EP0639634A1 - Kalzium und/oder Magnesium auch Schwefel und Stickstoff enthaltende Kolloidale Produkte, ihre Herstellung und ihre Verwendung, insbesondere als Schmieröladditive - Google Patents

Kalzium und/oder Magnesium auch Schwefel und Stickstoff enthaltende Kolloidale Produkte, ihre Herstellung und ihre Verwendung, insbesondere als Schmieröladditive Download PDF

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Publication number
EP0639634A1
EP0639634A1 EP94401783A EP94401783A EP0639634A1 EP 0639634 A1 EP0639634 A1 EP 0639634A1 EP 94401783 A EP94401783 A EP 94401783A EP 94401783 A EP94401783 A EP 94401783A EP 0639634 A1 EP0639634 A1 EP 0639634A1
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EP
European Patent Office
Prior art keywords
acid
mass
bis
thiadiazole
product according
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.)
Granted
Application number
EP94401783A
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English (en)
French (fr)
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EP0639634B1 (de
Inventor
Bruno Delfort
Bertrand Daoudal
Jacques Lallement
Jean-Claude Hipeaux
Maurice Born
Pierre Marchand
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • 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
    • 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 new colloidal products containing calcium and / or magnesium, as well as sulfur and nitrogen, their preparation and their use in particular as additives in lubricating oils.
  • Overbased detergent additives have been known for a long time. Some of them and their preparation have been described for example in US patents 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 3,953,519, 3,966,621, 4,148,740 and 4,505 .830 and French patent 2,101,813.
  • There are variants of the overbasing reaction which use in particular preformed carbonates from alkoxides and CO2 before being brought into contact with the alkaline or alkaline earth salt of the acid compound; they are described in particular in US patents 2,956,018, 3,932,289 and 4,104,180.
  • French patent FR-B-2645168 describes thiophosphorus compounds obtained by reaction of a sodium or calcium sulfonate overbased with sodium or calcium carbonate, with a phosphorus sulfide, in general P4S10, this reaction being optionally followed by a reaction with an active hydrogen compound, which could be water, methanol, isopropanol, phenol, acetic acid, dialkylphosphite, boric acid, phosphoric acid, ammonia, an amide, dimercaptothiadiazole, or a derivative thereof.
  • the compounds obtained, made soluble in a hydrocarbon medium by micellization can be used as antiwear and extreme pressure additives in lubricating oils.
  • French patent FR-B-2681872 describes and claims colloidal products containing boron and phosphorus, obtained by a process in which an alkali or alkaline earth sulfonate borate overbased is prepared; a phosphorus sulfide is reacted on this product and the resulting product is separated. These products are also used as antiwear and extreme pressure additives in lubricating oils and greases. Mention may also be made of French patent FR-B 2689031, which describes and claims colloidal products, which can also be used as antiwear and extreme pressure additives in lubricating oils.
  • an overbased detergent compound such as a sulfonate, a phenate, a salicylate or an alkaline or alkaline earth naphthenate overbased with a carbonate or an alkali or alkaline earth hydroxide
  • each number a is 1 or 2
  • x and z are each 1 or 2
  • y is zero or 1.
  • the sulfonates and / or phenates and / or overbased salycilates used as basic products for the preparation of the colloidal products of the invention have an alkaline reserve in the form of calcium or magnesium carbonate corresponding to a TBN (or base index total) which can go up to approximately 600 mg KOH / g of product.
  • the dicarboxylic acids used for the preparation of the colloidal products of the invention can be obtained in particular by reaction of a compound containing a dimercaptothiadiazole group of general formula: with at least one substituted monocarboxylic acid of general formula: (III) X- (CH2) a -COOH optionally in the presence of elemental sulfur.
  • y , n and a each have the same meaning as in formula (I) (Cf above) and X represents a halogen atom, for example chlorine, bromine, iodine or fluorine or a nitro group.
  • the reaction described above can be carried out in a basic medium, for example, in the presence of an alkali metal hydroxide (in particular sodium hydroxide or potassium hydroxide), or ammonium hydroxide.
  • an alkali metal hydroxide in particular sodium hydroxide or potassium hydroxide
  • ammonium hydroxide At the end of the reaction, neutralization in a strong acid medium, such as for example hydrochloric acid, sulfuric acid or phosphoric acid will generally be carried out.
  • the dicarboxylic acid obtained corresponds to the following general formula: which corresponds to formula (I) in which a would be replaced by c + 2 and x and z would each be equal to 1.
  • the modification of the overbased sulfonates by the dicarboxylic acids defined above consists in at least partial neutralization of their basicity reserve (TBN).
  • the preparation of the colloidal products according to the invention is generally carried out in an organic solvent which can more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a hydrocarbon cycloaliphatic (such as, for example, cyclohexane), an aromatic hydrocarbon (such as, for example, toluene or a xylene), optionally combined with tetrahydrofuran or methanol, used as co-solvents.
  • an organic solvent which can more particularly consist of an aliphatic hydrocarbon (such as for example a hexane, a heptane, an octane or a nonane), a hydrocarbon cycloaliphatic (such as, for example, cyclohexane), an aromatic hydrocarbon (such as, for example, toluene or a xylene), optionally combined with tetrahydrofur
  • a modification of the overbased sulfonate can be carried out jointly by reaction with other acids or various reagents which can be brought into play before or after sulfuric and nitrogenous dicarboxylic acid or at the same time as this.
  • the additional acids and reagents considered can be for example metaboric or orthoboric acids, carboxylic acids containing sulfur such as those described in the French patent application EN 92/03 789 already cited above, or also phosphoric and alkyl acids and / or phosphoric aryls.
  • the colloidal products obtained are stable, soluble in mineral and synthetic lubricants and are characterized by their nitrogen, sulfur and possibly boron content and by their calcium and / or magnesium content.
  • Their sulfur content in the active material can range up to about 30% by mass and the nitrogen content up to approximately 15% by mass.
  • Their calcium content in the active ingredient can range, for example, up to about 30% by mass and the magnesium content up to approximately 20% by mass.
  • the colloidal nature of the products of the invention is checked by dialysis through a latex membrane.
  • the nitrogen and sulfur analyzes locate these elements in the fraction that has not been dialyzed (concentrate) which constitutes the colloidal part of the additive.
  • the colloidal compounds containing sulfur and nitrogen according to the invention constitute excellent antiwear and extreme pressure additives.
  • 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. Significant mechanical stresses also appear during the machining of metals, whether cutting or forming.
  • colloidal compounds containing sulfur and nitrogen according to the invention are endowed with great thermal stability, which authorizes their use in lubricants subjected in service at very high temperatures which can reach 160 ° C., such as in some severe engine housings, in heavily loaded transmissions or high speed metal cutting.
  • 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 generally also 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, antifoam, dispersants, friction reducers, with which the products of the invention are compatible.
  • Examples A to F the synthesis of various acids which can be used in the preparation of the products according to the invention described in Examples 1 to 11 is described.
  • Examples 12 and 13 describe tests carried out on some of these products.
  • the product has the following characteristics (mass%):
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 90 ° C. and then a solution of 5.93 g (0.0223 mole or 0.0446 acid equivalent) of 3.3 'acid is introduced over 1 hour using the ampoule.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 90 ° C. and then a solution of 6.55 g (0.0223 mole or 0.0446 acid equivalent) of 4.4 'acid is introduced over 1 hour using the ampoule.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • an overbased alkaline reserve magnesium sulfonate (TBN) equivalent to 400 are introduced into a reactor equipped with a stirrer, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 90 ° C. and then a solution of 6.3 g (0.0237 mol or 0.0474 acid equivalent) of 3.3 ′ acid is introduced over the course of one hour using the bulb.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 130 ° C. and then a solution of 10.8 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm3 of xylene is introduced over 30 minutes at this temperature.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 130 ° C. and then a solution of 10.8 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.0154 acid equivalent) in 100 cm3 of xylene is introduced over 30 minutes at this temperature.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 130 ° C. and then a solution of 10.8 g is introduced over 30 minutes at this temperature.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 130 ° C. and then a solution of 63.4 g of an alkylarylsulfonic acid with a molar mass equivalent to 700 (or 0.09 acid equivalent) in 100 cm3 of xylene is introduced over 30 minutes at this temperature.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • 4.11 g of orthoboric acid (0.066 mol) dispersed in 30 cm3 of methanol are introduced and then the medium is brought to reflux for 1 hour. After azeotropic distillation of methanol and of the reaction water formed, the medium is cooled to 90 ° C.
  • an overbased alkaline reserve calcium sulfonate (TBN) equivalent to 500 are introduced into a reactor equipped with an agitator, a condenser, a Dean & Stark separator and a dropping funnel.
  • the medium is brought to 90 ° C. and then a solution of 5.98 g (0.0167 mole or 0.0334 acid equivalent) of 5.5 'acid is introduced over 1 hour using the ampoule.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Colloid Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
EP94401783A 1993-08-18 1994-08-03 Kalzium und/oder Magnesium auch Schwefel und Stickstoff enthaltende Kolloidale Produkte, ihre Herstellung und ihre Verwendung, insbesondere als Schmieröladditive Expired - Lifetime EP0639634B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9310128 1993-08-18
FR9310128A FR2709076B1 (fr) 1993-08-18 1993-08-18 Produits colloïdaux renfermant du calcium, et/ou du magnésium, ainsi que du souffre et de l'azote, leur préparation et leur utilisation notamment comme additifs dans les huiles lubrifiantes.

Publications (2)

Publication Number Publication Date
EP0639634A1 true EP0639634A1 (de) 1995-02-22
EP0639634B1 EP0639634B1 (de) 1999-12-29

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EP94401783A Expired - Lifetime EP0639634B1 (de) 1993-08-18 1994-08-03 Kalzium und/oder Magnesium auch Schwefel und Stickstoff enthaltende Kolloidale Produkte, ihre Herstellung und ihre Verwendung, insbesondere als Schmieröladditive

Country Status (8)

Country Link
US (1) US5462682A (de)
EP (1) EP0639634B1 (de)
JP (1) JPH0780280A (de)
AT (1) ATE188241T1 (de)
DE (1) DE69422348T2 (de)
ES (1) ES2142916T3 (de)
FR (1) FR2709076B1 (de)
PT (1) PT639634E (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996030467A1 (fr) * 1994-03-03 1996-10-03 Institut Français Du Petrole 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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585029A (en) * 1995-12-22 1996-12-17 Exxon Research And Engineering Company High load-carrying turbo oils containing amine phosphate and 2-alkylthio-1,3,4-thiadiazole-5-alkanoic acid
US5731274A (en) * 1996-09-11 1998-03-24 Exxon Research And Engineering Company Lithium complex grease with extended lubrication life
GB9900035D0 (en) * 1999-01-04 1999-02-24 Infineum Uk Ltd Overbased metal detergents
US20050065042A1 (en) * 2003-09-22 2005-03-24 Alltrista Zinc Products, L.P., An Indiana Limited Partnership Anti-corrosive engine oil system components
US20050061734A1 (en) * 2003-09-22 2005-03-24 Alltrista Zinc Products, L.P. Anti-corrosive engine oil system components

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0390664A2 (de) * 1989-03-30 1990-10-03 Institut Français du Pétrole Neue Thiophosphorverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Schmiermittelzusatzstoffe
EP0536020A1 (de) * 1991-09-30 1993-04-07 Institut Francais Du Petrole Bor, Schwefel und Phosphor enthaltende kolloidale Produkte, ihre Herstellung und ihre Verwendung als Schmieröladditive

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5256319A (en) * 1989-03-30 1993-10-26 Institut Francais Du Petrole New thiophosphoretted compounds, their preparation and their use as additives for lubricants
FR2689031B1 (fr) * 1992-03-26 1994-05-27 Inst Francais Du Petrole Produits collouidaux surbases, contenant du soufre organique et leur utilisation comme additifs detergents a action antiusure et extreme-pression dans les huiles lubrifiantes.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0390664A2 (de) * 1989-03-30 1990-10-03 Institut Français du Pétrole Neue Thiophosphorverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung als Schmiermittelzusatzstoffe
EP0536020A1 (de) * 1991-09-30 1993-04-07 Institut Francais Du Petrole Bor, Schwefel und Phosphor enthaltende kolloidale Produkte, ihre Herstellung und ihre Verwendung als Schmieröladditive

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996030467A1 (fr) * 1994-03-03 1996-10-03 Institut Français Du Petrole 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
US5696062A (en) * 1994-03-03 1997-12-09 Institut Francais Du Petrole Colloidal products containing calcium barium and/or magnesium also bismuth modified by the action of carboxylic acids containing sulphur and optionally nitrogen

Also Published As

Publication number Publication date
EP0639634B1 (de) 1999-12-29
US5462682A (en) 1995-10-31
ATE188241T1 (de) 2000-01-15
DE69422348T2 (de) 2000-06-08
FR2709076B1 (fr) 1995-10-06
ES2142916T3 (es) 2000-05-01
DE69422348D1 (de) 2000-02-03
PT639634E (pt) 2000-04-28
JPH0780280A (ja) 1995-03-28
FR2709076A1 (fr) 1995-02-24

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