EP0102254B1 - Superalkalised detergent-dispersant additive for lubricating oils - Google Patents

Abstract

Super-alkalinized lubricating oil additives and a method of making them are disclosed. A magnesium alkylbenzenesulfonate and a sulfurized alkylphenol are carbonated in the presence of an oil, magnesium oxide, a glycol, and an amine. The resulting medium is neutralized and super-alkalinized with lime, and the glycol and sediment are removed.

Description

The present invention relates to a new additive based on calcium and magnesium salts improving the detergency and dispersion properties of lubricating oils.

The Applicant has in fact found a detergent-dispersant additive having a TBN of at least 225, containing more than 3.8% by weight of magnesium and, generally, of the order of 2 to 3% by weight of calcium, this which gives said additive, in addition to the detergency and dispersion characteristics, a good activity as anti-wear.

It is known (European Application No. 3694) to prepare overbased detergent-dispersant additives containing small amounts of magnesium, by sulfurizing an alkylphenol in the presence of a low TBN magnesium alkylbenzene sulfonate, of lime and of glycol, as a precarbonant. the medium obtained then by overbasing and carbonating the precarbonated mixture obtained in the presence of lime and glycol.

It is also known (US Pat. No. 4,016,093) to treat sulfurized alkylphenols with a small amount of amine to remove the H ₂ S before being neutralized with an alkaline earth base.

• 1) à carbonater (1^re opération de carbonatation) un milieu réactionnel constitué :
  • d'un alkylbenzène sulfonate de Magnésium de TBN inférieur ou égal à 20 ;
  • d'un alkylphénol sulfurisé ;
  • d'une huile de dilution ;
  • d'un « lait de magnésie constitué d'oxyde de magnésium actif, de glycol et d'une amine,
  
  et ce jusqu'à obtenir un poids de sédiment inférieur à 1,5 % en poids par rapport au poids de milieu réactionnel.
• 2) à neutraliser et suralcaliniser par de la chaux l'alkylphénol sulfurisé présent dans ledit milieu.
• 3) éventuellement à carbonater (2^e opération de carbonatation) le mélange obtenu après élimination de l'eau.
• 4) à distiller le glycol
• 5) puis à filtrer pour éliminer les sédiments.

The new additive which is the subject of the invention is characterized in that it is obtained according to a process which consists:

• 1) carbonating ^(1st carbonation operation) a reaction medium consisting of:
  • a magnesium alkylbenzene sulfonate of TBN less than or equal to 20;
  • a sulfurized alkylphenol;
  • a dilution oil;
  • a "milk of magnesia consisting of active magnesium oxide, glycol and an amine,
  
  and this until a sediment weight of less than 1.5% by weight relative to the weight of reaction medium is obtained.
• 2) to neutralize and over-alkalinize with lime the sulfurized alkylphenol present in said medium.
• 3) optionally carbonating ^(2nd carbonation operation) the mixture obtained after elimination of water.
• 4) distilling the glycol
• 5) then filter to remove sediment.

The term “magnesium alkylbenzenesulfonate” denotes any solution containing from 25 to 80% by weight, preferably from 30 to 70% by weight of a magnesium alkylbenzenesulfonate in a dilution oil which may or may not be the same as that implemented to prepare the new additive.

Among the magnesium alkylbenzenesulfonates which can be used, mention may be made of the magnesium salts of sulfonic acids obtained by sulfonation of alkylbenzenes derived from olefins or from C ₁₅ -C ₃₀ olefin polymers.

Among the dilution oils which can be used, mention may preferably be made of paraffinic oils such as 100 Neutral oil; 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 magnesium alkylbenzenesulfonate) represents from 20 to 60% by weight of said product, preferably from 25 to 55% and very particularly from 30 to 45% by weight of said product.

où

• R représente un radical alkyl en C₉-C_3o (de préférence en C₉-C₂₂)
• x varie de 1 à 3
• y varie de 0 à 6

The term “sulfurized alkylphenol” is understood to mean the mixture obtained by sulfurization of the alkylphenol using sulfur or sulfur chloride, said mixture consisting mainly of non-sulfurized alkylphenol and sulfurized alkylphenol which may be represented by the following formula :

or

• R represents a C ₉ -C ₃₀ (preferably C ₉ -C ₂₂ ) alkyl radical
• x varies from 1 to 3
• y varies from 0 to 6

où x' varie de 1 à 3 et généralement de 1,4 à 2,5.A simplified representation of the said mixture constituting the “sulfurized alkylphenol may be the following average formula:

where x 'varies from 1 to 3 and generally from 1.4 to 2.5.

The term “active magnesium oxide” denotes magnesium oxide MgO with a specific surface greater than or equal to 80 m ² / g, for example between 100 and 170 m ² / g. By way of example, mention may be made of “Maglite DF with a specific surface area close to 140 m ² / g marketed by Merck and“ Ferumag with a specific surface area close to 160 m ² / g and marketed by Rhône-Poulenc.

Among the amines which can be used, mention may be made of: polyalkyleneamines, such as polyethyleneamines and very particularly ethylenediamine; etheramines and most particularly tris (3-oxa-6-amino hexyl) amine.

The amine used may be present in the “milk of magnesia from the start of the Fe carbonation operation or during it.

• - le rapport de la quantité d'alkylbenzènesulfonate de magnésium exprimée en moles d'acide alkylbenzènesulfonique à la quantité d'alkylphénolsulfurisé exprimée en moles d'alkylphénol soit compris entre 0,15 et 5,5, et de préférence entre 0,25 et 2 ;
• - la quantité de MgO actif corresponde à un « base ratio c'est-à-dire à un rapport moles de magnésium basique non fixé sur l'acide alkylbenzènesulfonique/moles de magnésium non basique fixé à l'acide alkylbenzènesulfonique, compris entre 5 et 14, et de préférence entre 7 et 11 ;
• - la quantité de glycol corresponde à un rapport molaire MgO/glycol compris entre 0,1 et 0,7, et de préférence entre 0,3 et 0,65 ;
• - la quantité d'amine corresponde à un rapport moles d'amine/moles de magnésium basique compris entre 0,01 et 0,4, et de préférence entre 0,04 et 0,25 ;
• - le rapport de la quantité de chaux exprimée en moles de chaux à la quantité d'alkylphénol sulfurisé exprimée en moles d'alkylphénol soit compris entre 0,2 et 2,5 et de préférence entre 0,4 et 2.

A good implementation of the process making it possible to prepare the new additive can be obtained by using quantities of reagents such as:

• the ratio of the amount of magnesium alkylbenzenesulfonate expressed in moles of alkylbenzenesulfonic acid to the amount of alkylphenolsulfurized expressed in moles of alkylphenol is between 0.15 and 5.5, and preferably between 0.25 and 2 ;
• the amount of active MgO corresponds to a “base ratio, that is to say to a ratio of moles of basic magnesium not fixed on alkylbenzenesulfonic acid / moles of non-basic magnesium fixed in alkylbenzenesulfonic acid, of between 5 and 14, and preferably between 7 and 11;
• - The amount of glycol corresponds to a MgO / glycol molar ratio of between 0.1 and 0.7, and preferably between 0.3 and 0.65;
• - The amount of amine corresponds to a mole amine / moles of basic magnesium ratio of between 0.01 and 0.4, and preferably between 0.04 and 0.25;
• - The ratio of the amount of lime expressed in moles of lime to the amount of sulfurized alkylphenol expressed in moles of alkylphenol is between 0.2 and 2.5 and preferably between 0.4 and 2.

The first carbonation operation is favorably carried out at a temperature which can range from 90 to 140 ° C. and preferably from 110 to 140 ° C., in one or more stages with the introduction of “milk of magnesia into the medium containing the magnesium alkylbenzenesulfonate , the sulfurized alkylphenol and the dilution oil in one or more stages, each stage of introduction of "milk of magnesia being followed by a stage of carbonation. It has been found that it is advantageous to carry out the first carbonation operation in two stages, the first stage in the presence of approximately 2/3 of the total quantity of milk of magnesia, then a second stage by adding the remaining quantity of "Milk of magnesia". It has also been found that the addition of an amount of water corresponding to a H ₂ O / MgO weight ratio of between 0.1 and 0.9 towards the end of the carbonation is favorable for the smooth running of the process.

The neutralization-over-alkalization operation of the alkylphenol sulfurized by lime is favorably carried out at a temperature between 110 and 145 ° C, and preferably between 120 and 140 ° C.

The possible second carbonation operation is favorably carried out at a temperature between 120 and 170 ° C, and preferably between 130 and 150 ° C, using a slight excess of CO ₂ .

The new additive which is the subject of the present invention has the advantage of being perfectly compatible with viscous oils, of containing a low level of sediment and of being slightly viscous.

The present invention also relates to the use of the new additive to improve the detergent, dispersing and anti-wear properties of lubricating oils.

The amount of additive to be used depends on the future use of said oils. Thus for a gasoline engine oil, the amount of additive to be added is generally between 1 and 3.5%; for a diesel engine oil it is generally between 1.8 and 5%, for a marine engine oil, this can go 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 in the presence of water or alcohols, for example ethyl alcohol, esters of dicarboxylic acids, liquid esters of phosphorus acids, alkylbenzenes and dialkylbenzenes, polyphenyls, alkylphenylethers, polymers of silicon.

Additional additives may also be present in said lubricating oils alongside the new additive of the invention; mention may, for example, be made of antioxidant additives. anti-corrosion, ashless dispersant additives ...

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

Description of the general mode of preparation A) Preparation of magnesium alkylbenzenesulfonate

• une solution à environ 70 % dans de l'huile de dilution 100N d'acide sulfonique de masse moléculaire 470 environ (masse du sel de sodium).
• de l'huile 100 Neutral
• une solution aqueuse à environ 50 % de chlorure de calcium
• de la « Maglite DE » de façon à obtenir un alkylbenzènesulfonate de magnésium de TBN voisin de 3
• puis du glycol en 5 minutes.

We load into a 3 liter flask:

• a solution of about 70% in 100N dilution oil of sulfonic acid of molecular weight 470 approximately (mass of the sodium salt).
• 100 Neutral oil
• an aqueous solution of approximately 50% calcium chloride
• "Maglite DE" so as to obtain a magnesium alkylbenzene sulfonate of TBN close to 3
• then glycol in 5 minutes.

The reaction medium is heated for 30 minutes at 110 ° C at atmospheric pressure. then 30 minutes under vacuum so as to distill the reaction water.

B) ^1st carbonation step

• du dodécylphénol (DDP) sulfurisé contenant environ 11 % en poids de soufre.

Then we load:

• sulfurized dodecylphenol (DDP) containing about 11% by weight of sulfur.

Milk of magnesia is prepared in a beaker by mixing, with stirring, active magnesium oxide, glycol and polyamine, milk which is added to the medium to be carbonated.

C0 ₂ is introduced at 110-120 ° C, then after 3 hours of carbonation at 135 ° C, water is introduced and the carbonation is continued for 1 hour 30 minutes.

The carbonated medium is placed under vacuum for 30 minutes.

C) Step of neutralization-over-alkalinization of the sulfurized alkylphenol with lime

After breaking the vacuum, the slaked lime is introduced at 120 ° C and then the medium is gradually placed under vacuum (120 102 Pa) and the mixture is heated to 130 ° C.

The vacuum is broken and then heated to 145 ° C.

D) Possible ^2nd carbonation step

The mixture obtained is carbonated for 2 hours at 145 ° C.

E) The glycol is distilled for 2 hours at 190 ° C under 66.5 10 ² Pa F) The product is then filtered Product Features

Sediment measurement

• - vitesse de rotation de la centrifugeuse 6 000 t/mn
• - force centrifuge relative 10 000
• - le produit à analyser est dilué au quart dans l'essence E (25 cm³ de produit à analyser + 75 cm³ d'essence E).
• - durée de la centrifugation 10 minutes.

The% of sediments are measured according to standard ASTMD 2273-67, with the following modifications, however:

• - speed of rotation of the centrifuge 6,000 rpm
• - relative centrifugal force 10,000
• - the product to be analyzed is diluted to a quarter in gasoline E (25 cm ³ of product to be analyzed + 75 cm ³ of gasoline E).
• - duration of centrifugation 10 minutes.

Compatibility testing # 1

This test is carried out by adding 10% by weight of product to be tested to an SAE 30 mineral oil. Storage of the solution obtained for 1 month at 20 ° C. and study of the appearance of the solution as a function of time.

• 1 pour un produit clair et brillant
• 2 pour un produit très légèrement trouble
• 3 pour un produit trouble.

We give the rating

• 1 for a clear and shiny product
• 2 for a very slightly cloudy product
• 3 for a cloudy product.

# 2

The finished product is added to an SAE 50 oil with a paraffinic tendency so as to obtain a solution containing 125 millimoles of calcium + magnesium.

• vitesse de rotation 6 000 t/mn
• force centrifuge relative 10 000
• durée de centrifugation 1 heure.

puis on mesure le taux de sédiments.The solution is stored for 24 hours and then centrifuged under the following conditions:

• rotation speed 6,000 rpm
• relative centrifugal force 10,000
• centrifugation time 1 hour.

then measure the sediment rate.

Examples 1 to 9

The quantities of reagents used in the various stages are indicated in Tables 1 and II; the results obtained are shown in Table II.

Example 10

The various steps described in Example 3 are carried out by replacing the ethylenediamine with an equivalent amount of tris (3-oxa-6-amino-hexyl) amine called “TOA”.

Examples 11 and 12

The various operations are carried out in the absence of amine.

The% of sediments obtained before neutralization cannot be lower than 5 and 4 respectively even by increasing the duration of carbonation.

Example 13

Preparation of magnesium alkylbenzene sulfonate of TBN close to 16.

• 500 g de solution à environ 70 % dans de l'huile 100 Neutral d'acide sulfonique de masse moléculaire 470.
• 615 g d'huile 100 Neutral
• 4 g d'une solution aqueuse à environ 50 % de chlorure de calcium.

We load into a 3 liter flask:

• 500 g of approximately 70% solution in 100 Neutral sulfonic acid oil with molecular weight 470.
• 615 g 100 Neutral oil
• 4 g of an aqueous solution of about 50% calcium chloride.

151.5 g of Maglite DE and 432 g of glycol are mixed in a beaker.

87 g of said mixture are loaded into the flask which is heated.

When the temperature reaches 110 ° C, the vacuum is tightened to the maximum and heated to 130 ° C.

At this stage the% of sediment is 0.3.

Carbonation

The vacuum is broken, 411 g of a sulfurized dodecylphenol containing approximately 11% sulfur are loaded, then the remaining 496 g of MgO + glycol mixture.

We begin the introduction of C0 ₂ ; after 2 hours of carbonation at atmospheric pressure the% of sediment is 4.

19 g of ethylenediamine are then introduced.

At the end of carbonation (5 h 30 min in total), the% of sediment is 1.2.

The carbonated medium is placed under vacuum.

Over-neutralization neutralization

The vacuum is broken and 100 g of slaked lime are loaded.

The flask is brought to 115 ° C under 346 10 ² Pa, then heated for 1 hour at 140 ° C under 346 10 ² Pa.

The glycol is distilled for 2 hours at 190 ° C under 66.5 10 ² Pa.

The% of raw sediment is 0.8.

We filter

Analysis of the finished product

Example 14

The operations described in Example 13 are carried out by however introducing the 19 g of ethylenediamine into the 496 g of MgO + glycol mixture.

The “milk of magnesia thus obtained is introduced in 3 times into the medium to be carbonated. each introduction being followed by a carbonation step, the interval between each introduction being approximately 1 hour.

Analysis of the finished product

(Voir Tableaux I et II p. 7 et 8)

(See Tables I and II p. 7 and 8)

Claims (12)

1. A novel additive which can be produced in accordance with a process characterised by :

a) carbonating (first carbonation operation) a reaction medium comprising :

- a magnesium alkylbenzene sulphonate with a TBN -- 20 ;

- a sulphurised alkylphenol ;

- a dilution oil ; and

- a « milk of magnesia formed by active magnesium oxide, glycol and an amine,

until a weight of sediment of less than 1.5 % by weight with respect to the weight of reaction medium is attained :

b) neutralising and overalkalinising by means of lime the sulphurised alkylphenol present in said medium ;

c) optionally carbonating (second carbonation operation) the mixture obtained after removal of the water ;

d) distilling the glycol ;

e) then filtering to eliminate the sediments ; and that the amounts of reactants used are such that :

- the ratio of the amount of magnesium alkylbenzene sulphonate expressed as moles of alkylbenzene sulphonic acid to the amount of sulphurised alkylphenol expressed as moles of alkylphenol is between 0.15 and 5.5 ;

- the amount of active MgO corresponds to a base ratio of between 5 and 14 ;

- the amount of glycol corresponds to an MgO/glycol molar ratio of between 0.1 and 0.7 ;

- the amount of amine corresponds to a ratio of moles of amine/moles of basic magnesium of between 0.01 and 0.4 ; and

- the ratio of the amount of lime expressed as moles of lime to the amount of sulphurised alkylphenol expressed as moles of alkylphenol is between 0.2 and 2.5.

2. A novel additive according to claim 1 characterised in that the amine is a polyethylene amine.

3. A novel additive according to claim 2 characterised in that the amine is ethylenediamine.

4. A novel additive according to claim 3 characterised in that the amine is an ether amine.

5. A novel additive according to claim 4 characterised in that the ether amine is tris(3-oxa-6-aminohexyl) amine.

6. A novel additive according to any one of the preceding claims characterised in that the amounts of reactants are such that :

- the ratio of the amount of magnesium alkylbenzene sulphonate expressed as moles of alkylbenzene sulphonic acid to the amount of sulphurised alkylphenol expressed as moles of alkylphenol is between 0.25 and 2 ;

- the amount of active MgO corresponds to a base ratio of between 7 and 11 ;

- the amount of glycol corresponds to an MgO/glycol molar ratio of between 0.3 and 0.65 ;

- the amount of amine corresponds to a ratio of moles of amine/moles of basic magnesium of between 0.04 and 0.25 ; and

- the ratio of the amount of lime expressed in moles of lime to the amount of sulphurised alkylphenol expressed as moles of alkylphenol is between 0.4 and 2.

7. A novel additive according to any one of the preceding claims characterised in that the first carbonation operation is effected at a temperature ranging from 90 to 140 °C in one or more stages with the introduction of the « milk of magnesia into the medium containing the magnesium alkylbenzene sulphonate, the sulphurised alkylphenol and the dilution oil in one or more stages, each stage of introducing « milk of magnesia being followed by a carbonation stage.

8. A novel additive according to any one of the preceding claims characterised in that the amine used is present in the « milk of magnesia from the beginning of the first carbonation operation or in the course thereof.

9. A novel additive according to any one of the preceding claims characterised in that an amount of water corresponding to an H₂0/MgO ratio by weight of between 0.1 and 0.9 is introduced towards the end of the carbonation step.

10. A novel additive according to any one of the preceding claims characterised in that the operation for neutralisation-over-alkalinisation of the sulphurised alkylphenol by the lime is effected at a temperature of between 110 and 145 °C.

11. A novel additive according to any one of the preceding claims characterised in that the optional second carbonation operation is carried out at a temperature of between 120 and 170 °C.

12. Application of the novel additive according to any one of the preceding claims for improving the detergent, dispersant and anti-wear properties of lubricating oils.