DK175287B1 - Sulfurized alkaline earth metal hydrocarbyl phenates, their preparation and 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

in DK 175287 B1

The invention generally relates to the preparation of sulfurized alkaline earth metal hydrocarbyl phenate additive concentrates, and their use as lubricating oil additives. More specifically, the invention relates to the preparation of additive concentrates containing sulfurized alkaline earth metal hydrocarbyl phenate, which concentrates have a high total base number (TBN) and an acceptable viscosity from sulfurized alkaline earth metal hydrocarbyl phenates with lower TBNs.

10 In internal combustion engines, by-products from the combustion chamber often pass the piston and mix with the lubricating oil. Many of these by-products form acidic materials in the lubricating oil. This is particularly prevalent in diesel engines operating on low-quality high-sulfur fuels 15 in which corrosive acids are produced by combustion. The acids incorporated in the lubricating oil may include sulfuric acids formed by the oxidation of sulfur, hydrogen halide acids derived from halogen-lead removers in the fuel and nitrogen acids 20 formed by oxidation of atmospheric nitrogen in the combustion chamber. Such acids cause sludge deposition and corrosion of bearings and engine parts, leading to rapid wear and early engine degradation.

A compound class commonly used to neutralize the acidic materials and disperse sludge in the lubricating oil are the sulfurized metal alkyl phenates, wherein the metal is an alkaline earth metal such as calcium, magnesium or barium. Both "normal" and "overbased" sulfurized 30 alkaline earth metal alkyl phenates have been used. The term "overbased" denotes the sulfurized alkaline earth metal alkyl phenates wherein the ratio of the number of equivalents of the alkaline earth metal part to the number of equivalents of phe-

I DK 175287 B1 I

I I

In the null part is greater than 1, and usually greater than I

In 1.2 and can be as high as 4.5 or higher. I I

In contrast, the equivalent ratio of soil I

In alkali metal and phenol in "normal" alkaline earth- I

In 5 metal alkyl phenates 1. The "overbased" material contains I

You thus keep an excess of the alkaline earth metal on the metal

In re more than 20% compared to that in the corresponding I

Earth alkaline metal present in "normal" material. By I

For this reason, "overbased" sulfurized alkaline earth- I

In 10 number alkyl phenates a greater ability to neutralize I

In acidic material than is the case with the corresponding I

In "normal" alkaline earth metal alkyl phenates. IN

In the prior art, many methods include

To produce both "normal" and "overbased"

In 15 sulfurated metal alkyl phenates. Such a method I

I for the preparation of "overbased" sulfurized alkylphe I

I nates, generally referred to as the method of "single I

In lime addition, "implies turnover, in the presence of I

In lubricating oil, of an alkyl phenol, sulfur, a hydroxy compound I

In the formation and excess of alkaline earth metal hydroxide (above the I

In the stoichiometric amount required to neutralize I

In the alkyl phenol) to form an intermediate after-I

Followed by carbonation, a top distillation (in order to

In remove unreacted hydroxy compound) and filtration. IN

I 25 The preparation of intermediate is accompanied by an interpretation

In equal viscosity, while the subsequent carbo- I

In wetting, the viscosity decreases to a relatively low I

In level. The viscosity increase accompanying formation I

I of the intermediate is undesirable because reaction mixture I

For 30 genes it becomes difficult to stir to the detriment of subsequent "I

In the end reactions. This increase in viscosity can be quite

You are shown at an acceptable level by introducing I

In less alkaline earth metal hydroxide in the reaction, but it I

B1 overbased alkylphenate product necessarily has a reduced neutralization ability. In order to obtain a high neutralization product and at the same time keep the viscosity of the intermediate within acceptable limits, the alkaline earth metal hydroxide can be added in two separate reaction steps (generally referred to as the "double lime addition" process) or in three separate reaction steps with subsequent carbonation steps. However, this approach involves relatively long portion processing times. Another alternative is to use viscosity reducing agents, such as tridecanol, 2-ethylhexanol or hydroxyl solvents of similar boiling range, in the preparation of the intermediate, but such auxiliary increases the raw material cost of the process. The highest total base number (TBN), measured in mg KOH / g, compatible with an acceptable viscosity and generally obtainable by the known methods, is approx. 300, but previously obtained 20 TBNs are generally in the range 200-300. It would clearly be desirable to prepare sulfurized alkaline earth metal alkyl phenate compositions with a high TBN, i.e. a TBN greater than 300, and preferably greater than 350. It would also be desirable to prepare 25 such materials from sulfurized alkaline earth metal alkyl phenates having a lower TBN. So far, it has not been found possible to win products with such high TBN because the use of larger concentrations of alkaline earth metal base leads to high viscous products which, instead of being "diluted" by subsequent carbonation experiments using excess carbon dioxide, are made insoluble. The present invention solves the problem and compositions having a TBN on it are obtained

I DK 175287 B1 I

I 4 I

In over 300 and in some cases greater than 350, at the same time

By maintaining an acceptable viscosity, i.e. and I

At viscosity lower than 1000 cSt, and avoided insoluble- I

Yours and the problem solving is based on a reaction path

In a composition containing a sulfurized alkaline earth metal alkyl I

In phenate to incorporate at least one carboxylic acid or acid

In shipping derivatives thereof with at least 10 carbon atoms in I

In molecules. IN

The use of carboxylic acids in the preparation I

In 10 of sulfurated alkaline earth metal alkyl phenates, not I

For now, see, for example, the patent publications I

In US-A-4,049,560 and EP-A-0.094,814. IN

In US-A-4,049,560, the preparation of an I

In overbased magnesium detergent by a method wherein I

Carbon dioxide is introduced into a reaction mixture containing I

You hold: I

In (a) 15-40% by weight of a sulfurized phenol or I

In thiophenol containing one or more hydrocarbons

In substituted substituents, or a phenol or thiophe- I

For 20 nol containing one or more hydrocarbylsubs

In stituents, or said phenol or thiophenol I

I containing one or more hydrocarbyl substituents

You enter with sulfur, I

In (b) 5-15% by weight of an organic sulfonic acid, an organ

In organic sulfonate or organic sulfate, I

In (c) 5-15% by weight of a glycol, a monovalent I

In (C1-C6alkanol or a (C2-C4) alkoxyalkanol, I

(D) 2-15% by weight of a magnesium hydroxide or active -

In magnesium oxide, I

(E) at least 0.1% by weight of a (Cj-C C q) carboxylic acid, and "I

(F) at least 10% by weight of a diluent oil

(Including any of components (a) and (b))

If present). IN

-------------- I

The amount of carboxylic acid (component (s)) is preferably in the range of 0.5 to 2.0% by weight. The product produced by this reaction is stated to have a TBN of approx. 200 to 250, e.g. ca. 225th

EP-A-0.094.814 discloses an additive concentrate for incorporation in a lubricating oil composition, which contains lubricating oil and from 10 to 90% by weight of an overbased sulfurized alkaline earth metal hydrocarbyl phenate treated either during or after the overbasing process. having from 0.1 to 10% by weight, preferably 2 to 6% by weight (based on the weight of the additive concentrate) of an acid of the formula:

R - CH - COOH

I (I) R 1 (wherein R is an unbranched (20 O 24) alkyl or alkenyl group and R 1 is hydrogen, a (C 1 -C 4 alkyl group 20 or a -CH 2 -C 30 H group) or a The object of the invention according to EP-A-0.094.814 is to solve problems associated with many additive concentrates containing overbased additives, namely lack of stability, which gives rise to sedimentation and foaming problems. EP-A-0.094.814 is not to produce phenates with a TBN greater than 300, and the phenates produced by the process of the present invention also have TBN values lower than 20,300, although they alleviate the stability and foaming problems .

Our European application publication number 0095322 describes a method of manufacture

I DK 175287 B1 I

i 6 I

I of either an alkaline earth metal alkylphenate or a sulfur

In recycled alkaline earth metal alkyl phenate, which method I

You include reaction at elevated temperature when present

In the room or in the absence of sulfur of an alkyl phenol I

I 5 with an alkaline earth metal base in the presence of an I

In solvent which is either an alkylene glycol alkyl I

In ether or a polyalkylene glycol alkyl ether of the formula: I

I R (0RX) X0R ^ I

I 10 I

In which R is one (C 1 -C 6 alkyl group, R 1 is alkylene, R 2 is I)

In hydrogen or (Cj-Cg) alkyl, and x is an integer in about I

In the range of 1 to 6 and an inorganic halide as catalyst I

I tor. It is believed to be preferred to add a small I

In an amount suitable up to 2% by weight of an acid, where one I

In suitable acid is stearic acid. It is believed that the addition I

I of stearic acid to the reactants increases the alkylphenates I

In the ability to minimize emulsion formation in water. IN

It can be concluded that the prior art in which I

In 20 carboxylic acids used, do not deal with I

In the problem of producing overbased sulfurized soils

In maybe alkali metal alkyl phenates with a TBN greater than 300 and I

In an acceptable viscosity. IN

In our co-pending European Application No. I

I 25 0271262, which requires the same priority day as the previous one

In the present application, describe an additive concentrate which I

You are suitable for incorporation into a finished lubricating oil composition

In sition, which additive concentrate contains: I

In (a) a lubricating oil,

In (b) a lubricating oil-soluble sulfurized soil alkali

In limetal hydrocarbyl phenate modified by incorporation

In portions of from more than 2 to less than 40 l

In% by weight based on the weight of the composition of one- I

(I) at least one carboxylic acid of the formula:

R - CH - COOH

Wherein R is a (C 10 -C 24) alkenyl group and R 1 is either hydrogen, a (C 1 -H 2 alkyl group or a 10 -CH 2 -COOH group or an anhydride, acid chloride or ester thereof or (ll) a di- or poly-carboxylic acid containing from 36 to 100 carbon, atoms or anhydride, acid chloride or ester thereof, the composition of which has a TBN 15 greater than 300.

Accordingly, in one embodiment, the present invention provides a process for preparing an additive concentrate suitable for incorporation into a finished lubricating oil composition, comprising: (a) a lubricating oil, (b) a lubricating oil-soluble sulfur alkaline earth hydrocarbyl modified hydrocarbyl. incorporating from more than 10 to 35% by weight, based on the weight of the concentrate of at least one carboxylic acid of the formula:

R - CH - COOH

In (I) R 1 where R is a straight-chain (C 1 -C 24) alkyl group and R 1 is hydrogen, or an anhydride, or

I DK 175287 B1 I

I I

In the ester derivative thereof, which concentrate has an I

In TBN greater than 300 and a viscosity at 100 ° of I

In less than 1000 mm2 .s-1 (cSt), which produces

In the process, turnover at elevated temp

In 5 rature of: I

In (A) a sulfurized alkaline earth metal hydrocarbylphe I

Tonight with a TBN less than the TBN for the final I

I give additive concentrate, I

In (B) an alkaline earth metal base added either in a single I

In 10 cold additions or as several additions on I

In intermediate steps during the reaction, I

I (C) either a polyhydric alcohol having from 2 to 4 L

In carbon atoms, a di- or tri- (C 2 -C 4) glycol, an I

In alkylene glycol alkyl ether or a polyalkylene I

In glycol alkyl ether, I

I (D) a lubricating oil, I

I (Ξ) carbon dioxide added after the addition or I

In each addition of component (B), and I

I (F) sufficient to provide from more I

In 20 than 35% by weight based on the weight of the concentrate

In the funnel of at least one carboxylic acid of the formula:

I R - CH - COOH I

I (i) I

I R1 I

wherein R is a (C10-C24) straight-chain alkyl, and I

I r! is hydrogen or an acid anhydride or I

Ester derivatives thereof, wherein the weight ratios of I -

In components (A) to (F) there are such that I

You prepare a concentrate with a TBN greater than I

I 300. I

9 DK 175287 B1

The process of the invention is advantageous because it provides a method of quality improvement of prior art products with low TBN or unspecified products for products with high TBN and acceptable viscosity. Furthermore, since hydrogen sulfide is not developed during the practice of the process of the invention, which is in contrast to more conventional processes for the preparation of sulfurated alkaline earth metal alkyl phenates by reaction of an alkyl phenol and sulfur, the problem of hydrogen sulfide removal is avoided so that fabrication can be allowed in environmentally sensitive areas, and it is possible to use less complicated plants.

Component (a) in the concentrate is a lubricating oil.

Suitably, the lubricating oil can be either an animal oil, a vegetable oil or a mineral oil. Suitably, the lubricating oil may be a petroleum-derived lubricating oil such as naphthene-based, paraffin-based, or mixed-base oils. Neutral solvent oils are particularly suitable. Alternatively, the lubricating oil may be a synthetic lubricating oil. Suitable synthetic lubricating oils include synthetic ester lubricating oils which contain diesters such as dioctyl adipate, dioctyl sebacate and tride siladipate, or polymeric hydrocarbon lubricating oils, for example liquid polyisobutenes and poly-α-olefins. The lubricating oil may suitably comprise from 10 to 90% by weight, preferably from 10 to 70% by weight of the concentrate.

Component (b) is a lubricating oil-soluble sulfurized alkaline earth metal hydrocarbyl phenate modified by incorporation of more than 10 to 35% by weight, based on the weight of the carboxylic acid concentrate. The alkaline earth metal may conveniently be strontium, calcium, magnesium or barium, preferably calcium, barium or magnesium, and especially calcium.

I DK 175287 B1 I

I 10 I

In the Hydrocarbylphenate portion of the sulfurized soil I

Preferably, perhaps alkali metal hydrocarbyl phenate is derived from I

In at least one alkyl phenol. The alkyl groups of the alkyl phenol I

You may be branched or unbranched. Suitable I

In 5 alkyl groups contain from 4 to 50, preferably from 9 L

I to 28 carbon atoms. A particularly suitable alkylphenol is I

The (C12 -alkyl) phenol is obtained by alkylation of phenol I

In with propylene tetramer. IN

In the sulfurized alkaline earth metal hydrocarbyl phenate I

I 10 is modified by incorporating at least one carbo-I

In xyl acid of formula (I) or an acid anhydride or I

In the ester derivative thereof. In the formula (I), R is preferably an I

In unbranched alkyl group. Preferred acids of formula I

I (I) are those where R is a straight-chain (C 10 -C 24) alkyl-I

In group, preferably (C18-C24) alkyl group, and R1 is hy1

In the drug. Examples of suitable saturated carboxylic acids with I

In formula (I), capric acid, lauric acid, myristin-I include

In acid, palmitic acid, stearic acid, arachic acid, behenic acid I

I and lignoceric acid. Mixtures of acids can also be used

December 20, such as fatty acids from rapeseed plants. IN

Particularly suitable mixtures of acids are the commercial I

In grades containing a range of acids, I-

In tende both saturated and unsaturated acids. Such mixtures I

Yeasts may be synthetically obtained or may be derived from na- I

In 25 solid products, such as cotton oil, peanut- I

In oil, coconut oil, flaxseed oil, palm kernel oil, .oli- I

In venison oil, corn oil, palm oil, castor oil, soybean oil- I

In Ile, sunflower oil, herring oil, sardine oil and sebum. . IN

Sulfurized acids and acid mixtures may also be used. IN

Instead of or in addition to the carboxylic acid, I may be used

In the acid anhydride or ester derivatives I

I of the acid, preferably the acid anhydride. It is preferred

However, in using a carboxylic acid or a mixture I

11 DK 175287 B1 of carboxylic acids. A preferred carboxylic acid of formula (I) is stearic acid.

Preferably, the carboxylic acid or carboxylic acids of formula (I), the acid anhydride or ester thereof are incorporated in an amount of more than 10 to 35% by weight, preferably from 12 to 20% by weight, e.g. 16% by weight, based on the weight of the concentrate. An advantage of incorporating more than 10% of the carboxylic acid or derivative thereof is generally a relatively lower concentrate viscosity.

Suitably, the alkaline earth metal may be present in the composition in an amount within the range of 10 to 20% by weight based on the weight of the concentrate.

Suitably, sulfur may be present in the concentrate in an amount in the range of 1 to 6% by weight, preferably 1.5 to 3% by weight, based on the weight of the concentrate.

Carbon dioxide may conveniently be present in the concentrate in an amount within the range of from 5 to 20% by weight, preferably 20 from 9 to 15% by weight, based on the weight of the concentrate.

The TBN of the concentrate is preferably greater than 350, especially greater than 400.

Suitably, the concentrate may have a viscosity, measured at 100 ° C, lower than 1000 cSt, preferably lower than 750 cSt and especially lower than 500 cSt.

Component (A) of the reaction mixture is a sulfurized alkaline earth metal hydrocarbyl phenate having a TBN lower than the TBN of the final product, i.e. generally lower than 300. Any sulfurized alkaline earth metal hydrocarbyl phenate may be used. The sulfurized alkaline earth metal hydrocarbyl phenate may be carbonated or non-carbonated. alkaline earth

I DK 175287 B1 I

I 12 I

In the portion and hydrocarbylphenate portion of the sulfurized soil I

Suitably, in alkali metal hydrocarbyl phenate may be, as I

In the above described. Methods for Preparing I

In sulfurated alkaline earth metal hydrocarbyl phenates, well-I

I knew the person skilled in the art. Alternatively, pre-I may be used

In the cursor of a sulfurized alkaline earth metal hydrocarbyl I

In phenate in the form of a non-sulfurized alkaline earth metal hy- I

In drocarbylphenate. IN

In the alkaline earth metal base (component B), suitable I

I 10 is an alkaline earth metal oxide or hydroxide, preferably I

In the hydroxide. For example, calcium hydroxide may be I

You add in the form of slaked lime. Preferred Soil Alkaline- I

In metals, calcium, magnesium and barium and in particular I

In calcium. The alkaline earth metal base should be added in a quantity of I

In relation to component (A) sufficient I

I to produce a product with a TBN greater than 300, I

Preferably in excess of 350. This amount will depend on an I

In a number of factors comprising the nature of the sulfurized soil I

In alkali metal hydrocarbyl phenate. The weight ratio of com

Typically, 20 ponent (B) and component (A) may be in the region I

I from 0.1 to 50, preferably from 0.2 to 5. Soil alkali I

In the metal base (B) can be added as a whole to the initial I

End reactants or partially to the initial reactants

You and the rest in one or more portions of one or I

In 25 more subsequent steps in the process. Component (B) I

Preferably, you are added in a single addition to those I

In initial reactants. IN

Component (C) is either a polyhydric alcohol with I

In 2-4 carbon atoms, a di- or tri- (C2-C4) glycol, an I

In alkylene glycol alkyl ether or a polyalkylene glycol alkyl-I

In ether. The polyhydric alcohol may conveniently be either I

In a divalent alcohol, for example ethylene glycol or I

In propylene glycol, or a trivalent alcohol, for example I

13 DK 175287 B1 pill glycerol. The di- or tri (C2-C4) glycol may conveniently be either diethylene glycol or triethylene glycol. Suitably, the alkylene glycol alkyl ether or polyalkylene glycol alkyl ether may have the formula: R (OR1) XOR2 (II) wherein R is a (C1-C8) alkyl group, R1 is an alkylene group, R2 is hydrogen or (C and x is an integer in the range of 1 to 6. Suitable solvents of formula (II) include monomethyl or dimethyl ethers of ethylene glycol, diethylene glycol, triethylglycol or tetraethylene glycol. A particularly suitable solvent is methyldigol 15 * Mixtures of glycols and glycol ethers of formula (II) may also be used. Using a glycol or glycol ether of formula (II) as a solvent, it is preferred, in combination, to use an inorganic halide, for example 20 ammonium chloride, and a lower one, i.e.

(Οχ-C4) carboxylic acid, for example acetic acid. Component (C) is preferably either ethylene glycol or methyldigol, the latter in combination with ammonium chloride and acetic acid.

Component (D) is a lubricating oil as described above in connection with the concentrate composition.

Component (E) is carbon dioxide which may be added in the form of a gas or a solid, preferably in the form of a gas. In the gaseous state, it can be suitably blown through the reaction mixture. It has been found that the incorporated amount of carbon dioxide generally increases with increasing concentrations of component (F). The carbon dioxide is preferably added

I DK 175287 B1 I

I 14 I

After a single addition of component (B) at the end I

In the reaction of component (A), (B), (C), I

In (D) and (F). IN

In Component (F) is a carboxylic acid of formula I

In 5 (1) or an acid anhydride or ester derivative thereof, as I

I described above in connection with concentrate composition

In the tion. The amount of the above required to

You provide from more than 10 to 35% by weight based on I

In the concentrate weight, as a first approximation will be I

In the amount derived from the concentrate. In calculating I

This quantity must be taken into account, for example, I

In water loss from carboxylic acids. IN

The reaction may be carried out in the presence of an I

In diluent. Suitable diluents are liquids I

I 15 with a volatility compatible with the process I

In implementation, ie. with such volatility that they easily

You can be stripped from the reaction mixture by reaction I

In closing. Examples of suitable diluents I

You comprise 2-ethyl-hexanol, iso-octanol, iso-heptanol and I

In tridecanol. IN

In Additional sulfur, ie. sulfur in addition to what you

You are already present as a result of component (A), you can

Add to the reaction mixture. An advantage of I

Adding further sulfur is that it increases I

In the amount of sulfur in the concentrate, which may be desirable

In certain applications. On the other hand, you lead

In sulfur addition to hydrogen sulphide development, I

To which, to some extent, the advantage of the invention is impaired

In the part, as discussed above. IN

The reaction is preferably carried out in presence I

I of a further component which is a catalyst for I

In the reaction. As an catalyst, an inorganic I can be used

In niche halide which may conveniently be either a hydro- I

B1 gene halide, an ammonium halide or a metal halide. The metal part of the metal halide may conveniently be zinc, aluminum or an alkaline earth metal, preferably calcium. Among the halides, the chloride is preferred. Suitable catalysts include hydrogen chloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride. The amount of catalyst used may suitably be up to 2.0% by weight.

The reaction of the components (A) - (F) and also the carbonation reaction can conveniently be carried out at elevated temperatures in the range of 120 to 200 ° C, preferably from ca. 130 to 165 ° C, but the temperatures selected in each case for the reaction of components (A) - (F) and for carbonation may, if desired, be different. The pressure may be atmospheric pressure, subatmospheric or superatmospheric pressure.

The concentrate can be recovered in a conventional manner, for example by distillative stripping of component (C) and diluents (if present).

Finally, it is preferred to filter the concentrate thus obtained. The process of the invention will generally produce a concentrate having an acceptable viscosity, i.e. a viscosity of less than 1000 cSt at 100 ° C, and can produce concentrates with a viscosity lower than 750 or 500 cSt at 100 ° C. Furthermore, the concentrates generally have desirable viscosity index properties. Such viscosimetric properties are advantageous because they facilitate processing (including filtration) of the concentrate. However, it is also possible to prepare concentrates with a viscosity higher than 1000 cSt at 100 ° C, i

I DK 175287 B1 I

I 16 I

Generally at higher TBN levels. Filtration of I

In such concentrates, there is a problem that you can

You dissolve by adding a diluent prior to I

In filtration and stripping of the diluent after I

In filtration. Alternatively, or further, con- I

In the center, dilute with lubricating oil and still retain an I

In TBN of over 300, in particular if the TBN for it thus I

The concentrate produced is high, for example over 400. I

In another embodiment, I provide

In the invention, an additive concentrate suitable for incorporating I

In a ring in a finished lubricating oil, which concentrate can win

In designing, at elevated temperature, (A) an I

In sulfurized alkaline earth metal hydrocarbyl phenate with a TBN I

In less than the TBN of the final additive concentrate, (B) I

In an alkaline earth metal base added either in a single addition

In theorem or as several additions on intermediate I

In steps of the reaction, (C) either a polyhydric alcohol I

I with from 2 to 4 carbon atoms, a di- or tri- (C2-C4) - I

In glycol, an alkylene glycol alkyl ether or a polyalkyl-I

In 20 englycol alkyl ether, (D) a lubricating oil, (E) carbon dioxide I

I added after the addition or each addition of the com

In ponent (B), and (F) sufficient to provide I

I from more than 10 to 35% by weight, based on the weight of the con

In the center, of either a carboxylic acid of formula (I) or I

For 25 an acid anhydride or ester derivative thereof, wherein I

By weight, the ratios of components (A) to (F) are such. IN

In that a concentrate having a TBN greater I is prepared

I than 300 and a viscosity at 100 ° of less than 1000 I

In mm2s_1 (cSt). IN

According to the last embodiment, I provide

In the invention, a finished lubricating oil composition, which I

In composition contains a lubricating oil and sufficient I

I of the additive concentrate described above to

You provide a TBN in the range of 0.5 to 120. I

17 DK 175287 B1

Preferably, the finished lubricating oil composition contains sufficient concentrate to provide a TBN within the range of 0.5 to 100.

The amount of concentrate present in the final lubricating oil will depend on the nature of the final application. Thus, for ship lubricating oils, the amount of concentrate composition present may be sufficient to provide a TBN within the range of 9 to 100, and for automotive engine 10 lubricating oils, the amount may conveniently be sufficient to provide a TBN within the range of 4 to 20.

The finished lubricating oil may also contain effective amounts of one or more other types of conventional lubricating oil additives, e.g. the finished lubricating oil composition either directly or through the concentrate composition.

The concentrate compositions of the present invention, in addition to being additives for incorporation in lubricating oil compositions, may also find use as fuel additives.

The invention is further described by the following examples.

The term "TBN" is used in all the examples.

This TBN ("Total Base Number") is the total base number in mg KOH / g measured by the method of ASTM D2896.

In all the examples, unless otherwise stated, a commercially available sulfurated calcium alkyl phenate derived from a (C1-2 alkyl) phenol is used. The phenate is supplied as a solution in lubricating oil which

I DK 175287 B1 I

I 1Θ I

You make up 36-40% by weight of the composition. The composition has I

In a TBN of 250 and the following composition: calcium (9.25 l

(Wt%), sulfur (3.25 wt%) and carbon dioxide (4.6 wt%). IN

When the "charge" in an example comprises lubricating oil, you are

In addition to the one in the phenate composition, it already contains I

You kept lubricating oil. IN

The viscosity is measured by the method of ASTM I

In D445. IN

In Example 1 I

I ίο I

In Quality Improvement of Sulfurized Calcium Alkyl Phenate. IN

In Charge I

I 15 Lubricating Oil 57 g I

In Sulfurated Calcium alkylphenate 206 g I

I Lime 49 g I

In Stearic acid 70 g I

I Calcium Chloride 4 g I

In 2-Ethyl-hexanol 112 g I

In the batch was heated to 145-165 ° C / 700 ram Hg I

In the addition of 36 g of ethylene glycol. It was held

Then for one hour at 165 ° C / 700 mm Hg. Carbon dioxide (50 l

In 25 g) was added at 165 ° C over 1 hour. Product I

I was cooled to 125 ° C / 700 mm Hg. Lime (33 g) was I

I added. The temperature was raised to 165 ° C / 700 mm Hg and I

You stayed at this temperature for one hour. Carbon dioxide (25 l

In g) was added at 165 ° C over one hour. Product I

I was then stripped at 200 ° C / 10 mm Hg. Finally I

In, the product was filtered. It was observed that I

The filtration rate was very fast. You won

In 437 g of product and 167 g of distillate. IN

19 DK 175287 B1

The product was analyzed for calcium, sulfur and carbon dioxide. Its TBN, BPHVI50 and viscosity at 100 ° C were determined. The BPHV1SO assay is a solubility test. Results from the test are given on a 5 scale 1 (very soluble, passed), 2 (limit case) and 3 (failure).

Results 10 Calcium = 13.9% by weight (corresponding to 96% retention in product of the added calcium).

Sulfur = 1.5% by weight (corresponding to 100% yield in the product of the sulfur added).

Carbon dioxide = 12.3% by weight (corresponding to 62% retention in the product of the applied CO 2).

TBN - 395 20 V100 - 228 cSt

BPHVI50 = 1A

Stearic acid = 16% by weight

This example shows that a product of low TBN 25 by the process of the invention can be converted into a product of high TBN and of acceptable viscosity.

Example 2 Charge:

Sulfurized calcium alkyl phenate 230 g

Lubricating oil 26 g

I DK 175287 B1 I

I 20 I

I Calcium Chloride 3 g I

In Procedure I

In 5 (a) the batch was heated to 100 ° C / 700 mm Hg. IN

Stearic acid (63 g) was added and the mixture I

You were stirred for 15 minutes. IN

In (b) 2-Ethyl-hexanol (190 g) was added at 100-110 L

In ° C / 700 mm Hg. IN

In 10 (c) lime (66g) was added at 110 ° C / 700 mm Hg I

(D) The mixture was heated to 165 ° C / 700 mm Hg, I

I and ethylene glycol (32 g) were quickly added (one I

In minutes). IN

I (e) The mixture was kept for 5 minutes at 165 ° C / 700 L

In 15 mm Hg. IN

I (f) Carbon dioxide (66 g) was added at 165 ° C / l

In the bar. IN

I (g) The solvent was recovered at 200 ° C / 100 mm I

I Hg. IN

In 20 (h) the stripped product was filtered. IN

In Product weights

In Crude product: 398 g I

I Distillate: 236 g I

Product composition after filtration 21 DK 175287 B1

The filtration rate was fast.

Calcium 14.1% by weight

Sulfur 2.0 wt% CO 12 12.9 wt% TBN 399 V100 825 cSt 10 stearic acid 15.8 wt%

Example 3

Charge: As in Example 2.

15

Course of action

As in Example 2 with the exception that the temperature was 145 ° C instead of 165 ° C in steps (d), 20 (e) and (f).

Product weights Crude product: 402 g 25 Distillate: 239 g

I DK 175287 B1 I

I 22 I

Product composition after filtration

In Calcium 13.9% by weight I

In Sulfur 1.2 wt% I

I 5 CO 2 13.9 wt% I

I TBN 392 I

I v100 206 cSt I

In Stearic Acid 15.7% by weight I

Example 4 I

I Charge; As in Example 2. I

In Procedure I

I 15 I

I As in Example 2 except that tem- I

At the temperature, 130 ° C instead of 165 ° C was in step (d), I

I (e) and (f) · I

I 20 Product weights I

In Crude product: 377 g I

I Distillate: 236 g I

25 Product composition after filtration I

In Calcium 13.7% by weight I

In Sulfur 2.1 wt% I

In CO 2 13.2 wt% I

I 30 TBN 380 I

I v100 99 cSt I

In Stearic acid 16.7 wt% I

DK 175287 B1 23

Example 5

charge; As in Example 3 except calcium chloride was omitted.

5

Course of action

As in Example 3.

10 Product weights Crude product: 388 g

Distillate: 239 g 15 Product composition after filtration

Calcium 11.9% by weight

Sulfur 2.1% by weight CO2 9.0% by weight TBN 331 V100 98 cSt V40 1490 CSt VI 148

Carboxylic acid 16.2% by weight 25

The filtration step (h) was very difficult.

This example, when compared to Example 3, shows the desirability of using a catalyst in the process of the invention. Although, in the absence of 30 catalyst, a lower V ^ q was obtained, at the expense of reduced calcium and carbon dioxide incorporation, and further filtration was difficult.

I DK 175287 B1 I

in 24 I

In Example 6 (not according to the invention) I

I Charge; IN

Sulfurized calcium alkylphenate 253 g I

I '5 Lubricating Oil (100 SN) 26 g I

I Calcium Chloride 4 g I

I 2-Ethyl-hexanol 190 g I

In Stearic acid 40 g I

Procedure I

In (a) the charge was heated to 120 ° C / 700 mm Hg and I

Then, in lime (36 g) was added. IN

I (b) The mixture was heated to 145-165 ° C under I

In the addition of ethylene glycol (32 g). IN

(C) The mixture was held for one hour at 165 ° C / 700 mm I

I Hg. IN

I (d) Carbon dioxide (44 g) was added at 165 ° C / 1 bar. IN

The mixture was cooled to 120 ° C and lime (25 L)

In 20 g) I was added

I (f) The mixture was maintained at 165 ° C / 700 mm Hg in one I

For hours. IN

I (g) Carbon dioxide (22 g) was added at 165 ° C / l bar I

I (h) Solvent was removed by stripping at I

At 200 ° C / 10 mm Hg. IN

I (i) The product was filtered. Filtration rate I

You were quick. IN

In Product Weight I

I 30 I

I Crude product: 401 g I

I Distillate: 239 g I

Product composition after filtration 25 DK 175287 B1

Calcium 14.3% by weight

Sulfur 2.1 wt% 5 C02 11.3 wt% TBN 405 V100 14Θ3 cSt

Stearic acid 10.0 wt% 10 This example shows that, although the viscosity is relatively high, it is possible to prepare a high TBN concentrate by incorporating 10 wt% stearic acid.

Example 7 15

Charge: As in Example 6 except that the phenate was increased from 250 g to 268 g and the stearic acid was increased from 40 g to 51 g.

Method

As in Example 6.

Product Weight 25 Crude product: 396 g

Distillate: 234 g

I DK 175287 B1 I

I 26 1

Product composition after filtration

In Calcium 14.5% by weight I

In Sulfur 2.2 weight * I

I 5 CO 2 13.1 wt% I

I TBN 399 I

I v100 706 cSt I

In Stearic acid 12.9 wt% I

This example shows that a concentrate with an I

In high TBN and with one compared to Example 6 lower I

In viscosity can be prepared at a stearic acid content of I

In 12.9% by weight based on the weight of the concentrate. IN

I 15 I

In Example 8 I

I Charge

Sulfurized calcium alkylphenate 230 g I

In 20 Lubricating Oil (SN 100) And I

I Calcium Chloride 3 g I

27 DK 175287 B1

Process (a) The batch was heated to 100 ° C, stearic acid (99 g) was then added and the mixture was stirred for 15 minutes.

(b) 2-Ethyl-hexanol (190 g) was added at 100-110 ° C.

(c) Lime (66 g) was added at 100-110 ° C / 2 "Hg (d) The mixture was heated to 145 ° C / 10 mm Hg, 10 and ethylene glycol (32 g) was added over 20 minutes.

(e) The mixture was kept for 5 minutes at 145 ° C / 10

Hg.

(f) Carbon dioxide (66 g) was added at 145 ° C

(G) The product was stripped at 200 ° C / 30M Hg.

(h) The product was filtered. The filtration rate was slow.

Product weight 20 Crude product: 398 g

Distillate: 209 g

I DK 175287 B1 I

I 28 I

Product composition after filtration

In Calcium 11.95 wt% I

In Sulfur 1.65 wt% I

I 5 CO 2 11.6 wt% I

I TBN 349 I

I v100 100 cSt I

I v40 974 cSt I

In Stearic acid 24.9 wt% I

I 10 I

I This example shows that it is possible to develop I

You place a concentrate with high TBN and low viscosity

I at a stearic acid content of 24.9 wt% I

I Comparison Test 1 I

I 13 I

In Charge: As in Example 3. I

In Procedure I

I 20 As in Example 3 except that I-

The ethylene glycol in step (d) was omitted. IN

In Product weights

Crude product: 382 g I

I Distillate: 200 g I

Product composition after filtration 29 DK 175287 B1

Calcium 8.4% by weight

Sulfur 2.3 wt% 5 ø2 4.4 wt% TBN 239 v100 41 cS ^

The filtration rate in step (h) was slow.

This is not an example of the invention, but has been introduced for the purpose of demonstrating that the presence of a component (C) is critical to the performance of the process of the invention.

Example 9

Charge: As in Example 3.

Method 20

As in Example 3 except that in step (d), the ethyl-englycol addition was reduced from 32 g to 16 g.

25 Product weights Crude product: 399 g

Distillate: 225 g

I DK 175287 B1 I

I 30 I

Product composition after filtration

In Calcium 13.7% by weight I

In Sulfur 2.0 wt% I

I 5 CO 2 13.5 wt% I

I TBN 395 I

I V100 182 cSt I

In Stearic Acid 15.8% by weight I

I The filtration rate in step (h) was slow. IN

I This example shows that the addition of ethyl I

In englycol can be reduced by 50% compared with Example I

In column 3. I

Example 13 I

In Charge I

Sulfurized calcium alkylphenate 230 g I

In grease oil 26 g I

I 20 Ammonium Chloride 4 g I

In Acetic Acid 2 g I

In Procedure I

I As in Example 3 except that in I

In step (b), instead of 2-ethyl-hexanol (190 g), I was added

In methyldiglycol (139 g) was added and in step (d) I was added

In the addition of ethylene glycol omitted. IN

Product weights 31 DK 175287 B1 Crude product: 390 g

Distillate: 166 g 5

Product composition after filtration

Calcium 14.1% by weight

Sulfur 2.9% by weight 10 CO2 14.2% by weight TBN 398 V100 210 CSt V40 3821 cSt VI 170 15 Stearic acid 16.2% by weight

The filtration rate in step (h) was fast.

This example demonstrates that methyldiglycol is effective as component (C).

20

Example 11

Charge: As in Example 3.

Method

As in Example 3, except that the pressure in step (d) was 270 mm Hg.

I DK 175287 B1 I

I 32 I

In Product Scales I

I Crude product: 402 g I

I Distillate: 238 g I

I I

Product composition after filtration

In Calcium 14.0% by weight I

In Sulfur 1.9% by weight I

I 10 CO 2 14.4 wt% I

I TBN 392 I

I v100 288 cSt I

In Stearic Acid 15.7% by weight I

Example 13 I

In Charge: As in Example 3. I

In Procedure I

I 20 I

I As in Example 3, except that in I

Instead of 190 g of 2-ethyl-hexanol, 40 g was used

In Product weights

I 25 I

In Crude product: 399 g I

I Distillate: 90 g I

Product composition after filtration 33 DK 175287 B1

Calcium 13.9% by weight

Sulfur 1.9 wt% CO 12 12 wt% 5 TBN 408 V100 387 cSt V40 7980 cSt VI 193

Stearic acid 15.8% by weight 10

Example 13

Charge: Sulfurized calcium alkyl phenate 230 g

Stearic acid 63 g

Calcium chloride 4 g

Linear C 1-6 olefin 26 g 2-Ethyl-hexanol 90 g

I DK 175287 B1 I

I 34 I

In Procedure I

In (a) The mixture was heated to 145-165 ° C / 700 mm I

In Hg with the addition of ethylene glycol (32 g). IN

I (b) The mixture was kept at 165 ° C / 700 mm I for 30 minutes

I 5 Hg. IN

In (c) CO 2 (38 g) was added at 165 ° C / 1 bar. IN

I (d) The mixture was cooled to 120 ° C and I

In 2-ethyl-hexanol (100 g) was added. IN

In (e) lime (66 g) was added. IN

In 10 (f) The mixture was maintained at 165 ° C / 700 mm Hg for 5 L

In minutes. IN

I (g) Carbon dioxide (66 g) was added. IN

I (h) The solvent was recovered by stripping at I

At 200 ° C / 10 mm Hg. IN

In (i) the product was filtered. IN

In Product weights

In Crude product: 385 g I

I Distillate: 256 g I

Product composition after filtration

In Calcium 14.8% by weight I

I 25 Sulfur 1.9 wt% I

In CO 2 13.4 wt% I

I TBN 424 I

I vioo 583 cSt I

I V40 13080 cSt I

30 I

VI 209 I

In Stearic acid 16.4% by weight I

DK 175287 B1

The filtration rate in step (i) was fast.

This example shows that a lubricating oil can be replaced by long carbon α-olefin (in this case C18).

5

Example 14

charge

Sulfurized calcium alkyl phenate (250 TBN) 233.5 g of 10 derived from a mixture of (C

Lubricating Oil (SN 100) 26 g

Calcium chloride 3 g 15

Process (a) The mixture was heated to 100 ° C, stearic acid (63 g) was added and the mixture was stirred for 15 minutes.

(b) 2-Ethyl-hexanol (194 g) was added at 100-110 ° C.

(c) Lime (66 g) was added at 110 ° C / 2 "Hg vacuum.

(d) The mixture was heated to 145 ° C / 10 "Hg and 25 ethylene glycol (32 g) was added over 20 minutes.

(e) The mixture was kept for 5 minutes at 145 ° C / 10

Hg.

(f) Carbon dioxide (66 g) was added.

(G) The product was stripped at 200 ° C / 30 "Hg.

(h) The product was filtered.

I DK 175287 B1 I

I 36 I

In Product weights

In Raw product: 365 g I

I Distillate: 250 g I

I 5 Composition of products after filtration I

In Calcium 14.0% by weight I

In Sulfur 1.84% by weight I

In CO 2 12.9 wt% I

I 10 TBN 401 I

I V100 81 cSt I

I V4Q 8365 cSt I

I VI 186 I

In Stearic acid 16.4% by weight I

I 15 I

This example shows that sulfurized calcium al- I

In cooling phenates derived from a mixture of I

In {C12 / c22 / c24 "alky1)" Piieno ^ er quality can be improved. IN

Example 15 I

In Charge: I

Sulfurized calcium alkyl phenate 181 g I

I 25 Lubricating Oil (SN 100) 50 g I

Calcium chloride 4 g I

In Rapstop fatty acid 62 g I

I 2-Ethyl-hexanol 190 g I

37 DK 175287 B1

Process (a) The mixture was heated to 120 ° C.

(b) Lime (43 g) was added at 120 ° C / 2 "Hg vacuum.

(C) Ethylene glycol (32 g) was added at 145-165 ° C / 2 "Hg.

(d) The mixture was kept at 165 ° C / 2 "for 1 hour.

(e) Carbon dioxide (44 g) was added.

(f) The mixture was cooled to 130 ° C and lime (29 10 g) was added at 130 ° C / 2 "Hg. 200 ° C / 10 mm Hg, (g) The mixture was maintained at 165 ° C / 2". Hg for 1 hour.

(h) Lime (22 g) was added at 165 ° C.

(I) The product was stripped at 200 ° C / 30 "Hg.

(j) The product was filtered.

Product weights 20 Crude product: 382 g

Distillate: 230 g

Product composition after filtration 25 calcium 14.0% by weight

Sulfur 1.8% by weight CO 2 12.3% by weight TBN 374 V- ^ oo 176 cSt 30 V40 2826 cSt VI 172

Stearic acid 16.2% by weight

This example shows that rapstop fatty acid can be used in the process of the invention.

I DK 175287 B1 I

i 38 I

In Example 16 I

In Charge I

Sulfurized calcium alkylphenate 230 g I

In 5 lubricating oil (SN 100) 26 g I

I Calcium Chloride 3 g I

In Procedure I

I 10 I

I As in Example 2, except that in I

In step (a) instead of stearic acid (63 g) I was used

In tall oil fatty acid (63 g). IN

I 15 Product weights

I Crude product: 380 g I

I Distillate: 223 g I

I Product composition after filtration I

In Calcium 14.0% by weight I

In Sulfur 2.09% by weight I

In CO 2 9.7 wt% I

I 25 TBN 380 I

I v100 263 cSt I

In Carboxylic Acid Content 16.6% by weight I

I (based on the weight I

I of the product ♦) 'I

I 30 I

This example shows that tall oil fatty acid can

You are used in the process of the invention. IN

DK 175287 B1 39

Example 17

Charge: As in Example 16.

5 Method

As in Example 16 except that instead of tallol fatty acid (63 g), a mixture of 52 g polyisobutyric anhydride (PIBSA) in SN 10 100 lubricating oil (TBN = 60 mg KOH / g) and stearic acid (47 g) was used. .

Produktvagte.

Crude product: 390 g Distillate: 219 g

Product composition after filtration

Calcium 13.1% by weight 20 Sulfur 1.8% by weight CO2 12.5% by weight TBN 260 ^ 100 416 CSt V40 12690 cSt 25 VI 164

Carboxylic acid content 12.1% by weight

Anhydride content 7.2% by weight based on product guard.

30

This example shows that carboxylic acid can be partially replaced by PIBSA by the process of the invention.

DK 175287 B1 I

40 I

Example 18 I

Charge: As in Example 16. I

Method I

As in Example 16, except that 1 I

instead of tall oil fatty acid (63 g) behenic acid I was used

(63 g). IN

10 I

Product weights I

Crude product: 402 g I

Distillate: 247 g I

15 I

Product composition after filtration I

Calcium 12.4% by weight I

Sulfur 1.9% by weight I

CO 2 11.4 wt% I

TBN 354 I

V10Q 141 cSt I

Behenoic acid 15.7% by weight I

This example shows that behenic acid can be used

as the carboxylic acid in the process of invention I

late. IN

Example 19 I

30 - I

Charge As in Example 15 except that in I

instead of rapstop fatty acid (62 g), pal-I was used

mitic acid (56.2 g). IN

41 DK 175287 B1

Method e

As in Example 15, except that steps (f), (g) and (h) were omitted.

5

Product weights Crude product: 312 g

Distillate: 222 g 10

Product composition after filtration

Calcium 11.7% by weight

Sulfur 1.9 wt% 15 CO 2 8.2 wt% TBN 332 v100 70 cS * · V40 831 cSt VI 156 20 Palmitic acid 18.0 wt%

This example shows that palmitic acid can be used in the process of the invention.

Example 20

Charge: As in Example 15.

Method 30

As in Example 15, except that steps (f), (g) and (h) were omitted.

I DK 175287 B1 I

I 42 I

In Product Scales I

In Crude product: 334 g I

I Distillate: 234 g I

I I

Product composition after filtration

In Calcium 11.8% by weight I

In Sulfur 1.8% by weight I

In 10 co2 10.9 wt% I

I TBN 321 I

I v100 168 cSt I

I V40 1009 CSt I

I VI 286 I

In carboxylic acid content 18.6 wt% I

I based on pro- I

In the scales weight. IN

I 20 Comparison Test 2 I

In Charge I

Sulfurized calcium alkylphenate 230 g I

I 25 Lubricating Oil 26 g I

I Calcium Chloride 3 g I

In Procedure I

I 30 - I

In (a) the mixture was heated to 100 ° C and I

In 2-ethyl-hexanol (190 g) was added. IN

In (b) Acetic acid (14 g) was added. IN

(C) The mixture became thick and heterogeneous and assumed a green color. Stirring was ineffective. The reaction was interrupted.

This test is not an example of the invention, but is merely for the purpose of showing that lower carboxylic acids, in this case acetic acid, cannot be used in the process of the invention.

Example 21

Charge As in Example 16 except that instead of the commercially available sulfurized calcium alkylphenate, a non-carbonated commercially available sulfurized calcium (2-alkyl) phenate (145 TBN) was used.

Process 20 As in Example 16, except that the lime amount in step (c) was increased from 66 g to 83 g and the carbon dioxide amount in step (f) was increased from 66 g to 83 g.

25 Product weights Crude product: 421 g

Distillate: 246 g

DK 175287 B1 I

Product composition after filtration I

Calcium 13.7% by weight I

Sulfur 1.9% by weight I

CO 2 10.3 wt% I

TBN 383 I

V100 137 cSt I

V4Q 2119 CSt I

VI 163 I

Carboxylic acid 15.0% by weight I

This example shows that a non-carbonated sulfuric I

straight calcium alkylphenate with low initial TBN can be used

turned to the method of the invention. IN

15 I

Example 22 I

Charge: I

20 Carbonated sulfurated calcium alkyl phenate I

(150 TBN) 230 g I

Stearic acid 40 g I

2-Ethyl-hexanol 90 g I

Calcium chloride 4 g I

25 I

Process I

(a) The mixture was heated from 145 to 165 ° C / 700 l

mm Hg with the addition of ethylene glycol (32 g). IN

(B) The mixture was kept at 165 ° C / 700 mm I for 30 minutes

Hg. IN

(c) CO 2 (38 g) was added at 165 ° C / 1 bar. IN

(d) The mixture was cooled to 120 ° C and I was added

Added 2-ethylhexanol (100 g) and lime (76 g) (e) The mixture was maintained at 165 ° C / 700 mm Hg for 60 minutes.

(f) Carbon dioxide (82 g) was added at 165 ° C / 1 bar.

(G) Solvent was diluted at 200 ° C / 10 mm Hg.

(h) The product was filtered.

Product weight 10 Crude product: 390 g

Product composition after filtration

Calcium 14.4% by weight 15 Sulfur 2.3% by weight CO2 11.6% by weight TBN 402 v100 674 cS

Stearic acid 10.3% by weight 20

This example shows that a sulfurized calcium alkyl phenate with low (150) TBN can be quality improved for a high TBN product.

Example 23

Charge: As in Example 14 except that instead of the sulfurized calcium alkylphenate derived from a mixture of alkyl phenols, a commercially available sulfurized calcium alkylphenate derived from (εΐ2-3 ** γ1) phenol (250 TBN) was used.

I DK 175287 B1 I

I 46 I

In Procedure I

I As in Example 14 except that in step I

In (b) instead of 2-ethyl-hexanol (194 g), iso-I was used

In 5 heptanol (190 g) and in step (d) the ethylene glycol became 1

You added quickly (1 minute 1 minute). IN

In Product weights

I Crude product: 402 g I

I Distillate: 239 g I

Product composition after filtration

Calcium 13.9% by weight I

In Sulfur 1.9% by weight I

In CO 2 12.0 wt% I

I TBN 391 I

I V10Q 313 cSt I

I 20 v40 6700 cSt I

I VI 177 I

In Stearic acid 15.7 wt.% I 1

The filtration rate was fast. IN

This example shows that iso-heptanol can be used

I was used as a solvent in the process of solution I

In the find. IN

Claims (25)

A process for preparing an additive concentrate suitable for incorporation into a finished lubricating oil composition, comprising: 35% by weight based on the weight of the concentrate of at least one carboxylic acid of the formula: R - CH - COOH I (I) R1 wherein R is a (C10 ~ C24) straight chain alkyl group and R1 is hydrogen or an anhydride or ester derivative thereof, which concentrate has a TBN greater than 300 and a viscosity at 100 ° C of less than 1000 mm 2 TBN less than the TBN of the finished additive concentrate, (B) an alkaline earth metal base added either in a cold addition to the initial reactants or as multiple additions at intermediate steps un there the reaction, (C) either a polyhydric alcohol having 2 to 4 carbon atoms, a di- or tri- (C 2 -C 4) glycol, an alkylene glycol alkyl ether or a polyalkylene glycol alkyl ether, ______________. - ______________ __ DK 175287 B1 I 48 I (D) a lubricating oil, I (E) carbodioxide added after the addition or In each addition of component (B), and I (F) sufficient to provide more than 5 to 10 to 35% by weight based on the weight of the concn. - In the funnel of at least one carboxylic acid of the formula: R - CH - COOH I in I The method of claim 1, wherein the lubricating oil I comprises from 10 to 90% by weight of the concentrate. IN A process according to either claim 1 or claim 20, wherein the alkaline earth metal in the lubricating oil-soluble sulfur alkali metal hydrocarbyl phenate is calcium, magnesium or barium. IN The process of claim 3, wherein the alkaline earth metal is calcium. IN A process according to any of the preceding claims wherein the hydrocarbylphenate portion of the oil-soluble sulfurated alkaline earth metal hydrocarbylphenate I is derived from at least one alkylphenol, wherein the alkyl group I or groups of the alkylphenol or phenols contain from 9 to 28 carbon atoms. The process according to claim 5, wherein the hydrocarbyl phenyl moiety is derived from a C 12 alkyl phenol produced by alkylation of phenol with propylene tetramer. In DK 175287 B1 A process according to any one of claims 1 to 6, wherein a mixture of carboxylic acids of formula (I) is incorporated which is a commercial grade containing a number of acids, including both saturated and unsaturated acids. Process according to any one of claims 1 to 6, wherein stearic acid is incorporated. A process according to any one of the preceding claims, wherein the carboxylic acid, anhydride or ester derivative thereof is incorporated into component (b) in an amount in the range of 12 to 24% by weight based on the weight of the concentrate. A method according to any one of the preceding claims, wherein the TBN of the concentrate is greater than 15,350. Is a hydrogen or an anhydride or an ester derivative I thereof, wherein the weight ratios of (A) to (F) I are such that a concentrate of I is prepared. a TBN greater than 300. I The method of claim 10, wherein the TBN of the concentrate is greater than 400. A process according to any one of the preceding claims, wherein the viscosity of the concentrate at 20 DEG C. is less than 750 cSt. The process of claim 12, wherein the viscosity of the concentrate at 100 ° C is less than 500 mm 2 .s-1 (cSt). A process according to any one of the preceding claims, wherein component (B) is lime. A method according to any one of the preceding claims, wherein the weight ratio of component (B) to component (A) is in the range of 0.2 to 5. A process according to any one of the preceding claims, wherein component (C) is ethylene glycol. A process according to any one of claims 1 to 15, wherein component (C) is methyldigol. A process according to any one of the preceding claims wherein carbon dioxide (component E) is added after a single addition of component (B) at the end of the reaction between components (A) to II (D). ) and F). IN A method according to any one of the preceding claims, wherein a diluent is present. I I , 20th A process according to any of the preceding claims wherein sulfur, in addition to that already present in component (A), is added to the reaction mixture. I I 10 A process according to any one of the preceding claims, wherein the reaction is carried out by the presence of a catalyst. IN The process according to claim 21, wherein the catalyst is an inorganic halide. I I 15 The process of claim 22, wherein the catalyst is calcium chloride. IN 24. Additive concentrate suitable for incorporation into II a final lubricating oil, which concentrate can be obtained by reacting at elevated temperature of (A) an II 20 sulfurized alkaline earth metal hydrocarbyl phenate with a TBN II less than the TBN for> the finished additive concentrate, II ( B) an alkaline earth metal base added either in a single II addition or as multiple additions to the introductory reactants at intermediate stages during the reaction; (C) either a polyhydric alcohol having 2 to 4 carbon atoms, a di- or tri- (C 2 -C 4) glycol, an alkylene glycol-alkyl ether or a polyalkylene glycol alkyl ether, (D) II a lubricating oil, (E) carbon dioxide added after the addition or each addition of component (B), and (F) to II sufficient to provide from 10 to 35% by weight II based on the weight of the concentrate of a carboxylic acid II of formula (I) or an acid anhydride or an ester derivative thereof, wherein the weight ratios of components (A) to (F) are such that a concentrate having a TBN greater than 300 and a viscosity at 100 ° C of less than 1000 mm2.s-1 (cSt). i ._ _____ i