EP0003694A1 - Method for preparing highly based detergents-dispersants for lubricating oils, and product thus obtained - Google Patents

Abstract

New process for preparing high alkalinity detergent-dispersants for lubricating oils. New process for the preparation of dispersing detergents consisting of: - sulfurizing an alkylphenol in the presence of a T.B.N.alkylbenzene sulfonate weak or zero, of an alkaline-earth base and of an alkylene glycol, - to precarbonate the mixture thus obtained, - to over-alkalinize and carbonate the precarbonated mixture obtained, using an alkaline-earth base, of CO2 and d 'an alkylene glycol, - and to remove excess alkylene glycol. These detergent-dispersants obtained can be used to improve the detergent-dispersant power of lubricating oils.

Description

The present invention relates to new detergent-dispersants of high alkalinity for lubricating oils.

• - sulfurisation d'un mélange contenant un alkylphénol, un alkylbenzène sulfonate métallique, selon un rapport molaire sulfonate/alkylphénol compris entre 0,01 et 1 , de préférence entre 0,01 et 0,05 , un monoalcool en C₈-C₁₈ , un oxyde ou hydroxyde de métal alcalino-terreux et du glycol,
• - précarbonatation du mélange sulfurisé,
• - addition d'oxyde ou d'hydroxyde de métal alcalino-terreux ,
• - carbonatation du mélange obtenu,
• - puis élimination du glycol et récupération du détergent-dispersant obtenu.

It is known from English Patent No. 1,015,759 to prepare high alkalinity detergent-dispersants by:

• sulfurization of a mixture containing an alkylphenol, a metallic alkylbenzene sulfonate, according to a sulfonate / alkylphenol molar ratio of between 0.01 and 1, preferably between 0.01 and 0.05, a C ₈ -C ₁₈ monoalcohol, an alkaline earth metal oxide or hydroxide and glycol,
• - precarbonation of the sulfurized mixture,
• - addition of alkaline earth metal oxide or hydroxide,
• - carbonation of the mixture obtained,
• - then elimination of the glycol and recovery of the detergent-dispersant obtained.

It has been found that if such a method makes it possible to prepare detergent-dispersants containing high percentages by weight of alkaline earth metal alkylates in a satisfactory manner, it did not make it possible to prepare detergent-dispersants containing high percentages by weight of alkaline earth metal alkylbenzene sylfonates. In fact, if a large quantity of starting alkylbenzene sulfonate relative to that of alkylphenol was used, the mixture to be sulfurized and carbonated would have such a viscosity that any sulfurization operation and carbonation would be impossible; this problem could possibly have been resolved by adding large amounts of C ₈ -c ₁ monoalcohol, which would then have presented serious drawbacks on the industrial level as regards the recycling of this monoalcohol in practically anhydrous form.

The Applicant has found a process which does not have these drawbacks and which makes it possible to prepare detergent-dispersants based on alkylbenzene sulfonates and metal alkylphenates from T.B.N. (Total Basic Number - Norm A.S.T.M. D 2896) greater than 250.

• - en ce que l'on fait réagir, à une température comprise entre 100 et 190°C, du soufre sur un alkylphénol portant un ou plusieurs substituants alk^yls en C₆-C₆₀ en présence d'une huile de dilution, d'un alkylbenzène sulfonate de métal alcalino-terreux de masse moléculaire supérieure à 300 et de T.B.N. inférieur ou égal à 170, d'une base dérivée de métaux alcalino-terreux et d'un alkylène glycol, la quantité d'alkylphénol mise en oeuvre étant comprise entre 5 et 35 parties en poids pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate, et la quantité d'alkylbenzène sulfonate étant comprise entre 95 et 65 parties en poids pour 100 parties en poids de mélange alkylphénol-alkylbenzène sulfonate ;
• - en ce que l'on précarbonate le mélange obtenu à une température comprise entre 100 et 250°C à l'aide de gaz carbonique ;
• - en ce que l'on suralcalinise et carbonate le mélange précarbonaté obtenu à l'aide d'une base choisie parmi les oxydes et les hydroxydes de métaux alcalino-terreux et de gaz carbonique en présence d'un alkylène glycol à une température comprise entre 100 et 250°C;
• - en ce que l'on élimine l'alkylène glycol en excès et en ce que l'on récupère le détergent-dispersant de haute alcalinité ainsi obtenu.

The process for the preparation of detergent-dispersants from alkaline earth metal alkylbenzene sulfonates, alkylene glycol, sulfur and carbon dioxide, which is the subject of the invention, is characterized:

• - in that one reacts, at a temperature between 100 and 190 ° C, sulfur on an alkylphenol carrying one or more substituents alk ^y ls C ₆ -C ₆₀ in the presence of a dilution oil, d '' an alkaline earth metal alkylbenzene sulfonate with a molecular mass greater than 300 and a TBN less than or equal to 170, of a base derived from alkaline earth metals and an alkylene glycol, the amount of alkylphenol used being between 5 and 35 parts by weight per 100 parts by weight of the alkylphenol-alkylbenzene sulfonate mixture, and the amount of alkylbenzene sulfonate being between 95 and 65 parts by weight per 100 parts by weight of the alkylphenol-alkylbenzene sulfonate mixture;
• - in that the mixture obtained is precarbonate at a temperature between 100 and 250 ° C using carbon dioxide;
• - in that the precarbonated mixture obtained is over-alkalinized and carbonated using a base chosen from the oxides and hydroxides of alkaline earth metals and carbon dioxide in the presence of an alkylene glycol at a temperature between 100 and 250 ° C;
• - in that the excess alkylene glycol is removed and in that the detergent-dispersant of high alkalinity thus obtained is recovered.

The term “alkylbenzene sulfonate” denotes any solution containing from 40 to 90% by weight, preferably 55 to 80% by weight. weight of an alkylbenzene sulfonate in a dilution oil which may or may not be the same as that used to carry out the process which is the subject of the invention.

• - l'étape de sulfurisation à partir d'un alkylbenzène sulfonate de T.B.N. inférieur ou égal à 50 à une température comprise entre 120 et 180°C, à une pression inférieure ou égale à la pression atmosphérique ; cette étape peut éventuellement être suivie d'un stade de déshydratation à une température supérieure comprise entre 130 et 185°C, de préférence entre 150 et 185°C, à une pression inférieure ou égale à la pression atmosphérique,
• - l'étape de précarbonatation à pression atmosphérique, à une température comprise entre 160 et 185°C,
• - l'étape de suralcalinisation-carbonatation au moins en une fois à une température comprise entre 120 et 180°C à une pression inférieure ou égale à la pression atmosphérique.

Preferably, we will realize:

• - The sulfurization step from an alkylbenzene sulfonate of TBN less than or equal to 50 at a temperature between 120 and 180 ° C, at a pressure less than or equal to atmospheric pressure; this step may optionally be followed by a dehydration stage at a higher temperature of between 130 and 185 ° C, preferably between 150 and 185 ° C, at a pressure less than or equal to atmospheric pressure,
• the precarbonation step at atmospheric pressure, at a temperature between 160 and 185 ° C,
• - The step of over-alkalinization-carbonation at least once at a temperature between 120 and 180 ° C at a pressure less than or equal to atmospheric pressure.

• - pour l'étape de sulfurisation :
  • . de préférence de 10 à 30 parties d'alkylphénol pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate,
  • . de préférence de 70 à 90 parties d'alkylbenzène sulfonate pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate,
  • . de 1 à 8 parties, de préférence de 2 à 5 parties de soufre pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate,
  • . de 7 à 20 parties, de préférence de 10 à 15 parties de base alcalino-terreuse pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate,
  • . de 7 à 20 parties, de préférence de 7 à 17 parties d'alkylène glycol pour 100 parties de mélange alkylphénol-alkylbenzène sulfonate ;
• - pour l'étape de carbonatation
  • . la quantité de C0₂ correspond, à plus ou moins 30 %, en poids près, à celle qui peut être complètement absorbée par le mélange sulfurisé ; de préférence cette quantité de C0₂ correspondra sensiblement à celle pouvant être complètement absorbée;
• - pour l'étape de suralcalinisation-carbonatation :
  • . de 5 à 15 parties, de préférence de 8 à 12 parties de base alcalino-terreuse pour 100 parties de mélange précarbonaté,
  • . de 5 à 50 parties, de préférence de 20 à 40 parties d'alkylène-glycol pour 100 parties de mélange précarbonaté,
  • . la quantité de C0₂ peut varier entre la quantité pouvant être complètement absorbée et un excès de 40 % en poids de cette quantité ; de préférence la quantité de C0₂ correspondra sensiblement à celle pouvant être absorbée.

The amounts of reagents that can be used to carry out the process of the invention are as follows:

• - for the sulfurization stage:
  • . preferably from 10 to 30 parts of alkylphenol per 100 parts of alkylphenol-alkylbenzene sulfonate mixture,
  • . preferably from 70 to 90 parts of alkylbenzene sulfonate per 100 parts of alkylphenol-alkylbenzene sulfonate mixture,
  • . from 1 to 8 parts, preferably from 2 to 5 parts of sulfur per 100 parts of alkylphenol-alkylbenzene sulfonate mixture,
  • . from 7 to 20 parts, preferably from 10 to 15 parts of alkaline earth base per 100 parts of alkylphenol-alkylbenzene sulfonate mixture,
  • . from 7 to 20 parts, preferably from 7 to 17 parts of alkylene glycol per 100 parts of alkylphenol-alkylbenzene sulfonate mixture;
• - for the carbonation stage
  • . the quantity of C0 ₂ corresponds, to more or less 30%, by weight, to that which can be completely absorbed by the sulfurized mixture; preferably this amount of C0 _{2 will} correspond substantially to that which can be completely absorbed;
• - for the over-alkalization-carbonation stage:
  • . from 5 to 15 parts, preferably from 8 to 12 parts of alkaline earth base per 100 parts of precarbonated mixture,
  • . from 5 to 50 parts, preferably from 20 to 40 parts of alkylene glycol per 100 parts of precarbonated mixture,
  • . the amount of CO ₂ can vary between the amount which can be completely absorbed and an excess of 40% by weight of this amount; preferably the amount of C0 _{2 will} correspond substantially to that which can be absorbed.

The over-alkalization-carbonation stage is preferably carried out in two stages.

Among the alkylphenols which can be used to carry out the process which is the subject of the invention, mention may preferably be made of those carrying one or more C9-C15 alkyl substituents, and very particularly nonyl, decyl, dodecyl or tetradecylphenols.

Among the alkylbenzene sulfonates which can be used, mention may be made of the salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from C15-C30 olefin polymers, and from alkaline earth metals such as calcium, barium, magnesium ...

Among the alkaline earth bases which can be used, mention may be made of calcium, barium, magnesium oxides or hydroxides; the alkaline earth metal from which the alkaline earth base is derived may or may not be the same as that from which the alkaline earth alkylbenzene sulfonate derived is used.

Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil, etc.: naphthenic or mixed oils may also be suitable. The amount of dilution oil that can be used is such that the amount of oil contained in the final product (including that from the starting alkylbenzene sulfonate) represents from 20 to 60% by weight of said product, from preferably from 25 to 55% and very particularly from 30 to 40% by weight of the said product.

Among the alkylene glycols which can be used, mention may very particularly be made of glycol. We can even in the sulfurization step, add up to 15 parts by weight per 100 parts by weight of the alkylphenol-alkylbenzene sulfonate mixture, of a monoalcohol such as ethylhexanol, tridecyl alcohol, oxo alcohols in CS-C14 and generally an alcohol having a boiling point higher than 120 ° C and preferably higher than 150 ° C.

One of the advantages of the process of the invention is that the presence of a monoalcohol in the sulfurization stage is not essential.

One of the characteristics of said process is that the addition of alkylene glycol both at the sulfurization stage and at the over-alkalinization-carbonation stage is essential.

Another characteristic of said process is that the weight of alkylphenol used relative to the weight of solution of the detergent-dispersant obtained is between approximately 8 and 18%.

The present invention also relates to detergents-dispersants of high alkalinity obtained by the process described above. These can be added to lubricating oils in amounts depending on the TBN of said detergent-dispersants, and depending on the future use of said oils; thus for a petrol engine oil, the amount of detergent-dispersant of TBN 300 for example to be added is generally between 1 and 2.5%; for a diesel engine oil it is generally between 1.8 and 4%; for marine engine oil this can be up to 25%.

The lubricating oils which can thus be improved can be chosen from a wide variety of lubricating oils, such as naphthenic, paraffinic and mixed base lubricating oils, other hydrocarbon lubricants, for example lubricating oils derived from products. coal, and synthetic oils, for example alkylene polymers, alkylene oxide type polymers and their derivatives, including alkylene oxide polymers prepared by polymerizing alkylene oxide to presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of liquid acids of phosphorus acids, alkylbenzenes and dial- kyl benzenes, polyphenyls, alkyl biphenyl ethers, silicon polymers.

Additional additives may also be present in said lubricating oils alongside the detergent-dispersants obtained according to the process of the invention; include, for example, anti-oxidant, anti-corrosion additives, ashless dispersant additives, etc.

The following examples are given for information only and cannot be considered as limiting the scope and the spirit of the invention.

Examples 1 to 3:

• - du dodécylphénol (DDP),
• - de l'huile 100 N,
• - une solution à environ 60 % dans de l'huile de dilution 100 N d'un alkylbenzène sulfonate de calcium (sulfonate Ca en abréviation) de masse moléculaire 470 environ (masse du sel de sodium), solution contenant 2,7 % de calcium et présentant un T.B.N. de 25 environ,
• - un antimousse commercialisé par Rhône-Poulenc sous la dénomination SI 200.

The general mode of preparation (five phases) of the overbased detergent-dispersants described in Examples 1 to 3 is given below, and in Table 1, the quantities of reagents necessary for their preparation. - 1 -phase ^era (sulfurization) are introduced into a 4 liter four-necked reactor equipped with a stirring system and a heating device:

• - dodecylphenol (DDP),
• - 100 N oil,
• - a solution of about 60% in 100 N dilution oil of a calcium alkylbenzene sulfonate (sulfonate Ca for short) of molecular weight about 470 (mass of the sodium salt), solution containing 2.7% of calcium and having a TBN of around 25,
• - an antifoam sold by Rhône-Poulenc under the name SI 200.

Then introduced with stirring lime and sulfur; the medium is brought to 145 ° C. under 260 mm of mercury, then glycol is added over 1 hour; it is heated to 165 ° C. and this temperature is maintained for 1 hour under 260 mm of mercury in order to completely eliminate the reaction water originating from the neutralization of the lime.

• - 2^ème-phase (précarbonatation) :

The eliminated water always carries with it a little glycol.

• - ^2nd phase (precarbonation):

After breaking the vacuum and heating to 180 ° C, a precarbonation operation is carried out at 180 "C using gas because bonique at atmospheric pressure until the end of absorption of C0 ₂ (this phase lasts approximately 2 hours). Water is removed by entraining as above a small amount of glycol. The precarbonated mixture thus obtained is analyzed; the result of this analysis is shown in Table 1. - 3 ^rd phase (over-alkalinization-carbonation):

• - 4^éme-phase (suralcalinisation-carbonatation) : L'opération de la 3^ème phase est réalisée une seconde fois.
• - 5^ème Phase (séparation) :

The precarbonated mixture is put under a pressure of 260 mm of mercury; a mixture of lime and glycol is introduced. The medium is dehydrated for 10 minutes at 145 ° C under 260 mm of mercury, then carbonated at 145 ° C using carbon dioxide for 25 minutes under 260 mm of mercury and then 35 minutes at atmospheric pressure.

• - 4 ^th -phase (superalkalisation-carbonation): The operation of the ^3rd stage is performed a second time.
• - ^5th phase (separation):

The superalkalinized and carbonated medium is brought to a temperature of 184 ° C under 300 mm of mercury; glycol distills; it is filtered to remove the sediments and a solution in 100 N oil of overbased detergent-dispersant, the characteristics of which are given in Table 1, is recovered.

Examples 4 to 6:

The operations described in Examples 1 to 3 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular weight of approximately 470, solution containing 3, 4% calcium and having a TBN about 45.

The amounts of reagents used are shown in Table II, the characteristics of the product obtained are shown in Table II '.

Examples 7 to 9:

The operations described in Examples 1 to 3 are carried out under the same conditions from a 60% solution in 100 N oil of a calcium alkylbenzene sulfonate with a molecular weight of approximately 470, solution containing 1.8% calcium and having a TBN no .

The amounts of reagents used are shown in Table III; the characteristics of the product obtained are shown in Table III '.

Examples 10 to 12:

The operations described in Examples 1 to 3 are carried out under the same conditions from an 80% solution in 100 N oil of a calcium alkylbenzene sulfonate, with a molecular mass of approximately 470, solution containing 3.37 % calcium and having a TBN of 33.

The quantities of reagents used are shown in Table IV; the characteristics of the product obtained are shown in Table IV '.

Example 13:

The operation described in Example 1 is carried out by replacing the solution of calcium sulfonate with a solution of approximately 60% in 100 N oil of a magnesium alkylbenzene sulfonate (sulfonate Mg for short) of molecular weight of Approximately 470, solution containing 1.5% magnesium and having a TBN about 20, in order to obtain a detergent-dispersant containing calcium and magnesium.

The amounts of reagents used are shown in Table V; the characteristics of the product are shown in Table V '.

Example 14:

The operation described in Example 4 is carried out by carrying out the sulfurization step at 165 ° C. at atmospheric pressure for 1 hour; the subsequent stage of dehydration is then superfluous.

The characteristics of the product obtained are similar to that of Example 4.

Example 15:

• - la quantité de glycol mise en oeuvre à l'étape de sulfurisation à 7,5 % ,
• - et celle mise en oeuvre à l'ensemble des étapes de suralcalinisation-carbonatation à 10 % ,
• - et en augmentant la quantité de CO₂ de 20 % en poids à l'étape de suralcalinisation-carbonatation.

The operation described in Example 1 is carried out by reducing:

• - the amount of glycol used in the 7.5% sulfurization step,
• - and that used in all of the 10% over-alkalinization-carbonation stages,
• - and by increasing the amount of CO ₂ by 20% by weight in the over-alkalinization-carbonation stage.

The characteristics of the product obtained are shown in Tables VI and VI '.

Claims (26)

1) Process for preparing detergent-dispersants from alkaline earth metal alkylbenzene sulfonates, alkylphenols, alkaline earth bases, alkylene glycol, sulfur and carbon dioxide, characterized: - in that one reacts at a temperature between 100 and 190 ° C sulfur on an alkylphenol carrying one or more C ₆ -C ₆₀ alkyl substituents in the presence of a dilution oil, an alkylbenzene sulfonate of alkaline earth metal of molecular mass greater than 300 and of TBN less than or equal to 170, of a base derived from alkaline earth metals and of an alkylene glycol, the amount of alkylphenol used being between 5 and 35 parts by weight per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture, and the amount of alkylbenzene sulfonate being between 95 and 65 parts by weight per 100 parts by weight of alkylphenol-alkylbenzene sulfonate mixture; - in that the mixture obtained is precarbonate at a temperature between 100 and 250 ° C using carbon dioxide; - in that the precarbonated mixture obtained is over-alkalinized and carbonated using a base chosen from the oxides and hydroxides of alkaline earth metals and carbon dioxide in the presence of an alkylene glycol at a temperature between 100 and 250'C; - in that the excess alkylene glycol is removed and in that the detergent-dispersant of high alkalinity thus obtained is recovered. 2) Process according to Claim 1, characterized in that the sulfurization step is carried out in the presence of: - 10 to 30 parts of alkylphenol per 100 parts of alkylphenol-alkylbenzene sulfonate mixture, - 90 to 70 parts of alkylbenzene sulfonate per 100 parts of alkylphenol-alkylbenzene sulfonate mixture. 3) Method according to Claim 1 or Claim 2, characterized in that: - the sulfurization stage is carried out at a temperature ture between 120 and 180 ° C, at a pressure less than or equal to atmospheric pressure, the precarbonation step is carried out at a temperature between 160 and 185 ° C at atmospheric pressure, - the step of superalkalisation-carbonation is carried out at a temperature between 120 and 180 ° C at a ^p res- sion less than or equal to atmospheric pressure. 4) Process according to any one of Claims 1 to 3, characterized in that the sulfurization step is followed by a dehydration stage at a higher temperature between 130 and 185 ° C at a pressure less than or equal to the atmospheric pressure. 5) Method according to any one of Claims 1 to 3, characterized in that the step of over-alkalinization-carbonation is carried out in at least one stage. 6) Method according to Claim 5, characterized in that the over-alkalinization-carbonation step is carried out in two stages. 7) Method according to any one of claims 1 to 4, characterized in that the sulfurization step is carried out in the presence of: - from 1 to 8 parts of sulfur per 100 parts of alkylphenol-alkylbenzene sulfonate mixture, - from 7 to 20 parts of alkaline earth base per 100 parts of alkylphenol alkylbenzene sulfonate mixture, - from 7 to 20 parts of alkylene glycol per 100 parts of alkylphenol-alkylbenzene sulfonate mixture. 8) Process according to Claim 7, characterized in that the sulfurization step is carried out in the presence of: - 2 to 5 parts of sulfur per 100 parts of alkylphenol-alkylbenzene sulfonate mixture, - 10 to 15 parts of alkaline earth base per 100 parts of alkylphenol-alkylbenzene sulfonate mixture, - 7 to 17 parts of alkylene glycol per 100 parts of alkylphenol-alkylbenzene sulfonate mixture. 9) Method according to any one of Claims 1 to 3, characterized in that the precarbonation step is carried out using an amount of 00 ₂ corresponding to more or less 30% by weight near that which can be completely absorbed by the sulfurized mixture. 10) Method according to Claim 9, characterized in that the precarbonation step is carried out using the amount of C0 _{2 which} can be completely absorbed by the sulfurized mixture. 11) Process according to any one of Claims 1, 2, 3 and 5, characterized in that the step of over-alkalinization-carbonation is carried out in the presence of: - from 5 to 15 parts by weight of alkaline earth base per 100 parts of precarbonated mixture, - from 5 to 50 parts of alkylene glycol per 100 parts of precarbonated mixture, - an amount of CO ₂ varying between the amount that can be completely absorbed and an excess of 40% by weight of this value. 12) Method according to Claim 11, characterized in that the step of over-alkalinization-carbonation is carried out in the presence of: - from 8 to 12 parts of alkaline earth base per 100 parts of precarbonated mixture, - from 20 to 40 parts of alkylene glycol per 100 parts of precarbonated mixture, - an amount of C0 ₂ corresponding to that which can be completely absorbed. 13) A method according to any one of Claims 1 and 3 characterized in that the amount of dilution oil is such that the amount of oil contained in the final detergent-dispersant product is between 20 and 60% of said product. 14) Method according to Claim 13, characterized in that said quantity of oil is such that the quantity of oil in the final product is between 25 and 55% of said product. 15) Method according to any one of Claims 1 and 2, characterized in that the weight of alkylphenol used relative to the weight of final detergent-dispersant product is between 8 and 18%. 16) Process according to any one of Claims 1 to 4, 7 and 8, characterized in that the alkylphenol used contains at least one C 9 -C 15 alk ^y l substituent 17) Method according to Claim 16, characterized in that the alkylphenol is chosen from nonyl, decyl and dodecyl. or tetradecylphenols. 18) Process according to any one of Claims 1 to 4, 7 and 8, characterized in that the alkaline earth metal alkylbenzene sulfonate has a T.B.N. of less than or equal to 50. 19) Process according to any one of Claims 1 to 4, 7, 8 and 18, characterized in that the alkylbenzene sulfonate is a calcium, barium or magnesium salt of a sulfonic acid obtained by sulfonation of a alkylbenzene derived from an olefin or a C ₁₅ -C ₃₀ olefin polymer. 20) Method according to any one of Claims 1 to 8, 11 and 12, characterized in that the base derived from alkaline earth metals is an oxide or hydroxide of calcium, barium or magnesium. 21) A method according to claim 20, characterized in that the alkaline earth metal from which the base is derived is the same as that from which the alkylbenzene sulfonate is derived. 22) Method according to Claim 20, characterized in that the alkaline earth metal from which the base is derived is not the same as that from which the alkylbenzene sulfonate is derived. 23) Process according to any one of Claims 1 to 8, 11 and 12, characterized in that the alkylene glycol is glycol. 24) Detergent-dispersant additives for lubricating oils obtained according to the process which is the subject of any one of Claims 1 to 23.