DE1545296A1 - Oil mixtures with additions of amides of high molecular weight carboxylic acids - Google Patents

Description

Description of oil mixtures with additions of amides of high molecular weight Carboxylic acids.

For this application, the priority of January 13, 1964 is changed from the USA patent application serial no. 337 187 claimed.

The invention relates to oil mixtures based on gasoline, fuels, Heating oils or lubricating oils, which are added as amides of high molecular weight carboxylic acids contain.

Lubricating oils for the modern piston internal combustion engines of high Compression ratio must have a strong cleaning ability, good sludge dispersibility and have a high resistance to oxidation, so that the motors are free of paint, Sludge and coke deposits remain. For such engines, therefore, high-performance lubricants are required with detergent action can be used to remove the Engine in high grade keep it clean and extend its lifespan.

The majority of the detergents previously used for engine lubricating oils, Sludge dispersants and antioxidants were metal compounds, especially Alkaline earth sulfonates, alkaline earth salts of alkylphenol sulfides, colloidal dispersions of metal carbonates (especially of alkaline earth carbonates) and the like. Even though these additives generally prove to be as sludge dispersants and detergents have proven to be quite satisfactory, their ash content is often a disadvantage because the ash collects in and there in the combustion chamber of the engine Ignition, spark plug contamination, valve combustion and similar undesirable Conditions caused. Because of this, ashless dispersants become as opposed to ash-forming ones Detergents such as the alkaline earth salts mentioned above are preferred. Ashless dispersants also offer advantages as additives to motor fuels, heating oils and diesel fuels.

It has now been found that effective, ash-free, mineral oil-soluble Sludge inhibitors and dispersants are suitable products that can be manufactured by having a halogenated olefin polymer of high molecular weight with a α, ß-unsaturated monocarboxylic acid to a high molecular weight monocarboxylic acid condensed with a long aliphatic chain and then with a polyalkylene polyamine converts to an amide.

The used to prepare the amides used according to the invention Olefin polymers are polymers of C2 to C5 monoolefins, e.g. B. polyethylene, Polypropylene or polyisobutylene, the olefin polymers a have an average molecular weight of about 600 to 3000 @. Particularly valuable Products are obtained when the molecular weight of the polyolefin is around 800 to 1900 is, especially in the case of polyisobutylene with acrylic acid. Such polymers contain about 40 to 250, preferably about 50 to 120 carbon atoms in the molecule. One such Polymer is halogenated with bromine or chlorine, preferably with chlorine, whereby a sufficient amount of hologen is applied to contain about 1 to 2 atoms of halogen to be introduced into each molecule of the olefin polymer. The halogenation can be im Range from room temperature to about 120 ° C can be carried out.

To facilitate the halogenation, the polymer can be used in one Solvents, such as carbon tetrachloride, are dissolved to reduce its viscosity, even if the use of a solvent is not absolutely necessary.

The time required for halogenation depends to a certain extent Depends on the rate at which the halogen is supplied. Usually 2 to 5 hours are sufficient for this. In a typical large-scale chlorination of a polyisobutylene with a molecular weight of 830 are used in one approach of 45 kg of polyisobutylene at a chlorination temperature of about 120 ° C. in the course initiated from 3 1/2 hours 4.5 kg of chlorine.

The halogenated polymer thus obtained is with an α, ß-unsaturated Monocarvonic acid with 3 to 8 carbon atoms condensed. Generally will here we use monocarboxylic acids with 3 or 4 carbon atoms in the molecule, because they are more readily available.

This subheading includes acrylic acid and α-methyl acrylic acid (d. H. 2-methylpropenoic acid) and crotonic acid or isocrotonic acid (ß-methylacrylacrylic acid). Other αβ-unsaturated monocarboxylic acids which can be used in the present invention are tiglic acid (α-methyl crotonic acid), angelioic acid (α-methyl isocrotonic acid), sorbic acid and cinnamic acid.

If necessary, instead of the free acids, their esters, such as B. ethyl methacrylate, can be used.

During the condensation of the halogenated polyolefin with the unsaturated one Monocarboxylic acid, the latter is halogenated in an amount of at least 1 mole per mole Polyolefins applied. Usually the acid will be in excess of up to about 1.5 to 2 moles of carboxylic acid per mole of halogenated polyolefin are used. The condensation temperature is about 150 to 260 ° C, preferably about 190 to 246 ° C. The condensation can take about 3 to 24 hours, but usually takes 6 to 18 hours.

After the reaction has ended, the excess acid from the mixture, for. B. be driven off with a stream of nitrogen at 204 to 260 C. ' The high molecular ones Monocarboxylic acids can also be produced using a so-called one-step process be by the halogenation of the olefin polymer in the presence of the αß-unsaturated Monocarboxylic acid is carried out. In this case, the monocarboxylic acid and the olefin polymer in the proportions given above in the reaction vessel mixed together, and the temperature is raised to the start of halogenation kept below about 66 ° C to prevent the homopolymerization of the ß-unsaturated monocarboxylic acid to prevent. Once the halogenation -has begun, the temperature can be increased up to 120 ° C. After the introduction of halogen The temperature can be increased to 150 to 260 ° C, so that the condensation reaction expires.

The high molecular weight monocarboxylic acid obtained in this way can further reacted with a polyalkylenepolyamine under reaction conditions, which favor the formation of amides. In general, this conversion takes place at one Molar ratio of monocarboxylic acid to polyamine in the range from @: 1 to 3: 1; man but can also work at higher molar ratios up to about 5: 1 if that Polyamine contains enough amino groups.

For the purposes of the invention, preference is given to those amides which are different from alkylene polyamines of the general formula derive, in which n has the value 2 or 3 and m is a number from 0 to 10. Particular compounds of this type are diethylenetriamine, tetraethylene pentamine, dipropylenetriamine, Qctaäthylenennonamin and tetrapropylenpentamin, N, N-di- (2-aminoethyl) -ethylenediamine can also be used. Other preferably used amides are those which differ from N-aminoalkylpiperazines of the general formula derive, in which n is a number from 1 to 3 and R is a hydrogen atom or an aminoalkyl radical having 1 to 3 carbon atoms. Particular examples of such compounds are N- (2-aminoethyl) piperazine, N- (2-aminoisopropyl) piperazine and N, N'-di-2-aminoethyl) piperazine.

As amides used according to the invention, however, one can also use those consisting of mixtures of different alkylene polyamines, mixtures of different N-aminoalkylpiperazines and mixtures of alkylene polyamines and N-aminoalkylpiperazines derive. The term "aliphati @@ hes polyamine" as used herein includes all of these Compounds and mixtures of compounds.

The e reaction temperatures for the amide formation reaction are in generally in the range of about 93 to 204 ° C.

Usually you will be in the narrower temperature range of about 120 to 177 ° C work. The reaction time depends to a certain extent on the temperature. The composition of the reaction mixture can be determined by the amount of the the implementation of separated water can be determined. If necessary, a water entrainer, such as heptane, can be used to drive off the water in the form of an azeotropic mixture.

The oil mixtures according to the invention, i.e. added to the most varied of oils be, whose range is from gasoline fractions 4ber fuel or. Medium fuels Boiling point extends to lubricating oils, the amides contain high molecular weight Carboxylic acids in concentrations of about 0.002 to 10% by weight.

The lubricating oils according to the invention contain the amides in concentrations from about 0.1 to 10% by weight, usually in concentrations of from about 0.1 to 5 Gow%.

The lubricating oils according to the invention which contain the amide additives belong not only to mineral lubricating oils, but also synthetic yole. The mineral lubricating oils can be of any preferred types, including those like them from the ordinary paraffinic, naphthenic, asphaltic or mixed base crude oils can be produced by refining. Synthetic too Hydrocarbon lubricants can be used. Other synthetic oils are sin Dioarboxylic acid esters, such as di-2-ethylhexyl sebacate, carbonic acid ester, phosphoric acid ester, halogenated hydrocarbons, polysilicones, polyglycols, glycol esters, such as C13 oxo acid diesters of tetraethylene glycol, and complex esters, e.g. B by reacting 1 mole of sebacic acid complex esters prepared with 2 moles of tetraethylene glycol and 2 moles of 2-ethylcaproic acid.

The additives used according to the invention can also be medium-sized distillates Settled area to prevent corrosion and the formation of sludge and sediment can be added in such fuel oils. For this purpose, the additives are in concentrations from about 0.002 to 2, generally from about 0.005 to 0.2 wt .-% applied. Petroleum distillates in the boiling range of around 150 to 482 ° C are used as fuel oils into consideration. Typical oils of this type are heating oils No. 1 and 2 according to the ASTM standard D-396-48T, grade 1D, 2D and 4D diesel fuels according to ASTM standard D-975-51T and various jet fuels. Since the oil additives are ash-free, they are suitable especially for those heating oils in which they do not leave glowing ashes and do not affect the quality of these distillates. The additives can also be used together with known, ash-free fuel oil additives, such as polymers of acrylic acid or Methacrylic acid esters, high molecular aliphatic amines, etc., can be used.

The high molecular weight amides contained in the blen according to the invention Acids can be used alone or in combination with other hydrocarbon-soluble Additives also in jet fuels and gasolines in concentrations of about 0.001 Up to 1.0% by weight are present as detergents and / or rust inhibitors.

The brenas containing the additives according to the invention, fuels or lubricating oils can also contain other additives known per se such as dyes, pour point depressants, wear-reducing agents, such as Tricresyl phosphate, zinc dialkyldithiophosphates with 3 to 8 carbon atoms, antioxidants, such as phenyl - @ - naphthylamine, tert. Octylphenyl sulfide, bisphenols, such as 4, 4'-methylene-bis- (2,6-di-tert. Butylphenol), agents for improving the viscosity index, such as polymethacrylic acid esters, Polyisobutylene, copolymers of fumaric acid alkyl esters and vinyl acetate and the like, as well as other dispersants.

The ému of the invention contained in the blen amide additives are used to increase the dispersing power and the cleaning effect of lubricating oils, which contain detergents already known in concentrations of about 0.5 to 5% by weight. If the known detergents or dispersants are metal-containing substances, they can be used together with the additives according to the invention, to further improve the sludge dispersibility and cleaning effect; without significantly increasing the formation of ash in the overall mixture. Such metal-containing Detergents or combined detergents and sludge inhibitors are e.g. B. the Alkaline earth @@. Ze of alkylated phenols or alkylated phenol sulfides, such as barium calcium nonylphenol sulfide, the so-called basic alkaline earth sulfonates and dispersions of barium carbonate or calcium carbonate in mineral oils, the various surfactants, such as. B. phosphorus sulphurized polyolefins contain.

The well-known sulfonates are oil-soluble alkaline earth salts of high molecular weight Sulphonic acids produced by sulphonating natural or synthetic hydrocarbons be won. Particular examples of suitable sulfonates are calcium petroleum sulfonate, Barium petroleum sulfonate, calcium di-C9 alkylbenzenesulfonate (with one of tripropylene group derived from C9) and barium C16-alkylbenzenesulfonate (with one derived from tetraisobutylene C16 group). The sulfonates can be neutral or over-neutralized with t bases or "strong" be alkaline "by having the metal base in excess over that for mere neutralization Contain the required amount and this excess of metal base with carbon dioxide is neutralized.

Metal salts of alkylphenols and alkylphenol sulfides are also known. Commonly used are metal salts of alkyl phenols having alkyl groups of 5 to 20 carbon atoms preferred, and an alkaline earth metal, e.g. B. calcium or barium, although sometimes also salts of aluminum, cobalt, Lead or tin.

A particular example is the barium salt of the product of the alkylation of phenol with tripropylene. Metal salts of the corresponding al @ ylphenol sulfides, e.g.

Barium tert. octyl phenol sulfide can be used.

Other oil additives that act as detergents are the conversion products of phosphorus sulphurized hydrocarbons with alkaline earth oxides or -hydroxydene, which are made by first adding a hydrocarbon with phosphorus sulfide and the reaction product with an alkaline earth metal hydroxide or oxide, e.g. B.

Barium hydroxide, preferably in the presence of an alkylphenol or an alkylphenol sulfide, and preferably also in the presence of carbon dioxide, react leaves.

The amide additives present in the oils according to the invention can also together with other ashless detergents or dispersants, e.g. B. the high molecular weight polymeric dispersants consisting of one or more polar Monomers such as vinyl acetate, vinyl pyrrolidone, methacrylic acid esters, fumaric acid esters and maleic acid esters, are present in the blen. These dispersants have molecular weights of about 500 to 50,000. An example of this is a copolymer from 65 to 85% by weight of fumaric acid esters of mixed C9 to C12 alcohols, 10 up to 20% by weight vinyl acetate and 5 to 15% by weight N-vinylpyrrolidone. Another example is a copolymer which, through conversion, has an average molecular weight of about 420 mixtures of funaric acid esters of hydrogenated tallow alcohols and fumaric acid esters of C8 oxo alcohols with vinyl acetate in a ratio of Vinyl acetate to & rB & ureestem von 3: 1 and 3 wt .-% maleic anhydride with the following Removal of the excess vinyl acetate is produced. The hydrogenated tallow alcohols are mainly C16 and C18 alcohols with lesser amounts of C12, C14 and C20 alcohols.

C8-oxo alcohols are produced by the conversion of carbon monoxide and hydrogen with mixed C3 to C4 olefins and hydrogenation of the aldehydes obtained in this way manufactured.

However, the so-called additional concentrates are also within the scope of the invention, which contain the amide additive in a higher concentration than it normally would by applying finished lubricant. These concentrates can be the additive contained in concentrations of 10 to 80% by weight on an active ingredient basis and the remainder consist of mineral oil. Such concentrates are particularly suitable for the addition add egg # to the finished lubricating oil mixture during the last mixing process. The additional concentrates can simply be made from an amide of the high molecular acid in a suitable mineral oil exist or also contain other additives that the lubricant at the same time should be added with the amide addition. If the amide additives e.g. B. together An additional concentrate can be used with detergents of a known type be prepared, which the amide additive in amounts of 30 to 60 wt .-% and a Metal sulfonate, e.g. B. Calcium petroleum sulfonate made from sulfonic acids with a molecular weight of 450, or a metal alkylphenol sulfide such as calcium nonylphenol sulfide, Contains in amounts of 5 to 20 wt .-% and the remainder consists of a mineral lubricating oil. In addition, the additional concentrate can also be a wear-reducing agent, such as a Zinc dialkyldithiophosphate, e.g. B. mixed zinc butyl and amyldithiophosphates, in Contain concentrations of 5 to 15% by weight.

Although the lubricating oil additives described here are primarily used for Crankcase lubricating oils are intended for motor vehicles, they can also be used by others Hydrocarbon oils, such as turbine oils, various technical oils, gear oils, hydraulic fluids, transmission fluids and the like will.

The following tests only serve to improve reworkability of the present invention.

Experiment 1 By a solution of 2000 g of polyisobutylene. (Molecular weight 950) in 1000 g of carbon tetrachloride is stirred for 4 hours at room temperature Chlorine passed.

Then the carbon tetrachloride is made by bubbling nitrogen through it driven off at 140 ° C. The chlorinated polyisobutylene has a chlorine content of 4, 33 wt%.

A mixture of 600 g of this chlorinated polyisobutylene and 55 g Acrylic acid is heated to 232 ° C. for 18 hours, during which hydrogen chloride is evolved. Then nitrogen is passed through the mixture for 1/2 hour at 232 ° C., whereupon the Mixture cooled to 121 ° C and filtered through a filter aid ("Dicalite") will. The product identified as polyisobutenylpropionic acid contains 0.3% by weight Chlorine and has a saponification number of 52.1 mg KOH / g.

Experiment 2 A mixture of 355 g of those prepared according to Experiment 1 Polyisobutenylpropionic acid, 132 g mineral oil (viscosity 150 BUS at 37.8 ° C) and 44 g of tetraethylene pentamine are heated to 149 ° C for 5 hours with stirring, wherein Nitrogen is constantly passed through the mixture to prevent the condensation to drive off the water split off from the monocarboxylic acid and the polyamine. The reaction product is through. the filter aid specified above is filtered and contains 2.63% by weight Nitrogen.

Experiment 3 A mixture of 710 g of one prepared according to Experiment 1 chlorinated polybutene (chlorine content 6.4% by weight; made from a polyisobutylene with a molecular weight of 830 by chlorination for 5 hours) and 88.6 g of methacrylic acid is heated to 232 ° C for 18 hours.

Then nitrogen is passed through the reaction mixture for 1 hour, to drive off the excess methacrylic acid. Thereupon the reaction mixture cooled to 121 ° C and filtered through the filter aid specified above. That Product has a saponification number of 39.0 mg KOH / g. The structure as a carboxylic acid is confirmed by the ultra-red spectrum.

Experiment 4 250 g of chlorinated polybutene (chlorine content 4, 18% by weight, produced by chlorinating polyisobutylene with a molecular weight of 950) and 27.5 g of crotonic acid are heated to 232 ° C. for 20 hours. Through the product nitrogen is passed in at 232 ° C. for 1/2 hour, whereupon the product is cooled to 121 ° C. and filtered through a filter aid (Dicalite). The product has a Saponification asahl of 1, 3 mg KOH / g and is considered by its ultrared spectrum as one Carboxylic acid identified.

Experiment 5 800 g of polyisobutylene (molecular weight 830) and 80 g of acrylic acid are heated to 38 ° C. Chlorine is added into the reaction mixture at a rate from 400 ml / min. initiated, and the temperature is increased to 121 ° C increased. After 2 hours, the chlorination is complete and the temperature is raised Maintained at 218 ° C for 18 hours. After passing nitrogen through for 1 hour 218 ° C, the reaction mixture is cooled to 121 ° C and by the above Filter aid filtered. The product has a saponification number of 38 mg KOH / g. The infrared spectrum is the same as that of the two-step method produced carboxylic acid. The product has a chlorine content of 0.42% by weight.

Experiment 6 500 g (0.4 mol) of the polyisobutenylpropionic acid prepared according to Experiment 1 with a saponification number of 48 mg KOH / g, 38 g (0.3 mol) tetraethylene pentamine, 228 g neural mineral oil (viscosity 150 BUS at 37.8 ° C) and 80 g heptane 6 hours heated to the reflux temperature of 145 to 148 ° C, with in a template according to Dean and Stark 9, 5 ml of water are collected. The heptane is made by passing it through Stripped of nitrogen on the steam bath and the product through a filter aid (Dicalite) filtered. The product has a nitrogen content of 1.65% by weight (theoretical 1.76% by weight). The structure as an amide is due to the ultrared spectrum confirmed.

Experiment 7 Do the procedure of Experiment 2 will be 443 g (0.34 moles) a polyisobutenylpropionic acid produced according to experiment 1 with a saponification number from 43 ag KOH / g and 19 g (0.1 mol) of tetraethylene pentamine in 194 g neutral mineral oil implemented as a diluent. The product contains 1, 02 % By weight nitrogen (theoretically 1.02% by weight N).

Experiment 8 540 g (0.5 mol) of the polyisobutenylpropionic acid prepared according to Experiment 1, 250 grams of neural mineral oil solvent and 51.5 (0.5 moles) diethylenetriamine are heated to 149 ° C for 3 to 6 hours, nitrogen flowing through the reaction mixture is passed to drive off the water of reaction. The product is filtered through a filter aid filtered and contains 2.5 wt .-% nitrogen.

Experiment 9 540 g (0.5 mol) of the polyisobutenylpropionic acid prepared according to Experiment 1, 256 g of neutral mineral oil as solvent and 64.5 g (0.5 mol) of N-aminoethylpiperazine are heated to 149 ° C for 3 to 6 hours, with nitrogen through the reaction mixture is passed to drive off the water of reaction. The product is filtered through a filter aid filtered and contains 2.47% by weight nitrogen.

Example 1 Using a mineral lubricating oil with a viscosity of 325 SUS at 37.8 ° C and a viscosity index of 100 as the oil base are the the following oil mixtures produced: Oil mixture 1 3.5% by weight of commercially available sludge inhibitor, 0.9 wt .-% zinc @ alkyldithiophosphate as a wear-reducing additive and 95.6 wt .-% Oil base.

Oil mixture 2 3.5% by weight of the same sludge inhibitor and 0.9% by weight the same wear-reducing additive as in oil mixture 1 together with 1.33 % By weight of the product produced according to experiment 2 and 94.27% by weight of an oil base.

Oil mixture 3 3, 5 wt .-% of the same sludge inhibitor and 0.9 wt .-% the same wear-reducing additive as in oil mixture 1 together with 1, 43% by weight of the product produced according to Experiment 7 and 94.17% by weight oil base.

The commercially available sludge inhibitor is a mineral oil solution by reacting a mixture of phosphorus sulphurized polyisobutylene and nonylphenol with barium hydroxide pentahydrate and passing carbon dioxide through the reaction mixture produced oil additive. The approximate analysis of the concentrate shows 27% by weight Phosphorus sulphurized polyisobutylene, 11.7% by weight nonylphenol, 10.6% by weight barium oxide, 2.5 wt% carbon dioxide and 48.2 wt% mineral oil.

The zinc dialkyldithiophosphate used as a wear-reducing additive is an oil solution consisting of 25% by weight of mineral lubricating oil and 75% by weight of a zinc dialkyldithiophosphate consists, which by implementing a mixture of isobutanol and mixed Amyl alcohols with phosphorus pentasulfide and subsequent neutralization with zinc oxide has been won.

The oil mixtures No., Is 2 and 3 are used to study their sludge dispersibility subjected to a sludge test carried out with periodic temperature changes, which, as experience has shown, results in similar amounts of n sludge deposits as in the Maintain city traffic with powerhouses when stopping and restarting frequently will. In this test @ a six-cylinder Ford engine runs on a dynamometer stand in alternating periods at 1500 rpm. The first period lasts 5 hours second period lasts 2 hours. In the second period the temperatures are in Oil sump and in the water jacket slightly higher than in the first. The two periods will be alternately repeated until the desired test time has elapsed. The b1 becomes as required so that the oil supply in the crankcase is always between 3, 3 and 3, 8 1 lies. At the end of selected periods of the test time, the engine is ready taken apart that the rocker arm assembly, the rocker arm cover, the cylinder head, the bumper chamber with its cover, the crankshaft and the oil pan by inspection can be visited. These parts are sorted according to the strength of the sludge deposit rated according to the CRC quality system, in which the number 10 is a complete pure engine part means and the value scale decreases up to a minimum value, the one covered with the largest possible Sohlammenge engine part. the end the quality values for the various engine parts becomes the mean formed, and this indicates the overall figure of merit for the engine.

The results of the g Sludge tests of oil mixtures 1, 2 and 3 are summarized in the table below.

The values show that the addition of those prepared according to Examples 2 and 7 Products the sludge dispersing power of the oil is greatly increased.

Quality values in the sludge test with periodic temperature change test time, Hrs. Oil: emic 1 oil mixture 2 oil mixture 3 21 9.9-42 8.6 9.94-63 6.9 9.94 9.84 84 5, 8 9, 85 9, 46 Example 2 A heating oil with a boiling range from 177 to 360 ° @ C, which is made from a mixture of split and unsplit mineral oil distillates exists, 0.02% by weight of the product prepared according to Experiment 7 is added.

Example 3 An alloyed crankcase lube oil is prepared meanwhile, a light mineral oil base with such an amount of a Viakosity index verbeaaerera, us to obtain an oil of Viakoaitätaklaaae SAE 10V-30, furthermore with 2, 3 wt .-% des Product prepared according to Yersuch 8, 1.1% by weight of a hydrocarbon sulfonic acid with an average molecular weight of 435 High alkalinity barium sulfonates (total basic number 60) and 0.75% by weight of one derived from a mixture of C4, C4 and C6 alcohols Zinc dialkyldithiophosphates is mixed.

Example 4 0.006% by weight of the concentrate described in Experiment 3 are added to leaded motor gasoline to have anti-rust and carburetor cleaning properties to rent.

Claims

Claims (3)

Claims Oil mixture based on gasoline, distillate propellants or fuels medium boiling point or lubricating oils, characterized by a content of one Monocarboxamide obtained by reacting a C2 to C5 monoolefin C40 to C250 polymer with a, B-unsaturated monocarboxylic acid, the 3 to Contains 8 carbon atoms, and subsequent conversion of the resulting high molecular weight Acid with an aliphatic polyamine in a molar ratio of polyamine to high molecular weight Acid from about 1: 1 to 1: 5t, in particular from about 1: 1 to 1: 3, obtained Has. 2. Oil mixture according to claim 1, characterized in that it is about Contains 0.002 to 10% by weight of the monocarboxamide. 3. Oil mixture according to claim 1 and 2, characterized in that it the monocarboxamide contains one which is different from acrylic acid, isobutylene and tetraethylene pentamine.