EP0786448B1 - Verfahren zur Herstellung eines Reaktionsproduktes bestehend aus einer Neutralisationsstufe von Alkylphenolen und einer Karboxylierungsstufe der hergestellten Alkylphenate - Google Patents
Verfahren zur Herstellung eines Reaktionsproduktes bestehend aus einer Neutralisationsstufe von Alkylphenolen und einer Karboxylierungsstufe der hergestellten Alkylphenate Download PDFInfo
- Publication number
- EP0786448B1 EP0786448B1 EP97102055A EP97102055A EP0786448B1 EP 0786448 B1 EP0786448 B1 EP 0786448B1 EP 97102055 A EP97102055 A EP 97102055A EP 97102055 A EP97102055 A EP 97102055A EP 0786448 B1 EP0786448 B1 EP 0786448B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkylphenol
- temperature
- linear
- alkylphenols
- total
- 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 - Lifetime
Links
- 0 CCC(C)(*)C=C[C@]1C(C(C)=C)O*O*1 Chemical compound CCC(C)(*)C=C[C@]1C(C(C)=C)O*O*1 0.000 description 1
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
Definitions
- the subject of the present invention is a process for preparing a product reaction which useful as additives detergent-dispersants for lubricating oils from type alkylsalicylates-alkylphenates, alkaline earth, sulfurized and overbased with improved properties foaming, compatibility and dispersion in oils and hydrolysis stability as well as the reaction product that may result from this process.
- the carboxylation step is carried out at high pressures generally between 5 and 15 ⁇ 10 5 Pa to convert the alkylphenate to alkylsalicylate.
- the additives obtained according to the present invention may have a high basicity, reflected by the BN of these additives and measured according to ASTM-D2896 and which can easily reach values from 250 to 350 and even more.
- additives according to the invention are based on alkaline earth metals, to the exclusion of all alkali metal, such as in particular sodium and potassium.
- the Applicant has found that the improvement of foaming, compatibility and dispersion properties and of hydrolysis stability of the additives thus obtained required the use of starting alkylphenols containing at least 35% and at most 85% by weight of alkylphenols in which the alkyl radical which contains from 12 to 40 atoms of carbon is linear and unbranched.
- alkylphenols in which the alkyl radical was generally a propylene tetramer, i.e. a dodecyl radical branched.
- the linear alkylphenols obtained by reaction of phenol with a linear olefin containing 12 to 40 and preferably 18 to 30 carbon atoms and originating usually ethylene, consist of a mixture of isomers monosubstituted in which the proportion of substituents linear alkyls in ortho and para positions and even meta is much better distributed, which makes them distinctly less reactive towards an alkaline earth base, since the phenol function is much less accessible by following a large steric hindrance due to the presence closer and generally more alkyl substituents heavy.
- alkaline earth additives overbased from mixtures of alkylphenol which may contain up to 85% by weight of linear alkyl radical in eliminating, in the neutralization step, the third solvent forming an azeotropic mixture with water and which was deemed essential up to now to react alkylphenols branched, more reactive, with alkaline earth base.
- the Applicant has achieved this by maintaining in this first neutralization step the presence of a carboxylic acid which serves as a calcium transfer agent from a mineral reagent to an organic reagent and by providing more extensive reaction conditions, i.e. temperature of at least 215 ° C with a gradual setting of the vacuum reactor, so as to reach an absolute pressure very low at most 7,000 Pa (70 mbar) at this temperature to facilitate the removal of water.
- a carboxylic acid which serves as a calcium transfer agent from a mineral reagent to an organic reagent
- more extensive reaction conditions i.e. temperature of at least 215 ° C with a gradual setting of the vacuum reactor, so as to reach an absolute pressure very low at most 7,000 Pa (70 mbar) at this temperature to facilitate the removal of water.
- alkaline earth bases which can be implemented to carry out the different stages of preparation of the additives according to the present invention, it is possible quote oxides or hydroxides of calcium, magnesium, barium or strontium and especially those of calcium.
- slaked lime corresponding to the chemical formula Ca (OH) 2 is preferred and will be used by way of illustration in the various examples under the name of lime.
- C 1 to C 4 carboxylic acids used in the neutralization step mention may be made of formic, acetic, propionic and butyric acids, which can be used alone or as a mixture.
- mixtures of these acids for example the formic acid-acetic acid mixture, according to an acetic acid / formic acid molar ratio included between 0.01 and 5, preferably between 0.25 and 2 and all particularly of the order of 1, as described in particular in French patent 2,625,220, applied for on December 23, 1987 by the OROGIL Company.
- alkylene glycols for the sulfurization-over-alkalization stage, we can quote ethylene glycol, propylene glycol, butylene glycol.
- the first neutralization step A) of alkylphenol is characterized by the use of a particular alkylphenol and reaction conditions, in particular of well determined temperature and pressure.
- an alkylphenol having a content of at least 35% by weight and which can range up to 85% in linear alkylphenol, in particular in which the linear alkyl radical contains a significant number of carbon atoms (from 18 to 30 carbon atoms) is particularly interesting because a long alkyl chain linear promotes compatibility and solubility of additives in lubricating oils.
- the neutralization reaction is carried out at a temperature of at least 215 ° C, with progressive setting under vacuum, so as to reach a very low pressure of at most 7,000 Pa (70 mbar) at 215 ° C.
- Step A) of neutralization can be carried out at a temperature of at least 220 ° C with progressive setting under vacuum, so as to reach a very low pressure of at most 7,000 Pa (70 mbar) at 220 ° C.
- Particularly advantageous conditions of implementation consists in carrying out the neutralization step A) at a temperature of at least 225 ° C, with setting progressive under vacuum, so as to reach a very low at most 7,000 Pa (70 mbar) at 225 ° C.
- the step of neutralization A) is carried out at a temperature of at least 240 ° C with progressive vacuuming, so as to reach a very low pressure of at most 7,000 Pa (70 mbar) at 240 ° C
- the alkylphenate obtained is preferably maintained for a period not exceeding 15 hours, generally between 2 and 6 hours, at a temperature of at least 215 ° C and a pressure absolute between 5,000 and 10 5 Pa (0.05 and 1.0 bar), especially between 10,000 and 20,000 Pa (0.1 and 0.2 bar).
- the neutralization reaction is carried out without that it is necessary to add in this step a third solvent forming an azeotrope with the water formed during this reaction.
- the second carboxylation step B) aims to transform part of the alkylphenate into alkylsalicylate by simply bubbling carbon dioxide into the reaction medium from the previous step of neutralization. It must take place under pressure to avoid any decarboxylation of the salicylate that forms.
- This carboxylation reaction of an alkylphenate containing at least 35% of relatively inert and heavy linear alkylphenate requires heating to a temperature which must be higher the less the pressure in the reactor. Thus, if it is desired to limit the pressure in the reactor to 3.5 ⁇ 10 5 Pa (3.5 bar) at most, it is advisable to operate at a temperature equal to or greater than 190 ° C.
- step B) of carboxylation is carried out using carbon dioxide at a temperature equal to or greater than 200 ° C., under a pressure of 4 ⁇ 10 5 Pa (4 bars)
- the transformation of the alkylphenate into an alkylsalicylate can involve the formation of alkylphenol, which should be convert to alkylphenate in the next step.
- the third step (C) of the process for preparing the additives according to the present invention is divided into a reaction C 1 of sulfurization and over-alkalization followed by a reaction C 2 of carbonation.
- reaction C 1 of sulfurization and over-alkalization is dangerous on an industrial scale because the addition of elemental sulfur to the reaction mixture at a temperature between 145 and 180 ° C results in a release of hydrogen sulfide which can only be controlled under certain conditions.
- this reaction could be controlled after cooling the product obtained at the end of the carboxylation stage at around 155 ° C, by loading elementary sulfur at this temperature then gradually for a period of 1 to two hours, a mixture of the alkaline earth base, a mono-alcohol boiling point above 150 ° C, at a temperature of 150 to 160 ° C and possibly alkylene glycol.
- the carbonation reaction C 2 by bubbling carbon dioxide in the reaction medium containing an excess of alkaline earth base relative to the alkylphenol which has reacted with sulfur at a temperature of 145 to 180 ° C. requires the presence of alkylene- glycol which must be added in this step C 2 if it has not been added in C 1 ; the purpose of this step C 2 is to transform the additional alkaline earth base into alkylphenate and finely divided calcium carbonate, the latter being trapped between the sulfurized alkylphenate and alkylsalicylate molecules and thus causing the alkalinization of the additive .
- the fourth stage of distillation D aims to eliminate the alkylene glycol and the mono-alcohol introduced into the reaction medium in the previous step to facilitate sulfurization, over-alkalization and carbonation of the additive according to the present invention.
- the fifth filtration step E aims to get rid of sediments and especially carbonate crystallized calcium which could have formed during the stages which clogs the filters installed on the lubrication oil circuits.
- the sixth and last degassing step to air F is important because it allows the additive to pass the hydrolysis stability test, which is not the case of an additive that would be manufactured exclusively at from a branched alkylphenol such as the dodecylphenol obtained by adding the propylene tetramer to phenol.
- the present invention also relates to the method correspondent for the preparation of these additives and compositions lubricating oil, especially for marine engines, but also for cars and railways containing a major proportion of lubricating oil and from 2 to 20% in weight of a detergent dispersant additive according to the invention.
- These additives can also be used in applications industrial like hydraulic oils in proportions which vary from 0.1 to 3% by weight.
- the final additive obtained had the following characteristics: ANALYZES OF THE PRODUCT OBTAINED IN EXAMPLE 1: Calcium,% 9.1 Sulfur,% 2.25 BN ASTM D 2896 255 Viscosity at 100 ° C (in m 2 / sx 10 6 ) 100
- the additive obtained has the following characteristics: % calcium 9 % sulfur 2.34 BN D 2896 261 salicylic acid index (mg KOH / g.) 33.6 Viscosity at 100 ° C (in m 2 / sx 10 6 ) 117 ASTM D130 copper blade 1a % Sedimentation (ASTM D 2273) (vol.) 0.02
- Formic and acetic acids are charged to a temperature below 80 ° C.
- the conditions are 5 hours at 200 ° C under a pressure of 3.5 x 10 5 Pa (3.5 bar) of CO2.
- the reactor is decompressed and cooled.
- the product is then transferred to a storage bin. A part of this product will be used for step C.
- the carboxylated product is loaded into the reactor and oil; it is stirred and heated.
- the reactor is then heated to 170 ° C. and is maintains for 2 hours under these conditions.
- CO2 is finally introduced in 1 hour 30 minutes minutes.
- Ethylene glycol and 2-ethylhexanol are eliminated by distillation.
- the final conditions are 1 h at 195 ° C under 6000 Pa (60 mbar).
- the product is filtered at 150 ° C under a pressure of 4 bars.
- the percentage of sediment is 2.4%.
- the above product is degassed in air at 120 ° C until obtaining a copper blade of rating 1A at ASTM D130 test, performed under the following conditions: 1 hour at 150 ° C.
- This phase is carried out under the conditions following: 200 ° C under a pressure of 3.5 x 10 Pa (3.5 bar) - duration: 7 h 00
- the main characteristics of the process followed in this example are a mixture of alkylphenols containing 30% linear alkylphenol, neutralization temperature between 145 and 195 ° C and the use of 2-ethylhexanol as an azeotropic solvent.
- the final additive obtained had the characteristics following:
- Example 19 This is how this proportion was 0% in Example 19, 20% in Example 20, 80% in Example 21 and 100% in Example 22. Only the Examples 16 and 21 form part of the invention.
- This method is inspired by the ASTM D method 2619 modified. Its purpose is to study sensitivity to the water of an oil and, is applicable to marine oils.
- the method consists in introducing a sample oil with demineralized water in a bottle and to agitate it in a thermostatically controlled oven. At the end of the test, the sample is dried, filtered and analyzed. Stability at hydrolysis is expressed by: the presence or absence of carbonate crystallized, characterized by IR spectrometry. The results are qualified as "GOOD” in the absence of crystallized carbonate and "BAD” in the presence of this last.
- the purpose of this method is to assess the properties dispersives of an oil or an additive and to predict its performance level (deposits, mud) compared to a reference oil.
- the spots are observed after 48 hours of rest, manually or using the CCD photometer.
- the dispersive power of the oil is obtained by comparing the sum of the 6 spots to the value found on one reference oils which should be tested in the same measurement series.
- the purpose of this method is to assess the appearance and storage stability of additives and corresponding oils containing them.
- This method is applicable to additives for lubricants.
- the additive and the corresponding oil the container are stored simultaneously at temperature ambient and hot for a specified period.
- Example 20 in which the proportion of alkylphenol linear in the mixture of starting alkylphenols was only 20% by weight does not allow to obtain satisfactory results in the stability tests at MAO 29 hydrolysis and MAO 25 compatibility.
- the lime first reacts with a branched alkylphenol R- ⁇ -OH to yield the following product (I): which being more basic than lime in an organic medium allows the neutralization of a 2nd alkylphenol mole R'- ⁇ -OH which can be linear.
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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)
Claims (6)
- Verfahren zur Herstellung eines Reaktionsprodukts, dadurch gekennzeichnet, dass es folgende Schritte umfasst:A) Neutralisieren eines Alkylphenols, das mindestens 35 und höchstens 85 Gew.% lineare Alkylphenole enthält, wobei die linearen Alkylradikale 12 bis 40 Kohlenstoffatome besitzen, in Mischung mit höchstens 15 Gew.% verzweigten Alkylphenolen, wobei die verzweigten Alkylradikale 9 bis 24 Kohlenstoffatome enthalten, durch eine Erdalkalibase in Gegenwart mindestens einer Carbonsäure, die 1 bis 4 Kohlenstoffatome enthält, wobei der Neutralisationsvorgang bei einer Temperatur von mindestens 215°C erfolgt, mit zunehmendem Unterdruck im Reaktor, in dem die Neutralisationsreaktion erfolgt, wobei das Reaktionswasser entfernt wird, in Abwesenheit eines jeglichen Lösungsmittels, das ein Azeotrop mit letzterem bilden könnte, wobei die Mengen der beteiligten Reaktanten bezogen auf die Molzahlen wie folgt sind:Erdalkalibase zu Gesamt-Alkylphenol im Bereich von 0,2 bis 0,7;Gesamt-Carbonsäure zu Gesamt-Alkylphenol im Bereich von 0,01 bis 0, 5;B) Carboxylieren des in Schritt A) erhaltenen Alkylphenats durch Umwandeln von mindestens 22 Molprozent des anfänglichen Alkylphenols in Alkylsalicylat (bestimmt als Salicylsäure) mit Kohlensäuregas bei einer Temperatur zwischen 180 und 240°C, unter einem Druck von Atmosphärendruck bis 15x105 Pa (15 Bar) über einen Zeitraum von einer bis acht Stunden.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das lineare Alkylradikal des linearen Alkylphenols 18 bis 30 Kohlenstoffatome enthält.
- Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass das verzweigte Alkylradikal des verzweigten Alkylphenols 12 Kohlenstoffatome enthält.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die eingesetzten Mengen der Reaktanten folgenden Molzahlen entsprechen:Erdalkalibase zu Gesamt-Alkylphenol im Bereich von 0,3 bis 0,5;Gesamt-Carbonsäure zu Gesamt-Alkylphenol im Bereich von 0,03 bis 0,15.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass Schritt B) bei einer Temperatur zwischen 190 und 220°C erfolgt.
- Reaktionsprodukt, gekennzeichnet, dass es gemäß einem Verfahren der Ansprüche 1 bis 5 hergestellt ist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9403138A FR2717491B1 (fr) | 1994-03-17 | 1994-03-17 | Additifs détergents-dispersants pour huiles lubrifiantes du type alkylsalicylates-alkylphénates, alcalino-terreux, sulfurisés et suralcalinisés. |
FR9403138 | 1994-03-17 | ||
EP95913194A EP0750659B1 (de) | 1994-03-17 | 1995-03-14 | Sulfurisierte und überalkalisierte erdalkalimetalle, alkylsalicylate-alkylphenate-alkylphenate detergent-dispergierzusätze für schmieröle |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95913194A Division EP0750659B1 (de) | 1994-03-17 | 1995-03-14 | Sulfurisierte und überalkalisierte erdalkalimetalle, alkylsalicylate-alkylphenate-alkylphenate detergent-dispergierzusätze für schmieröle |
EP95913194.7 Division | 1995-09-21 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0786448A2 EP0786448A2 (de) | 1997-07-30 |
EP0786448A3 EP0786448A3 (de) | 1997-08-13 |
EP0786448B1 true EP0786448B1 (de) | 2003-05-21 |
Family
ID=9461152
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97102055A Expired - Lifetime EP0786448B1 (de) | 1994-03-17 | 1995-03-14 | Verfahren zur Herstellung eines Reaktionsproduktes bestehend aus einer Neutralisationsstufe von Alkylphenolen und einer Karboxylierungsstufe der hergestellten Alkylphenate |
EP95913194A Expired - Lifetime EP0750659B1 (de) | 1994-03-17 | 1995-03-14 | Sulfurisierte und überalkalisierte erdalkalimetalle, alkylsalicylate-alkylphenate-alkylphenate detergent-dispergierzusätze für schmieröle |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95913194A Expired - Lifetime EP0750659B1 (de) | 1994-03-17 | 1995-03-14 | Sulfurisierte und überalkalisierte erdalkalimetalle, alkylsalicylate-alkylphenate-alkylphenate detergent-dispergierzusätze für schmieröle |
Country Status (7)
Country | Link |
---|---|
US (1) | US5808145A (de) |
EP (2) | EP0786448B1 (de) |
JP (1) | JPH09512287A (de) |
CA (1) | CA2181137A1 (de) |
DE (2) | DE69530852T2 (de) |
FR (1) | FR2717491B1 (de) |
WO (1) | WO1995025155A1 (de) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9611424D0 (en) * | 1996-05-31 | 1996-08-07 | Exxon Chemical Patents Inc | Overbased metal-containing detergents |
WO1998050500A1 (fr) * | 1997-05-07 | 1998-11-12 | Cosmo Research Institute | Composition d'huile lubrifiante, concentre de phenate de sulfure de metal alcalino-terreux hyperbasique utilise dans la preparation de cette composition et procede de preparation du concentre |
DE69812873T2 (de) * | 1998-01-30 | 2004-01-22 | Chevron Chemical S.A. | Schwefel- und alkalimetalfreie Schmieröladditive |
EP0985726B1 (de) * | 1998-09-09 | 2004-11-17 | Chevron Chemical S.A. | Verfahren zur Herstellung von Erdalkalimetall-Salzen mit hoher Basizität, insbesondere von einem an einem Ring gebundenen Hydrocarbylsalicylat-carboxylat |
US6348438B1 (en) | 1999-06-03 | 2002-02-19 | Chevron Oronite S.A. | Production of high BN alkaline earth metal single-aromatic ring hydrocarbyl salicylate-carboxylate |
EP1229101A1 (de) * | 2001-02-06 | 2002-08-07 | Infineum International Limited | Schmiermittel für Schiffsdieselmotor |
EP1236791A1 (de) * | 2001-02-16 | 2002-09-04 | Infineum International Limited | Überbasische Detergenszusatzstoffe |
EP1236792B1 (de) * | 2001-02-16 | 2007-01-03 | Infineum International LTD | Verwendung überbasischer Detergentien zum suspendieren von Asphaltenen |
US20040220059A1 (en) * | 2003-05-01 | 2004-11-04 | Esche Carl K. | Low sulfur, low ash, low and phosphorus lubricant additive package using overbased calcium oleate |
US20040224858A1 (en) * | 2003-05-06 | 2004-11-11 | Ethyl Corporation | Low sulfur, low ash, and low phosphorus lubricant additive package using overbased calcium phenate |
US7163911B2 (en) | 2003-05-22 | 2007-01-16 | Chevron Oronite Company Llc | Carboxylated detergent-dispersant additive for lubricating oils |
US20040235682A1 (en) * | 2003-05-22 | 2004-11-25 | Chevron Oronite Company Llc | Low emission diesel lubricant with improved corrosion protection |
US7494961B2 (en) * | 2004-06-29 | 2009-02-24 | Chevron Oronite Company Llc | Polyphenolics as lubricant oil additives |
EP1743933B1 (de) | 2005-07-14 | 2019-10-09 | Infineum International Limited | Verwendung zur Verbesserung der Kompatibilität eines Detergens mit Reibungsmodifikatoren in einer Schmiermittelzusammensetzung |
US7956022B2 (en) * | 2005-07-29 | 2011-06-07 | Chevron Oronite Company Llc | Low sulfur metal detergent-dispersants |
US7435709B2 (en) * | 2005-09-01 | 2008-10-14 | Chevron Oronite Company Llc | Linear alkylphenol derived detergent substantially free of endocrine disruptive chemicals |
EP1790710A1 (de) | 2005-11-25 | 2007-05-30 | Infineum International Limited | Verfahren zum Betrieb von Schiffs- oder stationären Dieselmotoren |
US20080153723A1 (en) | 2006-12-20 | 2008-06-26 | Chevron Oronite Company Llc | Diesel cylinder lubricant oil composition |
JP4994044B2 (ja) | 2007-01-05 | 2012-08-08 | シェブロンジャパン株式会社 | 潤滑油組成物 |
ES2627698T3 (es) | 2007-10-04 | 2017-07-31 | Infineum International Limited | Una composición de aceite lubricante |
US20100029525A1 (en) | 2008-07-31 | 2010-02-04 | Chevron Oronite Company Llc | Antiwear hydraulic fluid composition with useful emulsifying and rust prevention properties |
US8399388B2 (en) | 2009-07-01 | 2013-03-19 | Chevron Oronite Company Llc | Low temperature performance lubricating oil detergents and method of making the same |
FR2968011B1 (fr) | 2010-11-26 | 2014-02-21 | Total Raffinage Marketing | Composition lubrifiante pour moteur |
DK2607462T3 (da) | 2011-12-20 | 2014-03-31 | Infineum Int Ltd | Smøring af skibsmotor |
US10472584B2 (en) | 2015-07-30 | 2019-11-12 | Infineum International Ltd. | Dispersant additives and additive concentrates and lubricating oil compositions containing same |
US10487288B2 (en) | 2015-09-16 | 2019-11-26 | Infineum International Limited | Additive concentrates for the formulation of lubricating oil compositions |
US11168280B2 (en) | 2015-10-05 | 2021-11-09 | Infineum International Limited | Additive concentrates for the formulation of lubricating oil compositions |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB759344A (en) * | 1953-10-29 | 1956-10-17 | Bataafsche Petroleum | Improvements in or relating to the preparation of basic metallic compounds of alkyl phenols and alkyl salicylic acids |
US3036971A (en) | 1958-12-24 | 1962-05-29 | Socony Mobil Oil Co Inc | Lubricating oils containing carbonated basic sulfurized calcium phenates |
GB1094609A (en) | 1965-08-23 | 1967-12-13 | Lubrizol Corp | Oil soluble basic alkaline earth metal salts of phenol sulfides |
GB8613815D0 (en) * | 1986-06-06 | 1986-07-09 | Shell Int Research | Basic salt |
US4744921A (en) * | 1986-10-21 | 1988-05-17 | Chevron Research Company | Methods for preparing, group II metal overbased sulfurized alkylphenols |
JPH0676589B2 (ja) * | 1987-07-24 | 1994-09-28 | コスモ石油株式会社 | ヒドロキシアルキル安息香酸およびアルキルフェノ−ルのアルカリ土類金属塩硫化混合物の製造法 |
FR2625219B1 (fr) * | 1987-12-23 | 1990-12-21 | Orogil | Additifs detergents-dispersants a base de sels de metaux alcalino-terreux et alcalins pour huiles lubrifiantes |
FR2625220B1 (fr) * | 1987-12-23 | 1990-12-21 | Orogil | Procede de preparation d'additifs detergents-dispersants suralcalinises pour huiles lubrifiantes |
TW278098B (de) * | 1992-09-18 | 1996-06-11 | Cosmo Sogo Kenkyusho Kk | |
US5529705A (en) * | 1995-03-17 | 1996-06-25 | Chevron Chemical Company | Methods for preparing normal and overbased phenates |
-
1994
- 1994-03-17 FR FR9403138A patent/FR2717491B1/fr not_active Expired - Fee Related
-
1995
- 1995-03-14 EP EP97102055A patent/EP0786448B1/de not_active Expired - Lifetime
- 1995-03-14 DE DE69530852T patent/DE69530852T2/de not_active Expired - Fee Related
- 1995-03-14 US US08/704,530 patent/US5808145A/en not_active Expired - Fee Related
- 1995-03-14 CA CA002181137A patent/CA2181137A1/en not_active Abandoned
- 1995-03-14 JP JP7523881A patent/JPH09512287A/ja not_active Ceased
- 1995-03-14 WO PCT/FR1995/000299 patent/WO1995025155A1/fr active IP Right Grant
- 1995-03-14 EP EP95913194A patent/EP0750659B1/de not_active Expired - Lifetime
- 1995-03-14 DE DE69504479T patent/DE69504479T2/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US5808145A (en) | 1998-09-15 |
WO1995025155A1 (fr) | 1995-09-21 |
DE69530852T2 (de) | 2004-05-06 |
CA2181137A1 (en) | 1995-09-21 |
DE69504479T2 (de) | 1999-01-28 |
EP0750659B1 (de) | 1998-09-02 |
FR2717491B1 (fr) | 1996-06-07 |
JPH09512287A (ja) | 1997-12-09 |
DE69530852D1 (de) | 2003-06-26 |
FR2717491A1 (fr) | 1995-09-22 |
EP0750659A1 (de) | 1997-01-02 |
EP0786448A2 (de) | 1997-07-30 |
DE69504479D1 (de) | 1998-10-08 |
EP0786448A3 (de) | 1997-08-13 |
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