CA1253873A - Process for the preparation of sulphurized overbased salicylates - Google Patents
Process for the preparation of sulphurized overbased salicylatesInfo
- Publication number
- CA1253873A CA1253873A CA000484253A CA484253A CA1253873A CA 1253873 A CA1253873 A CA 1253873A CA 000484253 A CA000484253 A CA 000484253A CA 484253 A CA484253 A CA 484253A CA 1253873 A CA1253873 A CA 1253873A
- Authority
- CA
- Canada
- Prior art keywords
- overbased
- sulphurized
- process according
- meq
- salicylic acid
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
- C10M159/12—Reaction products
- C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
- C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
A B S T R A C T
PROCESS FOR THE PREPARATION OF SULPHURIZED
OVERBASED SALICYLATES
Process for the preparation of sulphurized overbased metal aliphatic hydrocarbon-substituted salicylates, wherein an aliphatic hydrocarbon-substituted salicylic acid is transformed into an overbased metal salicylate having a basicity index of at least 1.5 by means of a basic metal compound and carbon dioxide and then the overbased metal salicylate is sulphurized by heating with elemental sulphur.
PROCESS FOR THE PREPARATION OF SULPHURIZED
OVERBASED SALICYLATES
Process for the preparation of sulphurized overbased metal aliphatic hydrocarbon-substituted salicylates, wherein an aliphatic hydrocarbon-substituted salicylic acid is transformed into an overbased metal salicylate having a basicity index of at least 1.5 by means of a basic metal compound and carbon dioxide and then the overbased metal salicylate is sulphurized by heating with elemental sulphur.
Description
j38~73 P~OCESS FOR THE PR~PARATION OF SULPMURIZED
O~ERBASED SALICYLATES
This inventlon relates to a process for the preparation of sulphurized overbased metal alkyl-substituted salicylates, to products thus prepared and to oil composltions containing them.
From British paten~ specification 1,287,812 aliphatic hydrocarbon-substituted salicylates and oil compositlons containing them as detergents and wear inhibitors are already known. It discloses the reaction of an aliphatic hydrocarbon-substituted salicylic acld, or a metal salt thereof, withelemental sulphur, an alkaline earth base, e.g. a hydroxide, and a solvent, such as ethylene glycol, at at least 150C, and optionally further reactlon with carbon dioxide. A similar process is disclosed in British patent specl~ication 1,194,503.
However, it has been found that this known process shows the disadvantage of a substantial degree of decarboxylation during the reaction with sulphur.
It has now been found that a much lower degree of decarboxylation can be obtained by reaction of alkyl-substituted hydrocarbon-substltuted salicylic acid, or the metal salt thereof, with sulphur after overbasing with carbon dioxide, without loss of the excellent deteryent and anti-wear properties.
This invention therefore relates to a process for the preparation of sulphurized overbased alkaline earth metal C8-C30 alkyl-substituted salicylates, characterized in that the corresponding alkyl-substitu~ed salicylic acid is treated with an alkaline earth metal hydroxide and carbon dioxide in a hydrocarbon solvent to produce an overbased alkaline earth metal salicylate . .~
~L25~3873
O~ERBASED SALICYLATES
This inventlon relates to a process for the preparation of sulphurized overbased metal alkyl-substituted salicylates, to products thus prepared and to oil composltions containing them.
From British paten~ specification 1,287,812 aliphatic hydrocarbon-substituted salicylates and oil compositlons containing them as detergents and wear inhibitors are already known. It discloses the reaction of an aliphatic hydrocarbon-substituted salicylic acld, or a metal salt thereof, withelemental sulphur, an alkaline earth base, e.g. a hydroxide, and a solvent, such as ethylene glycol, at at least 150C, and optionally further reactlon with carbon dioxide. A similar process is disclosed in British patent specl~ication 1,194,503.
However, it has been found that this known process shows the disadvantage of a substantial degree of decarboxylation during the reaction with sulphur.
It has now been found that a much lower degree of decarboxylation can be obtained by reaction of alkyl-substituted hydrocarbon-substltuted salicylic acid, or the metal salt thereof, with sulphur after overbasing with carbon dioxide, without loss of the excellent deteryent and anti-wear properties.
This invention therefore relates to a process for the preparation of sulphurized overbased alkaline earth metal C8-C30 alkyl-substituted salicylates, characterized in that the corresponding alkyl-substitu~ed salicylic acid is treated with an alkaline earth metal hydroxide and carbon dioxide in a hydrocarbon solvent to produce an overbased alkaline earth metal salicylate . .~
~L25~3873
2 63293-2537 having a basicity of at least 1.5, and subsequently the overbased metal salicylate is sulphurized with elemental sulphur, wherein the molar ratio of S: substituted salicylic acid is 0.25 to 3, in the presence of a solvent chosen from the group consisting of an alkylene or polyalk~lene glycol, or a lower alkyl mono-ether thereof, at a temperature of about 100 to 250C.
The lnvention furthermore relates to the products thus prepared and to oil compositions containin~ them.
Of the alkaline earth metals, such as Ca, ~a, Sr and Mg calcium, barium and magnesium are preferred.
The overbasin~ step can be carried out by reacting the salicylic acid in a solvent, such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene, with the alkaline earth metal hydroxide and carbon dioxide, as described in e.g. British patent specification 786167.
To the resulting reaction mixture a li~ht mineral oil may be added and then the hydrocarbon solvent, and any water formed may be removed by distillation.
The basicity lndex (BI) of the overbased salicylate, defined as the equivalent ratio of metal:salicylic acid, is at least 1.5, preferably at least 3. It has been found that this is of importance in order to avoid any substantial amount of decarboxylation in the sulphurization step.
The sulphurization step can be carried out by contacting the resulting oil solution of the overbased salt with elemental sulphur, preferably in the presence of a solvent, at a temperature in the range of 100-250C, preferahly 150-225C, whereby the final temperature should be at least 175C and preferably at least 195C.
~ , . . .
~253f~73
The lnvention furthermore relates to the products thus prepared and to oil compositions containin~ them.
Of the alkaline earth metals, such as Ca, ~a, Sr and Mg calcium, barium and magnesium are preferred.
The overbasin~ step can be carried out by reacting the salicylic acid in a solvent, such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene, with the alkaline earth metal hydroxide and carbon dioxide, as described in e.g. British patent specification 786167.
To the resulting reaction mixture a li~ht mineral oil may be added and then the hydrocarbon solvent, and any water formed may be removed by distillation.
The basicity lndex (BI) of the overbased salicylate, defined as the equivalent ratio of metal:salicylic acid, is at least 1.5, preferably at least 3. It has been found that this is of importance in order to avoid any substantial amount of decarboxylation in the sulphurization step.
The sulphurization step can be carried out by contacting the resulting oil solution of the overbased salt with elemental sulphur, preferably in the presence of a solvent, at a temperature in the range of 100-250C, preferahly 150-225C, whereby the final temperature should be at least 175C and preferably at least 195C.
~ , . . .
~253f~73
3 63293-2537 The resulting oil solution of the sulphurized product may be fil~ered, if desired, and then be added to an oil, such as a lubricating oil or a fuel oil, including gasoline.
The above-mentioned solvent of the sulphurization step preferably is an alkylene or polyalkylene glycol or a lower alkyl monoether thereof, as disclosed in the above-mentioned British patent specificatiQns 1~287,812 and 1,194,503.
A promoter such as carboxylic acid or a metal salt thereof, as described in British patent specification 1,194,503 may also be present in the sulphurization step.
The molar ratio of S:substituted salicylic acid is e.g.
- 0.25 to 3, preferably 0.5 to 2.
Before or after sulphurl~ation the product may be reacted with a boron compound, such as boric acid, as described in the copending Canadian patent application 469,764.
The reaction products of this invention including mixtures thereo~ can be incorporated in oil compositions, in particular lubricating oil compositions or concentrates or fuels, e.g. automotive crankcase oils, in concentratlons within the range of 0.001 to 65, in particular 0.1 to 15 ~w based on the weight of the total compositions.
The lubricating oils to which the additives o~ the invention can be added include not only mineral lubricating oils, but synthetic oils also. Synthetic hydrocarbon lubricating oils may also be employed, as well as non-hydrocarbon syn~hetic oils including dibasic acid esters such as di-2-ethyl hexyl sebacate, carbonate esters, phosphate esters, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters such as C13 oxo acid . ~
~L253~373 3a 63293-2537 diesters of tetraethylene glycol, etc. Mixtures of these oils, in particular of mineral lubrleating oils, including hydrogenated oils, and synthetic lubricating oils, can also be used.
When used in gasoline or fuel oil, e.g. diesel fuel, etc., then usually 0.001 to 0.5 ~w, based on the weight of the total composition of the reaction product will be used. Usually concentrates comprising e.g. 15 to 65 ~w of said raaction product in a hydrocarbon diluent and 85 to 35 %w mineral lubrica~ing oil, are prepared for ease of handling.
'~
~2~;3873 In the above compositions other additives may also be pre-sent, including dyes, pour point depressants, anti-wear, e.g., tricresyl phosphate, zinc dithiophosphates, antioxidants such as phenyl-alpha-naphthyl-amine, bis-phenols such as 4,4'-methylene bis (3,6-di-tert-butylphenol), viscosity index improvers, such as hydrogenated (co)polymers of conjugated dienes and optionally styrene, ethylene-higher olefin copolymers, polymethylacrylates, polyisobutylene, and the like as well as ashless dispersants, such as reaction products of polyisobutylene, maleic anhydride and amines and/or polyols, or other metal-containing detergents, such as overbased metal salicylates.
Reaction products of amines, formaldehyde and alkyl phenols (Mannich bases) can also be present.
The invention is further illustrated by the following Examples.
Example 1 Overbased calcium C14 18-alkyl salicylate, having a BI of 3 (Product A), was pr`epared from C14 18-alkyl salicylic acid by means of calcium hydroxide and carbon dioxide, and was taken up in a mineral lubricating oil.
A reaction vessel (5 litre) was charged with 2500 g (2530 meq acid) of a concentrate of 67 %w of the overbased calcium C14 18-alkyl salicylate in 33 %w of the mineral lubricating oil, 80 g (2500 meq) elemental sulphur and 20 g ethylene glycol.
Under stirring this mixture was heated to 125 C and kept at that temperature for one hour. The temperature was then raised to 150 C and kept at that temperature for one hour at a pressure of about 550 mm Hg. Then the temperature was raised to 195 C and the pressure lowered to 50-60 mm Hg, these conditions were maintained for two hours. The reaction product was then allowed to cool to about 100 C before filtering through filter aid, to give a dark viscous product (yield: 2500 g, S: 1.6 %w ! (Product B). It ~ppeared that sulphurization at a lower temperature (175 C) resulted in some dissolved unreacted sulphur, which is inclined to precipitate on standing.
It furthermore appeared that during the sulphurization only ~3~7~3 , a small amount of decarboxylation occurred (9%; acid number of starting material 1.06 and of product 0.96; acid number in meq acid/g, determined after acidification with HCl, extraction with diethyl ether, phase separation and evaporation of the solvent) (same method in the following Examples).
Example 2 2500 g of a concentrate of 50 %w overbased calcium C14 18-alkylsalicylate (1625 meq) prepared from the alkyl salicylic acids, calcium hydroxide and carbon dioxide and having a B.I. of 7.72~in 50 %w mineral lubricating oil was sulphurised with 51.3 g of elemental sulphur (1603 meq) and 13 g of ethylene glycol according to the process described in example 1. Yield: 2453 g, S: 1.2 %w.
It appeared that during sulphurisation 2% decarboxylation occurred (acid number of starting material 0.79 meq/g and of product 0.77 meq/g).
Example 3 250 g of a concentrate of 62 %w overbased magnesium C14 18 alkylsalicylate (213.5 meq) having a B.I. of 7.2 in 38 %w mineral lubricating oil was sulphurised with 6.58 g of elemental sulphur (205.6 meq) and 1.7 g of ethylene glycol according to the process described in example 1. Yield: 243.6 g, S: 0.94 %w.
It appeared that during sulphurisation 3% decarboxylation occurred (acid number of starting material 1.02 meq/g and of product 1.00 meq/g).
Comparative Experiment 1 To 97-6 g (205 meq) of neat C14 18 alkyl salicylic acids were added 37.9 g (1025 meq) of Ca(OH)2 and 69.5 g of a mineral lubricating oil, resulting in a 1.0 meq/g mixture of acids.
133.2 g of this mixture (133.2 meq), 4.26 g of S (133.2 meq) and 1.0 g of ethylene glycol were heated under stirring to 125 C
and kept at that temperature for one hour. The temperature was further raised to 150 C (1 hour, pressure: 550 mm Hg) and 195 C (2 hours, 50-60 mm Hg). The reaction mixture was cooled, diluted with n-hexane, filtered through filter aid and finally ~2~31~3 evaporated to yield a very viscous, dark material. Yield: 112.3 g, S: 1.6 %.
It appeared that during the sulphurisation 20% decarboxy-lation occurred (acid number of starting material 1.22 meq/g and of product 0.95 meq/g).
Comparative Experiment 2 2500 g of a concentrate of 58 %w overbased calcium C1~ 18-alkylsalicylate (2300 meq) having a B.I. of 1. 28 in 42 %w mineral lubricating oil was sulphurised with 77 g elemental sulphur (2406 meq) and 19 g of ethylene glycol according to the proces decribed in example 1. Yield: 2496 g, S: 1.3 %w.
It appeared that during sulphurization 28% decarboxylation occurred ~acid number of starting material 0.92 meq/g and of product 0.66 meq/g).
TESTS
In two 15W40 mineral lubricating oils (1 and 2), containing commercial dispersant, detergent and anti-oxidant additives, the products A and B (see Example 1) were tested.
Formulation I contained Product A in an amount of 0.14 %w as Ca in lubricating oil 1. Formulation II contained lubricating oil 1 and 0.14 %w (as Ca) of Product B. Formulations III and IV
comprised lubricating oil 2 with 0.19 %w as Ca of Product A and B, respectively.
Formulations I and II were tested in the CRC L38 test (AS1~1 STP 509A, part IV) in which the bearing weight loss is determined. The results are represented in Table I:
TABLE I
Formulation I II
Bearing weight loss, mg 45.4 33.6 It appears that use of the sulphurized product results in a reduction of the bearing weight loss.
;3~73 Formulations III and IV were tested in the MS Sequence IIID
engine test in which the cam and lifter wear and cleanliness performance were determined.
The results are shown in Tabl.e II:
TABLE II
Test 1 2 3 4 Formulation III III IV IV
Maximum cam and lifter wear, mm 0.55 0.77 0.38 0.50 .
Average cam and lifter wear, mm 0.26 0.24 0.14 0.12 Average sludge rating (10 being clean) 9.66 9.58 9.63 9.58 .
It appears that use of the sulphurized products results in a reduction of the cam and lifter wear. The cleanliness rating remained about the same.
The above-mentioned solvent of the sulphurization step preferably is an alkylene or polyalkylene glycol or a lower alkyl monoether thereof, as disclosed in the above-mentioned British patent specificatiQns 1~287,812 and 1,194,503.
A promoter such as carboxylic acid or a metal salt thereof, as described in British patent specification 1,194,503 may also be present in the sulphurization step.
The molar ratio of S:substituted salicylic acid is e.g.
- 0.25 to 3, preferably 0.5 to 2.
Before or after sulphurl~ation the product may be reacted with a boron compound, such as boric acid, as described in the copending Canadian patent application 469,764.
The reaction products of this invention including mixtures thereo~ can be incorporated in oil compositions, in particular lubricating oil compositions or concentrates or fuels, e.g. automotive crankcase oils, in concentratlons within the range of 0.001 to 65, in particular 0.1 to 15 ~w based on the weight of the total compositions.
The lubricating oils to which the additives o~ the invention can be added include not only mineral lubricating oils, but synthetic oils also. Synthetic hydrocarbon lubricating oils may also be employed, as well as non-hydrocarbon syn~hetic oils including dibasic acid esters such as di-2-ethyl hexyl sebacate, carbonate esters, phosphate esters, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters such as C13 oxo acid . ~
~L253~373 3a 63293-2537 diesters of tetraethylene glycol, etc. Mixtures of these oils, in particular of mineral lubrleating oils, including hydrogenated oils, and synthetic lubricating oils, can also be used.
When used in gasoline or fuel oil, e.g. diesel fuel, etc., then usually 0.001 to 0.5 ~w, based on the weight of the total composition of the reaction product will be used. Usually concentrates comprising e.g. 15 to 65 ~w of said raaction product in a hydrocarbon diluent and 85 to 35 %w mineral lubrica~ing oil, are prepared for ease of handling.
'~
~2~;3873 In the above compositions other additives may also be pre-sent, including dyes, pour point depressants, anti-wear, e.g., tricresyl phosphate, zinc dithiophosphates, antioxidants such as phenyl-alpha-naphthyl-amine, bis-phenols such as 4,4'-methylene bis (3,6-di-tert-butylphenol), viscosity index improvers, such as hydrogenated (co)polymers of conjugated dienes and optionally styrene, ethylene-higher olefin copolymers, polymethylacrylates, polyisobutylene, and the like as well as ashless dispersants, such as reaction products of polyisobutylene, maleic anhydride and amines and/or polyols, or other metal-containing detergents, such as overbased metal salicylates.
Reaction products of amines, formaldehyde and alkyl phenols (Mannich bases) can also be present.
The invention is further illustrated by the following Examples.
Example 1 Overbased calcium C14 18-alkyl salicylate, having a BI of 3 (Product A), was pr`epared from C14 18-alkyl salicylic acid by means of calcium hydroxide and carbon dioxide, and was taken up in a mineral lubricating oil.
A reaction vessel (5 litre) was charged with 2500 g (2530 meq acid) of a concentrate of 67 %w of the overbased calcium C14 18-alkyl salicylate in 33 %w of the mineral lubricating oil, 80 g (2500 meq) elemental sulphur and 20 g ethylene glycol.
Under stirring this mixture was heated to 125 C and kept at that temperature for one hour. The temperature was then raised to 150 C and kept at that temperature for one hour at a pressure of about 550 mm Hg. Then the temperature was raised to 195 C and the pressure lowered to 50-60 mm Hg, these conditions were maintained for two hours. The reaction product was then allowed to cool to about 100 C before filtering through filter aid, to give a dark viscous product (yield: 2500 g, S: 1.6 %w ! (Product B). It ~ppeared that sulphurization at a lower temperature (175 C) resulted in some dissolved unreacted sulphur, which is inclined to precipitate on standing.
It furthermore appeared that during the sulphurization only ~3~7~3 , a small amount of decarboxylation occurred (9%; acid number of starting material 1.06 and of product 0.96; acid number in meq acid/g, determined after acidification with HCl, extraction with diethyl ether, phase separation and evaporation of the solvent) (same method in the following Examples).
Example 2 2500 g of a concentrate of 50 %w overbased calcium C14 18-alkylsalicylate (1625 meq) prepared from the alkyl salicylic acids, calcium hydroxide and carbon dioxide and having a B.I. of 7.72~in 50 %w mineral lubricating oil was sulphurised with 51.3 g of elemental sulphur (1603 meq) and 13 g of ethylene glycol according to the process described in example 1. Yield: 2453 g, S: 1.2 %w.
It appeared that during sulphurisation 2% decarboxylation occurred (acid number of starting material 0.79 meq/g and of product 0.77 meq/g).
Example 3 250 g of a concentrate of 62 %w overbased magnesium C14 18 alkylsalicylate (213.5 meq) having a B.I. of 7.2 in 38 %w mineral lubricating oil was sulphurised with 6.58 g of elemental sulphur (205.6 meq) and 1.7 g of ethylene glycol according to the process described in example 1. Yield: 243.6 g, S: 0.94 %w.
It appeared that during sulphurisation 3% decarboxylation occurred (acid number of starting material 1.02 meq/g and of product 1.00 meq/g).
Comparative Experiment 1 To 97-6 g (205 meq) of neat C14 18 alkyl salicylic acids were added 37.9 g (1025 meq) of Ca(OH)2 and 69.5 g of a mineral lubricating oil, resulting in a 1.0 meq/g mixture of acids.
133.2 g of this mixture (133.2 meq), 4.26 g of S (133.2 meq) and 1.0 g of ethylene glycol were heated under stirring to 125 C
and kept at that temperature for one hour. The temperature was further raised to 150 C (1 hour, pressure: 550 mm Hg) and 195 C (2 hours, 50-60 mm Hg). The reaction mixture was cooled, diluted with n-hexane, filtered through filter aid and finally ~2~31~3 evaporated to yield a very viscous, dark material. Yield: 112.3 g, S: 1.6 %.
It appeared that during the sulphurisation 20% decarboxy-lation occurred (acid number of starting material 1.22 meq/g and of product 0.95 meq/g).
Comparative Experiment 2 2500 g of a concentrate of 58 %w overbased calcium C1~ 18-alkylsalicylate (2300 meq) having a B.I. of 1. 28 in 42 %w mineral lubricating oil was sulphurised with 77 g elemental sulphur (2406 meq) and 19 g of ethylene glycol according to the proces decribed in example 1. Yield: 2496 g, S: 1.3 %w.
It appeared that during sulphurization 28% decarboxylation occurred ~acid number of starting material 0.92 meq/g and of product 0.66 meq/g).
TESTS
In two 15W40 mineral lubricating oils (1 and 2), containing commercial dispersant, detergent and anti-oxidant additives, the products A and B (see Example 1) were tested.
Formulation I contained Product A in an amount of 0.14 %w as Ca in lubricating oil 1. Formulation II contained lubricating oil 1 and 0.14 %w (as Ca) of Product B. Formulations III and IV
comprised lubricating oil 2 with 0.19 %w as Ca of Product A and B, respectively.
Formulations I and II were tested in the CRC L38 test (AS1~1 STP 509A, part IV) in which the bearing weight loss is determined. The results are represented in Table I:
TABLE I
Formulation I II
Bearing weight loss, mg 45.4 33.6 It appears that use of the sulphurized product results in a reduction of the bearing weight loss.
;3~73 Formulations III and IV were tested in the MS Sequence IIID
engine test in which the cam and lifter wear and cleanliness performance were determined.
The results are shown in Tabl.e II:
TABLE II
Test 1 2 3 4 Formulation III III IV IV
Maximum cam and lifter wear, mm 0.55 0.77 0.38 0.50 .
Average cam and lifter wear, mm 0.26 0.24 0.14 0.12 Average sludge rating (10 being clean) 9.66 9.58 9.63 9.58 .
It appears that use of the sulphurized products results in a reduction of the cam and lifter wear. The cleanliness rating remained about the same.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of sulphurized overbased alkaline earth metal C8-C30 alkyl-substituted salicylates, characterized in that the corresponding alkyl-substituted salicylic acid is treated with an alkaline earth metal hydroxide and carbon dloxide in a hydrocarbon solvent to produce an overbased alkaline earth metal salicylate having a basicity of at least 1.5, and subsequently the overbased metal salicylate is sulphurized with elemental sulphur, wherein the molar ratio of S:
substituted salicylic acid is 0.25 to 3, in the presence of a solvent chosen from the group consisting of an alkylene or polyalkylene glycol, or a lower alkyl mono-ether thereof, at a temperature of about 100° to 250°C.
substituted salicylic acid is 0.25 to 3, in the presence of a solvent chosen from the group consisting of an alkylene or polyalkylene glycol, or a lower alkyl mono-ether thereof, at a temperature of about 100° to 250°C.
2. A process according to claim 1 wherein the hydrocarbon solvent is xylene.
3. A process according to claim 1 wherein a promoter is also present during the sulphurization step.
4. A process according to claim 1 wherein the basicity index of the overbased salicylate is at least 3.
5. A process according to claim 1 wherein the sulphurization is carried out at a temperature in the range of 150 - 225°C.
6. A process according to claim 1 wherein the molar ratio of S: substituted salicylic acid is 0.5 to 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8417297 | 1984-07-06 | ||
| GB848417297A GB8417297D0 (en) | 1984-07-06 | 1984-07-06 | Preparation of sulphurized overbased salicylates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253873A true CA1253873A (en) | 1989-05-09 |
Family
ID=10563523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000484253A Expired CA1253873A (en) | 1984-07-06 | 1985-06-17 | Process for the preparation of sulphurized overbased salicylates |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0168880B1 (en) |
| JP (1) | JPS6124560A (en) |
| BR (1) | BR8503201A (en) |
| CA (1) | CA1253873A (en) |
| DE (1) | DE3564570D1 (en) |
| GB (1) | GB8417297D0 (en) |
| SG (1) | SG7090G (en) |
| ZA (1) | ZA855048B (en) |
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| JPS63266424A (en) * | 1987-04-24 | 1988-11-02 | Alps Electric Co Ltd | Liquid crystal display element |
| GB8714922D0 (en) * | 1987-06-25 | 1987-07-29 | Shell Int Research | Lubricating oil composition |
| JPH0676589B2 (en) * | 1987-07-24 | 1994-09-28 | コスモ石油株式会社 | Process for the preparation of alkaline earth metal sulphurised mixtures of hydroxyalkylbenzoic acids and alkylphenols |
| JPH083767Y2 (en) * | 1992-07-09 | 1996-01-31 | 日本ピラー工業株式会社 | Shaft seal device |
| MX9305120A (en) * | 1992-09-04 | 1994-03-31 | Lubrizol Corp | SULFURATED OVERBASED COMPOSITIONS. |
| TW278098B (en) * | 1992-09-18 | 1996-06-11 | Cosmo Sogo Kenkyusho Kk | |
| US6828415B2 (en) | 1993-02-19 | 2004-12-07 | Zentaris Gmbh | Oligopeptide lyophilisate, their preparation and use |
| JPH1161165A (en) * | 1997-06-12 | 1999-03-05 | Tonen Corp | Friction reducing agent comprising metallic salicylate and lubricating oil composition containing the same |
| US7136522B2 (en) * | 2002-10-09 | 2006-11-14 | Xerox Corporation | Systems for spectral multiplexing of source images to provide a composite image, for rendering the composite image, and for spectral demultiplexing of the composite image to animate recovered source images |
| JP2005220197A (en) * | 2004-02-04 | 2005-08-18 | Nippon Oil Corp | Lubricating oil composition to be brought into contact with lead-containing metal material |
| US7956022B2 (en) | 2005-07-29 | 2011-06-07 | Chevron Oronite Company Llc | Low sulfur metal detergent-dispersants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2319662A (en) * | 1941-10-31 | 1943-05-18 | American Cyanamid Co | Lubricating oils |
| US2311931A (en) * | 1941-12-27 | 1943-02-23 | American Cyanamid Co | Lubricant |
| USRE22910E (en) * | 1941-12-31 | 1947-09-02 | E-oxcxs-m | |
| US2336074A (en) * | 1942-05-16 | 1943-12-07 | American Cyanamid Co | Lubricating oil |
| GB786167A (en) * | 1954-09-27 | 1957-11-13 | Shell Res Ltd | Improvements in or relating to the preparation of basic oil-soluble polyvalent metalsalts of organic acids and solutions of said basic salts in oils, and the resultingsalts |
| GB825315A (en) * | 1957-02-18 | 1959-12-16 | Socony Mobil Oil Co Inc | Complex carbonated metal salts of alkyl phenol sulphides |
| GB1094609A (en) * | 1965-08-23 | 1967-12-13 | Lubrizol Corp | Oil soluble basic alkaline earth metal salts of phenol sulfides |
| US3595791A (en) * | 1969-03-11 | 1971-07-27 | Lubrizol Corp | Basic,sulfurized salicylates and method for their preparation |
| SU644811A1 (en) * | 1975-07-14 | 1980-02-05 | Всесоюзный научно-исследовательский институт по переработке нефти | Method of preparing sulfide alkylphenolate additive to lubricating oils |
| GB1597482A (en) * | 1977-01-28 | 1981-09-09 | Exxon Research Engineering Co | Metal phenates |
| US4228022A (en) * | 1979-06-28 | 1980-10-14 | Chevron Research Company | Sulfurized alkylphenol-olefin reaction product lubricating oil additive |
| US4320016A (en) * | 1979-09-24 | 1982-03-16 | Texaco Inc. | Carbon dioxide-blown overbased calcium alkylphenolate lubricating compositions |
| IN155264B (en) * | 1979-11-07 | 1985-01-12 | Lubrizol Corp | |
| EP0094814B1 (en) * | 1982-05-14 | 1989-04-19 | Exxon Research And Engineering Company | Lubricating oil additives |
-
1984
- 1984-07-06 GB GB848417297A patent/GB8417297D0/en active Pending
-
1985
- 1985-06-17 CA CA000484253A patent/CA1253873A/en not_active Expired
- 1985-07-04 JP JP14760585A patent/JPS6124560A/en active Granted
- 1985-07-04 BR BR8503201A patent/BR8503201A/en not_active IP Right Cessation
- 1985-07-04 EP EP85201083A patent/EP0168880B1/en not_active Expired
- 1985-07-04 ZA ZA855048A patent/ZA855048B/en unknown
- 1985-07-04 DE DE8585201083T patent/DE3564570D1/en not_active Expired
-
1990
- 1990-02-05 SG SG70/90A patent/SG7090G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ZA855048B (en) | 1986-02-26 |
| DE3564570D1 (en) | 1988-09-29 |
| JPH0580517B2 (en) | 1993-11-09 |
| EP0168880A1 (en) | 1986-01-22 |
| BR8503201A (en) | 1986-03-25 |
| EP0168880B1 (en) | 1988-08-24 |
| JPS6124560A (en) | 1986-02-03 |
| SG7090G (en) | 1990-07-13 |
| GB8417297D0 (en) | 1984-08-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |