CA1253872A - Process for the preparation of sulphurized salicylates - Google Patents
Process for the preparation of sulphurized salicylatesInfo
- Publication number
- CA1253872A CA1253872A CA000484166A CA484166A CA1253872A CA 1253872 A CA1253872 A CA 1253872A CA 000484166 A CA000484166 A CA 000484166A CA 484166 A CA484166 A CA 484166A CA 1253872 A CA1253872 A CA 1253872A
- Authority
- CA
- Canada
- Prior art keywords
- sulphurized
- sulphur
- process according
- product
- salicylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
- C10L1/2418—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides containing a carboxylic substituted; derivatives thereof, e.g. esters
Abstract
A B S T R A C T
PROCESS FOR THE PREPARATION OF SULPHURIZED SALICYLATES
Process for the preparation of a sulphurized, metal aliphatic hydrocarbon-substituted salicylate, wherein an aliphatic hydrocarbon-substituted phenol is sulphurized, and the resulting product is transformed into an alkali metal salicylate with an alkali metal hydroxide and carbon dioxide.
The product thus obtained is optionally transformed in an overbased metal salicylate.
PROCESS FOR THE PREPARATION OF SULPHURIZED SALICYLATES
Process for the preparation of a sulphurized, metal aliphatic hydrocarbon-substituted salicylate, wherein an aliphatic hydrocarbon-substituted phenol is sulphurized, and the resulting product is transformed into an alkali metal salicylate with an alkali metal hydroxide and carbon dioxide.
The product thus obtained is optionally transformed in an overbased metal salicylate.
Description
PROCESS FOR THE PREPARATION OF SULPHURIZED SALICYLATES
This invention relat~s to a process for the preparation of sulphurized, optionally overbased metal aliphatic hydrocarbon-substituted salicylates, to products thus prepared and to oil compositions containing them.
From British patent specification 1,287,812 such products and oil compostions containing them as detergents and wear inhibitors are already known. It discloses the reaction of an aliphatic hydrocarbon-substituted salicylic acid, or a metal salt thereof, with elemental sulphur, an alkaline earth base, e.g. a hydroxide, and a solvent, such as ethylene glycol, at at least 150C, and optionally further reaction with carbon dioxide. A
similar process is disclosed in British patent specification 1,194,503. A further process is given in UK patent specification 825,315 which describes the reaction of an alkyl phenol sulphide with a metal alcoholate followed by carbon dioxide, to yield a complex carbonated metal salt. Such products contain the carbon dioxide in the form of carbonate or bicarbonate, and therefore differ fro~l the alkyl salicylates whose preparation forms the object of the present invention.
However, it has been found that this known process shows the disadvantage of a substantial degree of decarboxylation during the reaction of the salicylic acid, or a metal salt thereof, with sulphur.
It has now been found that this problem can be avoided by first sulphurizing an aliphatic hydrocarbon-substituted phenol and then transforming the reaction product into a salicylic acid ~' ~
L253~72 -la- 63293-2539 or metal salt thereof.
This invention therefore relates to a process for the preparation of a sulphurized, C8-C30 alkyl-substituted metal salicylate, characterized in that a C8-C30 alkyl phenol is sul-phurized with a sulphur halide in an aliphatic hydrocarbon solvent, or with elemental sulphur in the presence of a base catalyst and a solvent chosen from an alkylene or polyalkylene glycol or a lower alkylmonoether thereof at a temperature of from 100C to 250C, and the molar ratio of S:substituted phenol is 0.25 to 3 and the resulting product is transformed into an alkali metal salicylate with an alkali metal hydroxide and carbon dioxide.
The product thus obtained is optionally transformed into an overbased metal salicylate.
The invention furthermore relates tothe products thus prepared and to oil compositions containing them.
~L253872 ., . ~
This invention relat~s to a process for the preparation of sulphurized, optionally overbased metal aliphatic hydrocarbon-substituted salicylates, to products thus prepared and to oil compositions containing them.
From British patent specification 1,287,812 such products and oil compostions containing them as detergents and wear inhibitors are already known. It discloses the reaction of an aliphatic hydrocarbon-substituted salicylic acid, or a metal salt thereof, with elemental sulphur, an alkaline earth base, e.g. a hydroxide, and a solvent, such as ethylene glycol, at at least 150C, and optionally further reaction with carbon dioxide. A
similar process is disclosed in British patent specification 1,194,503. A further process is given in UK patent specification 825,315 which describes the reaction of an alkyl phenol sulphide with a metal alcoholate followed by carbon dioxide, to yield a complex carbonated metal salt. Such products contain the carbon dioxide in the form of carbonate or bicarbonate, and therefore differ fro~l the alkyl salicylates whose preparation forms the object of the present invention.
However, it has been found that this known process shows the disadvantage of a substantial degree of decarboxylation during the reaction of the salicylic acid, or a metal salt thereof, with sulphur.
It has now been found that this problem can be avoided by first sulphurizing an aliphatic hydrocarbon-substituted phenol and then transforming the reaction product into a salicylic acid ~' ~
L253~72 -la- 63293-2539 or metal salt thereof.
This invention therefore relates to a process for the preparation of a sulphurized, C8-C30 alkyl-substituted metal salicylate, characterized in that a C8-C30 alkyl phenol is sul-phurized with a sulphur halide in an aliphatic hydrocarbon solvent, or with elemental sulphur in the presence of a base catalyst and a solvent chosen from an alkylene or polyalkylene glycol or a lower alkylmonoether thereof at a temperature of from 100C to 250C, and the molar ratio of S:substituted phenol is 0.25 to 3 and the resulting product is transformed into an alkali metal salicylate with an alkali metal hydroxide and carbon dioxide.
The product thus obtained is optionally transformed into an overbased metal salicylate.
The invention furthermore relates tothe products thus prepared and to oil compositions containing them.
~L253872 ., . ~
-2- 63293-2539 Suitable aliphatic hydrocarbon-substituted phenols are described in the above-mentioned British patent specificiations.
Preferred are C8-C3-Oalkyl phenols-These phenols may be sulphurized with sulphur halides,preferably sulphur chlorides such as SC12 and in particular S2C12.
Elemental sulphur can also be used.
The sulphurization with sulphur halide is carried out in an aliphatic hydrocarbon solvent, e.g. n-hexane. The use of aromatic solvents, such as xylene, should be avoided otherwise these solvents may also be sulphurized with the sulphur halide.
The reaction can be carried out at ambient temperature, although some heating may be applied, e.g. up to 60C.
The sulphurization with elemental sulphur can be carried out by contacting the phenols with sulphur in the presence of a solvent such as ethylene glycol and a base catalyst such as lime (Ca(O~)2) at a temperature in the range of 100-250C, pre-ferably 150-225C, whereby the final temperature should preferably be at least 175C and more preferably at least 195C.
The above-mentioned solvent used in the sulphurization step is an alkylene or polyalkylene glycol or a lower alkyl monoether thereof, as disclosed in the above-mentioned British patent specificiations 1,287,812 and 1,194,503. Most preferably the solvent is ethylene glycol.
A promotor 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.
.,~
~5387Z
,~...~
Preferred are C8-C3-Oalkyl phenols-These phenols may be sulphurized with sulphur halides,preferably sulphur chlorides such as SC12 and in particular S2C12.
Elemental sulphur can also be used.
The sulphurization with sulphur halide is carried out in an aliphatic hydrocarbon solvent, e.g. n-hexane. The use of aromatic solvents, such as xylene, should be avoided otherwise these solvents may also be sulphurized with the sulphur halide.
The reaction can be carried out at ambient temperature, although some heating may be applied, e.g. up to 60C.
The sulphurization with elemental sulphur can be carried out by contacting the phenols with sulphur in the presence of a solvent such as ethylene glycol and a base catalyst such as lime (Ca(O~)2) at a temperature in the range of 100-250C, pre-ferably 150-225C, whereby the final temperature should preferably be at least 175C and more preferably at least 195C.
The above-mentioned solvent used in the sulphurization step is an alkylene or polyalkylene glycol or a lower alkyl monoether thereof, as disclosed in the above-mentioned British patent specificiations 1,287,812 and 1,194,503. Most preferably the solvent is ethylene glycol.
A promotor 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.
.,~
~5387Z
,~...~
-3- 63293-2539 The molar ratio of S:substituted phenol is e.g. 0.25 to 3, preferably 0.5 to 2.
The resulting product is acidified if necessary to transform any phenate to phenol.
The transformation of the sulphurized phenols into a salicylate is preferably carried out via the Kolbe synthesis by reaction with sodium hydroxide and carbon dioxide as described in the above-mentioned British patent specifications and in British patent specificiation 786,167.
This sulphurized salicylic acid salt is a useful inter-mediate for the preparation of the corresponding overbased salicylates, which combine good detergency with reduced wear in lubricating oil compositions. Suitable metals of the overbased metal salicylate are e.g. alkali metals, such as Li,Cs, Na and K, alkaline earth metals, such as Ca, Ba, Sr and ~g, and polyvalent metals, such as Zn and Cr.
Alkaline earth metals, such as calcium, barium and mag-nesium are preferred. Therefore the sulphurized alkali metal salicylate is suitably transformed into the corresponding salicylic acid, which is converted with a basic alkaline earth metal com-pound, preferably the hydroxide, and carbon dioxide into an over-based alkaline earth metal salicylate. The degree of overbasing is expressed as the basicity index (BI) defined as the equivalent ratio of metal: salicylic acid.
The overbasing of the sulphurized alkali metal salicylate ~253872 -3a- 63293-2539 may be carried out by acidification and reaction in a solvent, such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene, with the basic metal compound and carbon dioxide, as described in e.g. British patent specification 786,167.
To the resulting reaction mixture a light mineral oil may be added and then the hydrocarbon s~olvent, and any water formed may be removed by distillation.
The resulting oil solution of the sulphurized product may be filtered, if aesired, and then be added to an oil, such as a lubricating oil or a fuel oil, including gasoline.
Before or after sulphurization the product may be re-acted 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 thereof can be incorporated in oil compositions, in particular lubricating oil compositions or concentrates or fuels, e.g. auto-mOtive crankcase oils, in concentrations within the range of 0.001 to 65, in particular 0.1 to 15~w based on the weight of .~ "
~L~253E~7~2 the total compositions.
The lubricating oils to which the additives of 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 synthetic 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 diesters of tetraethylene glycol, etc. Mixtures of these oils, in particular of mineral lubricating 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 con-centrates comprising e.g. 15 to 65 70w of said reaction product in a hydrocarbon diluent and 85 to 35 %w mineral lubricating oil, are prepared for ease of handling.
In the`above compositions other additives may also be pre-sent, including dyes, pour point depressants, anti-wear, e.g., tricresyl phosphate, ~inc 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 li~e 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.
- ~a 2~i3~2 Example 1 Preparation of sulphurized alkyl phenol.
A reaction vessel (5 litre) was charged with 2000 g tetra-propenylphenol (7520 meq), 122 g calcium hydroxide (3300 meq), 364 g elemental sulphur (11375 meq) and 74 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 kept at 50-60 mm Hg for two hours. The reaction product was cooled, solvent was added and the mixture was filtered. The solvent was removed leaving a dark, viscous product (yield:
2266 g; S: 8.2 %w) (Product A).
Example 2 Preparation of sulphuriæed alkyl phenol.
To a reaction vessel (2 litre) containing 524 g tetrapro-penylphenol (2002 meq) and 520 g n-hexane a solution of 67.5 g S2C12 (1000 meq of sulphur) in 70 g n-hexane was added dropwise at such a rate that the temperature was kept constant at 20-40 C.
When the S2C12 addition was complete (2-3 hrs) the reaction mixture was rinsed with nitrogen and the solvent removed under reduced pressure (yield: 557 g; S: 5.0 %w) (Product B).
These Examples show that sulphurization with elemental sulphur as well as with S2C12 is feasible.
Example 3 The product from example 2 was diluted with 500 g of xylene and then heated to 135 C in a nitrogen atmosphere. An aqueous solution of 100 g sodium hydroxide (25 % excess on OH intake) in 120 g water was added carefully (to prevent foaming) and water was distilled off. The solution was carboxylated at 140 C and 14 bar CO2 pressure. After acidification and water wash the yield was 587 g of sulphuriæed salicylic acids, acid number 1.98 meq/g and sulphur content 4.72 %w (Product C).
5 3~37 2 Example _ A solution of 200 g of the sulphurized alkylsalicylates of example 3 (396 meq) in 200 g of xylene and 120 g of methanol was treated with 59 g of Ca(OH)2 (1595 meq) for lh at 55 C. The reaction product was filtered and the solvents were evapora~ed under reduced pressure resulting in a product (223 g) with 6.8 %w Ca, 3.9 %w S and a B.I. of 1.5 (Product D).
Example 5 A solution of 200 g of the sulphurized alkylsalicylates of example 3 (396 meq) in 200 g of xylene and 120 g of methanol was treated with 59 g of Ca(OH)2 (1595 meq) for lh at 55C. Subse-quently 13.9 g of C02 (632 meq) was introduced. Workingup yielded 253.5 g of a product with 11.5%w Ca, 3.7 %w S and a B.I. of 3.0 (Product E).170 g of product E was mixed with 155 g of mineral lubricating oil, resulting in an oil concentrate with 6.0 %w Ca, 1.9 %w S and a B.I. of 3.0 (product F).
Comperative Experiment To 97.6 g (205 meq) of neat C14 18 alkyl salicylic acids were added 37.9 (1025 meq) of Ca(OH)2 and 69.5 g of a mineral lubri-cating 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 evaporated to yield a very viscous, dark material. Yield: 112.3 g, S: 1.6 %w.
It appeared that during the sulphurization 20% decarboxy-lation occurred (acid number of starting material 1.22 meq/g and of product 0.95 meq/g, determined after acidification with HCl extraction with diethyl ether, phase separation and evaporation of the solvent).
TESTS
In two CRC L38 tests (ASTM STP 509 A, part IV) the performance of product F (see Example 5) was compared with that of unsulphurized overbased Ca C14 18-alkyl salicylate. Thereto two for~ulations were prepared, formulation I comprising a 15W40 mineral lubricating oil containing commercial dispersant, detergent and anti-oxidant additives and 0.14 %w (as Ca) of overbased Ca C14 18-alkyl salicylate (B.I. = 3), and formulation II comprising the same 15W40 lubricating oil and 0.14 ~Ow (as Ca) of product F.
The results of the CRC L38 tests, in which the bearing weight loss is determined, are shown in Table I.
TABLE I
Formulation I II
Bearing weight loss, mg 45.4 29.6 " " " " 45.7 36.7 . ' ' ' ``
It appears that use of the sulphurized product of the invention results in a reduction of the bearing weight loss.
The resulting product is acidified if necessary to transform any phenate to phenol.
The transformation of the sulphurized phenols into a salicylate is preferably carried out via the Kolbe synthesis by reaction with sodium hydroxide and carbon dioxide as described in the above-mentioned British patent specifications and in British patent specificiation 786,167.
This sulphurized salicylic acid salt is a useful inter-mediate for the preparation of the corresponding overbased salicylates, which combine good detergency with reduced wear in lubricating oil compositions. Suitable metals of the overbased metal salicylate are e.g. alkali metals, such as Li,Cs, Na and K, alkaline earth metals, such as Ca, Ba, Sr and ~g, and polyvalent metals, such as Zn and Cr.
Alkaline earth metals, such as calcium, barium and mag-nesium are preferred. Therefore the sulphurized alkali metal salicylate is suitably transformed into the corresponding salicylic acid, which is converted with a basic alkaline earth metal com-pound, preferably the hydroxide, and carbon dioxide into an over-based alkaline earth metal salicylate. The degree of overbasing is expressed as the basicity index (BI) defined as the equivalent ratio of metal: salicylic acid.
The overbasing of the sulphurized alkali metal salicylate ~253872 -3a- 63293-2539 may be carried out by acidification and reaction in a solvent, such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene, with the basic metal compound and carbon dioxide, as described in e.g. British patent specification 786,167.
To the resulting reaction mixture a light mineral oil may be added and then the hydrocarbon s~olvent, and any water formed may be removed by distillation.
The resulting oil solution of the sulphurized product may be filtered, if aesired, and then be added to an oil, such as a lubricating oil or a fuel oil, including gasoline.
Before or after sulphurization the product may be re-acted 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 thereof can be incorporated in oil compositions, in particular lubricating oil compositions or concentrates or fuels, e.g. auto-mOtive crankcase oils, in concentrations within the range of 0.001 to 65, in particular 0.1 to 15~w based on the weight of .~ "
~L~253E~7~2 the total compositions.
The lubricating oils to which the additives of 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 synthetic 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 diesters of tetraethylene glycol, etc. Mixtures of these oils, in particular of mineral lubricating 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 con-centrates comprising e.g. 15 to 65 70w of said reaction product in a hydrocarbon diluent and 85 to 35 %w mineral lubricating oil, are prepared for ease of handling.
In the`above compositions other additives may also be pre-sent, including dyes, pour point depressants, anti-wear, e.g., tricresyl phosphate, ~inc 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 li~e 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.
- ~a 2~i3~2 Example 1 Preparation of sulphurized alkyl phenol.
A reaction vessel (5 litre) was charged with 2000 g tetra-propenylphenol (7520 meq), 122 g calcium hydroxide (3300 meq), 364 g elemental sulphur (11375 meq) and 74 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 kept at 50-60 mm Hg for two hours. The reaction product was cooled, solvent was added and the mixture was filtered. The solvent was removed leaving a dark, viscous product (yield:
2266 g; S: 8.2 %w) (Product A).
Example 2 Preparation of sulphuriæed alkyl phenol.
To a reaction vessel (2 litre) containing 524 g tetrapro-penylphenol (2002 meq) and 520 g n-hexane a solution of 67.5 g S2C12 (1000 meq of sulphur) in 70 g n-hexane was added dropwise at such a rate that the temperature was kept constant at 20-40 C.
When the S2C12 addition was complete (2-3 hrs) the reaction mixture was rinsed with nitrogen and the solvent removed under reduced pressure (yield: 557 g; S: 5.0 %w) (Product B).
These Examples show that sulphurization with elemental sulphur as well as with S2C12 is feasible.
Example 3 The product from example 2 was diluted with 500 g of xylene and then heated to 135 C in a nitrogen atmosphere. An aqueous solution of 100 g sodium hydroxide (25 % excess on OH intake) in 120 g water was added carefully (to prevent foaming) and water was distilled off. The solution was carboxylated at 140 C and 14 bar CO2 pressure. After acidification and water wash the yield was 587 g of sulphuriæed salicylic acids, acid number 1.98 meq/g and sulphur content 4.72 %w (Product C).
5 3~37 2 Example _ A solution of 200 g of the sulphurized alkylsalicylates of example 3 (396 meq) in 200 g of xylene and 120 g of methanol was treated with 59 g of Ca(OH)2 (1595 meq) for lh at 55 C. The reaction product was filtered and the solvents were evapora~ed under reduced pressure resulting in a product (223 g) with 6.8 %w Ca, 3.9 %w S and a B.I. of 1.5 (Product D).
Example 5 A solution of 200 g of the sulphurized alkylsalicylates of example 3 (396 meq) in 200 g of xylene and 120 g of methanol was treated with 59 g of Ca(OH)2 (1595 meq) for lh at 55C. Subse-quently 13.9 g of C02 (632 meq) was introduced. Workingup yielded 253.5 g of a product with 11.5%w Ca, 3.7 %w S and a B.I. of 3.0 (Product E).170 g of product E was mixed with 155 g of mineral lubricating oil, resulting in an oil concentrate with 6.0 %w Ca, 1.9 %w S and a B.I. of 3.0 (product F).
Comperative Experiment To 97.6 g (205 meq) of neat C14 18 alkyl salicylic acids were added 37.9 (1025 meq) of Ca(OH)2 and 69.5 g of a mineral lubri-cating 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 evaporated to yield a very viscous, dark material. Yield: 112.3 g, S: 1.6 %w.
It appeared that during the sulphurization 20% decarboxy-lation occurred (acid number of starting material 1.22 meq/g and of product 0.95 meq/g, determined after acidification with HCl extraction with diethyl ether, phase separation and evaporation of the solvent).
TESTS
In two CRC L38 tests (ASTM STP 509 A, part IV) the performance of product F (see Example 5) was compared with that of unsulphurized overbased Ca C14 18-alkyl salicylate. Thereto two for~ulations were prepared, formulation I comprising a 15W40 mineral lubricating oil containing commercial dispersant, detergent and anti-oxidant additives and 0.14 %w (as Ca) of overbased Ca C14 18-alkyl salicylate (B.I. = 3), and formulation II comprising the same 15W40 lubricating oil and 0.14 ~Ow (as Ca) of product F.
The results of the CRC L38 tests, in which the bearing weight loss is determined, are shown in Table I.
TABLE I
Formulation I II
Bearing weight loss, mg 45.4 29.6 " " " " 45.7 36.7 . ' ' ' ``
It appears that use of the sulphurized product of the invention results in a reduction of the bearing weight loss.
Claims (7)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for the preparation of a sulphurized, C8-C30 alkyl-substituted metal salicylate, characterized in that a C8-C30 alkyl phenol is sulphurized with a sulphur halide in an aliphatic hydrocarbon solvent, or with elemental sulphur in the presence of a base catalyst and a solvent chosen from an alkylene or polyalkylene glycol or a lower alkylmono-ether thereof at a temperature of from 100°C to 250°C, and the molar ratio of S:substituted phenol is 0.25 to 3 and the resulting product is transformed into an alkali metal salicylate with an alkali metal hydroxide and carbon dioxide.
2. Process according to claim 1, wherein the alkali metal salicylate is acidified into the corresponding salicylic acid which is converted into an overbased alkaline earth metal salicylate with carbon dioxide and an alkaline earth metal hydroxide.
3. Process according to claim 1, wherein the sulphurization is carried out with elemental sulphur.
4. Process according to claim 1, wherein the sulphurization is carried out with a sulphur halide.
5. Process according to claim 1, wherein the molar ratio of S:substituted phenol is 0.5 to 2.
6. Process according to claim 4, wherein the sulphur halide is S2C12.
7. Process according to claim 4, wherein the sulphur halide sulphurization reaction is carried out at an elevated temperature of up to about 60°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB848417299A GB8417299D0 (en) | 1984-07-06 | 1984-07-06 | Preparation of sulphurized salicylates |
| GB8417299 | 1984-07-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1253872A true CA1253872A (en) | 1989-05-09 |
Family
ID=10563525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000484166A Expired CA1253872A (en) | 1984-07-06 | 1985-06-17 | Process for the preparation of sulphurized salicylates |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0168111B1 (en) |
| JP (1) | JPS6124562A (en) |
| BR (1) | BR8503203A (en) |
| CA (1) | CA1253872A (en) |
| DE (1) | DE3564262D1 (en) |
| GB (1) | GB8417299D0 (en) |
| SG (1) | SG6890G (en) |
| ZA (1) | ZA855051B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8714922D0 (en) * | 1987-06-25 | 1987-07-29 | Shell Int Research | Lubricating oil composition |
| US6235688B1 (en) | 1996-05-14 | 2001-05-22 | Chevron Chemical Company Llc | Detergent containing lithium metal having improved dispersancy and deposit control |
| 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 |
| CN113026528A (en) * | 2021-03-10 | 2021-06-25 | 浙江中天恒筑钢构有限公司 | Method for mounting mountain forest space curve steel structure plank road |
Family Cites Families (14)
| 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 |
| US3595790A (en) * | 1969-10-22 | 1971-07-27 | Lubrizol Corp | Oil soluble highly basic metal salts of organic acids |
| GB1443329A (en) * | 1973-10-22 | 1976-07-21 | Exxon Research Engineering Co | Thio bisalkylphenols and their use as anti-oxidants in lubricating oils |
| SU644811A1 (en) * | 1975-07-14 | 1980-02-05 | Всесоюзный научно-исследовательский институт по переработке нефти | Method of preparing sulfide alkylphenolate additive to lubricating oils |
| GB2031422B (en) * | 1978-09-14 | 1983-05-11 | Mitsui Toatsu Chemicals | Preparation of 2,2'-bis(4-substituted-phenol sulfides |
| JPS60147497A (en) * | 1984-01-09 | 1985-08-03 | Cosmo Co Ltd | Preparation of salicylate-containing basic alkaline earth metal sulfide phenate type detergent |
| JPS60168793A (en) * | 1984-02-13 | 1985-09-02 | Cosmo Co Ltd | Production of basic sulfurized alkaline earth metal phenate detergent |
-
1984
- 1984-07-06 GB GB848417299A patent/GB8417299D0/en active Pending
-
1985
- 1985-06-17 CA CA000484166A patent/CA1253872A/en not_active Expired
- 1985-07-04 DE DE8585201084T patent/DE3564262D1/en not_active Expired
- 1985-07-04 EP EP85201084A patent/EP0168111B1/en not_active Expired
- 1985-07-04 BR BR8503203A patent/BR8503203A/en not_active IP Right Cessation
- 1985-07-04 JP JP14760785A patent/JPS6124562A/en active Granted
- 1985-07-04 ZA ZA855051A patent/ZA855051B/en unknown
-
1990
- 1990-02-05 SG SG68/90A patent/SG6890G/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0580519B2 (en) | 1993-11-09 |
| EP0168111A1 (en) | 1986-01-15 |
| ZA855051B (en) | 1986-02-26 |
| GB8417299D0 (en) | 1984-08-08 |
| BR8503203A (en) | 1986-03-25 |
| SG6890G (en) | 1990-07-13 |
| DE3564262D1 (en) | 1988-09-15 |
| JPS6124562A (en) | 1986-02-03 |
| EP0168111B1 (en) | 1988-08-10 |
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