WO1996030467A1 - Produits colloïdaux contenant du calcium, du baryum et/ou du magnesium ainsi que du bismuth, modifies par action d'acides carboxyliques contenant du soufre et eventuellement de l'azote - Google Patents
Produits colloïdaux contenant du calcium, du baryum et/ou du magnesium ainsi que du bismuth, modifies par action d'acides carboxyliques contenant du soufre et eventuellement de l'azote Download PDFInfo
- Publication number
- WO1996030467A1 WO1996030467A1 PCT/FR1995/000382 FR9500382W WO9630467A1 WO 1996030467 A1 WO1996030467 A1 WO 1996030467A1 FR 9500382 W FR9500382 W FR 9500382W WO 9630467 A1 WO9630467 A1 WO 9630467A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- colloidal product
- carboxylic acid
- product according
- sulfur
- Prior art date
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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
- C10M159/24—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
Definitions
- the present invention relates to colloidal products containing calcium and / or magnesium as well as bismuth, modified by the action of acids containing sulfur and optionally nitrogen.
- overbased colloidal products of this parallel application can be used as additives with antiwear and extreme pressure action in mineral or synthetic lubricating oils and in greases.
- Colloidal product of the present invention can be defined in a general way, in that they are obtained by a process which comprises neutralizing the less partial of the basic reserve of an overbased colloidal product comprising calcium, barium or magnesium carbonate dispersed in the form of micelles in an organic medium by at least one sulfonated bismuth compound corresponding to one of the general formulas:
- R 1 represents a monovalent linear or branched aliphatic hydrocarbon radical containing from 8 to 36 carbon atoms and R 2 represents a hydrogen atom or a linear or branched monovalent aliphatic hydrocarbon radical containing from 8 to 36 carbon atoms , said at least partial neutralization being effected by means of at least one carboxylic acid containing sulfur or at least one carboxylic acid containing sulfur and nitrogen.
- the starting overbased colloidal products generally have a basicity reserve in the form of calcium carbonate, barium or magnesium represented by a TBN (total base index) of up to about 550 mg of potassium hydroxide / g of product ( up to around 10 meq basic / g).
- TBN total base index
- carboxylic acids containing sulfur which are designated by "small sulfur carboxylic acids” and which correspond to the general formula are considered in the invention:
- R 3 and R 4 each represent a divalent hydrocarbon radical, for example an alkylene radical of 1 to 6 carbon atoms; or a phenylidene radical.
- R- * 5 represents a single bond or a divalent hydrocarbon radical, for example an alkylene radical of 1 to 4 carbon atoms
- X represents a hydrogen atom or a carboxylic group;
- x and y each have an average value of 1 to 4 when R 5 is a divalent hydrocarbon radical and the sum (x + y) has an average value of 1 to 4 when R- '' represents a single bond.
- R * is a divalent hydrocarbon radical and X a carboxylic group
- the acids are of the form: HOOC - R 3 - S x - R 5 - S y - R 4 - COOH and we can give as examples: methylene acids - and ethylene-bis (thio-. dithio- and trithio-acetic) and methylene- and ethylene-bis (thio-, dithio- and trithio-propionic) acids.
- the dicarboxylic acids corresponding to the general formula are more particularly considered:
- each number has. is 1 or 2
- dicarboxylic acids of formula (IV) that can be used in the preparation of colloidal products of the invention include: 3.3 '- (1,3,4 - thiadiazole -2,5 - diyl) bis (3-thiapropanoic) acid, 4,4' - (1,3,4 - thiadiazole -2,5) acid - diyl) bis (4-thiabutanoic), 4.4 'acid - (1,3,4 - thiadiazole -2,5 - diyl) bis (3,4-dithiabutanoic), 5.5' acid - (1,3,4 - thiadiazole -2.5 -diyl) bis (4,5-dithiapentanoic), bis (3- (5 thio-1,3,4-thiadiazole-2-yl) -3-thiapropanoic) acid , and bis (4- (5 thio-1, 3,4-thiadiazole-2-yl) -4-thiabutanoic acid).
- the reaction is generally carried out in an organic solvent which may more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a cycloaliphatic hydrocarbon (such as for example cyclohexane). an aromatic hydiocarbon (such as, for example, toluene or a xylene), optionally combined with tetrahydrofuran or methanol, used as co-solvents.
- an organic solvent which may more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a cycloaliphatic hydrocarbon (such as for example cyclohexane).
- an aromatic hydiocarbon such as, for example, toluene or a xylene
- tetrahydrofuran or methanol
- the colloidal nature of the products of the invention is checked by dialysis through a latex membrane.
- the sulfur and, where appropriate, nitrogen analyzes locate these elements in the fraction not having dialysis (concentrate) which constitutes the colloidal part of the product.
- the neutralization of the basicity reserve of the overbased colloidal product can be partial or total.
- the proportion of sulfur-containing and optionally nitrogen-containing carboxylic acid is generally such that it can neutralize the overbased colloidal product at a rate which can range up to approximately 50% of its total base index (TBN); most often between 10 and 30% of it.
- a modification of the overbased colloidal compound can be carried out jointly by reaction with other acids or various reagents, which can be brought into play before or after the sulfur-containing carboxylic acid, and where appropriate nitrogenous or at the same time time as this one.
- the additional acids and reagents considered can be, for example, metabolic or orthoboric acids, or else phosphoric and alkyl-, aryl- and / or alkylarylphosphoric acids.
- the colloidal products obtained are stable, soluble in mineral and synthetic lubricants and are characterized by their sulfur content in the active material which can range up to around 30% by mass and, where appropriate, by their nitrogen content which can range up to '' at around 15% by mass.
- Colloidal compounds containing sulfur and optionally nitrogen, according to the invention are excellent anti-wear additives and extreme pressure.
- Antiwear and extreme pressure additives are incorporated into lubricants when they are intended to lubricate organs subjected to significant mechanical stresses, such as distribution in heat engines, gears, bearings or stops. High mechanical constraints also appear lo s of metal machining, that else there is cutting or forming.
- the colloidal compounds containing sulfur and optionally nitrogen according to the invention are endowed with great thermal stability, which allows their use in lubricants subjected in service at very high temperatures which can reach 160 °. C, as in some severe engine housings, in heavily loaded transmissions or cutting metal at high speed.
- the products of the invention as additives for lubricating oils and greases, they can be incorporated into them, for example at an active material concentration of 0.1 to 25% by mass, preferably from 1 to 15 % by mass.
- Lubricating oils also generally contain one or more other additives such as additives improving the viscosity index, additives for lowering the pour point, antioxidants, anti-rust, anti-corrosion additives of copper, detergents, antiwear, defoamers, dispersants, friction reducers, with which the products of the invention are compatible.
- Examples A and B describe the preparation of two bismuth sulfonates corresponding to formulas (I) and (II).
- Examples 1 and 2 describe the preparation of intermediate overbased colloidal products using bismuth sulfonates prepared as described in Examples A and B. These examples do not in themselves form part of the invention.
- Examples 3 to 6 illustrate the preparation of products according to the invention, that is to say having undergone the modification of their basicity reserve by a sulfuric acid or by a sulfuric and nitrogenous acid.
- Examples 7 and 8 describe determinations and tests carried out with the intermediate products of Examples 1 and 2 and the products of Examples 3 to 6 according to the invention.
- 74.20 g of a bismuth alkylarylsulfonate obtained as described in Example B containing 24 are introduced into a reactor equipped with an agitator, a device for introducing gaseous carbon dioxide and a thermometer. 1% by mass of bismuth which is dissolved in 166.9 g of mineral oil 130 Neutral, 800 cm 3 of xylene. 30 cm 3 of methanol, 1.3 cm 3 of water and 2.6 cm 3 of ammonia. 34.3 g (0.464 mole) of lime Ca (OH) 2 are dispersed in this solution and under vigorous stirring, 16.3 g (0.371 mole) of carbon dioxide gas is introduced by bubbling in 40 minutes at a temperature n ' not exceeding 45 ° C.
- Bi 1.17% by mass
- Ca 3.50% by mass
- S 2.30% by mass
- N 0.25% by mass
- active material 20.90% by mass.
- 60 g of the product prepared in Example 2 60 g of a mineral oil are introduced into a reactor equipped with an agitator, a dropping funnel, a thermometer and a Dean and Stark separator. 130 Neutral and 200 cm 3 of xylene. The medium is brought to a temperature of between 70 ° C and 90 ° C, then a solution of 2.59 g (0.0098 mole) of acid 3.3 is introduced over the course of an hour using the ampoule. '- (1,3,4-thiadiazole -2,5 diyl) bis (3-thiapropanoic) in 30 cm 3 of tetrahydrofuran.
- the intermediate products and the products of the invention are evaluated for their antiwear and extreme pressure properties in a 130 Neutral lubricating oil.
- the performances are evaluated on a 4-ball machine according to the ASTM D 2783 method.
- the results are collated in table n c 2.
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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)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9402573A FR2716891B1 (fr) | 1994-03-03 | 1994-03-03 | Produits colloïdaux contenant du calcium, du baryum et/ou du magnésium ainsi que du bismuth, modifiés par action d'acides carboxyliques contenant du soufre et éventuellement de l'azote. |
EP95914427A EP0763081A1 (fr) | 1994-03-03 | 1995-03-27 | Produits collo daux contenant du calcium, du baryum et/ou du magnesium ainsi que du bismuth, modifies par action d'acides carboxyliques contenant du soufre et eventuellement de l'azote |
US08/750,003 US5696062A (en) | 1994-03-03 | 1995-03-27 | Colloidal products containing calcium barium and/or magnesium also bismuth modified by the action of carboxylic acids containing sulphur and optionally nitrogen |
JP8528980A JPH10501583A (ja) | 1994-03-03 | 1995-03-27 | カルシウム、バリウム、マグネシウムのうちの少なくとも一つ、並びにビスマスを含むコロイド物質であり、硫黄と場合によっては窒素とを含むカルボン酸の作用によって改質されるコロイド物質 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9402573A FR2716891B1 (fr) | 1994-03-03 | 1994-03-03 | Produits colloïdaux contenant du calcium, du baryum et/ou du magnésium ainsi que du bismuth, modifiés par action d'acides carboxyliques contenant du soufre et éventuellement de l'azote. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996030467A1 true WO1996030467A1 (fr) | 1996-10-03 |
Family
ID=9460734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1995/000382 WO1996030467A1 (fr) | 1994-03-03 | 1995-03-27 | Produits colloïdaux contenant du calcium, du baryum et/ou du magnesium ainsi que du bismuth, modifies par action d'acides carboxyliques contenant du soufre et eventuellement de l'azote |
Country Status (5)
Country | Link |
---|---|
US (1) | US5696062A (fr) |
EP (1) | EP0763081A1 (fr) |
JP (1) | JPH10501583A (fr) |
FR (1) | FR2716891B1 (fr) |
WO (1) | WO1996030467A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2716891B1 (fr) * | 1994-03-03 | 1996-06-14 | Inst Francais Du Petrole | Produits colloïdaux contenant du calcium, du baryum et/ou du magnésium ainsi que du bismuth, modifiés par action d'acides carboxyliques contenant du soufre et éventuellement de l'azote. |
US20030036485A1 (en) * | 2001-07-18 | 2003-02-20 | Sanborn Robert H. | Motor oil fortifier |
EP2201042B1 (fr) * | 2007-09-13 | 2012-06-27 | ExxonMobil Research and Engineering Company | Melange en ligne de plastifiants avec un polymere de base |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB997335A (en) * | 1961-07-17 | 1965-07-07 | Continental Oil Co | Process for preparing inorganic dispersions |
EP0390664A2 (fr) * | 1989-03-30 | 1990-10-03 | Institut Français du Pétrole | Nouveaux composés thiophosphores leur préparation et leur utilisation comme additifs pour lubrifiants |
EP0536020A1 (fr) * | 1991-09-30 | 1993-04-07 | Institut Francais Du Petrole | Produits colloidaux renfermant du bore, du soufre et du phosphore, leurs préparations et leurs utilisations comme additifs pour lubrifiants |
EP0562912A1 (fr) * | 1992-03-26 | 1993-09-29 | Institut Francais Du Petrole | Produits colloidaux surbasés contenant du soufre organique et leur utilisation comme additifs détergents à action antiusure et extrême-pression dans les huiles lubrifiantes |
EP0598646A1 (fr) * | 1992-11-18 | 1994-05-25 | Institut Francais Du Petrole | Produits colloidaux renfermant du soufre, et/ou du phosphore, et/ou du bore, leur préparation et leur utilisation comme additifs pour lubrifiants |
EP0639634A1 (fr) * | 1993-08-18 | 1995-02-22 | Institut Français du Pétrole | Produits colloidaux renfermant du calcium, et/ou du magnésium, ainsi que du soufre et de l'azote, leur préparation et leur utilisation notamment comme additifs dans les huiles lubrifiantes |
FR2716891A1 (fr) * | 1994-03-03 | 1995-09-08 | Inst Francais Du Petrole | Produits colloïdaux contenant du calcium, du baryum et/ou du magnésium ainsi que du bismuth, modifiés par action d'acides carboxyliques contenant du soufre et éventuellement de l'azote. |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3929650A (en) * | 1974-03-22 | 1975-12-30 | Chevron Res | Extreme pressure agent and its preparation |
US4198317A (en) * | 1978-07-25 | 1980-04-15 | Phillips Petroleum Company | Passivation of metals which contaminate cracking catalysts with antimony tris (hydrocarbyl sulfonate) |
US4468339B1 (en) * | 1982-01-21 | 1989-05-16 | Aqueous compositions containing overbased materials | |
FR2715401B1 (fr) * | 1994-01-26 | 1996-04-05 | Inst Francais Du Petrole | Nouveaux composés sulfonés du bismuth, leur préparation et leur utilisation notamment pour la préparation de produits colloidaux surbasés, eux-mêmes utilisables comme additifs pour lubrifiants. |
-
1994
- 1994-03-03 FR FR9402573A patent/FR2716891B1/fr not_active Expired - Fee Related
-
1995
- 1995-03-27 WO PCT/FR1995/000382 patent/WO1996030467A1/fr not_active Application Discontinuation
- 1995-03-27 US US08/750,003 patent/US5696062A/en not_active Expired - Fee Related
- 1995-03-27 EP EP95914427A patent/EP0763081A1/fr not_active Withdrawn
- 1995-03-27 JP JP8528980A patent/JPH10501583A/ja active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB997335A (en) * | 1961-07-17 | 1965-07-07 | Continental Oil Co | Process for preparing inorganic dispersions |
EP0390664A2 (fr) * | 1989-03-30 | 1990-10-03 | Institut Français du Pétrole | Nouveaux composés thiophosphores leur préparation et leur utilisation comme additifs pour lubrifiants |
EP0536020A1 (fr) * | 1991-09-30 | 1993-04-07 | Institut Francais Du Petrole | Produits colloidaux renfermant du bore, du soufre et du phosphore, leurs préparations et leurs utilisations comme additifs pour lubrifiants |
EP0562912A1 (fr) * | 1992-03-26 | 1993-09-29 | Institut Francais Du Petrole | Produits colloidaux surbasés contenant du soufre organique et leur utilisation comme additifs détergents à action antiusure et extrême-pression dans les huiles lubrifiantes |
FR2689031A1 (fr) * | 1992-03-26 | 1993-10-01 | Inst Francais Du Petrole | Produits colloïdaux surbasés, contenant du soufre organique et leur utilisation comme additifs détergents à action antiusure et extrême-pression dans les huiles lubrifiantes. |
EP0598646A1 (fr) * | 1992-11-18 | 1994-05-25 | Institut Francais Du Petrole | Produits colloidaux renfermant du soufre, et/ou du phosphore, et/ou du bore, leur préparation et leur utilisation comme additifs pour lubrifiants |
EP0639634A1 (fr) * | 1993-08-18 | 1995-02-22 | Institut Français du Pétrole | Produits colloidaux renfermant du calcium, et/ou du magnésium, ainsi que du soufre et de l'azote, leur préparation et leur utilisation notamment comme additifs dans les huiles lubrifiantes |
FR2716891A1 (fr) * | 1994-03-03 | 1995-09-08 | Inst Francais Du Petrole | Produits colloïdaux contenant du calcium, du baryum et/ou du magnésium ainsi que du bismuth, modifiés par action d'acides carboxyliques contenant du soufre et éventuellement de l'azote. |
Also Published As
Publication number | Publication date |
---|---|
FR2716891B1 (fr) | 1996-06-14 |
US5696062A (en) | 1997-12-09 |
FR2716891A1 (fr) | 1995-09-08 |
JPH10501583A (ja) | 1998-02-10 |
EP0763081A1 (fr) | 1997-03-19 |
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