Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
  • C10M159/12—Reaction products
  • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
  • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals

Definitions

• the present invention relates to overbased alkaline or alkaline earth phenates with a high alkaline value containing an organic phosphorus derivative and their use in lubricant formulations.
• Overbased phenates are alkali or alkaline earth metal salts of phenols overbased by carbonation with carbon dioxide.
• the term overbased is used to designate the excess of alkali or alkaline earth metal over the stoichiometric amount necessary to neutralize the phenol.
• overbased phenates is that of a colloidal dispersion, the micelles of which contain the alkali or alkaline earth metal carbonate formed during carbonation.
• the micelles are stabilized by alkaline or alkaline earth phenates which have a detergent effect.
• overbased phenates are particularly useful in the lubricants used in internal combustion engines of the "gasoline” or “diesel” type, whether these are land or marine engines.
• Overbased phenates also improve the resistance to oxidation of the oils in which they are incorporated. This property is more particularly marked when sulfurized phenols are used. This function is particularly appreciated for lubricating formulations subjected to severe thermal constraints, such as for example in highly supercharged diesel engines. Overbased sulfurized phenates are in practice more used than their non-sulfurized counterparts.
• Overbased phenates are characterized by their alkaline value (VA) expressed in mg of KOH per gram of product. It is determined by titration using a strong acid according to standard ASTM D-2896. A high alkalinity reserve results in a high VA.
• VA alkaline value
• European patent applications 0300486 and 0259974 describe a process at high temperature, around 160 ° C and at a pressure higher than atmospheric pressure. This process only makes it possible to obtain overbased phenates of high alkaline value provided that an alkysulfonate is associated with the alkylphenate during carbonation.
• French patent 2305494 relates to a low temperature process, around 50 ° C.
• the alkaline value of the phenates alone never exceeds 240.
• these products have the disadvantage of being unstable over time and of having a high viscosity. These processes therefore do not allow the synthesis of phenates of high alkaline value.
• the overbased phenates carbonated in the presence of organic phosphorus derivatives have an alkaline value higher than that of the overbased phenates of the prior art. At the same time their stability is better and their viscosity sufficiently low so that no handling problem appears.
• British patent application 2197336 relates to the addition of catalytic quantities of an oil-soluble zinc dialkyldithiophosphate to an alkaline phenate, but it is a use as a sulfurization catalyst, in a two-step process comprising sulfurization phenol and carbonation.
• sulfurization temperature between 145 and 165 ° C, the dialkyldithiophosphate decomposes into mercaptan and olefin, and in the carbonation stage the mixture no longer contains organic phosphorus.
• the invention therefore relates to an overbased alkaline or alkaline earth phenate, obtained by carbonation of a mixture containing a phenolic compound, an derivative of an alkali or alkaline earth metal, chosen from oxides, hydroxides or alcoholates, a nitrogen and / or oxygenated promoter , a hydrocarbon solvent and optionally a diluent oil and water, characterized in that the mixture contains phosphorus in the form of an organic derivative.
• the overbased phenates obtained according to the invention are in the form of a colloidal dispersion, clear and stable.
• Their alkaline value (VA) is greater than or equal to 250.
• VA alkaline value
• the processes of the prior art did not make it possible to obtain phenates with VA greater than 240.
• the higher values were only obtained with mixtures of phenates and sulfonates.
• the presence of the organic phosphorus derivative gives the overbased phenates according to the invention enhanced antioxidant properties as well as antiwear properties.
• non-metallic compounds are preferably used.
• non-metallic organic phosphorus derivatives are chosen from phosphites, phosphoramides, derivatives of phosphoric, thiophosphoric, dithiophosphoric, trithiophosphoric, tetrathiophosphoric acids and their organic salts.
• Use is more particularly made of phosphosulphurous derivatives such as thiophosphoric or dithiophosphoric acids and their organic salts and preferably derivatives of dithiophosphoric acids and their organic salts.
• dihydrocarbyldithio-phosphoric acids of general formula are generally used where R and R ′, identical or different, represent linear or branched C Problems to C20 alkyl chains, aliphatic or aromatic rings.
• diethyldithiophosphoric acid diisopropyldithiophosphoric acid, dicyclohexyldithiophosphhoric acid or dicrésyldithiophophoric acid.
• the overbased phenates obtained according to the invention contain 0.5% to 10% by weight and preferably 1 to 5% by weight of phosphorus.
• the mixture to be carbonated must contain at least 3% phosphorus in the form of an organic derivative.
• the dihydrocarbyldithiophosphoric acids of general formula (I) can be prepared by the action of phosphorus pentasulfide on an alcohol or phenol of general formula R-OH or a mixture of alcohols or phenols of formula R-OH and R′-OH.
• the molar ratio of phosphorus pentasulfide to alcohol or phenol must be at least 1 to 4.
• the reaction can be carried out at a temperature between 40 and 200 ° C, this depending on the type of alcohol or phenol selected.
• dialkyldithiophosphoric acids The methods of preparation of dialkyldithiophosphoric acids are described in American patents 3089850, 3101096, 3293181 and 3489682.
• the phenolic compounds are generally alkylphenols, comprising one or more linear or branched C1 to C30 alkyl groups. To ensure solubility to the corresponding alkali or alkaline earth phenates, in the dilution oil, the total number of carbons of the alkyl group (s) must be equal to or greater than eight.
• the alkylphenols can be prepared by the reaction of an olefin or of a mixture of olefins with phenol, in the presence of a catalyst at a temperature between 60 and 200 ° C.
• the alkylphenols used can optionally be sulfurized by the action of elemental sulfur at temperatures ranging from 150 to 200 ° C., or by the action of a sulfur halide such as mono or sulfur dichloride.
• the sulfurized product contains 1 to 1.5 sulfur atoms per phenolic nucleus, but its structure is not precisely known.
• alkali or alkaline earth metal derivatives oxides, hydroxides or alcoholates are used.
• the preferred derivatives are oxides and hydroxides.
• the reaction medium is added to stoichiometric excess relative to the phenolic compound.
• the stoichiometric excess can vary between 5: 1 and 30: 1.
• the oxygenated promoter is generally an aliphatic or aromatic alcohol, an alkoxyalkanol, a glycol or even an alkanolamine.
• C al to C20 aliphatic alcohols or their mixtures are preferably used.
• the aliphatic alcohols can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
• the molar ratio of the oxygenated promoter to the phenolic compound is generally between 1 to 30.
• the use of a nitrogenous promoter is optional.
• the nitrogenous promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary C2 to C10 amines and their salts, polyamines or alkanolamines as well as nitro mineral compounds.
• ammonia, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine, as well as calcium nitrate are preferred.
• the molar ratio of the nitrogenous promoter to the phenolic compound is generally between 0.05 and 30.
• the hydrocarbon solvent allows perfect homogenization of the various reactants as well as a lowering of the viscosity, which will subsequently facilitate the recovery of solid carbonation residues.
• the solvent generally represents 10 to 70% by weight of the reaction mixture.
• the solvents used are the Chat to C ar aliphatic or aromatic compounds.
• the preferred solvents are aromatic solvents, such as benzene, toluene, xylene, ethylbenzene and chlorinated aromatics. Their choice is dictated by the characteristics of the additive collected, by their boiling point and by the boiling point of the azeotropes which they can form with oxygenated compounds and water.
• the handling of overbased phenates is facilitated by the addition of a diluent oil.
• the oil represents approximately 20 to 50% by weight of the additive obtained. This can be added to the reaction medium before carbonation or even after this, that is to say just before the removal of the solvents.
• the diluting oils used are of a paraffinic nature, of the 100 or 150 Neutral Solvent type or of a predominantly naphthenic nature such as 100-150 Pale Solvent.
• the carbonation reaction can be carried out after optional addition of water to the reaction medium.
• the addition of water is particularly beneficial when the alkali or alkaline earth metal derivative is an oxide.
• the amount of water added is such that the water / metal oxide molar ratio is of the order of 5.
• the neutralization reaction of the phenolic compound is carried out at a temperature between about 30 and 120 ° C and preferably at a temperature between 50 and 100 ° C, for a period of about 0.5 to 4 hours.
• the organic phosphorus derivative is added to the reaction medium.
• the phosphorus concentration in the reaction medium must be greater than or equal to 3%.
• the molar ratio of carbon dioxide introduced to the stoichiometric excess of alkali or alkaline earth metal is between 0.6 and 1.2.
• the mixture is optionally stabilized by heating under vacuum or under a stream of nitrogen, so as to eliminate the oxygenated promoters of low boiling point and the water added, as well as the water produced by the carbonation reaction. Solid residues are removed, generally by centrifugation and / or filtration using diatomaceous earth.
• the diluent oil has not been added before carbonation, it is then added before the elimination of the hydrocarbon solvent and possibly the alcohol. The latter are removed by heating under vacuum at temperatures of the order of 100 to 200 ° C.
• the overbased phenates obtained according to the invention are brown in color and stable over time. Their viscosity is such that they can be handled at room temperature. They contain 0.5 to 10% by weight and preferably 1 to 5% of phosphorus.
• overbased phenates are fully compatible with hydrocarbons. They are incorporated into lubricating oils of natural or synthetic origin at a concentration of between approximately 0.5 and 40% by weight and preferably between 1 and 30% by weight.
• the lubricant compositions thus obtained may contain other additives, with antiwear, dispersant, antioxidant effect and polymers improving the viscosity index.
• the basicity of the overbased phenates is characterized by their alkaline value (VA) expressed in mg KOH / g of product.
• VA alkaline value
• the solution is cooled and filtered on a 0.22 ⁇ m Millipore filter, then the solvent evaporated.
• Example A The procedure is as in Example A except that 220.8 g of anhydrous ethanol are used in place of methanol.
• Example A The procedure is as in Example A except that 288 g of isopropyl alcohol are used.
• Example A The procedure is as in Example A except that 66.7 g of phosphorus pentasulfide and 240 g of cyclohexanol are used.
• Example A The procedure is as in Example A except that 400 ml of toluene is used in place of carbon tetrachloride, 66.7 g of phosphorus pentasulfide, and 259.2 g of para-cresol.
• 77.8 g of dodecylphenol and 20 g of sulfur chloride are introduced into a 250 ml reactor fitted with a condenser, a temperature control and a gas bubbling device at a temperature of 20 ° C. to 30 ° C. vs.
• the mixture is heated under nitrogen sweep and with stirring for 1 hour at 150 ° C., then 1 hour at 180 ° C. and finally 1 hour at 200 ° C.
• a sulfurized dodecylphenol is collected, the respective chlorine and sulfur contents of which are 2200 ppm and 11.4%.
• the mixture is brought to reflux for 0.75 h before elimination of the water produced by the neutralization of the sulfurized dodecylphenol.
• 50 ml of methanol are added before carbonation with carbon dioxide of the stoichiometric excess of lime, at a temperature of 40 ° C.
• the residual water and methanol are removed by heating under partial vacuum before recovering the solid residues by filtration.
• 30 g of 100 Neutral diluent oil are added before removing the solvent.
• Example 1 The procedure is as in Example 1 with the difference that 16 g of the product of Example B are added just before the carbonation operation.
• the procedure is the same as in Example 1 except that the residues are removed by centrifugation.
• This overbased sulfurized phenate containing a phosphosulfur compound is remarkably stable when diluted in oil after several months.
• Example 3 The procedure is as in Example 3 except that 15 g of ammonium diethyldithiophosphate at 95% purity of JANSSEN CHEMICA are added in place of the product of Example B.
• the overbased sulfurized phenate collected at a VA 250 and its viscosity is 70 Pa.s.
• the calcium and phosphorus contents of the additive are 8.1% and 2.1% respectively.
• the product has good stability when diluted in oil after several months.
• Example 3 The procedure is as in Example 3, with the difference that 25 g of slaked lime are introduced into the initial mixture.
• the additive has a viscosity of 200 Pa.s and its stability when diluted in oil is good.
• Example 6 The procedure is as in Example 6 with the difference that 48.5 g of the product of Example F are introduced into the initial mixture.
• the additive has a viscosity of 250 Pa.s and its stability when diluted in oil is good.
• test matrices correspond to lubricants for marine engines on the one hand and for land engines on the other.
• the products are firstly tested in simple dilution.
• Table I shows that the new overbased phenates containing a phosphorus compound are perfectly stable in dilution whereas this is not the case for the conventional overbased phenates prepared by a "low temperature" process.
• the products are then tested in a lubricant formulation for marine engines (cylinder oil).
• the basicity of the oil is 70 mg KOH / g including only 10 mg KOH / g provided by the overbased sulfurized phenate containing a phosphorus compound.
• Table II shows a significant reduction in wear with the overbased sulfurized phenate containing a phosphosulfur compound.
• Lubricant formulations for land diesel engines contain 2.8% overbased phenate and 1.5% phosphorus. This phosphorus is provided on the one hand by the phosphosulfur compound, on the other hand by the zinc dialkyldithiophosphate (DTPZ)
• Table III shows that there is a significant reduction in wear.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

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Citations (4)

• 1989
  • 1989-12-28 FR FR8917350A patent/FR2656624A1/fr active Pending
• 1990
  • 1990-12-20 EP EP19900403691 patent/EP0436422B1/de not_active Expired - Lifetime
  • 1990-12-27 JP JP41479090A patent/JPH04130191A/ja active Pending

Patent Citations (4)

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