SE463770B - LUBRICAN OIL ADDITION CONTAINING A COMPLEX OF A BORED ALKYL CATACOL AND AN ALKYL OR ALKENYL SUCCINIMIDE, LUBRIC OIL COMPOSITION CONTAINING THIS ADDITION AND THE USE OF THE COMPOSITION COMPOSITION COMPOSITION - Google Patents

Description

2 (Tx a] 1% of the present invention relates to lubricating oil additive comprising a complex prepared by reacting a drilled alkyl catechol and an oil-soluble alkyl or alkenyl succinimide, wherein the weight ratio of alkyl or the alkenyl succinimide of the borated alkyl catechol ranges from 3: 1 to 16: 1.

Thus, in one aspect, the present invention further relates to a lubricating oil composition comprising an oil having a lubricating viscosity and from 0.5 to 20% by weight, based on the total lubricating oil composition, of a complex prepared by reacting (a) a borated alkyl catechol and ( b) an oil-soluble alkyl or alkenyl mono- or bis-succinimide, wherein the weight percent ratio of the alkyl or alkaenyl succinimide to the borated alkyl catechol ranges from 3: 1 to 16: 1.

Other additives may also be present in the lubricating oil to obtain a proper balance of properties, such as dispersibility, corrosion, abrasion and oxidative inhibition, which are critical to the proper operation of an internal combustion engine.

In yet another aspect of the present invention, there is provided the use of the lubricating oil composition to reduce the fuel consumption of an internal combustion engine by treating the moving surfaces thereof with the lubricating oil composition described above. Specifically, improvements in fuel per mile from 1% to 2% can be obtained by using the composition of the present invention. This fuel economy improvement can be obtained in both compression-ignition engines, i.e. diesel engines, and spark ignition engines, i.e. gasoline engines.

In addition, lubricating oil compositions containing the borated alkyl catechol-succinimide complex of the present invention have been found to have antioxidant properties and, when used in diesel engines, prevent diesel deposition.

The complex between borated alkyl catechol and alkenyl or alkyl succinimide can be prepared in situ. That is, when borated alkyl catechol and a sufficient amount of alkenyl or alkyl succinimide to stabilize the borated alkyl catechol against hydrolysis are added to the lubricating oil, the complex is formed in situ.

In this aspect, the present invention relates to a lubricating oil composition comprising an oil having a lubricating viscosity and an effective amount to reduce friction of a borated alkyl catechol and an effective amount of alkyl succinimide to stabilize it. brushed the alkyl catechol against hydrolysis.

When the lubricating oil is used in this way, other additives may also be present in the lubricating oil in order to obtain a proper balance of properties, such as dispersion, corrosion, abrasion and oxidation, which are critical for the proper operation of an internal combustion engine.

Thus, another aspect of the present invention is a lubricating oil composition particularly useful in the crankcase of an internal combustion engine for the purpose of improving the fuel consumption of the engine, which composition comprises (a) a major amount of an oil of lubricating viscosity and (b) an effective amount , calculated on the total lubricating oil composition, of each of the following: an alkenyl succinimide, a borated alkyl catechol and optionally 0.1 to 4% by weight of a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, 4. 0.3 to 10% by weight of a neutral or alkaline or alkaline earth metal hydrocarbyl sulphonate or mixtures thereof, 5. 0.2 to 27% by weight of a neutral or overbased alkylated alkali or alkaline earth metal phenolate or mixtures thereof.

In yet another aspect of the present invention, there is provided a method of reducing fuel consumption of an internal combustion engine by treating the moving surfaces thereof with the lubricating oil composition described above.

DETAILED DESCRIPTION OF THE INVENTION The drilled alkyl catechols are prepared by drilling an alkyl catechol with boric acid while removing the reaction water. Suitably enough boron is present, so that each boron will react with from 1.5 to 2.5 hydroxyl groups present in the reaction mixture.

The reaction can be carried out at a temperature in the range of 60 ° C to 135 ° C, in the absence or presence of any suitable organic solvent, such as methanol, benzene, xylenes, toluene, neutral oil and the like. The alkyl catechols or mixtures thereof which can be used to prepare the borated alkyl catechols used in the present invention are suitably monoalkyl catheters. carbon of the formula I OH wherein R represents alkyl, which contains 10 to 30 carbon atoms and suitably from 16 to 26 carbon atoms. Also up to 25% by weight but preferably less than 10% by weight of the monoalkyl catechols may have the R group in a position adjacent to ortho to one of the hydroxy groups and have the formula II R H O also included among the alkyl catechols which can be used to prepare the borated alkyl catechols of the present invention are dialkyl catechols, which usually have the formula III OH R OH III / wherein R is defined as above. Trialkyl catechols can also be used although they are not preferred.

Among the alkyl catechols that can be used are decyl catechol, undecyl catechol, dodecyl catechol, tetradecyl catechol, pentadecyl catechol, hexadecyl catechol, octadecyl catechol, eicosyl catechol , such as a mixture of C 14 -C 18 alkyl catechols or a mixture of C 15 -C 25 alkyl catechols may be used.

The alkyl catechols of formula III can be prepared by reacting a C10 to C39 olefin, such as a branched olefin or a straight chain alpha-olefin containing 10 to 30 carbon atoms, with pyrocatechol in the presence of a sulfonic acid catalyst at a temperature from about 60 ° C to 200 ° C, and preferably 125 ° to 180 ° C in a substantially inert solvent at atmospheric pressure. Examples of the inert solvents include benzene, toluene, chlorobenzene and "250 Thinner", which is a mixture of aromatics, paraffins and naphthenes.

The term "branched olefin" means that the branching occurs at the double bond. The term "straight chain alpha-olefin" means that the alpha-olefin contains little (less than 10 X) or no branch at the double bond or elsewhere.

A product which is predominantly monoalkyl catechol can be prepared using molar ratios of reactants and suitably a 10 X molar excess of branched olefin or alpha-olefin over catechol is used. When using molar ratios, products obtained are usually monoalkyl catechols but contain some amounts of dialkyl catechols. In any case, molar excess pyrocatechol (i.e., 2 equivalents of pyrocatechol for each equivalent of olefin) can be used to increase the monoalkylation if predominantly monoalkyl catechol is desired. Predominantly, dialkyl catechols can be prepared by using two equivalents of pyrocatechol of the same or different olefins.

The use of a branched olefin results in a greater proportion of alkyl catechols of formula I than the use of straight chain alpha-olefins. Use of such branched olefins usually results in more than 90% alkyl catechol of formula I and less than 10% alkyl catechol of formula II.

The borated alkyl catechols are stabilized against hydrolysis by reacting the catechols with an alkyl or alkenyl mono- or bis-succinimide. In the suitable embodiment, an alkyl or alkenyl monosuccinimide is used.

The oil-soluble alkenyl or alkyl mono- or bis-succinimides used in the present invention are generally known as lubricating oil detergents and are described in U.S. Pat. Nos. 2,992,708, 3,018,291, 3,024,237. , 3,100,573, 3,219,666, 3,172,892 and 3,272,746, the disclosures of which are incorporated by reference. The alkenyl succinimides are the reaction product of a polyolefin polymer-substituted succinic anhydride with an amine, preferably a polyalkylene polyamine. The polyolefin polymer-substituted succinic anhydrides are obtained by reacting a polyolefin polymer or a derivative thereof with maleic anhydride. Thus, succinic anhydride obtained is reacted with the amine compound. The preparation of the alkenyl succinimides has been described many times in the art. See e.g. U.S. Pat. Nos. 3,390,082, 3,219,666 and 3,172,892, the disclosures of which are incorporated herein by reference. Reduction of the alkenyl-substituted succinic anhydride gives in yields the corresponding alkyl derivatives. A product comprising predominantly mono- or bis-succinimide can be prepared by controlling the molar ratios of the reactants. Thus, for example, if one mole of amine is reacted with one mole of alkenyl or alkyl-substituted succinic anhydride, a predominantly monosuccinimide product will be prepared. If two moles of the succinic anhydride are reacted per mole of polyamine, a bis-succinimide will be prepared.

Particularly good results are obtained with the lubricating oil compositions of the present invention, when the alkenyl succinimide is a monosuccinimide prepared from a polyisobutylene-substituted succinic anhydride of a polyalkylene polyamine.

Polyisobutylene, from which polyisobutylene-substituted succinic anhydride is obtained by polymerizing the isobutylene, can vary widely in its compositions. The average number of carbon atoms can range from 30 or less to 250 or more with a obtained average average molecular weight of about 400 or less to 3000 or more. Preferably, the average number of carbon atoms per polyisobutylene molecule will range from about 50 to about 100 with the polyisobutylene having a numerical average molecular weight of about 600 to about 1500. More suitably, the average number of carbon atoms per polyisobutylene molecule will range from about 60 to 90 and the numerical average molecular weight ranges. from about 800 to 1300. Polyisobutylene is reacted with maleic anhydride according to well known methods to give in polyisobutylene-substituted succinic acid, e.g. U.S. Pat. Nos. 4,388,471 and 4,450,281.

In the preparation of alkenyl succinimide, the sub- W !! i u d. See the substituted succinic anhydride to react with a polyalkylene polyamide to yield the corresponding succinimide in exchange. Each alkylene radical of the polyalkylene polyamine usually has up to about 8 carbon atoms. The number of alkylene radicals can range up to about B. The alkylene radical is exemplified by rock, propylene, butene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, etc. The number of amino groups is usually, but not necessarily, one greater than the number of alkylene radicals present. in the amine, i.e., if a polyalkylene polyamine contains 3 alkylene radicals, it will usually contain 4 amino radicals. The number of amino radicals can range up to about 9. Preferably, the alkylene radical contains from about 2 to about 4 carbon atoms and all amine groups are primary or secondary. In this case, the number of amine groups exceeds the number of alkylene groups by 1. Preferably, the polyalkylene polyamine contains from 3 to 5 amine groups. Specific examples of polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, tripropylenetetramine, tetraethylenepentamine, trimethylenediamine, pentaethylenehexamine, ditriamine, tri (hexamethylene) tetramine, etc.

Other amines suitable for preparing alkylene succinimide for use in the present invention include the cyclic amines, such as piperazine, morpholine and dipiperazines.

Suitably the alkylene succinimides used in the compositions of the present invention have the following formula: wherein R a represents an alkenyl group, suitably a substantially saturated hydrocarbon. , which is prepared by polymerizing aliphatic monoolefins. Suitably R 1 is prepared from isobutylene and has an average number of carbon atoms and a numerical average molecular weight, as described above; B. The "alkene" radical essentially denotes a hydrocarbyl group which contains up to about 8 carbon atoms and which suitably contains from about 2-4 carbon atoms as described hereinabove. ; c. A represents a hydrocarbyl group, an amine-substituted hydrocarbyl group or hydrogen. The hydrocarbyl group and the amine-substituted hydrocarbyl groups are usually alkyl- and amino-substituted alkyl analogs of the alkylene radicals described above. Suitably A denotes hydrogen. d. n denotes an integer from about 1 to 10 and suitably from about 3-5.

The alkenyl succinimide is present in the lubricating oil compositions of the invention in an amount effective to stabilize the borated alkyl catechols against hydrolysis to act as a dispersant and prevent the deposition of impurities formed in the oil during operation of the engine.

The exact structure of the complex of the present invention is not known. Certainly, however, while not limiting the present invention to any theory, it is believed to be compounds in which boron is either complexed with, or the salt of, one or more nitrogen atoms of basic nitrogen contained in succinimide. Therefore, it is advisable that the alkenyl succinimide contains at least 2 and preferably 3-5 basic nitrogen per atom.

The complex can be formed by reacting the borated alkyl catechol and succinimide together at a temperature above the melting point of the reactant mixture and below the decomposition temperature, or in a diluent in which both reactants are soluble. For example, the reactants may be combined in the proper ratio in the absence of a solvent to form a homogeneous product, which may be added to the oil, or the reactants may be combined in the proper ratio in a solvent, such as toluene or chloroform, the solvent. evaporated and the complex thus formed can be added to the oil. Alternatively, the complex may be prepared in a lubricating oil such as a concentrate containing from about 20% to 90% by weight of the complex, which concentrate may be added in appropriate amounts to the lubricating oil in which it is to be used or the complex may be prepared directly in the lubricating oil in which it is to be be used. The diluent is suitably inert to reactant formed products and is used in an amount sufficient to ensure solubility of the reactants and to allow the mixture to be effectively stirred.

Temperatures for preparing the complex may range from 25 ° C to 200 ° C and suitably 25 ° C to 100 ° C depending on whether the complex is prepared pure or in a diluent, i.e. lower temperatures can be used when a solvent is used.

An effective amount of succinimide is added to stabilize the borated alkyl catechols against hydrolysis. In general, the weight percent ratios of succinimide to borated alkyl catechol used to form the complex are in the range of 3: 1 to 16: 1 and preferably from 3: 1 to 10: 1 and most preferably 3: 1 to 6: 1. This latter condition is suitable and the complex is manufactured and / or stored clean or in the absence of solvent or lubricating oil and under atmospheric conditions.

As used herein, the term "stabilized against hydrolysis" means that the borated alkyl catechol-succinimide complex does not form a precipitate due to hydrolysis of the borated catechol for a period of at least three months, when stored at room temperature (about 15-25 ° C) and ambient humidity.

The amount of complexes required to be effective in reducing friction in lubricating oil compositions can range from 0.5 to 20% by weight. However, in the suitable embodiment, it is desirable to add sufficient complexes so that the amount of borated catechol is added at a range from 0.1 to about 4% by weight of the total lubricating composition and is suitably present in the range from 0.2 to 2% by weight and most preferably 0.5 to 1%. The succinimide is present in the complex of the invention in an amount effective to stabilize the borated alkyl catechol against hydrolysis and which allows the borated alkyl catechol to function as an effective friction reducing agent.

The succinimide in the complex also acts as a dispersant and prevents the deposition of pollutants, which are formed in the oil during operation of the engine.

In general, the complexes of the present invention can also be used in combination with other additive systems in conventional amounts for their known purposes. 10 15 20 25 30 35 40 10: ¿I? ?:? Ü For example, for use in modern crankcase lubricants, the above-described base composition will be formulated with complementary additives to provide the necessary stability, cleaning ability, dispersing ability, anti-wear and anti-corrosion properties.

Thus, as another embodiment of the present invention, the lubricating oils to which the complexes have been added, prepared by bringing the borated alkyl catechols and succinimides, may contain an alkali or alkaline earth metal hydrocarbyl sulfonate, an alkali or alkaline earth metal phenolate and metal salt from Group II of dihydrocarbyl dithiophosphate. Also because the succinimides act as excellent dispersants, additional succinimide can be added to the lubricating oil compositions, over the amounts added in the form of the complex with the borated alkyl catechols. The amount of succinimides can range up to 20% by weight of the total lubricating oil compositions.

The alkali or alkaline earth metal hydrocarbyl sulfonates may be either petroleum sulfonate, synthetically alkylated aromatic sulfonates or aliphatic sulfonates, such as those derived from polyisobutylene. One of the more important functions of the sulfonates is to act as a detergent and dispersant. These sulfonates are well known in the art.

The hydrocarbyl group must have a sufficient number of carbon atoms to make the sulfonate molecule oil-soluble. Suitably the hydrocarbyl moiety has at least 20 carbon atoms and may be aromatic or aliphatic, but is usually alkyl aromatic. Most suitable for use are calcium, magnesium or barium sulfonates, which are aromatic in nature.

Some sulfonates are typically prepared by sulfonating a petroleum fraction with aromatic groups, usually mono- or dialkylbenzene groups, and then forming the metal salt of the sulfonic acid material. Other materials used to prepare these sulfonates include synthetically alkylated benzene and aliphatic hydrocarbons prepared by polymerizing a mono- or diolefin, for example a polyisobutenyl group prepared by polymerizing isobutylene. The metal salts are formed directly or by metathesis using well known methods. The sulfonates can be neutral or overbased with base numbers up to about 400 or more. v) 10 15 20 25 30 35 11 1 plumbing Carbon dioxide and calcium hydroxide or ox oxide are the most commonly used materials for producing the basic or overbased sulfonates. Mixtures of neutral and overbased sulfonates can be used. The sulfonates are commonly used to provide from 0.3 to 10% by weight of the total composition. Suitably the neutral sulfonates are present in from 0.4 to 5% by weight of the total composition and the overbased sulfonates are present in from 0.3 to 3% by weight of the total composition.

The phenolates for use in the present invention are the conventional products which are alkali or alkaline earth metal salts of alkylated phenols. One of the functions of the phenolates is to act as a detergent and dispersant.

Among other things, it prevents the deposition of pollutants, which form during operation at high temperature of the engine. The phenols may be mono- or polyalkylated.

The alkyl portion of the alkyl phenolate is present to provide oil solubility of the phenolate. The alkyl moiety can be obtained from naturally occurring or synthetic sources. Naturally occurring sources include petroleum hydrocarbons, such as white oil and wax. While derived from petroleum, the hydrocarbon moiety is a mixture of different hydrocarbyl groups, the specific composition of which depends on the particular oil feedstock used as a feedstock. Suitable synthetic sources include various commercially available alkenes and alkane derivatives which, when reacted with phenol, yield in exchange an alkylphenol. Suitable radicals obtained include butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl, triacontyl and the like. Other suitable synthetic sources of the alkyl radical include olefin polymers, such as polypropylene, polybutene, polyisobutylene and the like.

The alkyl group may be straight chain or branched chain, be saturated or unsaturated (if unsaturated, it preferably does not contain more than 2 and usually not more than 1 site of olefinic unsaturation). The alkyl radicals will usually contain from 4 to 30 carbon atoms. Generally, when the phenol is monoalkyl substituted, the alkyl radical should contain at least 8 carbon atoms. The phenolate may be sulfurized, if desired. It can be either neutral or overbased and will, if overbased TFC, have a base number of up to 200 to 300 or more.

Mixtures of neutral and overbased phenolates can be used.

The phenolates are usually present in the oil to provide from 0.2 to 27% by weight of the total composition. Suitably the neutral phenolates are present from 0.2 to 9% by weight of the total composition and the overbased phenolates are present from 0.2 to 13% by weight of the total composition. Most preferably, the overbased phenolates are present from 0.2 to 5% by weight of the total composition. Suitable metals are calcium, magnesium, strontium or barium.

The sulfurized alkaline earth metal alkyl phenolates are suitable. These salts are obtained by a variety of methods, such as treating the neutralization product of an alkaline earth metal base and an alkylphenol with sulfur. Suitably, the sulfur, in elemental form, is added to the neutralization product and reacted at elevated temperatures to produce the sulfurized alkaline earth metal alkyl phenolate.

If more alkaline earth metal base was added during the neutralization reaction than was necessary to neutralize the phenol, a basic sulfurized alkaline earth metal alkyl phenolate is obtained. See e.g. the method of Walker et al., U.S. Pat. No. 2,680,096. Additional basicity can be obtained by adding carbon dioxide to the basic sulfurized alkaline earth metal alkyl phenolate. The excess alkaline earth metal base can be added afterwards to the sulfurization step but is usually added at the same time as the alkaline earth metal base is added to neutralize the phenol.

Carbon dioxide and calcium hydroxide or oxide are the most commonly used materials for preparing the basic or "overbased" phenolates. A process in which basic sulfurized alkaline earth metal alkyl phenolates are prepared by adding carbon dioxide is disclosed in Hanneman, U.S. Pat. No. 3,178,368.

The metal salts from group II of dihydrocarbyl dithiophosphoric acids show abrasion, antioxidant and thermal stability properties. Group II metal salts of phosphorodithioic acids have been described previously. See, for example, U.S. Pat. No. 3,390,080, columns 6 and 7, in which these compounds and their preparation are generally described. Suitably the Group II metal salts of the dihydrocarbyl dithiophosphoric acids for use in the lubricating oil composition of the present invention contain from about 4 to about 12 carbon atoms in each of the hydrocarbyl radicals and may be the same or different and may be aromatic, alkyl or cycloalkyl. Suitable hydrocarbyl groups are alkyl groups containing from 4 to 8 carbon atoms and corresponding to butyl, isobutyl, sec-butyl, hexyl, isohexyl, octyl, 2-ethylhexyl and the like. The metals suitable for forming these salts include barium, calcium, strontium, zinc and cadmium, of which zinc is suitable.

Suitably the Group II metal salt of a dihydrocarbyl dithiophosphoric acid has the following formula: R 0 S 2 \ P / H 30 / \ S M1 wherein: e. R 2 and R 3 each independently represent hydrocarbyl radicals as described above, and f. M1 represents a metal cation from Group II as described above.

The dithiophosphoric acid salt is present in lubricating oil compositions of the present invention in an amount effective to inhibit abrasion and oxidation of the lubricating oil. The amount ranges from about 0.1 to about 4% by weight of the total composition, suitably the salt is present in an amount ranging from 0.2 to about 2.5% by weight of the total lubricating oil composition. The final lubricating oil composition will usually contain 0.025% 0.25% by weight of phosphorus and preferably 0.05 to 0.15% by weight.

The finished lubricating oil can be for one or more purposes. Multi-purpose lubricating oils are prepared by adding viscosity index (VI7) enhancers. Typical viscosity index improvers are polyalkyl methacrylates, ethylene-propylene copolymers, styrene-diene copolymers and the like. suitable for use in the formulations of the present invention The lubricating oil used in the compositions of the present invention may be mineral oil or synthetic oils having a lubricating viscosity and suitably suitable for use in the crankcase of a Crankcase lubricating oils usually have a viscosity of about 1300 mm2 / S - 1a ° C to 22.7 mm2 / S at 99 ° C. The lubricating oils can be derived from synthetic or natural sources. Mineral oil for use as a base oil in the present invention includes paraffin, naphthenic and other oils commonly used in lubricating oil compositions. accepts both synthetic hydrocarbon oils and synthetic esters. Useful synthetic hydrocarbon oils include liquid polymers of alpha-olefins of proper viscosity.

Particularly useful are the hydrogenated liquid oligomers of C5-12 alpha-olefins, such as 1-decentrimer. Likewise, alkyl viscosities of proper viscosity, such as didodecyl benzene, can be used. Useful synthetic esters include the esters of both monocarboxylic acid and polycarboxylic acids as well as monohydroxyalkanols and polyols. Typical examples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyladipate, dilauryl sebacate and the like. Complex esters prepared from mixtures of mono- and dicarboxylic acid and mono- and dihydroxy-alkanols can also be used.

Mixtures of hydrocarbon oils with synthetic oils are also useful. For example, mixtures of 10 to 25% by weight of hydrogenated 1-decentrimer with 75 to 90% by weight of 150 SUS (100 ° F) mineral oil give an excellent lubricating oil base.

Additive concentrates are also included within the scope of the present invention. They usually comprise from about 90 to 20% by weight of an oil of lubricating viscosity and from about 20 to 90% by weight of the complex additive of the present invention. Typically, the concentrates contain sufficient diluent to make them easy to handle during shipping and storage. Suitable diluents for the concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate can be easily mixed with the lubricating oils to prepare lubricating oil compositions. Suitable lubricating oils, which can be used as diluents, typically have viscosities in the range of from about 35 to about 500 Saybolt Universal Seconds (SUS) at 38 ° C, although an oil of lubricating viscosity may be used.

I) 10 15 20 25 30 35 40 15 àáš ?? fi Other additives that may be present in the preparation include rust inhibitors, foam inhibitors, corrosion inhibitors, metal deactivators, pour point depressants, antioxidants and a variety of other well known additives.

The following examples are given to specifically illustrate the invention. These examples and illustrations are not to be construed as limiting the scope of the invention in any way.

EXAMPLES Example 1 Preparation of C14-C18 alkyl catechol To a 3 liter flask equipped with stirrer, Dean Stark trap, condenser and nitrogen inlet and outlet was added 759 g of a C14-C13 alpha-olefin (2% C14, 30% C15, 30 % C15, 28% C17 and 10% C13), 330 g of pyrocatechol, 165 g of a sulfonic acid cation exchange resin (polystyrene crosslinked with divinylbenzene), catalyst (Amberlyst lß supplied by Rohm and Haas) and 240 ml of toluene. The reaction mixture is heated to 150 ° C to 160 ° C for about 7 hours with stirring under a nitrogen atmosphere. The reaction mixture was evaporated by heating to 160 ° C under vacuum (0.4 mm Hg). The product was filtered hot over supercell (SCC) to give 908.5 g of C 14 -C 13 alkyl-substituted pyrocatechol. The product had a hydroxyl number of 259. In a similar manner, it is prepared by substituting an equivalent amount of each of a C12 alpha-olefin, a C14 alpha-olefin and a C18 alpha-olefin in the above process, corresponding to alkyl catechols.

Example 2 Preparation of C15-C25 alkyl catechol To a 3 liter flask equipped with stirrer, Dean Stark trap, condenser and nitrogen inlet and outlet was added 759 g of a mixture of C15 to C25 olefin (less than C14 - 2.7%, C14 - 0.32, C15 - 1.3%, C15 - 8.01, C20 - 44.41, C22 - 29.3%, C24 - 11.2%, C25 - 2.21, C28 - 0.4 X , C30 - 0.2X) (containing at least 40% branching, available from Ethyl Corp.), 330 g of pyrocatechol crosslinked with divinylbenzene), catalyst (Amberlyst IÉÉ to 165 g of a sulfonic acid cation exchange resin 10 15 20 25 30 35 40 16 WG available from Rohm and Haas, Philadelphia, Pennsylvania) and 240 ml of toluene. The reaction mixture was heated to 150 ° C to 160 ° C for about 7 hours with stirring under a nitrogen atmosphere. The reaction mixture was evaporated by heating to 160 ° C under vacuum (0.4 mm Hg). The product was filtered hot over diatomaceous earth to give 971 g of a liquid C15 to C25 alkyl-substituted pyrocatechol.

Example Gel 3 Preparation of C 14 -C 13 alkyl catechol borated 906 g of C 14 -C 15 alkyl catechol were added 124 g of boric acid and 900 ml of toluene. The reaction mixture was heated to 105 to 188 ° C for about 8 hours under a nitrogen atmosphere at azeotropic conditions. 93 ml of water was collected with a Dean Stark trap. The reaction product was filtered and evaporated on a rotor evaporator under vacuum to 155 ° C to yield 930 g of the title product.

Example Gel 4 An oil mixture was prepared as set forth in Table I using CitCon 100N oil and containing 1.0! of the borated alkyl catechol prepared according to Example 3.

TABLE I Time - Preparation days Observation Base oil 1-3 light and clear Base oil + 1 weight-Z drilled 1 obscure and acyl catechol from ex. 3 precipitate formed Example 5 1 part by weight of the borated alkyl catechol prepared according to Example 3, and 3 parts by weight of a 48% by weight of polyisobutenyl succinimide (prepared by bringing polyoobutylene succinic anhydride, wherein numerical average molecular weight) The polyisobutenyl content was about 950, and tetraethylene pentamine to react in a molar ratio of amine to anhydride of 0.87) solution in oil (CitCon 100N) was heated together while mixing with a hot plate to 100 ° C in 0 ° C. ,5 hours. 20 ml of the reaction mixture was placed in a 100 ml beaker and stored. A 100 ml beaker containing 20 ml of borated alkyl catechol only, heated to 150 ° C, and no succinimide, was also stored for comparison.

The borated alkyl catechol hydrolyzed and formed a skin on the surface thereof as it cooled the borated alkyl catechol-succinimide complexed material remained light and clear after one week of storage. Even after 3 weeks, the test remained clear.

Example 6 Tests were performed showing improvements in fuel economy obtained by adding lubricating oil compositions of the present invention to the crankcase of an automobile engine.

In this test, a "350 CID Oldsmobile" engine was run on a dynamometer. An engine oil system was devised to provide proper engine lubrication and also to provide the ability to change the oil without stopping the engine. In principle, a dry sump system was used with an external pump that provided lubrication to the engine. This pump was connected through valves to four external sumps. The position of the valves determined the oil used.

This test was performed with base oil and then with the same oil, which contained 1% by weight of borated C14-C18 alkyl catechol, prepared according to Example 3. Percentage improvements in fuel economy using the compositions of the present invention compared to the base oil shown in Table II.

Table II Fuel Economics of Basic Concentrations of Sample Concentration Weight-Z 1 Improvement 1 1.5 10 18 18 \ 'ä z 1 a I I; F] w 'If / The comparisons described above were made with fully prepared "Exxon 150N" oil containing 3.5 X of a polyisobutenyl succinimide of tetraethylene pentamine, 30 mmol / kg overbased magnesium hydrocarbyl sulfonate, mmol / kg overbased calcium hydrocarbyl olephonate phenolate, 8.5 mmol / kg zinc-0,0-di (2-ethylhexyl) dithiophosphate, 8 mmol / kg of a mixed zinc dialkyl dithiophosphate from sec-britanol, butyl isobutyl carbinol, 0.5 X sulfurized calcium polypropylene 1.5% of a sulfurized molybdenic acid succinimide complex and sufficient amount of an amine-substituted ethylene / propylene copolymer to give a "1OW30" oil in this formulation and improver are also prepared crankcase oils, each containing 0.5 to 2% by weight of borated C15-C24 monoalkyl catechol, drilled C14-C13 dialkyl catechol and the like instead of drilled C14-C18 alkyl catechol in Example 3 of the above formulations, also effective in reducing the fuel consumption of an internal combustion engine.

IN)

Claims (18)

10 15 20 25 30 35 19 CT åíàš '77 PATENTKRAV A lubricating oil additive comprising a complex prepared by reacting a borated alkyl catechol and an oil-soluble alkyl or alkenyleuccinimide, wherein the weight percentage ratio of the alkyl or alkenyl succinimide to the borated alkyl catechol ranges from 3: 1 to 16: 1. The lubricating oil additive of claim 1, wherein the alkyl group of the borated alkyl catechol contains from 10 to 30 carbon atoms and the succinimide is a polyisobutenylsuccinimide of a polyalkylene polyamine. A lubricating oil additive according to claim 2, wherein the succinimide is a polyisobutenylsuccinimide of triethylenetetramine or polyisobutenylsuccinimide of tetraethylenepentamine. The lubricating oil additive according to claim 2, wherein the alkyl group of borated alkyl catechol is a mixture of alkyl groups containing 14-26 carbon atoms. The lubricating oil additive of claim 2, wherein the alkyl groups of borated alkyl catechol are a mixture of alkyl groups containing 14 to 18 carbon atoms. A lubricating oil composition comprising a major amount of an oil having a lubricating viscosity of from 0.5 to 20% by weight, based on the total lubricating oil composition, of a friction reducing complex, which complex is prepared by reacting a drilled alkyl catechol and an oil-soluble alkyl or alkenyl succinimide, wherein the weight percent ratio of the alkyl or alkenyl succinimide to the borated alkyl catechol ranges from 3: 1 to 16: 1. The lubricating oil composition of claim 6, wherein the alkyl group of borated alkyl catechol is a mixture of C 14 -C 25 alkyl groups and the succinimide is a polyisobutenylsuccinimide of a polyalkylene polyamine. The lubricating oil composition of claim 6, wherein the alkyl group of borated alkyl catechol is a mixture of C 14 -C 13 alkyl groups. A lubricating oil composition according to claim 7, wherein the succinimide is a polyieobutenylauccinimide of triethylenetetramine or polyisobutenylsuccinimide of tetraethylenepentamine. 10 15 20 25 30 35 40 20 465 Wi; A lubricating oil composition according to claim 6, comprising a major amount of an oil having a lubricating viscosity of 0.1 to 4% by weight, based on the total lubricating oil composition, of a borated alkyl catechol and an effective amount of an alkenyl succinimide to stabilize borated alkyl catechol against hydrolysis. The lubricating oil composition of claim 10, wherein the alkyl group of borated alkyl catechol contains from 10 to 30 carbon atoms and the alkenyl succinimide is a polyisobutenyl succinimide of a polyalkylene polyamine. The lubricating oil composition of claim 11, wherein the alkenyl succinimide is a polyisobutenyl succinimide of triethylenetetramine or polyisobutenyl succinimide of tetraethylenepentamine. The lubricating oil composition of claim 11, wherein the alkyl group of borated alkyl catechol is a mixture of alkyl groups containing from 14 to 18 carbon atoms. The lubricating oil composition of claim 11, wherein the alkyl group of borated alkyl catechol is a mixture of alkyl groups containing from 14 to 26 carbon atoms. A lubricating oil composition according to claim 6, comprising (a) a major amount of an oil having a lubricating viscosity and Cb) an effective amount, based on the total lubricating oil composition, of any of the following: 1. an alkenyl succinimide, 2. a borated alkyl catechol and optionally 3. 0.1 to 4% by weight of a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, 4. 0.3 to 10% by weight of a neutral or overbased alkali or alkaline earth metal hydrocarbyl sulfonate or mixtures thereof, 5. 0.2 to 27% % by weight of a neutral or overbased alkylated alkali or alkaline earth metal phenolate or mixtures thereof. A lubricating oil composition according to claim 15, wherein (1) alkenylsuccinimide is a polyisobutenylsuccinimide of a polyalkylene polyamine, (2) borated alkyl catechol is a borated C 14 -C 13 alkyl catechol, (3) the metal salt of the dihydrocarbyl dithiophosphoryl acid contains the alkyl group carbon atoms, (4) the metal of the neutral or overbased alkali or alkaline earth metal sulphonate is calcium, magnesium or barium or mixtures thereof, (5) the metal of the neutral or overbased alkali or alkaline earth metal phenolate is calcium, magnesium or barium. A lubricating oil composition according to claim 15, wherein (1) alkenylsuccinimide is a polyisobutenylsuccinimide of triethylenetetramine or polyisobutenylsuccinimide of tetraethylenepentamine, 1 (2) borated alkyl catechol is a borated C 14 -C 13 alkylcatalkyl, (3) metaphysalkyl , 0-di (2-ethylhexyl) dithiophosphate, zinc-0,0-di (isobutyl / mixed primary hexyl) dithiophosphate or zinc-0,0-di (sec-butyl / mixed secondary hexyl) dithiophophate, (4) the metal salt of the sulfonate is an overbased magnesium or calcium hydrocarbyl sulfonate, (5) the metal salt of the phenolate is an overbased sulfurized calcium or magnesium monoalkylated phenolate. Use of a composition according to claim 6, 10 or 15 to reduce the fuel consumption of an internal combustion engine.