DE2401668A1 - Viscosity index improver for hydrocarbon fuels - mixture of di-N-hydrocarbyl-substituted succinamic acid, and ethylene/vinyl acetate copolymer - Google Patents

Abstract

Compsn. for improving the flow of motor-fuels and other hydrocarbon fuels consists of a mixt. of (I) a 12-28C hydrocarbyl-succinamic and disubstd. on the N atoms by 12-28C hydrocarbyl groups, or the 1-30C hydrocarbylamine salt, and (II) an ethylene/vinyl acetate polymer with a vinyl acetate content of 10-40 wt.%, and a mol. wt. of 1600-10,000. Compsn. shows synergistic effect in the lowering of poor points, and general improvement in flow properties.

Description

Additive for Improving Flow Properties The invention relates focus on admixtures to improve the fluidity of fuels.

In colder regions you often have the particularly annoying problem the flowability of middle distillates such as diesel fuels and light heating oils etc. to do. The bad Flow properties hinder the inflow from fuel to internal combustion engines or heating systems, the flow property these fuels, especially those with high paraffin contents, are mixed with falling temperatures worse. This deterioration of the flow properties at low temperatures is due to waxy substances in the fuel, which crystallize and thereby make the fuel semi-solid or gel-like and make it practically unpumpable. The problem becomes particularly acute when in the pump line Filters are used as these filters hold the waxy crystals in place and clog quickly.

The flow properties of these fuels are usually thereby improves the fact that an additive is added to the fuel mixture, which improves the flowability improved. These additives set the amount of waxy substances that are exposed crystallize in the fuel, not down, they modify size, Shape and surface of these crystals due to absorption and / or mixed crystallization and reduce the occlusion of the liquid medium by the crystals 0 Rs thus causes a change in the crystal structure of the paraffin and the tiles of liquid hedium.

Many researchers have the flow properties with the pour point or Related cloud point. But it has been shown that the attraction the pour point and / or cloud point of waxy fuels Some are unreliable about the flow properties of the fuel mixture For example, additives are particularly effective in Humiliation of the pour point of a fuel, but it shows only a modest effect on the improvement of the flow properties. Because of this lack of reliability Other tests have been developed to make predictions about the pleating properties of fuels to make. One of these tests is the "Cold Filter Plugging Point" Test "(DIN 51428), which is largely used as a measure of the serviceability of a fuel used in diesel engines at low temperatures.

Numerous patents are known in which a large number of pour point depressants, some of which are particularly effective to improve the flowability of fuels.

Pour point depressants are, for example, naphthalenes, which are chlorinated with Paraffins are alkylated, homo- and copolymers of hydrocarbon olefins, methacrylates, Vinyl esters, alkyl styrene, etc. In U.S. Patent 3,544,467 a pour point depressant is described which also has excellent ostschutz properties owns. This additive is an alkenyl succinamic acid which is disubstituted on the nitrogen atom with long-chain alkyl groups. It will also noted that these new compounds in combination-with ethylene-oleefin copolymers are effective as pour point depressants.

Even if the combination described above is satisfactory behavior shows in the lowering of the pour point, it was found in further research found a previously unknown combination that not only lowers the pour point, but also particularly effective in improving the sealing properties is.

According to the invention contain additives to improve the flow properties of waxy hydrocarbon fuels, a mixture of (1) one with 012 to C28 hydrocarbon radicals substituted succinamic acid on the nitrogen atom is disubstituted with O12 to C28 hydrocarbon groups, and (2) an ethylene-vinyl acetate polymer, the 10 to 40 Gewichiw percent vinyl acetate and a molecular weight between 1600 and about 10,000 owns. The succinamic acid is produced by reaction of the hydrocarbon-substituted succinic anhydride with a secondary one Amine at a temperature of about 650C to 120 cm The ethylene-vinyl acetate polymer is commercially available and can be obtained by numerous conventional polymerization processes can be obtained.

It was found that a middle distillate after the addition of small amounts the inventive combination in the "Cold Filter Plugging Point Test" drastically Decreased values gives 0 The exact mechanism by which the two components lowering the pour point is not known, but it has been found that the Both compounds complement each other in synergistic ways, resulting in a combination with properties superior to those of any additive alone.

The flow properties of distillate oils can be significantly improved by adding to the fuel: (1) 10 to 10,000 ppm of a hydrocarbyl-substituted succinamic acid, which in a preferred embodiment is the general formyl in which R is a hydrocarbon radical having 12 to 28 carbon atoms, preferably 16 to 22 carbon atoms, and 0 to 1 olefinically unsaturated bond, and X and X1 are hydroxyl groups or di (C12 to C28 hydrocarbon) -substituted secondary amino groups, where one of the substituents X and X1 is hydroxyl, and (2) 1 to 2000 ppm of an ethylene-vinyl acetate polymer which contains 10 to 40 percent by weight vinyl acetate and has an average (number average) molecular weight between 1600 and about 10000% .

The radical R in the above formula is preferably a straight-chain Alkyl or alkenyl such as lauryl, hexadecyl, octadecyl, tetradecyl, heptadecyl, Eicosyl, docosyl, hexadecenyl, octadecenyl, myristyl, palmityl, stearyl, behenyl, Cerotyl, Palmitoleyl, Oleyl, etc.

The hydrocarbon-substituted secondary amino group has the following general formula - NYY1 wherein Y and Y1 are aliphatic hydrocarbon radicals with 12 to 28 carbon atoms, and preferably 16 to 22 carbon atoms (suitable Groups are listed in the definition for R above).

Y and Y1 can be aliphatically saturated or aliphatically unsaturated be and are generally free of acetylene bonds, so alkyl or alkenyl groups. There can be 1 or 2 olefinic double bonds. Y and Y1 can be identical or different, straight-chain or branched, preferably they are straight-chain. The branches usually do not have more than 1 carbon atom, are therefore ethyl groups. The junction with the Nitrogen can be on a terminal or an internal carbon atom.

As can be seen from the formula above, it doesn't matter which one Position the alkyl or alkenyl group in relation to the carboxamide or carboxyl group Einniont Due to the large volume of the amine, however, the usual preparation process produces using succinic anhydride, as the main product, a compound that carries the alkyl or alkenyl group in ß-position to the carboxamide group. In this scale, as this is the more accessible compound, this derivative is preferred. What but as far as applicability is concerned, either isomer or a mixture of the two can be used Isomers are used.

The individual compounds or mixtures of compounds can also can be used as additives to improve the flow properties. Mixtures of compounds with different C and / or N substituents, both homologues like isomers, are often used when referring to the individual precursors of succinamic acid are not easily accessible.

Examples of substituted succinamic acids are: N, N-dihexadecyl-hexadecylsuccinamic acid, N-hexadecyl-N-octadecyl-octadecylsuccinamic acid, N, N-Dihexadeceny -C20} -alkenylsuccinamic acid, N-Hezadecenyl-N-eicosenyl-octadecylsuccinamic acid, N, N-dioctadecenyl- (C1 6-O18) alkenyl succinamic acid etc.

As mentioned above, the succinamic acid can be in the form of the amine salt, but are preferably used as a mixture of acid and amine salt.

The amine salt or acid or mixtures thereof can be represented by the following formula: wherein R is as defined above and one of the substituents X2 and X is - NYY1, wherein Y and Y1 have been defined as 3 above. The other of the substituents X2 and X has the 3 formula: - OH (NHY2Y3) n where Y2 and Y are hydrogen, an aliphatic hydrocarbon radical with 1 to 30 carbon atoms or an oxyaliphatic hydrocarbon radical (in the 1 ether oxygen atom in the nitrogen bonded radical is present which is at least in the ß-position to the nitrogen atom) with 3 to 30 carbon atoms. Y2 and lt can also be combined and form a heterocyclic ring with 5 to 7 members in which nitrogen and oxygen are the only heteroatoms. The index n varies from 0 to 1, preferably from 0.1 to 0.9. This means that 10 to 90 mol percent of the succinamic acid is in the form of the salt.

The aliphatic hydrocarbon groups can be saturated or unsaturated be and usually do not own more than 2 Ethylenically unsaturated Ties. The total number of carbon atoms in iMY2Y3 is from 0 to 60, usually 1 to 4o.

The groups listed for Y and lt1 can also be used for Y2 and Y. will. But as mentioned earlier, primary amines can work just as well as secondary Amines can be used to form the salt. If another amine is used to form the Salt is used when it was used to make succinamic acid, What will be discussed in the following, usually results in a mixture of Salt; both the added amine and the secondary, for the preparation of the succinamic acid used amines take part in the salt formation.

Amines that can be used to form the salts are, for example Di-secbutylamine, heptylamine, dodecylamine, octadecylamine, t; -butylamine, morpholine, Diethylamine, methoxybutylamine, methoxyhexylamine, etc.

The alkenyl succinamic acids according to the invention can be easily prepared by adding an alkyl or alkenyl succinic anhydride with the desired secondary amine at a temperature in the range of about 650C to 120C in approximately equimolar amounts without a solvent or in the presence of an inert solution means is brought to implementation. The reaction time is generally about 15 minutes up to 1 hour. This implementation is known to the person skilled in the art and does not require any further details here Explanation.

The alkyl or alkenyl succinic anhydride required for the reaction used can be a single compound or a mixture of compounds be. This means that there can be different alkyl or alkenyl groups with different ones Number of Carbon atoms or various linkage points on the succinic anhydride group can be used. It can also be a single one Isomer can be applied. Because mixtures are generally more accessible they are preferred in the appropriate wetness. In many balls there are mixtures used by aliphatic hydrocarbon-substituted succinic anhydrides, in which not a single homologue is present in an amount of more than 25 tlol percent is.

Different secondary amines can be used which are the same aliphatic hydrocarbon groups and also different aliphatic hydrocarbon groups in the molecule 0 There can be alkyl or alkenyl substituents on nitrogen be present, each having at least 14 carbon atoms. The difference between the two aliphatic hydrocarbon groups on nitrogen is not critical, but is generally less than 8 carbon atoms, mostly less than 6 carbon atoms0 In most cases these are aliphatic hydrocarbon groups straight chain, i.e.

normal, with the amino nitrogen having an inner or a terminal Carbon atom is linked.

It was found that when main and succinic anhydride approximately in a molar ratio of 1: 1 are used, depending on the reaction conditions a considerable amount of amine can remain unreacted and the salt obtained Forms succinamic acid. In some cases up to 30 percent of the amine remains unreacted and form a considerable amount of salt, therefore the salt often makes up 10 to 30 mole percent der-total succinimidic acid from. However, unreacted anhydride groups can also be used in A certain amount remain in the reaction mixture, which is then added to the additive mixture be dragged along, which is used to improve the flowability.

In cases where significant amounts of water are used during the implementation are present, this water can react with succinic anhydride and form succinic acid. Venn the temperature for the formation of succinic anhydride is not high enough, the succinic acid is likely to remain as such or forms the amine salt with unreacted main.

Therefore, the mixtures of succinamic acid salts in general only using a 1: 1 molar ratio for amine to succinic anhydride and should not be attempted to be a full implementation to achieve or to work with a molar excess of amine, leave the amine salts easily gain by adding the amine to the succinamic acid, the addition can be done directly or in an inert solvent. Slight heating can facilitate implementation.

The second component according to the invention is an ethylene-vinyl acetate polymer, the 10 to 40 percent by weight, preferably 20 to 30 percent by weight of vinyl acetate and an average molecular weight between 1600 and about 10,000, preferably 2000 and 5000, and in the most favorable case between 2200 and 3000. The polymer Small amounts of other monomers can be added or bound to the polymer chain contain. Other monomers that can be used are, for example, acrylates, kiethacrylate, methylol methacrylate, vinyl ethers, vinyl olefins such as propylene, isobutylene etc., vinyl ketones etc. These 2) (number average) other monomers must not be more than 35 percent by weight of the polymer, preferably less than 20 percent by weight and in the cheapest hall less than 10 percent by weight.

The polymers are commercially available, so a detailed one is given Description of a manufacturing process is not required here.

Except for the substituted succinamic acid and the ethylene-vinyl acetate polymer can also use other additives in the mixture to improve flowability and be present in the fuel.

A frequently used additive is a demulsifier. Numerous demulsifiers are commercially available and can be used here. A particularly effective demulsifier is an alkoxy-modified polyalkylphenol with methylene bridges, which has the following structural formula: wherein: U is an alkylene of 2 to y carbon atoms, preferably 2 carbon atoms; T is an alkyl having 4 to 15 carbon atoms, preferably 6 to 12 carbon atoms; m is an integer from 4 to 10, preferably 5 to 8, where at least 80 percent of the Slko chains are in the specified range; n1 is an integer from 2 to 10, preferably 4 to 8; and A is hydrogen or methylol (- CH2OH), the same or different.

Compounds of the above structure can by condensing a alkylated phenol can be prepared with formaldehyde, initially a polyalkylated Phenol is obtained with methylene bridges, which then with an alkylene oxide such as ethylenolide or propylene oxide is unset. A particularly effective demulsifier is produced by reacting 5 moles of an alkylphenol with 4-5 moles of formaldehyde and the following Implementation of the reaction product with about 30 moles of ethylene oxide.

Suitable alkylphenols are, for example, p-isobutylphenol, p-hexylphenol, p-octylphenol, p-nonylphenol, p-tripropylene phenol USWo Another type of demulsifier is an ammonia-neutralized sulfonated alkylphenol.These compounds have the following general structure: wherein R1 is a hydrocarbon radical having 4 to 15 carbon atoms, preferably 6 to 12 carbon atoms.

These compounds are made by sulfonating an alkylated phenol and subsequent neutralization of the sulfonation product with ammonia obtained0 A Another type of emulsifier is an oxyalkylated glycol.

These compounds are made by reacting a polyhydroxy alcohol such as ethylene glycol, trimethylene glycol, etc. obtained with ethylene or propylene oxide. Many of these compounds are under the trademark Pluronics by the Wyandotte Chemical Company. They are polyethers with terminal hydroxyl groups, which are produced by Block copolymerization of ethylene oxide and propylene oxide The ethylene oxide blocks act as hydrophilic and the propylene oxide blocks as hydrophobic Groups. The products are in a wide range of molecular weights and with different Ethylene oxide to propylene oxide block ratios available.

The above demulsifiers can be used individually or as mixtures to be brought. A particularly effective demulsifier is a mixture of 10 to 90 Parts of an alkoxy-modified polyalkylphenol containing methylene bridges, 10 to 90 parts of an ammonia-neutralized, sulfonated alkylphenol and 10 to 90 parts of an oxyalkylated Elylcol, based on 100 parts of the application Brought total demulsifier.

The demulsifier can be added to the additive mixture, which is used to improve the Flowability is used, with or without the aid of a solvent added will. In general, however, an inert, stable, organic solvent is used Suitable solvents are, for example, those below under the description of concentrates listed for the additive mixture.

The substituted succinamic acids (if these are mentioned is, the salts or combinations of acids and salts are included) in combination with the ethylene-vinyl acetate polymers can be used in a wide variety of fuels hydrocarbon-based, if there is an improvement in these the? let properties is required.

The compositions according to the invention are particularly suitable for middle distillates.

Products of natural origin as well as synthetic fuels can in connection with the additives according to the invention which improve the permeability be used.

Usually at least 35 ppm or more of the active ingredient will be found improving mixture applied. In general, the amount of Additive at less than about 2 weight percent and often less than 1 weight percent based on fuel, but usually in the range of 35 ppm to fooo ppm.

The ratio of succinamic acid to ethylene vinyl acetate polymers is generally about 0.25 to 50 parts succinamic acid per part of the polymer, but usually about 5 to 20 parts succinamic acid per 1 part of the polymer.

The compositions according to the invention for improving the flowability can be used in the presence of various other additives, as they are common in compounded fuels. Except for the flowability improver can rust inhibitors, dyes, detergents, dispersants, antioxidants, Antistatic agents, metal deactivators, ignition accelerators, antiquals etc.

to be present. Usually these other additives are in bulk from about 0.001 to 5 percent by weight.

The following Table I contains the concentrations of the various Components that may be present to improve the pleat properties of a fuel to improve effectively.

TABLE 1 Composition of the fuel mixture Pure range Hydrocarbon fuel (wt.%) 95 - # 100 Succinamic acid * (ppm) 10 - 10,000 Ethylene vinyl acetate polymer (ppm) 1 - 2,000 Demulsifier (ppm) 0.1 - 50 Other additives ( E.) O - 5 Preferred Range Hydrogen Fuel (wt.%) 98 - # 100 Succinamic Acid * (ppm) 30 - 1,000 Ethylene Vinyl Acetate Polymer (ppm) 2 - 100 Demulsifier (ppm) 0.5 - 15 Others Additives (% by weight) O - 1 hydrogen-substituted succinamic acid as defined in the formula above.

In many cases it is beneficial to use the mixture for improvement add the flowability as a concentrate to simplify transport and a convenient addition. to allow the fuel. In general is a Solvent required to keep the concentrate in a dispersed or liquid state to keep. Any stable organic solvent can be used that a corresponding dissolving power for the succinamic acid and the ethylene-vinyl acetate polymers owns and proportionately to these components is inert. Suitable solvents are aliphatic and aromatic hydrocarbons, aliphatic ethers, halogenated hydrocarbons and preferably mixed aromatics (i.e.

Xylenes from reformate fractions) or aliphatics within the range boil from 1500C to 3700C0 The concentrations of the various components, including of the demulsifier in the concentrate generally range from 4 to 95 Parts by weight of succinamic acid, 0.2 to 30 parts by weight of ethylene-vinyl acetate polymers, 0 to 2 (preferably 0.01 to 1.5 parts by weight demulsifier and 0 to 95 (preferably 10 to 50 parts by weight of solvent per 100 parts of concentrate.

The following examples serve to illustrate the implementation of certain tests Embodiments of the invention are not intended to be limiting in the claims defined within the scope of the invention.

EXAMPLE 1 This example serves to illustrate the preparation of a typical hydrocarbon-substituted succinamic acid disubstituted on the nitrogen atom.

9.072 kg of C15-20-1 olefins are placed in a vessel and with 1.234 kg of a silica-alumina catalyst (known under the trade name Aero Cat.) Mixed. The mixture is stirred for a further half an hour in order to To disperse catalyst, 362.87 kg of the C15-20-1 olefins are then added. It is niin heated and the mixture is stirred for 3 hours kept at a temperature of 2050C. At the beginning, the temperature of the reaction mixture rises due to the heat generated during the conversion to 218 ° C. The termination of the Isomerization can be recognized by the disappearance of an infrared band at 910 cm-1. The reaction mixture is then filtered, and the isomerized olefin distilled at 180 ° C and 100 mm Hg.

The distillation is finished when the boiler temperature reaches 302 ° C Has.

Then 510 parts by weight of the above prepared C15 20 -, - olefin placed in a reaction vessel with 100 parts by weight of maleic anhydride (the Molar ratio of olefin to maleic anhydride is 2: 1). The mixture is made with nitrogen flushed through and the system closed. It is heated and stirred and the mixture held at 232 ° C. The pressure in the system is about 2.8 kg / cm2 (25 psig) as a result of the developed maleic anhydride vapors. The reaction is complete in about 3 hours, which can be seen from the disappearance of an infrared band at 840 cml. That Excess olefin is then removed by vacuum distillation.

Then 343 parts by weight of the alkenyl succinic anhydride in Another reaction vessel is introduced, and 520 parts of a di-N- (hydrogenated Tallow) amine added.

This product is sold under the trademark Armor Chemical Co. Armies expelled 2HT.

The mixture is heated to 65 ° C. and gives the corresponding N-disubstituted one Alkenyl succinamic acid (DTASA). A sample of the product is isolated and tested through Characterized titration and infrared spectrum.

EXAMPLE 2 This example serves to demonstrate the fact that With the combination according to the invention, there is a deep "cold filter plugging point" (CFPP) can be achieved. This CFPP test determines the capability of a fuel measured, a very fine filter element to be flowed through below its training point The test recently became official as a determination method for low temperature serviceability recognized for critical European diesel engines. Performing the test and Devices are described in DIN 51428.

In short, the test consists of that a fixed volume of the oil to be tested at gradually falling temperatures through a standardized Wire mesh filter (350 U.S. mesh) is sent. Because of the paraffin that separates out causes the flow rate to decrease and it may become a the filter becomes completely clogged. The temperature at which there is no flow more takes place, is known as the "Cold Filter Plugging Point" and is in close to -16.7 ° C.

The samples contain different amounts of an ethylene-vinyl acetate copolymer, a disubstituted likenylsuccinamic acid, prepared according to Example 1, and different amounts of a demulsifier in a straight run diesel oil (base oil), that was made from a crude oil from the Middle East / North Africa and a dead center of -6.70G. The oil samples were tested and the results are in the table II listed.

TABLE II Cold Filter Plugging Point Test Additives in Base Oil CFPP Test type conc. (Ppm) (° C) 1 core --- - 5.6 2 DTASA 80 - 5f6 3 DTASA 400 - 5.6 4 Ethylene-vinyl acetate 25 -10.0 5 Ethylene-vinyl acetate 125 -11.1 6 Ethylene-vinyl acetate'1 250 -11.1 7 DTASA * 71 ethylene vinyl acetate ** 2.5 -11.1 demulsifier *** 0.5 8 DTASA * SEI 189 ethylene vinyl acetate ** 15 - 16.7 demulsifier *** 1.5 9 DTASA u 213 ethylene vigacetate 7.5 -17.8 Demulsifier 1.5 1DTASA is a di-N-alkenylsuccinamic acid based of hydrogenated tallow prepared by the method of Example 1.

11An ethylene-vinyl acetate copolymer from Allied Chemical Company, which is sold under the brand name "AC-402". The copolymer contains 25% by weight vinyl acetate and has a molecular weight of about 2300.

*** The demulsifier (Tretolite L1649) is a combination of: (1) a sulfonated ammonia neutralized alkylphenol; (2) an oxyalkylated one Glycol; and (3) an alkoxy-modified polyalkylphenol with methylene bridges.

As can be seen from the table above, the addition of the changes above-described di-N-alkenylsuccinamic acid (DTASA) alone the temperature of the CFPP at no concentration while using the ethylene vinyl acetate alone lowered the temperature by 5.5 ° C at a concentration of 250 ppm. The combination of 213 ppm DTASA with 7.5 ppm ethylene vinyl acetate and 1.5 ppm demulsifier on the other hand lowered the CFPP temperature by 12.2 ° C. This is the strong synergism between DTASA and ethylene vinyl acetate have been shown to lower CFPP.

EXAMPLE 3 This example is intended to demonstrate that the temperature of the The pour point does not make reliable predictions about the flow properties of a distillate oil allowed. In this test the pour point of all in Example 2 is used Mixtures measured. The pour point is determined in accordance with ASTM D-97. In table III below is the pour point of the samples pooling with that given in Example 2 Cold Filter Plugging Point (CFPP) listed.

TABLE III Pour Point Test Additives in Base Oil CFPP Pour Point Mixture Type Conc. (Ppm) (° C) (° C) 1 None --- - 5.6 - 9.5 2 DTASA * 80 - 5.6 - 20.5 3 DTAS * 400 - 5.6 - 28.9 4 EVA ** 25 - 10.0 - 12.2 5 EVA ** 125 - 11.1 - 23.3 6 EVA ** 250 - 11.1-7 DTASA * 71 EVA ** 2.5 - 11.1 - 17.8 Demulsifier *** 0.5 8 DTASA * 189 EVA ** 15 - 16.7 - 28.9 demulsifier 1.5 9 DTASA * 213 EVA ** 7.5 - 17.8 - 26.1 demulsifier *** 1.5 K * DTASA as defined in table II ** EVA (ethylene vinyl acetate) as in table II defined *** Demulsifier as defined in Table II.

The above table shows that the measurement of the pour point fails, when it comes to determining the flow properties of a distillate oil. A Comparison of test mixtures 3 and 8 shows that both compositions have the same pour points to have; but with regard to the flow properties, mixture 8 is far compared to mixture 3 think.

EXAMPLE 4 This example demonstrates the superior properties of combination according to the invention with regard to water sensitivity.

In this test, 300 ml of the oil to be tested together with 3 ml of sea water was placed in a high performance mixer (Waring Co.). The content runs for 30 seconds at 7000 rpm. touched.

The mixture is observed visually after 1 hour and 24 hours was left alone. The turbidity of the oil is rated on a scale from 1 to 5, in which 1 is clear and transparent, while 5 means dull.

The test mixtures contain different amounts of an ethylene-vinyl acetate copolymer, a disubstituted alkenyl succinamic acid and a demulsifier in a straight run diesel oil, that came from the Middle East / North Africa and has a cloud point of -6.70C would have. The samples are subjected to the above test, the haze is measured and recorded in the following table IV.

TABLE IV Water Sensitivity Additives in Base Oil Yellowing Rating Hrs.) Mixture type Conc. (Ppm) 1 24 1 None --- 5 4 2 Demulsifier *** only 1.5 5 3 3 DTASA * only 240 5 3 4 DTASA 240 2 1 1.5 Demulsifier 5 EVA only 75 5 3 6 Demulsifier *** 1.5 5 3 EVA ** 75 7 DTASA * 115 5 3 EVA ** 8 DTASA * 216 5 3 EVA ** 7.5 9 DTASA * 115 2 1 EVA ** 30 Demulsifier *** 1.5 * DTASA defined in Table II ** EVA (ethylene vinyl acetate), defined in Table II *** Demulsifier defined in Table II.

Table IV above shows a comparison of mixtures 1, 2, 3 and 4 that the combination (mixture 4) of demulsifier and DTASA is the most remarkable Trtibung of 2 after one hour and 1 after 24, while the individual components in the oil no rating better than 5 after 1 hour and 3 after 24 hours could get. A comparison of mixtures 2, 5, 6, 7 and 8 with mixture 9 shows that the combination of DTASA, ethylene vinyl acetate and demulsifier regarding the turbidity behavior is superior to the individual components.

EXAMPLE 5 This example serves to illustrate the preparation of a preferred combination according to the invention. The mixture in question is produced by combining the following components are: (1) an ethylene vinyl acetate polymer (referred to as "EVA Polymer" in Table Y) having a molecular weight of about 2350 and a vinyl acetate content of about 25 percent by weight (the polymer should also contain smaller amounts of a third component). The polymer will from Apollo Chemical Company under the trade designation Apollo WD-22 as 25 % strength by weight solution in an aromatic solvent sold; (2) an N-disubstituted one Alkenyl succinamic acid based on hydrogenated tallow (in Table V as "DTASAn designated), prepared according to the method of Example 1; and (3) about 1 percent by weight a demulsifier (Tretolite L-1649).

Different base oils are used.

The compositions and the "Cold Filter Plugging Point" for everyone Mixtures tested are listed in Table V.

TABLE V Compositions CFPP Mixture Base Oil Additive Conc. (Ppm) (° C) 1 Diesel oil A --- --- - 6.7 2 Diesel oil A DTASA 80 EVA Polymer 20 -13.3 3 Diesel oil A DTASA 240 EVA Polymer 60 -16.7 4 Diesel oil B --- --- - 8.3 5 Diesel oil B DTASA 80 -11.1 EVA polymer 20 6 Diesel oil B DTASA 240 EVA polymer 60 -13.9 7 Light heating oil C --- --- - 6.7 8 Light heating oil C DTASA 240 EVA polymer 60 9 Diesel gas oil D --- --- - 9.5 10 Diesel gas oil D DTASA 240 EVA Polymer 60 11 Light heating oil E --- --- - 4.5 12 Light heating oil E DTASA 240 EVA Polymer 6o -12.8 All base oils are straight-run distillates in the boiling range of 150 ° C to 400 ° C, made from mixtures of Arabic and North African Crude oil were produced. The cloud points of these products are in the range of - 10 ° C to - 3.4 ° C.

Claims (15)

P a t e n t a n 5 p r ü c h e & Composition to improve the flow properties, marked by a mixture of (l) a C12- to C28-hydrocarbyl-substituted succinamic acid, which is disubstituted on the nitrogen atom with C12 to C28 hydrocarbon groups, or their salt with a C1 to C30 hydrocarbon amine or mixtures of acid and salt, and (2) an ethylene-vinyl acetate polymer that is from 10 to 40 percent by weight Contains vinyl acetate and has a molecular weight between 1600 and about lo ooo. 2. Composition according to claim 1, characterized in that the succinamic acid has the general formula where R is a Cl2 to C28 hydrocarbon radical with o to 1 olefinically unsaturated bonds, and -X and X1 are a hydroxyl group or a secondary amino radical disubstituted with Cl2 to C28 hydrocarbon groups, where one of the substituents X or X1 is a hydroxyl group. 3. Composition according to claim 1, characterized in that the succinamic acid or its amine salt has the general formula wherein R is a C12-C28 hydrocarbon radical with 0 to 1 olefinically unsaturated bond, and X and X1 are hydroxyl or -OH (NHY2Y3) or a sec-amino radical disubstituted with C28 hydrocarbon groups, where one of the substituents X or X1 is hydroxyl or -OH (NHY2Y3), and Y2 and Y3 can be the same or different and are hydrocarbon groups with 1 to 30 carbon atoms or alkoxy groups with 3 to 30 carbon atoms, which together with the nitrogen to which they are linked, are a heterocyclic ring with 5 to 7 ring members can form. 4. Composition according to claim 1, 2 or 3, characterized in that that a demulsifier is also present in the additive. 5. Composition according to claim 4, characterized in that the Demulsifier an alkoxy-modified polyalkylphenol containing methylene bridges, an ammonia neutralized, sulfonated alkylphenol or an oxyalkylated one Glycol or a mixture of these compounds. 6. Composition according to claim 4, characterized in that the demulsifier (i) is an alkoxy-modified, methylene bridges-containing polyalkylphenol of the formula wherein U is an alkylene with 2 to 3 carbon atoms or a corresponding mixture of different alkylene groups, T is an alkyl with 4 to 15 carbon atoms, m is an integer from 4 to 10, n1 is an integer from 2 to 10 and A is hydrogen or methylol, or (2) an ammonia-neutralized, sulfonated alkylphenol of the formula wherein R is a hydrocarbon radical having 4 to 15 carbon atoms, or (3) an oxyalkylated glycol, or (4) a mixture of these compounds. 7. Composition according to one of the preceding claims, characterized characterized in that the succinamic acid in an amount of 0.25 to 50 parts by weight is present per part by weight of the polymer. 8. Composition according to any one of the preceding claims, characterized characterized in that it contains an inert, stable, organic solvent. 9. Composition according to any one of claims 1 to 6, characterized marked, that they are 4 to 95 parts by weight of the succinamic acid or its amine salt or one Mixture of acid and salt, 0.2 to 30 parts by weight of the ethylene-vinyl acetate polymer, 0 to 2 parts by weight of a demulsifier and 0 to 95 parts by weight of an inert, contains stable, organic solvent, the parts by weight per 100 parts of the concentrate. 10. Composition according to one of the preceding claims, characterized characterized in that the additive is admixed with a fuel based on hydrocarbons will. 11. Fuel mixture, characterized in that it is at least 95 percent by weight of a distillate oil and a composition according to any one of the claims 1 to 9 to improve the flow properties. 12. Fuel mixture according to claim 11, characterized in that the succinamic acid or its amine salt or the mixture of acid and salt in one Amount from 10 to 10,000 ppm and the ethylene-vinyl acetate polymer in an amount from 1 to 2,000 ppm is present. 130 Method of making a composition for improvement the flow properties according to one of claims 1 to 3, characterized in that that are combined: (1) a C12-C28 hydrocarbon-substituted succinamic acid, which is disubstituted on the nitrogen atom with C12-C28 hydrocarbon groups, or their amine salt, in which the amine component contains C1-C30 hydrocarbon groups, or a mixture of zu and salt, and (2) an ethylene-vinyl acetate polymer, containing 10 to 40 weight percent vinyl acetate and a molecular weight between 1600 and about 10,000 owns. 14. Process for improving the flow properties of a distillate oil, characterized in that a composition according to any one of the claims is added to the oil 1 to 9 is added. 15. Composition as an additive to a distillate oil, characterized in that it contains: (1) a succinamic acid or its amine salt with the following general formula wherein R is a C12-C28 hydrocarbon radical with 0 to 1 olefinically unsaturated bond, and X and X1 are hydroxyl or OH (NHY2Y3) or a sec-amino radical disubstituted with C12-C28 hydrocarbon groups, one of the substituents X or X1 being hydroxyl or -OH (NHY Y), and 23 Y2 and Y can be the same or different and are carbon-3 hydrogen groups with 1 to 30 carbon atoms or alkoxy groups with 3 to 30 carbon atoms, which together with the nitrogen to which they are linked are also a heterocyclic Ring with 5 to 7 ring members, and (2) a demulsifier which is (1) an alkoxy-modified methylene bridge-containing polyslkylphenol of the formula wherein U is an alkylene with 2 to 3 carbon atoms or a corresponding mixture of different alkylene groups, T is an alkyl with 4 to 15 carbon atoms, m is an integer from 4 to 10, n1 is an integer from 2 to 10 and A is hydrogen or methylol, or (2) an ammonia-neutralized, sulfonated alkylphenol of the formula wherein R is a hydrocarbon radical having 4 to 15 carbon atoms, or (3) an oxyalkylated glycol, or (4) a mixture of these compounds.