EP0168111B1 - Procédé de préparation de salicylates sulfurés - Google Patents
Procédé de préparation de salicylates sulfurés Download PDFInfo
- Publication number
- EP0168111B1 EP0168111B1 EP85201084A EP85201084A EP0168111B1 EP 0168111 B1 EP0168111 B1 EP 0168111B1 EP 85201084 A EP85201084 A EP 85201084A EP 85201084 A EP85201084 A EP 85201084A EP 0168111 B1 EP0168111 B1 EP 0168111B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sulphurized
- process according
- salicylate
- product
- aliphatic hydrocarbon
- 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
Links
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
Definitions
- This invention relates 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.
- U.K. Patent Specification 825315 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 from the alkyl salicylates whose preparation forms the object of the present invention.
- This invention therefore relates to a process for the preparation of sulphurized metal aliphatic hydrocarbon-substituted salicylates, characterized in that 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 into an overbased metal salicylate.
- the invention furthermore relates to the products thus prepared and to oil composition containing them.
- Suitable aliphatic hydrocarbon-substituted phenols are described in the above-mentioned British Patent Specifications. Preferred are C 8 _ 3o -alkyl phenols.
- phenols may be sulphurized with sulphur halides, preferably sulphur chlorides such as SCI 2 and in particular S 2 C1 2 . Elemental sulphur can also be used.
- sulphur halides preferably sulphur chlorides such as SCI 2 and in particular S 2 C1 2 . Elemental sulphur can also be used.
- the sulphurization with sulphur halide is preferably carried out in a solvent such as aliphatic hydrocarbons, e.g. n-hexane.
- a solvent such as aliphatic hydrocarbons, e.g. n-hexane.
- 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 60°C.
- 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(OH) 2 ) at a temperature in the range of 100-250°C, preferably 150-225°C, whereby the final temperature should preferably be at least 175°C and more preferably at least 195°C.
- a solvent such as ethylene glycol
- a base catalyst such as lime (Ca(OH) 2 )
- the above-mentioned solvent used in the sulphurization step preferably is an alkylene or polyalkylene glycol or a lower alkyl monoether thereof, as disclosed in the above-mentioned British Patent Specifications 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.
- 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 above-mentioned British Patent Specifications and in British Patent Specification 786,167.
- This sulphurized salicylic acid salt is a useful intermediate 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 Mg, and polyvalent metals, such as Zn and Cr.
- Alkaline earth metals such as calcium, barium and magnesium 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 compound, preferably the hydroxide, and carbon dioxide into an overbased 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 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 British Patent Specification 786,167.
- a solvent such as a hydrocarbon solvent, preferably an aromatic hydrocarbon solvent, such as xylene
- a light mineral oil may be added and then the hydrocarbon solvent, and any water formed may be removed by distillation.
- the resulting oil solution of the sulphurized product may be filtered, if desired, and then be added to an oil, such as a lubricating oil or a fuel oil, including gasoline.
- an oil such as a lubricating oil or a fuel oil, including gasoline.
- the product Before or after sulphurization the product may be reacted with a boron compound, such as boric acid, as described in the copending British Patent Application 8330441.
- a boron compound such as boric acid
- 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., automotive crankcase oils, in concentrations 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 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 C 13 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.
- additives may also be present, 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.
- dyes e.g., tricresyl phosphate, zinc dithiophosphates
- antioxidants such as phenyl-alpha-
- Reaction products of amines, formaldehyde and alkyl phenols can also be present.
- reaction vessel (5 litre) was charged with 2000 g tetrapropenylphenol (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 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 C0 2 pressure. After acidification and water wash the yield was 587 g of sulphurized salicylic acids, acid number 1.98 meq/g and sulphur content 4.72% w (Product C).
Claims (7)
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 (2)
Publication Number | Publication Date |
---|---|
EP0168111A1 EP0168111A1 (fr) | 1986-01-15 |
EP0168111B1 true EP0168111B1 (fr) | 1988-08-10 |
Family
ID=10563525
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85201084A Expired EP0168111B1 (fr) | 1984-07-06 | 1985-07-04 | Procédé de préparation de salicylates sulfurés |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0168111B1 (fr) |
JP (1) | JPS6124562A (fr) |
BR (1) | BR8503203A (fr) |
CA (1) | CA1253872A (fr) |
DE (1) | DE3564262D1 (fr) |
GB (1) | GB8417299D0 (fr) |
SG (1) | SG6890G (fr) |
ZA (1) | ZA855051B (fr) |
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 (ja) * | 2004-02-04 | 2005-08-18 | Nippon Oil Corp | 鉛含有金属材料と接触する潤滑油組成物 |
US7956022B2 (en) * | 2005-07-29 | 2011-06-07 | Chevron Oronite Company Llc | Low sulfur metal detergent-dispersants |
CN113026528A (zh) * | 2021-03-10 | 2021-06-25 | 浙江中天恒筑钢构有限公司 | 一种山林空间曲线钢结构栈道安装方法 |
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 |
IT1044574B (it) * | 1975-07-14 | 1980-03-31 | Liquichimica Robassomero Spa | Additivo detergentfe per la sua preparazione |
GB2031422B (en) * | 1978-09-14 | 1983-05-11 | Mitsui Toatsu Chemicals | Preparation of 2,2'-bis(4-substituted-phenol sulfides |
JPS60147497A (ja) * | 1984-01-09 | 1985-08-03 | Cosmo Co Ltd | サリチレ−トを含有する塩基性硫化アルカリ土類金属フエネ−ト型清浄剤の製造方法 |
JPS60168793A (ja) * | 1984-02-13 | 1985-09-02 | Cosmo Co Ltd | 塩基性硫化アルカリ土類金属フエネ−ト型清浄剤の製造法 |
-
1984
- 1984-07-06 GB GB848417299A patent/GB8417299D0/en active Pending
-
1985
- 1985-06-17 CA CA000484166A patent/CA1253872A/fr not_active Expired
- 1985-07-04 DE DE8585201084T patent/DE3564262D1/de not_active Expired
- 1985-07-04 EP EP85201084A patent/EP0168111B1/fr not_active Expired
- 1985-07-04 ZA ZA855051A patent/ZA855051B/xx unknown
- 1985-07-04 JP JP14760785A patent/JPS6124562A/ja active Granted
- 1985-07-04 BR BR8503203A patent/BR8503203A/pt not_active IP Right Cessation
-
1990
- 1990-02-05 SG SG68/90A patent/SG6890G/en unknown
Also Published As
Publication number | Publication date |
---|---|
SG6890G (en) | 1990-07-13 |
ZA855051B (en) | 1986-02-26 |
JPH0580519B2 (fr) | 1993-11-09 |
JPS6124562A (ja) | 1986-02-03 |
BR8503203A (pt) | 1986-03-25 |
GB8417299D0 (en) | 1984-08-08 |
DE3564262D1 (en) | 1988-09-15 |
CA1253872A (fr) | 1989-05-09 |
EP0168111A1 (fr) | 1986-01-15 |
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