EP0390664A2 - New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives - Google Patents

New thiophosphorous compounds, a process for preparing same and use of said compounds as lubricant additives Download PDF

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Publication number
EP0390664A2
EP0390664A2 EP90400818A EP90400818A EP0390664A2 EP 0390664 A2 EP0390664 A2 EP 0390664A2 EP 90400818 A EP90400818 A EP 90400818A EP 90400818 A EP90400818 A EP 90400818A EP 0390664 A2 EP0390664 A2 EP 0390664A2
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EP
European Patent Office
Prior art keywords
composition according
mass
phosphorus
reaction
overbased
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
EP90400818A
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German (de)
French (fr)
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EP0390664B1 (en
EP0390664A3 (en
Inventor
Guy Parc
Nicole Thevenin
Maurice Born
Jacques Lallement
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12Reaction products
    • C10M159/20Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/24Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing sulfonic radicals
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    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/14Water
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    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/24Compounds containing phosphorus, arsenic or antimony
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    • C10M125/00Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/26Compounds containing silicon or boron, e.g. silica, sand
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    • C10M129/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04Hydroxy compounds
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    • C10M129/02Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/26Carboxylic acids; Salts thereof
    • C10M129/28Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M129/30Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 7 or less carbon atoms
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    • C10M133/04Amines, e.g. polyalkylene polyamines; Quaternary amines
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Definitions

  • the present invention relates to new thiophosphorus compounds soluble in mineral oils obtained by reaction of at least one phosphorus sulfide with at least one so-called "overbased" detergent sulfonate.
  • an overbased detergent sulfonate can be defined as consisting of a surfactant consisting essentially of an alkaline or alkaline earth salt of a sulfonic acid containing oleophilic groups and which keeps acid salts in colloidal dispersion.
  • weak minerals such as CO2, H2S and alkaline or alkaline earth bases.
  • the reaction product between the phosphorus sulfide and the overbased detergent sulfonate can optionally be treated with at least one active hydrogen compound which can be water, an alcohol, a phenol, a carboxylic acid, a ester-acid, a mineral acid, a mineral base, an amine, an amide or a mercaptan.
  • active hydrogen compound can be water, an alcohol, a phenol, a carboxylic acid, a ester-acid, a mineral acid, a mineral base, an amine, an amide or a mercaptan.
  • the present invention also relates to the preparation of these new thiophosphorus compounds and their use as additives in mineral and synthetic lubricants.
  • these new additives have anti-wear and extreme pressure properties which are particularly advantageous for application to motor oils, gear oils, hydraulic fluids, lubricating greases or oils for working with metals. .
  • Antiwear and extreme pressure additives are incorporated in 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.
  • transmission oils two types of additive are widely used: phospho-sulfur additives and additives based on potassium borate dispersion.
  • the main disadvantage of mineral oils containing phospho-sulfur additives is their thermal instability, which begins to manifest from 120-130 ° C. However, it is not uncommon for temperatures of 150 ° C to be reached in the transmissions of heavy goods vehicles or passenger cars used under severe conditions. Transmission oils based on potassium borate are significantly more thermally stable, but are sensitive to water, which is unacceptable for certain uses. More effective antiwear and extreme pressure additives, more thermally stable and having less interactions with the other additives in the formulations are actively sought.
  • micellar thiophosphorus compounds of the present invention can be generally defined as being obtained by reaction of at least one overbased sulfonate (A) with a phosphorus sulfide (B), the reaction product possibly being brought into contact with at least one compound with hy active drogen (C).
  • a and B, and optionally the subsequent treatment with C can advantageously be carried out in a solvent (D).
  • Compound A is an overbased sulfonate obtained from at least one alkali or alkaline earth metal salt of at least one acid compound chosen from sulfonic acids, natural or synthetic.
  • the overbasification of the alkali or alkaline earth metal salts of these acids is generally carried out in the presence of a promoter, by treating an excess of oxide or hydroxide of alkali or alkaline earth metal suspended in the reaction medium , by a weak acid such as CO2, SO2, H2S, or H3BO3.
  • the most used cations for overbasification are sodium, magnesium, calcium and barium used in the form of their oxide or hydroxide.
  • the promoter is an alcohol, particularly methanol, an alkylphenol or an amino compound such as ammonia, an amine or an amino alcohol.
  • the most commonly used weak acid is CO2.
  • overbased additives The preparation of overbased additives is well known and is described for example in the patents: US 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 4,148,740 and 4,505,830 and the French patent 2 101 813.
  • 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.
  • the sulfonic acids for the manufacture of overbased sulfonates which can be used according to the invention are known and described in numerous patents, for example in French patent 2 101 813, pages 5 and 6.
  • the hydrocarbon portion of the molecule advantageously has a molecular weight at less than 370 to ensure the miscibility of the corresponding sulfonates in mineral oils.
  • They may be so-called "natural" acids, resulting from the sulfonation of petroleum cuts, or of synthetic acids prepared by sulfonation of charges prepared by synthetic route: alkenyl hydrocarbons, such as polyisobutenes (US Pat. 4,159,956), alkylaryl hydrocarbons such as for example post-dodecylbenzenes obtained as tail product of the manufacture of dodecylbenzene.
  • overbased compounds A preferred according to the invention are the sodium or calcium sulfonates overbased with sodium carbonate or calcium carbonate.
  • the overbased sulfonates A which can be used according to the invention have an alkalinity expressed in terms of TBN (equivalent alkalinity expressed in milligrams of KOH per g of product) between 50 and 550 (or from 0.9 to 10 basic equivalents per kg) and preferably between 150 and 450 (i.e. 2.7 to 8 basic equivalents per kg).
  • TBN equivalent alkalinity expressed in milligrams of KOH per g of product
  • 150 and 450 i.e. 2.7 to 8 basic equivalents per kg.
  • Compound B is a phosphorus sulfide such as P4S7, P4S9, P4S10.
  • P4S10 is the preferred phosphorus sulfide according to the invention.
  • Compound C which can be optionally used is a compound containing an active hydrogen; it can be water, an alcohol such as methanol or isopropanol, a phenol, an acid such as a carboxylic acid such as acetic acid, an acid ester such as a dialkylphosphite, a mineral acid such as acid boric or phosphoric acid, a base such as ammonia or an amine, an amide, a mercaptan, such as dimercaptothiadiazole or its derivatives substituted formula
  • the molar quantity of compound C introduced relative to the molar quantity of phosphorus provided by the phosphorus sulphide can vary in a ratio of between 0.1 and 5, and preferably between 0.3 and 3.
  • the preferred compounds C according to the invention are ammonia, isopropanol, dialkylphosphites, boric acid, mercaptans, in particular derivatives of dimercaptothiadiazole.
  • the solvent D possibly used makes it possible to reduce the viscosity of the reaction medium and thus to improve the contact of the reactants.
  • solvents which can be used according to the invention, mention may be made of cyclohexane, toluene, xylenes and in general hydrocarbon fractions having a boiling range of between 60 and 150 ° C. and preferably between 90 and 120 ° C.
  • the additives obtained according to the invention can have a certain reactivity with respect to copper alloys.
  • the use of sequestering additives of the dimercaptothiadiazole type in doses of between 0.25 and 0.75% by mass in the final formulations leads to entirely satisfactory behavior with respect to copper.
  • the dose required is lower when compound C is itself a derivative of mercaptothiadiazole. It can go for example up to 0.5% by mass.
  • Another characteristic of the present invention is that, within the defined limits, the products obtained retain the colloidal state by giving solutions in the hydrocarbons perfectly clear and stable over time.
  • the process for manufacturing the compounds according to the invention comprises the following steps:
  • Step 1
  • the reaction of phosphorus sulfide on overbased sulfonate can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 85 and 120 ° C.
  • the reaction between the phosphorus sulphide, solid reagent and the overbased additive is facilitated by good stirring of the reaction medium and by the possible use of a hydrocarbon solvent D.
  • the phosphorus sulphide can be gradually introduced into the reaction medium, but it can also be introduced entirely at the start of handling into the overbased compound optionally dissolved in a hydrocarbon solvent, provided that the temperature of the reaction medium is less than about 60 ° C.
  • the reaction is then started by gradually raising the temperature in the ranges indicated above.
  • Compound C with active hydrogen can be in gaseous, liquid or solid form and the means of introduction into the reaction medium will be appropriate to its physical state.
  • the reaction can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 25 and 120 ° C.
  • filtration and elimination of solvents and any excess of reagent.
  • the filtration step is not always necessary, steps 1 and 2 leading in most cases to homogeneous liquid mixtures.
  • filtration can be carried out before the removal of solvent D, for example on simple cellulose disks, or on layers of filtering agents of the diatomite type or of natural silica of volcanic origin. Filtration can also be carried out after removal of the solvents. In this case, it is advantageous to carry out hot filtration, for example from 90 to 120 ° C and under a pressure of 2 to 5 bars.
  • the distillation of the solvent can be carried out in the reactor itself.
  • the elimination of the last traces is facilitated by a nitrogen stripping. It can also be carried out in a thin film evaporator.
  • the product obtained after filtration and elimination of the toluene, ie 253.3 g, has the following characteristics: Ca: 14.2% mass P: 0.88% mass S: 2.25% mass
  • Example 6 The procedure is as in Example 6 until complete reaction of the P4S10. The temperature being maintained at 90 ° C., 49.5 g of didodecylphosphite dissolved in 50 ml of toluene are introduced over 1 hour. Then the temperature is brought to 115 ° C. and is maintained for 3 hours.
  • the products described in the previous examples were evaluated for their antiwear and extreme pressure properties in a lubricating oil.
  • the base mineral oil used is a 130 Neutral with the following characteristics: Kinematic viscosity at 40 ° C: 25.5 mm2 / s Kinematic viscosity at 100 ° C: 4.7 mm2 / s Viscosity index: 101 Pour point: - 15 ° C Sulfur content: 0.46% mass
  • the anti-wear efficiency is evaluated on a 4-ball machine operating for 1 hour under loads of 40 and 60 daN at a speed of 1500 rpm, according to the NF E48-617 method.
  • the average footprint diameter observed on the 3 lower balls are as follows: Products Footprint diameter (mm) 40 daN 60 daN Oil 130 N 1.72 2.22 Oil + 5.3% of the product of Ex. 1 0.48 0.65 Oil + 12% of the product of Ex. 1 0.34 0.39 Oil + 5.3% of the product of Ex. 2 0.44 0.62 Oil + 5.3% of the product of Ex. 3 0.43 0.59 Oil + 5.3% of the product of Ex. 4 0.48 0.70 Oil + 5.3% of the product of Ex. 5 0.44 0.57 Oil + 5.3% of the product of Ex.
  • the extreme pressure properties in the lubricating oils of the products according to the invention were measured on a FZG gear machine according to the CEC method L-07-A-71 with the procedure A / 16.6 / 90, that is to say ie using the gear type A, with a circumferential speed at the pitch diameter of 16.6 m / s and at the temperature of 90 ° C at the start of each load bearing.
  • the mineral oil used is the base 130 N described above. Method B of visual rating was used.
  • the extreme pressure efficiency is all the more pronounced the higher the load level reached.
  • the temperature of the oil was also recorded at the end of the bearing 12 which is in relation to the forces dissipated in the friction.
  • the objective of this test was to replace the antiwear additive and the detergent additive with an additive according to the invention.
  • a conventional dispersant additive of the succinimide type usually used to satisfy the requirements of cold dispersivity was used.
  • test bench is driven by an electric motor and operates according to the following cycle: 1 minute at 750 rpm 2 minutes at 1500 rpm
  • the springs, under maximum lift, are rated at 1200 N.
  • the duration of the test is 50 hours and the oil temperature is regulated at 50 ° C.
  • the rockers are weighed and rated according to a scale which defines four typical aspects.
  • This test uses a PEUGEOT PC7 bridge to which torque peaks of the order of 340 Nm are applied.
  • the crown is examined without dismantling all the series of 20 torque peaks.
  • the test is continued up to 80 peaks of torque, after which the bridge is dismantled and the surfaces of the pinion and the crown are examined.
  • the result is given as a percentage of the bearing surface deteriorated by seizing (scoring).
  • the additives are compared in an identical base oil (100 neutral solvent).
  • a comparative test was carried out with an extreme pressure additive sold under the name of ANGLAMOL 99 (registered trademark), extreme pressure additive widely used in hypoid bridges.
  • Product of Example 12 12.9 * 2.0 * 7.2% after deduction of the dilution oil.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

On décrit une nouvelle classe d'additifs antiusure et extrême-pression constituée de composés thiophosphorés obtenus par réaction de sulfures de phosphore, et notamment de décasulfure de phosphore P₄S₁₀, avec des additifs détergents surbasiques. Le produit de réaction peut être éventuellement traité par au moins un composé à hydrogène actif: eau, alcool, phénol, acide, ammoniac, amine, amide et/ou mercaptan.A new class of anti-wear and extreme-pressure additives is described consisting of thiophosphorus compounds obtained by reacting phosphorus sulphides, and in particular phosphorus decasulphide P₄S₁₀, with overbased detergent additives. The reaction product can optionally be treated with at least one active hydrogen compound: water, alcohol, phenol, acid, ammonia, amine, amide and/or mercaptan.

Description

La présente invention concerne de nouveaux composés thiophosphorés solubles dans les huiles minérales obtenus par réaction d'au moins un sulfure de phos­phore avec au moins un sulfonate détergent dit "surbasique".The present invention relates to new thiophosphorus compounds soluble in mineral oils obtained by reaction of at least one phosphorus sulfide with at least one so-called "overbased" detergent sulfonate.

D'une manière générale, un sulfonate détergent surbasique peut être défini comme constitué d'un agent tensioactif consistant essentiellement en un sel al­calin ou alcalino-terreux d'un acide sulfonique renfermant des groupes oléophiles et qui maintient en dispersion colloïdale des sels d'acides faibles minéraux tels que CO₂, H₂S et de bases alcalines ou alcalino-terreuses.In general, an overbased detergent sulfonate can be defined as consisting of a surfactant consisting essentially of an alkaline or alkaline earth salt of a sulfonic acid containing oleophilic groups and which keeps acid salts in colloidal dispersion. weak minerals such as CO₂, H₂S and alkaline or alkaline earth bases.

Selon l'invention, le produit de réaction entre le sulfure de phosphore et le sulfonate détergent surbasique peut être éventuellement traité par au moins un composé à hydrogène actif qui peut être de l'eau, un alcool, un phénol, un acide carboxylique, un ester-acide, un acide minéral, une base minérale, une amine, un amide ou un mercaptan.According to the invention, the reaction product between the phosphorus sulfide and the overbased detergent sulfonate can optionally be treated with at least one active hydrogen compound which can be water, an alcohol, a phenol, a carboxylic acid, a ester-acid, a mineral acid, a mineral base, an amine, an amide or a mercaptan.

La présente invention concerne également la préparation de ces nouveaux com­posés thiophosphorés et leur utilisation comme additifs dans les lubrifiants minéraux et synthétiques. En particulier, on a découvert que ces nouveaux ad­ditifs présentaient des propriétés antiusure et extrême-pression particulièrement intéressantes pour l'application aux huiles pour moteurs, aux huiles d'engrenages, aux fluides hydrauliques, aux graisses lubrifiantes ou aux huiles pour le travail des métaux.The present invention also relates to the preparation of these new thiophosphorus compounds and their use as additives in mineral and synthetic lubricants. In particular, it has been discovered that these new additives have anti-wear and extreme pressure properties which are particularly advantageous for application to motor oils, gear oils, hydraulic fluids, lubricating greases or oils for working with metals. .

Les additifs antiusure et extrême-pression sont incorporés aux lubrifiants lorsque ceux-ci sont destinés à lubrifier des organes soumis à des contraintes mécaniques importantes, tels que la distribution dans les moteurs thermiques, les engrenages, les roulements ou les butées. Des contraintes mécaniques importantes appa­raissent également lors de l'usinage des métaux, qu'il s'agisse de coupe ou de formage.Antiwear and extreme pressure additives are incorporated in 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.

Les additifs antiusure les plus largement utilisés dans les moteurs sont les dialkyldithiophosphates de zinc, mais l'efficacité de ces additifs est atténuée par la présence de dispersants azotés, probablement à cause de la formation de complexes de coordination entre ces deux types d'additifs. Or les huiles mo­teurs modernes exigent des quantités importantes de dispersants, notamment pour être conformes à l'essai VE de la spécification SG de l'American Petroleum Institute. La teneur accrue en additif nécessaire pour maintenir constantes les qualités antiusure se traduit par une augmentation de la teneur en phosphore des huiles moteurs, alors que c'est précisément l'inverse qui est recherché pour l'efficacité maximale des pots catalytiques destinés à réduire la pollution par les gaz d'échappementThe most widely used wear additives in engines are zinc dialkyldithiophosphates, but the effectiveness of these additives is mitigated by the presence of nitrogen dispersants, probably due to the formation of coordination complexes between these two types of additives. However, modern motor oils require significant quantities of dispersants, in particular to comply with the VE test of the SG specification of the American Petroleum Institute. The increased content of additive necessary to keep the antiwear qualities constant results in an increase in the phosphorus content of engine oils, whereas it is precisely the reverse that is sought for the maximum efficiency of catalytic converters intended to reduce the exhaust gas pollution

En ce qui concerne les huiles de transmission, deux types d'additifs sont large­ment utilisés : les additifs phospho-soufrés et les additifs à base de dispersion de borate de potassium. Le principal inconvénient des huiles minérales renfer­mant des additifs phospho-soufrés est leur instablilité thermique, qui commence à se manifester dès 120-130°C. Or il n'est pas rare que des températures de 150°C soient atteintes dans les transmissions de poids lourds ou de voitures particulières utilisées dans des conditions sévères. Les huiles de transmission à base de borate de potassium sont nettement plus stables thermiquement, mais sont sensibles à l'eau, ce qui est rédhibitoire pour certains usages. Des addi­tifs antiusure et extrême-pression plus efficaces, plus stables thermiquement et présentant moins d'interactions avec les autres additifs dans les formulations sont activement recherchés.With regard to transmission oils, two types of additive are widely used: phospho-sulfur additives and additives based on potassium borate dispersion. The main disadvantage of mineral oils containing phospho-sulfur additives is their thermal instability, which begins to manifest from 120-130 ° C. However, it is not uncommon for temperatures of 150 ° C to be reached in the transmissions of heavy goods vehicles or passenger cars used under severe conditions. Transmission oils based on potassium borate are significantly more thermally stable, but are sensitive to water, which is unacceptable for certain uses. More effective antiwear and extreme pressure additives, more thermally stable and having less interactions with the other additives in the formulations are actively sought.

Les composés thiophosphorés micellaires de la présente invention peuvent être définis d'une manière générale comme étant obtenus par réaction d'au moins un sulfonate surbasé (A) avec un sulfure de phosphore (B), le produit réactionnel pouvant être éventuellement mis au contact avec au moins un composé à hy­ drogène actif (C). La réaction entre A et B, et éventuellement le traitement subséquent par C, peut avantageusement être effectuée dans un solvant (D).The micellar thiophosphorus compounds of the present invention can be generally defined as being obtained by reaction of at least one overbased sulfonate (A) with a phosphorus sulfide (B), the reaction product possibly being brought into contact with at least one compound with hy active drogen (C). The reaction between A and B, and optionally the subsequent treatment with C, can advantageously be carried out in a solvent (D).

Le composé A est un sulfonate surbasique obtenu à partir d'au moins un sel de métal alcalin ou alcalino-terreux d'au moins un composé acide choisi parmi les acides sulfoniques, naturels ou synthétiques. La surbasification des sels de métaux alcalins ou alcalino-terreux de ces acides s'effectue en général en présence d'un promoteur, en traitant un excès d'oxyde ou d'hydroxyde de métal alcalin ou alcalino-terreux en suspension dans le milieu réactionnel, par un acide faible tel que CO₂, SO₂, H₂S, ou H₃BO₃. Les cations les plus utilisés pour la sur­basification sont le sodium, le magnésium, le calcium et le baryum utilisés sous forme de leur oxyde ou hydroxyde. Le promoteur est un alcool, particulièrement le méthanol, un alkylphénol ou un composé aminé tel que l'ammoniaque, une amine ou un amino-alcool. L'acide faible le plus couramment utilisé est le CO₂.Compound A is an overbased sulfonate obtained from at least one alkali or alkaline earth metal salt of at least one acid compound chosen from sulfonic acids, natural or synthetic. The overbasification of the alkali or alkaline earth metal salts of these acids is generally carried out in the presence of a promoter, by treating an excess of oxide or hydroxide of alkali or alkaline earth metal suspended in the reaction medium , by a weak acid such as CO₂, SO₂, H₂S, or H₃BO₃. The most used cations for overbasification are sodium, magnesium, calcium and barium used in the form of their oxide or hydroxide. The promoter is an alcohol, particularly methanol, an alkylphenol or an amino compound such as ammonia, an amine or an amino alcohol. The most commonly used weak acid is CO₂.

La préparation des additifs surbasiques est bien connue et est décrite par exem­ple dans les brevets : US 2 865 956, 3 150 088, 3 537 996, 3 830 739, 3 865 737, 4 148 740 et 4 505 830 et le brevet français 2 101 813. Il existe des variantes de la réaction de surbasification qui font notamment appel à des carbonates préformés à partir d'alcoxydes et de CO₂ avant la mise en contact avec le sel alcalin ou alcalino-terreux du composé acide ; elles sont décrites notamment dans les brevets US 2 956 018, 3 932 289 et 4 104 180.The preparation of overbased additives is well known and is described for example in the patents: US 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 4,148,740 and 4,505,830 and the 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.

Les acides sulfoniques pour la fabrication des sulfonates surbasiques utilisables selon l'invention sont connus et décrits dans de nombreux brevets, par exemple dans le brevet français 2 101 813, pages 5 et 6. La portion hydrocarbonée de la molécule présente avantageusement une masse moléculaire au moins égale à 370 pour assurer la miscibilité des sulfonates correspondants dans les huiles minérales. Il peut s'agir d'acides dits "naturels", issus de la sulfonation de coupes pétrolières, ou d'acides synthétiques préparés par sulfonation de charges préparés par voie synthétique : les hydrocarbures alkényliques, tels que poly­isobutènes (brevet US 4 159 956), les hydrocarbures alkylaryliques comme par exemple les post-dodécylbenzènes obtenus comme produit de queue de la fab­rication de dodécylbenzène.The sulfonic acids for the manufacture of overbased sulfonates which can be used according to the invention are known and described in numerous patents, for example in French patent 2 101 813, pages 5 and 6. The hydrocarbon portion of the molecule advantageously has a molecular weight at less than 370 to ensure the miscibility of the corresponding sulfonates in mineral oils. They may be so-called "natural" acids, resulting from the sulfonation of petroleum cuts, or of synthetic acids prepared by sulfonation of charges prepared by synthetic route: alkenyl hydrocarbons, such as polyisobutenes (US Pat. 4,159,956), alkylaryl hydrocarbons such as for example post-dodecylbenzenes obtained as tail product of the manufacture of dodecylbenzene.

Les composés A surbasiques préférés selon l'invention sont les sulfonates de sodium ou de calcium surbasés par le carbonate de sodium ou le carbonate de calcium.The overbased compounds A preferred according to the invention are the sodium or calcium sulfonates overbased with sodium carbonate or calcium carbonate.

Les sulfonates surbasiques A utilisables selon l'invention ont une alcalinité ex­primée en terme de TBN (alcalinité équivalente exprimée en milligramme de KOH par g de produit) comprise entre 50 et 550 (soit de 0,9 à 10 équivalents basiques par kg) et de préférence entre 150 et 450 (soit de 2,7 à 8 équivalents basiques par kg).The overbased sulfonates A which can be used according to the invention have an alkalinity expressed in terms of TBN (equivalent alkalinity expressed in milligrams of KOH per g of product) between 50 and 550 (or from 0.9 to 10 basic equivalents per kg) and preferably between 150 and 450 (i.e. 2.7 to 8 basic equivalents per kg).

Le composé B est un sulfure de phosphore tel que P₄S₇, P₄S₉, P₄S₁₀. P₄S₁₀, est le sulfure de phosphore préféré selon l'invention. Le sulfure de phosphore est utilisé en quantité telle que le rapport P molaire/EB, où EB représente l'équivalent basique de l'additif surbasique, est compris entre 0,002 et 0,15 et de préférence entre 0,02 et 0,12. Au delà du rapport P molaire/EB = 0,15, la réaction entre l'additif surbasique et le sulfure de phosphore risque d'être incomplète.Compound B is a phosphorus sulfide such as P₄S₇, P₄S₉, P₄S₁₀. P₄S₁₀, is the preferred phosphorus sulfide according to the invention. The phosphorus sulfide is used in an amount such that the P mol / EB ratio, where EB represents the basic equivalent of the overbased additive, is between 0.002 and 0.15 and preferably between 0.02 and 0.12. Above the molar P / EB ratio = 0.15, the reaction between the overbased additive and the phosphorus sulphide may be incomplete.

Le composé C pouvant être éventuellement utilisé est un composé renfermant un hydrogène actif ; ce peut être de l'eau, un alcool tel que le méthanol ou l'isopropanol, un phénol, un acide tel qu'un acide carboxylique comme l'acide acétique, un ester acide comme un dialkylphosphite, un acide minéral comme l'acide borique ou l'acide phosphorique, une base comme l'ammoniac ou une amine, un amide, un mercaptan, tel que le dimercaptothiadiazole ou ses dérivés substitués de formule

Figure imgb0001
Compound C which can be optionally used is a compound containing an active hydrogen; it can be water, an alcohol such as methanol or isopropanol, a phenol, an acid such as a carboxylic acid such as acetic acid, an acid ester such as a dialkylphosphite, a mineral acid such as acid boric or phosphoric acid, a base such as ammonia or an amine, an amide, a mercaptan, such as dimercaptothiadiazole or its derivatives substituted formula
Figure imgb0001

La quantité molaire du composé C introduite par rapport à la quantité molaire de phosphore apporté par le sulfure de phosphore, peut varier dans un rapport compris entre 0,1 et 5, et de préférence entre 0,3 et 3.The molar quantity of compound C introduced relative to the molar quantity of phosphorus provided by the phosphorus sulphide can vary in a ratio of between 0.1 and 5, and preferably between 0.3 and 3.

Les composés C préférés selon l'invention sont l'ammoniac, l'isopropanol, les dialkylphosphites, l'acide borique, les mercaptans, en particulier les dérivés du dimercaptothiadiazole.The preferred compounds C according to the invention are ammonia, isopropanol, dialkylphosphites, boric acid, mercaptans, in particular derivatives of dimercaptothiadiazole.

Le solvant D éventuellement utilisé permet de réduire la viscosité du milieu réactionnel et ainsi d'améliorer le contact des réactifs. Comme exemples de solvants utilisables selon l'invention, on peut citer le cyclohexane, le toluène, les xylènes et de façon générale les coupes d'hydrocarbures ayant un intervalle d'ébullition compris entre 60 et 150°C et de préférence entre 90 et 120°C.The solvent D possibly used makes it possible to reduce the viscosity of the reaction medium and thus to improve the contact of the reactants. As examples of solvents which can be used according to the invention, mention may be made of cyclohexane, toluene, xylenes and in general hydrocarbon fractions having a boiling range of between 60 and 150 ° C. and preferably between 90 and 120 ° C.

Les additifs obtenus selon l'invention peuvent présenter une certaine réactivité vis-a-vis des alliages cuivreux. L'utilisation d'additifs séquestrants du type dimercaptothiadiazole à des doses comprises entre 0,25 et 0,75 % en masse dans les formulations finales conduit à un comportement entièrement satisfaisant vis-­à-vis du cuivre. La dose requise est inférieure lorsque le composé C est lui-même un dérivé du mercaptothiadiazole. Elle peut aller par exemple jusqu'à 0,5 % en masse.The additives obtained according to the invention can have a certain reactivity with respect to copper alloys. The use of sequestering additives of the dimercaptothiadiazole type in doses of between 0.25 and 0.75% by mass in the final formulations leads to entirely satisfactory behavior with respect to copper. The dose required is lower when compound C is itself a derivative of mercaptothiadiazole. It can go for example up to 0.5% by mass.

La nature des composés formés au cours de la réaction n'est pas connue avec certitude. On peut supposer que les sulfures de phosphore réagissent sur la dis­persion colloïdale du sel d'acide faible et de base alcaline ou alcanino-terreuse, pour former des thiophosphates minéraux alcalins ou alcalino-terreux. Cette hypothèse se trouve confortée par le fait que lors de la dialyse en milieu hydro­carbure des produits selon l'invention, la totalité du phosphore est retrouvée dans la fraction non dialysée.The nature of the compounds formed during the reaction is not known with certainty. It can be assumed that the phosphorus sulphides react on the colloidal dispersion of the salt of weak acid and of alkaline or alkaline earth base, to form alkaline or alkaline earth mineral thiophosphates. This hypothesis is supported by the fact that during dialysis in a hydrocarbon medium of the products according to the invention, all of the phosphorus is found in the non-dialyzed fraction.

Une autre caractéristique de la présente invention est que, dans les limites définies, les produits obtenus conservent l'état colloïdal en donnant des solutions dans les hydrocarbures parfaitement limpides et stables dans le temps.Another characteristic of the present invention is that, within the defined limits, the products obtained retain the colloidal state by giving solutions in the hydrocarbons perfectly clear and stable over time.

Le procédé de fabrication des composés selon l'invention comporte les étapes suivantes:The process for manufacturing the compounds according to the invention comprises the following steps:

Etape 1 :Step 1 :

La réaction du sulfure de phosphore sur le sulfonate surbasique peut être effectuée à une pression comprise entre la pression atmosphérique et environ 5 bars absolus (0,5 MPa), à une température comprise entre 60 et 130°C et de préférence entre 85 et 120°C. La réaction entre le sulfure de phosphore, réactif solide et l'additif surbasique est facilitée par une bonne agitation du milieu réactionnel et par l'emploi éventuel d'un solvant hydrocarboné D. Le sulfure de phosphore peut être introduit progressivement dans le milieu réactionnel, mais il peut également être introduit en totalité en début de manipulation dans le composé surbasique éventuellement dissous dans un solvant hydrocarboné, à condition que la température du milieu réactionnel soit inférieure à environ 60°C. La réaction est déclenchée alors en élevant progressivement la température dans les fourchettes indiquées ci-dessus.The reaction of phosphorus sulfide on overbased sulfonate can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 85 and 120 ° C. The reaction between the phosphorus sulphide, solid reagent and the overbased additive is facilitated by good stirring of the reaction medium and by the possible use of a hydrocarbon solvent D. The phosphorus sulphide can be gradually introduced into the reaction medium, but it can also be introduced entirely at the start of handling into the overbased compound optionally dissolved in a hydrocarbon solvent, provided that the temperature of the reaction medium is less than about 60 ° C. The reaction is then started by gradually raising the temperature in the ranges indicated above.

Etape 2:2nd step:

Le composé C à hydrogène actif peut se présenter sous forme gazeuse, liquide ou solide et les moyens d'introduction dans le milieu réactionnel seront appropriés à son état physique. La réaction peut être effectuée à une pression comprise entre la pression atmosphérique et environ 5 bars absolus (0,5 MPa), à une température comprise entre 60 et 130°C et de préférence entre 25 et 120°C.Compound C with active hydrogen can be in gaseous, liquid or solid form and the means of introduction into the reaction medium will be appropriate to its physical state. The reaction can be carried out at a pressure between atmospheric pressure and about 5 bar absolute (0.5 MPa), at a temperature between 60 and 130 ° C and preferably between 25 and 120 ° C.

Etape 3:Step 3:

Filtration et élimination des solvants et de l'excès éventuel de réactif. L'étape de filtration n'est pas toujours nécessaire, les étapes 1 et 2 conduisant dans la plupart des cas à des mélanges liquides homogènes. Lorsque la filtration s'impose, elle peut être réalisée avant l'élimination du solvant D, par exemple sur de simples disques de cellulose, soit sur des couches d'agents filtrants de type diatomite ou de silice naturelle d'origine volcanique. On peut également procéder à la filtration après élimination des solvants. Dans ce cas, il est avan­tageux d'effectuer la filtration à chaud, par exemple de 90 à 120°C et sous une pression de 2 à 5 bars.Filtration and elimination of solvents and any excess of reagent. The filtration step is not always necessary, steps 1 and 2 leading in most cases to homogeneous liquid mixtures. When filtration is required, it can be carried out before the removal of solvent D, for example on simple cellulose disks, or on layers of filtering agents of the diatomite type or of natural silica of volcanic origin. Filtration can also be carried out after removal of the solvents. In this case, it is advantageous to carry out hot filtration, for example from 90 to 120 ° C and under a pressure of 2 to 5 bars.

La distillation du solvant peut être réalisée dans le réacteur lui-même. L'éli­mination des dernières traces est facilitée par un stripping à l'azote. Elle peut être également effectuée dans un évaporateur à film mince.The distillation of the solvent can be carried out in the reactor itself. The elimination of the last traces is facilitated by a nitrogen stripping. It can also be carried out in a thin film evaporator.

Les exemples suivants illustrent l'invention. Ils ne doivent en aucune manière être considérés comme limitatifs.The following examples illustrate the invention. They should in no way be considered as limiting.

EXEMPLE 1EXAMPLE 1

Dans un réacteur agité et sous couverture d'azote, on introduit 292,8 g d'un sulfonate de calcium surbasé par du carbonate de calcium dont le TBN est de 410 mg KOH/g (soit un nombre d'équivalents basiques de 7,32 par kg) et 300 ml de toluène. Lorsque le mélange est homogène, 25,7 g (0,058 mole) de P₄S₁₀ sont introduits dans le réacteur et la température est progressivement portée à 90°C, puis maintenue à ce niveau pendant 2 heures. Les effluents gazeux sont absorbés dans une solution de potasse à 10 %. Le mélange réactionnel est alors porté au reflux ; la température se stabilise à 115°C. Après 2 heures à cette température, le toluène est distillé sous courant d'azote, puis le produit de réaction est maintenu à 155°C pendant 2 heures tandis que le barbotage d'azote est poursuivi. Le produit est finalement flltré sur terre filtrante à 100°C, sous pression de 3 bars d'azote. On obtient finalement 301 g d'un produit ayant l'analyse élémentaire suivante:
Ca : 14,7 % masse
P : 2,00 % masse
S : 4,2 % masse
292.8 g of a calcium sulfonate overbased with calcium carbonate, the TBN of which is 410 mg KOH / g (ie a number of basic equivalents of 7, are introduced into a stirred reactor under nitrogen blanket) 32 per kg) and 300 ml of toluene. When the mixture is homogeneous, 25.7 g (0.058 mole) of P₄S₁₀ are introduced into the reactor and the temperature is gradually brought to 90 ° C, then maintained at this level for 2 hours. The gaseous effluents are absorbed in a 10% potash solution. The reaction mixture is then brought to reflux; the temperature stabilizes at 115 ° C. After 2 hours at this temperature, the toluene is distilled under a stream of nitrogen, then the reaction product is kept at 155 ° C. for 2 hours while the nitrogen bubbling is continued. The product is finally filtered on filter earth at 100 ° C, under pressure of 3 bars of nitrogen. 301 g of a product are finally obtained having the following elementary analysis:
Ca: 14.7% mass
P: 2.00% mass
S: 4.2% mass

EXEMPLE 2EXAMPLE 2

Il est procédé comme à l'exemple 1 jusqu'à la fin du reflux de 2 heures à 115°C. A ce moment, on fait barboter 12 g d'ammoniac (0,706 mole) dans le mélange réactionnel. La durée d'introduction est de 1,5 heures. On fait ensuite passer un courant d'azote pour chasser l'excès d'ammoniac et le mélange réactionnel est filtré sur terre filtrante. Le toluène est distillé du mélange réactionnel à l'évaporateur rotatif. On recueille finalement 307,4 g d'un produit dont l'analyse est la suivante :
Ca : 14,5 % masse
P : 2,06 % masse
S : 4,25 % masse
M : 0,58 % masse
The procedure is as in Example 1 until the end of the 2 hour reflux at 115 ° C. At this point, 12 g of ammonia (0.706 mol) are bubbled into the reaction mixture. The introduction time is 1.5 hours. A stream of nitrogen is then passed to remove the excess ammonia and the reaction mixture is filtered on filter earth. The toluene is distilled from the reaction mixture on a rotary evaporator. 307.4 g of a product are finally collected, the analysis of which is as follows:
Ca: 14.5% mass
P: 2.06% mass
S: 4.25% mass
M: 0.58% mass

EXEMPLE 3EXAMPLE 3

Dans un réacteur agité et sous couverture d'azote, 293,7 g du sulfonate sur­basique utilisé dans les exemples précédents sont dissous dans 300 ml de toluène. 23 g (0,052 mole) de P₄S₁₀ sont alors progressivement introduits dans le réacteur à la température de 90°C. Après la fin de l'introduction de P₄S₁₀, le mélange réactionnel est maintenu à cette température pendant encore 2 heures, puis le mélange est porté à reflux à 115°C pendant 1 heure pour s'assurer que la réaction est complète. La température est alors ramenée à 65°C et l'on in­troduit progressivement 29,7 g (0,495 mole) d'isopropanol dilués dans 50 ml de toluène, puis le milieu réactionnel est maintenu à 75°C pendant 3 heures. Après refroidissement, le mélange est filtré sur terte d'infusoire et les composés volatils sont éliminés à l'évaporateur rotatif. On obtient finalement 313,2 g d'un produit dont l'analyse est la suivante:
Ca : 14,2 % masse
P : 1,87 % masse
S : 3,25 % masse
In a stirred reactor and under a nitrogen blanket, 293.7 g of the overbased sulfonate used in the previous examples are dissolved in 300 ml of toluene. 23 g (0.052 mole) of P₄S₁₀ are then gradually introduced into the reactor at the temperature of 90 ° C. After the end of the introduction of P₄S₁₀, the reaction mixture is maintained at this temperature for another 2 hours, then the mixture is brought to reflux at 115 ° C for 1 hour to ensure that the reaction is complete. The temperature is then brought back to 65 ° C. and 29.7 g (0.495 mol) of isopropanol diluted in 50 ml of toluene are gradually introduced, then the reaction medium is maintained at 75 ° C. for 3 hours. After cooling, the mixture is filtered on a diatomaceous earth and the volatile compounds are eliminated on a rotary evaporator. 313.2 g of a product are finally obtained, the analysis of which is as follows:
Ca: 14.2% mass
P: 1.87% mass
S: 3.25% mass

EXEMPLE 4EXAMPLE 4

IL est procédé comme à l'exemple 3 à la différence près que l'on introduit pro­gressivement 5 g (0,278 mole) d'eau à la place de l'isopropanol dilué dans le toluène. On récupère finalement 294,1 g d'un produit ayant la composition suivante:
Ca : 14,4 % masse
P : 1,84 % masse
S : 2,85 % masse
IT is carried out as in Example 3 with the difference that 5 g (0.278 mole) of water are gradually introduced in place of the isopropanol diluted in toluene. Finally recovered 294.1 g of a product having the following composition:
Ca: 14.4% mass
P: 1.84% mass
S: 2.85% mass

EXEMPLE 6EXAMPLE 6

La réaction est effectuée dans les mêmes conditions qu'à l'exemple 3, à la différence près que l'alcool utilisé est le méthanol. La quantité de méthanol in­troduite dans les mêmes conditions que ci-dessus est de 16 g (0,5 mole). Après flltration, puis élimination des composés volatils, on recueille finalement 310,7 g d'un produit dont l'analyse est la suivante:
Ca : 14,4 % masse
P : 1,99 % masse
S : 3,8 % masse
The reaction is carried out under the same conditions as in Example 3, with the difference that the alcohol used is methanol. The amount of methanol introduced under the same conditions as above is 16 g (0.5 mole). After filtration, then elimination of the volatile compounds, 310.7 g of a product are finally collected, the analysis of which is as follows:
Ca: 14.4% mass
P: 1.99% mass
S: 3.8% mass

EXEMPLE 6EXAMPLE 6

Dans un réacteur agité et sous couverture d'azote sont introduits 244,75 g du sulfonate surbasique utilisé dans les exemples précédents et 250 ml de toluène. Le mélange est porté à 85-90°C. On introduit alors 18,7 g (0,042 mole) de P₄S₁₀ en 1 heure, les effluents gazeux sont recueillis dans une solution de potasse à 10 %. Le mélange est maintenu agité à la température de 90°C pendant 3 heures supplémentaires. Tout le P₄S₁₀ est alors entré en réaction. On introduit en­suite 10,2 g d'un dérivé de dimercaptothiadiazole vendu par la société AMOCO sous la dénomination commerciale AMOCO 153 en solution dans une masse équivalente de toluène. La température est portée à 115°C et est maintenue pendant 1,5 heure. Le toluène est ensuite distillé sous courant d'azote. On récupère finalement 263,1 g d'un liquide visqueux dont les concentrations en calcium, phosphore soufre et azote sont les suivantes :
Ca : 14,3 % masse
P : 1,71 % masse
S : 5,3 % masse
N : 0,31 % masse
244.75 g of the overbased sulfonate used in the previous examples and 250 ml of toluene are introduced into a stirred reactor under a nitrogen blanket. The mixture is brought to 85-90 ° C. Then introduced 18.7 g (0.042 mole) of P₄S₁₀ in 1 hour, the gaseous effluents are collected in a 10% potassium hydroxide solution. The mixture is kept stirred at the temperature of 90 ° C for an additional 3 hours. All the P₄S₁₀ then entered a reaction. Then introduced 10.2 g of a dimercaptothiadiazole derivative sold by the company AMOCO under the trade name AMOCO 153 in solution in an equivalent mass of toluene. The temperature is brought to 115 ° C. and is maintained for 1.5 hours. The toluene is then distilled under a stream of nitrogen. 263.1 g of a viscous liquid are finally recovered, the calcium, phosphorus sulfur and nitrogen concentrations of which are as follows:
Ca: 14.3% mass
P: 1.71% mass
S: 5.3% mass
N: 0.31% mass

EXEMPLE 7EXAMPLE 7

Il est procédé comme à l'exemple 1, mais avec les quantités suivantes de réactifs:
- sulfonate surbasique utilisé dans les examples précédents = 247,7 g
- P₄S₁₀ = 8,25(0,019 mole)
- toluène = 250 ml
The procedure is as in Example 1, but with the following amounts of reactants:
- overbased sulfonate used in the previous examples = 247.7 g
- P₄S₁₀ = 8.25 (0.019 mole)
- toluene = 250 ml

Le produit obtenu après filtration et élimination du toluène, soit 253,3 g, présente les caractéristiques suivantes :
Ca : 14,2 % masse
P : 0,88 % masse
S : 2,25 % masse
The product obtained after filtration and elimination of the toluene, ie 253.3 g, has the following characteristics:
Ca: 14.2% mass
P: 0.88% mass
S: 2.25% mass

EXEMPLE 8EXAMPLE 8

IL est procédé comme à l'exemplè 5 jusqu'à réaction complète du P₄S₁₀. On introduit alors en une heure 24,5 g d'acide borique. Le mélange est ensuite porté à reflux à 115°C pendant 1,5 heure. Après filtration sur filtre de cellulose et évaporation du solvant, on obtient 266,3 g d'un produit dont l'analyse est la suivante :
Ca : 14,0 % masse
P : 1,69 % masse
S : 4,2 % masse
B : 1,51 % masse
IT is carried out as in Example 5 until complete reaction of the P₄S₁₀. 24.5 g of boric acid are then introduced in one hour. The mixture is then brought to reflux at 115 ° C for 1.5 hours. After filtration through a cellulose filter and evaporation of the solvent, 266.3 g of a product are obtained, the analysis of which is as follows:
Ca: 14.0% mass
P: 1.69% mass
S: 4.2% mass
B: 1.51% mass

EXEMPLE 9EXAMPLE 9

Il est procédé comme à l'exemple 6 jusqu'à réaction complète du P₄S₁₀. La température étant maintenue à 90°C, on introduit en 1 heure 49,5 g de di­dodécylphosphite en solution dans 50 ml de toluène. Puis la température est portée à 115°C et est maintenue pendant 3 heures.The procedure is as in Example 6 until complete reaction of the P₄S₁₀. The temperature being maintained at 90 ° C., 49.5 g of didodecylphosphite dissolved in 50 ml of toluene are introduced over 1 hour. Then the temperature is brought to 115 ° C. and is maintained for 3 hours.

Le toluène est ensuite distillé sous courant d'azote. On récupère finalement 302 g d'un liquide visqueux dont l'analyse est la suivante:
Ca : 12,2 % masse
P : 2,78 % masse
S : 3,45 % masse
The toluene is then distilled under a stream of nitrogen. Finally, 302 g of a viscous liquid are recovered, the analysis of which is as follows:
Ca: 12.2% mass
P: 2.78% mass
S: 3.45% mass

EXEMPLE 10EXAMPLE 10

La réaction est effectuée avec les mêmes quantités de réactifs et dans les mêmes conditions qu'à l'exemple 3, à la différence près que la réaction est effectuée dans un réacteur sous pression en Hastelloy (marque déposée), muni d'un système d'agitation magnétique rigoureusement étanche. Après refroidissement, le réacteur est ramené à la pression atmosphérique et on procède à la filtration et à l'élimination des composés volatils. Après ces opérations, on récupère 315,1 g d'un produit de composition suivante:
Ca : 14,1 % masse
P : 1,95 % masse
S : 4,5 % masse
The reaction is carried out with the same quantities of reagents and under the same conditions as in Example 3, with the difference that the reaction is carried out in a pressure reactor made of Hastelloy (registered trademark), equipped with a system rigorously sealed magnetic stirring. After cooling, the reactor is brought back to atmospheric pressure and the volatile compounds are filtered and eliminated. After these operations, 315.1 g of a product of the following composition are recovered:
Ca: 14.1% mass
P: 1.95% mass
S: 4.5% mass

EXEMPLE 11EXAMPLE 11

La réaction est effectuée dans les mêmes conditions qu'à l'exemple 1, à la différence près que l'on utilise comme composé A, 324,5 g d'un sulfonate de sodium surbasé par du carbonate de calcium ayant un TBN de 370 mg KOH/g (soit un nombre d'équivalents basiques de 6,6/kg). On récupère finalement 342,1 g d'un produit de composition suivante:
Ca : 11,3 % masse
Ma : 1,30 % masse
P : 1,92 % masse
S : 3,70 % masse
The reaction is carried out under the same conditions as in Example 1, with the difference that 324.5 g of a sodium sulfonate overbased with calcium carbonate having a TBN of 370 is used as compound A mg KOH / g (i.e. a number of basic equivalents of 6.6 / kg). 342.1 g of a product of the following composition are finally recovered:
Ca: 11.3% mass
Ma: 1.30% mass
P: 1.92% mass
S: 3.70% mass

EXEMPLE 12EXAMPLE 12

La réaction est effectuée avec les mêmes quantités de réactifs et dans les mêmes conditions qu'à l'exemple 3, à la différence près qu'à la suite du reflux de 1 heure à 115°C et avant l'introduction de l'isopropanol, 6,4 g (0,043 mole) de 2,5 dimercapto-1,3,4-thiadiazole sont ajoutés progressivement au milieu réactionnel dont la température a été préalablement ramenée à 90°C.
L'addition d'isopropanol et la fin de la fabrication sont ensuite conduits selon les indications de l'exemple 3. On obtient finalement 323,4 g d'un liquide visqueux dont l'analyse est la suivante:
Ca : 14,0 % masse
P : 1,94 % masse
S : 4,62 % masse
N : 0,45 % mase
The reaction is carried out with the same amounts of reagents and under the same conditions as in Example 3, with the difference that after refluxing for 1 hour at 115 ° C. and before the introduction of isopropanol 6.4 g (0.043 mole) of 2.5 dimercapto-1,3,4-thiadiazole are gradually added to the reaction medium, the temperature of which has previously been brought to 90 ° C.
The addition of isopropanol and the end of the production are then carried out according to the indications in Example 3. Finally, 323.4 g of a viscous liquid are obtained, the analysis of which is as follows:
Ca: 14.0% mass
P: 1.94% mass
S: 4.62% mass
N: 0.45% mase

EXEMPLE 13EXAMPLE 13 EVALUATION DES PROPRIÉTÉS ANTIUSURE ET EXTRÊME-PRESSIONEVALUATION OF THE WEAR AND EXTREME-PRESSURE PROPERTIES

Les produits décrits dans les exemples précédents ont été évalués pour leur propriétés antiusure et extrême-pression dans une huile lubrifiante. L'huile minérale de base utilisée est une 130 Neutral de caractéristiques suivantes :
Viscosité cinématique à 40°C : 25,5 mm²/s
Viscosité cinématique à 100°C : 4,7 mm²/s
Index de viscosité : 101
Point d'écoulement : - 15°C
Teneur en soufre : 0,46 % masse
The products described in the previous examples were evaluated for their antiwear and extreme pressure properties in a lubricating oil. The base mineral oil used is a 130 Neutral with the following characteristics:
Kinematic viscosity at 40 ° C: 25.5 mm² / s
Kinematic viscosity at 100 ° C: 4.7 mm² / s
Viscosity index: 101
Pour point: - 15 ° C
Sulfur content: 0.46% mass

(a) ESSAI 4 BILLES(a) 4 BALL TEST

L'efficacité antiusure est évaluée sur machine à 4 billes fonctionnant pendant 1 heure sous des charges de 40 et 60 daN une vitesse de 1500 t/min, selon la méthode NF E48-617. Les moyennes du diamètre d'empreinte observées sur les 3 billes inférieures sont les suivantes : Produits Diamètre d'empreinte (mm) 40 daN 60 daN Huile 130 N 1,72 2,22 Huile + 5,3 % du produit de l'Ex. 1 0,48 0,65 Huile + 12 % du produit de l'Ex. 1 0,34 0,39 Huile + 5,3 % du produit de l'Ex. 2 0,44 0,62 Huile + 5,3 % du produit de l'Ex. 3 0,43 0,59 Huile + 5,3 % du produit de l'Ex. 4 0,48 0,70 Huile + 5,3 % du produit de l'Ex. 5 0,44 0,57 Huile + 5,3 % du produit de l'Ex. 6 0,60 0,71 Huile + 12 % du produit de l'Ex. 7 0,36 0,42 Huile + 5,3 % du produit de l'Ex. 8 0,34 0,41 Huile + 4,0 % du produit de l'Ex. 9 0,36 0,45 Huile + 5,3 % du produit de l'Ex. 10 0,42 0,60 Huile + 12 % du produit de l'Ex. 11 0,49 0,53 The anti-wear efficiency is evaluated on a 4-ball machine operating for 1 hour under loads of 40 and 60 daN at a speed of 1500 rpm, according to the NF E48-617 method. The average footprint diameter observed on the 3 lower balls are as follows: Products Footprint diameter (mm) 40 daN 60 daN Oil 130 N 1.72 2.22 Oil + 5.3% of the product of Ex. 1 0.48 0.65 Oil + 12% of the product of Ex. 1 0.34 0.39 Oil + 5.3% of the product of Ex. 2 0.44 0.62 Oil + 5.3% of the product of Ex. 3 0.43 0.59 Oil + 5.3% of the product of Ex. 4 0.48 0.70 Oil + 5.3% of the product of Ex. 5 0.44 0.57 Oil + 5.3% of the product of Ex. 6 0.60 0.71 Oil + 12% of the product of Ex. 7 0.36 0.42 Oil + 5.3% of the product of Ex. 8 0.34 0.41 Oil + 4.0% of the product of Ex. 9 0.36 0.45 Oil + 5.3% of the product of Ex. 10 0.42 0.60 Oil + 12% of the product of Ex. 11 0.49 0.53

(b) ESSAI FZG(b) FZG TEST

Les propriétés extrême-pression dans les huiles lubrifiantes des produits selon l'invention ont été mesurées sur machine d'engrenages FZG selon la méthode CEC L-07-A-71 avec la procédure A/16,6/90, c'est-à-dire utilisant l'engrenage de type A, avec une vitesse circonférentielle au diamètre primitif de 16,6 m/s et à la température de 90°C au début de chaque palier de charge. L'huile minérale utilisée est la base 130 N décrite ci-dessus. La méthode B de cotation visuelle a été utilisée. L'efficacité extrême-pression est d'autant plus prononcée que le palier de charge atteint est plus élevé. Lorsque cela a été possible, on a également relevé la température de l'huile à la fin du palier 12 qui est en relation avec les forces dissipées dans les frottements. Une température plus basse traduit un coefficient de frottement plus faible dans les conditions de l'essai. Les résultats obtenus figurent dans le tableau suivant : Produits Palier de détérioration t° à la fin du palier 12 (°C) Huile 130 N 4 - Huile + 5,3 % du produit de l'Ex. 1 13 142 Huile + 12 % du produit de l'Ex. 1 > 13 134 Huile + 5,3 % du produit de l'Ex. 2 > 13 145 Huile + 5,3 % du produit de l'Ex. 3 > 13 143 Huile + 5,3 % du produit de l'Ex. 5 10 - Huile + 5,3 % du produit de l'Ex. 6 > 13 145 Huile + 12 % du produit de l'Ex. 7 13 158 Huile + 6,5 % d'additif extrême-pression phospho-soufré classique > 13 162 Huile + 12 % d'additif au triborate de potassium > 13 154 Huile + 1,2 % de di(éthylhexyl)dithiophosphate de zinc 9 - The extreme pressure properties in the lubricating oils of the products according to the invention were measured on a FZG gear machine according to the CEC method L-07-A-71 with the procedure A / 16.6 / 90, that is to say ie using the gear type A, with a circumferential speed at the pitch diameter of 16.6 m / s and at the temperature of 90 ° C at the start of each load bearing. The mineral oil used is the base 130 N described above. Method B of visual rating was used. The extreme pressure efficiency is all the more pronounced the higher the load level reached. When possible, the temperature of the oil was also recorded at the end of the bearing 12 which is in relation to the forces dissipated in the friction. A lower temperature translates to a lower coefficient of friction under the conditions of the test. The results obtained are shown in the following table: Products Deterioration level t ° at the end of stage 12 (° C) Oil 130 N 4 - Oil + 5.3% of the product of Ex. 1 13 142 Oil + 12% of the product of Ex. 1 > 13 134 Oil + 5.3% of the product of Ex. 2 > 13 145 Oil + 5.3% of the product of Ex. 3 > 13 143 Oil + 5.3% of the product of Ex. 5 10 - Oil + 5.3% of the product of Ex. 6 > 13 145 Oil + 12% of the product of Ex. 7 13 158 Oil + 6.5% classic phospho-sulfur extreme pressure additive > 13 162 Oil + 12% potassium triborate additive > 13 154 Oil + 1.2% zinc di (ethylhexyl) dithiophosphate 9 -

L'ensemble de ces résultats montrent que les produits selon l'invention ont des propriétés extrême-pression très prononcées et que le coefficient de frot­tement est inférieur à celui des additifs extrême-pression classiques puisque les températures enregistrées en fin de palier 12 sont nettement inférieures, ce qui constitue un avantage évident dans des conditions sévères d'utilisation: boîtes de vitesse et pont-arrière de poids lourds à faible vitesse sous couple élevé, réducteurs ferroviaires de trains à grande vitesse, réducteurs d'hélicoptères, etc...All of these results show that the products according to the invention have very pronounced extreme pressure properties and that the coefficient of friction is lower than that of conventional extreme pressure additives since the temperatures recorded at the end of level 12 are much lower. , which is an obvious advantage under severe conditions of use: gearboxes and rear axle of heavy goods vehicles at low speed with high torque, railway reducers for high speed trains, helicopter reducers, etc.

EXEMPLE 14EXAMPLE 14 ESSAI D'USURE DE DISTRIBUTION DE MOTEUR THERMIQUE:ENGINE TIMING DISTRIBUTION WEAR TEST:

En vue de déterminer le comportement d'additifs selon l'invention dans la lu­brification des moteurs, il a été procédé à des essais d'usure sur une maquette de distribution came-basculeurs de moteur PEUGEOT XL5. L'arbre à cames est en fonte coulée trempée, les basculeurs sont en acier 42C2 trempé et nitruré en bain de sel sans cyanure (procédé SURSULF). La base lubrifiante est une 175 Neutral Solvant dont les principales caractéristiques sont les suivantes:
Viscosité cinématique à 40°C : 33,7 mm²/s
Viscosité cinématique à 100°C : 5,7 mm²/s
Index de viscosité : 108
Point d'écoulement : -9°C
In order to determine the behavior of additives according to the invention in the lubrication of the engines, wear tests were carried out on a cam-rocker distribution model of the PEUGEOT XL5 engine. The camshaft is made of hardened cast iron, the rockers are made of hardened and nitrided 42C2 steel in a salt bath without cyanide (SURSULF process). The lubricant base is a 175 Neutral Solvent, the main characteristics of which are as follows:
Kinematic viscosity at 40 ° C: 33.7 mm² / s
Kinematic viscosity at 100 ° C: 5.7 mm² / s
Viscosity index: 108
Pour point: -9 ° C

L'objectif visé dans cet essai était de remplacer l'additif antiusure et l'additif détergent par un additif selon l'invention. Par contre, un additif dispersant classique de type succinimide habituellement utilisé pour satisfaire les exigences de dispersivité à froid a été utilisé.The objective of this test was to replace the antiwear additive and the detergent additive with an additive according to the invention. On the other hand, a conventional dispersant additive of the succinimide type usually used to satisfy the requirements of cold dispersivity was used.

Le banc d'essai est entrainé par un moteur électrique et fonctionne selon le cycle suivant:
1 minute à 750 t/min
2 minutes à 1500 t/min
The test bench is driven by an electric motor and operates according to the following cycle:
1 minute at 750 rpm
2 minutes at 1500 rpm

Les ressorts, sous levée maximale, sont tarés à 1200 N. La durée de l'essai est de 50 heures et la température de l'huile est régulée à 50°C. A l'issue de l'essai, les basculeurs sont pesés et cotés selon une échelle qui définit quatre aspects-types.The springs, under maximum lift, are rated at 1200 N. The duration of the test is 50 hours and the oil temperature is regulated at 50 ° C. At the end of the test, the rockers are weighed and rated according to a scale which defines four typical aspects.

La formulation I comportant un additif selon l'invention a la composition suiv­ante:
-produit de l'exemple 6 = 5,3 % en masse
- additif dispersant = 5 % en masse
- base 175 N = 89,7 % en masse
The formulation I comprising an additive according to the invention has the following composition:
-product of Example 6 = 5.3% by mass
- dispersing additive = 5% by mass
- base 175 N = 89.7% by mass

A titre de comparaison, une huile II à base d'additifs conventionnels a été essayée dans des conditions identiques. Sa composition est la suivante:
-Additifs antiusure (dialkyldithiophosphate de zinc) correspondant à 1400 ppm de zinc) = 1,70 % en masse
- additif détergent = 3,6 % en masse
- additif dispersant = 5 % en masse
- base 175 N = 89,7 % en masse
For comparison, an oil II based on conventional additives was tested under identical conditions. Its composition is as follows:
-Anti-wear additives (zinc dialkyldithiophosphate) corresponding to 1400 ppm zinc) = 1.70% by mass
- detergent additive = 3.6% by mass
- dispersing additive = 5% by mass
- base 175 N = 89.7% by mass

Les résultats obtenus sont indiqués ci-dessous: Formulation Usure moyenne par basculeur (mg) Mérite/100 I 27,8 41 II 36,4 25 The results obtained are shown below: Formulation Average wear per rocker (mg) Merit / 100 I 27.8 41 II 36.4 25

Ils montrent une moindre usure et un meilleur aspect des basculeurs avec la formule utilisant l'additif selon l'invention.They show less wear and a better appearance of the rockers with the formula using the additive according to the invention.

EXEMPLE 15EXAMPLE 15 ESSAI DE GRIPPAGE SUR PONT HYPOÏDE:TRIPPING TEST ON HYPOID BRIDGE:

Le banc utilisé et les condi­tions d'essais sont décrits en détail dans une communication au 7ème Colloque international sur la lubrification automobile. Esslingen ; 16-18 janvier 1990. (The screening of E.P. oil formulas by the use of a new hypoïd gear axle test. G. VENIZELOS, G. LASSAU, P. MARCHAND).The bench used and the test conditions are described in detail in a communication to the 7th International Symposium on automotive lubrication. Esslingen; January 16-18, 1990. (The screening of EP oil formulas by the use of a new hypoid gear axle test. G. VENIZELOS, G. LASSAU, P. MARCHAND).

Cet essai utilise un pont PEUGEOT PC7 sur lequel on applique des pics de couple de l'ordre de 340 N.m. La couronne est examiné sans démontage toutes les séries de 20 pics de couple. En l'absence d'usure anormale, l'essai est pour­suivi jusqu'à 80 pics de couple, après quoi le pont est démonté et les surfaces du pignon et de la couronne sont examinées. Le résultat est donné en pourcentage de la surface portante détériorée par grippage (scoring).
Les additifs sont comparés dans une huile de base identique (100 neutral solvant). Un essai comparatif a été effectué avec un aditif extrême-pression commercialisé sous la dénomination d'ANGLAMOL 99 (marque déposée), additif extrême-­pression largement utilisé dans les ponts hypoïdes. Produit Concentration (% masse) Scoring (%) après 80 pics de couple ANGLAMOL 99 6,5 2,25 Produit de l'exemple 12 12,9* 2,0 * 7,2 % après déduction de l'huile de dilution.
This test uses a PEUGEOT PC7 bridge to which torque peaks of the order of 340 Nm are applied. The crown is examined without dismantling all the series of 20 torque peaks. In the absence of abnormal wear, the test is continued up to 80 peaks of torque, after which the bridge is dismantled and the surfaces of the pinion and the crown are examined. The result is given as a percentage of the bearing surface deteriorated by seizing (scoring).
The additives are compared in an identical base oil (100 neutral solvent). A comparative test was carried out with an extreme pressure additive sold under the name of ANGLAMOL 99 (registered trademark), extreme pressure additive widely used in hypoid bridges. Product Concentration (mass%) Scoring (%) after 80 torque peaks ANGLAMOL 99 6.5 2.25 Product of Example 12 12.9 * 2.0 * 7.2% after deduction of the dilution oil.

Claims (10)

1. Composition d'additif thiophosphoré, caractérisée en ce qu'elle est obtenue par réaction d'un sulfonate de sodium ou de calcium surbasifié par du cabon­ate de sodium ou de calcium, présentant de 0,9 à 10 équivalents basiques par kilogramme, avec un sulfure de phosphore, utilisé en une proportion telle que le rapport du phosphore molaire à l'équivalent basique du sulfonate surbasifié soit de 0,002 à 0,15.1. Composition of thiophosphorus additive, characterized in that it is obtained by reaction of a sodium or calcium sulfonate overbased with sodium or calcium cabonate, having from 0.9 to 10 basic equivalents per kilogram, with a phosphorus sulfide, used in a proportion such that the ratio of molar phosphorus to the basic equivalent of the overbased sulfonate is from 0.002 to 0.15. 2. Composition selon la revendication 1, caractérisée en ce que ledit sulfure de phosphore est choisi parmi P₄S₇, P₄S₉etP₄S₁₀.2. Composition according to claim 1, characterized in that said phosphorus sulphide is chosen from P₄S₇, P₄S₉etP₄S₁₀. 3. Composition selon l'une des revendications 1 et 2, caractérisée en ce que ledit sulfure de phosphore est P₄S₁₀.3. Composition according to one of claims 1 and 2, characterized in that said phosphorus sulfide is P₄S₁₀. 4. Composition selon l'une des revendications 1 à 3, caractérisée en ce que la réaction est effectuée à une pression comprise entre la pression atmosphérique et 0,5 MPa et à une température de 60 à 130°C.4. Composition according to one of claims 1 to 3, characterized in that the reaction is carried out at a pressure between atmospheric pressure and 0.5 MPa and at a temperature of 60 to 130 ° C. 5. Composition selon l'une des revendications 1 à 4, caractérisée en ce que le produit de réaction du sulfonate surbasifié avec le sulfure de phosphore est mis en contact avec au moins un composé à hydrogène actif choisi parmi l'eau, les al­cools, les phénols, les acides carboxyliques, les ester-acides, les acides minéraux, les bases minérales, les amines, les amides et les mercaptans.5. Composition according to one of claims 1 to 4, characterized in that the reaction product of the overbased sulfonate with phosphorus sulfide is brought into contact with at least one active hydrogen compound chosen from water, alcohols, phenols, carboxylic acids, ester acids, mineral acids, mineral bases, amines, amides and mercaptans. 6. Composition selon la revendication 5, caractérisée en ce que ledit com­posé à hydrogène actif et choisi parmi l'eau, le méthanol, l'isopropanol, un phénol, l'acide acétique, un dialkylphosphite, l'acide borique, l'acide phospho­rique, l'ammoniac, une amine, un amide, le dimercaptothiadiazole ou un dimer­captothiadiazole substitué de formule
Figure imgb0002
où R est un atome d'hydrogène pour x = 1, ou R est un groupement hydrocar­byle pour x de 1 à 5.
6. Composition according to claim 5, characterized in that said active hydrogen compound and chosen from water, methanol, isopropanol, a phenol, acetic acid, a dialkylphosphite, boric acid, acid phosphoric acid, ammonia, an amine, an amide, dimercaptothiadiazole or a substituted dimercaptothiadiazole of formula
Figure imgb0002
where R is a hydrogen atom for x = 1, or R is a hydrocarbyl group for x from 1 to 5.
7. Composition selon l'une des revendications 5 à 6, caractérisée en ce que ledit composé à hydrogène actif est utilisé en une quantité molaire de 0,1 à 5 par mole de phosphore apporté par le sulfure de phosphore.7. Composition according to one of claims 5 to 6, characterized in that said active hydrogen compound is used in a molar amount of 0.1 to 5 per mole of phosphorus provided by the phosphorus sulfide. 8. Composition selon l'une des revendications 5 à 7, caractérisée en ce que la mise en contact avec ledit composé à hydrogène actif est effectuée à une pression comprise entre la pression atmosphérique et 0,5 MPa et à une température de 60 à 130°C.8. Composition according to one of claims 5 to 7, characterized in that the contacting with said active hydrogen compound is carried out at a pressure between atmospheric pressure and 0.5 MPa and at a temperature of 60 to 130 ° C. 9. Composition selon l'une des revendications 1 à 8, caractérisée en ce qu'elle est préparée au sein d'un solvant hydrocarboné bouillant entre 60 et 150°C.9. Composition according to one of claims 1 to 8, characterized in that it is prepared in a hydrocarbon solvent boiling between 60 and 150 ° C. 10. Utilisaiton d'une composition selon l'une des revendications 1 à 9, comme additif dans une huile minérale ou synthétique, ou dans une graisse lubrifiante, à une concentration de 0,5 à 20 % en masse.10. Use of a composition according to one of claims 1 to 9, as an additive in a mineral or synthetic oil, or in a lubricating grease, at a concentration of 0.5 to 20% by mass.
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JPH02286791A (en) 1990-11-26
FR2645168B1 (en) 1993-02-05
DE69002511T2 (en) 1993-11-18
EP0390664B1 (en) 1993-08-04
EP0390664A3 (en) 1990-12-12
JP2916644B2 (en) 1999-07-05
FR2645168A1 (en) 1990-10-05
CA2013458C (en) 2002-04-23
ES2060085T3 (en) 1994-11-16
CA2013458A1 (en) 1990-09-30
US5080812A (en) 1992-01-14
DE69002511D1 (en) 1993-09-09
DK0390664T3 (en) 1993-12-06

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