EP1451271A2 - Additives for low-sulphur mineral oil distillates, containing an ester of an alkoxylated polyol and a polar nitrogenous paraffin dispersant - Google Patents

Abstract

The invention relates to additives for middle distillates having a maximal sulphur content of 0.05 wt. %. Said additives contain at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one polar nitrogenous paraffin dispersant (D).

Description

 description

Additives for low sulfur mineral oil distillates, comprising an ester of an alkoxylated polyol and a polar nitrogen-containing paraffin dispersant

The invention relates to additives for low-sulfur mineral oil distillates with improved cold flowability and paraffin dispersion, comprising an ester of an alkoxylated polyol and a polar nitrogen-containing paraffin dispersant, additized fuel oils and the use of the additive.

In the course of the declining oil reserves, crude oils, which are becoming more and more problematic, are extracted and processed as energy demand increases. In addition, the requirements for the fuel oils such as diesel and heating oil produced from them are becoming increasingly demanding, not least due to legislative requirements. Examples of this are the reduction in the sulfur content, the limitation of the boiling point and the aromatic content of middle distillates, which force the refineries to constantly adapt the processing technology. In many cases, this leads to an increased proportion of paraffins in middle distillates, especially in the chain length range from C-iβ to C ₂₄ , which in turn has a negative influence on the cold flow properties of these fuel oils.

Crude oils and middle distillates obtained by distilling crude oils such as gas oil, diesel oil or heating oil contain different amounts of n-paraffins depending on the origin of the crude oils, which crystallize out as platelet-shaped crystals when the temperature is lowered and partly agglomerate with the inclusion of oil. This crystallization and agglomeration leads to a deterioration in the flow properties of the oils or distillates, as a result of which faults can occur during the extraction, transport, storage and / or use of the mineral oils and mineral oil distillates. When mineral oils are transported through pipelines, the crystallization phenomenon can lead to deposits on the pipe walls, especially in winter, in individual cases, for example when a pipeline is at a standstill, even causing it to become completely blocked. In the storage and processing of mineral oils, it may also be necessary in the winter Store mineral oils in heated tanks. In the case of mineral oil distillates, the filters in diesel engines and combustion plants may become clogged as a result of the crystallization, which prevents safe metering of the fuels and, under certain circumstances, completely stops the fuel or heating medium supply.

In addition to the classic methods of removing the crystallized paraffins (thermal, mechanical or with solvents), which only refer to the removal of the precipitates that have already formed, chemical additives (so-called flow improvers) have been developed in recent years. Through physical interaction with the precipitating paraffin crystals, these cause their shape, size and adhesion properties to be modified. The additives act as additional crystal nuclei and partially crystallize with the paraffins, which results in a larger number of smaller paraffin crystals with a changed crystal shape. The modified paraffin crystals are less prone to agglomeration, so that the oils mixed with these additives can still be pumped or processed at temperatures which are often more than 20 ° C. lower than with non-additive oils.

Typical flow improvers for crude oils and middle distillates are copolymers and terpolymers of ethylene with carboxylic acid esters of vinyl alcohol.

Another task of flow improver additives is to disperse the wax crystals, i.e. the delay or prevention of sedimentation of the paraffin crystals and thus the formation of a paraffin-rich layer on the bottom of storage containers.

Certain poly (oxyalkylene) compounds and alkylphenol resins are also known in the prior art, to which middle distillates are added as additives.

EP-A-0 061 895 discloses cold flow improvers for mineral oil distillates which contain esters, ethers or mixtures thereof. The esters / ethers contain two linear saturated C-io to C ₃₀ alkyl groups and a polyoxyalkylene group with 200 to 5000 g / mol.

EP-0 973 848 and EP-0 973 850 disclose mixtures of esters of alkoxylated alcohols with more than 10 C atoms and fatty acids with 10 - 40 C atoms in combination with ethylene copolymers as flow improvers.

EP-A-0 935 645 discloses alkylphenol aldehyde resins as a lubricant-improving additive in low-sulfur middle distillates.

EP-A-0857776 and EP-A-1 088 045 disclose methods for improving the flowability of mineral oils and mineral oil distillates containing paraffin by adding ethylene copolymers and alkylphenol-aldehyde resins and optionally further nitrogen-containing paraffin dispersants.

The above-described flow-improving and / or paraffin-dispersing action of the known paraffin dispersants is not always sufficient, so that when the oils cool, large paraffin crystals form in part, which lead to filter blockages and, due to their higher density, sediment over time and thus to formation a layer rich in paraffin on the bottom of storage containers. Problems occur particularly when additives are added to paraffin-rich and narrow-cut distillation cuts with boiling ranges of 20-90% by volume less than 120 ° C, especially less than 100 ° C. The situation is particularly problematic with low sulfur winter qualities with cloud points below -5 ° C; here it is often not possible to achieve sufficient paraffin dispersion by adding known additives.

The object was therefore to improve the flowability, and in particular the paraffin dispersion, in the case of mineral oils or mineral oil distillates by adding suitable additives.

Surprisingly, it has now been found that an additive which, in addition to polar nitrogen-containing paraffin dispersants, also contains certain esters of alkoxylated polyols contains a particularly good cold flow improver for low-sulfur fuel oils.

The invention thus relates to additives for middle distillates with a maximum sulfur content of 0.05% by weight, containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D).

The invention further relates to middle distillates with a maximum sulfur content of 0.05% by weight, which contain an additive which contains at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D).

Another object of the invention is the use of an additive containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D) to improve the cold flow properties and paraffin dispersion of middle distillates with a maximum of 0.05% by weight .-% sulfur content.

The invention further relates to a process for improving the cold flow properties of middle distillates with a maximum sulfur content of 0.05% by weight by adding an additive containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one to the middle distillates polar nitrogen-containing paraffin dispersant (D).

The esters (A) are derived from polyols with 3 or more OH groups, in particular from glycerol, trimethylolpropane, pentaerythritol and the oligomers with 2 to 10 monomer units, such as polyglycerol, which are accessible by condensation. The polyols are generally reacted with 1 to 100 mol of alkylene oxide, preferably 3 to 70, in particular 5 to 50 mol, of alkylene oxide per mol of polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and Butylene oxide. The alkoxylation takes place according to known processes.

The fatty acids suitable for the esterification of the alkoxylated polyols preferably have 8 to 50, in particular 12 to 30, especially 16 to 26, carbon atoms. Suitable fatty acids are, for example, lauric, tridecane, myristic,

Pentadecanoic, palmitic, margaric, stearic, isostearic, arachic and behenic acid, oleic and erucic acid, palmitoleic, myristoleic, ricinoleic acid as well as fatty acid mixtures obtained from natural fats and oils. Preferred fatty acid mixtures contain more than 50% of fatty acids with at least 20 carbon atoms. Preferably less than 50% of the fatty acids used for the esterification contain double bonds, in particular less than 10%; in particular, they are largely saturated. Mostly saturated means an iodine number of the fatty acid used of up to 5 g I per 100 g fatty acid. The esterification can also be carried out using reactive derivatives of fatty acids such as esters with lower alcohols (e.g. methyl or ethyl esters) or anhydrides.

Mixtures of the above fatty acids with fat-soluble, polyvalent carboxylic acids can also be used to esterify the alkoxylated polyols. Examples of suitable polyvalent carboxylic acids are dimer fatty acids,

Alkenyl succinic acids and aromatic polycarboxylic acids and their derivatives such as anhydrides and C to Cs esters. Alkenyl succinic acids and their derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred. Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride. The polyvalent ones are preferred

Carboxylic acids are used in minor proportions of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.

Esters and fatty acids are used for the esterification based on the content of hydroxyl groups on the one hand and carboxyl groups on the other hand in a ratio of 1.5: 1 to 1: 1.5, preferably 1.1: 1 to 1: 1.1, in particular equimolar. The paraffin-dispersing effect is particularly pronounced when with an excess of acid of up to 20 mol%, especially up to 10 mol%, in particular up to 5 mol% is worked.

The esterification is carried out using customary methods. Has proven particularly the reaction of Polyolalkoxylat with fatty acid, optionally in the presence of catalysts such as para-toluene sulfonic acid, C ₂ - to C ₅₀ - alkyl benzene-sulphonic acids, methanesulphonic acid or acid ion exchangers. The water of reaction can be separated off by direct condensation or preferably by azeotropic distillation in the presence of organic solvents, in particular aromatic solvents such as toluene, xylene or else higher-boiling mixtures such as ^® Shellsol A, Shellsol B, Shellsol AB or Solvent Naphtha. The esterification is preferably carried out completely, ie 1.0 to 1.5 mol of fatty acid per mol of hydroxyl groups are used for the esterification. The acid number of the esters is generally below 15 mg KOH / g, preferably below 10 mg KOH / g, especially below 5 mg KOH / g.

The polar nitrogen-containing paraffin dispersants (D) contained in the additive according to the invention are low-molecular or polymeric, oil-soluble nitrogen compounds, e.g. Amine salts, amides and / or imides which are obtained by reacting aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines with 8 to 36 carbon atoms, in particular dicocos fatty amine, ditallow fatty amine and distearyl amine. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols, the reaction products of alkenylspirobislactones with amines and reaction products of terpolymers based on α, β-unsaturated dride, dicarboxylic acids Unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. Some suitable paraffin dispersants (D) are listed below.

The paraffin dispersants (D) mentioned below are partly by Reaction of compounds containing an acyl group with an amine. This amine is a compound of the formula NR ⁶ R ⁷ R ⁸ , in which R ⁶ , R ⁷ and R ^{8 can be the} same or different, and at least one of these groups for C ₈ -C ₃₆ alkyl, C ₆ - C ₃₆ cycloalkyl, C ₈ -C ₃₆ alkenyl, in particular C ₂ -C ₂ alkyl, C ₂ -C ₂₄ alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (A-0) _x -E or - (CH ₂ ) _n -NYZ, where A is an ethylene or propylene group, x is a number from 1 to 50, E = H, -CC ₃ o-alkyl, C ₅ -C ₂ -cycloalkyl or C ₆ -C ₃ o-aryl, and n is 2, 3 or 4, and Y and Z independently of one another are H, Cι- C _{3 is} o-alkyl or - (A-0) _x . Acyl group is understood here to mean a functional group of the following formula:

> C = 0

1. Reaction products of alkenyl spirobislactones of the formula

where R is in each case C ₈ -C ₂₀ o-alkenyl, with amines of the formula NR ⁶ R ⁷ R ⁸ . Suitable reaction products are listed in EP-A-0 413 279. Depending on the reaction condition, amides or amide ammonium salts are obtained in the reaction of compounds of the formula with the amines.

2. Amides or ammonium salts of aminoalkylene polycarboxylic acids with secondary amines of the formulas R ⁶ .R ⁶

N-CO-CH ₂ CH ₂ -CO-N ^

R7 ^ \ ^ R ⁷

^ N-CO-CH ₂ CH ₂ -CO-N ^

R ⁷ _R 7

in which

R ^{10 is} a straight-chain or branched alkylene radical with 2 to 6

Carbon atoms or the rest of the formula

CH ₂ -COON _χ

R ⁷

in which R ⁶ and R ^{7 are} in particular alkyl radicals having 10 to 30, preferably 14 to 24, carbon atoms, the amide structures also partially or completely in the form of the ammonium salt structure of the formula

R ⁷

can be present. The amides or amide-ammonium salts or ammonium salts, for example of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diamine tetraacetic acid, are reacted with 0.5 to 1.5 moles of amine, preferably 0.8 to 1.2 moles, by reaction of the acids Amine obtained per carboxyl group. The reaction temperatures are about 80 to 200 ° C, with

Production of the amides, a continuous removal of the water of reaction formed. However, the reaction does not have to be carried out completely to give the amide; on the contrary, 0 to 100 mol% of the amine used can be present in the form of the ammonium salt. The compounds mentioned under B1) can also be prepared under analogous conditions.

As amines of the formula

R ⁷

Dialkylamines are particularly suitable in which R ⁶ , R ^{7 is} a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms. Dioleylamine, dipalmitinamine, dicoconut fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned in particular.

3. Quaternary ammonium salts of the formula

⁺ NR ⁶ R ⁷ R ⁸ R ¹¹ X ^"

wherein R ⁶ , R ⁷ , R ^{8 have} the meaning given above and R ¹¹ for C1-C3 ₀ -alkyl, preferably C ₁ -C ₂₂ alkyl, -C-C ₃₀ alkenyl, preferably Cι-C- ₂₂ alkenyl, Benzyl or a radical of the formula - (CH ₂ -CH ₂ -0) nR ¹² , where R ^{12 is} hydrogen or a fatty acid radical of the formula C (0) -R ¹³ , where R ¹³ = C ₆ - C o-alkenyl, n is a number from 1 to 30 and X is halogen, preferably chlorine, or a methosulfate. Examples of such quaternary ammonium salts are: dihexadecyldimethylammonium chloride,

Distearyldimethylammonium chloride, quaternization products of esters of di- and triethanolamine with long-chain fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and

Fatty acid mixtures, such as coconut fatty acid, tallow fatty acid, hydrogenated tallow fatty acid, tall oil fatty acid), such as N-Methyltriethanolammoniumdistearylester chloride, N-Methyltriethanolammoniumdistearylestermethosulfat, N, N-dimethyl diethanolammoniumdistearylesterchlorid, N-dioleyl ester Methyltriethanolammonium- chloride, N-Methyltriethanolammoniumtrilaurylestermethosulfat, N-Methyltriethanolammoniumtristearylestermethosulfat and mixtures thereof ,

Compounds of the formula

in which R ^{14 stands} for CONR ⁶ R ⁷ or C0 ₂ ^"+ H ₂ NR ⁶ R ⁷ ,

R ¹⁵ and R ¹⁶ for H, CONR ¹⁷ ₂₎ C0 ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or

-NCOR ¹⁷ stand, and

R ^{17 is} alkyl, alkoxyalkyl or polyalkoxyalkyl and at least 10

Has carbon atoms.

Preferred carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellite, pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (anhydride), maleic acid (anhydride), alkenyl succinic acid (anhydride). The formulation (anhydride) means that the anhydrides of the acids mentioned are preferred acid derivatives.

When the compounds of the above formula are amides or amine salts, they are preferably of a secondary amine which is a hydrogen and

Contains carbon-containing group containing at least 10 carbon atoms.

It is preferred that R ^{17 contains} 10 to 30, in particular 10 to 22, for example 14 to 20 carbon atoms and preferably straight-chain or at the 1- or

2-position is branched. The other hydrogen and carbon containing groups can be shorter, e.g. contain less than 6 carbon atoms or, if desired, can have at least 10 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl

(Behenyl) a.

Polymers are also suitable which contain at least one amide, imide or ammonium group bonded directly to the backbone of the polymer, the amide, imide or ammonium group having at least one

Alkyl group of at least 8 carbon atoms on the nitrogen atom. Such polymers can be produced in various ways. One way is to use a polymer containing multiple carboxylic acid or anhydride groups and react that polymer with an amine of the formula NHR ⁶ R ⁷ to obtain the desired polymer.

Suitable polymers are generally to copolymers of unsaturated esters such as Cι-C ₄ -alkyl (meth) acrylates, fumarate (Cι-C ₄ o-alkyl esters), C ₁ -C ₄ alkyl vinyl ethers 0-, Cι-C-4 ₀ - Alkyl vinyl esters or C ₂ -C ₄ o-olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as carboxylic acid anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, haconic acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride) suitable.

Carboxylic acids are preferably with 0.1 to 1.5 mol, in particular 0.5 to 1.2 mol, amine per acid group, carboxylic anhydrides preferably with 0.1 to 2.5, in particular 0.5 to 2.2 mol, amine per

Acid anhydride group implemented, depending on the reaction conditions, amides, ammonium salts, amide ammonium salts or imides. Thus, copolymers containing unsaturated carboxylic anhydrides give half amide and half amine salts when reacted with a secondary amine due to the reaction with the anhydride group. By

Heating can be split off to form the diamond, water.

Particularly suitable examples of polymers containing amide groups for use according to the invention are:

5. Copolymers (a) of a dialkyl fumarate, maleate, citraconate or

itaconate with maleic anhydride, or (b) vinyl esters, e.g.

Vinyl acetate or vinyl stearate with maleic anhydride, or (c) one

Dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride and vinyl acetate.

Particularly suitable examples of these polymers are copolymers of didodecyl fumarate, vinyl acetate and maleic anhydride; Ditetradecyl fumarate, vinyl acetate and maleic anhydride; Di-hexadecyl fumarate, vinyl acetate and maleic anhydride; or the corresponding copolymers, in which the itaconate is used instead of the fumarate.

In the above examples of suitable polymers, the desired amide is obtained by reacting the polymer containing anhydride groups with a secondary amine of the formula HNR ⁶ R ⁷ (optionally also with an alcohol if an ester amide is formed). When polymers containing an anhydride group are reacted, the resulting amino groups will be ammonium salts and amides. Such polymers can be used provided that they contain at least two amide groups.

It is essential that the polymer containing at least two amide groups contain at least one alkyl group with at least 10 carbon atoms. This long-chain group, which can be a straight-chain or branched alkyl group, can be bound via the nitrogen atom of the amide group.

The suitable amines can be represented by the formula R ⁶ R ⁷ NH and the polyamines by R ⁶ NH [R ¹⁹ NH] _X R ⁷ , where R ^{19 is} a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is a whole Number, preferably between 1 and 30. Preferably one of the two or both R ⁶ and R ⁷ contain at least 10 carbon atoms, for example 10 to 20 carbon atoms, for example dodecyl, tetradecyl, hexadecyl or octadecyl.

Examples of suitable secondary amines are dioctylamine and those which

Contain alkyl groups with at least 10 carbon atoms, for example didecylamine, didodecylamine, dicocosamine (ie mixed Ci ₂ -Ci ₄ amines), dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approximately 4% by weight nC ₁₄ alkyl, 30 % By weight nC-io-alkyl, 60% by weight n-Ciβ-alkyl, the rest is unsaturated).

Examples of suitable polyamines are N-octadecyl propane diamine, N, N'-dioctadecyl propane diamine, N-tetradecyl butane diamine and N.N'-dihexadecyl hexane diamine. N-Cocospropylenediamine (C ₁₂ C ₁₄ - alkyl propylene diamine), N-tallow propylene diamine (Ci ₆ / Ci ₈ alkyl propylene diamine).

The amide-containing polymers usually have an average number-average molecular weight of 1000 to 500,000, for example 10,000 to 100,000. Copolymers of styrene, its derivatives or aliphatic olefins with 2 to 40 C atoms, preferably with 6 to 20 C atoms and olefinically unsaturated carboxylic acids or carboxylic anhydrides which are reacted with amines of the formula HNR ⁶ R ⁷ . The reaction can be carried out before or after the polymerization.

In particular, the structural units of the copolymers derive from e.g. Maleic acid, fumaric acid, haconic acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and of the copolymers.

Suitable comonomers are: styrene and alkylstyrenes, straight-chain and branched olefins having 2 to 40 carbon atoms, and mixtures thereof with one another. Examples include: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene,

Dodecene, tetradecene, hexadecene, octadecene. Styrene and isobutene are preferred, styrene is particularly preferred.

Examples of polymers which may be mentioned in detail are: polymaleic acid, a molar, alternating styrene / maleic acid copolymer, randomly constructed styrene / maleic acid copolymers in a ratio of 10:90 and an alternating copolymer of maleic acid and i-butene. The molar masses of the polymers are generally 500 g / mol to 20,000 g / mol, preferably 700 to 2000 g / mol.

The reaction of the polymers or copolymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is used in amounts of about one mole per mole of polymerized dicarboxylic anhydride, ie about 0.9 to 1.1 moles / mole. The use of larger or smaller amounts is possible, but has no advantage. If larger amounts than one mole are used, ammonium salts are obtained in part, since the formation of a second amide group leads to higher temperatures, longer residence times and Circulation of water required. If amounts less than one mole are used, there is no complete conversion to the monoamide and a correspondingly reduced effect is obtained.

Instead of the subsequent implementation of the carboxyl groups in the form of

Dicarboxylic anhydrides with amines to give the corresponding amides can sometimes be advantageous to prepare the monoamides of the monomers and then to copolymerize them directly during the polymerization. In most cases, however, this is technically much more complex because the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then copolymerization is no longer possible.

7. Copolymers consisting of 10 to 95 mol% of one or more

Alkyl acrylates or alkyl methacrylates with -CC ₂₆ alkyl chains and from 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, the copolymer being largely reacted with one or more primary or secondary amines to form the monoamide or amide / ammonium salt of the dicarboxylic acid , ,

The copolymers consist of 10 to 95 mol%, preferably 40 to

95 mol% and particularly preferably 60 to 90 mol% of alkyl (meth) acrylates and 5 to 90 mol%, preferably 5 to 60 mol% and particularly preferably 10 to 40 mol% of the olefinic unsaturated dicarboxylic acid derivatives. The alkyl groups of the alkyl (meth) acrylates contain from 1 to 26, preferably 4 to 22 and particularly preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, up to 20% by weight of cyclic and / or branched portions can also be present.

Examples of particularly preferred alkyl (meth) acrylates are n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof. Examples of ethylenically unsaturated dicarboxylic acids are maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic acid or their anhydrides and fumaric acid. Maleic anhydride is preferred.

Compounds of the formula HNR ⁶ R ^{7 are} suitable as amines.

As a rule, it is advantageous to use the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, e.g. Maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, since the anhydrides generally copolymerize better with the (meth) acrylates. The anhydride groups of the copolymers can then be reacted directly with the amines.

The reaction of the polymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is in amounts of about one to two moles per mole of polymerized dicarboxylic anhydride, i.e. about 0.9 to 2.1 mol / mol applied. The use of larger or smaller amounts is possible, but has no advantage. If more than two moles are used, free amine is present. If amounts less than one mole are used, there is no complete conversion to the monoamide and a correspondingly reduced effect is obtained.

In some cases it may be advantageous if the amide / ammonium salt structure is built up from two different amines. For example, a copolymer of lauryl acrylate and maleic anhydride can first be reacted with a secondary amine, such as hydrogenated ditaig fatty amine, to the amide, after which the free carboxyl group originating from the anhydride is neutralized with another amine, for example 2-ethylhexylamine, to form the ammonium salt. The reverse procedure is also conceivable: first, with ethylhexylamine to form the monoamide, then with ditaigfatty amine to form the ammonium salt. O At least one amine is preferably used, which has at least one straight-chain, unbranched alkyl group with more than 16 carbon atoms. It is immaterial whether this amine is present in the structure of the amide structure or as the ammonium salt of dicarboxylic acid.

Instead of the subsequent reaction of the carboxyl groups or of the dicarboxylic anhydride with amines to give the corresponding amides or amide / ammonium salts, it can sometimes be advantageous to prepare the monoamides or amide / ammonium salts of the monomers and then to polymerize them directly in the polymerization. In most cases, however, this is technically much more complex, since the amines can attach to the double bond of the monomeric dicarboxylic acid and then copolymerization is no longer possible.

Terpolymers based on α, β-unsaturated dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols, which are characterized in that they contain 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 1 and / or 3, and optionally 2, the structural units 2 originating from unreacted anhydride residues,

_R 22

(R ²³ ),

(R ²³ ) a

(D

^0: 0

_R2 2 ι (R ²³ ) _b

_R 22 I ⁽ F ²³⁾ _b

(R 23) _£

(3)

0 = C C O

N

R ⁶

in which

R ²² and R ²³ independently of one another are hydrogen or methyl, a, b is zero or one and a + b is one,

R ²⁴ and R ^{25 are} identical or different and for the groups -NHR ⁶ ,

N (R ⁶ ) ₂ and / or -OR ²⁷ , and R ^{27 stands} for a cation of the formula H ₂ N (R ⁶ ) ₂ or H ₃ NR ⁶ ,

19-80 mol%, preferably 39-60 mol% of bivalent structural units of the

Formula 4

CH, (4)

wherein

R ι28 ^Ö hydrogen or Cι-C ₄ alkyl and

R ²⁹ mean Ce-Ceo alkyl or C ₆ -C ₈ aryl and

1 to 30 mol%, preferably 1 to 20 mol% of bivalent structural units of the formula 5

_R 30

(5)

CH,

R ³³ - 0 - (CH ₂ -CH-0) _m - R 32

R 31 wherein

R ^{30 is} hydrogen or methyl, R ^{31 is} hydrogen or C 1 -C ₄ -alkyl, R ^{33 is} CrC ₄ -alkylene, m is a number from 1 to 100,

R ^{32 is} C ₁ -C ₂₄ alkyl, C ₅ -C ₂ o-cycloalkyl, C ₆ -C ₁₈ aryl or -C (0) -R ³⁴ , where R ^{34 is} CrC ^ alkyl, C ₅ -Cι ₀ - Cycloalkyl or C ₆ -C ₁₈ aryl.

The aforementioned alkyl, cycloalkyl and aryl radicals can optionally be substituted. Suitable substituents of the alkyl and aryl radicals are, for example, (CrC ₆ ) alkyl, halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and (-C-Ce) alkoxy.

Here, alkyl stands for a straight-chain or branched hydrocarbon radical. The following may be mentioned in detail: n-butyl, tert-butyl, n-hexyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, dodecenyl, tetrapropenyl, tetradecenyl, pentapropenyl, hexadecenyl, octadecenyl and eicosanyl or mixtures, such as coconut alkyll , Taigfettalkyl and Behenyl.

Cycloalkyl here stands for a cyclic aliphatic radical with 5-20 carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and cyclohexyl.

Aryl here stands for an optionally substituted aromatic

Ring system with 6 to 18 carbon atoms. The terpolymers consist of the bivalent structural units of the formulas 1 and 3 and 4 and 5 and, if appropriate, 2. They only contain, in a manner known per se, the end groups formed in the polymerization by initiation, inhibition and chain termination.

Structural units of the formulas 1 to 3 are derived in particular from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 6 and 7 _R 22 _R 23

_R 22

H ₂ C - R ²³

(7)

such as maleic anhydride, itaconic anhydride, citraconic anhydride, preferably maleic anhydride.

The structural units of the formula 4 are derived from the α, β-unsaturated compounds of the formula 8.

H ₂ C

The following α, β-unsaturated olefins may be mentioned by way of example: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, diisobutylene and α-olefins, such as decene, dodecene, tetradecene, pentadecene, Hexadecene, octadecene, C ₂ o-α-olefin, C ₂ 4-α-olefin, C _30- α-olefin, tripropenyl, tetrapropenyl, pentapropenyl and mixtures thereof. Preferred are α-olefins with 10 to 24 C atoms and styrene, particularly preferred are α-olefins with 12 to 20 C atoms. The structural units of the formula 5 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 9.

_R 30

(9)

H ₂ C -

R ³³ - 0 - (CH ₂ - CH - 0) _m - R ³²

The monomers of formula 9 are etherification products (R ³² = -C (0) R ³⁴ ) or esterification products (R ³²

, 34 32

C (0) R ^M ) of polyoxyalkylene ether (R ^ = H).

The polyoxyalkylene ethers (R ³² = H) can be prepared by known methods by adding α-olefin oxides, such as ethylene oxide, propylene oxide and / or butylene oxide, to polymerizable lower, unsaturated alcohols of the formula 10

_R 30

(10)

produce. Such polymerizable lower unsaturated alcohols are e.g. Allyl alcohol, methallyl alcohol, butenols such as 3-buten-1-ol and 1-buten-3-ol or methyl butenols such as 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol and 3-methyl-3-buten-1-ol. Addition products of ethylene oxide and / or propylene oxide onto allyl alcohol are preferred.

Subsequent etherification of these polyoxyalkylene ethers to give compounds of the formula 9 with R ³² = CrC ₂₄ alkyl, cycloalkyl or aryl is carried out by processes known per se. Suitable methods are, for example, from J. March, Advanced Organic Chemistry, 2nd edition, pp. 357f (1977) known. These etherification products of the polyoxyalkylene ethers can also be prepared by adding α-olefin oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide, to alcohols of the formula 11

R ³² - OH (1 1)

wherein R ³² is C 1 -C ₂₄ alkyl, C ₅ -C ₂ o-cycloalkyl or C ₆ -Ci ₈ aryl, by known processes and with polymerizable lower, unsaturated halides of the formula 12

R ⁷

(12)

H ₂ CCZW

implemented, where W stands for a halogen atom. The chlorides and bromides are preferably used as halides. Suitable manufacturing processes are e.g. in J. March, Advanced Organic

Chemistry, 2nd edition, p.357f (1977).

The esterification of the polyoxyalkylene ethers (R ³² = -C (0) -R ³⁴ ) takes place by reaction with common esterification agents, such as carboxylic acids, carboxylic acid halides, carboxylic acid anhydrides or

Carboxylic acid esters with CrC- ₄ alcohols. The halides and anhydrides of CrC ₄₀ alkyl, C ₅ -C ₈ cycloalkyl or C ₆ -C ₈ aryl carboxylic acids are preferably used. The esterification is generally carried out at temperatures from 0 to 200 ° C., preferably 10 to 100 ° C.

For the monomers of formula 9, the index m indicates the degree of alkoxylation, i.e. the number of moles of α-olefin added per mole of formula 20 or 21.

Examples of suitable primary amines suitable for the preparation of the terpolymers are the following: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or also N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

Examples of secondary amines suitable for the preparation of the terpolymers are: didecylamine, ditetradecylamine, distearylamine, dicocosfatty amine, ditaigfatty amine and mixtures thereof.

The terpolymers have K values (measured according to Ubbelohde in a 5% strength by weight solution in toluene at 25 ° C.) of 8 to 100, preferably 8 to 50, corresponding to average molecular weights (M _w ) of between approximately 500 and 100,000. Suitable examples are listed in EP 606 055.

Reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic anhydride groups, characterized in that they contain 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 13 and 15 and optionally 14

o = c

(R ²³

_R 39 where

R ²² and R ²³ independently of one another are hydrogen or methyl, a, b is zero or 1 and a + b is 1,

37 -OH, -O- [-C-C ₃₀ alkyl], -NR ⁶ R ⁷ , -O ^s N ^r R ⁶ R ⁷ H ₂ 38 = R ³⁷ or NR ⁶ R ³⁹ With

A = ethylene or propylene group x = 1 to 50

E = H, CC ₃ o-alkyl, C ₅ -C ₂ cycloalkyl or C ₆ -C ₃₀ aryl, and 80 - 20 mol%, preferably 60 - 40 mol% of bivalent

Structural units of formula 4 contain.

Specifically, the structural units of the formulas 13, 14 and 15 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 6 and / or 7.

The structural units of the formula 4 are derived from the α, β-unsaturated olefins of the formula 8. The aforementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8.

The radicals R37 and R38 in formula 13 and R39 in formula 15 are derived from polyetheramines or alkanolamines of the formulas 16 a) and b), amines of the formula NR6R7R8 and, if appropriate, from alcohols having 1 to 30 carbon atoms. H - N - Z - (O - CH - CH ₂ ) _n - O - R ⁵⁵

_R 53 _R 54 (16a)

Mean in it

R ^{53 is} hydrogen, C ₆ -C ₄₀ alkyl or

Z - (O - CH - CH ₂ ) _n - O - R ⁵⁵

(16c)

^ 54

R ^{54 is} hydrogen, -CC ₄ alkyl

R ^{55 is} hydrogen, CC alkyl, C ₅ to C ₁₂ cycloalkyl or C ₆ to

C ₃₀ aryl R ⁵⁶ , R ⁵⁷ independently of one another hydrogen, Ci to C ₂₂ alkyl,

C ₂ - to C ₂₂ -alkenyl or Z - OH Z C - ₂ - to C ₄ -alkylene n is a number between 1 and 1000.

To derivatize the structural units of the formulas 6 and 7, preference is given to mixtures of at least 50% by weight alkylamines of the formula HNR ⁶ R ⁷ R ⁸ and at most 50% by weight polyetheramines,

Alkanolamines of the formulas 16 a) and b) are used.

The polyetheramines used can be prepared, for example, by reductive amination of polyglycols. Furthermore, polyetheramines with a primary amino group can be produced

Addition of polyglycols to acrylonitrile and subsequent catalytic hydrogenation. In addition, polyetheramines are produced by the reaction of Polyethers with phosgene or thionyl chloride and subsequent amination to polyetheramine accessible. The polyetheramines used according to the invention are (for example) commercially available under the name ^® Jeffamine (Texaco). Their molecular weight is up to 2000 g / mol and the ethylene oxide / propylene oxide ratio is from 1:10 to 6: 1.

A further possibility for derivatizing the structural units of the formulas 6 and 7 consists in using an alkanolamine of the formulas 16a) or 16b) instead of the polyetheramines and subsequently subjecting them to an oxyalkylation.

0.01 to 2 mol, preferably 0.01 to 1 mol, of alkanolamine are used per mol of anhydride. The reaction temperature is between 50 and 100 ° C (amide formation). In the case of primary amines, the reaction takes place at temperatures above 100 ° C. (imide formation).

The oxyalkylation is usually carried out at temperatures between 70 and 170 ° C. with the catalysis of bases, such as NaOH or NaOCH3, by gassing up alkylene oxides, such as ethylene oxide (EO) and / or propylene oxide (PO). Usually 1 to 500, preferably 1 to 100, moles of alkylene oxide are added per mole of hydroxyl groups.

Examples of suitable alkanolamines are: monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol, isopropanol, diglycolamine, 2-amino-2-methyl propanol and mixtures thereof.

The following may be mentioned as primary amines, for example: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropyenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

Examples of secondary amines are: didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, Dietary fatty amine and mixtures thereof.

Examples of alcohols include:

Methanol, ethanol, propanol, isopropanol, n-, sec-, tert-butanol, octanol, tetradecanol, hexadecanol, octadecanol, tallow fatty alcohol, behenyl alcohol and mixtures thereof. Suitable examples are listed in EP-A-688 796.

10. copolymers and terpolymers of NC ₆ -C ₂₄ alkyl maleimide with C ₃ -C ₃ o-vinyl esters, vinyl ethers and / or olefins having 1 to 30 C atoms, such as styrene or α-olefins. These are accessible on the one hand by reacting a polymer containing anhydride groups with amines of the formula H2NR6 or by imidation of the dicarboxylic acid and subsequent copolymerization. Preferred dicarboxylic acid is maleic acid or maleic anhydride. Copolymers of 10 to 10 are preferred

90% by weight of C ₆ -C ₂₄ -α-olefins and 90 to 10% by weight of NC ₆ -C ₂₂ - alkyl maleimide.

In a preferred embodiment of the invention, the additives and fuel oils according to the invention which contain the constituents (A) and (D) can also be added to ethylene copolymers (B), alkylphenol-aldehyde resins (C) and / or comb polymers. Preferred embodiments are therefore also fuel oils according to the invention which contain ethylene copolymers (B), alkylphenol-aldehyde resins (C) and / or comb polymers, and the use according to the invention of additives which contain ethylene copolymers (B), alkylphenol-aldehyde resins (C) and / or comb polymers , and the corresponding procedure.

Copolymer B) is preferably an ethylene copolymer with an ethylene content of 60 to 90 mol% and a comonomer content of 10 to 40 mol%, preferably 12 to 18 mol%. Suitable comonomers are vinyl esters of aliphatic carboxylic acids with 2 to 15 carbon atoms. Preferred vinyl esters for copolymer B) are vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl octanoate, Vinyl 2-ethylhexanoate, vinyl laurate and vinyl ester of neocarboxylic acids, here in particular of neononanoic acid, neodecanoic acid and neoundecanoic acid. Particularly preferred are an ethylene-vinyl acetate copolymer, an ethylene-vinyl propionate copolymer, an ethylene-vinyl acetate-vinyl octanoate terpolymer, an ethylene-vinyl acetate-vinyl-2-ethylhexanoate terpolymer, an ethylene-vinyl acetate-neononanoic acid vinyl ester terpolymer or an ethylene Vinyl acetate neodecanoic acid vinyl ester terpolymer. Preferred acrylic acid esters are acrylic acid esters with alcohol residues from 1 to 20, in particular from 2 to 12 and especially from 4 to 8 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. The copolymers can contain up to 5% by weight of further comonomers. Such comonomers can be, for example, vinyl esters, vinyl ethers, alkyl acrylates, alkyl methacrylates with C to C ₂ o-alkyl radicals, isobutylene and olefins. Hexene, isobutylene, octene and / or diisobutylene are preferred as higher olefins. Other suitable comonomers are olefins such as propene, hexene, butene, isobutene, diisobutylene, 4-methylpentene-1 and norbornene. Ethylene-vinyl acetate-diisobutylene and ethylene-vinyl acetate-4-methylpentene-1 terpolymers are particularly preferred.

The copolymers preferably have melt viscosities at 140 ° C. of 20 to 10,000 mPas, in particular 30 to 5000 mPas, especially 50 to 2000 mPas.

The copolymers (B) can be prepared by the customary copolymerization processes, such as, for example, suspension polymerization, solvent polymerization, gas phase polymerization or high-pressure bulk polymerization. High-pressure bulk polymerization is preferred at pressures of preferably 50 to 400, in particular 100 to 300 MPa and temperatures of preferably 50 to 350, in particular 100 to 250 ° C. The reaction of the monomers is initiated by radical initiators (radical chain initiators). This class of substances includes, for example, oxygen, hydroperoxides, peroxides and azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxide carbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl peryl peryl peroxide, dicuryl peryl peryl peroxide, dicuryl peryl peroxide , Di (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in amounts of 0.01 to 20% by weight, preferably 0.05 to 10% by weight, based on the monomer mixture.

High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tubular reactors, carried out batchwise or continuously, tubular reactors have proven particularly useful. Solvents such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, benzene or toluene can be contained in the reaction mixture. The solvent-free mode of operation is preferred. In a preferred embodiment of the polymerization, the mixture of the monomers, the initiator and, if used, the moderator, is fed to a tubular reactor via the reactor inlet and via one or more side branches. The monomer streams can have different compositions (EP-A-0 271 738).

Examples of suitable copolymers or terpolymers are:

Ethylene-vinyl acetate copolymers with 10-40% by weight of vinyl acetate and 60-90% by weight of ethylene;

the ethylene-vinyl acetate-hexene terpolymers known from DE-A-34 43 475;

the ethylene-vinyl acetate-diisobutylene terpolymers described in EP-B-0 203 554;

the mixture known from EP-B-0 254 284 of an ethylene-vinyl acetate-diisobutylene terpolymer and an ethylene / vinyl acetate copolymer;

the mixtures disclosed in EP-B-0 405 270 of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-vinylpyrrolidone terpolymer;

the ethylene / vinyl acetate / isobutyl vinyl ether described in EP-B-0 463 518 terpolymers;

the copolymers of ethylene with alkylcarboxylic acid vinyl esters disclosed in EP-B-0 491 225;

the ethylene / vinyl acetate / neononanoic acid vinyl ester or neodecanoic acid vinyl ester terpolymers known from EP-B-0 493 769 which, in addition to ethylene, contain 10-35% by weight of vinyl acetate and 1-25% by weight of the respective neo compound;

the terpolymers described in DE-A-196 20 118 made of ethylene, the vinyl ester of one or more aliphatic C ₂ - to C ₂ o-monocarboxylic acids and 4-methylpentene-1;

the terpolymers disclosed in DE-A-196 20 119 made of ethylene, the vinyl ester of one or more aliphatic C ₂ - to C ₂ o-monocarboxylic acids and bicyclo [2.2.1] hept-2-ene.

The ethylene copolymers can be used individually or as a mixture of different types of polymers.

Alkylphenol-aldehyde resins (C) are known in principle and are described, for example, in the Römpp Chemie Lexikon, 9th edition, Thieme Verlag 1988-92, Volume 4, pp. 3351 ff. The alkyl radicals of the o- or p-alkylphenol have 1-50, preferably 4-20, in particular 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl, n- and iso-decyl , n- and iso-dodecyl as well as tetrapropenyl, pentapropenyl and polyisobutenyl. The alkylphenol-aldehyde resin can also contain up to 50 mole percent phenol units. The same or different alkylphenols can be used for the alkylphenol-aldehyde resin. The aliphatic aldehyde in the alkylphenol-aldehyde resin has 1-10, preferably 1-4

Carbon atoms and can carry other functional groups such as aldehyde or carboxyl groups. It is preferably formaldehyde. The molecular weight of the alkylphenol-aldehyde resins is 400-10,000, preferably 400-5000 g / mol. The prerequisite here is that the resins are oil-soluble.

The alkylphenol-aldehyde resins are prepared in a known manner by basic catalysis, in which case condensation products of the resol type are formed, or by acidic catalysis, in which condensation products of the novolak type are formed.

The condensates obtained in both ways are suitable for the compositions according to the invention. The condensation in the presence of acidic catalysts is preferred.

To produce the alkylphenol-aldehyde resins, a bifunctional o- or p-alkylphenol with 1 to 50 carbon atoms, preferably 4 to 20, in particular 6 to 12 carbon atoms per alkyl group, or mixtures thereof and an aliphatic aldehyde with 1 to 10 carbon atoms are reacted with one another, about 0.5-2 moles, preferably 0.7-1.3 moles and in particular equimolar amounts of aldehyde being used per mole of alkylphenol compound.

Suitable alkylphenols are in particular C ₄ - to Cso-alkylphenols such as o- or p-cresol, n-, sec- and tert-butylphenol, n- and i-pentylphenol, n- and iso-hexylphenol, n- and iso -Octylphenol, n- and iso-nonylphenol, n- and iso-decylphenol, n- and iso-dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, tripropenylphenol, tetrapropenylphenol and polyi (isobutenyl) phenol. The alkylphenols are preferably para-substituted. They are preferably substituted at most 7 mol%, in particular at most 3 mol%, with more than one alkyl group.

Particularly suitable aldehydes are formaldehyde, acetaldehyde, butyraldehyde and glutaraldehyde, formaldehyde is preferred.

The formaldehyde can be used in the form of paraformaldehyde or in the form of a preferably 20-40% strength by weight aqueous formalin solution. Appropriate amounts of trioxane can also be used. The reaction of alkylphenol and aldehyde is usually carried out in the presence of alkaline catalysts, for example alkali metal hydroxides or alkylamines, or of acidic catalysts, for example inorganic or organic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid, sulfamido acids or haloacetic acids, and in the presence of water Azeotropic organic solvent, for example toluene, xylene, higher aromatics or mixtures thereof. The reaction mixture is heated to a temperature of 90 to 200 ° C., preferably 100-160 ° C., the water of reaction formed being removed during the reaction by azeotropic distillation. Solvents that are under the conditions of

Condensation no protons can remain in the products after the condensation reaction. The resins can be used directly or after neutralization of the catalyst, if appropriate after further dilution of the solution with aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or solvents such as ^® Solvent Naphtha, ^® Shellsol AB, ^® Solvesso 150, ^® Solvesso 200, ^® Exxsol, ^® ISOPAR and ^® Shellsol D types.

The alkylphenol resins can then optionally be alkoxylated by reaction with 1 to 10, especially 1 to 5, mol of alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide per phenolic OH group.

Finally, in a further embodiment of the invention, the additives and middle distillates according to the invention can contain comb polymers. This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Plate and VP Shibaev, J. Polym. Sei. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable ones Comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a Ce to C ₂₄ α-olefin and an N-Cβ to C22 alkylmaleimide (see EP 0 320 766), and further esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

Comb polymers can, for example, by the formula

A H H

c - c C C m

D M N

to be discribed. Mean in it

A R \ COOR ', OCOR', R "-COOR 'or OR';

DH, CH ₃ , A or R;

E H or A;

G H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;

M H, COOR ", OCOR", OR "or COOH;

N H, R ", COOR", OCOR, COOH or an aryl radical;

R 'is a hydrocarbon chain of 8-150 carbon atoms;

R "is a hydrocarbon chain of 1 to 10 carbon atoms; m is a number between 0.4 and 1.0; and n is a number between 0 and 0.6.

The mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants, resins or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.

The additive components according to the invention can be added to mineral oils or mineral oil distillates separately or in a mixture. In a preferred embodiment, the individual additive components or else the corresponding mixture are added in one before the addition to the middle distillates organic solvents or dispersants dissolved or dispersed. The solution or dispersion generally contains 5-90, preferably 5-75,% by weight of the additive or additive mixture.

Suitable solvents or dispersants are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, for example gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as solvent naphtha, ^® Shellsol AB, ^® Solvesso 150, ^® Solvesso 200, ^® Exxsol, ^® ISOPAR and ^® Shellsol D types. If necessary, polar solubilizers such as 2-ethylhexanol, decanol, iso-decanol or iso-tridecanol can also be added.

Mineral oils or mineral oil distillates improved in their cold properties by the additives according to the invention contain 0.001 to 2, preferably 0.005 to 0.5% by weight of the additives, based on the mineral oil or mineral oil distillate.

The additives according to the invention are particularly suitable for improving the cold flow properties of animal, vegetable or mineral oils. At the same time, they improve the dispersion of the failed paraffins below the cloud point. They are particularly well suited for use in middle distillates. Middle distillates are mineral oils that are obtained by distilling crude oil and boil in the range of 120 to 450 ° C, such as kerosene, jet fuel, diesel and heating oil. The additives according to the invention are preferably used in low-sulfur middle distillates which contain 350 ppm sulfur and less, particularly preferably less than 200 ppm sulfur and in particular less than 50 ppm sulfur. The additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 365 ° C., in particular 350 ° C. and in special cases below 330 ° C. and in addition to high paraffin contents with 18 to

24 carbon atoms contain only small amounts of paraffins with chain lengths of 24 and more carbon atoms. They can also be used as components in lubricating oils. The mineral oils or mineral oil distillates can also contain other conventional additives such as dewaxing agents, corrosion inhibitors, antioxidants, lubricity additives, sludge inhibitors, cetane number improvers, detergent additives, dehazers, conductivity improvers or dyes.

Examples

The following esters A) were used as a 50% solution in aromatic solvent (EO stands for ethylene oxide; PO stands for propylene oxide):

Table 1: Characterization of the esters used (component A)

Characterization of the ethylene copolymers used as flow improvers (component B)).

The viscosity is determined in accordance with ISO 3219 / B using a rotary viscometer (Haake RV20) with a plate and cone measuring system at 140 ° C.

The additives are used to improve handling as 50% solutions in solvent naphtha or kerosene.

Characterization of the alkylphenol-aldehyde resins used (component C)) C 1) nonylphenol-formaldehyde resin C 2) dodecylphenol-formaldehyde resin C 3) C2o / 24-alkylphenol-formaldehyde resin

Characterization of the paraffin dispersants used (component D))

D 1) reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine D 2) reaction product of a terpolymer of C ₄ / C _{6 6} -α-olefin,

Maleic anhydride and allyl polyglycol with 2 equivalents of ditaig fatty amine.

Characterization of the test oils:

The boiling data are determined in accordance with ASTM D-86, the CFPP value in accordance with EN 116 and the cloud point in accordance with ISO 3015. Table 2: Characteristic data of the test oils

Effectiveness of the additives

Table 4 describes the effectiveness of the additives according to the invention, together with ethylene copolymers for mineral oils and mineral oil distillates, which is superior to the prior art, using the CFPP test (Cold Filter Plugging Test according to EN 1 16). The paraffin dispersion in middle distillates was determined as follows in the short sediment test:

150 ml of the middle distillates mixed with the additive components given in the table were cooled in 200 ml measuring cylinders in a refrigerator at -2 ° C./hour to -13 ° C. and stored at this temperature for 16 hours. The volume and appearance of both the sedimented paraffin phase and the oil phase above it were then determined and assessed visually. A small amount of sediment with a homogeneously cloudy oil phase or a large sediment volume with a clear oil phase show good paraffin dispersion. In addition, the lower 20% by volume were isolated and the cloud point determined in accordance with ISO 3015. A slight deviation of the cloud point of the lower phase (CP «s) from the blank value of the oil shows a good paraffin dispersion. Table 3: CFPP effectiveness in test oil 1

The CFPP activity of the esters A according to the invention was measured in combination with equal amounts of C and D in test oil 1 as follows:

Table 4: CFPP effectiveness in test oil 2

The additive components A were mixed with 5 parts B2) and tested for their CFPP activity in test oil 2.

Table 5: CFPP and dispersing effect in test oil 3

For the dispersion tests in test oil 3, an additional 200 ppm of additive B1) was added in all measurements.

Table 6: CFPP and dispersing effect in test oil 4

For the dispersion tests in test oil 4, an additional 200 ppm of additive B1 was added in all measurements.

Table 7: CFPP and dispersing effect in test oil 1

For the dispersion tests in test oil 1, an additional 75 ppm of additive B3 was added in all measurements

Claims

claims

1. Additives for middle distillates with a maximum sulfur content of 0.05% by weight, containing at least one fatty acid ester of alkoxylated polyols with at least 3 OH groups (A) and at least one polar nitrogen-containing paraffin dispersant (D).

2. Additives according to claim 1, wherein the alkoxylated polyol (A) is derived from a polyol reacted with 1 to 100 mol of alkylene oxide and having three or more OH groups.

3. Additives according to claim 1 and / or 2, wherein the alkoxylated polyol (A) is esterified with a fatty acid having 8 to 50 carbon atoms.

4. Additives according to one or more of claims 1 to 3, wherein the alkoxylated polyol (A) is esterified with a mixture of at least one fatty acid having 8 to 50 carbon atoms and at least one fat-soluble, polyvalent carboxylic acid.

5. Additives according to one or more of claims 1 to 4, wherein the alkoxylated polyol (A) is derived from glycerol.

6. Additives according to one or more of claims 1 to 5, wherein the fatty acid ester (A) has an OH number of less than 15 mg KOH / g.

7. Additives according to one or more of claims 1 to 6, wherein the polar nitrogen-containing paraffin dispersant is a low-molecular or polymeric, oil-soluble nitrogen compound which is obtained by reacting aliphatic or aromatic amines with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides is available is included.

8. Additives according to one or more of claims 1 to 7, wherein an amine salt and / or amide of secondary fatty amines having 8 to 36 carbon atoms is contained as the polar nitrogen-containing paraffin dispersant.

9. Additives according to one or more of claims 1 to 8, wherein at least one ethylene copolymer (B) is additionally contained.

10. Additives according to claim 9, wherein the ethylene copolymer (B) contains at least one unsaturated vinyl ester of an aliphatic carboxylic acid having 2 to 15 carbon atoms.

11. Additives according to claim 9 and / or 10, wherein the ethylene copolymer (B) contains 10 to 40 mol% of comonomers in addition to ethylene.

12. Additives according to one or more of claims 1 to 11, wherein at least one alkylphenol-aldehyde resin (C) is additionally contained.

13. Additives according to claim 12, wherein the alkyl radicals of the alkylphenol-aldehyde resin (C) have 1 to 50 carbon atoms.

14. Additives according to claim 12 and / or 13, wherein the alkylphenol-aldehyde resin (C) is derived from at least one aldehyde having 1 to 10 carbon atoms.

15. Dispersion of an additive according to one or more of claims 1 to 14 in an organic solvent or dispersant, containing 5 to 90 wt .-% of the additive.

16. Middle distillates with a maximum of 0.05 wt .-% sulfur content, which contain an additive according to one or more of claims 1 to 14.

17. Use of an additive according to one or more of claims 1 to 14 to improve the cold flow properties and paraffin dispersion of middle distillates with a maximum of 0.05 wt .-% sulfur content.