 1977-03-10 1978-10-02 Ciba Geigy Ag Trithioo and tetrathio phosphoric triester process for preparing same and lubricant composition containing same
FR2383190A1 (en) * 1977-03-10 1978-10-06 Ciba Geigy Ag
FR2383191A1 (en) * 1977-03-10 1978-10-06 Ciba Geigy Ag PHOSPHORIC AND PHOSPHORUS THIOESTERS FOR USE AS LUBRICANT ADDITIVES
US4189453A (en) * 1977-03-10 1980-02-19 Ciba-Geigy Corporation Processes for the production of sulphur-containing esters of phosphoric acid and phosphorous acid
US4197209A (en) * 1977-03-10 1980-04-08 Ciba-Geigy Corporation Lubricant compositions containing sulfur-containing esters of phosphoric acid
US4251469A (en) * 1977-03-10 1981-02-17 Ciba-Geigy Corporation Sulphur-containing esters of phosphoric acid
JPH0146557B2 (en) * 1977-03-10 1989-10-09 Ciba Geigy
EP0337084A1 (en) * 1988-04-11 1989-10-18 Hüls Aktiengesellschaft Stabilizer mixtures, their use and moulding compositions and moulded parts stabilized therewith
US6534452B1 (en) * 2001-03-27 2003-03-18 Exxonmobil Research And Engineering Company Long-life lubricating oil with wear prevention capability
EP1392804A2 (en) * 2001-03-27 2004-03-03 ExxonMobil Research and Engineering Company Long-life lubricating oil with wear prevention capability
EP1392804A4 (en) * 2001-03-27 2009-08-05 Exxonmobil Res & Eng Co Long-life lubricating oil with wear prevention capability

Similar Documents

Publication Publication Date Title
US2680123A (en) Zinc salt of mixed ester thiophosphates
US3361672A (en) Stabilized organic compositions
US2795552A (en) Lubricant compositions
US3869394A (en) Lubricant composition and method
US3350348A (en) Lubricating oil additives
US3844960A (en) Lubricant compositions
US2805997A (en) Lubricant composition
US2683691A (en) Extreme pressure lubricants
US2786812A (en) Mineral oil compositions containing tincontaining dithiophosphate compounds
US3374291A (en) Trithiophosphites of mercapto acid esters
US2614990A (en) Lubricating composition of matter
US2783202A (en) Corrosion preventing agent
US2743235A (en) Mineral oil composition
US2760937A (en) Phosphorus-containing lubricant additives
US2905639A (en) Lubricating oil compositions
US2713557A (en) Basic phenates to inhibit silver corrosion in thiophosphate-containing lubricating oils
US2673839A (en) Lubricating oil composition
US3029268A (en) Thioether containing esters of dithiophosphoric acid, and salts thereof
US2809162A (en) Corrosion inhibited lubricant composition
US3361671A (en) Lubricant compositions containing mixed dithiophosphoric dicarboxylic acid anhydrides and substituted amine detergents
US3780145A (en) Triphenyl phosphates
US2599341A (en) New phosphorus containing compounds
US2874120A (en) Lubricating oil compositions
US4348291A (en) Novel phosphoramides, lubricating compositions and method of improving wear and extreme pressure characteristics of lubricating oil
US3164580A (en) Phosphosulfurized esters of amino acids