US4288335A
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Novel metallic dithiophosphates and their use as additives for lubricating oils
Assignee: Orogil SA
•
Filing: 1980-03-04
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Granted: 1981-09-08
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Expires: 2000-03-04
Abstract
Abstract Metallic dithiophosphates of the formula: ##STR1## in which R 1 is an alkyl, alkenyl, cycloaliphatic, aryl, or heterocyclic radical, R 2 and R 3 are alkyl radicals, preferably C 1 -C 4 radicals, and m represents the valence of the metal M, M being a metal of Groups IIB, IIIB, IVB, or VIII of the Periodic System of Elements, preferably zinc. They are obtained by the action of P 2 S 5 on a monoester alcohol of the formula: ##STR2## and then by reaction of a metal oxide, such as zinc oxide, with the dithiophosphoric acid formed. These metallic dithiophosphates are useful as extreme-pressure and anti-wear additives for lubricating oils in amounts of between 0.2 and 10 percent, referred to the weight of lubricating oils.
Inventors
- 👤 Georges Rivier
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-06 19:26
CPC Classifications
C; C07; C07F; C07F9/00; C07F9/02; C07F9/06; C07F9/16; C07F9/165; C07F9/1651; C10; C10M; C10M137/00; C10M137/02; C10M137/04; C10M137/10; C10M2223/00; C10M2223/02; C10M2223/04; C10M2223/045; C10N; C10N2010/00; C10N2010/02; C10N2010/04; C10N2010/08; C10N2010/14; C10N2010/16; C10N2040/00; C10N2040/08; C10N2040/20; C10N2040/22; C10N2040/25; C10N2040/252; C10N2040/253
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
128 words
A metallic dithiophosphate having the formula: ##STR33## in which: R 1 represents: (a) a linear or branched alkyl radical containing from about 1 to 24 carbon atoms; (b) a linear or branched alkenyl radical containing from about 2 to 24 carbon atoms; (c) a saturated or unsaturated cycloaliphatic or polycycloaliphatic radical containing from about 3 to 20 carbon atoms; (d) an aryl radical containing from 6 to 14 carbon atoms; (e) a heterocyclic radical containing one or more heteroelements selected from among nitrogen, sulfur and oxygen; R 2 and R 3 are alkyl radicals containing from about 1 to 12 carbon atoms; m represents the valence of the metal M; M represents a metal of groups IIB, IIIB, IVB, or VIII of the Periodic System of the Elements.
Claim 2
Dependent Claim
128 words
A metallic dithiophosphate having the formula: ##STR33## in which: R 1 represents: (a) a linear or branched alkyl radical containing from about 1 to 24 carbon atoms; (b) a linear or branched alkenyl radical containing from about 2 to 24 carbon atoms; (c) a saturated or unsaturated cycloaliphatic or polycycloaliphatic radical containing from about 3 to 20 carbon atoms; (d) an aryl radical containing from 6 to 14 carbon atoms; (e) a heterocyclic radical containing one or more heteroelements selected from among nitrogen, sulfur and oxygen; R 2 and R 3 are alkyl radicals containing from about 1 to 12 carbon atoms; m represents the valence of the metal M; M represents a metal of groups IIB, IIIB, IVB, or VIII of the Periodic System of the Elements.
Claim 3
Dependent Claim
45 words
A metallic dithiophosphate according to claim 1, wherein the alkyl radical is substituted by at least one member selected from the class consisting of phenyl, halo, and heterocyclic groups containing at least one heterocyclic element selected from the class consisting of nitrogen, sulfur, and oxygen.
Claim 4
Dependent Claim
45 words
A metallic dithiophosphate according to claim 1, wherein the alkenyl radical is substituted by at least one member selected from the class consisting of phenyl, halo, and heterocyclic groups containing at least one heterocyclic element selected from the class consisting of nitrogen, sulfur, and oxygen.
Claim 5
Dependent Claim
33 words
A metallic dithiophosphate according to claim 1, wherein the cycloaliphatic or polycycloaliphatic radical is substituted by at least one alkyl group containing from about 1 to 12 carbon atoms or a halogen atom.
Claim 6
Dependent Claim
34 words
A metallic dithiophosphate according to claim 1, wherein the aryl radical is substituted by at least one alkyl group containing from about 1 to 12 carbon atoms, or a halogen, or halo alkyl group.
Claim 7
Dependent Claim
31 words
A metallic dithiophosphate according to claim 1, wherein the heterocyclic radical is substituted by at least one alkyl group containing from about 1 to 12 carbon atoms or a halogen atom.
Claim 8
Dependent Claim
13 words
A metallic dithiophosphate according to claim 1, wherein the metal M is zinc.
Claim 9
Dependent Claim
47 words
A metallic dithiophosphate according to claim 1, wherein R 1 contains from about 1 to 17 carbon atoms when it represents an alkyl radical, from about 2 to 17 carbon atoms when it represents an alkenyl radical, and 6 carbon atoms when it represents an aryl radical.
Claim 10
Dependent Claim
21 words
A metallic dithiophosphate according to claim 1, wherein R 2 and R 3 contain from about 1 to 4 carbon atoms.
Claim 11
Dependent Claim
27 words
A metallic dithiophosphate according to claim 9, wherein R 2 and R 3 represent a member selected from the class consisting of methyl, ethyl, and butyl radicals.
Claim 12
Dependent Claim
47 words
A metallic dithiophosphate according to claim 1, wherein R 1 represents one of the following radicals: methyl, 1,2-dichloro-ethyl, heptyl, 10-bromo-decyl, 8,9-dibromo-hepta-decyl, heptadecyl, vinyl, phenylvinylene, 2-furyl-vinylene, isopropenyl, decenyl, heptadecenyl, cyclopropyl, cyclohexyl, cyclohexenyl, C 19 H 29 derived from abietic acid, phenyl, p-chlorophenyl, p-trifluoromethylphenyl, 2,3-dimethyl-1-phenyl, p-octylphenyl, 2-furyl-4-methyl-5-thiazolyl, and 3-pyridyl.
Claim 13
Dependent Claim
91 words
A method of preparing a metallic dithiophosphate according to claim 1, comprising reacting a monoester alcohol of the formula: ##STR34## with an amount of P 2 S 5 in excess of about 5 to 20 mol percent referred to the amount of P 2 S 5 stoichiometrically necessary in order to obtain a dithiophosphoric acid of the formula: ##STR35## and reacting the resultant dithiophosphoric acid with an amount of basic compound of metal M which is between the amount stoichiometrically necessary to neutralize the dithiophosphoric acid and twice said stoichiometric amount.
Claim 14
Dependent Claim
16 words
A method according to claim 12, wherein the basic compound of metal M is zinc oxide.
Claim 15
Dependent Claim
85 words
A method according to claim 12, wherein the dithiophosphoric acid is prepared at a temperature of between about 50° and 200° C. with an amount of P 2 S 5 corresponding to a 5 percent molar excess referred to the stoichiometric amount and the dithiophosphoric acid is neutralized by the basic compound of metal M at a temperature between about 20° and 200° C. with an amount of basic compound of metal M which is between about 1.1 times and 1.5 times the stoichiometric amount.
Claim 16
Dependent Claim
33 words
A method according to claim 14, wherein the dithiophosphoric acid is prepared at a temperature between about 70° and 150° C. and is neutralized at a temperature between about 60° and 150° C.
Claim 17
Independent Claim
80 words
A method according to any of Claims 12 to 15, wherein the monoester alcohols employed are those derived from alcohols selected from among neopentylglycol and 2-ethyl-2-n-butyl-1,3-propanediol and acids selected from among acetic acid, 2,3-dichloro-propanoic acid, octanoic acid, 11-bromo-undecanoic acid, 9,10-dibromooctadecanoic acid, stearic acid, acrylic acid, cinnamic acid, 2-furanacryclic acid, methacrylic acid, undecylenic acid, oleic acid, cyclopropane-carboxylic acid, 1-cyclohexene carboxylic acid, cyclohexane-carboxylic acid, abietic acid, benzoic acid, p-chlorobenzoic acid, p-trifluoromethylbenzoic acid, 2,3-dimethylbenzoic acid, p-n-octyl-benzoic acid, 2-furan-carboxylic acid, 4-methylthiazol-5-carboxylic acid, and acid.
Claim 18
Dependent Claim
30 words
A lubricating composition comprising a major proportion of at least one lubricating oil and between about 0.2 and 10 percent by weight of a metallic dithiophosphate according to claim 1.
Claim 19
Dependent Claim
30 words
A lubricating composition comprising a major proportion of at least one lubricating oil and between about 0.2 and 10 percent by weight of a metallic dithiophosphate according to claim 7.
Claim 20
Dependent Claim
30 words
A lubricating composition comprising a major proportion of at least one lubricating oil and between about 0.2 and 10 percent by weight of a metallic dithiophosphate according to claim 11.
Claim 21
Dependent Claim
114 words
A metallic dithiophosphate having the formula: ##STR36## in which: R 1 represents: (a) a linear or branched alkyl radical containing from about 1 to 24 carbon atoms; (b) a linear or branched alkenyl radical containing from about 2 to 24 carbon atoms; (c) a saturated or unsaturated cycloaliphatic or polycycloaliphatic radical containing from about 3 to 20 carbon atoms; or (d) an aryl radical containing from 6 to 14 carbon atoms; R 2 and R 3 are alkyl radicals containing from about 1 to 12 carbon atoms; m represents the valence of the metal M; and M represents a metal of groups IIB, IIIB, IVB, or VIII of the Periodic System of the Elements.
Claim 22
Dependent Claim
114 words
A metallic dithiophosphate having the formula: ##STR36## in which: R 1 represents: (a) a linear or branched alkyl radical containing from about 1 to 24 carbon atoms; (b) a linear or branched alkenyl radical containing from about 2 to 24 carbon atoms; (c) a saturated or unsaturated cycloaliphatic or polycycloaliphatic radical containing from about 3 to 20 carbon atoms; or (d) an aryl radical containing from 6 to 14 carbon atoms; R 2 and R 3 are alkyl radicals containing from about 1 to 12 carbon atoms; m represents the valence of the metal M; and M represents a metal of groups IIB, IIIB, IVB, or VIII of the Periodic System of the Elements.
Claim 23
Dependent Claim
27 words
A metallic dithiophosphate according to claim 20, wherein the alkyl radical is substituted by at least one member selected from the class consisting of phenyl and halo.
Claim 24
Dependent Claim
27 words
A metallic dithiophosphate according to claim 20, wherein the alkenyl radical is substituted by at least one member selected from the class consisting of phenyl and halo.
Claim 25
Dependent Claim
33 words
A metallic dithiophosphate according to claim 20, wherein the cycloaliphatic or polycycloaliphatic radical is substituted by at least one alkyl group containing from about 1 to 12 carbon atoms or a halogen atom.
Claim 26
Dependent Claim
34 words
A metallic dithiophosphate according to claim 20, wherein the aryl radical is substituted by at least one alkyl group containing from about 1 to 12 carbon atoms, or a halogen, or halo alkyl group.
Claim 27
Dependent Claim
13 words
A metallic dithiophosphate according to claim 20, wherein the metal M is zinc.
Claim 28
Dependent Claim
47 words
A metallic dithiophosphate according to claim 20, wherein R 1 contains from about 1 to 17 carbon atoms when it represents an alkyl radical, from about 2 to 17 carbon atoms when it represents an alkenyl radical, and 6 carbon atoms when it represents an aryl radical.
Claim 29
Dependent Claim
21 words
A metallic dithiophosphate according to claim 20, wherein R 2 and R 3 contain from about 1 to 4 carbon atoms.
Claim 30
Dependent Claim
27 words
A metallic dithiophosphate according to claim 27, wherein R 2 and R 3 represent a member selected from the class consisting of methyl, ethyl, and butyl radicals.
Claim 31
Dependent Claim
44 words
A metallic dithiophosphate according to claim 1, wherein R 1 represents one of the following radicals: methyl, 1,2-dichloro-ethyl, heptyl, 10-bromo-decyl, 8,9-dibromo-heptadecyl, heptadecyl, vinyl, phenylvinylene, isopropenyl, decenyl, heptadecenyl, cyclopropyl, cyclohexyl, cyclohexenyl, C 19 H 29 derived from abietic acid, phenyl, p-chlorophenyl, p-trifluoromethylphenyl, 2,3-dimethyl-1-phenyl, and p-octylphenyl.
Claim 32
Dependent Claim
91 words
A method of preparing a metallic dithiophosphate according to claim 20, comprising reacting a monoester alcohol of the formula: ##STR37## with an amount of P 2 S 5 in excess of about 5 to 20 mol percent referred to the amount of P 2 S 5 stoichiometrically necessary in order to obtain a dithiophosphoric acid of the formula: ##STR38## and reacting the resultant dithiophosphoric acid with an amount of basic compound of metal M which is between the amount stoichiometrically necessary to neutralize the dithiophosphoric acid and twice said stoichiometric amount.
Claim 33
Dependent Claim
16 words
A method according to claim 30, wherein the basic compound of metal M is zinc oxide.
Claim 34
Dependent Claim
85 words
A method according to claim 30, wherein the dithiophosphoric acid is prepared at a temperature of between about 50° and 200° C. with an amount of P 2 S 5 corresponding to a 5 percent molar excess referred to the stoichiometric amount and the dithiophosphoric acid is neutralized by the basic compound of metal M at a temperature between about 20° and 200° C. with an amount of basic compound of metal M which is between about 1.1 times and 1.5 times the stoichiometric amount.
Claim 35
Dependent Claim
33 words
A method according to claim 32, wherein the dithiophosphoric acid is prepared at a temperature between about 70° and 150° C. and is neutralized at a temperature between about 60° and 150° C.
Claim 36
Independent Claim
73 words
A method according to any of claims 30 to 33, wherein the monoester alcohols employed are those derived from alcohols selected from among neopentylglycol and 2-ethyl-2-n-butyl-1,3-propanediol and acids selected from among acetic acid, 2,3-dichloro-propanoic acid, octanoic acid, 11-bromoundecanoic acid, 9,10-dibromo-octadecanoic acid, stearic acid, acrylic acid, cinnamic acid, methacrylic acid, undecylenic acid, oleic acid, cyclopropane-carboxylic acid, 1-cyclohexene carboxylic acid, cyclohexane-carboxylic acid, abietic acid, benzoic acid, p-chlorobenzoic acid, p-tri-fluoromethylbenzoic acid, 2,3-dimethylbenzoic acid, and p-n-octyl-benzoic acid.
Claim 37
Dependent Claim
30 words
A lubricating composition comprising a major proportion of at least one lubricating oil and between about 0.2 and 10 percent by weight of a metallic dithiophosphate according to claim 20.
Claim 38
Dependent Claim
30 words
A lubricating composition comprising a major proportion of at least one lubricating oil and between about 0.2 and 10 percent by weight of a metallic dithiophosphate according to claim 25.
Claim 39
Dependent Claim
30 words
A lubricating composition comprising a major proportion of at least one lubricating oil and between about 0.2 and 10 percent by weight of a metallic dithiophosphate according to claim 29.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-09-07 | 1985-03-09 | 1985-09-08 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-09-07 | 1989-03-09 | 1989-09-08 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-09-07 | 1993-03-09 | 1993-09-08 | $7700.00 | Window Closed / Lapsed |