CA2096896A1 - Salts of mercaptocarboxylic acid derivatives and their use as detergent additives - Google Patents
Salts of mercaptocarboxylic acid derivatives and their use as detergent additivesInfo
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- CA2096896A1 CA2096896A1 CA 2096896 CA2096896A CA2096896A1 CA 2096896 A1 CA2096896 A1 CA 2096896A1 CA 2096896 CA2096896 CA 2096896 CA 2096896 A CA2096896 A CA 2096896A CA 2096896 A1 CA2096896 A1 CA 2096896A1
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- cycloalkyl
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-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B1/00—Engines characterised by fuel-air mixture compression
- F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
- F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Lubricants (AREA)
- Furan Compounds (AREA)
- Pyridine Compounds (AREA)
Abstract
ABSTRACT
SALTS OF MERCAPTOCARBOXYLIC ACID
DERIVATIVES AND THEIR USE AS DETERGENT ADDITIVES
The invention provides calcium and magnesium salts of a mercaptocarboxylic acid derivative of the general formula:
R - S - (CR1R2) - COOH (I) in which n is 1 to 10; R represents an alkyl group, optionally substituted by a cycloalkyl, heterocyclyl or aryl group; or a cycloalkyl group optionally substituted by an alkyl group; and R1 and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl and aryl groups; subject to the total number of carbon atoms in the derivative being in the range from 12 to 50; a process for preparing the salts; and lubricating oil compositions and concentrates containing the salts.
SALTS OF MERCAPTOCARBOXYLIC ACID
DERIVATIVES AND THEIR USE AS DETERGENT ADDITIVES
The invention provides calcium and magnesium salts of a mercaptocarboxylic acid derivative of the general formula:
R - S - (CR1R2) - COOH (I) in which n is 1 to 10; R represents an alkyl group, optionally substituted by a cycloalkyl, heterocyclyl or aryl group; or a cycloalkyl group optionally substituted by an alkyl group; and R1 and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl and aryl groups; subject to the total number of carbon atoms in the derivative being in the range from 12 to 50; a process for preparing the salts; and lubricating oil compositions and concentrates containing the salts.
Description
2~96~9G
SALTS OF MEQCAPTOCARBO m IC ACID
DERIVATIVES AND THEIR USE AS DETERGENT ADDITIVES
The present invention relates to salts, in particular calcium and magnesium salts, of certain mercaptocarboxylic acid derlvatives, a process for thelr preparation, and lubricating oil compositions and concentrates containing them.
It is known from GB-A-532,676 to prepare thioethers and/or mercaptans by reacting unsaturated hydrocarbons with compounds of the general formula RSH where R ~s hydrogen or an organic radical in the presence of peroxides ant of iron, chromium, magnesium, aluminium, thorium, uranium, cerium, lanthanum, beryllium, osmium, molybdenum, vanadium and manganese salts of strong, inorganic acids. As examples of unsaturated hydrocarbons are mentioned ethylene, butene-l, butene- 2, hexene-l, cetene, acetylene, hexyne-l, cetyn-2, styrene, phenyl acetylene, cyclohexene, butadiene and pinene. Thioglycolic acid is mentioned as an example of a compound of the general formula RSH. GB-A-532,676 contains no disclosure of any use of the resulting thioethers or mercaptans.
GB-A- 835,987 discloses lubricating compositions comprising a ma~or proportion of a lubricating oil and a synergistic admixture of from 0.005 to l.O~w each of a branched Cg to Cl7 alkylmercap-toacetic acid ant a barium or calcium C6 to C12 branchet chsin tialkyl naphthaleno sulphonate, to impart superior rust inhibitlon to the composition. There is no suggestion that any derivative of the alkylmercaptoacetic acit might be used in place of or in adtition to the acit Per se.
In accortance with the present invention there are providet alkaline earth metal salts selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of the general formula:
.
2Q9~9~
R _ S _ (CRlR2)n - COOH (I) in which n is 1 to 10; R represents an alkyl group, optionally substituted by a cycloal~yl, heterocyclyl or aryl group; or a cycloalkyl group optionally substituted by an alkyl group; and and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl and aryl groups; sub~ect to the total number of carbon atoms in the derivative being in the range from 12 to 50.
The mercaptocarboxylic acid derivative of formula I preferably contains from 12 to 30, and especially 16 to 21, carbon atoms.
In this specification, unless otherwise stated, an alkyl group or alkyl moiety in an alkoxy, alkylthio or aralkyl group may be linear or branched and preferably contains up to 6, more preferably up to 10, and especially up to 20, carbon atoms. The substituent(s) in a substituted, branched alkyl group may be located either on the main chain or on the side-chain(s) of the alkyl group. A cycloalkyl group may contain from 3 to 8, preferably 3 to 6, carbon atoms. A heterocyclyl group may be any saturated or unsaturated ring system, e.g. a C5 7 ring system, containing at least one heteroatom selected rom oxygsn, nitrogen and sulphur, 5- and 6- membered rings being especially preferred, e.g. a tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrshydrothiophenyl or thiophenyl (thienyl) group. An aryl group may bo any aromstic hydrocarbon group, especially a phenyl or naphthyl group.
The preferred salts o the present invention are calcium salts.
In formula I above, n preferably ranges from 1 to 6, more preferably from 1 to 4, ant is especially 1.
R preferably represents a Cl-C20 alkyl group, optionally substituted by one or more substituents selected from C3-C8 cycloalkyl, tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, thiophenyl, phenyl and naphthyl groups; or a 3~
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C3-C8 cycloalkyl group optionally substituted by one or more Cl-C10 alkyl groups.
More preferably, R represents a C10-C20 alkyl group, optionally substituted by one or two substituents selected from C3-C6 cycloalkyl, tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, ehiophenyl~ phenyl and naphthyl groups; or a C3-C6 cycloalkyl group optionally substituted by one or two Cl-C6 alkyl groups.
Particularly preferred derivatives of formula I above are those in which R represents a C14-Clg alkyl group.
Preferably Rl and R are independently selected from hydrogen atoms, and hydroxyl, carboxyl, Cl-C10 alkyl, Cl-C10 alkoxy, Cl-C10 alkylthio, C3-C8 cycloalkyl, benzyl, phenyl and naphthyl groups.
More preferably R and R are independently selected from hydrogen atoms, and hydroxyl, carboxyl, Cl-C6 alkyl, Cl-C6 alkoxy, Cl-C6 alkylthio, C3-C6 cycloalkyl, benzyl, phenyl and naphthyl groups.
Most preferably, Rl and R2 represent hydrogen atoms.
It will be apprec~ated that when n is greater than 1, the -CR R groups can be the same as or different from one another.
A particularly preferred sub-group of compounds of formula I
is that in which n is 1, R represents a C14-Clg alkyl group and each of R and R represents a hydrogen atom.
The calcium and magnesium salts of the present invention may be neutral salts, i.e. those containing stoichiometrically equivalent amounts of metal and carboxylate moieties, or they may be overbased salts, as hereinafter defined. Overbased salts are preferred.
The present invention further provides a process for the preparation of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as defined above, which comprises reacting a mercaptocarboxylic acid derivative of formula I above with an oxide or hydroxide of calcium or magnesium.
2~ ,9~
SALTS OF MEQCAPTOCARBO m IC ACID
DERIVATIVES AND THEIR USE AS DETERGENT ADDITIVES
The present invention relates to salts, in particular calcium and magnesium salts, of certain mercaptocarboxylic acid derlvatives, a process for thelr preparation, and lubricating oil compositions and concentrates containing them.
It is known from GB-A-532,676 to prepare thioethers and/or mercaptans by reacting unsaturated hydrocarbons with compounds of the general formula RSH where R ~s hydrogen or an organic radical in the presence of peroxides ant of iron, chromium, magnesium, aluminium, thorium, uranium, cerium, lanthanum, beryllium, osmium, molybdenum, vanadium and manganese salts of strong, inorganic acids. As examples of unsaturated hydrocarbons are mentioned ethylene, butene-l, butene- 2, hexene-l, cetene, acetylene, hexyne-l, cetyn-2, styrene, phenyl acetylene, cyclohexene, butadiene and pinene. Thioglycolic acid is mentioned as an example of a compound of the general formula RSH. GB-A-532,676 contains no disclosure of any use of the resulting thioethers or mercaptans.
GB-A- 835,987 discloses lubricating compositions comprising a ma~or proportion of a lubricating oil and a synergistic admixture of from 0.005 to l.O~w each of a branched Cg to Cl7 alkylmercap-toacetic acid ant a barium or calcium C6 to C12 branchet chsin tialkyl naphthaleno sulphonate, to impart superior rust inhibitlon to the composition. There is no suggestion that any derivative of the alkylmercaptoacetic acit might be used in place of or in adtition to the acit Per se.
In accortance with the present invention there are providet alkaline earth metal salts selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of the general formula:
.
2Q9~9~
R _ S _ (CRlR2)n - COOH (I) in which n is 1 to 10; R represents an alkyl group, optionally substituted by a cycloal~yl, heterocyclyl or aryl group; or a cycloalkyl group optionally substituted by an alkyl group; and and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl and aryl groups; sub~ect to the total number of carbon atoms in the derivative being in the range from 12 to 50.
The mercaptocarboxylic acid derivative of formula I preferably contains from 12 to 30, and especially 16 to 21, carbon atoms.
In this specification, unless otherwise stated, an alkyl group or alkyl moiety in an alkoxy, alkylthio or aralkyl group may be linear or branched and preferably contains up to 6, more preferably up to 10, and especially up to 20, carbon atoms. The substituent(s) in a substituted, branched alkyl group may be located either on the main chain or on the side-chain(s) of the alkyl group. A cycloalkyl group may contain from 3 to 8, preferably 3 to 6, carbon atoms. A heterocyclyl group may be any saturated or unsaturated ring system, e.g. a C5 7 ring system, containing at least one heteroatom selected rom oxygsn, nitrogen and sulphur, 5- and 6- membered rings being especially preferred, e.g. a tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrshydrothiophenyl or thiophenyl (thienyl) group. An aryl group may bo any aromstic hydrocarbon group, especially a phenyl or naphthyl group.
The preferred salts o the present invention are calcium salts.
In formula I above, n preferably ranges from 1 to 6, more preferably from 1 to 4, ant is especially 1.
R preferably represents a Cl-C20 alkyl group, optionally substituted by one or more substituents selected from C3-C8 cycloalkyl, tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, thiophenyl, phenyl and naphthyl groups; or a 3~
2~96~
C3-C8 cycloalkyl group optionally substituted by one or more Cl-C10 alkyl groups.
More preferably, R represents a C10-C20 alkyl group, optionally substituted by one or two substituents selected from C3-C6 cycloalkyl, tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, ehiophenyl~ phenyl and naphthyl groups; or a C3-C6 cycloalkyl group optionally substituted by one or two Cl-C6 alkyl groups.
Particularly preferred derivatives of formula I above are those in which R represents a C14-Clg alkyl group.
Preferably Rl and R are independently selected from hydrogen atoms, and hydroxyl, carboxyl, Cl-C10 alkyl, Cl-C10 alkoxy, Cl-C10 alkylthio, C3-C8 cycloalkyl, benzyl, phenyl and naphthyl groups.
More preferably R and R are independently selected from hydrogen atoms, and hydroxyl, carboxyl, Cl-C6 alkyl, Cl-C6 alkoxy, Cl-C6 alkylthio, C3-C6 cycloalkyl, benzyl, phenyl and naphthyl groups.
Most preferably, Rl and R2 represent hydrogen atoms.
It will be apprec~ated that when n is greater than 1, the -CR R groups can be the same as or different from one another.
A particularly preferred sub-group of compounds of formula I
is that in which n is 1, R represents a C14-Clg alkyl group and each of R and R represents a hydrogen atom.
The calcium and magnesium salts of the present invention may be neutral salts, i.e. those containing stoichiometrically equivalent amounts of metal and carboxylate moieties, or they may be overbased salts, as hereinafter defined. Overbased salts are preferred.
The present invention further provides a process for the preparation of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as defined above, which comprises reacting a mercaptocarboxylic acid derivative of formula I above with an oxide or hydroxide of calcium or magnesium.
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The mercaptocarboxylic acid derivative of formula I is conveniently dissolved in an organic solvent and the resulting solution mixed with a stoichiometric equivalent amount of a suspension of a hydroxide and/or oxide of calcium or magnesium conveniently in the same solvent to yield the neutral calcium or magnesium salt of the formula I compound. The presence of an initial, small amount of water is beneficial in that it enhances the rate of reaction. The reaction rate is also enhanced by removing water formed during the reaction azeotropically. The neutral salt is subsequently purified according to conventional known techniques and, if desired, converted to an overbased salt by mixing in an organic solvent with further of the hydroxide and/or oxide of calcium or magnesium, a promoter and a small amount of water and passing carbon dioxide through the reaction mixture.
The overbased salt can, alternatively, be obtained directly from the mercaptocarboxylic acid derivative of formula I by treating the derivative in the same way as the neutral salt as described above.
In the present context, an overbased salt denotes a salt in which the basicity index (BI), defined as the equivalent ratio of total calcium or magnesium to calcium or magnesium salt of the mercaptocarboxylic acid derivative of formula I (as determined by potentiometric titration), is greater than 1. Detailed descriptions of overbasing processes are given in many patent specifications, for example GB-A-786,167.
The organic solvent may conveniently be a hydrocarbon, such as an aromatic hydrocarbon or a hydrocarbon fraction rich in aromatics, such as gasoline, with compounds such as benzene, toluene, or especially, xylene being preferred.
The promoter may, for example, be a Cl-C3 alcohol, preferably methanol. The amount of water used is conveniently in the range from O.S to 1.5 mol per equivalent mercaptocarboxylic acid derivative, or calcium or magnesium salt thereof.
Certain of the mercaptocarboxylic acid derivatives of formula I are known materials, e.g. from GB-A-532,676 discussed above.
2~96~9~
The overbased salt can, alternatively, be obtained directly from the mercaptocarboxylic acid derivative of formula I by treating the derivative in the same way as the neutral salt as described above.
In the present context, an overbased salt denotes a salt in which the basicity index (BI), defined as the equivalent ratio of total calcium or magnesium to calcium or magnesium salt of the mercaptocarboxylic acid derivative of formula I (as determined by potentiometric titration), is greater than 1. Detailed descriptions of overbasing processes are given in many patent specifications, for example GB-A-786,167.
The organic solvent may conveniently be a hydrocarbon, such as an aromatic hydrocarbon or a hydrocarbon fraction rich in aromatics, such as gasoline, with compounds such as benzene, toluene, or especially, xylene being preferred.
The promoter may, for example, be a Cl-C3 alcohol, preferably methanol. The amount of water used is conveniently in the range from O.S to 1.5 mol per equivalent mercaptocarboxylic acid derivative, or calcium or magnesium salt thereof.
Certain of the mercaptocarboxylic acid derivatives of formula I are known materials, e.g. from GB-A-532,676 discussed above.
2~96~9~
The mercaptocarboxylic acid derivatives of formula I as defined above may conveniently be prepared, for example, as described in GB-A-532,676, by reacting, in the presence of a peroxide, 3 compound of the general formula:
s R' - H (II) with a compound of the general formula:
HS - (CR R )n ~ COOH (III) wherein n i9 1 to 10; R' represents an alkenyl group, optionally substituted by a cycloalkyl, heterocyclyl or aryl group; or a cycloalkenyl group optionally substituted by an alkyl group; and and R2 are as defined above; sub~ect to the total number of carbon atoms in the compounds of formulae II and III taken together being in the range from 12 to 50.
The compounds of formula I above may also conveniently be prepared from the compounds of formulae II and III above by the methods of R~hlmann, Gramer, Heuchel and Schrapler, J. Prakt.
Chem., (4) 10, 316 (1960); Ueibull, Arkiv ~emi. Mineral. Geol., 23A, No. 18 (1946); Henkel and Cie GmbH, GB-A-470,717 [Chem. Abs., 32, 593 (1938)]; Smith and Hernestam, Acta Chem. Scand., 8, 1111 (1954); Holmberg, Arkiv Kemi. Mineral. Geol., 15A, No. 21 (1942);
Cunneen, J. Chem. Soc., 1947, 36 (references 466, 468, 481, 483, 490 and 108 respectively which are listed in Table XB, pp. 262-267 in "Organic Reactions", Volume 13 (John Wiley & Sons Inc., New York, London, 1963)); or by processes analogous thereto.
Certain mercaptocarboxylic acid derivatives of formula I as defined above, wherein n is at least 2, may alternatively be prepared by reacting, in the presence of ultra-violet light and, optionally, oxygen and a mercury salt, a compound of the general formula:
R - SH (IV) 2Q96~g~
s R' - H (II) with a compound of the general formula:
HS - (CR R )n ~ COOH (III) wherein n i9 1 to 10; R' represents an alkenyl group, optionally substituted by a cycloalkyl, heterocyclyl or aryl group; or a cycloalkenyl group optionally substituted by an alkyl group; and and R2 are as defined above; sub~ect to the total number of carbon atoms in the compounds of formulae II and III taken together being in the range from 12 to 50.
The compounds of formula I above may also conveniently be prepared from the compounds of formulae II and III above by the methods of R~hlmann, Gramer, Heuchel and Schrapler, J. Prakt.
Chem., (4) 10, 316 (1960); Ueibull, Arkiv ~emi. Mineral. Geol., 23A, No. 18 (1946); Henkel and Cie GmbH, GB-A-470,717 [Chem. Abs., 32, 593 (1938)]; Smith and Hernestam, Acta Chem. Scand., 8, 1111 (1954); Holmberg, Arkiv Kemi. Mineral. Geol., 15A, No. 21 (1942);
Cunneen, J. Chem. Soc., 1947, 36 (references 466, 468, 481, 483, 490 and 108 respectively which are listed in Table XB, pp. 262-267 in "Organic Reactions", Volume 13 (John Wiley & Sons Inc., New York, London, 1963)); or by processes analogous thereto.
Certain mercaptocarboxylic acid derivatives of formula I as defined above, wherein n is at least 2, may alternatively be prepared by reacting, in the presence of ultra-violet light and, optionally, oxygen and a mercury salt, a compound of the general formula:
R - SH (IV) 2Q96~g~
with a compound of the general formula:
CR R - CR (CR R )( 2) ~ COOH (V) wherein n, R, Rl and R2 are as defined above, sub~ect to the total number of carbon atoms in the compounds of formulae IV and V taken together being in the range from 12 to 50, e.g. according to the methods of Kaneko and Mii, J. Chem. Soc. Japan, 59, 1382 (1938) [Chem. Abs., 33, 2106 (1939)]; Koenig and Swern, J. Am. Chem. Soc., 79, 4235 (1957) (references 183 and 456 listed in Table XA, pp.
247-261 in "Organic Reactions~, Volume 13, (John Wiley & Sons Inc., New York, London, 1963)); or by processes analogous thereto.
The coLpounds of formulae II, III, IV and V are known compounds or can be prepared by processes analogous to known processes.
The alkaline earth metal salts according to the present invention may be used as detergent additives in lubricating oils.
Accordingly, the present invention further provides a lubricating oil composition comprising a ma~or proportion of a lubricating oil and a minor proportion, preferably from 0.1 to 20%w, more preferably from 0.1 to 10%w, and especially from 0.2 to 5%w, based on the total composition, of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid terivative of formula I as definet above.
Suitable lubricsting oils are natural, mineral or synthetic lubricating oils.
Natural lubricating oils include animal and vegetable oils, such as castor oil. Mineral oils comprise the lubricating oil fractions derived from crude oils, coal or shale, which fractions may have been sub~ected to certain treatments such as clay-acid, solvent or hydrogenation treatments. Synthetic lubricating oils include syhthetic poly~ers of hydrocarbons, modified alkylene oxide polymers, and ester lubricants, which are known in the art. These lubricating oils are preferably crankcase lubricating oils for spark-ignition and compression-ignition engines, but include also 2~9~9~
CR R - CR (CR R )( 2) ~ COOH (V) wherein n, R, Rl and R2 are as defined above, sub~ect to the total number of carbon atoms in the compounds of formulae IV and V taken together being in the range from 12 to 50, e.g. according to the methods of Kaneko and Mii, J. Chem. Soc. Japan, 59, 1382 (1938) [Chem. Abs., 33, 2106 (1939)]; Koenig and Swern, J. Am. Chem. Soc., 79, 4235 (1957) (references 183 and 456 listed in Table XA, pp.
247-261 in "Organic Reactions~, Volume 13, (John Wiley & Sons Inc., New York, London, 1963)); or by processes analogous thereto.
The coLpounds of formulae II, III, IV and V are known compounds or can be prepared by processes analogous to known processes.
The alkaline earth metal salts according to the present invention may be used as detergent additives in lubricating oils.
Accordingly, the present invention further provides a lubricating oil composition comprising a ma~or proportion of a lubricating oil and a minor proportion, preferably from 0.1 to 20%w, more preferably from 0.1 to 10%w, and especially from 0.2 to 5%w, based on the total composition, of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid terivative of formula I as definet above.
Suitable lubricsting oils are natural, mineral or synthetic lubricating oils.
Natural lubricating oils include animal and vegetable oils, such as castor oil. Mineral oils comprise the lubricating oil fractions derived from crude oils, coal or shale, which fractions may have been sub~ected to certain treatments such as clay-acid, solvent or hydrogenation treatments. Synthetic lubricating oils include syhthetic poly~ers of hydrocarbons, modified alkylene oxide polymers, and ester lubricants, which are known in the art. These lubricating oils are preferably crankcase lubricating oils for spark-ignition and compression-ignition engines, but include also 2~9~9~
hydraulic lubricants, metal-working fluids and automatic transmission fluids.
Preferably the lubricating base oil component of the compositions according to the present invention is a mineral lubricating oil or a mixture of mineral lubricating oils, such as those sold by member companies of the Royal Dutch/Shell ~roup under the designations "HVI", or "XHVI" (Trade Mark).
The viscosity of the lubricating base oils present in the compositions according to the present invention may vary within wide ranges, and is generally fr~om 3 to 35 mm2~s at 100C.
The lubricating o~l compositions of the present invention may further contain a number of other additives, such as antioxidants, anti-wear agents, ashless dispersants such as polyolefin-substituted succinimides, e.g. those described in GB-A-2 231 873, friction modifiers, foam inhibitors, corrosion inhibitors, viscosity index improvers, and pour point depressants, as can be established by a person skilled in the art.
The present invention still further provides a lubricating oil concentrate comprising from 10 to 80~w, based on the total concentrate, of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as defined above. Such a concentrate generally comprises an inert carrier fluid and one or more additives in a concentrated form. The inert carrier fluid is conveniently a lubricating oil.
The present invention still further provides a process for preparing a lubricating oil composition which comprises mixing a lubricating base oil with an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as defined above, or with a lubricatlng oil concentrate according to the invention.
The invention will be further understood from the following illustrative examples.
209689~
Preferably the lubricating base oil component of the compositions according to the present invention is a mineral lubricating oil or a mixture of mineral lubricating oils, such as those sold by member companies of the Royal Dutch/Shell ~roup under the designations "HVI", or "XHVI" (Trade Mark).
The viscosity of the lubricating base oils present in the compositions according to the present invention may vary within wide ranges, and is generally fr~om 3 to 35 mm2~s at 100C.
The lubricating o~l compositions of the present invention may further contain a number of other additives, such as antioxidants, anti-wear agents, ashless dispersants such as polyolefin-substituted succinimides, e.g. those described in GB-A-2 231 873, friction modifiers, foam inhibitors, corrosion inhibitors, viscosity index improvers, and pour point depressants, as can be established by a person skilled in the art.
The present invention still further provides a lubricating oil concentrate comprising from 10 to 80~w, based on the total concentrate, of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as defined above. Such a concentrate generally comprises an inert carrier fluid and one or more additives in a concentrated form. The inert carrier fluid is conveniently a lubricating oil.
The present invention still further provides a process for preparing a lubricating oil composition which comprises mixing a lubricating base oil with an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as defined above, or with a lubricatlng oil concentrate according to the invention.
The invention will be further understood from the following illustrative examples.
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Example 1 (i) Preparation of Linear C14 C18-alkylmercaptoacetic acids Into a 11 three-necked round bottomed flask provided with a stirrer, thermowell and condensor were introduced 160g (1.74 mol) mercaptoacetic acid, 311g (1,39 mol) of a mixture of C14-C18- alpha olefins derived from the "S~ELL" Higher Olefins Process (the molar rstio C14:C16:C18 being 1:2:1) and 0.33g lauryl peroxide. The reaction mixture was heated to 80C with vigorous stirring and the temperature rose to 110C as a result of exothermic reaction.
Further portions of 0.33g lauryl peroxide were added to the reaction mixture after 1~ and 5 hours reaction at 80C. The total reaction time at 80C was 7~ hours. The reaction mixture was subsequently distilled at 100 to 200C at a pressure of 200Pa to remove unreacted olefins and mercaptoacetic acid. 396g (89% yield based on olefin) of a mixture of linear C14-C18-alkylmercaptoacetic acids were obtained as a ~olid residue melting around 80C and having an acid content, as tetermined by titration with O.lN
potassium hydroxide in isopropanol, of 3.10 mmol/g (theoretical acid content, 3.16 mmol/g).
(ii) Preparation of Overbased Calcium Salts of Linear C14-C18-alkylmercaptoacetic acids Into a 31 glass reactor was introduced a solution of 389g (1.21 equivalents) of the mixture of linear C14-C18-alkylmercaptoacetlc acids obtained in (i) above in 2023g xylene (0.5 meq. acid/g). To this solution were added 201g (2.71 mol; 5.42 equivalents) calcium hydroxide and the resulting suspension stirred for 1 hour at 40C. Subsequently, 268g methanol (97~) (lO~w, baset on total weight of acid, xylene and methanol) were added to the suspension, the reaction temperature was increased to 60C and 2.05 equivalents carbon dioxide gas were introduced at a rate of 0.08 equivalent carbon dioxide gas per equivalent acid per minute. The equivalent ratio of acid: calcium hydroxide: carbon dioxide gas was 1:4.5:1.7. The slurry thus 2~96~9~
g formed was centrifuged for 2 hours at 2800rpm and at 20C to yield a precipitate of unreacted calcium hydroxide and two liquid layers, a thin, upper layer containing mainly methanol, and a main, lower layer containing xylene and overbased calcium salts of the linear C14-C18-alkylmercaptoacetic acids. The upper methanol layer was removed, followed by decantation of the lower xylene layer (2091g).
Analysis of the xylene layer by acidification with hydrochloric acid in isopropanol and then titration with 0.5N potassium hydroxide in isopropanol showed it to contain 2.92%w calcium and the basicity index of the overbased calcium salts to be 3.63. 621g "HVI 60" base oil (a bright and clear high viscosity index base oil having viscosity at 100C of 4.4 to 4.9 mm /s (ASTM D445) and minimum flash point 200C (ASTM D92)) were then added to the xylene layer and the xylene removed from the oil mixture by distillation at 130C and 200 Pa pressure to afford an oil concentrate containing the overbased calcium salts. The oil concentrate was found to have a calcium content of 5.92~w and a viscosity at 100C
of 10.1 mm /9 . The basicity index of the overbased calcium salts was 3.59.
~0 Example 2 (i) Preparation of Branched C -C -slkylmercaptoacetic aclds Into a 21 three-necked round bottomed flask provided with a stirrer, thermowell and condensor were introduced 736g (8 mol) 2S mercaptoacetic acid, 920g (4 mol) of a mixture of C14-Clg internal olefins having avorage molecular weight 230, derived from the "SHELL" Higher Olefins Process, and 9.2g ditertiarybutyl peroxide.
The reaction mixture was heated to 140C with vigorous stirring.
Further portions of 9.2g ditertiarybutyl peroxide were added to the reaction mixture after 2~, 5 and 7~ hours reaction at 140C. The total reaction time at 140C was 22 hours. The reaction mixture, which was composed of two liquid layers - an upper and a lower layer, was transferred to a separatory funnel and the lower layer removed and discarded. The remaining upper layer was distilled at 100 to 200C under vacuum to afford 1055g of a mixture of branched 2~9629~
C14-Clg-alkylmercaptoacetic acids as a solid residue having an acid content (determined as in Example l(i) above) of 2.97 meq./g (theoretical acid content 3.11 meq./g).
(ii) Preparation of ~verbased Calcium Salts of Branched C14-Clg -alkylmercaptoacetic acids Into a 51 glass reactor was introduced a solution of 500g (1485 milli-equivalents) of the mixture of branched C14-Clg-alkylmercaptoacetic acids obtained in (i) above in 2470g xylene (0.5 meq. acid/g), To this solution were added 231g (6237 milli-equivalents) calcium hydroxide and the resulting suspension stirred for 1 hour at 50C. Subsequently, 330g methanol (97~) (lO~w, based on total weight of acid, xylene and methanol) were added to the suspension, the reaction temperature was increased to 60C and 2524 milli-equivalents carbon dioxide gas were introduced at a rate of 0.085 equivalent carbon dioxide gas per equivalent acid per minute. The milli-equivalent ratio of acid: calcium hydroxide: carbon dioxide gas was 1:4,2:1.7. The slurry thus formed was centrifuged for 2 hours at 2400 rpm and at 20C to yield a precipitate of unreacted calcium hydroxide and two liquid layers, a thin, upper layer containing mainly methanol, and a main, lower layer containing xylene and overbased calcium salts of the branched C14-Clg-alkylmercaptoacetic acids. The upper methanol layer was removed, followed by decantation of the lower xylene layer (2940g).
Analysis of the xylene layer by acidification with hydrochloric acld in isopropanol and then titration with 0.5N potassium hydroxide in isopropanol showed it to contain 2.93%w calcium and the basicity index of the overbased calcium salts to be 2.84. 903g "HVI 60" base oil were then added to the xylene layer and the xylene removed from the oil mixture by distillation at 140C and lOOPa pressure to afford an oil concentrate containing the overbased calcium salts. The oil concentrate was found to have a calcium content of 5.88%w and a viscosity at 100C of 10.0 mm2/s.
The basicity index of the overbased calciu~ salts was 2.82.
2~9~
Example 3 Stability of Luboil Compositions In order to assess the formation of haze and/or deposits, 15g samples of the oil concentrates obtained in Example l(ii) and S Example 2(ii) above were each diluted with 85g of a mixture of "HVI
160B" base oil (a bright and clear high viscosity index base oil having kine~stic viscosity at 100C of 10.7 to 11.8 mm2/s (ASTM
D445) and minimum flash point of 218 to 228CC (ASTM D92)) and "HVI
650" base oil (a bright and clear high viscosity index base oil having kinematic viscosity at 100C of 30.5 to 33.5 mm /s (ASTM
D445) and minimum flash point of 267C (ASTM D92)), the mass ratio of ~HVI 160B" base oil to "HVI 650" base oil in the mixture being 3.25:1. The resulting compositions were stored in tubes at lOO~C
and after 2 and 7 days they were visually assessed for amount of deposits and for brightness. The amount of deposits was expressed in % by volume. The brightness was classified as "bright" (B) or "hazy" (H). The results obtained are shown in Table I below.
Table I
ExampleLuboil Stability*
No.2 Days 7 Days * expressed are ~ v/v deposits/brightness Example 4 EnRine Test Performance The oil concentrate obtained in Example 2(ii) sbove was blended in an amount giving 4.7%w overbased calciu~ salts in a base oil containing an additive package comprising VI ~viscosity index) -~ improver, ashless dispersant, zinc-based anti-wear additive and polymethacrylate pour-point depressant. The resulting oil was 20~C. ~
evaluated according to sequence 5E ASTM (as described in "Sequence SE test procedure~, 7th draft dated 19th May 1988; ASTM Monitoring Centre, 4400 5th Avenue, Pittsburgh, USA). The sequence 5E test is a gasoline engine test required for the API SG lubricant specification. It tests the ability of an oil to control sludge and varnish deposits and valve train wear in a 2.3 litre Ford four cylinder gasoline engine run under a cyclic operating procedure designed to simulate stop-go running conditions. The results obtained are shown in Table II following:
Table II
~ngine Test Exa~ple ACW inches x 10 3 No. AES AEV(m x 10 ) 2 9.47 8.415.90 (149.86) AES - Average Engine Sludge ) (Scale 0 to lQ, where AEV - Average Engine Varnish ) 10 representc zero sludge or varnish) ACU - Average Cam Lobe Wear
Further portions of 0.33g lauryl peroxide were added to the reaction mixture after 1~ and 5 hours reaction at 80C. The total reaction time at 80C was 7~ hours. The reaction mixture was subsequently distilled at 100 to 200C at a pressure of 200Pa to remove unreacted olefins and mercaptoacetic acid. 396g (89% yield based on olefin) of a mixture of linear C14-C18-alkylmercaptoacetic acids were obtained as a ~olid residue melting around 80C and having an acid content, as tetermined by titration with O.lN
potassium hydroxide in isopropanol, of 3.10 mmol/g (theoretical acid content, 3.16 mmol/g).
(ii) Preparation of Overbased Calcium Salts of Linear C14-C18-alkylmercaptoacetic acids Into a 31 glass reactor was introduced a solution of 389g (1.21 equivalents) of the mixture of linear C14-C18-alkylmercaptoacetlc acids obtained in (i) above in 2023g xylene (0.5 meq. acid/g). To this solution were added 201g (2.71 mol; 5.42 equivalents) calcium hydroxide and the resulting suspension stirred for 1 hour at 40C. Subsequently, 268g methanol (97~) (lO~w, baset on total weight of acid, xylene and methanol) were added to the suspension, the reaction temperature was increased to 60C and 2.05 equivalents carbon dioxide gas were introduced at a rate of 0.08 equivalent carbon dioxide gas per equivalent acid per minute. The equivalent ratio of acid: calcium hydroxide: carbon dioxide gas was 1:4.5:1.7. The slurry thus 2~96~9~
g formed was centrifuged for 2 hours at 2800rpm and at 20C to yield a precipitate of unreacted calcium hydroxide and two liquid layers, a thin, upper layer containing mainly methanol, and a main, lower layer containing xylene and overbased calcium salts of the linear C14-C18-alkylmercaptoacetic acids. The upper methanol layer was removed, followed by decantation of the lower xylene layer (2091g).
Analysis of the xylene layer by acidification with hydrochloric acid in isopropanol and then titration with 0.5N potassium hydroxide in isopropanol showed it to contain 2.92%w calcium and the basicity index of the overbased calcium salts to be 3.63. 621g "HVI 60" base oil (a bright and clear high viscosity index base oil having viscosity at 100C of 4.4 to 4.9 mm /s (ASTM D445) and minimum flash point 200C (ASTM D92)) were then added to the xylene layer and the xylene removed from the oil mixture by distillation at 130C and 200 Pa pressure to afford an oil concentrate containing the overbased calcium salts. The oil concentrate was found to have a calcium content of 5.92~w and a viscosity at 100C
of 10.1 mm /9 . The basicity index of the overbased calcium salts was 3.59.
~0 Example 2 (i) Preparation of Branched C -C -slkylmercaptoacetic aclds Into a 21 three-necked round bottomed flask provided with a stirrer, thermowell and condensor were introduced 736g (8 mol) 2S mercaptoacetic acid, 920g (4 mol) of a mixture of C14-Clg internal olefins having avorage molecular weight 230, derived from the "SHELL" Higher Olefins Process, and 9.2g ditertiarybutyl peroxide.
The reaction mixture was heated to 140C with vigorous stirring.
Further portions of 9.2g ditertiarybutyl peroxide were added to the reaction mixture after 2~, 5 and 7~ hours reaction at 140C. The total reaction time at 140C was 22 hours. The reaction mixture, which was composed of two liquid layers - an upper and a lower layer, was transferred to a separatory funnel and the lower layer removed and discarded. The remaining upper layer was distilled at 100 to 200C under vacuum to afford 1055g of a mixture of branched 2~9629~
C14-Clg-alkylmercaptoacetic acids as a solid residue having an acid content (determined as in Example l(i) above) of 2.97 meq./g (theoretical acid content 3.11 meq./g).
(ii) Preparation of ~verbased Calcium Salts of Branched C14-Clg -alkylmercaptoacetic acids Into a 51 glass reactor was introduced a solution of 500g (1485 milli-equivalents) of the mixture of branched C14-Clg-alkylmercaptoacetic acids obtained in (i) above in 2470g xylene (0.5 meq. acid/g), To this solution were added 231g (6237 milli-equivalents) calcium hydroxide and the resulting suspension stirred for 1 hour at 50C. Subsequently, 330g methanol (97~) (lO~w, based on total weight of acid, xylene and methanol) were added to the suspension, the reaction temperature was increased to 60C and 2524 milli-equivalents carbon dioxide gas were introduced at a rate of 0.085 equivalent carbon dioxide gas per equivalent acid per minute. The milli-equivalent ratio of acid: calcium hydroxide: carbon dioxide gas was 1:4,2:1.7. The slurry thus formed was centrifuged for 2 hours at 2400 rpm and at 20C to yield a precipitate of unreacted calcium hydroxide and two liquid layers, a thin, upper layer containing mainly methanol, and a main, lower layer containing xylene and overbased calcium salts of the branched C14-Clg-alkylmercaptoacetic acids. The upper methanol layer was removed, followed by decantation of the lower xylene layer (2940g).
Analysis of the xylene layer by acidification with hydrochloric acld in isopropanol and then titration with 0.5N potassium hydroxide in isopropanol showed it to contain 2.93%w calcium and the basicity index of the overbased calcium salts to be 2.84. 903g "HVI 60" base oil were then added to the xylene layer and the xylene removed from the oil mixture by distillation at 140C and lOOPa pressure to afford an oil concentrate containing the overbased calcium salts. The oil concentrate was found to have a calcium content of 5.88%w and a viscosity at 100C of 10.0 mm2/s.
The basicity index of the overbased calciu~ salts was 2.82.
2~9~
Example 3 Stability of Luboil Compositions In order to assess the formation of haze and/or deposits, 15g samples of the oil concentrates obtained in Example l(ii) and S Example 2(ii) above were each diluted with 85g of a mixture of "HVI
160B" base oil (a bright and clear high viscosity index base oil having kine~stic viscosity at 100C of 10.7 to 11.8 mm2/s (ASTM
D445) and minimum flash point of 218 to 228CC (ASTM D92)) and "HVI
650" base oil (a bright and clear high viscosity index base oil having kinematic viscosity at 100C of 30.5 to 33.5 mm /s (ASTM
D445) and minimum flash point of 267C (ASTM D92)), the mass ratio of ~HVI 160B" base oil to "HVI 650" base oil in the mixture being 3.25:1. The resulting compositions were stored in tubes at lOO~C
and after 2 and 7 days they were visually assessed for amount of deposits and for brightness. The amount of deposits was expressed in % by volume. The brightness was classified as "bright" (B) or "hazy" (H). The results obtained are shown in Table I below.
Table I
ExampleLuboil Stability*
No.2 Days 7 Days * expressed are ~ v/v deposits/brightness Example 4 EnRine Test Performance The oil concentrate obtained in Example 2(ii) sbove was blended in an amount giving 4.7%w overbased calciu~ salts in a base oil containing an additive package comprising VI ~viscosity index) -~ improver, ashless dispersant, zinc-based anti-wear additive and polymethacrylate pour-point depressant. The resulting oil was 20~C. ~
evaluated according to sequence 5E ASTM (as described in "Sequence SE test procedure~, 7th draft dated 19th May 1988; ASTM Monitoring Centre, 4400 5th Avenue, Pittsburgh, USA). The sequence 5E test is a gasoline engine test required for the API SG lubricant specification. It tests the ability of an oil to control sludge and varnish deposits and valve train wear in a 2.3 litre Ford four cylinder gasoline engine run under a cyclic operating procedure designed to simulate stop-go running conditions. The results obtained are shown in Table II following:
Table II
~ngine Test Exa~ple ACW inches x 10 3 No. AES AEV(m x 10 ) 2 9.47 8.415.90 (149.86) AES - Average Engine Sludge ) (Scale 0 to lQ, where AEV - Average Engine Varnish ) 10 representc zero sludge or varnish) ACU - Average Cam Lobe Wear
Claims (10)
1. An alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of the general formula R - S - (CR1R2)n - COOH (I) in which n is 1 to 10; R represents an alkyl group, optionally substituted by a cycloalkyl, heterocyclyl or aryl group; or a cycloalkyl group optionally substituted by an alkyl group; and R1 and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, alkyl, alkoxy, alkylthio, cycloalkyl, aralkyl and aryl groups; subject to the total number of carbon atoms in the derivative being in the range from 12 to 50,
2. A salt as claimed in claim 1, wherein, in formula I, R
represents a C1-C20 alkyl group, optionally substituted by one or more substituents selected from C3-C8 cycloalkyl, tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, thiophenyl, phenyl and naphthyl groups; or a C3-C8 cycloalkyl group optionally substituted by one or more C1-C10 alkyl groups.
represents a C1-C20 alkyl group, optionally substituted by one or more substituents selected from C3-C8 cycloalkyl, tetrahydrofuranyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, thiophenyl, phenyl and naphthyl groups; or a C3-C8 cycloalkyl group optionally substituted by one or more C1-C10 alkyl groups.
3. A salt as claimed in claim 1 or claim 2, wherein, in formula I, R represents a C10-C20 alkyl group, optionally substituted by one or two substituents selected from C3-C6 cycloalkyl, tetrahydro-furanyl, furanyl, piperidinyl, pyridinyl, tetrahydrothiophenyl, thiophenyl, phenyl and naphthyl groups; or a C3-C6 cycloalkyl group optionally substituted by one or two C1-C6 alkyl groups.
4. A salt as claimed in any one of claims 1 to 3, wherein, in formula I, R1 and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio, C3-C8 cycloslkyl, benzyl, phenyl and naphthyl groups
5. A salt as claimed in any one of the preceding claims, wherein, in formula I, R1 and R2 are independently selected from hydrogen atoms, and hydroxyl, carboxyl, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, C3-C6 cycloalkyl, benzyl, phenyl and naphthyl groups.
6. A salt as claimed in any one of the preceding claims, wherein, in formula I, n is 1, R represents a C14-C19 alkyl group and each of R and a represents a hydrogen atom.
7. A salt as claimed in any one of the preceding claims which is a calcium salt.
8. A process for the preparation of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as claimed in any one of the preceding claims, which comprises reacting a mercaptocarboxylic acid derivative of formula I as defined in any one of the preceding claims with an oxide or hydroxide of calcium or magnesium.
9. A lubricating oil composition comprising a major proportion of a lubricating oil and a minor proportion of an alkaline earth metal salt selected from calcium and magnesium salts of a mercapto-carboxylic acid derivative of formula I as claimed in any one of claims 1 to 7.
10. A lubricating oil concentrate comprising from 10 to 80%w, based on the total concentrate, of an alkaline earth metal salt selected from calcium and magnesium salts of a mercaptocarboxylic acid derivative of formula I as claimed in any one of claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92305281.5 | 1992-06-09 | ||
| EP92305281 | 1992-06-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2096896A1 true CA2096896A1 (en) | 1993-12-10 |
Family
ID=8211395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2096896 Abandoned CA2096896A1 (en) | 1992-06-09 | 1993-05-25 | Salts of mercaptocarboxylic acid derivatives and their use as detergent additives |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0656761A (en) |
| CA (1) | CA2096896A1 (en) |
| DE (1) | DE69304611T2 (en) |
-
1993
- 1993-05-25 CA CA 2096896 patent/CA2096896A1/en not_active Abandoned
- 1993-06-08 DE DE1993604611 patent/DE69304611T2/en not_active Expired - Fee Related
- 1993-06-08 JP JP13784693A patent/JPH0656761A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0656761A (en) | 1994-03-01 |
| DE69304611T2 (en) | 1997-02-06 |
| DE69304611D1 (en) | 1996-10-17 |
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