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
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  • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/04—Hydroxy compounds
  • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/26—Carboxylic acids; Salts thereof
  • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
  • C10M129/40—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms monocarboxylic
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/26—Carboxylic acids; Salts thereof
  • C10M129/28—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
  • C10M129/38—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms
  • C10M129/42—Carboxylic acids; Salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having 8 or more carbon atoms polycarboxylic
• • 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
  • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
  • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
  • C10M129/26—Carboxylic acids; Salts thereof
  • C10M129/48—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring
  • C10M129/54—Carboxylic acids; Salts thereof having carboxyl groups bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups
• • 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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
  • C10M135/10—Sulfonic acids or derivatives thereof
• • 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
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/20—Thiols; Sulfides; Polysulfides
  • C10M135/28—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring
  • C10M135/30—Thiols; Sulfides; Polysulfides containing sulfur atoms bound to a carbon atom of a six-membered aromatic ring containing hydroxy groups; Derivatives thereof
• • 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
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  • 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
• • C—CHEMISTRY; METALLURGY
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  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
• • 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
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
  • C10M169/042—Mixtures of base-materials and additives the additives being compounds of unknown or incompletely defined constitution only
• • 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
  • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/02—Hydroxy compounds
  • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
  • C10M2207/028—Overbased salts thereof
• • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/26—Overbased carboxylic acid salts
  • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
  • C10M2219/046—Overbased sulfonic acid salts
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/088—Neutral salts
• • 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
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
  • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
  • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
  • C10M2219/089—Overbased salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/04—Groups 2 or 12
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/06—Groups 3 or 13
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

• the present invention relates to oil dispersible com- pounds of organic acids containing Cerium, and oil dispersible overbased organic salts containing Cerium and an alkaline earth metal, their synthesis method and use in lubricating oils as detergent additives, anti-friction additives, additives for extreme-pressure tribological cou- plings and also as additives for improving the quality of diesel engine emissions.
• Cerium-based compounds are well-known in the state of the art, as combustion-enhancing additives for fuels, for reducing the emissions of pollutants, such as par- ticulate, unburned hydrocarbons, carbon monoxide and nitrogen oxides.
• pollutants such as par- ticulate, unburned hydrocarbons, carbon monoxide and nitrogen oxides.
• the use of a blend of Cerium enolate and Iron enolate is described, and in the USA patent applications 2005/0160663 and 2007/015656 the use is described of compounds contain- ing Cerium, Iron or Platinum as fuel additives.
• DPF Diesel Particulate Filter
• This tem- perature can be suitably lowered with the use of additives in the fuel which exert a catalytic action.
• fuel additives containing Cerium compounds for the catalytic regeneration of particulate filters in diesel engines, is known in the state of the art.
• Patent application EP 1344812-A1 describes the use, as additive for diesel fuels, of overbased salts of various metals, of which preferred metals are Iron and Cerium.
• overbased products described in the European patent which are dispersed in oil or solvent, are metal phenates, sulphurized metal phenates, metal salicy- lates, alkyl-aryl metal sulphonates and metal carboxylates, of which carboxylates are preferred.
• the overbased additive can be previously mixed with the fuel or mixed with the fuel on the vehicle. In that patent the synthesis of those products is not described.
• compounds containing Cerium as additives for lubricants . It is known that some Cerium compounds give lubricating oils antiwear and antifriction properties.
• Patent application JP 2004/182829 describes the use of an additive for lubricating oils containing boron and a dispersion of metal oxides, among which Cerium oxide, for improving the antifriction properties of the oil and reducing the content of toxic substances in the exhaust gases.
• Patent application US 2004/194454 describes a lubri- eating oil with antiwear properties, containing or- ganometallic compounds of Cerium, which when fed to the fuel of a diesel engine equipped with a particulate filter (DPF) , facilitates the regeneration of the filter promoting the catalytic oxidation of the particulate.
• German patent DE 3926817 describes the use of lubricating oils containing cerium or cerium alloys for reducing the pollutants contained in exhaust gases.
• the present invention therefore relates to oil dis- persible acid organic compounds containing Cerium, and oil dispersible overbased salts of organic acids containing Ce- rium and an alkaline earth metal, their synthesis method and use in lubricating oils as detergent additives, anti- wear additives, antifriction additives, additives for extreme-pressure tribological couplings and also as additives for improving the quality of the emissions of diesel en- gines .
• the use of these additives in lubricating oils for diesel engines allows the compounds containing Cerium to be conveyed onto the particulate trap for the treatment of exhaust gases improving its efficiency.
• An object of the present invention therefore relates to compounds of organic acids containing Cerium, dispersible in mineral oil.
• a further object of the present invention relates to the synthesis process of the above Cerium compounds of organic acids, which consists in the partial or total neu- tralization of organic acids with a basic compound of Cerium.
• These products have a Cerium content corresponding to a ratio between the Cerium equivalents and those of organic acid ranging from 0.1 to 1.2, preferably from 0.4 to 1.
• Another object of the present invention relates to overbased salts of organic acids, containing Cerium and an alkaline earth metal, dispersible in mineral oil.
• a further object of the present invention relates to a synthesis process of the above overbased salts, which consists in: i) treating Cerium compounds of organic acids with a hydroxide or oxide of an alkaline earth metal and subsequent carbonation with carbon dioxide; or ii) treating a mixture, consisting of Cerium compounds of organic acids and an organic acid, with a hydroxide or ox- ide of an alkaline earth metal and subsequent carbonation with carbon dioxide,- or iii) treating, in a single step, an organic acid with a basic Cerium compound and with a hydroxide or oxide of an alkaline earth metal and subsequent carbonation with carbon dioxide.
• the overbased salts of organic acids, containing Cerium and alkaline earth metal, object of the present invention have a Cerium content corresponding to a ratio between the equivalents of Cerium and those of organic acid ranging from 0.1 to 1.2, preferably from 0.4 to 1 and a content of alkaline earth metal corresponding to a ratio between the equivalents of alkaline earth metal and the equivalents of organic acid ranging from 1 to 40, preferably from 5 to 30.
• Preferred alkaline earth metals are Mag- nesium and Calcium.
• the preferred alkaline earth metal is Calcium .
• the objective of the synthesis methods, object of the present invention is not only to prepare salts containing Cerium, but also to obtain a stable colloidal dispersion of these salts in a lubricating base.
• the achievement of this objective is not easy; if the synthesis is not effected with all the necessary expedients, the additive can be difficult to filter or the coagulation of the colloid may occur with the formation of gel.
• the synthesis of the above Cerium compounds of organic acids comprises the reaction in the presence of the following components :
• Component A) can be :
• A-I) a sulphonic acid having the formula (R 1 J n -A-SO 3 H (I) wherein R 1 is a linear or branched alkyl group containing from 6 to 40 carbon atoms or R 1 is an alkyl substituent deriving from a polymer of a C 2 -C 6 olefin; A is a C 6 -C 2O aromatic hydrocarbon, an aliphatic hydrocarbon having from 5 to 20 carbon atoms. A is preferably benzene, naphthalene, toluene, xylenes and more preferably benzene; n is zero or an integer ranging from 1 to 5, preferably 1, 2 or 3, more preferably 1 or 2.
• Examples of sulphonic acids which can be used are di- alkyl benzene sulphonic acids and mono-alkyl benzene sulphonic acids.
• Examples of di-alkyl benzene sulphonic acids are: dinonyl benzene sulphonic acid, didecyl benzene sulphonic acid, diundecyl benzene sulphonic acid, didodecyl benzene sulphonic acid, dialkyl benzene sulphonic acids which contain alkyl substituents deriving from polypropylene, polyisobutene and poly-1-butene, or mixtures of the above acids.
• Examples of mono-alkyl benzene sulphonic acids which can be used are those containing alkyl substituents deriving from polypropylene, polyisobutene or mixtures of the above acids.
• the preferred sulphonic acids have an acid content ranging from 60 to 99% by weight, preferably from 70 to 90% by weight and have an inorganic acidity, expressed as sulphuric acid, preferably lower than 5% by weight.
• A-2) a carboxylic acid having the formula:
• R 2 is a linear or branched alkyl or alkenyl group, containing from 6 to 40 carbon atoms and preferably from 10 to 24 ;
• R 3 is either hydrogen, an alkyl group containing from 1 to
• saturated carboxylic acids having formula (II) are capric acid, lauric acid, myristic acid, stearic acid, isostearic acid, arachidic acid, behenic acid and lignoceric acid.
• unsaturated carboxylic acids having formula (II) are lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, linoleic acid and linolenic acid.
• Mixtures of acids can be used, such as mixtures of synthetic and natural acids, containing both saturated and unsaturated acids.
• alkyl-substituted salicylic acids are those containing alkyl substituents deriving from polypropylene, polyisobutene and poly-1-butene.
• A-4) a phenol or sulphurized phenol, optionally substituted with linear or branched alkyl groups, in a number ranging from 1 to 3 , preferably from 1 to 2 , containing from 6 to 40 carbon atoms.
• phenols or alkyl-substituted sulphurized phenols are those containing alkyl substituents deriving from polypropylene, polyisobutene and poly-1- butene .
• Component (A) can also be a mixture of organic acids (A-I) , (A-2) , (A-3) and (A-4) .
• Component (A) is preferably a sulphonic acid.
• Component (B) is a basic compound of Cerium in oxidation state (IV) , such as Cerium hydroxide (IV) , Cerium oxide (IV) or a mixture thereof; or a basic compound of Cerium in oxidation state (III) , such as Cerium carbonate (III) .
• the quantity of basic Cerium compound used corre- sponds to a ratio between the equivalents of the basic Cerium compound and the organic acid equivalents ranging from 0.2 to 2, preferably from 0.5 to 1.5.
• Component (C) is a solvent or mixture of solvents selected from: a hydrocarbon solvent which can be both aromatic and aliphatic.
• suitable hydrocarbon solvents include benzene; alkyl-substituted benzene, such as for example toluene, xylenes, halogen-substituted benzenes; aliphatic paraffins, such as hexane and heptane; cyclo- aliphatic paraffins.
• the preferred solvent is toluene.
• Component (D) is a promoter of the neutralization re- action selected from:
• D-I an alcohol containing from 1 to 20 carbon atoms, such as for example methanol or 2-ethyl hexanol .
• D-4) a ketone containing from 1 to 20 carbon atoms, such as cyclohexanone .
• D-5) an ester of a carboxylic acid, such as ethyl acetate.
• the preferred promoters are water and methanol. The promoter is added in a quantity corresponding to a weight percentage, calculated with respect to the basic cerium compound, ranging from 5 to 800, preferably from 10 to 500.
• component (E) which is a lubricating base oil, as solvent, into the product.
• the lubricating base oil can be of an animal, vegetable, mineral origin, or it can be a synthetic oil.
• Mineral and synthetic lubricating base oils are preferred. Suitable mineral lubricating base oils are those deriving from petroleum, such as for example, naphthene-based oils, paraffin-based oils or a mixture of these.
• Suitable synthetic lubricating base oils are esters, such as dioctyl adipate, dioctyl sebacate, tri-decyl adipate, or polymeric hydrocarbons, such as for example, poly-alpha-olefins or liquid polyisobutenes .
• Particularly preferred lubricating base oils are mineral-based oils .
• the lubricating base oil when used, is added at the beginning of the reaction together with the other reagents, or during the reaction, or at the end of the reaction, in a quantity corresponding to a weight percentage, calculated with respect to the organic acid (A) , ranging from 30 to 800, preferably from 50 to 300.
• the synthesis, object of the present invention, of the compound of organic acids containing Cerium can be carried out by adding components (A) , (B) , (D) , optionally (C) , and (E) to the reaction in any order.
• the synthesis is preferably effected by mixing all the components (A) , (B) , (D) , optionally (C) , and (E) at the beginning, or it can be carried out by initially adding component (B) to a mixture consisting of component (D) and optionally component (C) and subsequently adding component (A) .
• component (E) when used, is added at the beginning to- gether with components (D) and (C) , or subsequently to com- ponent (A) , or a fraction of (E) is added at the beginning together with components (D) and (C) and the remaining fraction of (E) is subsequently added to component (A) .
• the temperature at which the reaction is carried out ranges from 15 to 200 0 C, preferably from 30 to 150 0 C.
• the selection of the optimum temperature depends on the kind of solvent used.
• the product is recovered by separating, through distillation, the promoter (D) , in- eluding the reaction water, and the solvent (C) , if present. If the synthesis has been effected by adding the lubricating base oil (E) , the product at the end is obtained as an oil solution.
• the distillation of the solvents is carried out by in- creasing the temperature to a maximum value of 200 0 C, preferably up to 160 0 C and maintaining the product at this temperature for the time necessary for obtaining the complete removal of the solvents .
• the distillation of the solvents can be effected at atmospheric pressure, or under vacuum, or partly at atmospheric pressure and partly under vacuum.
• the product is filtered using a filtration aid, or, alternatively, it can be centrifuged.
• the synthesis method comprises the reaction between the following components:
• the compound of organic acids containing Cerium which is part of component (Al) is that characterized by a Cerium content corresponding to a ratio between the equivalents of Cerium and those of organic acid, from which it derives, ranging from 0.1 to 1.2, preferably from 0.4 to 1. Increasing of Cerium content lead to a more difficult formation of a stable colloidal dispersion of the overbased salt con- taining Cerium and an alkaline earth metal.
• the organic acid optionally contained in the component (Al) is equal to component (A) , already described.
• the mixture consisting of the compound of organic acids containing Cerium and an organic acid can contain a weight percentage of the compound containing Cerium varying from 10 to 99, preferably from 40 to 90 .
• Component (Bl) is a basic component of an alkaline earth metal, preferably a basic compound of Calcium, Magnesium, Barium, more preferably a basic compound of Calcium.
• the basic compound is preferably an oxide or hydroxide.
• bases are Calcium oxide (CaO) or Calcium hydroxide (Ca(OH) 2 ).
• Component B(I) can be completely added at the beginning of the reaction, or it can be partly added at the beginning and partly in different intermediate points of the reaction.
• the quantity of basic compound of alkaline earth metal used corresponds to a ratio between the equivalents of the basic compound of alkaline earth metal and those of component (Al) , ranging from 1 to 40, preferably from 5 to 30.
• Component (Cl) is the solvent, the same as component (C), already described above.
• the solvent is used in a quantity corresponding to a weight percentage, calculated with respect to the component (Al), ranging from 10 to 500, preferably from 50 to 300.
• Component (Dl) is the promoter, the same as component
• component (D) is carbon dioxide, used for carbonating the excess of component (Bl) contained in the product and subsequently added to each addition of component (Bl) .
• the carbon dioxide can be added as a gas or as a solid, preferably as a gas.
• the quantity of carbon dioxide used corresponds to a ratio between the equivalents of carbon dioxide and those of alkaline earth metal base, ranging from 0.6 to 1.1, preferably from 0.7 to 0.9.
• the carbon dioxide is preferably added in defect with respect to the base to be carbonated (oxide or hydroxide) in order to sta- bilize the colloidal dispersion of the product, facilitating its subsequent filtration.
• component (El) in the product, as solvent, which is a lubricating base oil, the same as com- ponent (E), described above.
• the lubricating base oil when used, is added at the beginning of the synthesis together with the other reagents, or during the synthesis, or at the end of the synthesis, in a quantity corresponding to a weight percentage, calculated with respect to component (Al) ranging from 30 to 800, preferably from 50 to 300.
• the synthesis, object of the present invention, of overbased salts of organic acids, containing Cerium and an alkaline earth metal, carried out by over-basifying a compound of organic acids containing Cerium, or a mixture of said compound with an organic acid, can be effected by add- ing components (Al) , (Bl) , (Cl) , (Dl) , optionally (El) to the reaction in any order.
• Component (Fl) must be added subsequently to component (Bl) .
• the synthesis can be conveniently carried out by initially adding component (Bl) to a mixture consisting of component (Cl) and a part of component (El) and subsequently adding component (Al) . After adding component (Dl) the carbonation is carried out with carbon dioxide (component Fl) , after which a second part of component (El) is added and after maturation the remaining quantity of (El) is added.
• the synthesis can also be carried out by initially adding component (Bl) to a mixture consisting of component (Cl) , component (Dl) and a part of component (El) and subsequently adding component (Al) . Carbonation is then carried out with carbon dioxide (component Fl) , after which a second part of component (El) is added and after maturation the remaining quantity of (El) is added.
• the temperature at which the first part of the synthesis is carried out which consists of the neutralization and overbasifying reactions, ranges from 15°C to 200 0 C, preferably from 30 0 C to 15O 0 C. The selection of the optimum temperature depends on the nature of the solvent used.
• the carbonation reaction is carried out at a temperature ranging from 1O 0 C to 150 0 C, preferably from 15°C to 100 0 C.
• the addition of the carbon diox- ide as gas is performed over a period of time ranging from 10 minutes to 6 hours, preferably from 1 to 4 hours.
• the carbonation is followed by maturation, which is carried out at a temperature ranging from 30 0 C to 150 0 C, for a time ranging from 10 minutes to 4 hours, preferably from 20 min- utes to 3 hours.
• the product is recovered by separating through distillation, the promoter (Dl) , including the reaction water, and the solvent (Cl) . If the synthesis has been carried out by adding lubricating base oil (El), the end-product is obtained as an oil-solution.
• the distillation of the solvents is effected by increasing the temperature to a maximum value of 200 0 C, preferably up to 16O 0 C and maintaining the product at this temperature for the time necessary for obtaining the complete removal of the solvents.
• the distillation of the solvents can be effected at atmospheric pressure, or under vacuum, or partly at atmospheric pressure and partly under vacuum.
• the product is filtered using a filtration coadjuvant, or, alternatively it can be centrifuged.
• the synthesis method comprises reaction between the following components:
• C2) A basic compound of an alkaline earth metal,- D2) A solvent or mixture of solvents; E2) A promoter or mixture of promoters; F2) Optionally lubricating oil; G2) Carbon dioxide.
• Component (A2) is an organic acid, the same as component (A) , previously described.
• Component (B2) is a basic compound of Cerium the same as component (B) , previously described.
• the quantity of basic compound of Cerium used corresponds to a ratio between the equivalents of the basic compound of Cerium and those of organic acid ranging from 0.2 to 2, preferably from 0.5 to 1.5.
• Component (C2) is a basic compound of an alkaline earth metal, the same as component (Bl) , previously described.
• the quantity of basic compound of alkaline earth metal used corresponds to a ratio between the equivalents of the basic compound of alkaline earth metal and those of component (A2) , ranging from 1 to 40, preferably from 5 to 30.
• Component (D2) is the solvent, the same as component (C) , previously described.
• the solvent is used in a quan- tity corresponding to a weight percentage, calculated with respect to component (A2) , ranging from 10 to 500, preferably from 50 to 300.
• Component (E2) is the promoter of the neutralization and carbonation reactions, the same as component (D) , pre- viously described.
• the promoter is added in a quantity corresponding to a weight percentage, calculated with respect to the sum of the basic compounds (B2) and (C2) , ranging from 2 to 500, preferably from 5 to 300.
• Component (G2) is carbon dioxide, which is used as component (Fl) , previously described.
• the quantity of carbon dioxide used corresponds to a ratio between the equivalents of carbon dioxide and those of the base in excess with respect to the organic acid, ranging from 0.6 to 1.1, preferably from 0.7 to 0.9.
• the carbon dioxide is pref- erably added in defect with respect to the base to be carbonated (oxide or hydroxide) in order to stabilize the colloidal dispersion of the product, facilitating its subsequent filtration.
• component (F2) which is a lubri- eating oil, in the product, as solvent, the same as component (E), described above.
• the lubricating base oil when used, is added at the beginning of the synthesis together with the other reagents, or during the synthesis, or at the end of the synthesis, in a quantity corresponding to a weight percentage, calculated with respect to component (A2) ranging from 30 to 800, preferably from 50 to 300.
• Other components can be optionally added to promote the carbonation, control the variation in the viscosity and improve the filterability, such as for example short-chain carboxylic acids and inorganic halides.
• the synthesis, object of the present invention, of overbased salts of organic acids, containing Cerium and an alkaline earth metal, carried out in a single step by treating an organic acid with basic compounds of Cerium and basic compounds of alkaline earth metal can be effected by adding components (A2) , (B2) , (C2) , (D2) , (E2) , optionally (F2) , to the reaction in any order.
• Component (G2) must be added subsequently to compo- nents (B2) and (C2) .
• the synthesis can be conveniently carried out, for example, by initially adding component (B2) to a mixture consisting of component (D2) and a part of component (F2) and subsequently adding component (A2) .
• Component (C2) is then added followed by component (E2) and the carbonation is subsequently carried out with carbon di- oxide (component G2) , after which a second part of component (F2) is added and after maturation the remaining quantity of (F2) is added.
• the synthesis can also be carried out by initially adding component (B2) to a mixture con- sisting of component (D2) , component (E2) and a part of component (F2) and subsequently adding component (A2) .
• Component (C2) is then added and carbonation is subsequently effected with carbon dioxide (component G2) , after which a second part of component (F2) is added and, after matura- tion, the remaining quantity of (F
• the product is recovered by separating through distillation, the promoter (E2) , including the reaction water, and the solvent (D2) . If the synthesis has been carried out by adding lubricating base oil (F2) , the end-product is obtained as an oil-solution.
• the distillation of the solvents is effected as already described in cases i) and ii) of the synthesis of overbased salts of Cerium and alkaline earth metal.
• the product is filtered using a filtration aid, or, alternatively, it can be centrifuged.
• the oil-dispersions of organic acids compounds containing Cerium and overbased salts of organic acids containing Cerium and alkaline earth metals, object of the present invention can be used in lubricating compositions as additives with detergent properties, capable of limiting the formation of deposits.
• the overbased salts of organic acids containing Cerium and alkaline earth metals, containing a large basicity reserve are also capable of neutralizing the acid products formed in the lubricating oil of an internal combustion engine preventing corrosion phenomena.
• the compounds, object of the present invention can also be used in lubricating compositions as additives capable of improving the antifriction and antiwear properties and as additives for extreme-pressure tribological cou- plings.
• the above compounds can also be used in lubricating compositions for improving the quality of internal combustion engine emissions.
• the use of these additives in lubricating oils for diesel engines allows the compounds containing Cerium to be conveyed onto the particulate trap for the treatment of exhausted gases improving its efficacy.
• a further object of the present invention therefore relates to lubricating compositions containing one or more lubricating base oils of a synthetic, mineral, vegetable or animal origin and the compounds, object of the present invention.
• the compounds of organic acids containing Cerium, as well as the overbased salts of organic acids containing Cerium and an alkaline earth metal can be used in lubricat- ing compositions, individually or in a combination, at an individual concentration, expressed as weight percentage with respect to the lubricating oil, ranging from 0.2 to 10, preferably from 0.5 to 7.
• lubricating compositions used for example as oils for motor vehicles, can also contain, in addition to the above additives, other detergent, antifriction, antiwear additives and supplementary additives for extreme-pressure tribological couplings, antioxidants, dispersants, additives for improving the viscosity index, additives for lowering the slip point and others.
• the parameter TBN total base number
• the synthesis reactions of the additives containing Cerium are carried out in a Mettler RC-I calorimeter consisting of a 5 -necked jacketed glass reactor, having a volume of 2 litres, ther- mostat-regulated by circulation in the jacket of a fluid coming from a thermocryostat and equipped with: a mechanical blade stirrer; a Claisen condenser cooled with tap water, connected to a vacuum line and equipped with a flask for collecting the distillate; a bottom outlet with a tef- Ion tap through which carbon dioxide is bubbled into the reaction mass; a thermocouple for measuring the temperature.
• the system is controlled by a computer, which allows the desired heating and cooling programs to be set.
• the feeding of the carbon dioxide is effected by a cylinder, positioned on a balance, which is connected to the bottom of the reactor by means of a rubber tube .
• the distillation is continued, reducing the pressure to 100 mbar, for an overall time of 60 minutes, in order to remove the re- sidual volatile substances.
• the quantity of distillate collected is equal to 101.7 g.
• the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 1.8% by volume.
• the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a jacketed steel filter having a volume of 1 litre, with a filtering surface consisting of an 80 mesh steel net. A cake of filtering earth is prepared on the filter before the filtration.
• the filtration is effected at a temperature of 160 0 C and with a pressure of 5 atmospheres of nitrogen.
• the product After filtration, the product has the following characteristics :
• the distillation is continued, reducing the pressure to 100 mbar, for an overall time of 60 minutes, in order to remove the residual volatile substances.
• the quantity of distillate col- lected is equal to 641.9 g.
• the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 2% by volume.
• the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a jacketed steel filter, as described in example 1.
• the filtration is effected at a temperature of 160 0 C and with a pressure of 5 atmospheres of nitrogen.
• the reaction mixture is heated from 28°C to 50 0 C in 30 minutes to allow the maturation of the colloidal dispersion.
• the temperature is maintained at 5O 0 C for 20 minutes and 145.8 g of lubricating oil SN150 are then added.
• the temperature is brought from 50 0 C to 65 0 C in 40 minutes and the post -maturation sediments are determined with the method ASTM D96, proving to be 1.6% by volume.
• the volatile substances are removed by distillation using the following heating program: • from 65°C to 73°C in 90 minutes at atmospheric pressure
• the distillation is continued, reducing the pressure to 100 mbar, for an overall time of 60 minutes, in order to remove the re- sidual volatile substances.
• the quantity of distillate collected is equal to 997.3 g.
• the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 1% by volume.
• the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a steel fil- ter, as described in example 1.
• the filtration is effected at a temperature of 160 0 C and with a pressure of 5 atmospheres of nitrogen.
• 396 g of methanol and 20.8 g of water are added, maintaining the temperature at 4O 0 C for 10 minutes.
• the reactor is prepared for the carbonation phase, in which carbon dioxide is introduced into the reaction mix- ture, through the valve situated at the bottom of the reactor, at a flow-rate of 15 Nl/hour, in order to dose 113.5 g of carbon dioxide in 165 minutes.
• the reaction mixture is heated from 28 0 C to 5O 0 C in 30 minutes to allow the maturation of the colloidal dispersion.
• the temperature is maintained at 5O 0 C for 20 minutes and 148.6 g of lubricating oil SN150 are then added.
• the temperature is brought from 50 0 C to 65°C in 40 minutes and the post-maturation sediments are determined with the method ASTM D96, proving to be 1.6% by volume. At this point the volatile substances are removed by distilla- tion using the procedure described in example 3. The quantity of distillate collected is equal to 996 g. At the end of the stripping, the product has a content of sediments, measured in heptane according to the method ASTM D96, equal to 1.8% by volume.
• the product is treated with a quantity of filtration earth equal to 3% by weight and is filtered on a steel filter, as described in example 1.
• the filtration is effected at a temperature of 16O 0 C and with a pressure of 5 atmos- pheres of nitrogen.
• the product After filtration, the product has the following characteristics :
• the engine test illustrated hereunder, is suitable for evaluating the impact of the lubricant on the particu- late after-treatment systems of diesel internal combustion engines. This evaluation is effected through the collection and analysis of the ash accumulated on the filter. The test is suitably accelerated with the forced increase in the oil consumption, obtained with a method described in patent US 5,913,253. This method envisages the injection of oil into the suction collector to simulate an increase in the drawing from the suction valves, from the seals on the shaft of the turbocompressor and through the ventilation circuit of the engine base. This method allows the following experi- mentation objectives to be reached:
• Particulate filter The oil tank is connected to a load cell for measuring the quantity of oil consumed.
• the heater has the function of increasing the temperature of the oil to lower the viscosity and guarantee a sufficiently pulverized spray.
• the injector is of the single-hole type normally used in Diesel engines for fuel injection.
• the test bench was equipped with a continuous detection system of the quantity of oil injected.
• the detection of the quantity of oil consumed by the engine was obtained by weighing the oil discharged from the engine every 120 hours .
• the high load functioning period was specifically established for ensuring a sufficient regeneration of the filtering element by reaction between the oxygen present and the particulate.
• test cycle is shown in Table 1, which indicates functioning times, regime conditions, motor load and temperature of the exhaust gases (which, as can be seen, represent the main parameter capable of governing the regeneration) , for a test period of 2 hours, to be suitably repeated to cover an accumulation of 120 hours, which proved optimum for the rapid screening of different oils in limited time periods
• Table 1 indicates functioning times, regime conditions, motor load and temperature of the exhaust gases (which, as can be seen, represent the main parameter capable of governing the regeneration) , for a test period of 2 hours, to be suitably repeated to cover an accumulation of 120 hours, which proved optimum for the rapid screening of different oils in limited time periods Table 1
• Example 5 An engine test was carried out, using the apparatus described above and illustrated in the enclosed Figure and under the operating conditions indicated in Table 1, using as lubricating oil (oil 1) a semi-synthetic oil SAE 10W-40 grade, containing the additive of example 2 at a concentration equal to 0.9% by weight and the additive of example 3 at a concentration equal to 2% by weight, in addition to other additives normally used in a lubricating oil.
• lubricating oil oil 1
• SAE 10W-40 grade a semi-synthetic oil SAE 10W-40 grade
• a reference test was also effected under the same operating conditions for comparative purposes, using a second lubricating oil (oil 2) , which only differs from the previous oil in the substitution of the additives containing Cerium with traditional detergents containing Calcium.
• a reference gas oil was used, as fuel, for the experimentation, characterized by a very low sulphur content (S ⁇ 10 ppm) and without additivation.
• the deposit accumulated on the particulate filters was removed from the filters and subsequently characterized.
• the identification of the elements and compounds present in the deposit was effected by scanning electron microscope analysis (SEM) equipped with EDX (Energy Dispersive X-Ray) module. Table 3 shows the list of elements identified and the relative percentage determined.
• the Sulphur has been omitted as this element is characteristic of both the lubricant and the fuel and also because it has been ascertained that most of the sulphur is not collected on the filter, but passes through it in gaseous form.
• Oil 1 The lubricant called Oil 1 was evaluated on this engine in the test described of 120 hours under mixed functioning conditions (30 hours at high power + 90 hours at intermediate power) without revealing significant engine performances variations.
• the oil consumption which is considered a health index of the engine, as it tends to rise in the presence of wear or the formation of deposits which hinder the correct movement of the elastic strips, did not show any significant variations with respect to the com- parative test effected on Oil 2, containing classical Calcium-based detergents, and with respect to the average consumption of the engine calculated on the values acquired during 6 different tests (Table 5) Table 5
• Example 3 The antifriction and antiwear properties of the over- based sulphonates containing Cerium and Calcium were evaluated according to the method DIN 51384, using the SRV test equipment.
• the additive tested is that of Example 3 having the following main characteristics:
• the test was carried out on 5% by weight solutions of the additives in mineral lubricating oil SN 150.
• the operating conditions used are the following:
• the extreme pressure properties of the overbased sul- phonates containing Cerium and Calcium were evaluated according to the method ASTM D3233 (Falex Pin & Vee Block method) .
• the additive tested is that of Example 3, whose behaviour was compared with that of a traditional overbased sulphonate containing Calcium, whose characteristics have already been described in Example 6.
• the test was carried out on solutions at 5% by weight of additives in mineral lubricating oil SN 150.
• the operating conditions used are the following:

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