FI93654B - Sulfurized alkaline earth metal hydrocarbyl phenates, their preparation and their use - Google Patents

Abstract

An additive concentrate suitable for incorporation into a finished lubricating oil composition, the additive concentrate comprising: (a) a lubricating oil, (b) a lubricating oil soluble sulphurised alkaline earth metal hydrocarbyl phenate modified by incorporation of from greater than 2 to 35% by weight based on the weight of the composition of either (i) at least one carboxylic acid having the formula:- R - @@ - COOH (I) wherein R is a C10 to C24 alkyl or alkenyl group and R<1> is either hydrogen, as C1 to C4 alkyl group or a -CH2-COOH group, or an anhydride, acid chloride or ester thereof or (ii) a di- or polycarboxylic acid containing from 36 to 100 carbon atoms or an anhydride, acid chloride or ester thereof, the composition having a TBN greater than 300.

Description

Q7 ^ C / I> j D j t

Sulfurized alkaline earth metal hydrocarbyl phenates, their preparation and their use

The present invention relates generally to sulfurized alkaline earth metal hydrocarbyl phenates, their preparation and their use as lubricating oil additives. In particular, the present invention relates to a process for the preparation of sulfurized alkaline earth metal hydrocarbylphenate-containing additive concentrates having a high total base number (TBN) and an acceptable viscosity using sulfurized alkaline earth metal hydrocarbylphenates having a lower TBN than the final concentrate TBN.

In an internal combustion engine, by-products often move from the combustion chamber 15 past the piston and mix with the lubricating oil. Many of these by-products form acidic substances in lubricating oil. This is especially characteristic of diesel engines using low-quality fuels with a high sulfur content, which produces corrosive acids on combustion. The acids thus introduced into the lubricating oil may be sulfuric acids formed during the oxidation of the sulfur, hydrohalic acids due to the halogenated lead scrubbers in the fuel, and nitric acids formed by the oxidation of atmospheric nitrogen in the combustion chamber. Such acids cause sludge build-up and corrosion of bearings and engine parts, leading to rapid wear and early engine failure.

One group of compounds commonly used to neutralize acidic substances and disperse sludge in lubricating oil are Embroidered metal alkyl phenates in which the metal is an alkaline earth metal such as calcium, magnesium or barium. Both "normal" and "superbasic" sulfurized alkaline earth metal alkyl phenates have been used.

35 The term "superbasic" is used to describe those sulfurized O 1, XC Λ 2 ^ · ~> O j ~ r alkaline earth metal alkyl phenates in which the ratio of the number of equivalents of the alkaline earth metal solution to the number of equivalents of the phenol moiety is greater than 1, and is generally greater than 1.2 and can be as high as 4.5 or 5 higher. In contrast, the equivalent ratio of alkaline earth metal moiety to phenol moiety in • normal “alkaline earth metal alkyl phenates is 1. Thus, a“ superbasic ”substance contains more than 20% more alkaline earth metal11 than the corresponding“ normal ”material. greater ability to neutralize an acidic substance than the corresponding "normal" alkaline earth metal alkyl phenates are capable of.

The prior art discloses many methods for preparing both "normal" and "overbased" embroidered metal allyl phenylates. According to one such process, the preparation of "overbased" embroidered alkyl phenates, commonly referred to as the "simple lime addition" process, involves reacting alkylphenol, in the presence of a lubricating oil, sulfur, a hydroxyl-20-alkyl halide-alkali metal alkali metal hydroxide stoichiometric amount) to form an intermediate, followed by treatment with carbon dioxide and distillation (to remove unreacted hydroxyl-containing compound) and filtration. The formation of the intermediate is associated with a significant increase in viscosity, while subsequent treatment with carbon dioxide reduces the viscosity to a relatively low level. The viscosity of the intermediate associated with the formation of the intermediate. Renemation is not desirable because the reaction mixture becomes difficult to stir, which is detrimental to subsequent reactions. Although this increase in viscosity can be adjusted to an acceptable level by including less alkaline earth metal hydroxide in the reaction, the overbased alkyl phenate product inevitably has a reduced 93654 3 neutralizing ability. In order to obtain a product with a high neutralizing capacity and at the same time to adjust the viscosity of the intermediate to acceptable limits, alkaline earth metal hydroxide can be added in two (commonly referred to as the "double lime addition" method) or three separate reaction steps followed by carbon dioxide treatment steps. However, this method requires relatively long processing times. An alternative method is to use viscosity reducing agents such as tridecanol, 2-ethylhexanol or a boiling hydroxyl-containing solvent at the same boiling point in the preparation of the intermediate, but such means increases the raw material costs of the process. The highest total base number (TBN), expressed as 15 mg KOH / g, which is consistent with acceptable viscosity and is generally achievable by prior art methods, is about 300, although prior art TBN values are generally between 200 and 300. It would, of course, be desirable to prepare Embroidered primer-20 lime metal alkyl phenate compositions having a high TBN value, i. The TBN is greater than 300 and preferably greater than 350. It would also be desirable to prepare such materials from embroidered ground alkali metal alkyl phenates having a lower TBN. Until now, it has not been possible to achieve products with such a high TBN value, because the use of higher concentrations of alkaline earth sludge results in highly viscous products which, instead of being "thinned" by subsequent carbonation treatments using excess carbon dioxide, other-30 become insoluble. In the present invention, these objects have been achieved and thus products with a TBN of more than 300 and in some cases greater than 350 have been obtained, while the viscosity has remained acceptable, i. the viscosity is less than 1,000 x 6 "6 m 2 / s, while insolubility is avoided by including in the reaction mixture, which contains embroidered iria-alkali metal alkylphenate, at least one carboxylic acid or an acid derivative thereof, having at least 10 carbon atoms in the molecule.

The use of carboxylic acids in the production of embroidered alkaline earth-5 metal alkyl phenates is not new, cf. for example US-A-4 049 560 and EP-AO 094 814.

U.S. Pat. No. 4,049,560 discloses the preparation of a superbasic magnesium detentent by a process in which carbon dioxide is introduced into a reaction mixture comprising: 10 (a) 15 to 40% by weight of embroidered phenol or thiophenol containing one or more hydrocarbyl substituents, or phenol or thiophenol containing one or more hydrocarbyl substituents, or said phenol or thiophenol containing one or more hydrocarbyl substituents together with sulfur, (b) 5-15% by weight of an organic sulfonic acid, an organic sulfonate or an organic sulfate, (c) 5-15% by weight of glycol, 1-value C 1-5 -alkanol or C 1-5 -alkoxyalkanol, 20 (d) 2-15% by weight of magnesium hydroxide or active magnesium oxide, (e) at least 0.1% by weight of % C, Igg carboxylic acid, its anhydride or ammonium salt of said CMg carboxylic acid, an amine salt, a salt of a Group I metal or a Group II metal, and (f) at least 10% by weight of a diluent oil (i.e. including all components (a) and (b)).

The amount of the carboxylic acid [component (e)] is preferably between 0.5 and 2.0% by weight. The product prepared by this reaction is said to have a TBN value of about 200-250, e.g. about 225.

EP-A-0 094 814 discloses an additive concentrate for inclusion in a lubricating oil composition comprising a lubricating oil, 10 to 90% by weight of the overbased sulfur-alkaline earth metal hydrocarbyl phenate used.

3 7 £ C A

; -j Ou-t treated either during or after the superbasification process with 0.1 to 10, preferably 2 to 6% by weight (based on the weight of the additive concentrate) of an acid of the formula: 5 R - CH - COOH (I) I.

R1 (wherein R is a straight-chain C10-24 alkyl or alkenyl group and R1 is hydrogen, a C1-4 alkyl group or a CH2-COOH group) or an anhydride or a salt thereof. The object of EP-A-0 094 814 is to solve the problems which arise when using many additive concentrates containing excess additives, namely the lack of stability, which causes sedimentation and foaming problems. EP-A-0 094 814 does not have the problem of producing phenates with TBN values greater than 300, and phenates prepared by the process of the invention, although they solve stability and foaming problems, do have TBN values less than 300 .

It can be concluded that the prior art using carboxylic acids is not suitable for the preparation of overbased Embroidered Alkaline Alkali Metal Alkyl 25-Phenates having TBN values greater than 300 and having an acceptable viscosity.

Accordingly, an object of the present invention is to provide a process for preparing an additive concentrate suitable for incorporation into a finished lubricating oil composition, which process is characterized by reacting at elevated temperature (A) a Titten alkaline earth metal hydrocarbyl phenate having a TBN of less than the final * 6 QX £ ς / 1 ^ VJ O 't (B) alkaline earth metal base, added either in one addition to the initial reagents or so that part is added to the initial reagents and the remainder in one or more parts to later or later steps in the process, (C) either a polyhydric alcohol having 2 to 4 carbon atoms, a di- or tri (C2-C4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, (D) a lubricating oil, 10 (E) carbon dioxide added to the addition of component (B), or after each addition thereof, and (F) ri more than 2% and not more than 35% by weight, based on the weight of the concentrate, of either (i) at least one carboxylic acid of the formula R - CH - COOH (I) R 'wherein R is a C10-24 alkyl or alkenyl group, and R * is either 20 hydrogen, a C 1-4 alkyl group or a -CH 2 CO 2 H group, or an anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an anhydride or ester thereof, wherein the components (A ) - (F) the weight ratio is such that a concentrate with a TBN of more than 300 and a viscosity of less than 1000 x 10 "6 m 2 / s at 100 ° C is obtained.

Component (D) of the composition is a lubricating oil. The ointment oil may conveniently be either of animal origin, vegetable oil or mineral oil. The lubricating oil may suitably be a petroleum-derived lubricating oil, such as a naphthenic-based, 30 paraffin-based or mixed-base oil. Soluble neutral oils are particularly suitable. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthetic lubricating oils include synthetic ester-type lubricating oils such as diesters such as dioctyl adipate, dioctyl acacate and tridecyl adipate, or polymeric hydrocarbon lubricating oils, for example, liquid polyisobutylenes and polyalpha-olefins. The lubricating oil may suitably be present in an amount of 10 to 90% by weight, preferably 10 to 70% by weight of the composition.

5 Component (A) is a sulfurized alkaline earth hydrocarbon phenate soluble in lubricating oil. The alkaline earth metal may suitably be strontium, calcium, magnesium or barium, preferably calcium, barium or magnesium, more preferably calcium.

The hydrocarbylphenate moiety of the sulfurized alkaline earth metal hydrocarbylphenate is preferably derived from at least one alkylphenol. The alkyl groups of the alkylphenol contain 4 to 50, preferably 9 to 28 carbon atoms. One particularly suitable alkylphenol is C12 alkylphenol obtained by alkylation of phenol with a propylene tetramer.

The sulfurized alkaline earth metal hydrocarbyl phenate is modified by including either compound (i) or (ii). As for case (i), this means at least one carboxylic acid of formula (I), or an acid anhydride or ester thereof. R in formula (I) is preferably a non-branched alkyl or alkenyl group. Preferred acids of formula (I) are those wherein R is a straight chain c 10-24 alkyl group; more preferably a straight chain C 18-24 alkyl group, and R 1 is hydrogen. Examples of suitable saturated carboxylic acids of formula (I) are capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid and lignoseric acid. Examples of suitable unsaturated acids of formula (I) are lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid, erucic acid, castor oil acid, linoleic acid and linolenic acid. Acid mixtures can also be used, for example rapeseed fatty acids. Particularly suitable acid mixtures are those commercial grade mixtures containing a number of 35 acids with both saturated and unsaturated 93654 k δ acids. Such mixtures can be obtained synthetically or can be derived from natural products, for example cottonseed oil, peanut oil, coconut oil, linseed oil, palm kernel oil, olive oil, shea butter, corn oil, palm oil, castor oil, soybean oil, soybean oil, soybean oil, soybean oil, soybean oil, soybean oil. can also be used. Instead of or in addition to the carboxylic acid, an acid anhydride or acid ester derivatives, preferably an acid anhydride, can be used. However, it is recommended to use a carboxylic acid or a mixture of carboxylic acids. A preferred carboxylic acid of formula (I) is stearic acid.

Instead of or in addition to (i), the Teaked alkaline earth metal hydrocarbylphenate may be modified by incorporating a compound (ii) which is a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an acid anhydride or ester derivative thereof, preferably anhydride. (ii) is preferably polyisobutylene succinic acid or polyisobutylene succinic anhydride.

Preferably, the carboxylic acid (s) of formula (I), di- or polycarboxylic acid or their acid anhydride or ester are included in an amount greater than 10% up to 35%, more preferably 12 to 20% by weight, for example about 16% by weight. One advantage of increasing the amount of carboxylic acid greater than 10% or a derivative thereof is generally the relatively low viscosity of the concentrate.

The alkaline earth metal may conveniently be present in the composition in an amount of from 10 to 20% by weight based on the weight of the composition.

Sulfur may suitably be present in the composition in an amount ranging from 1 to 6%, preferably from 1.5 to 3% by weight based on the weight of the composition.

93654 9

Carbon dioxide may suitably be present in the composition in an amount ranging from 5 to 20, preferably 9 to 15% by weight based on the weight of the composition.

The composition preferably has a TBN of greater than 5,350, more preferably greater than 400.

The viscosity of the composition, measured at 100 ° C, may suitably be less than 1000 x 10 "6 m 2 / s (1000 cSt), preferably less than 750 x ΙΟ" 6 m 2 / s, more preferably less than 500 x "" 6 m2 / s.

The process according to the invention is advantageous in that it provides a process for improving the quality of low-TBN products known from the prior art, i.e. products which do not meet the quality requirements, in order to obtain products with a high TBN value and an acceptable viscosity. In addition, since hydrogen sulfide is not generated by the process of the invention, in contrast to processes for the production of embroidered alkaline earth metal alkylphenates prepared by reacting alkylphenol and sulfur, more conventionally avoids the problem of hydrogen sulfide disposal, enabling production in less environmentally sensitive locations.

Component (A) of the reaction mixture is a sulfurized alkaline earth metal hydrocarbyl phenate having a TBN value lower than the TBN value of the final product, i. generally less than 300. Any Embroidered alkaline earth metal hydrocarbyl phenate can be used. The sulfurized alkaline earth metal hydrocarbyl phenate may or may not be treated with carbon dioxide. The alkaline earth metal portion and the hydrocarbyl phenate portion of the sulfurized alkaline earth metal hydrocarbyl phenate may suitably be as described above. Methods for preparing embroidered alkaline earth metal hydrocarbyl phenates are well known in the art. Alternatively, sulfurized alkaline earth metal hydrocarbyl phenate precursors can be used in the form of non-sulfurized alkaline earth metal hydrocarbyl phenate and sulfur.

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The alkaline earth metal base (component B) may suitably be an alkaline earth metal oxide or hydroxide, preferably a hydroxide. Calcium hydroxide can be added, for example, in the form of slaked lime. Preferred alkaline earth metals 5 are calcium, magnesium and barium and more preferably calcium. An amount of alkaline earth metal base relative to component (A) should be added which is sufficient to give a product having a TBN value of more than 300, preferably more than 350. This amount depends on many factors, e.g. the nature of the sulfurized 10 alkaline earth metal hydrocarbyl phenate. The weight ratio of component (B) to component (A) may typically be suitably between 0.1 and 50, preferably between 0.2 and 5. The alkaline earth metal base (B) may be added in whole or in part to the reactants initially used. and the remainder in one or more doses at a later stage or steps in the process. Preferably, component (B) is preferably added as a single addition to the initially used reactants.

Component (C) is either a polyhydric alcohol having 2 to 4 carbon atoms, a di- or tri (C 2-4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether. The polyhydric alcohol may suitably be either a polyhydric alcohol, for example ethylene glycol or propylene glycol, or a polyhydric alcohol, for example glycerol. The di- or tri- (C 2-4) glycol may suitably be either diethylene glycol or triethylene glycol. The alkylene glycol alkyl ether or polyalkylene glycol alkyl ether may suitably have the following formula R (O 'R') x R 2 (II) wherein R is a C 1-6 alkyl group, R 1 is an alkylene group, R 2 is hydrogen or C 1-6 alkyl and x is an integer from 1 to 6.

Suitable solvents of formula (II) are ethylene glycol 93654 11

Monomethyl or dimethyl ethers of diethylene glycol, triethylene glycol or tetraethylene glycol. One particularly suitable solvent is methyl digol (CH 2 OCH 2 CH 2 OCl 2 Cl 2 OH). Mixtures of glycols and glycol ethers of formula (II) may also be used. When glycol or a glycol ether of formula (II) is used as solvent, it is preferred to use together with them an inorganic halide, for example ammonium chloride, and a lower, i. CM carboxylic acid, for example acetic acid. Component (C) is preferably either ethylene glycol or methyl digol, the latter together with ammonium chloride and acetic acid.

Component (E) is carbon dioxide which can be added in gaseous or solid form, preferably in gaseous form. In gaseous form, it can be suitably blown through the reaction mixture. It has been found that the amount of carbon dioxide incorporated generally increases with increasing concentrations of component (F). Carbon dioxide is preferably added after a single addition of component (B) after completion of the reaction between components (A), (B), (C), (D) and (F).

Component (F) is either a carboxylic acid of formula (I), a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an acid anhydride or ester thereof, as described above. The amount required above to be more than 2% by weight but not more than 35% by weight based on the weight of the concentrate is first estimated to obtain the desired amount in the concentrate. In order to calculate this amount, provision must be made, for example, for the reduction in water due to carboxylic acids.

The reaction can be performed in the presence of a diluent. Suitable diluents are liquids whose volatility is consistent with the operation of the process, i. their volatility is such that they can be easily distilled off from the reaction mixture after completion of the reaction. Pre-35 examples of suitable diluents include 2-ethylhexanol, isooctanol, isoheptanol and tridecanol.

t 12 93654

Sulfur can be added to the reaction mixture, i.e. in addition to the sulfur already present due to component (A). The addition of additional is also an advantage in that it increases the amount of sulfur in the concentrate, which may be desirable for certain applications. On the other hand, the addition of sulfur leads to the formation of hydrogen sulfide, thus reducing to some extent the advantage of the invention, as mentioned above.

The reaction is preferably carried out in the presence of an additional component which is a suitable catalyst for the reaction. As the catalyst-10, an inorganic halide may be used, which may suitably be either a hydrogen halide, an ammonium halide or a metal halide. The metal part of the metal halide may suitably be zinc, aluminum or an alkaline earth metal, preferably calcium. Of the halides, chloride is preferred.

Suitable catalysts are hydrogen chloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride. The amount of catalyst used may suitably not exceed 2.0% (w / w).

The reaction of components (A) to (F) and also the carbonation reaction may be carried out at suitably elevated temperatures between 120 and 200 ° C, preferably between about 130 and 165 ° C, although the actual temperatures selected for components (A) to ( F) for the reaction and carbonation, may be different if desired. The pressure can be atmospheric-25 he pressure, atmospheric pressure lower or higher.

The concentrate can be recovered by conventional means, for example by distilling off component (C) and the diluent (if any).

Finally, it is preferable to filter the concentrate thus obtained. The process of the invention generally produces a concentrate of acceptable viscosity, i. a viscosity of less than 1,000 x 10 "* m2 / s at 100 ° C, and concentrates with a viscosity of less than 750 x 10" 6 m2 / s or 500 x 10 "6 m2 / s 100 can be obtained ° C.

93654 13

In addition, concentrates generally have desirable viscosity index properties. Such viscometric properties are advantageous because they facilitate the handling of the concentrate (e.g. filtration). However, it is also possible to prepare concentrates with a viscosity higher than 1,000 x 10-6 m 2 / s at 100 ° C, generally at higher TBN values. Filtration of such concentrates poses a problem which can be solved by adding a diluent before filtration and distilling off the diluent 10 after filtration. Alternatively or in addition, the concentrate may be diluted with lubricating oil and still have a TBN value greater than 300, especially if the concentrate, as prepared, has a high TBN value, for example more than 400.

The invention also relates to a finished lubricating oil composition comprising a lubricating oil and a sufficient additive concentrate prepared as described above to obtain a TBN value between 0.5 and 120.

Preferably, the finished lubricating oil composition contains 20 sufficient additive concentrates to obtain a TBN value between 0.5 and 100.

The amount of additive concentrate present in the finished lubricating oil depends on the nature of the end use. Thus, for lubricating oils used in marine engines, the amount of additive concentrate present may be suitably sufficient to have a TBN value between 9 and 100, and for lubricating oils used in automotive engines may be suitably sufficient to obtain a TBN value between 4 and 20.

The finished lubricating oil may also contain effective amounts of one or more types of conventional lubricating oil additives, such as viscosity index improvers, antiwear agents, antioxidants, dispersants, anti-rust agents, pour point depressants, or the like. may be incorporated into the finished lubricating oil composition either directly or through the concentrate composition. ί 14 'Ί' Λ ", il s. · U“.

In addition to being used as additives for inclusion in lubricating oil compositions, the additive concentrates of the invention may also find use as fuel additives.

The invention is further illustrated by the following examples.

The term "TBN" is used in all examples. TBN is a total base number expressed as mg KOH / g as measured by the ASTM D2896 method.

In all examples, unless specifically stated otherwise, commercially embroidered calcium alkyl phenate derived from C 1-2 alkylphenol was used. Phenate 15 is added as a solution to a lubricating oil constituting 36-40% (w / w) of the composition. The composition has a TBN of 250 and contains: calcium (9.25% w / w), sulfur (3.25% w / w) and carbon dioxide (4.6% w / w).

If, in one example, the "batch" contains ointment-20 oil, this is in addition to what is already present in the phenate composition.

Viscosity was measured by the ASTM D445 method.

Example 1

Improving the quality of sulfurized calcium alkylphenate

Input:

Lubricating oil 57 g

Sulfurized calcium alkyl phenate 206 g

Lime 49 g 30 Stearic acid 70 g

Calcium chloride 4 g 2-ethylhexanol 112 g

The batch was heated to 145-165 ° C / 93 kPa (700 mmHg) while 36 g of ethyl 35 glycene was added. The mixture was kept for one hour at 165 ° C / 700 ~ f / Γ Λ 'av U / 1 y · .; l> -J τ at 15 mmHgrn pressure. Carbon dioxide (50 g) was added at 165 ° C over one hour. The product was cooled to 125 ° C / 700 mmHg. Lime (33 g) was added. The temperature was raised to 165 ° C / 700 mmHg and the product was kept at this temperature for 5 hours. Carbon dioxide (25 g) was added at 165 ° C over 1 hour. Volatiles were distilled off from the product at 200 ° C / l at a pressure of 1.3 kPa (10 mmHg). Finally, the product was filtered. It was found that the filtration rate was very fast. 437 g of product and 10,167 g of distillate were obtained.

The product was analyzed for calcium, sulfur and carbon dioxide. Its TBN value, BPHVI50 value and viscosity at 100 ° C were determined. The BPHV150 assay is a solubility test. The results of the experiment are expressed using the scale = 1 (highly soluble; valid), 2 (borderline case) and 3 (rejected). Score

Calcium 13.9% (w / w) (equivalent to 96% retention of calcium in the product) 20 Sulfur 1.5% (w / w) (equivalent to 100% retention of sulfur in the product)

Carbon dioxide 12.3% (w / w) (corresponding to a 62% retention of CO2 charged to the product 25) TBN 395 V, oo 228 X 10 "* m2 / s

BPHVI50 IA

Stearic acid 16% (w / w) This example shows that a product with a low TBN value can be converted to a product with a high TBN value with an acceptable viscosity by the process of the invention.

16 93654

Example 2 Input:

Sulfurized calcium alkyl phenate 230 g

Lubricating oil 26 g 5 Calcium chloride 3 g

Method: (a) The charge was heated to 100 ° C / 93 kPa (700 mmHg). Stearic acid (63 g) was added and the mixture was stirred for 15 minutes, 10 (b) 2-ethylhexanol (190 g) was added at 100-110 ° C / 700 mmHg, (c) lime (66 g) was added at 110 ° C: (d) the mixture was heated to 165 ° C / 700 mmHg and ethylene glycol (32 g) was added rapidly (within one minute), (e) the mixture was held for five minutes at 165 ° C. at a pressure of 700 mmHg, (f) then carbon dioxide (66 g) was added at 165-20 ° C / 100 kPa (1 bar), (g) the solvent was removed at 200 ° C / l , At a pressure of 3 kPa (10 mmHg) and (h) the product from which the solvent had been removed was filtered.

25 Product weights

Crude product 398 g

Distillate 236 g

Composition of the product after filtration

The filtration rate was fast.

.30 Calcium 14.1% w / w

Sulfur 2.0% w / w CO2 12.9% w / w TBN 399

V100 825 X 10 · 6 m2 / S

35 Stearic acid 15.8% w / w c s r a y -j 0 u -f 17

Example 3

Input: Same as in Example 2.

Method: Same as Example 2, except that the temperature was 145 ° C instead of 165 ° C in steps (d), (e) and 5 (f).

product Weights

Crude product 402 g

Distillate 239 g

Composition of the product after filtration 10 Calcium 13.9% w / w

Sulfur 1.9% w / w CO2 13.9% w / w TBN 392

V100 206 X 10'6 m2 / S

15 Stearic acid 15.7% w / w

Example 4

Input: Same as in Example 2.

Method: Same as Example 2, except that the temperature was 130 ° C instead of 165 ° C in steps (d), (e) and 20 (f).

product Weights

Crude product 377 g

Distillate 236 g

Composition of the product after filtration 25 Calcium 13.7% w / w

Sulfur 2.1% w / w C02 13.2% w / w TBN 380 V, oo 99 X ΙΟ-6 m2 / s • 30 Stearic acid 16.7% w / w

Example 5

Batch: Same as in Example 3, except that calcium chloride was not used.

Method: Same as in Example 3.

i 18 93654

product Weights

388 g of crude product

Distillate 239 g

Composition of the product after filtration 5 Calcium 11.9% w / w

Sulfur 2.1% w / w C02 9.0% w / w TBN 331 V100 98 x 10-6 m2 / s 10 V40 1,490 x 10-6 m2 / s VI 148

Stearic acid 16.2% w / w

Filtration step (h) was very difficult.

This example compared to Example 3 shows that it is desirable to use a catalyst in the process of the invention. Although a lower V100 value was obtained in the absence of catalyst, this was achieved at the expense of reduced incorporation of calcium and carbon dioxide, and in addition, filtration was difficult.

20 Example 6

Input:

Sulfurized calcium alkyl phenate 253 g

Lubricating oil (100 SN) 26 g

Calcium chloride 4 g 2-ethylhexanol 190 g

Stearic acid 40 g

Method: (a) The batch was heated to 120 ° C / 93 kPa (700 mmHg) and then lime (36 g) was added, (b) the mixture was heated to 145-165 ° C while ethylene glycol was added ( 32 g), (c) the mixture was kept for one hour at 165 ° C / 700 mmHg, (d) carbon dioxide (44 g) was added at 165 ° C / 100 at 35 kPa (1 bar), 93654 19 (e) the mixture was cooled to 120 ° C and lime (25 g) was added, (f) the mixture was kept at 165 ° C / 700 inmHg for 1 hour, 5 (g) carbon dioxide (22 g) was added at 165 ° C (h) the solvent was distilled off at 200 ° C / l at a pressure of 1.3 kPa (10 mmHg) and (i) the product was filtered off. The filtration rate was fast.

10 Product weights

Crude product 401 g

Distillate 239 g

Product composition after filtration Calcium 14.3% w / w 15 Sulfur 2.1% w / w CO2 11.3% w / w TBN 405

Vlot) 1 483 x 10- * m2 / s

Stearic acid 10% w / w This example shows that it is possible to prepare a concentrate with a high TBN value, even if the viscosity is relatively high, by including 10% (w / w) stearic acid in the concentrate. Example 7 25 Input:

Same as Example 6, except that the amount of phenate was increased from 250 g to 268 g and the amount of stearic acid was increased from 40 g to 51 g.

Method: Same as in Example 6.

30 Product weights

Crude product 396 g

Distillate 234 g

Product composition after filtration Calcium 14.5% w / w 35 Sulfur 2.2% w / w 20 v XR Δ ./· ·. /% C02 13.1% w / w TBN 399 V100 706 x 10'6 m2 / s

Stearic acid 12.9% w / w This example shows that a concentrate with a high TBN value and a lower viscosity compared to Example 6 can be prepared with a stearic acid content of 12.9% (w / w) based on the weight of the concentrate.

10 Example 8

Input:

Sulfurized calcium alkyl phenate 230 g

Lubricating oil (SN 100) 0 g

Calcium chloride 3 g Method: (a) The batch was heated to 100 ° C, then stearic acid (99 g) was added and the mixture was stirred for 15 minutes, (b) 2-ethylhexanol (190 g) was added at 100-110-20 ° C: (c) lime (66 g) was added at 110 ° C / 6.8 kPa (50.8 mmHg) vacuum, (d) the mixture was heated to 145 ° C / 33.9 kPa (254 mmHg) and ethylene glycol (32 g) was added over 20 minutes, (e) the mixture was kept for five minutes at 145 ° C / 254 mmHg, (f) carbon dioxide (66 g) was added at 145 ° C, ( g) volatiles were distilled from the product at 200 ° C to .30 / 101.6 kPa (762 mmHg), and (h) the product was filtered. The filtration rate was slow.

product Weights

Crude product 398 g

Distillate 209 g 35 Composition of the product after filtration li 93654 21

Calcium 11.95% w / w

Sulfur 1.65% w / w C02 11.6% w / w TBN 349 5 V100 1 00 x ΙΟ "6 m2 / s V40 974 x ΙΟ * m2 / s

Stearic acid 24.9% w / w This example shows that it is possible to prepare a concentrate with a high TBN value with a low viscosity of al-10 with a stearic acid content of 24.9% (w / w).

Comparative test 1

Input: Same as in Example 3.

Method Same as Example 3, except that the addition of ethylene glycol in step (d) was omitted.

product Weights

382 g of crude product

Distillate 200 g 20 Composition of the product after filtration

Calcium 8.4% w / w

Sulfur 2.3% w / w CO2 4.4% w / w TBN 239

25 V100 41 X 10 "6 m2 / S

The filtration rate in step (h) was slow.

This is not an example according to the present invention and is included for this purpose to show that the presence of component (C) is essential for carrying out the process according to the invention.

Example 9 Input:

Same as in Example 3.

Method: 35 Same as Example 3, except that the amount of ethylene glycol ϊ 22 93654 Kol added in step (d) was reduced from 32 g to 16 g.

product Weights

Crude product 399 g 5 Distillates 225 g

Product composition after filtration Calcium 13.7% w / w

Sulfur 2.0% w / w CO2 13.5% w / w 10 TBN 395 V, oo 182 x 10-6 m2 / s

Stearic acid 15.8% w / w

The filtration rate in step (h) was slow.

This example shows that the amount of ethylene glycol li-15 can be reduced by 50% compared to Example 3.

Example 10 Input:

Sulfurized calcium alkyl phenate 230 g 20 Lubricating oil (100 SN) 26 g

Ammonium chloride 4 g

Acetic acid 2 g

Procedure: Same as in Example 3, except that in step (b) 25 methyl methylglycol (130 g) was added instead of 2-ethylhexanol (190 g) and in step (d) the addition of ethylene glycol was omitted.

product Weights

Crude product 390 g • 30 Distillates 166 g

Composition of the product after filtration Calcium 14.1% w / w

Sulfur 2.0% w / w C02 14.2% w / w 35 TBN 398 9365 4 23 V100 210 X ΙΟ · 6 τη2 / s

V40 3,821 X ΙΟ'6 m2 / S

VI 170

Stearic acid 16.2% w / w The filtration rate in step (h) was fast.

This example shows that methyl diglycol is effective as component (C).

Example 11

Input: Same as in Example 3.

10 Method:

Same as in Example 3, except that in step (d) the pressure was 36 kPa (270 mmHg).

product Weights

Crude product 402 g 15 Distillate 238 g

Composition of the product after filtration Calcium 14.0% w / w

Sulfur 1.9% w / w CO2 14.4% w / w 20 TBN 392

V100 2 8 8 X 10-6 m2 / S

Stearic acid 15, 7% w / w

Example 12

Input: Same as in Example 3.

25 Method:

Same as in Example 3, except that 40 g was used instead of 190 g of 2-ethylhexanol.

product Weights

Crude product 399 g. 30 Distillates 90 g

Composition of the product after filtration Calcium 13, 9% w / w

Sulfur 1.9% w / w C02 12.1% w / w 35 TBN 408> 3654 24 V100 387 χ ΙΟ'6 m2 / s

V40 7 980 X ΙΟ'6 in2 / S

VI 193

Stearic acid 15, 8% w / w Example 13

Input:

Sulfurized calcium alkyl phenate 230 g

Stearic acid 63 g

Calcium chloride 4 g 10 Linear C, 8-alpha-olefin 26 g 2-ethylhexanol 90 g

Method: (a) The mixture was heated to 145-165 ° C / 93 kPa (700 mmHg) while ethylene glycol (32 g) was added, (b) the mixture was held for 30 minutes at 165 ° C / 700 mmHg, (c) CO 2 (38 g) was added at 165 ° C / 100 kPa (1 bar), the mixture was cooled to 120 ° C and 2-ethylhexanol (100 g) was added. g), (e) lime (66 g) was added, (f) the mixture was kept at 165 ° C / 700 mmHg for five minutes, 25 (g) carbon dioxide (66 g) was added, (h) the solvent was recovered by distillation At 200 ° C / 1.3 kPa (10 mmHg), and (i) the product was filtered.

Product weights 30 Crude product 385 g

Distillate 256 g

Composition of the product after filtration Calcium 14.8% w / w

Sulfur 1.9% w / w 35 co2 13.4% w / w

II

25 9 3 654 TBN 424

V, oo 583 X 10’6 m2 / S

V40 13 080 X 10'6 m2 / s VI 209 5 Stearic acid 16.4% w / w

The filtration rate in step (i) was fast.

This example shows that the lubricating oil can be replaced by an alpha-olefin having a long carbon chain (in this case C18).

10 Example 14

Input:

Sulfurized calcium alkyl phenate (250 TBN) derived from a mixture of Cc / C22 / C24 alkylphenols 233.5 g 15 Lubricating oil (SN 100) 26 g

Calcium chloride 3 g

Method: (a) The mixture was heated to 100 ° C, stearic acid (63 g) was added and the mixture was stirred for 15 minutes, (b) 2-ethylhexanol (194 g) was added at 100-110 ° C, (c) ) lime (66 g) was added at 110 ° C / 6.8 kPa (50.8 mmHg) in vacuo, 25 (d) the mixture was heated to 145 ° C / 33.9 kPa (254 mmHg) and ethylene glycol (32 g) was added over 20 minutes, (e) the mixture was kept for five minutes at 145 ° C / 254 mmHg, • 30 (f) carbon dioxide (66 g) was added, (g) volatiles were distilled off from the product At 200 ° C / 101.6 kPa (762 mmHg), and (h) the product was filtered.

«26 93654

product Weights

385 g of crude product

Distillate 250 g

Composition of the product after filtration 5 Calcium 14.0% w / w

Sulfur 1.84% w / w C02 12.9% w / w TBN 401 V100 81 X 10'6 m2 / s 10 V40 8 385 x 10 · * m2 / s VI 186

Stearic acid 16.4% w / w This example shows that the quality of embroidered calcium alkyl phenates derived from a mixture of C12 / C22 / C24 alkylphenols can be improved.

Example 15 Input:

Sulfurized calcium alkyl phenate 181 g

Lubricating oil (SN 100) 50 g 20 Calcium chloride 4 g

Rapeseed fatty acids 62 g 2-ethylhexanol 190 g

Method: (a) The mixture was heated to 120 ° C, 25 (b) lime (43 g) was added at 120 ° C / 6.8 kPa (50.8 mmHg) vacuum, (c) ethylene glycol (32 g ) was added between 145-165 ° C / 50.8 mmHg, (d) the mixture was maintained at 165 ° / 50.8 mmHg. For 30 hours, (e) carbon dioxide (44 g) was added, (f) the mixture was cooled to 130 ° C and lime (29 g) was added at 130 ° C / 50.8 mmHg, (g) the mixture was kept 165 ° C / 50.8 mmHg for 35 hours, 27 C -7 £ C Λ> u Dun h) lime (22 g) was added at 165 ° C, (i) volatiles were distilled off from the product at 250 ° At C / 101.6 kPa (762 mmHg), (j) the product was filtered.

5 Product weights

382 g of crude product

Distillate 230 g

Product composition after filtration Calcium 14.0% w / w 10 Sulfur 1.8% w / w C02 12.3% w / w TBN 374 V, oo 17 6 x ΙΟ * m2 / s V40 2 826 x ΙΟ- * m2 / s 15 VI 172

Carboxylic acid content 16.2% w / w This example shows that rapeseed fatty acids can be used in the process of the invention.

Example 16 20 Input:

Sulfurized calcium alkyl phenate 230 g

Lubricating oil (SN 100) 26 g

Calcium chloride 3 g

Method: Same as in Example 2, except that in step (a) tall oil fatty acid (63 g) was used instead of stearic acid (63 g).

product Weights

380 g of crude product. 30 Distillates 223 g

Composition of the product after filtration Calcium 14.0% w / w

Sulfur 2.09% w / w C02 9.7% w / w 35 TBN 380 93654 28 V100 263 χ ΙΟ · 6 m2 / s

Carboxylic acid content 16.6% (w / w) based on the weight of the product This example shows that tall oil fatty acid can be used in the process according to the invention.

Example 17

Input: Same as in Example 16.

Method: 10 Same as in Example 16, except that a mixture of 52 g of a mixture of polyisobutylene succinic anhydride (PIBSA) SN 100 lubricating oil (TBN = 60 mg KOH / g) and stearic acid (47 g) was used instead of tall oil fatty acid (63 g).

15 Product weights

390 g of crude product

Distillate 219 g

Product composition after filtration Calcium 13.1% w / w 20 Sulfur 1.8% w / w co2 12.5% w / w TBN 360

VIOO 416 X 10-6 m2 / S

V40 12 690 X 10 * 6 m2 / S

25 VI 164

Carboxylic acid content 12.1% (w / w)

Anhydride content 7.2% (w / w) based on the weight of the product This example shows that the carboxylic acid can be partially replaced by PIBSA in the process according to the invention.

Example 18

Input: Same as in Example 16.

Method: 35 Same as Example 16 except that behenic acid (63 g) was used instead of tall oil fatty acid (63 g).

93654 29

product Weights

Crude product 402 g

Distillate 247 g

Composition of the product after filtration 5 Calcium 12.4% w / w

Sulfur 1.9% w / w CO 2 11/4% w / w TBN 354 V100 141 x 10 "6 m2 / s 10 Benoic acid 15.7% w / w This example shows that behenic acid can be used as a carboxylic acid in the process according to the invention.

Example 19 15 Input:

Same as Example 15, except that palmitic acid (56.2 g) was used instead of rapeseed fatty acids (62 g).

Method: 20 Same as in Example 15, except that steps (f), (g) and (h) were omitted.

product Weights

Crude product 312 g

Distillate 222 g 25 Composition of the product after filtration

Calcium 11/7% w / w

Sulfur 1.9% w / w COj 8.2% w / w TBN 332 30 Vioo 70 X 10-6 m2 / s

V40 831 X 10 · 6 m2 / S

VI 156

Palmitic acid 18.0% w / w This example shows that palmitic acid can be used in the process of the invention.

53654 30

Example 20

Input: Same as in Example 15.

Method:

Same as Example 15, except that steps (f), 5 (g) and (h) were omitted.

product Weights

334 g of crude product

Distillate 234 g

Composition of the product after filtration 10 Calcium 11.8% w / w

Sulfur 1.8% w / w CO2 10.9% w / w TBN 321

V, oo 168 X ΙΟ * m2 / S

15 V40 1 009 x 10 * m2 / s VI 286

Carboxylic acid content 18.6% (w / w) based on the weight of the product 20 Comparative test 2

Input:

Sulfurized calcium alkyl phenate 230 g

Lubricating oil 26 g

Calcium chloride 3 g Method: (a) The mixture was heated to 100 ° C and 2-ethylhexanol (190 g) was added, (b) acetic acid (14 g) was added, (c) the mixture became thick and heterogeneous and turned green. The confusion was ineffective.

The reaction was stopped.

This experiment is not an example of the present invention and is included herein for the sole purpose of showing that lower carboxylic acids, in this case acetic acid, cannot be used in the process of the invention.

»I

c 7, -: c λ J JUJ1 31

Example 21 Input:

Same as Example 16, except that non-carboxylated, commercial Embroidered Calcium C12 alkyl phenate (145 TBN) was used instead of commercial sulfurized calcium alkyl phenate.

Method:

Same as Example 16, except that in step (c) the amount of lime was increased from 66 g to 83 g, and in step 10 (f) the amount of carbon dioxide was increased from 66 g to 83 g.

product Weights

Crude product 421 g

Distillate 246 g

Composition of the product after filtration 15 Calcium 13.7% w / w

Sulfur 1.9% w / w C02 10.3% w / w TBN 383 V100 137 x 10- * m2 / s 20 V40 2 119 x ΙΟ "6 m2 / s VI 163

Carboxylic Acid 15.0% w / w This example demonstrates that non-carbonated, embroidered calcium alkylphenate with a low initial TBN value can be used in the process of the invention.

Example 22 Input:

Carbonated, Embroidered Calcium Alkyl-30 Phenate (150 TBN) 253 g

Stearic acid 40 g 2-ethylhexanol 90 g

Calcium chloride 4 g k> 3654 32

Method: (a) The mixture was heated from 145 ° C to 165 ° C / 93 kPa (700 mmHg) while ethylene glycol (32 g) was added, 5 (b) the mixture was kept at 165 ° C / 700 mmHg for 30 minutes, (c) carbon dioxide (38 g) was added at 165 ° C / 100 kPa (1 bar), (d) the mixture was cooled to 120 ° C and 2- ethylhexanol (100 g) and lime (76 g), (e) the mixture was kept for 60 minutes at 165 ° C / 700 mmHg, (f) carbon dioxide (82 g) was added at 165 ° C / l bar, (g) the solvent was recovered at 200 ° C / l at a pressure of 1.3 kPa (10 mmHg), and (h) the product was filtered.

product Weights

Product weight 390 g 20 Composition of the product after filtration

Calcium 14.4% w / w

Sulfur 2.3% w / w co2 11.6% w / w TBN 402

• 25 V, oo 674 x 10'6 m2 / S

Stearic acid 10.3% w / w This example shows that sulfurized calcium alkyl phenate with a low (150) TBN value can be qualitatively improved to a product with a high TBN value.

30 Example 23

Input:

Same as Example 14, except that instead of sulfurized calcium alkyl phenate derived from a mixture of alkylphenols, commercial Embroidered Calcium Alkylphenate derived from C12 alkylphenol (250 TBN) was used.

w * v ^ A S: i OJt 33

Method:

Same as Example 14, except that in step (b) isoheptanol (190 g) was used instead of 2-ethylhexanol (194 g) and in step (d) ethylene glycol was added rapidly (within one minute).

product Weights

Crude product 402 g

Distillate 239 g

Composition of the product after filtration 10 Calcium 13.9% w / w

Sulfur 1.9% w / w C02 12.0% w / w TBN 391 V, oo 313 X ΙΟ * 6 m2 / s 15 V40 6 700 x 10 · 6 m2 / s VI 177

Stearic acid 15.7% w / w

The filtration rate was fast.

This example demonstrates that isoheptanol can be used as a solvent in the process of the invention.

Claims (16)

A process for preparing an additive concentrate suitable for incorporation with a finished lubricating composition, characterized in that at an elevated temperature, a sulfurized alkaline earth metal hydrocarbyl compound having a TBN value less than TBN is reacted of the final additive concentrate, (B) an alkaline earth metal base which is added either in a batch to the reagents initially used or so that a portion is added to the initially used reagents and ether in one or more batches to (later) react (C) either a polyhydric alcohol of 2-4 carbon atoms, di- or tri (C2-C4) glycol, alkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide added after the addition 20 or each addition of component (B), and (F) either (i) at least one carboxylic acid of the formula R - CH - COOH (I) I. R1 wherein R is a C10.24 alkyl or alkenyl group and R1 is either hydrogen, a C 1-4 alkyl group or -CH 2 COOH group or an anhydride or ester thereof, or (ii) di- or polycarboxylic acid having 36 to 100 carbon atoms or an anhydride or esters thereof, sufficient to afford 2 and not more than 35% by weight thereof, calculated on the weight of the concentrate, the weight ratio of components (A) to (F) being such that a concentrate having a TBN value exceeding 300 and at 100 ° C a viscosity is formed. which is less than 35 1000 x 10 · 6 ro2 / s. 2. A process as claimed in claim 1, characterized in that the alkaline earth metal of the sulfurized alkaline earth metal hydrocarbyl phenate soluble in lubricating oil is calcium. 3. A process according to claim 1 or 2, characterized in that at least one carboxylic acid of formula (I) is incorporated, wherein R is an unbranched alkyl or alkenyl group. A process according to claim 3, characterized in that in the carboxylic acid of formula (I) R represents a straight-chain C10.24 alkyl group and R 1 is hydrogen. Process according to any one of claims 1-4, characterized in that a mixture of carboxylic acids of formula (I) is incorporated therein, the mixture being of commercial quality and containing a number of acids which include both saturated and unsaturated acids. 6. A process according to any of claims 1-4, characterized in that stearic acid is incorporated therein. Process according to any of the preceding claims, characterized in that either component b) (i) or component (b) (ii) is introduced in an amount of more than 10 and not more than 35% by weight, calculated on the weight of the concentrate. Method according to any of the preceding claims, characterized in that the TBN value of the composition exceeds 400. Process according to any of the preceding claims, characterized in that the viscosity of the concentrate at 100 ° C is less than 500 x 10 6 m / s. Process according to any of the preceding claims, characterized in that the component (B) is lime. Process according to any of the preceding claims, characterized in that the carbon dioxide (component E) is added after the addition of component (B) after the completion of the reaction between components (A) - ( D) and (F). Process according to any of the preceding claims, characterized in that the reaction takes place in the presence of a catalytic converter. 13. A process according to claim 12, characterized in that the catalytic converter is calcium chloride. A finished lubricating oil composition, characterized in that it comprises a lubricating oil and the additive concentrate prepared according to any one of claims 1 to 13 in a sufficient quantity to achieve a TBN value in the range 0.5 - 120. Finished butter joi jcompositon according to claim 14, characterized in that the lubricating oil is a marine lubricating oil and that sufficient auxiliary concentrate is present to achieve a TBN value in the range 9-100. 16. Finished lubricant composition according to claim 14, characterized in that the lubricating oil is a car engine lubricant and that sufficient auxiliary concentrate is present to achieve a TBN value in the range 4-20.