JPH0631383B2 - Alkaline earth metal hydrocarbyl phenates, their sulfurized derivatives, their production 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

DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to alkaline earth metal hydrocarbyl phenates.
ates) and their sulfurized derivatives, their manufacture and their use as lubricating oil additives. In particular, the present invention relates to additive concentrates containing alkaline earth metal hydrocarbylphenates and their sulfurized derivatives, having a high total base number (TBN) and an acceptable viscosity, their preparation and their use. It relates to their use as lubricating oil additives.

In an internal combustion engine, by-products from the combustion chamber are often blown off by the piston and mix with the lubricating oil. Many of these by-products form acidic substances within the lubricating oil. This is especially true when diesel engines are run on low quality, high sulfur containing fuels, where combustion produces corrosive acids. As a result, as the acids mixed in the lubricating oil, there are sulfur acids produced by oxidation of sulfur, hydrohalic acids derived from halogen lead promoter in fuel, and nitric acids generated by oxidation of nitrogen in the air in the combustion chamber. Can be mentioned. These acids cause sludge precipitation and corrosion of bearings and engine parts, leading to rapid engine wear and premature failure.

There are metal alkylphenates and sulfurized metal alkylphenates as one of the compounds usually used for neutralizing acidic substances and dissipating sludge in lubricating oil.
Here, the metal is an alkaline earth metal such as calcium, magnesium or barium. Both "regular" and "overbased" alkaline earth alkylphenates have been used. The term "overbased" refers to the valence of the alkaline earth metal part relative to the valence of the phenol part.
It is used to describe alkaline earth metal alkylphenates with a number of equivalents greater than 1, and is typically greater than 1.2 and sometimes 4.5 or greater. In contrast, the ratio of the alkaline earth metal part to the valency of the phenolic part is 1 for "normal" alkaline earth metal alkylphenates. Thus, an "overbased" material contains excess of over 20% of the alkaline earth metal present in the corresponding "normal" material. Because of this, "overbased" alkaline earth metal alkylphenates have a greater ability to neutralize acidic materials than the corresponding "normal" alkaline earth metal alkylphenates.

The prior art teaches numerous methods of making both "normal" and "overbased" metal alkylphenates. One such method for making "overbased" alkylphenates is generally to prepare lubricating oils, hydroxyl compounds and excess alkaline earth metal hydroxides (alkylphenols) in the presence or absence of alkylphenols, sulfur. (Above the stoichiometric ratio required to neutralize) to form an intermediate product, followed by carbonation, heading distillation (to remove unreacted hydroxyl compounds) and filtration. Including “single lime additio
n) ”process. The production of intermediate products is accompanied by a significant increase in viscosity, while the subsequent carbonation reduces the viscosity to a relatively low level. This is undesirable as it is difficult to stir and is detrimental to subsequent reactions, while this increase in viscosity is brought to an acceptable level by incorporating a smaller amount of alkaline earth metal hydroxide during the reaction. It can also be adjusted, but the overbased alkylphenate product necessarily has a reduced ability to neutralize: a product with a high neutralization capacity is reached and at the same time the viscosity of the intermediate product is tolerated. The alkaline earth metal hydroxide in order to adjust it within the limit (usually twice lime addition method, double lime addi
It is also possible to add in three separate reaction steps, followed by a carbonation step. However, this method involves relatively long batch times.
Another alternative method is to use a viscosity reducing agent such as tridecanol, 2-ethylhexanol, or a similar boiling range hydroxyl solvent in the preparation of the intermediate product, but such a solution is Increase raw material costs of the method. The highest total base number
The base number, TBN, expressed in mg KOH / g) is in agreement with the acceptable viscosity and is usually about 300 achieved by the prior art methods, whereas typical prior art TBNs range from 200 to 300. Is. It is clearly a desirable objective to produce an additive concentrate containing an alkaline earth metal alkylphenate or a sulfurized derivative thereof and having a high TBN, ie a TBN of greater than 300, preferably greater than 350. To date, even higher concentrations of alkaline earth metal bases result in highly viscous products that are insoluble rather than "diluted" in subsequent attempts to carbonate with excess carbon dioxide. It has been impossible to obtain products with such high TBN. The present inventor has achieved this object, whereby the number of TBs in excess of 300 and sometimes 350 is exceeded.
N, while having an acceptable viscosity, that is, a viscosity of less than 1,000 cSt at 100 ° C., is not insoluble when mixed in the reaction mixture, and has at least 10 carbon atoms in the molecule. A product having a fixed amount of carboxylic acids or acid derivatives was obtained.

It is not new to use carboxylic acids for the preparation of alkaline earth metal alkylphenates and their sulfurized derivatives or to combine them in lubricating oil compositions, for example US-A-3372116; GB-A. -1440261; US-A-40
See 49560 and EP-A-0094814.

US-A-3372116 discloses (A) hydrocarbon-substituted phenols having at least 6 carbon atoms in the hydrocarbon substituent between about 25 ° C and the reflux temperature, at least 6 carbon atoms of said phenol. A mixture of up to an equivalent amount of a hydrocarbon-substituted succinic acid or anhydride having as a hydrocarbon substituent, or a substantially neutral alkali metal salt or alkaline earth metal salt thereof, or both, and (B)
In producing a basic metal phenate by reacting about 1 to 10 equivalents of calcium or strontium base per equivalent of (A) and (C) carbon dioxide, about 0.00 per equivalent of calcium or strontium base.
An improved process is disclosed which comprises reacting in the presence of 2-0.2 equivalents of a carboxylic acid having up to about 100 carbon atoms, or its alkali metal, alkaline earth metal, zinc or lead salts. Preferred carboxylic acids contain up to about 10 carbon atoms, more preferably 1
Monocarboxylic acids having up to 0 carbon atoms and their alkaline earth metal salts. In many of the examples, water and carboxylate salt are used. The inventor not only wanted to avoid the presence of water, but also found that the carboxylate salt is essentially insoluble in the system and therefore cannot be used in the process of the invention. US-A-3372
The process of 116 does not use enough phenol to produce a phenate with a TBN of greater than 300, based on the proportion of alkaline earth metal base.

GB-A-1440261 is a mixture of a lubricating oil, a detergent or dispersant additive, and at least two carboxylic acids, one of which has a melting point of at least 2.
The number of carbon atoms per molecule at 0 ° C. is 30 or less, the melting point of the other acid is lower than 20 ° C., and the weight ratio of the low melting point acid to the high melting point acid is 1.5: 1 to 8: Disclosed is a lubricating oil composition comprising a mixture such as 1. The detergent can be an overbased phenate and is considered optimal.
To 100 TBN. In the lubricating oil composition, the mixture of acids is present in an amount of 0.05 to 2.0% by weight.

US-A-4049560 describes (a) sulfurized phenols or sulfurized thiophenols having one or more hydrocarbyl substituents, or phenols or thiophenols having one or more hydrocarbyl substituents, Or 15-40% by weight of the phenol or thiophenol having 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 to 15% by weight of glycol, C ₁ to C ₅ monohydroxyalkanol or C ₂ to C ₄ alkoxyalkanol, (d) 2 to 15% by weight of magnesium hydroxide or active magnesium oxide, (e) ) carboxylic acid from _{C 1 C 18,} their anhydrides, or ammonium, salts of amine, C from the _{C 1} At least 0.1 wt% of a metal salt of a metal or Group II Group I of ₈ carboxylic acid, and (f) a diluent oil ((a) and (b) is in components include any ones) of at least 10 wt% The production of an overbased magnesium detergent by a method of introducing carbon dioxide into a reaction mixture containing is disclosed. Carboxylic acid (component
The amount of (e)) preferably ranges from 0.5 to 2.0% by weight. The product produced by the reaction is about 200 to 2
It is said to have a TBN of 50, for example about 225.

EP-A-0094814 describes lubricating oils and 0.1 to 10, preferably 2 to 6% by weight (based on the weight of additive concentrate) of formula (I). (Wherein R is a C ₁₀ to C ₂₄ unbranched alkyl or alkenyl group, and R ¹ is hydrogen, a C ₁ to C ₄ alkyl group or a —CH ₂ —COOH group). Addition to a lubricating oil composition comprising 10 to 90% by weight of an acid or its anhydride or salt thereof and an overbased alkaline earth metal hydrocarbyl sulfurized phenate treated during or after the overbasing step. Disclosed is an additive concentrate for. EP-A-00
The object of the invention of 94814 is to solve the problem faced by many additive concentrates containing overbased additives, namely the problem of precipitation or foaming due to lack of stability. The problem of EP-A-0094814 is T greater than 300
It illustrates the solution of the problems of stability and foaming with a TBN value of less than 300, rather than the problem of producing a phenate additive concentrate having BN and the phenate additive concentrate produced by the method of the invention. That was the challenge.

Conventional techniques using carboxylic acids have a T of over 300.
It can be concluded that the problem of producing an additive concentrate containing BN and an overbased alkaline earth metal hydrocarbyl phenate having an acceptable viscosity is not addressed.

Accordingly, one aspect of the present invention is to provide an additive concentrate suitable for incorporation into a final lubricating oil composition, the additive concentrate comprising an additive concentrate for a final lubricating oil composition. Where (a) lubricating oil, (b) (i) formula (I) (Wherein R is a C ₁₀ to C ₂₄ alkyl or alkenyl group, and R ¹ is hydrogen, a C ₁ to C ₄ alkyl group, or a CH ₂ —COOH group). An acid, or an anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an anhydride thereof,
Alternatively, either an ester or an ester is reacted at a ratio of more than 2% by weight and less than 40% by weight with respect to the weight of the concentrate, and is modified by incorporating it. An additive concentrate containing an earth metal hydrocarbyl phenate, having a TBN of more than 300 and a viscosity at 100 ° C. of less than 1000 cSt.

Component (a) of the additive concentrate is a lubricating oil. The lubricating oil is preferably animal oil, vegetable oil or mineral oil. The lubricating oil is preferably a petroleum-derived lubricating oil such as naphthene oil, paraffin oil or mixed base crude oil. Solvent neutral oils are particularly suitable. Alternatively, the lubricating oil may be a synthetic lubricating oil. Synthetic lubricating oils preferably include synthetic ester lubricating oils, which include diesters such as di-octyl adipate, di-octyl sebacate and tridecyl adipate, or liquid polyisobutenes and poly-alpha olefins. Mention may be made of polyhydrocarbon lubricating oils such as classes. Suitably, the lubricating oil comprises 10 to 90% by weight, preferably 10 to 70% by weight, based on the composition.

Component (b) is soluble in a lubricating oil and is sulfurized by being modified by incorporating more than 2 and less than 40% by weight of either (i) or (ii) with respect to the weight of the additive concentrate. Alternatively, it is a non-sulfurized, preferably sulfurized, alkaline earth metal hydrocarbylphenate. The alkaline earth metal is preferably strontium, calcium, magnesium or barium, preferably calcium, barium or magnesium, more preferably calcium. The hydrocarbylphenate portion of the alkaline earth metal hydrocarbylphenate is preferably derived from at least one alkylphenol. The alkyl group of the alkylphenol may be branched or unbranched. Suitable alkyl groups contain 4 to 50, preferably 9 to 28 carbon atoms. A particularly suitable alkylphenol is a C ₁₂ -alkylphenol obtained by alkylating phenel with propylene tetramer.

The alkaline earth metal hydrocarbyl phenate is
It is modified by incorporating (i) or (ii). With regard to (i), this is at least one carboxylic acid having formula (I), or an acid anhydride, acid chloride or ester thereof. R in formula (I) is preferably an unbranched alkyl or alkenyl group. Preferred acids of formula (I) are those where R is C ₁₀ to C ₂₄ , more preferably a C ₁₈ to C ₂₄ straight chain alkyl group, and R ¹ is hydrogen. Suitable examples of the saturated carboxylic acid of the formula (I) include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and lignoceric acid. Preferable examples of the unsaturated acid of the formula (I) include laurolenic acid, myristolenic acid, palmitoleic acid, oleic acid, gadolenic acid, eric acid, ricinoleic acid, linoleic acid and linolenic acid. A mixture of acids,
For example, rape top fatty acid
Classes can also be used. A particularly suitable acid mixture is a commercial grade containing a range of acids, including both saturated and unsaturated acids. Such mixtures can be obtained synthetically, or with cotton oil,
Edible root nut oil, coconut oil, flaxseed oil,
It is derived from natural products such as palm keinel oil, olive oil, corn oil, coconut oil, castor oil, soybean oil, sunflower oil, herring oil, sardine oil, and beef tallow. Sulfuric acids and acid mixtures can also be used. Instead of or in addition to the carboxylic acid, an acid anhydride, acid chloride, or ester derivative of the acid, preferably an acid anhydride can be used. However, it is preferable to use a carboxylic acid or a mixture of carboxylic acids. The preferred carboxylic acid of formula (I) is stearic acid.

Alternatively to or in addition to (i), the alkaline earth metal hydrocarbyl phenate can be modified by the mixing of (ii), which comprises a di- or poly-carbon containing from 36 to 100 carbon atoms. Carboxylic acid, or an acid anhydride thereof, or an ester derivative, preferably an acid anhydride thereof. Preferred is (ii) polyisobutene succinic acid or polyisobutene succinic anhydride.

Preferably, the carboxylic acid (s) represented by formula (I),
The di- or polycarboxylic acid, or its acid anhydride or ester is more than 10 to 3% by weight of the composition.
Up to 5% by weight, more preferably 12 to 20% by weight,
For example, it is mixed in an amount of about 16% by weight. The advantage of mixing more than 10% carboxylic acid or its derivatives is usually to give a relatively low thickener viscosity.

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

The alkaline earth metal hydrocarbyl phenate may be sulfurized or non-sulfurized, and is preferably sulfurized.

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

Suitably, carbon dioxide is present in the additive concentrate in an amount of 5 to 20, preferably 9 to 15, based on the weight of the additive concentrate.
It can be present in an amount in the range of weight percent.

Preferably the TBN of the additive concentrate is greater than 350, more preferably greater than 400.

The additive concentrate has a viscosity of 1000 cSt measured at 100 ° C.
It is preferred to have a viscosity of less than 500, preferably less than 500 cSt.

In another aspect, the present invention provides an additive concentrate suitable for incorporation into a finished lubricating oil, which concentrate (A) (i) hydrocarbylphenol or (ii) at elevated temperature.
i) Hydrocarbyl phenol or sulfur,
(B) an alkaline earth metal base added either in a single addition or in multiple additions at an intermediate point during the reaction,
(C) Polyhydric alcohol having 2 to 4 carbon atoms, di- or tri- (C ₂ to C ₄ ) glycol, alkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D) lubricating oil, ( E) carbon dioxide added after single addition or each addition of component (B), and (F) a sufficient amount of (i) to be more than 2 and less than 40% by weight with respect to the weight of the concentrate. ) Reacting a carboxylic acid having formula (I), or an acid anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an acid anhydride or ester thereof. The weight proportions of components (A) to (F) obtained according to the invention are such that a concentrate with a TBN of more than 300 is produced.

In yet another aspect, the present invention provides a method for producing an additive concentrate incorporated in a final lubricating oil, which method comprises reacting the above-mentioned components (A) to (F) at elevated temperature. The weight proportions of components (A) to (F) are such that a concentrate with a TBN of more than 300 is produced.

Component (A) of the reaction mixture is either (i) hydrocarbyl phenol or (ii) hydrocarbyl phenol and sulfur. If the components (A) (i) are used,
The product is an alkaline earth metal hydrocarbyl phenate, and if component (A) (ii) is used, the product is a sulfurized alkaline earth metal hydrocarbyl phenate. The hydrocarbylphenol used is an alkylphenol from which the preferred hydrocarbylphenate moiety described above is derived.

The alkaline earth metal base (component B) is preferably an alkaline earth metal oxide or hydroxide, preferably a hydroxide. For example, calcium hydroxide can be added, for example, in the form of slaked lime. Preferred alkaline earth metals are calcium, magnesium and barium, more preferably calcium. The alkaline earth metal base should be added in an amount sufficient to produce a product having a TBN in excess of 300, preferably in excess of 350, in proportion to component (A). This amount will depend on various factors, including the nature of the sulfurized alkylphenol, but will be higher than the amounts commonly used in prior art methods. Typically, component (B) relative to component (A)
The weight ratio of is suitably from 0.2 to 50, preferably from 0.4 to 10. The alkaline earth metal base (B) may be added in total to the original reactants, or a portion may be added to the original reactants with the remainder being one or more portions, followed by subsequent additions in the process. It can also be added in steps or in several steps. TB over 350
In order to produce N and an additive concentrate having a viscosity below 1000 cSt at 100 ° C., component (B) is added at least twice, preferably in more additions and component (F) is added. 10% by weight, based on the weight of the concentrated product
It is particularly preferable to add it in an amount of over.

Component (C) is either a polyhydric alcohol having 2 to 4 carbon atoms, a di- or tri- (C ₂ -C ₄ ) glycol alkyl ether. The polyhydric alcohol is preferably a dihydric alcohol such as ethylene glycol or propylene glycol, or a trihydric alcohol such as glycerol. The di - or tri - glycol (a C ₂ to C ₄₎ is preferably either a diethylene or triethylene glycol. The alkylene glycol alkyl ether or polyalkylene glycol alkyl ether has the formula (II) R (OR ¹ ) _x OR ² ... (II) (wherein R is a C ₁ to C ₆ alkyl group, and R ¹ is The alkylene group, R ² is hydrogen or C ₁ to C ₆ alkyl, and x is an integer in the range of 1 to 6). Suitable solvents having formula (II) include monomethyl or dimethyl ethers of ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol. Particularly suitable solvents are Mechirujigoru _{(CH 3 OCH 2 CH 2 OCH} 2 CH 2 OH).
Mixtures of glycols of formula (II) and glycol ethers can also be used. In order to use the glycol or glycol ether of the formula (II) as a solvent, an inorganic halide such as ammonium chloride and a carboxylic acid such as acetic acid, which is lower, that is, C ₁ to C ₄ , are used in combination therewith. Preferably component (C) is either ethylene glycol or methyldigol, the latter being a combination with ammonium chloride and acetic acid.

Component (D) is a lubricating oil as described above for additive concentrates.

Component (E) is carbon dioxide, which can be added in the form of a gas or solid, preferably in gaseous form. Bubbling through the reaction mixture is preferred in the gas state.
The present inventor has found that generally, as the concentration of the component (F) increases, the amount of carbon dioxide mixed in increases. To produce a concentrate having a TBN of greater than about 350, it is preferred to add carbon dioxide sequentially after each of the two, or preferably multiple, additions of component (B).

Component (F) is a carboxylic acid of formula (I), a di- or polycarboxylic acid containing from 36 to 100 carbon atoms, or an acid anhydride, acid chloride or ester thereof, as described above for the additive concentrate composition. . The abovementioned amounts required to be more than 2 and less than 40% by weight, based on the weight of the concentrate, are the amounts desired in the concentrate as the first approximation. To calculate this amount, for example, the disappearance of water from the carboxylic acid should be allowed.

The reaction can be carried out in the presence of a diluent. Suitable diluents are volatile liquids which are compatible with the operation of the process, that is to say they can be easily removed from the reaction mixture at the end of the reaction. Suitable diluents may include 2-ethylhexanol, iso-octanol, iso-peptanol and tri-decanol.

The reaction is preferably carried out in the presence of a component which serves as a catalyst for the reaction. As the catalyst, an inorganic halide which is preferably any of hydrogen halide, ammonium halide and metal halide can be used. Suitably the metal part of the metal halide is zinc, aluminum or an alkaline earth metal, preferably calcium. Of the halides, chloride is preferred. Suitable catalysts may include hydrogen chloride, calcium chloride, ammonium chloride, aluminum chloride and zinc chloride, preferably calcium chloride. The amount of catalyst used is preferably up to 2.0% (weight / weight).

The reaction of components (A)-(F) and the carbonation reaction are preferably carried out at elevated temperatures in the range of 120 to 200, preferably about 130 to 165 ° C, although the reaction of components (A)-(F) , And the actual temperature selected for carbonation may vary if desired. The pressure can be atmospheric pressure, reduced pressure, or increased pressure.

The concentrate may be recovered by conventional methods, for example by separating component (C) and diluent (if any) by distillation.

Finally, it is preferred to filter the concentrate thus obtained. In general, the method of the present invention produces a concentrate having an acceptable viscosity, ie less than 1000 cSt at 100 ° C, and 750 or 5 at 100 ° C.
It is possible to produce concentrates with viscosities less than 00 cSt. Moreover, the concentrates generally have favorable viscosity index properties. Such viscosity characteristics are advantageous because they facilitate the process of the concentrate, including filtration. However, generally at high TBN levels, 100 at 100 ° C
It is also possible to produce concentrates with viscosities above 0 cSt. There is a problem in filtering such concentrates, but this can be solved by adding a diluent prior to filtration and removing the diluent after filtration. On the other hand, for example, 10
It has a viscosity of more than 1000 cSt at 0 ° C., for example 35
A highly viscous concentrate that also has a high TBN, such as greater than 0, can be maintained at a TBN of greater than 300 while still being diluted with lubricating oil, which facilitates filtration.

As a final aspect, the present invention provides a final lubricating oil composition, which comprises a lubricating oil and a TBN of 0.5 to 120.
Sufficient amount of the above-mentioned additive concentrate is included so as to be within the range.

Preferably the final lubricating oil composition has a TBN of 0.5 to 10
Sufficient amount of the additive concentrate is included so as to be in the range of 0.

The amount of additive concentrate present in the final lubricating oil depends on the type of final use. Therefore, marine lubricants (marine
For lubricating oil), the amount of additive concentrate present is
TBN is an amount sufficient to be in the range of 9 to 100, and in the case of automobile engine lubricating oil, the amount is preferably TB
It is preferable that the amount of N is in the range of 4 to 20.

The final lubricating oil comprises one or more other types of conventional lubricating oil additives such as viscosity index improvers, antiwear agents, antioxidants, dispersants, rust inhibitors, pour point depressants, etc. Can be included in the final lubricating oil composition either directly or via the concentrate composition.

In addition to their use as additives incorporated into lubricating oils, the additive concentrates of the present invention may also find application as fuel additives.

Now, the present invention will be described in more detail with reference to the following examples.

The word "TBN" is used in all examples. TBN is AST
It is the total number of bases expressed in mgKOH / g when measured by the method of MD2896.

The viscosity was measured by the method of ASTM D445.

In all examples except where otherwise stated, commercial product C in which phenol was alkylated with propylene tetramer
₁₂ -alkylphenol was used.

Example 1 Filling amount: C ₁₂ -Alkylphenol: 75 g Lubricating oil (100 SN): 131 g Lime: 82 g Sulfur: 23 g Stearic acid: 70 g Calcium chloride: 4 g 2-Ethylhexanol: 112 g Method (a) The filling material is 145- Ethylene glycol (36 g) was added while heating to 165 ° C./700 mmHg, (b) the mixture was heated at 165 ° C./700 mmHg for 1 hour, and (c) carbon dioxide (40 g) was added at 165 ° C./1 bar. d) cooling the mixture to 12.5 ° C / 700 mmHg, (e) adding lime (35 g) at 125 ° C / 700 mmHg, (f) heating the mixture at 165 ° C / 700 mmHg for 1 hour, and (g) carbon dioxide ( 20 g) was added at 165 ° C./1 bar, (h) the product was then freed from the solvent at 200 ° C./10 mmHg and (i) the product was filtered. The filtration rate was fast.

Product weight Crude product: 436 g Distillate: 169 g Product composition after filtration Calcium: 14.1% w / w Sulfur: 2.9% w / w CO ₂ : 12.4% w / w TBN: 396 V ₁₀₀ : 308 cSt BPHV 150 : 1 stearic acid: 16.1% w / w This example illustrates that a high TBN additive concentrate of acceptable viscosity can be produced by the "double lime addition" process according to the present invention.

Example 2 Filling amount: Same as Example 1, except that the amount of lime in the filling was increased from 82 g to 117 g corresponding to the total amount of lime added in Example 1 twice.

Method As in Example 1 except that the amount of carbon dioxide added in step (c) was increased from 40 g to 60 g and steps (d), (e), (f) and (g) were omitted. Is. The filtration rate in the final step was slow.

Product weight Crude product: 514 g Product composition after filtration Calcium: 14.1% w / w Sulfur: 3.0% w / w CO ₂ : 12.3% w / w TBN: 390 V ₁₀₀ : 7600 cSt Stearic acid: 13.6% w / w This example shows that an added thickener phenate with high TBN can be produced by a single lime addition process, but under the conditions of the example, the product viscosity is not acceptable for commercial operation unless diluted with lubricating oil. It is a thing.

Example 3 Filling amount: The same as in Example 1.

In the step (g), the amount of carbon dioxide is increased from 20 g to 40 g,
And as in Example 1, except that the following steps are added after step (g) and before steps (h) and (i): (j) cooling the mixture to 120 ° C., (k) Lime (35 g) was added at 120 ° C., (l) the mixture was heated at 165 ° C./700 mmHg, and (m) carbon dioxide (50 g) was added to the mixture.

Product weight Crude product: 484 g Distillate: 169 g Product composition after filtration Calcium: 15.8% w / w Sulfur: 2.6% w / w CO ₂ : 15.0% w / w TBN: 439 V ₁₀₀ : 506 cSt stearic acid Example: 14.5% w / w This example demonstrates that a high TBN additive concentrate can be produced by the method of the present invention with three lime additions.

Example 4 Filling amount: The same as Example 1 except that the amount of lubricating oil was reduced from 131 g to 158 g and the amount of stearic acid was reduced from 70 g to 43 g.

Method Same as Example 1 except that the mixture was cooled to 135 ° C instead of 125 ° C in step (d).

Product weight Crude product: 442 g Distillation product: 155 g Product composition after filtration Calcium: 14.1% w / w Sulfur: 2.9% w / w CO ₂ : 11.9% w / w TBN: 393 V ₁₀₀ : 3440 cSt stearin Acid: 9.8% w / w This example shows that the acid content is 1 by comparing with Example 1.
High TBN products can be produced below 0% w / w,
It was demonstrated that the viscosity of the product was high.

Example 5 Filler: C ₁₂ -Alkylphenol: 35.3 g Lubricating oil (SN 100): 131 g Sulfur: 14.7 g Calcium chloride: 4.0 g Stearic acid: 109.1 g 2-Ethylhexanol: 224 g Method (a) The mixture Heat to 120 ° C, add (b) lime (82g) under reduced pressure at 120 ° C / 2 inch Hg, and (c) ethylene glycol (36g) at 145-165 ° C.
1/2 inch Hg, (d) the mixture is left at 165 ° C./2 inch Hg for 1 hour, (e) carbon dioxide (40 g) is added, (f) the mixture is cooled to 130 ° C., and lime is added. (35g)
At 130 ° C./2 inch Hg, (g) the mixture was left at 165 ° C./2 inch Hg for 1 hour, (h) carbon dioxide (20 g) was added at 165 ° C., and (i) 200 from the product. The solvent was removed at 30 ° C./30 inches Hg and (j) the product was filtered.

Product weight Crude product: 397 g Distillation product: 245 g Product composition after filtration Calcium: 13.6% w / w Sulfur: 1.2% w / w CO ₂ : 13.9% w / w TBN: 376 V ₁₀₀ : 142 cSt V ₄₀ : 1881 cSt VI: 180 Carboxylic Acid: 27.5% w / w This example shows that a high TBN product with an acceptable viscosity gives stearic acid 27.5% w / w based on the weight of the final product.
It was shown concretely that it can be obtained by adding and using w.

Example 6 loading: C _{12 -} reduced to 15.6g amount of the alkylphenol from 35.3 g, and with the exception that increasing the amount of stearic acid from 109.1g to 128.7 g, the same as in Example 5.

Method The same as in Example 5.

Product weight Crude product: 416 g Distillation product: 242 g Product composition after filtration Calcium: 14.5% w / w Sulfur: 1.0% w / w CO ₂ : 13.6% w / w TBN (mg KOH / g): 395 V ₁₀₀ : 255 cSt V ₄₀ : 3100 cSt VI: 221 Stearic acid: 30.9% w / w In this example, the high TBN product had a stearic acid content of 30.9.
It was shown concretely that it can be obtained by% w / w.

Examples 7 to 13 Filling amount: As shown in the table.

Method (a) A mixture of alkylphenol, lubricating oil, calcium chloride, stearic acid and 2-ethylhexanol was added to 12
Heat to 0 ℃ / 700mmHg, (b) Add lime at 120 ℃ / 700mmHg, (c) Add ethylene glycol from 145 to 165 ℃ / 700m
mHg and add the mixture at 165 ° C / 700 mmHg 1
After standing for a period of time, (d) carbon dioxide was added at 165 ° C / 1 bar, (e) solvent was recovered at 200 ° C / 10 mmHg, and (f) the product was filtered.

As shown in the product weight table.

The product composition after filtration is as shown in the table.

This example demonstrates that additive concentrates with TBN greater than 300 have a stearic acid content range of 2.6% by weight concentrate.
It was shown concretely that it can be manufactured by the single lime addition method in the whole range from 1 to 29.7% w / w.

Example 14 Filling amount: C ₁₂ -Alkylphenol: 64 g Lubricating oil (SN 100): 111 g Sulfur: 20 g Stearic acid: 59 g Calcium chloride: 4 g 2-Ethylhexanol: 190 g Method (a) The filling material at 120 ° C / 700 mmHg. Heat, (b) add lime (70 g), (c) add ethylene glycol (32 g) while heating the mixture from 145 ° C to 165 ° C / 700 mmHg, (d) add 165 ° C / 700 mmHg to the mixture. Left for 5 minutes, (e) carbon dioxide (44 g) is added at 165 ° C./1 bar, (f) the mixture is cooled to 120 ° C. and lime (60 g)
(G) the mixture is left at 165 ° C / 700mmHg for 5 minutes, (h) carbon dioxide (44g) is added at 165 ° C / 1 bar, and (i) solvent is removed from the product at 200 ° C / 10mmHg. Recovered and (j) the product was filtered.

Product weight Crude product: 408 g Distillation product: 245 g Product composition after filtration Calcium: 16.0% w / w Sulfur: 2.6% w / w CO ₂ : 14.6% w / w TBN: 450 V ₁₀₀ : 488 cSt stearin Acid: 14.5% w / w This example demonstrates that an additive concentrate having a TBN as high as 450 and having an acceptable viscosity can be prepared by the method of the present invention.

Example 15 Filling amount: C ₁₂ -Alkylphenol: 64 g Lubricating oil (SN 100): 111 g Sulfur: 20 g Stearic acid: 59 g Acetic acid: 2 g Ammonium chloride: 3 g Methyldiglycol: 40 g Method (a) The filling material is 120 ° C. / Heat at 100 mmHg, (b) Add lime (70 g), (c) Add dimethyldiglycol (90 g) while heating the mixture from 145 ° C to 165 ° C / 700 mmHg, and (d) add 165 ° C to the mixture. / 700 mmHg for 1 hour, (e) carbon dioxide (34 g) was added, (f) the mixture was cooled to 120 ° C., and lime (30 g)
(G) the mixture is left at 165 ° C./700 mmHg for 1 hour, (h) carbon dioxide (17 g) is added, (i) the solvent is removed at 200 ° C./10 mmHg and recovered, and (j) The product was filtered.

Product weight Crude product: 361 g Distillation product: 146 g Product composition after filtration Calcium: 14.1% w / w Sulfur: 2.7% w / w CO ₂ : 12.4% w / w TBN: 394 V ₁₀₀ : 164 cSt stearin Acid: 16.3% w / w This example illustrates that methyldiglycol can be used as component (C) and ammonium chloride can be used as a catalyst in the process of the invention.

Example 16 _{loading: C 12} - alkyl phenol: 64 g Lubricating oil _{(SN 100): 73g C 18} - linear alpha - olefin: 38 g Sulfur: 23 g Stearic acid: 59 g Calcium chloride: 3 g 2-ethyl hexanol: 190 g process step ( C) using ethylene glycol (31 g) instead of methyl glycol (90 g), and step (d) and
Similar to Example 15 except that (g) left the mixture at 165 ° C./700 mmHg for 10 minutes instead of 1 hour.

Product weight Crude product: 373 g Distillation product: 239 g Product composition after filtration Calcium: 14.4% w / w Sulfur: 2.3% w / w CO ₂ : 13.3% w / w TBN: 405 V ₁₀₀ : 460 cSt stearin Acid: 15.8% w / w This example illustrates that long carbon chain alpha-olefins can be mixed during the reaction.

Example 17 The same as Example 16 except that polyisobutene (38 g) having an Mn of 500 was used instead of the C ₁₈ -alpha-olefin (38 g).

Method As in Example 16.

Product weight Crude product: 363 g Distillation product: 246 g Product composition after filtration Calcium: 14.3% w / w Sulfur: 2.8% w / w CO ₂ : 13.8% w / w TBN: 406 V ₁₀₀ : 697 cSt V ₄₀ : 26,600 cSt VI: 175 stearic acid: 16.3% w / w This example illustrates that polyisobutene can be mixed during the reaction.

Example 18 Filling amount: C ₁₂ -Alkylphenol: 55.2 g Lubricating oil (SN 100): 131 g Sulfur: 23 g Calcium chloride: 4 g Tallow Fally Acid: 89.8 g 2-Ethylhexanol: 112 g Method step (f), Same as Example 5 except that (g) and (h) are omitted, that is, a single lime addition method is adopted.

Product weight crude product: 396 g of distilled product: product composition calcium after 151g filtration: 10.8% w / w _{Sulfur: 3.1% w / w CO 2} : 11.3% w / w TBN: 305 V 100: 388 cSt V ₄₀ : 20,000 cSt VI: 101 Carboxylic acid: 22.7% w / w This example demonstrated that a high TBN-containing concentrate can be obtained using tallow fatty acid.

Comparative Example Filling amount: C ₁₂ -Alkylphenol: 75 g Lubricating oil (SN 100): 131 g Sulfur: 23 g Calcium chloride: 4 g Acetic acid: 15 g 2-Ethylhexanol: 112 g Method Same as (a)-(d) of Example 5. is there. The mixture then became a thick, heterogeneous mass. Agitation was not effective and the mixture gelled on cooling. The reaction was not continued.

This comparative example specifically showed that acetic acid cannot be used in the method of the present invention.

Example 19 Filling amount: C ₁₂ -Alkylphenol: 135 g Lubricating oil (SN 100): 131 g Lime: 82 g Sulfur: 23 g Stearic acid: 10 g Calcium chloride: 4 g Method (a) The filling is heated to 145 ° C./700 mmHg, Iso-
Octanol (112g) was added, (b) the mixture was heated from 145 ° C to 165 ° C / 700mmHg, and ethylene glycol (36g) was added, and (c) the mixture was left at 165 ° C / 700mmHg for 1 hour. , (D) carbon dioxide (28 g) was added at 165 ° C / 1 bar, (e) solvent was removed at 210 ° C / 10 mmHg to recover, and (f) the product was filtered.

Product weight Crude product: 380 g Distillation product: 144 g Product composition after filtration Calcium: 10.8% w / w Sulfur: 3.6% w / w CO ₂ : 6.0% w / w TBN: 301 V ₁₀₀ : 216 cSt stearin Acid: 2.6% w / w

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C10M 125: 00 125: 06 125: 10 129: 08 129: 10 129: 16 129: 40 129: 42 129: 70 129: 93 129: 95 145: 24) C10N 10:04 20:00 Z 8217-4H 20:02 30:02 40:25 70:00 (72) Inventor Crawford John UK Surrey C3 36 BIA Chi Ke Talam Rocksford Road 13 Southcott (No Address) (72) Inventor O'Corner Sean Patrick UK North Humberside Beverly Saint Martins Court 31 (56) Reference JP 59-25343 (JP, A) US Patent 4328111 (US, A)

Claims (30)

[Claims] 1. An additive concentrate for a final lubricating oil composition comprising: (a) a lubricating oil; (b) (i) a formula (I). (Wherein R is a C ₁₀ to C ₂₄ alkyl or alkenyl group, and R ¹ is hydrogen, a C ₁ to C ₄ alkyl group, or a CH ₂ —COOH group). An acid, or an anhydride or ester thereof, or (ii) a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an anhydride thereof,
Alternatively, either an ester or an ester is reacted at a ratio of more than 2% by weight and less than 40% by weight with respect to the weight of the concentrate, and is modified by incorporating it. An additive concentrate containing an earth metal hydrocarbyl phenate, having a TBN of more than 300 and a viscosity at 100 ° C. of less than 1000 cSt. 2. The additive concentrate according to claim 1, wherein the lubricating oil is included in an amount of 10 to 90% by weight of the concentrate. 3. The alkaline earth metal hydrocarbylphenate soluble in a lubricating oil, wherein the alkaline earth metal is calcium, magnesium, or barium. Additive concentrate. 4. The additive concentrate according to claim 3, wherein the alkaline earth metal is calcium. 5. The alkaline earth metal hydrocarbyl phenate is a sulfurized alkaline earth metal hydrocarbyl phenate, according to any one of claims 1 to 4.
Additive concentrate according to paragraph. 6. The hydrocarbylphenate moiety of the alkaline earth metal hydrocarbylphenate is derived from at least one alkylphenol, and the alkylphenol or the alkyl group or groups of the phenol has 9 to 28 carbon atoms. The additive concentrate according to any one of claims 1 to 5, which comprises: 7. A hydrocarbyl phenate portion obtained by alkylating phenol with propylene tetramer, C
Claim 5 from ₁₂ -alkylphenol
The additive concentrate according to the item. 8. At least one having the formula (I), wherein R is an unbranched alkyl or alkenyl group.
The additive concentrate according to any one of claims 1 to 7, wherein the carboxylic acid is mixed. 9. A carboxylic acid of formula (I) wherein R is C
₁₀ is a linear alkyl group of C _24, and R ¹ is hydrogen, the additive concentrate ranges eighth claim of claim. 10. Additive according to any one of claims 1 to 7, which is admixed with a mixture of carboxylic acids of the formula (I) containing both saturated and unsaturated acids. Concentrate. 11. The additive concentrate according to claim 1, which is mixed with stearic acid. 12. A di- or polycarboxylic acid containing 36 to 100 carbon atoms or its anhydride is mixed,
The additive concentrate according to any one of claims 1 to 7. 13. The additive concentrate according to claim 12, which is mixed with either polyisobutene succinic acid or polyisobutene succinic anhydride. 14. A composition according to claim 1, wherein either component (b) (i) or component (b) (ii) is incorporated in an amount of more than 10 and up to 35% by weight, based on the weight of the concentrate. Item 1 to 1
Item 4. The additive concentrate according to any one of items 3. 15. The method according to claim 14, wherein component (b) (i) or (b) (ii) is incorporated in an amount in the range of 12 to 20% by weight, based on the weight of the concentrate. Additive concentrate. 16. The additive concentrate according to claim 1, wherein the composition has a TBN of more than 350. 17. The additive concentrate according to claim 15, wherein the composition has a TBN of more than 400. 18. The method according to any one of claims 1 to 17, wherein the viscosity at 100 ° C. is less than 500 cSt.
Additive concentrate according to paragraph. 19. At high temperature, either (A) (i) hydrocarbylphenol or (ii) hydrocarbylphenol and sulfur, (B) single addition, or multiple times at an intermediate point in the middle of the reaction. Alkaline earth metal bases added by any of the additions, (C) polyhydric alcohols having 2 to 4 carbon atoms, di- or tri- (C ₂ to C ₄ ).
Glycol, any of alkylene glycol alkyl ether or polyalkylene glycol alkyl ether, (D) lubricating oil, (E) component (B) added once or carbon dioxide added subsequently to each addition,
And (F) a sufficient amount of (i) a carboxylic acid having the following formula (I) or an acid anhydride or ester thereof so as to be more than 2% by weight and less than 40% by weight based on the weight of the concentrate.
Or (ii) reacting a di- or polycarboxylic acid containing 36 to 100 carbon atoms, or an acid anhydride or ester thereof, with components (A) to (F)
A method for making a final additive concentrate for a lubricating oil composition, wherein the weight ratio is such that a concentrate having a TBN of greater than 300 is produced. (Wherein R is a C ₁₀ to C ₂₄ alkyl or alkenyl group, and R ¹ is hydrogen, a C ₁ to C ₄ alkyl group or a CH ₂ —COOH group). 20. The method according to claim 19, wherein the component (B) is lime. 21. The method according to claim 19 or 20, wherein the weight ratio of component (B) to component (A) is in the range of 0.4 to 10. 22. The method according to any one of claims 19 to 21, wherein the component (C) is ethylene glycol. 23. The method according to any one of claims 19 to 21, wherein the component (C) is methyldigol. 24. Carbon dioxide (component E) is added subsequent to the addition of two or more components (B).
Item 24. The method according to any one of items 23 to 23. 25. The method according to any one of claims 19 to 24, wherein a diluent is present. 26. The method according to any one of claims 19 to 25, wherein the reaction is carried out in the presence of a catalyst. 27. The method of claim 26, wherein the catalyst is calcium chloride. 28. A lubricating oil and additive concentrate suitable for incorporation into the final lubricating oil composition, comprising: (a) a lubricating oil, (b) (i) a formula (I). (Wherein R is a C ₁₀ to C ₂₄ alkyl or alkenyl group, and R ¹ is hydrogen, a C ₁ to C ₄ alkyl group, or a CH ₂ —COOH group). 2% by weight, based on the weight of the concentrate, of an acid, an anhydride or an ester thereof, or (ii) a di- or polycarboxylic acid containing 36 to 100 carbon atoms, an anhydride or an ester thereof.
Of the alkaline earth metal hydrocarbyl phenate, which is soluble in lubricating oil and is sulfurized or non-sulfurized, which is modified by being mixed in a proportion of more than 40% by weight and less than 40% by weight, and has a TBN of more than 300 and 100 Additive concentrates with viscosities less than 1000 at 0.degree.
A final lubricating oil composition comprising an amount sufficient to range from 5 to 120. 29. The final lubricating oil composition of claim 28, wherein the lubricating oil is a marine lubricating oil and the additive concentrate is present in an amount sufficient to provide a TBN in the range of 9 to 100. object. 30. The final lubricating oil according to claim 28, wherein the lubricating oil is an automotive lubricating oil and the additive concentrate is present in an amount sufficient to bring the TBN in the range of 4 to 20. Composition.