DE3233645C2 - Use a lubricant to reduce fuel consumption - Google Patents

Description

The invention relates to the Ver improvement of the operation of internal combustion engines, ins especially the reduction in fuel consumption by lubricants used in such engines Reduction in fuel consumption can be used nen.

In view of the recent oil shortage, the rising cost of petroleum products and the need the conservation of natural resources such as petroleum is a driving force saving material is an important factor in the construction of Motors and the selection of the materials used in them. A The lowest possible fuel consumption is both in the outward direction look at the conservation of the raw material as well as under the Ge point of view of economy for the user worth it.

The invention is based on the object Uses of compositions with lubricating properties to provide for internal combustion engines that reduce fuel consumption Reduce. This object is achieved by the invention solved.

The invention relates to  Use a lubricant to reduce the Fuel consumption in an internal combustion engine a larger proportion of a lubricating oil and a smaller one Proportion of at least one ester of the general formula contains

wherein R³ represents an essentially unbranched alkyl or alkenyl radical having 8 to 30 carbon atoms,
the radicals R⁴ independently of one another are hydrogen atoms or alkyl or alkenyl radicals having at most 18 carbon atoms, at least one of the radicals R⁴ being an alkyl or alkenyl radical.

The compounds used in the invention are Esters of substituted succinic acids. Any carbon atom of the residue R³ can be bound to the succinic acid residue be, either directly or through a methylene group. The Be drawing "essentially unbranched" means that the Balance no more than about 2 methyl groups as substituents contains.

Substituted succinic acids and their derivatives, such as An hydrides, acid halides or esters of this type can be found in favorably by reacting maleic or fumaric acid or a derivative thereof, preferably maleic anhydride, with one or more olefins with 8 to 30 coals atoms are manufactured that meet the required ge have a chain-chain character. There are numerous such olefins either pure or in the form of technical mixtures in the Han del available. The olefinically unsaturated bonds can be terminal or medium-sized. You can accordingly as vinyl, vinylidene or internal olefinic There are groups. Many of these compounds contain preferably vinyl and vinylidene groups, which are defined by For meln

CH₂ = CHR and CH₂ = CR₂

can be reproduced, the radicals R independently represent alkyl radicals from one another.

The reaction between the olefin or olefin mixture and Maleic anhydride or a similar acid or derivative is a typical "en reaction" that leads to the emergence of a new carbon-carbon single bond between the Maleic acid or similar residue and the olefin leads where the double bond shifts in the olefin. The Be  conditions of this implementation are known.

The alkenyl radicals R⁴ in the compounds of the general For mel I can up to 18, preferably up to about 12 coals atoms of matter. Suitable residues of this type are allyl, Butenyl, hexenyl, octenyl, decenyl, dodecenyl and octa decenyl radicals, all isomers being included. Be the lower alkenyl radicals are particularly preferred, in particular the residues with 2 to 4 carbon atoms.

The esters used are preferably acidic esters, so that at least one of the radicals R⁴ is a hydrogen atom and at least one is an alkenyl rest means.

According to the invention, esters such as those above are particularly preferred Substituted succinic acid esters described above, in which a radical R⁴ is a hydrogen atom and the other an alkenyl radical having 1 to 4 carbon atoms, in particular which is an allyl group.

The acidic esters can be prepared by conventional methods be, for example by implementing at least one ge suitable polycarboxylic acid or a derivative thereof with min least an unsaturated alcohol. Here is the number equivalents of alcohol at least 1 less than the number of equivalents of the acid or acid derivative. The substituted succinic anhydrides are preferred Acid derivatives. However, substituted Bern can also be used rock acids or acid halides can be used. in the the latter case then the remaining acid halide residues are hydrolyzed to free acid groups.  

The examples illustrate the invention. Parts and percent gifts refer to weight unless otherwise stated is specified. The acid number is determined at Use of phenolphthalein as an indicator. Examples 1 to 9 serve to explain the production of the used according to the invention Links.

example 1

A mixture of 500 parts (3.74 equivalents) of dodecenylber succinic anhydride and 109 parts (1.87 equivalents) allyl alcohol is heated to 110 ° C for 10 hours with stirring. There after 2 further portions of allyl alcohol, namely 2.5 and 6.5 parts, added and the mixture for a further 4 hours is heating. Then the reaction mixture is in a vacuum steamed. The residue obtained is the acidic allyl ester, which has an acid number of 173.6.

Example 2

A reaction vessel is charged with 2254 parts (23 mol) of maleic anhydride and then mixed with 5700 parts (25 mol) of an industrial mixture of C _15-18 predominantly straight-chain α-olefins. The resulting mixture is heated under nitrogen to 209 to 214 ° C for about 15 hours. Then 1500 parts of textile spirit are added and the mixture is stirred for a further hour. The reaction mixture is then filtered through a filter aid and evaporated in vacuo to remove volatile constituents. The residue obtained is filtered again. The desired substituted succinic anhydride is obtained as the filtrate.

A mixture of 485 g (2.94 equivalents) of the substituted Succinic anhydride and 85.9 g (1.47 equivalents) allyl alcohol is heated to 110 ° C for 9 1/2 hours with stirring. Then the mixture is mixed with 150 ml of toluene and the Removal of water distilled azeotropically. The toluene will then distilled off under vacuum. Two more shares  Allyl alcohol, namely 10.6 and 10.1 g, can be added, and that The mixture is heated to about 110 ° C. for a further 7 hours. After that the reaction mixture is turned on under reduced pressure steams. The residue obtained is the acidic allyl ester; it has an acid number of 154.

Example 3

A portion of the technical α- used in Example 2 Olefin mixture is 10 hours in the presence of an acid Ion exchange resin for isomerization at 180 to 195 ° C heated. The isomerized mixture is then mixed with malein implemented acid anhydride. The substituted Bern obtained Rock acid anhydride is reacted with allyl alcohol. At the These implementations are essentially the conditions of Example 2 applied, except that the azeotropic Distillation in the presence of toluene is omitted. The Product is the desired acidic allyl ester with an acid number from 147.

Example 4

Example 3 is repeated using an industrial mixture of C _15-20 predominantly straight-chain α-olefins. A similar product with an acid number of 136.6 is obtained.

Example 5

Example 3 is essentially repeated, a technical mixture of C _16-18 predominantly straight-chain α-olefins isomerizing and the isomerized mixture being reacted with maleic anhydride. The substituted succinic anhydride obtained is converted into the acidic allyl ester, which has an acid number of 118.

Example 6

Example 2 is essentially repeated, a technical mixture of C _18-24 olefins, which mainly contains vinyl and vinylidene-containing α-olefins, is reacted with maleic anhydride. The substituted succinic anhydride obtained is reacted with allyl alcohol. The desired acidic allyl ester with an acid number of 111 is obtained.

Examples 7 and 8

Examples 4 and 5 are repeated, acidic allyl esters being prepared from substituted succinic anhydrides in which the substituents are derived from a technical mixture of C _24-28 α-olefins or the isomerized derivative thereof. The products obtained have an acid number of 79.7 and 87.6, respectively.

The lubricants of the present invention contain, as additives, those described Compositions containing esters in which you ever contributes to reducing fuel consumption You can get a variety of lubricants sets including natural and synthetic Lubricant oils and their mixtures. This lubricant also include lubricating oils for crankcases of gasoline engines and diesel engines including automotive and almost wagon engines, two stroke engines, aircraft piston engines and Ship and rail diesel engines. You can also for gas engines, stationary engines and turbines be applied.

Examples of natural oils are petroleum and with solvents mineral oil treated with acid or acid paraffinic, naphthenic or mixed paraffinic naphthenic basis. Also oils with lubricant viscos that are derived from coal or shale oil  suitable as base oils.

Examples of synthetic lubricating oils are given if halogen-substituted hydrocarbon-based oils, such as polymerized and mixed-polymerized olefins, such as Polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylenes, poly-1-hexenes, poly-1-octenes and Poly-1-decenes and their mixtures, alkylbenzenes, such as dodecyl benzenes, tetradecylbenzenes, dinonylbenzenes and di-2-ethyl hexylbenzenes, polyphenyls such as diphenyls, terphenyls and alkylated polyphenyls, alkylated diphenyl ethers and alky gated diphenyl sulfides and their derivatives, analogs and homo lied.

Other suitable synthetic lubricating oils are alkylene oxide polymers and mixed polymers and their derivatives, in which the terminal hydroxyl groups have been modified, for example, by esterification or etherification. Examples are oils which have been prepared by polymerizing ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers, such as methylpolyisopropylene glycol ether with an average molecular weight of 1000, diphenyl ether of polyethylene glycol with a molecular weight of 500 to 1000 and diethyl ether of polypropylene glycol with a molecular weight from 1000 to 1500, or their mono- and polycarboxylic esters, such as their acetic acid esters, mixed te C _3-8 fatty acid esters or C₁₃ oxoacid diesters of tetra ethylene glycol.

Other examples of synthetic lubricating oils are the Esters of dicarboxylic acids, such as phthalic acid, succinic acid, Maleic acid, azelaic acid, suberic acid, sebacic acid, fumar acid, adipic acid and malonic acid, with a variety of Alcohols, such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol mono ether and propylene glycol. Specific examples of these esters  and dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate and the mixed esters of 1 mole of sebacic acid with 2 moles Tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Further examples of synthetic oils are esters of C _5-12 monocarboxylic acids with polyols and polyol ethers, such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol.

Examples of silicone-based oils are polyalkyl, poly aryl, polyalkoxy or polyaryloxysiloxanes. examples for Silicate-based oils are tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methyl-2- ethylhexyl) silicate, tetra (p-tert-butylphenyl) silicate, Hexyl- (4-methyl-2-pentoxy) -disoloxane, poly- (methyl) -siloxanes and poly (methylphenyl) siloxanes. Examples of others synthetic lubricants are liquid esters from Phos acids containing phosphorus, such as tricresyl phosphate, trioctyl phosphate and diethyl ester of decylphosphonic acid and poly mere tetrahydrofurans.

In the lubricants used according to the invention, non-refined te, refined and re-refined oils can be used. Non-refined oils are made directly from the natural or synthetic starting products without further purification won. For example, they are straight from the retort holding shale oil, obtained directly from distillation tenes petroleum and one obtained directly from the esterification Ester oil used without further treatment non-refined oils. Refined oils are the non-raf Finished oils similar, but were found in at least one Cleaning level to improve at least one of your own shaft treated. Many such cleaning techniques such as distillation, solvent extraction, acid or base  extraction, filtration or perculation are known. Again refined oils are obtained by similar processes, how they are used to extract the refined oils. These procedures are applied to refined oils that have already been used. The re-refined oils are also known as regenerated or remanufactured oils. They are often additionally using removal procedures used additives and oil decomposition products treated.

The invention relates to a method for ver reduction of fuel consumption for internal combustion engines gates, which is characterized in that the engine in Operation lubricated with a lubricant that exists from a larger amount of a lubricating oil and a little tere amount of at least one ester of the above general formula I. in the R³ and R⁴ the above have given meaning.

The esters of general formula I include, among others the analogue new central esters and alkanol esters. The neutral esters can are produced in the usual way, for example after analogous processes as used to prepare the acidic Al Kenylester were explained, but at least 2 equi valente and often more alcohol per equivalent of acid or Acid derivative is used. Suitable esters (acid and neutral ones) of this type can also be obtained from alkanols, such as methanol, Ethanol, the propanols, butanols, hexanols, octanols, Decanols, dodecanols and octadecanols are obtained, with all isomers included. Those are preferred  Alkanols with 1 to 4 carbon atoms, especially n-propa nol.

Preferred for use according to the invention are each but the acidic esters of the general formula I.

In the example below, the preparation of an alkyl esters explained for use according to the invention.

Example 9

The substituted succinic anhydride from Example 6 is similarly with an equivalent amount of N-propanol implemented. The desired acidic n-propyl is used as the product Get ester with an acid number of 126.

The composition containing an ester is used for the Purposes of the invention the lubricating oils in an amount that is sufficient to reduce fuel consumption other. This amount is usually about 0.05 to 5.0 Ge percent by weight, preferably about 0.1 to 2.0 per weight cent.

The lubricants used according to the invention can also be other Additions together with the ester-containing compounds hold. Examples of such additives are auxiliaries with Detergent or dispersant properties of the ash-forming and ashless type, corrosion and oxidation inhibito ren, pour point depressants, high pressure additives, color stabilizers catalysts and anti-foaming agents.

Examples of ash-forming detergents are oil-soluble neutral and basic salts of alkali or alkaline earth metals with sulfonic acids, carboxylic acids or organic Phosphoric acids that have at least one direct carbon Have phosphorus bond, such as in the  Treatment of polyolefins such as polyisobutene with a Mo molecular weight of 1000, with a phosphorizing agent, such as phosphorus trichloride, phosphorheptasulfide, phosphorus penta sulfide, phosphorus trichloride and sulfur, white phosphorus and a sulfur halide or phosphorothioic acid chloride can be put. Sodium, potassium, Li thium, calcium, magnesium, strontium and barium salts of these acids used.

The term "basic salt" refers to metal salts, where the metal in stoichiometrically larger amounts than the organic acid residue is present. Generally who the basic salts by heating a mineral oil solution of an acid with a stoichiometric excess a metal compound, such as metal oxide, hydroxide, carbonate, bicarbonate or sulfide at temperatures above 50 ° C and Obtain filtering of the reaction product. To record of a large excess of the metal a promoter may be used in the neutralization. At games for promoters are phenolic substances like phenol, Naphthol, alkylphenols, thiophenol and sulfurized alkyl phenols and condensation products from formaldehyde with a phenolic substance, alcohols, such as methanol, 2-propanol, Octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol and cyclohexyl alcohol, amines such as aniline, phenylene diamine, phenothiazine, phenyl-β-naphthylamine and dodecalamine. A manufacturing method for ba is particularly preferred sische salts, in which an acid with an excess of alkaline earth metal neutralizing agent and min least an alcohol promoter is mixed and the Ge then mix at higher temperatures, for example se at 60 to 200 ° C, carbonated.

The ashless detergents and Dispersants are referred to as such, although each after its constitution, the dispersant in Ver  combustion non-volatile components, such as boron oxide or Phosphorus pentoxide, can develop; but it contains in space mean no metal and therefore forms during combustion no ashes containing metal. There are numerous means known type, all for using the fiction suitable lubricants are suitable. Examples of ashless Detergents and dispersants are:

• (1) Reaction products of carboxylic acids or their deri vaten, which is at least about 34 and preferably at least contain about 54 carbon atoms with nitrogen tendency compounds, such as amines, organic hydroxyl bonds, such as phenols and alcohols and / or basic organic substances. Examples of these carboxylic acid dispersers sants are in numerous U.S. patents, such as the U.S. Patent 32 72 746, 33 81 022 and 42 34 435.
• (2) reaction products of relatively high molecular weight ali phatic or alicyclic halides with amines preferably polyalkylene polyamines. These can be called "amine Dispersants "and are described, for example, in US Pat. Nos. 32 75 554, 34 38 757, 34 54 555 and 35 65 804, described.
• (3) reaction products of alkylphenols in which the Alkyl group has at least about 30 carbon atoms, with aldehydes, especially formaldehyde, and amines, ins special polyalkylene polyamines known as "Mannich-Dis persants ". Examples of this are in U.S. Patents 3,368,972, 3,413,347 and 3,980,569 wrote.
• (4) Products made by post-treatment of carboxylic acid, Amin or Mannich dispersants with reagents such as urine substance, thiourea, carbon disulfide, aldehydes, Ke toning, carboxylic acids, hydrocarbon-substituted Bern  succinic anhydrides, nitriles, epoxides, boron compounds or phosphorus compounds can be obtained. Examples there for are described in numerous US-PS.
• (5) copolymers of monomers as oil solubilizers such as decyl methacrylate, vinyl decyl ether and high moles kular olefins with monomers that have polar substituents have, for example aminoalkyl acrylates or acrylic amides and poly (oxyethylene) substituted acrylates. These Copolymers are referred to as "polymer dispersants" draws. Examples of this are in US Pat. No. 5,329,658, 34 49 250, 35 19 565, 36 66 730, 36 87 849 and 37 02 300 described.

Examples of high pressure additives, corrosion inhibitors and Oxidation inhibitors are chlorinated aliphatic carbons Hydrogen, such as chlorinated paraffin wax, organic Sulfides and polysulfides such as benzyl disulfide, bis (chlor benzyl) disulfide, dibutyl tetrasulfide, vice versa with sulfur set oleic acid methyl ester, alkyl reacted with sulfur phenols, dipentene reacted with sulfur, with sulfur converted terpene, reacted with phosphorus and sulfur Hydrocarbons, such as reaction products of a phosphorus sulfides with turpentine or oleic acid methyl ester, phosphorus acid esters, such as the di- and tri-hydrocarbon phosphites, e.g. B. dibutyl phosphite, diheptyl phosphite, dicyclohexylphos phit, pentylphenyl phosphite, dipentylphenyl phosphite, tri decylphosphite, distearylphosphite, dimethylnaphthylphos phite, oleyl-4-pentylphenyl phosphite, polypropylene (moles molecular weight 500) -substituted phenylphosphites, Diiso butyl-substituted phenyl phosphites, metal thiocarbamates, such as zinc dioctyldithiocarbamate and bariumheptylphenyldi thiocarbamate, salts of dithiophosphoric acids with metal len of the second group, such as zinc dicyclohexyldithiophosphate, Zinc dioctyl dithiophosphate, barium di (heptylphenyl) di thiophosphate, cadmium dinonyl dithiophosphate and the zinc salt of a dithiophosphoric acid produced by  Reacting phosphorus pentasulfide with an equimolar Ge mix of isopropyl alcohol and n-hexyl alcohol.

The compositions used according to the invention can be used in the lubricant tel can be added directly. However, they are preferred with an essentially inert, usually liquid organic diluents, such as mineral oil, naphtha, Benzene, toluene or xylene to form an additional concentrate trates, diluted. These concentrates generally contain about 5 to 50 percent by weight of the composition used in the invention and can additionally one or more known Zu sentences included.

The lubricants listed in Table I below are specific examples of assembly tongues that are suitable for the purposes of the invention. All the quantities stated refer to mineral oil on the amounts without that used as a diluent Oil. The presence of the ester-containing compounds of the Er the lubricants cause a reduction of fuel consumption when used in internal combustion motors.

Claims (6)

1. Use of a lubricant to reduce fuel consumption in an internal combustion engine, which contains a larger proportion of a lubricating oil and a smaller proportion of at least one ester of the general formula wherein R³ represents an essentially unbranched alkyl or alkenyl radical having 8 to 30 carbon atoms,
the radicals R⁴ independently of one another are hydrogen atoms or alkyl or alkenyl radicals having at most 18 carbon atoms, at least one of the radicals R⁴ being an alkyl or alkenyl radical. 2. Use according to claim 1, characterized in that the radical R⁴ contains at most 12 carbon atoms and the radical R³ has 12 to 25 carbon atoms. 3. Use according to claim 2, characterized in that a radical R⁴ contains 1 to 4 carbon atoms. 4. Use according to claim 3, characterized in that  the radical R⁴ is an alkenyl radical with 2 to 4 carbon atoms is. 5. Use according to claim 4, characterized in that the rest R⁴ is an allyl group. 6. Use according to claim 3, characterized in that the radical R⁴ is an n-propyl group.