EP1116780A1 - Polyfunctional additive for fuel oils - Google Patents

Abstract

Additive for improving the cold flow and lubricating properties of diesel fuel comprises an oil-soluble amphiphile and an ethylene/vinyl carboxylate/vinyl neocarboxylate terpolymer. Additive for improving the cold flow and lubricating properties of diesel fuel comprises: (a) 5-95 wt.% of at least one oil-soluble amphiphile of formula (I) and (II): (b) 5-95 wt.% of a terpolymer having a melt viscosity of 20-10,000 mPas at 140 degrees C and comprising vinyl 2-4C carboxylate units (10-35 mole%), vinyl 8-15C neocarboxylate units (1-15 mole%) and ethylene units (to 100 mole%). R<1)<CO-X-R<2>)y (I) R<1>-X-R<2> (II) R<1> = 1-50C alkyl, alkenyl, hydroxyalkyl or aryl; X = NH, NR<3>, O or S; y = 1-4; R<2> = H or OH-substituted 2-10C alkyl; R<3> = 1-20C alkyl or N-containing and OH-substituted 2-10C alkyl. Independent claims are also included for the following; (1) diesel fuel containing the additive; (2) a mixture of the additive and a paraffin dispersant of formula (III) or a comb polymer of formula (IV) in a ratio of 1:10 to 20:1 R<51> = 4-50C alkyl or alkenyl; R<52> = ethylene and propylene; n = 5-100; p = 0-50; A = R', COOR', OCOR', RCOOR' or OR'; D = H, Me, A or R; E = H or A; G = H, R, RCOOR', aryl or heterocyclyl; M = H, COOR, OCOR, OR or COOH; N = H, R, COOR, OCOR, COOH or aryl; R' = 8-150C hydrocarbyl; R = 1-10C hydrocarbyl; m = 0.4-1.0; n = 0-0.6.

Description

The present invention relates to an additive for fuel oils containing Ethylene / vinyl ester terpolymers and amphiphilic, lubricity-improving additives, as well as its use to improve cold flow and Lubrication properties of the oils thus added.

Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5 wt .-% and more sulfur, when burning causes the formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further. The introduction of the standard relating to diesel fuels EN 590 currently writes a maximum sulfur content of 500 ppm before. In Scandinavia, fuel oils are already coming in at less than 50 ppm and in exceptional cases with less than 10 ppm sulfur. This Fuel oils are usually made by taking those from petroleum Fractions obtained by distillation hydrogenated refined. In the Desulphurization also removes other substances that Give fuel oils a natural lubricating effect. About these substances include polyaromatic and polar compounds.

However, it has now been shown that the friction and wear reducing Properties of fuel oils with increasing desulfurization become worse. Often these properties are so poor that the materials lubricated by fuel, e.g. the distributor injection pumps from Diesel engines can be expected to eat after a short time got to. The further lowering of the 95% distillation point below 370 ° C, partly below 350 ° C or below 330 ° C further exacerbates this problem.

Approaches are therefore described in the prior art which provide a solution to this Problems (so-called lubricity additives).

EP-A-0 764 198 discloses additives which improve the lubricating effect of fuel oils improve, and the polar nitrogen compounds based on alkylamines or Contain alkylammonium salts with alkyl radicals of 8 to 40 carbon atoms.

EP-A-0 743 974 discloses the use of mixtures of lubricity additives (Esters of polyhydric alcohols and carboxylic acids with 10 to 25 carbon atoms or Dicarboxylic acids) and flow improvers made from ethylene / unsaturated ester copolymers to synergistically improve the lubricating effect of highly desulfurized oils.

EP-A-0 807676 discloses the use of a mixture of a carboxylic acid amide and a cold flow improver and / or an ashless one
Dispersant to improve the cold flow properties of low-sulfur fuel oil.

EP-A-0 680 506 discloses the use of esters of mono- or polyvalent Carboxylic acids with mono- or polyhydric alcohols as Lubricity-improving additive to fuel oils.

The use of cold flow improvers in fuel oils is necessary because Crude oils and middle distillates obtained by distilling crude oils such as gas oil, Different amounts of diesel oil or heating oil depending on the origin of the crude oils long-chain paraffins (waxes) contained in solution. At low temperatures these paraffins separate out as platelet-shaped crystals, sometimes under Inclusion of oil. This makes the flowability of the crude oils and that of them distillates obtained significantly impaired. Solid deposits occur that frequently lead to disruptions in the extraction, transport and use of mineral oils and lead petroleum products. So it happens at low ambient temperatures, e.g. in the cold season for diesel engines and combustion plants Clogging of the filters, which prevent safe metering of the fuels and finally result in an interruption in the fuel or heating medium supply. Also conveying mineral oils and mineral oil products through pipelines larger distances can e.g. in winter due to the precipitation of paraffin crystals be affected.

It is known to increase the undesired crystal growth by means of suitable additives prevent and thus counteract an increase in the viscosity of the oils. Such additives, they are known as pour point lower or Flow improvers are known to change the size and shape of the wax crystals and thus counteract an increase in the viscosity of the oils.

EP-A-0 807 642 discloses cold flow improvers based on terpolymers which Contain structural units of ethylene, vinyl acetate and 4-methylpentene-1, EP-A-807 643 based on ethylene, vinyl acetate and norbornene.

It has been shown that in low-sulfur and paraffin-rich oils synergistic additive combinations of the prior art in particular cold blending, which is becoming increasingly important in practice, i.e. the Mixing additives in cold oils to filtration problems above the cloud Lead points of the additive oils. This often leads to one Impairment of the lubrication effect by the flow improver and the oils do not show the properties expected from the components. This will e.g. in the Case of the additives according to EP-A-0 743 974 due to their poor solubility Flow improver component causes it to become constipated Fuel filters can come. The lubricants are probably from the absorbs more difficult soluble components of the flow improver.

The object of the present invention was to find additive combinations which are in Middle distillates largely freed from sulfur and aromatic compounds lead to an improvement in the lubricating effect. At the same time, these additives are said to also contain a proportion as a cold flow improver, in the oils mentioned is soluble and effective as such, and the effect of the lubricity additive supports, and vice versa.

Surprisingly, it was found that additives that are in addition to lubricating amphiphile terpolymers made of ethylene, vinyl esters and contain certain olefins that have the required properties.

A) 5 - 95 Gew.-% mindestens eines öllöslichen Amphiphils der Formel (1)

und/oder R¹ ― X ― R² worin R¹ einen Alkyl-, Alkenyl-, Hydroxyalkyl- oder aromatischen Rest mit 1 bis 50 Kohlenstoffatomen, X NH, NR³, O oder S, y = 1, 2, 3 oder 4, R² Wasserstoff oder einen Hydroxylgruppen tragenden Alkylrest mit 2 bis 10 Kohlenstoffatomen und R³ Wasserstoff, einen Stickstoff und/oder Hydroxylgruppen tragenden Alkylrest mit 2 bis 10 Kohlenstoffatomen oder C₁-C₂₀-Alkyl bedeutet,

B) 5 bis 95 Gew.-% eines Terpolymers, enthaltend 3 bis 18 mol-% Struktureinheiten, abgeleitet aus dem Vinylester einer Carbonsäure mit 2 bis 4 C-Atomen, 0,5 bis 10 mol-% Struktureinheiten, abgeleitet aus dem Vinylester einer Neocarbonsäure mit 8 bis 15 Kohlenstoffatomen, und Struktureinheiten aus Ethylen ad 100 mol-% mit einer bei 140°C gemessenen Schmelzviskosität von 20 bis 10.000 mPas.

The invention relates to additives for improving the cold flow and lubrication properties of fuel oils, consisting of

A) 5-95% by weight of at least one oil-soluble amphiphile of the formula (1)

and or R ¹ - X - R ² wherein R ^{1 is} an alkyl, alkenyl, hydroxyalkyl or aromatic radical having 1 to 50 carbon atoms, X NH, NR ³ , O or S, y = 1, 2, 3 or 4, R ^{2 is} hydrogen or an alkyl radical carrying hydroxyl groups 2 to 10 carbon atoms and R ^{3 is} hydrogen, a nitrogen and / or hydroxyl-bearing alkyl radical having 2 to 10 carbon atoms or C ₁ -C ₂₀ alkyl,

B) 5 to 95% by weight of a terpolymer containing 3 to 18 mol% of structural units derived from the vinyl ester of a carboxylic acid having 2 to 4 carbon atoms, 0.5 to 10 mol% of structural units derived from the vinyl ester of one Neocarboxylic acid with 8 to 15 carbon atoms, and structural units made of ethylene ad 100 mol% with a melt viscosity of 20 to 10,000 mPas measured at 140 ° C.

Another object of the invention are fuel oils, the said Contain additives.

Another object of the invention is the use of additives for simultaneous improvement of the lubrication and cold flow properties of Fuel oils.

Preferred proportions of A) and B) are between 10 and 90% by weight, in particular 20 to 80 wt .-% and especially 40 to 60 wt .-%.

The oil-soluble amphiphile (component A) preferably comprises a radical R ¹ having 5 to 40, in particular 12 to 35, carbon atoms. R ¹ is particularly preferably linear or branched and contains 1 to 3 double bonds in the case of linear radicals. The radical R ² preferably has 2 to 8 carbon atoms and can be interrupted by nitrogen and / or oxygen atoms. In a further preferred embodiment, the sum of the carbon atoms of R ¹ and R ^{2 is} at least 10, in particular at least 15. In a further preferred embodiment, component A carries 2 to 5 hydroxyl groups, each carbon atom not carrying more than one hydroxyl group.

In a preferred embodiment of the invention, X in formula 1 has the Meaning of oxygen. In particular, they are fatty acids and esters between carboxylic acids and dihydric or polyhydric alcohols. Preferred esters contain at least 10, especially at least 12 carbon atoms. Prefers is also that the esters contain free hydroxyl groups, the esterification of the Polyol is not complete with the carboxylic acid. Suitable polyols are for example ethylene glycol, propylene glycol, diethylene glycol and higher Alkoxylation products, glycerin, trimethylolpropane, pentaerythritol, diglycerin and higher condensation products of glycerin as well as sugar derivatives. Others too Polyols containing heteroatoms, such as triethanolamine, are suitable.

If X is a nitrogen-containing residue, reaction products of ethanolamine are Diethanolamine, hydroxypropylamine, dihydroxypropylamine, n-methylethanolamine, Diglycolamine and 2-amino-2-methylpropanol are suitable. The implementation takes place preferably by amidation, the resulting amides also containing free OH groups wear. Examples include fatty acid monoethanolamides and diethanolamides and called -N-methylethanolamide.

R ³ preferably represents a hydroxyl-bearing alkyl radical having 3 to 8 carbon atoms, or preferably C ₂ to C ₁₈ alkyl, in particular C ₄ to C ₁₂ alkyl.

worin R¹ die oben angegebene Bedeutung hat, R⁴¹ einen Rest der Formel 3a -(R⁴³-NR⁴⁴)_m-R⁴⁵ und R⁴² einen Rest der Formel 3b -(R⁴³-NR⁴⁴)_n-R⁴⁵ bedeutet, R⁴³ für eine C₂- bis C₁₀-Alkylengruppe steht, R⁴⁴ Wasserstoff, Methyl, C₂- bis C₂₀-Alkyl, einen Rest der Formel 3c

oder einen Alkoxyrest, und R⁴⁵ H oder einen Rest der Formel 3c bedeutet, und m und n jeweils unabhängig voneinander eine ganze Zahl von 0 bis 20 bedeuten, wobei vorzugsweise

a) m und n nicht gleichzeitig null bedeuten, und

b) die Summe aus m und n mindestens 1 und höchstens 20 ist.

In one embodiment, the multifunctional additive can contain, as component A, compounds of the formula 3.

wherein R ^{1 has} the meaning given above, R ^{41 is} a radical of the formula 3a - (R ⁴³ -NR ⁴⁴ ) _m -R ⁴⁵ and R ^{42 is} a radical of the formula 3b - (R ⁴³ -NR ⁴⁴ ) _n -R ⁴⁵ means, R ^{43 represents} a C ₂ - to C ₁₀ -alkylene group, R ^{44 is} hydrogen, methyl, C ₂ - to C ₂₀ -alkyl, a radical of formula 3c

or an alkoxy radical, and R ^{45 is} H or a radical of the formula 3c, and m and n each independently represent an integer from 0 to 20, preferably

a) m and n do not simultaneously mean zero, and

b) the sum of m and n is at least 1 and at most 20.

R ⁴³ preferably represents a C ₂ - to C ₈ -, in particular a C ₂ - to C ₄ -rest. The polyamine from which the structural unit formed from R ⁴¹ , R ⁴² and the nitrogen atom connecting them is derived is preferably ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or a higher homologue of aziridine such as polyethyleneimine, and mixtures thereof. Parts of the amino group can be alkylated. Sternamines and dendrimers are also suitable. This is understood to mean polyamines with generally 2-10 nitrogen atoms which are connected to one another via —CH ₂ —CH ₂ groups and which are saturated in the marginal position with acyl or alkyl radicals.

R ⁴⁴ preferably represents hydrogen, an acyl radical or an alkoxy group of the formula - (OCH ₂ CH ₂ ) _n -, where n is an integer between 1 and 10, and mixtures thereof.

worin

R⁴⁶

die Bedeutung von R¹,

R⁴⁷

die Bedeutung von R¹ oder H oder -[CH₂-CH₂-O-]_p-H und

R⁴⁸

die Bedeutung von R² haben können und

p

eine ganze Zahl von 1 bis 10 bedeuten,

mit der Maßgabe, dass mindestens einer der Reste R⁴⁶, R⁴⁷ und R⁴⁸ eine OH-Gruppe trägt. Als Beispiel sei y-Hydroxybuttersäuretalgfettamid genannt.Compounds of the formula 3d are also suitable as an amphiphile

wherein

R ⁴⁶

the meaning of R ¹ ,

R ⁴⁷

the meaning of R ¹ or H or - [CH ₂ -CH ₂ -O-] _p -H and

R ⁴⁸

can have the meaning of R ² and

p

is an integer from 1 to 10,

with the proviso that at least one of the radicals R ⁴⁶ , R ⁴⁷ and R ⁴⁸ carries an OH group. As an example, y- hydroxybutyric acid tallow amide may be mentioned.

The amides are generally by condensation of the polyamines with the Carboxylic acids or their derivatives such as esters or anhydrides. It are preferably 0.2 to 1.5 mol, in particular 0.3 to 1.2 mol, especially 1 mol Acid used per base equivalent. The condensation is preferably carried out at Temperatures between 20 and 300 ° C, especially between 50 and 200 ° C below Distilling off the water of reaction. Solvents may be preferred aromatic solvents such as benzene, toluene, xylene, trimethylbenzene and / or commercial solvent mixtures such as B. Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200 are added to the reaction mixture. The Products according to the invention generally have a titratable Base nitrogen of 0.01 - 5% and an acid number of less than 20 mg KOH / g, preferably less than 10 mg KOH / g.

y preferably takes the values 1 or 2. Examples of preferred connecting groups with y = 2 are derivatives of dimer fatty acids and alkenylsuccinic anhydrides. The latter can carry linear as well as branched alkyl radicals, ie they can be derived from linear α-olefins and / or from oligomers of lower C ₃ -C ₅ olefins such as poly (propylene) or poly (isobutylene).

Preferred polyols have 2 to 8 carbon atoms. They preferably wear 2, 3, 4 or 5 hydroxyl groups, but no more than they contain carbon atoms. The The carbon chain of the polyols can be straight-chain, branched, saturated or unsaturated be and optionally contain heteroatoms. It is preferably saturated.

Preferred carboxylic acids, from which the compounds of formula 1 are derived let, or represent the compounds of formula 1, have 5 to 40, especially 12 to 30 carbon atoms. The carboxylic acid preferably has one or two carboxyl groups. The carbon chain of the carboxylic acids can straight chain, branched, saturated or unsaturated. Preferably contain more than 50% of the carboxylic acids (mixtures) used at least one Double bond. Examples of preferred carboxylic acids include caprylic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Elaidic acid, linoleic acid, linolenic acid and behenic acid, and carboxylic acids with Heteroatoms such as ricinoleic acid. Furthermore, dimer and trimer fatty acids, such as they e.g. are accessible by oligomerization of unsaturated fatty acids, as well Alkenyl succinic acids are used.

In a preferred embodiment, component A uses ethers and amines of the formula 2. These are partial ethers of polyols, such as, for example, glycerol monooctadecyl ether or hydroxyl-bearing amines, as are obtainable, for example, by alkoxylation of amines of the formula R ¹ NH ₂ or R ¹ R ³ NH with alkylene oxides, preferably ethylene oxide and / or propylene oxide. 1-10, in particular 1-5, mol of alkylene oxide are preferably used per H atom of nitrogen.

The vinyl esters of a carboxylic acid contained in the terpolymer of component B) 2 to 4 carbon atoms ("short-chain vinyl ester") are preferably vinyl acetate or Vinyl propionate.

ab, die insgesamt 8 bis 15 Kohlenstoffatome aufweisen. R und R¹ sind lineare Alkylreste. Vorzugsweise handelt es sich bei den Neocarbonsäuren um Neononan-, Neodecan-, Neoundecan- oder Neododecansäure.The vinyl esters of neocarboxylic acids also contained in the terpolymer of component B) are derived from neocarboxylic acids of the formula

from which have a total of 8 to 15 carbon atoms. R and R ¹ are linear alkyl radicals. The neocarboxylic acids are preferably neononanoic, neodecanoic, neoundecanoic or neododecanoic acid.

The molar proportions of the short-chain vinyl esters in the terpolymer B) are preferably 8 to 16 mol%. The molar proportions of vinyl neocarboxylic acid are preferably 1 to 8 mol%. The total comonomer content is between 8 and 19, in particular between 9 and 16 mol%.

Terpolymers according to the invention are particularly suitable for use in the additive according to the invention with a melt viscosity of 50 to 5000 mPas, preferably 30 to 1000 mPas and in particular 50 to 500 mPas, measured according to ISO 3219 (B) at 140 ° C. .
Mixtures of the monomers are used to prepare the terpolymers from ethylene, the vinyl ester of an aliphatic linear or branched monocarboxylic acid which contains 2 to 40 carbon atoms in the molecule, and neocarboxylic acid vinyl esters.

The starting materials are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A21, Pages 305 to 413). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably one turns high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out. The reaction of the monomers is caused by radicals initiators (radical chain initiators) initiated. To this class of substance belong e.g. Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, Dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'azobis (2-methylbutyronitrile). The initiators are individual or as a mixture of two or more substances in amounts from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.

The desired melt viscosity of the terpolymers is set for a given composition of the monomer mixture by varying the reaction parameters pressure and temperature and, if appropriate, by adding moderators. Hydrogen, saturated or unsaturated hydrocarbons, for example propane, aldehydes, for example propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or alcohols, for example butanol, have proven suitable as moderators. Depending on the desired viscosity, the moderators are used in amounts of up to 20% by weight, preferably 0.05 to 10% by weight, based on the monomer mixture.
In order to obtain terpolymers suitable for use in the additives according to the invention, monomer mixtures are used which, apart from ethylene and optionally a moderator, contain 5 to 40% by weight, preferably 10 to 40% by weight, short-chain vinyl ester and 1 to 40% by weight. % Contain vinyl neocarboxylic acid.

With the one that differs from the composition of the terpolymer The composition of the monomer mixture is carried by the different ones Polymerization rate of the monomers calculation. The polymers fall as colorless melts that turn into wax-like solids at room temperature freeze.

For the production of additive packages for special problem solutions the additives according to the invention also together with one or more oil-soluble Co-additives are used, which alone have the cold flow properties and / or lubricating effect of crude oils, lubricating oils or fuel oils improve. Examples of such co-additives paraffin dispersants are alkylphenol aldehyde resins and comb polymers.

Paraffin dispersants reduce the size of the wax crystals and cause that the paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed. Have become paraffin dispersants oil-soluble polar compounds with ionic or polar groups, e.g. Amine salts and / or amides proven by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides can be obtained. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented Reaction products of alkenyl spirobis lactones with amines and Reaction products of terpolymers based on α, β-unsaturated Dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols. Alkylphenol-formaldehyde resins are also available Paraffin dispersants suitable. The following are some suitable ones Paraffin dispersants listed.

1. Umsetzungsprodukte von Alkenyl-spirobislactonen der Formel 4

wobei R jeweils C₈-C₂₀₀-Alkenyl bedeutet, mit Aminen der Formel NR⁶R⁷R⁸. Geeignete Umsetzungsprodukte sind in EP-A-0 413 279 aufgeführt. Je nach Reaktionsbedingung erhält man bei der Umsetzung von Verbindungen der Formel (4) mit den Aminen Amide oder Amid-Ammoniumsalze.

2. Amide bzw. Ammoniumsalze von Aminoalkylenpolycarbonsäuren mit sekundären Aminen der Formeln 5 und 6

in denen
R¹⁰ einen geradkettigen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen oder den Rest der Formel 7

in der R⁶ und R⁷ insbesondere Alkylreste mit 10 bis 30, bevorzugt 14 bis 24 C-Atomen bedeuten, wobei die Amidstrukturen auch zum Teil oder vollständig in Form der Ammoniumsalzstruktur der Formel 8

vorliegen können. Die Amide bzw. Amid-Ammoniumsalze bzw. Ammoniumsalze z.B. der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure werden durch Umsetzung der Säuren mit 0,5 bis 1,5 Mol Amin, bevorzugt 0,8 bis 1,2 Mol Amin pro Carboxylgruppe erhalten. Die Umsetzungstemperaturen betragen etwa 80 bis 200°C, wobei zur Herstellung der Amide eine kontinuierliche Entfernung des entstandenen Reaktionswasser erfolgt. Die Umsetzung muss jedoch nicht vollständig zum Amid geführt werden, vielmehr können 0 bis 100 Mol-% des eingesetzten Amins in Form des Ammoniumsalzes vorliegen. Unter analogen Bedingungen können auch die unter B1) genannten Verbindungen hergestellt werden.Als Amine der Formel 9

kommen insbesondere Dialkylamine in Betracht, in denen R⁶, R⁷ einen geradkettigen Alkylrest mit 10 bis 30 Kohlenstoffatomen, vorzugsweise 14 bis 24 Kohlenstoffatomen, bedeutet. Im einzelnen seien Dioleylamin, Dipalmitinamin, Dikokosfettamin und Dibehenylamin und vorzugsweise Ditalgfettamin genannt.

3. Quartäre Ammoniumsalze der Formel 10 ⊕NR⁶R⁷R⁸R¹¹X^⊖ wobei R⁶, R⁷, R⁸ die oben gegebene Bedeutung haben und R¹¹ für C₁-C₃₀-Alkyl, bevorzugt C₁-C₂₂-Alkyl, C₁-C₃₀-Alkenyl, bevorzugt C₁-C₂₂-Alkenyl, Benzyl oder einen Rest der Formel -(CH₂-CH₂-O)_n-R¹² steht, wobei R¹² Wasserstoff oder ein Fettsäurerest der Formel C(O)-R¹³ ist, mit R¹³ = C₆-C₄₀-Alkenyl, n eine Zahl von 1 bis 30 und X für Halogen, bevorzugt Chlor, oder ein Methosulfat steht. Beispielhaft für derartige quartäre Ammoniumsalze seien genannt: Dihexadecyldimethylammoniumchlorid, Distearyldimethylammoniumchlorid, Quaternisierungsprodukte von Estern des Di- und Triethanolamins mit langkettigen Fettsäuren (Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Behensäure, Ölsäure und Fettsäuremischungen, wie Cocosfettsäure, Talgfettsäure, hydrierte Talgfettsäure, Tallölfettsäure), wie N-Methyltriethanolammoniumdistearylester-chlorid, N-Methyltriethanolammoniumdistearylestermethosulfat, N,N-Dimethyldiethanolammoniumdistearylesterchlorid, N-Methyltriethanolammonium-dioleylester-chlorid, N-Methyltriethanolammoniumtrilaurylestermethosulfat, N-Methyltriethanolammoniumtristearylestermethosulfat und deren Mischungen.

4. Verbindungen der Formel 11

in denen R¹⁴ für CONR⁶R⁷ oder CO₂ ^{- +}H₂NR⁶R⁷ steht,
R¹⁵ und R¹⁶ für H, CONR¹⁷ ₂, CO₂R¹⁷ oder OCOR¹⁷, -OR¹⁷, -R¹⁷ oder -NCOR¹⁷ stehen, und
R¹⁷ Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl ist und mindestens 10 Kohlenstoffatome aufweist. Bevorzugte Carbonsäuren bzw. Säurederivate sind Phthalsäure(anhydrid), Trimellit, Pyromellit(dianhydrid), Isophthalsäure, Terephthalsäure, Cyclohexandicarbonsäure(anhydrid), Maleinsäure(anhydrid), Alkenylbernsteinsäure(anhydrid). Die Formulierung (anhydrid) bedeutet, dass auch die Anhydride der genannten Säuren bevorzugte Säurederivate sind.Wenn die Verbindungen der Formel (11) Amide oder Aminsalze sind, sind sie vorzugsweise von einem sekundären Amin, das eine Wasserstoff und Kohlenstoff enthaltende Gruppe mit mindestens 10 Kohlenstoffatomen enthält.Es ist bevorzugt, dass R¹⁷ 10 bis 30, insbesondere 10 bis 22, z.B. 14 bis 20 Kohlenstoffatome enthält und vorzugsweise geradkettig oder an der 1- oder 2-Position verzweigt ist. Die anderen Wasserstoff und Kohlenstoff enthaltenden Gruppen können kürzer sein, z.B. weniger als 6 Kohlenstoffatome enthalten, oder können, falls gewünscht, mindestens 10 Kohlenstoffatome aufweisen. Geeignete Alkylgruppen schließen Methyl, Ethyl, Propyl, Hexyl, Decyl, Dodecyl, Tetradecyl, Eicosyl und Docosyl (Behenyl) ein.Des weiteren sind Polymere geeignet, die mindestens eine Amid- oder Ammoniumgruppe direkt an das Gerüst des Polymers gebunden enthalten, wobei die Amid- oder Ammoniumgruppe mindestens eine Alkylgruppe von mindestens 8 C-Atomen am Stickstoffatom trägt. Derartige Polymere können auf verschiedene Arten hergestellt werden. Eine Art ist, ein Polymer zu verwenden, das mehrere Carbonsäure oder -Anhydridgruppen enthält, und dieses Polymer mit einem Amin der Formel NHR⁶R⁷ umzusetzen, um das gewünschte Polymer zu erhalten.Als Polymere sind dazu allgemein Copolymere aus ungesättigten Estern wie C₁-C₄₀-Alkyl(meth)acrylaten, Fumarsäuredialkylester, C₁-C₄₀-Alkylvinylethern, C₁-C₄₀-Alkylvinylestern oder C₂-C₄₀-Olefinen (linear, verzweigt, aromatisch) mit ungesättigten Carbonsäuren bzw. deren reaktiven Derivaten, wie z.B. Carbonsäureanhydriden (Acrylsäure, Methacrylsäure, Maleinsäure, Fumarsäure, Tetrahydrophthalsäure, Citraconsäure, bevorzugt Maleinsäureanhydrid) geeignet. Carbonsäuren werden vorzugsweise mit 0,1 bis 1,5 mol, insbesondere 0,5 bis 1,2 mol Amin pro Säuregruppe, Carbonsäureanhydride vorzugsweise mit 0,1 bis 2,5, insbesondere 0,5 bis 2,2 mol Amin pro Säureanhydridgruppe umgesetzt, wobei je nach Reaktionsbedingungen Amide, Ammoniumsalze, Amid-Ammoniumsalze oder Imide entstehen. So ergeben Copolymere, die ungesättigte Carbonsäureanhydride enthalten, bei der Umsetzung mit einem sekundären Amin auf Grund der Reaktion mit der Anhydridgruppe zur Hälfte Amid und zur Hälfte Aminsalze. Durch Erhitzen kann unter Bildung des Diamids Wasser abgespalten werden.Besonders geeignete Beispiele amidgruppenhaltiger Polymere zur erfindungsgemäßen Verwendung sind:

5. Copolymere (a) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid, oder (b) von Vinylestern, z.B. Vinylacetat oder Vinylstearat mit Maleinsäureanhydrid, oder (c) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid und Vinylacetat. Besonders geeignete Beispiele für diese Polymere sind Copolymere von Didodecylfumarat, Vinylacetat und Maleinsäureanhydrid; Ditetradecylfumarat, Vinylacetat und Maleinsäureanhydrid; Di-hexadecylfumarat, Vinylacetat und Maleinsäureanhydrid; oder den entsprechenden Copolymeren, bei denen anstelle des Fumarats das Itaconat verwendet wird.In den oben genannten Beispielen geeigneter Polymere wird das gewünschte Amid durch Umsetzung des Polymers, das Anhydridgruppen enthält, mit einem sekundären Amin der Formel HNR⁶R⁷ (gegebenenfalls außerdem mit einem Alkohol, wenn ein Esteramid gebildet wird) erhalten. Wenn Polymere, die eine Anhydridgruppe enthalten, umgesetzt werden, werden die resultierenden Aminogruppen Ammoniumsalze und Amide sein. Solche Polymere können verwendet werden, mit der Maßgabe, dass sie mindestens zwei Amidgruppen enthalten. Es ist wesentlich, dass das Polymer, das mindestens zwei Amidgruppen enthält, mindestens eine Alkylgruppe mit mindestens 10 Kohlenstoffatomen enthält. Diese langkettige Gruppe, die eine geradkettige oder verzweigte Alkylgruppe sein kann, kann über das Stickstoffatom der Amidgruppe gebunden vorliegen.Die dafür geeigneten Amine können durch die Formel R⁶R⁷NH und die Polyamine durch R⁶NH[R¹⁹NH]_xR⁷ wiedergegeben werden, wobei R¹⁹ eine zweiwertige Kohlenwasserstoffgruppe, vorzugsweise eine Alkylen- oder kohlenwasserstoffsubstituierte Alkylengruppe, und x eine ganze Zahl, vorzugsweise zwischen 1 und 30 ist. Vorzugsweise enthalten einer der beiden oder beide Reste R⁶ und R⁷ mindestens 10 Kohlenstoffatome, beispielsweise 10 bis 20 Kohlenstoffatome, zum Beispiel Dodecyl, Tetradecyl, Hexadecyl oder Octadecyl.Beispiele geeigneter sekundärer Amine sind Dioctylamin und solche, die Alkylgruppen mit mindestens 10 Kohlenstoffatomen enthalten, beispielsweise Didecylamin, Didodecylamin, Dicocosamin (d.h. gemischte C₁₂-C₁₄-Amine), Dioctadecylamin, Hexadecyloctadecylamin, Di-(hydriertes Talg)-Amin (annähernd 4 Gew.-% n-C₁₄-Alkyl, 30 Gew.-% n-C₁₀-Alkyl, 60 Gew.-% n-C₁₈-Alkyl, der Rest ist ungesättigt).Beispiele geeigneter Polyamine sind N-Octadecylpropandiamin, N,N'-Dioctadecylpropandiamin, N-Tetradecylbutandiamin und N,N'-Dihexadecylhexandiamin. N-Cocospropylendiamin (C₁₂/C₁₄-Alkylpropylendiamin), N-Talgpropylendiamin (C₁₆/C₁₈-Alkylpropylendiamin).Die amidhaltigen Polymere haben üblicherweise ein durchschnittliches Molekulargewicht (Zahlenmittel) von 1000 bis 500 000, zum Beispiel 10 000 bis 100 000.

6. Copolymere des Styrols, seiner Derivate oder aliphatischer Olefine mit 2 bis 40 C-Atomen, bevorzugt mit 6 bis 20 C-Atomen und olefinisch ungesättigten Carbonsäuren oder Carbonsäureanhydriden, die mit Aminen der Formel HNR⁶R⁷ umgesetzt sind. Die Umsetzung kann vor oder nach der Polymerisation vorgenommen werden. Im einzelnen leiten sich die Struktureinheiten der Copolymere von z.B. Maleinsäure, Fumarsäure, Tetrahydrophthalsäure, Citraconsäure, bevorzugt Maleinsäureanhydrid ab. Sie können sowohl in Form ihrer Homopolymeren als auch der Copolymeren eingesetzt werden. Als Comonomere sind geeignet: Styrol und Alkylstyrole, geradkettige und verzweigte Olefine mit 2 bis 40 Kohlenstoffatomen, sowie deren Mischungen untereinander. Beispielsweise seien genannt: Styrol, α-Methylstyrol, Dimethylstyrol, α-Ethylstyrol, Diethylstyrol, i-Propylstyrol, tert.-Butylstyrol, Ethylen, Propylen, n-Butylen, Diisobutylen, Decen, Dodecen, Tetradecen, Hexadecen, Octadecen. Bevorzugt sind Styrol und Isobuten, besonders bevorzugt ist Styrol.Als Polymere seien beispielsweise im einzelnen genannt: Polymaleinsäure, ein molares, alternierend aufgebautes Styrol/Maleinsäure-Copolymer, statistisch aufgebaute Styrol/Maleinsäure-Copolymere im Verhältnis 10:90 und ein alternierendes Copolymer aus Maleinsäure und i-Buten. Die molaren Massen der Polymeren betragen im allgemeinen 500 g/mol bis 20 000 g/mol, bevorzugt 700 bis 2000 g/mol.Die Umsetzung der Polymeren oder Copolymeren mit den Aminen erfolgt bei Temperaturen von 50 bis 200°C im Verlauf von 0,3 bis 30 Stunden. Das Amin wird dabei in Mengen von ungefähr einem Mol pro Mol einpolymerisiertem Dicarbonsäureanhydrid, d.i. ca.0,9 bis 1,1 Mol/Mol, angewandt. Die Verwendung größerer oder geringerer Mengen ist möglich, bringt aber keinen Vorteil. Werden größere Mengen als ein Mol angewandt, erhält man zum Teil Ammoniumsalze, da die Bildung einer zweiten Amidgruppierung höhere Temperaturen, längere Verweilzeiten und Wasserauskreisen erfordert. Werden geringere Mengen als ein Mol angewandt, findet keine vollständige Umsetzung zum Monoamid statt und man erhält eine dementsprechend verringerte Wirkung. Anstelle der nachträglichen Umsetzung der Carboxylgruppen in Form des Dicarbonsäureanhydrids mit Aminen zu den entsprechenden Amiden kann es manchmal von Vorteil sein, die Monoamide der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Mono- und Dicarbonsäure anlagern können und dann keine Copolymerisation mehr möglich ist.

7. Copolymere, bestehend aus 10 bis 95 Mol-% eines oder mehrerer Alkylacrylate oder Alkylmethacrylate mit C₁-C₂₆-Alkylketten und aus 5 bis 90 Mol-% einer oder mehrerer ethylenisch ungesättigter Dicarbonsäuren oder deren Anhydriden, wobei das Copolymere weitgehend mit einem oder mehreren primären oder sekundären Aminen zum Monoamid oder Amid/Ammoniumsalz der Dicarbonsäure umgesetzt ist. Die Copolymeren bestehen zu 10 bis 95 Mol-%, bevorzugt zu 40 bis 95 Mol-% und besonders bevorzugt zu 60 bis 90 Mol-% aus Alkyl(meth)acrylaten und zu 5 bis 90 Mol-%, bevorzugt zu 5 bis 60 Mol-% und besonders bevorzugt zu 10 bis 40 Mol-% aus den olefinisch ungesättigten Dicarbonsäurederivaten. Die Alkylgruppen der Alkyl(meth)acrylate enthalten aus 1 bis 26, bevorzugt 4 bis 22 und besonders bevorzugt 8 bis 18 Kohlenstoffatome. Sie sind bevorzugt geradkettig und unverzweigt. Es können jedoch auch bis zu 20 Gew.-% cyclische und/oder verzweigte Anteile enthalten sein.Beispiele für besonders bevorzugte Alkyl(meth)acrylate sind n-Octyl(meth)acrylat, n-Decyl(meth)acrylat, n-Dodecyl(meth)acrylat, n-Tetradecyl(meth)acrylat, n-Hexadecyl(meth)acrylat und n-Octadecyl(meth)acrylat sowie Mischungen davon.Beispiele ethylenisch ungesättigter Dicarbonsäuren sind Maleinsäure, Tetrahydrophthalsäure, Citraconsäure und Itaconsäure bzw. deren Anhydride sowie Fumarsäure. Bevorzugt ist Maleinsäureanhydrid. Als Amine kommen Verbindungen der Formel HNR⁶R⁷ in Betracht.In der Regel ist es von Vorteil, die Dicarbonsäuren in Form der Anhydride, soweit verfügbar, bei der Copolymerisation einzusetzen, z.B. Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid und Tetrahydrophthalsäureanhydrid, da die Anhydride in der Regel besser mit den (Meth)acrylaten copolymerisieren. Die Anhydridgruppen der Copolymeren können dann direkt mit den Aminen umgesetzt werden.
Die Umsetzung der Polymeren mit den Aminen erfolgt bei Temperaturen von 50 bis 200°C im Verlauf von 0,3 bis 30 Stunden. Das Amin wird dabei in Mengen von ungefähr einem bis zwei Mol pro Mol einpolymerisiertem
Dicarbonsäureanhydrid, d.i. ca. 0,9 bis 2,1 Mol/Mol angewandt. Die Verwendung größerer oder geringerer Mengen ist möglich, bringt aber keinen Vorteil. Werden größere Mengen als zwei Mol angewandt, liegt freies Amin vor. Werden geringere Mengen als ein Mol angewandt, findet keine vollständige Umsetzung zum Monoamid statt und man erhält eine dementsprechend verringerte Wirkung.In einigen Fällen kann es von Vorteil sein, wenn die Amid/Ammoniumsalzstruktur aus zwei unterschiedlichen Aminen aufgebaut wird. So kann beispielsweise ein Copolymer aus Laurylacrylat und Maleinsäureanhydrid zuerst mit einem sekundären Amin, wie hydriertem Ditalgfettamin zum Amid umgesetzt werden, wonach die aus dem Anhydrid stammende freie Carboxylgruppe mit einem anderen Amin, z.B. 2-Ethylhexylamin zum Ammoniumsalz neutralisiert wird. Genauso ist die umgekehrte Vorgehensweise denkbar: Zuerst wird mit Ethylhexylamin zum Monoamid, dann mit Ditalgfettamin zum Ammoniumsalz umgesetzt. Vorzugsweise wird dabei mindestens ein Amin verwendet, welches mindestens eine geradkettige, unverzweigte Alkylgruppe mit mehr als 16 Kohlenstoffatomen besitzt. Es ist dabei nicht erheblich, ob dieses Amin am Aufbau der Amidstruktur oder als Ammoniumsalz der Dicarbonsäure vorliegt. Anstelle der nachträglichen Umsetzung der Carboxylgruppen bzw. des Dicarbonsäureanhydrids mit Aminen zu den entsprechenden Amiden oder Amid/Ammoniumsalzen, kann es manchmal von Vorteil sein, die Monoamide bzw. Amid/Ammoniumsalze der Monomeren herzustellen und dann bei der Polymerisation direkt einzupolymerisieren. Meist ist das jedoch technisch viel aufwendiger, da sich die Amine an die Doppelbindung der monomeren Dicarbonsäure anlagern können und dann keine Copolymerisation mehr möglich ist.

8. Terpolymere auf Basis von α,β-ungesättigten Dicarbonsäureanhydriden, α,β-ungesättigten Verbindungen und Polyoxyalkylenethern von niederen, ungesättigten Alkoholen, die dadurch gekennzeichnet sind, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 12 und/oder 14, sowie gegebenenfalls 13 enthalten, wobei die Struktureinheiten 13 von nicht umgesetzten Anhydridresten stammen,

wobei

R²² und R²³ unabhängig voneinander Wasserstoff oder Methyl,

a, b gleich Null oder Eins und a + b gleich Eins,

R²⁴ und R²⁵ gleich oder verschieden sind und für die Gruppen -NHR⁶, N(R⁶)₂ und/oder -OR²⁷ stehen, und R²⁷ für ein Kation der Formel H₂N(R⁶)₂ oder H₃NR⁶ steht,

19 - 80 Mol-%, bevorzugt 39-60 Mol-% an bivalenten Struktureinheiten der Formel 15

worin

R²⁸ Wasserstoff oder C₁-C₄-Alkyl und

R²⁹ C₆-C₆₀-Alkyl oder C₆-C₁₈-Aryl bedeuten und

1 - 30 Mol-%, bevorzugt 1 - 20 Mol-% an bivalenten Struktureinheiten der Formel 16

worin

R³⁰ Wasserstoff oder Methyl,

R³¹ Wasserstoff oder C₁-C₄-Alkyl,

R³³ C₁-C₄-Alkylen,

m eine Zahl von 1 bis 100,

R³² C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl, C₆-C₁₈-Aryl oder -C(O)-R³⁴, wobei

R³⁴ C₁-C₄₀-Alkyl, C₅-C₁₀-Cycloalkyl oder C₆-C₁₈-Aryl,

enthalten. Die vorgenannten Alkyl-, Cycloalkyl- und Arylreste können gegebenenfalls substituiert sein. Geeignete Substituenten der Alkyl- und Arylreste sind beispielsweise (C₁-C₆)-Alkyl, Halogene, wie Fluor, Chlor, Brom und Jod, bevorzugt Chlor und (C₁-C₆)-Alkoxy.Alkyl steht hier für einen geradkettigen oder verzweigten Kohlenwasserstoffrest. Im einzelnen seien genannt: n-Butyl, tert.-Butyl, n-Hexyl, n-Octyl, Decyl, Dodecyl, Tetradecyl, Hexadecyl, Octadecyl, Dodecenyl, Tetrapropenyl, Tetradecenyl, Pentapropenyl, Hexadecenyl, Octadecenyl und Eicosanyl oder Mischungen, wie Cocosalkyl, Talgfettalkyl und Behenyl.Cycloalkyl steht hier für einen cyclischen aliphatischen Rest mit 5 - 20 Kohlenstoffatomen. Bevorzugte Cycloalkylreste sind Cyclopentyl und Cyclohexyl.Aryl steht hier für einen gegebenenfalls substituiertes aromatisches Ringsystem mit 6 bis 18 Kohlenstoffatomen.Die Terpolymere bestehen aus den bivalenten Struktureinheiten der Formeln 12 und 14 sowie 15 und 16 und ggf. 13. Sie enthalten lediglich noch in an sich bekannter Weise die bei der Polymerisation durch Initiierung, Inhibierung und Kettenabbruch entstandenen Endgruppen.Im einzelnen leiten sich Struktureinheiten der Formeln 12 bis 14 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 17 und 18

wie Maleinsäureanhydrid, Itaconsäureanhydrid, Citraconsäureanhydrid, bevorzugt Maleinsäureanhydrid, ab.
Die Struktureinheiten der Formel 15 leiten sich von den α,β-ungesättigten Verbindungen der Formel 19 ab.

Beispielhaft seien die folgenden α,β-ungesättigten Olefine genannt: Styrol, α-Methylstyrol, Dimethylstyrol, α-Ethylstyrol, Diethylstyrol, i-Propylstyrol, tert.-Butylstyrol, Diisobutylen und α-Olefine, wie Decen, Dodecen, Tetradecen, Pentadecen, Hexadecen, Octadecen, C₂₀-α-Olefin, C₂₄-α-Olefin, C₃₀-α-Olefin, Tripropenyl, Tetrapropenyl, Pentapropenyl sowie deren Mischungen. Bevorzugt sind α-Olefine mit 10 bis 24 C-Atomen und Styrol, besonders bevorzugt sind α-Olefine mit 12 bis 20 C-Atomen.Die Struktureinheiten der Formel 16 leiten sich von Polyoxyalkylenethern niederer, ungesättigter Alkohole der Formel 20 ab.

Bei den Monomeren der Formel 20 handelt es sich um Veretherungsprodukte (R³² = -C(O)R³⁴) oder Veresterungsprodukte (R³² = -C(O)R³⁴) von Polyoxyalkylenethern (R³² = H).Die Polyoxyalkylenether (R³² = H) lassen sich nach bekannten Verfahren durch Anlagerung von α-Olefinoxiden, wie Ethylenoxid, Propylenoxid und/oder Butylenoxid an polymerisierbare niedere, ungesättigte Alkohole der Formel 21

herstellen. Solche polymerisierbaren niederen ungesättigten Alkohole sind z.B. Allylalkohol, Methallylalkohol, Butenole, wie 3-Buten-1-ol und 1-Buten-3-o oder Methylbutenole, wie 2-Methyl-3-buten-1-ol, 2-Methyl-3-buten-2-ol und 3-Methyl-3-buten-1-ol. Bevorzugt sind Anlagerungsprodukte von Ethylenoxid und/oder Propylenoxid an Allylalkohol.Eine nachfolgende Veretherung dieser Polyoxyalkylenether zu Verbindungen der Formel 20 mit R³² = C₁-C₂₄-Alkyl, Cycloalkyl oder Aryl erfolgt nach an sich bekannten Verfahren. Geeignete Verfahren sind z.B. aus J. March, Advanced Organic Chemistry, 2. Auflage, S. 357f(1977) bekannt. Diese Veretherungsprodukte der Polyoxyalkylenether lassen sich auch herstellen, indem man α-Olefinoxide, bevorzugt Ethylenoxid, Propylenoxid und/oder Butylenoxid an Alkohole der Formel 22 R³² - OH worin R³² gleich C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl oder C₆-C₁₈-Aryl, nach bekannten Verfahren anlagert und mit polymerisierbaren niederen, ungesättigten Halogeniden der Formel 23

umsetzt, wobei W für ein Halogenatom steht. Als Halogenide werden bevorzugt die Chloride und Bromide eingesetzt. Geeignete Herstellungsverfahren werden z.B. in J. March, Advanced Organic Chemistry, 2.Auflage, S.357f (1977) genannt. Die Veresterung der Polyoxyalkylenether (R³² = -C(O)-R³⁴) erfolgt durch Umsetzung mit gängigen Veresterungsmitteln, wie Carbonsäuren, Carbonsäurehalogeniden, Carbonsäureanhydriden oder Carbonsäureestern mit C₁-C₄-Alkoholen. Bevorzugt werden die Halogenide und Anhydride von C₁-C₄₀-Alkyl-, C₅-C₁₀-Cycloalkyl- oder C₆-C₁₈-Arylcarbonsäuren verwendet. Die Veresterung wird im allgemeinen bei Temperaturen von 0 bis 200°C, vorzugsweise 10 bis 100°C durchgeführt.Bei den Monomeren der Formel 20 gibt der Index m den Alkoxylierungsgrad, d.h. die Anzahl der Mole an α-Olefin an, die pro Mol der Formel 20 oder 21 angelagert werden.Als zur Herstellung der Terpolymere geeignete primäre Amine seien beispielsweise die folgenden genannt:
n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin, n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.Als zur Herstellung der Terpolymere geeignete sekundäre Amine seien beispielsweise genannt: Didecylamin, Ditetradecylamin, Distearylamin, Dicocosfettamin, Ditalgfettamin und deren Mischungen. Die Terpolymeren besitzen K-Werte (gemessen nach Ubbelohde in 5 gew.-%iger Lösung in Toluol bei 25°C) von 8 bis 100, bevorzugt 8 bis 50, entsprechend mittleren Molekulargewichten (M_w) zwischen ca. 500 und 100.000. Geeignete Beispiele sind in EP 606 055 aufgeführt.

9. Umsetzungsprodukte von Alkanolaminen und/oder Polyetheraminen mit Polymeren enthaltend Dicarbonsäureanhydridgruppen, dadurch gekennzeichnet, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 25 und 27 und gegebenenfalls 26

wobei

R²² und R²³

unabhängig voneinander Wasserstoff oder Methyl,

a, b

gleich Null oder 1 und a + b gleich 1,

R³⁷ =

-OH, -O-[C₁-C₃₀-Alkyl], -NR⁶R⁷, -O^sN^rR⁶R⁷H₂

R³⁸ =

R³⁷ oder NR⁶R³⁹

R³⁹ =

-(A-O)_x-E

mit

A =

Ethylen- oder Propylengruppe

x =

1 bis 50

E =

H, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl oder C₆-C₃₀-Aryl

bedeuten, und
80 - 20 Mol-%, bevorzugt 60 - 40 Mol-% an bivalenten Struktureinheiten der Formel 15 enthalten. Im einzelnen leiten sich die Struktureinheiten der Formeln 25, 26 und 27 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 17 und/oder 18 ab.Die Struktureinheiten der Formel 15 leiten sich von den α,β-ungesättigten Olefinen der Formel 19 ab. Die vorgenannte Alkyl-, Cycloalkyl- und Arylreste haben die gleichen Bedeutungen wie unter 8.Die Reste R³⁷ und R³⁸ in Formel 25 bzw. R³⁹ in Formel 27 leiten sich von Polyetheraminen oder Alkanolaminen der Formeln 28 a) und b), Aminen der Formel NR⁶R⁷R⁸ sowie gegebenenfalls von Alkoholen mit 1 bis 30 Kohlenstoffatomen ab.

Darin bedeuten

R⁵³

Wasserstoff, C₆-C₄₀-Alkyl oder

R⁵⁴

Wasserstoff, C₁-C₄-Alkyl

R⁵⁵

Wasserstoff, C₁- bis C₄-Alkyl, C₅- bis C₁₂-Cycloalkyl oder C₆- bis C₃₀-Aryl

R⁵⁶, R⁵⁷

unabhängig voneinander Wasserstoff, C₁- bis C₂₂-Alkyl, C₂- bis C₂₂-Alkenyl oder Z - OH

Z

C₂- bis C₄-Alkylen

n

eine Zahl zwischen 1 und 1000.

Zur Derivatisierung der Struktureinheiten der Formeln 17 und 18 wurden vorzugsweise Gemische aus mindestens 50 Gew.-% Alkylaminen der Formel HNR⁶R⁷R⁸ und höchstens 50 Gew.-% Polyetheraminen, Alkanolaminen der Formeln 28 a) und b) verwendet.Die Herstellung der eingesetzten Polyetheramine ist beispielsweise durch reduktive Aminierung von Polyglykolen möglich. Des weiteren gelingt die Herstellung von Polyetheraminen mit einer primären Aminogruppe durch Addition von Polyglykolen an Acrylnitril und anschließende katalytische Hydrierung. Darüber hinaus sind Polyetheramine durch Umsetzung von Polyethern mit Phosgen bzw. Thionylchlorid und anschließende Aminierung zum Polyetheramin zugänglich. Die erfindungsgemäß eingesetzten Polyetheramine sind (z.B.) unter der Bezeichnung ®Jeffamine (Texaco) kommerziell erhältlich. Ihr Molekulargewicht beträgt bis zu 2000 g/mol und das Ethylenoxid-/Propylenoxid-Verhältnis beträgt von 1:10 bis 6:1.
Eine weitere Möglichkeit zur Derivatisierung der Struktureinheiten der Formeln 17 und 18 besteht darin, dass anstelle der Polyetheramine ein Alkanolamin der Formel eingesetzt und nachfolgend einer Oxalkylierung unterworfen wird. Pro Mol Anhydrid werden 0,01 bis 2 Mol, bevorzugt 0,01 bis 1 Mol Alkanolamin eingesetzt. Die Reaktionstemperatur beträgt zwischen 50 und 100°C (Amidbildung). Im Falle von primären Aminen erfolgt die Umsetzung bei Temperaturen oberhalb 100°C (Imidbildung).Die Oxalkylierung erfolgt üblicherweise bei Temperaturen zwischen 70 und 170°C unter Katalyse von Basen, wie NaOH oder NaOCH₃, durch Aufgasen von Alkylenoxiden, wie Ethylenoxid (EO) und/oder Propylenoxid (PO). Üblicherweise werden pro Mol Hydroxylgruppen 1 bis 500, bevorzugt 1 bis 100 Mol Alkylenoxid zugegeben.Als geeignete Alkanolamine seien beispielsweise genannt: Monoethanolamin, Diethanolamin, N-Methylethanolamin, 3-Aminopropanol, Isopropanol, Diglykolamin, 2-Amino-2-methylpropanol und deren Mischungen.Als primäre Amine seien beispielsweise die folgenden genannt: n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin, n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.Als sekundäre Amine seien beispielsweise genannt:
Didecylamin, Ditetradecylamin, Distearylamin, Dicocosfettamin, Ditalgfettamin und deren Mischungen.Als Alkohole seien beispielsweise genannt:
Methanol, Ethanol, Propanol, Isopropanol, n-, sek.-, tert.-Butanol, Octanol, Tetradecanol, Hexadecanol, Octadecanol, Talgfettalkohol, Behenylalkohol und deren Mischungen. Geeignete Beispiele sind in EP-A-688 796 aufgeführt.10. Co- und Terpolymere von N-C₆-C₂₄-Alkylmaleinimid mit C₁-C₃₀-Vinylestern, Vinylethern und/oder Olefinen mit 1 bis 30 C-Atomen, wie z.B. Styrol oder α-Olefinen. Diese sind zum einen durch Umsetzung eines Anhydridgruppen enthaltenden Polymers mit Aminen der Formel H₂NR⁶ oder durch Imidierung der Dicarbonsäure und anschließende Copolymerisation zugänglich. Bevorzugte Dicarbonsäure ist dabei Maleinsäure bzw. Maleinsäureanhydrid. Bevorzugt sind dabei Copolymere aus 10 bis 90 Gew.-% C₆-C₂₄-α-Olefinen und 90 bis 10 Gew.-% N-C₆-C₂₂-Alkylmaleinsäureimid.Zur Optimierung der Eigenschaften als Fließverbesserer und/oder Lubricity-Additiv können die erfindungsgemäßen Additive ferner in Mischung mit Alkylphenol-Formaldehydharzen eingesetzt werden. In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei diesen Alkylphenol-Formaldehydharzen um solche der Formel

worin R⁵¹ für C₄-C₅₀-Alkyl oder -Alkenyl, [O-R⁵²] für Ethoxy- und/oder Propoxy, n für eine Zahl von 5 bis 100 und p für eine Zahl von 0 bis 50 steht.Schließlich werden in einer weiteren Variante der Erfindung die erfindungsgemäßen Additive zusammen mit Kammpolymeren verwendet. Hierunter versteht man Polymere, bei denen Kohlenwasserstoffreste mit mindestens 8, insbesondere mindestens 10 Kohlenstoffatomen an einem Polymerrückgrat gebunden sind. Vorzugsweise handelt es sich um Homopolymere, deren Alkylseitenketten mindestens 8 und insbesondere mindestens 10 Kohlenstoffatome enthalten. Bei Copolymeren weisen mindestens 20 %, bevorzugt mindestens 30 % der Monomeren Seitenketten auf (vgl. Comb-like Polymers-Structure and Properties; N.A. Platé and V.P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).Beispiele für geeignete Kammpolymere sind z.B. Fumarat/Vinylacetat-Copolymere (vgl. EP 0 153 176 A1), Copolymere aus einem C₆- bis C₂₄-α-Olefin und einem N-C₆- bis C₂₂-Alkylmaleinsäureimid (vgl. EP-A-0 320 766), ferner veresterte Olefin/ Maleinsäureanhydrid-Copolymere, Polymere und Copolymere von α-Olefinen und veresterte Copolymere von Styrol und Maleinsäureanhydrid.Beispielsweise können Kammpolymere durch die Formel

beschrieben werden. Darin bedeuten

A

R', COOR', OCOR', R"-COOR' oder OR';

D

H, CH₃, A oder R";

E

H oder A;

G

H, R", R"-COOR', einen Arylrest oder einen heterocyclischen Rest;

M

H, COOR", OCOR", OR" oder COOH;

N

H; R", COOR", OCOR, COOH oder einen Arylrest;

R'

eine Kohlenwasserstoffkette mit 8-150 Kohlenstoffatomen;

R"

eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;

m

eine Zahl zwischen 0,4 und 1,0; und

n

eine Zahl zwischen 0 und 0,6.

The paraffin dispersants mentioned below are produced in part by reacting compounds which contain 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 ₁₂ -C ₂₄ alkyl, C ₁₂ -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 - (AO) _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, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₃₀ aryl, and n is 2, 3 or 4, and Y and Z independently of one another are H, C ₁ -C ₃₀ - Alkyl or - (AO) _x mean. Acyl group is understood here to mean a functional group of the following formula: (> C = O)

1. Reaction products of alkenyl spirobislactones of the formula 4

where R is in each case C ₈ -C ₂₀₀ 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 (4) with the amines.

2. Amides or ammonium salts of aminoalkylene polycarboxylic acids with secondary amines of the formulas 5 and 6

in which
R ^{10 is} a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula 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 8

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 mol of amine, preferably 0.8 to 1.2 mol, by reacting the acids Amine obtained per carboxyl group. The reaction temperatures are about 80 to 200 ° C., the water of reaction formed being continuously removed to produce the amides. However, the reaction does not have to be carried out completely to give the amide; rather, 0 to 100 mol% of the amine used can be in the form of the ammonium salt. The compounds mentioned under B1) can also be prepared under analogous conditions, as amines of the formula 9

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 formula 10 ⊕NR ⁶ R ⁷ R ⁸ R ¹¹ X ^⊖ where R ⁶ , R ⁷ , R ^{8 have} the meaning given above and R ¹¹ for C ₁ -C ₃₀ alkyl, preferably C ₁ -C ₂₂ alkyl, C ₁ -C ₃₀ alkenyl, preferably C ₁ -C ₂₂ - Alkenyl, benzyl or a radical of the formula - (CH ₂ -CH ₂ -O) _n -R ¹² , where R ^{12 is} hydrogen or a fatty acid radical of the formula C (O) -R ¹³ , with R ¹³ = C ₆ -C _40- alkenyl, n is a number from 1 to 30 and X represents halogen, preferably chlorine, or a methosulfate. Exemplary of such quaternary ammonium salts include: dihexadecyl, distearyldimethylammonium chloride, quaternization products of esters of di- and triethanolamine with long-chain fatty acids (lauric 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) as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleylester chloride, N-methyltriethanolammonium trilaurylestermethosulfonate mixed methosulfate.

4. Compounds of formula 11

in which R ^{14 stands} for CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ ,
R ¹⁵ and R ^{16 represent} H, CONR ¹⁷ ₂ , CO ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or -NCOR ¹⁷ , and
R ^{17 is} alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms. Preferred carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellite, pyromellite (dianhydride), isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride). The formulation (anhydride) means that the anhydrides of the acids mentioned are also preferred acid derivatives. If the compounds of the formula (11) are amides or amine salts, they are preferably of a secondary amine which contains a hydrogen and carbon-containing group with 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 is preferably straight-chain or branched at the 1- or 2-position. The other hydrogen and carbon containing groups can be shorter, eg 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). Also suitable are polymers which contain at least one amide or ammonium group directly attached to the backbone of the polymer, the amide - Or ammonium group carries 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 that contains 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. As polymers, copolymers of unsaturated esters such as C ₁ are generally used for this purpose -C ₄₀ alkyl (meth) acrylates, fumaric acid dialkyl esters, C ₁ -C ₄₀ alkyl vinyl ethers, C ₁ -C ₄₀ alkyl vinyl esters or C ₂ -C ₄₀ 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, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride). Carboxylic acids are preferably reacted with 0.1 to 1.5 mol, in particular 0.5 to 1.2 mol, of amine per acid group, carboxylic anhydrides preferably with 0.1 to 2.5, in particular 0.5 to 2.2 mol, of amine per acid anhydride group , whereby, depending on the reaction conditions, amides, ammonium salts, amide-ammonium salts or imides are formed. 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. Water can be split off by heating to form the diamond. Particularly suitable examples of amide group-containing polymers for use in accordance with the invention are:

5. Copolymers (a) of a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) of vinyl esters, for example vinyl acetate or vinyl stearate with maleic anhydride, or (c) of a dialkyl fumarate, maleate, citraconate or itaconate 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 a Alcohol if an ester amide is formed). If 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 bonded 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 are represented, wherein R ^{19 is} a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is an integer, preferably between 1 and 30. Preferably one or both of the radicals 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 C ₁₂ -C ₁₄ amines), dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approximately 4% by weight nC ₁₄ alkyl, 30% by weight nC ₁₀ - Alkyl, 60% by weight nC ₁₈ alkyl, the rest is unsaturated). Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-cocospropylene diamine (C ₁₂ / C ₁₄ alkyl propylene diamine), N-tallow propylene diamine (C ₁₆ / C ₁₈ alkyl propylene diamine). The amide-containing polymers usually have an average molecular weight (number average) of 1000 to 500,000, for example 10,000 to 100,000 .

6. Copolymers of styrene, its derivatives or aliphatic olefins having 2 to 40 carbon atoms, preferably having 6 to 20 carbon 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 are derived from, for example, maleic acid, fumaric 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, and styrene is particularly preferred. Examples of polymers 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 from 500 g / mol to 20,000 g / mol, preferably from 700 to 2000 g / mol. The reaction of the polymers or copolymers with the amines takes place at from 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 requires higher temperatures, longer residence times and water separation. 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 reaction of the carboxyl groups in the form of the dicarboxylic anhydride with amines to give the corresponding amides, it 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 C ₁ -C ₂₆ -alkyl chains and 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, the copolymer being largely with a or more primary or secondary amines is converted to the monoamide or amide / ammonium salt of 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 olefinically 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. In general, it is advantageous to use the dicarboxylic acids in the form of the anhydrides, if available, in the copolymerization, for example maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride, since the anhydrides in the Better copolymerize 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 polymerized in amounts of approximately one to two moles per mole
Dicarboxylic anhydride, di 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 less than one mole is used, there is no complete conversion to the monoamide and the effect is reduced accordingly. 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 ditallow 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 give the ammonium salt. The reverse procedure is also conceivable: First the reaction with ethylhexylamine to form the monoamide, then with ditallow fatty amine to the ammonium salt. 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.

8. 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 12 and / or 14 and optionally 13, the structural units 13 originating from unreacted anhydride residues,

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 the} same or different and stand for the groups -NHR ⁶ , N (R ⁶ ) ₂ and / or -OR ²⁷ , and R ²⁷ for a cation of the formula H ₂ N (R ⁶ ) ₂ or H ₃ NR ⁶ stands,

19-80 mol%, preferably 39-60 mol%, of bivalent structural units of the formula 15

wherein

R ^{28 is} hydrogen or C ₁ -C ₄ alkyl and

R ^{29 is} C ₆ -C ₆₀ alkyl or C ₆ -C ₁₈ aryl and

1 to 30 mol%, preferably 1 to 20 mol% of bivalent structural units of the formula 16

wherein

R ^{30 is} hydrogen or methyl,

R ^{31 is} hydrogen or C ₁ -C ₄ alkyl,

R ³³ C ₁ -C ₄ alkylene,

m is a number from 1 to 100,

R ^{32 is} C ₁ -C ₂₄ alkyl, C ₅ -C ₂₀ cycloalkyl, C ₆ -C ₁₈ aryl or -C (O) -R ³⁴ , where

R ^{34 is} C ₁ -C ₄₀ alkyl, C ₅ -C ₁₀ cycloalkyl or C ₆ -C ₁₈ aryl,

contain. The aforementioned alkyl, cycloalkyl and aryl radicals can optionally be substituted. Suitable substituents of the alkyl and aryl radicals are, for example, (C ₁ -C ₆ ) alkyl, halogens such as fluorine, chlorine, bromine and iodine, preferably chlorine and (C ₁ -C ₆ ) alkoxy. Alkyl here is a straight-chain or branched hydrocarbon residue. 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 , Tallow fatty alkyl 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 12 and 14 as well as 15 and 16 and possibly 13. They only contain in themselves The end groups formed during the polymerization by initiation, inhibition and chain termination are known. In particular, structural units of the formulas 12 to 14 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 17 and 18

such as maleic anhydride, itaconic anhydride, citraconic anhydride, preferably maleic anhydride.
The structural units of the formula 15 are derived from the α, β-unsaturated compounds of the formula 19.

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 ₂₀ -α-olefin, C ₂₄ -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 16 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula 20.

The monomers of the formula 20 are etherification products (R ³² = -C (O) R ³⁴ ) or esterification products (R ³² = -C (O) R ³⁴ ) of polyoxyalkylene ethers (R ³² = H) .The polyoxyalkylene ethers (R ³² = H) can be obtained by known processes by adding α-olefin oxides, such as ethylene oxide, propylene oxide and / or butylene oxide, to polymerizable lower, unsaturated alcohols of the formula 21

produce. Such polymerizable lower unsaturated alcohols are, for example, allyl alcohol, methallyl alcohol, butenols, such as 3-buten-1-ol and 1-buten-3-o, or methylbutenols, 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 20 with R ³² = C ₁ -C ₂₄ -alkyl, cycloalkyl or aryl is carried out by processes known per se. Suitable processes are known, for example, from J. March, Advanced Organic Chemistry, 2nd edition, pp. 357f (1977). 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 22 R ³² - OH wherein R ^{32 is} equal to C ₁ -C ₂₄ alkyl, C ₅ -C ₂₀ cycloalkyl or C ₆ -C ₁₈ aryl, by known methods and with polymerizable lower, unsaturated halides of the formula 23

implemented, where W stands for a halogen atom. The chlorides and bromides are preferably used as halides. Suitable production processes are mentioned, for example, in J. March, Advanced Organic Chemistry, 2nd edition, p.357f (1977). The esterification of the polyoxyalkylene ethers (R ³² = -C (O) -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 C ₁ -C ₄ alcohols. The halides and anhydrides of C ₁ -C ₄₀ alkyl, C ₅ -C ₁₀ cycloalkyl or C ₆ -C ₁₈ aryl carboxylic acids are preferably used. The esterification is generally carried out at temperatures from 0 to 200 ° C., preferably 10 to 100 ° C. In the case of the monomers of the formula 20, the index m indicates the degree of alkoxylation, ie the number of moles of α-olefin which per mole of Formula 20 or 21 can be added. 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, Dicocosfettamin, Ditalgfettamin and their mixtures. 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.

9. 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 25 and 27 and optionally 26

in which

R ²² and R ²³

independently of one another hydrogen or methyl,

a, b

is zero or 1 and a + b is 1,

R ³⁷ =

-OH, -O- [C ₁ -C ₃₀ alkyl], -NR ⁶ R ⁷ , -O ^s N ^r R ⁶ R ⁷ H ₂

R ³⁸ =

R ³⁷ or NR ⁶ R ³⁹

R ³⁹ =

- (AO) _x -E

With

A =

Ethylene or propylene group

x =

1 to 50

E =

H, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₃₀ aryl

mean and
Contain 80 - 20 mol%, preferably 60 - 40 mol% of bivalent structural units of the formula 15. Specifically, the structural units of the formulas 25, 26 and 27 are derived from α, β-unsaturated dicarboxylic anhydrides of the formulas 17 and / or 18. The structural units of the formula 15 are derived from the α , β-unsaturated olefins of the formula 19. The abovementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8. The radicals R ³⁷ and R ³⁸ in formula 25 and R ³⁹ in formula 27 are derived from polyetheramines or alkanolamines of the formulas 28 a) and b), amines of the formula NR ⁶ R ⁷ R ⁸ and optionally from alcohols having 1 to 30 carbon atoms.

Mean in it

R ⁵³

Hydrogen, C ₆ -C ₄₀ alkyl or

R ⁵⁴

Hydrogen, C ₁ -C ₄ alkyl

R ⁵⁵

Hydrogen, C ₁ - to C ₄ -alkyl, C ₅ - to C ₁₂ -cycloalkyl or C ₆ - to C ₃₀ -aryl

R ⁵⁶ , R ⁵⁷

independently of one another hydrogen, C ₁ - to C ₂₂ -alkyl, C ₂ - to C ₂₂ -alkenyl or Z - OH

Z.

C ₂ to C ₄ alkylene

n

a number between 1 and 1000.

Mixtures of at least 50% by weight of alkylamines of the formula HNR ⁶ R ⁷ R ⁸ and at most 50% by weight of polyetheramines, alkanolamines of the formulas 28 a) and b) were preferably used to derivatize the structural units of the formulas 17 and 18 the polyetheramines used are possible, for example, by reductive amination of polyglycols. Furthermore, polyetheramines with a primary amino group can be prepared by adding polyglycols to acrylonitrile and subsequent catalytic hydrogenation. In addition, polyetheramines are accessible by reacting polyethers with phosgene or thionyl chloride and subsequent amination to give the polyetheramine. 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 17 and 18 consists in that an alkanolamine of the formula is used instead of the polyetheramines and subsequently subjected 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 catalysis of bases, such as NaOH or NaOCH ₃ , by gassing 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-methylpropanol 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-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof. Examples of secondary amines are :
Didecylamine, Ditetradecylamine, Distearylamine, Dicocosfettamin, Ditalgfettamin and their mixtures. Examples of alcohols are:
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 ₁ -C ₃₀ vinyl esters, vinyl ethers and / or olefins with 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 H ₂ NR ⁶ or by imidation of the dicarboxylic acid and subsequent copolymerization. Preferred dicarboxylic acid is maleic acid or maleic anhydride. Copolymers of 10 to 90% by weight of C ₆ -C ₂₄ -α-olefins and 90 to 10% by weight of NC ₆ -C ₂₂ -alkylmaleinimide are preferred. To optimize the properties as a flow improver and / or lubricity additive, the additives of the invention are also used in a mixture with alkylphenol-formaldehyde resins. In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those of the formula

where R ^{51 is} C ₄ -C ₅₀ alkyl or alkenyl, [OR ⁵² ] is ethoxy and / or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50 Another variant of the invention uses the additives according to the invention together with 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 Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C ₆ - to C ₂₄ -α-olefin and an NC ₆ - to C ₂₂ -alkyl maleimide (cf. EP-A -0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride. For example, comb polymers can be represented by the formula

to be discribed. Mean in it

A

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

D

H, 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 '

a hydrocarbon chain with 8-150 carbon atoms;

R "

a hydrocarbon chain of 1 to 10 carbon atoms;

m

a number between 0.4 and 1.0; and

n

a number between 0 and 0.6.

The mixing ratio (in parts by weight) of the additives according to the invention Paraffin dispersants or comb polymers are 1:10 to 20: 1, preferably 1: 1 to 10: 1.

The additives according to the invention are suitable, the cold flow and Lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of to improve alcoholic fuels and mineral oils. You are for that Particularly suitable for use in middle distillates. As middle distillates One particularly refers to those mineral oils which are obtained by distilling crude oil be obtained and boiling in the range of 120 to 450 ° C, for example Kerosene, jet fuel, diesel and heating oil. Preferably, the invention Additives used in such middle distillates, which do not exceed 500 ppm, in particular less than 200 ppm sulfur and in special cases less than Contain 50 ppm sulfur. These are generally such Middle distillates which have been subjected to hydrogenation refining and therefore only small amounts of polyaromatic and polar compounds contain, which give them a natural lubricating effect. The Additives according to the invention are also preferably used in such Middle distillates used, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C. The effectiveness of the mixtures is better than from the individual components and compared to the mixtures would be expected according to the prior art. In particular, the additive combinations according to the invention under cold blending conditions, when the temperature of the oil in the additive is low, i.e. below 40 ° C, is especially below 20 ° C and especially below 10 ° C.

The additive components according to the invention can be mineral oils or Mineral oil distillates can be added separately or in a mixture. When using Mixtures have solutions or dispersions of 10 to 90% by weight, preferably 20-80 wt .-%, the additive combination contain proven. Suitable Solvents or dispersing agents are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g. 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. Through the additives in their lubricating and / or cold flow properties improved mineral oils or Mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight Additive based on the distillate.

The additives can be used alone or together with other additives e.g. with other pour point depressants, dewaxing aids, Corrosion inhibitors, antioxidants, conductivity improvers, Mud inhibitors, dehazers and additives to lower the cloud point. These additives can be added to the oil together with those of the invention Additive components or separately.

The effectiveness of the additives according to the invention as a lubricity enhancer and Cold flow improvers are explained in more detail by the following examples.

Examples

Characterization of the test oils Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Cloud Point (CP) (° C) + 1 - 9.6 - 3.2 - 4.3 - 26.8 Cold Filter Plugging Point (CFPP) (° C) - 2nd - 14 - 6th - 6th - 27 Pour point (PP) (° C) - 3rd - 12th -9 -12 -27 n-paraffin content (% by weight) 23 21.5 18.9 18.2 16.8 Initial boiling point (IBP) (° C) 163 172 187.9 186.9 185.8 Boiling range 90% - 20% (K) 104 76.9 99.8 102.2 89.9 FBP-90% (K) 27 18th 24.2 19.0 21 End of boiling point (FBP) (° C) 332 336 359.6 358.6 320.7 density 0.828 0.831 0.8432 0.8417 0.8193 S content (ppm) 290 35 54.2 478 6 HFRR-WSD (µm) 571 670 617 541 694 Average differential time (ADT) 5.3 4.2 6.1 5.9 4.5

The boiling characteristics were determined in accordance with ASTM D-86 the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.

The solubility behavior of the additives is determined according to the British Rail Test as follows: 400 ppm of a dispersion of the additive combination heated to 22 ° C are metered into 200 ml of the test oil heated to 22 ° C (see Table 3) and shaken vigorously for 30 seconds. After 24 hours of storage at + 3 ° C for 15 seconds and then again shaken mm ml at 3 ° C in three portions of 50 through a 1.6 μ m-glass fiber microfilter (i 25; Whatman GFA, Order No. 1,820,025 ) filtered. The ADT value is calculated as follows from the three filtration times T ₁ , T ₂ and T ₃ : ADT = (T 3rd - T 1 ) T 2 · 50

An ADT value <15 is considered as an indication that the gas oil in normal cold weather can be used satisfactorily. Products with ADT values > 25 are said to be non-filterable.

The lubricating effect of the additives was determined using an HFRR device from PCS Instruments performed. The additives tempered at 22 ° C become the dosed at 22 ° C oil and shaken vigorously for 30 seconds. To 24 hours storage at + 3 ° C, the oil is tested according to the conditions of the British Rail filtered and the lubricating effect on the filtrate determined in the HFRR test. The High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986 and is carried out at 60 ° C. The Results are as a coefficient of friction (Friction) and Wear Scar (WSD) specified. Show a low coefficient of friction and a lower wear scar a good lubricating effect.

Polymers:

Polymer A: Ethylen/Vinylacetat (Vergleich)

Polymer B: Ethylen/Vinylacetat/Neodecansäurevinylester

Polymer C: EthylenNinylacetat/Neodecansäurevinylester

Polymer D: Ethylen/Vinylacetat/Neododecansäurevinylester

Polymer E: Ethylen/Vinylpropionat/Neodecansäurevinylester

Eigenschaften der Fließverbesserer-Polymere Polymer Ethylengehalt mol-% Vinylestergehalt mol-% Neoestergehalt mol-% V₁₄₀ mPas A 85,2 14,8 - 125 B 90 4 6 105 C 84,5 13 2,5 230 D 86 10 4 195 E 85 13 2 170 The polymers are terpolymers of ethylene, a short-chain vinyl ester and the vinyl ester of a neocarboxylic acid ("Neoester") of the following type:

Polymer A: ethylene / vinyl acetate (comparison)

Polymer B: ethylene / vinyl acetate / vinyl neodecanoate

Polymer C: ethylene vinyl acetate / vinyl neodecanoate

Polymer D: Ethylene / vinyl acetate / vinyl neododecanoate

Polymer E: ethylene / vinyl propionate / vinyl neodecanoate

Properties of the flow improver polymers polymer Ethylene content mol% Vinyl ester content mol% Neoester content mol% V ₁₄₀ mPas A 85.2 14.8 - 125 B 90 4th 6 105 C. 84.5 13 2.5 230 D 86 10 4th 195 E 85 13 2 170

For the application tests, the polymers were 50% in kerosene set.

The viscosity was determined using a rotary viscometer (Haake RV 20) with plate-cone measuring system at 140 ° C, in accordance with ISO 3219 (B).

Paraffin dispersants:

For use as a flow improver and / or lubricity additive, the additives according to the invention furthermore in a mixture with paraffin dispersants be used.

The employed Wachsdispergator (F) is a mixture of 2 parts of a terpolymer of C _14/16 -α-olefin, maleic anhydride and 2 equivalents of di-tallow Allylpolyglykol with and a part of nonylphenol-formaldehyde resin.

For the application tests, both components were 50% in Solvent naphtha difficult to adjust.

Amphiphiles

Amphiphil 1:

Glycerinmonooleat

Amphiphil 2:

Polyisobutenylbernsteinsäureanhydrid, mit Diethylenglykol zweifach verestert gemäß Beispiel 1 aus WO-97/45507

Amphiphil 3:

Ölsäurediethanolamid

Amphiphil 4:

C₁₈H₃₅-O-CH₂-CH(OH)-CH₂OH
(C₁₈-Kette ist technischer Schnitt)

Amphiphil 5:

Ölsäure

Amphiphil 6:

Tallölfettsäure

The following oil-soluble amphiphiles were used:

Amphiphile 1:

Glycerol monooleate

Amphiphile 2:

Polyisobutenyl succinic anhydride, twice esterified with diethylene glycol according to Example 1 from WO-97/45507

Amphiphile 3:

Oleic acid diethanolamide

Amphiphile 4:

C ₁₈ H ₃₅ -O-CH ₂ -CH (OH) -CH ₂ OH
(C ₁₈ chain is technical cut)

Amphiphile 5:

Oleic acid

Amphiphile 6:

Tall oil fatty acid

Lubrication effect and cold flow improvement

To carry out the inventive and comparative examples, the cold flow improver polymers mentioned and, if appropriate, in addition the wax dispersant mentioned were mixed with the amphiphiles mentioned.

Claims (11)

Additives to improve the cold flow and lubrication properties of fuel oils, consisting of A) 5-95% by weight of at least one oil-soluble amphiphile of the formula 1

and / or 2 R ¹ - X - R ² wherein R ^{1 is} an alkyl, alkenyl, hydroxyalkyl or aromatic radical having 1 to 50 carbon atoms, X NH, NR ³ , O or S, y = 1, 2, 3 or 4, R ^{2 is} hydrogen or an alkyl radical carrying hydroxyl groups 2 to 10 carbon atoms and R ^{3 is} a nitrogen and / or hydroxyl-bearing alkyl radical having 2 to 10 carbon atoms or C ₁ -C ₂₀ alkyl, B) 5 to 95% by weight of a terpolymer containing 10 to 35 mol% of structural units derived from the vinyl ester of a carboxylic acid having 2 to 4 carbon atoms, 1 to 15 mol% of structural units derived from the vinyl ester of a neocarboxylic acid 8 to 15 carbon atoms, and structural units made of ethylene ad 100 mol% with a melt viscosity of 20 to 10,000 mPas measured at 140 ° C. Additives according to claim 1, characterized in that R ¹ and R ² together contain at least 15 carbon atoms. Additives according to claim 1 and / or 2, characterized in that Component A) an ester of a carboxylic acid with a polyol having 2 to 8 Is carbon atoms. Additives according to one or more of claims 1 to 3, characterized in that R ¹ comprises 5 to 40 carbon atoms. Additives according to one or more of claims 1 to 4, characterized characterized in that component A is a fatty acid alkanolamine or is a fatty acid alkanolamide. Additives according to one or more of claims 1 to 5, characterized characterized in that the terpolymers of component B have a melt viscosity at 50 to 5000 mPas at 140 ° C. Additives according to one or more of claims 1 to 6, characterized characterized in that the terpolymers of component B) Neocarboxylic acid vinyl esters are the vinyl esters of neononane, neodecane or Contain neoundecanoic acid. Additives according to one or more of claims 1, 2, 4, 6 and 7, characterized characterized in that component A is a fatty acid having 12 to 30 carbon atoms is. Fuel oils containing additives according to one or more of the claims 1 to 8. Use of additives according to one or more of claims 1 to 8 to simultaneously improve the lubricating effect and cold flow properties of Fuel oils. Mixtures of additives according to one or more of claims 1 to 8 with paraffin dispersants of the formula

wherein R ^{51 is} C ₄ -C ₅₀ alkyl or alkenyl, [OR ⁵² ] for ethoxy and / or propoxy, n for a number from 5 to 100 and p for a number from 0 to 50 or comb polymers of the formula

wherein

A

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

D

H, 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 '

a hydrocarbon chain with 8-150 carbon atoms;

R "

a hydrocarbon chain of 1 to 10 carbon atoms;

m

a number between 0.4 and 1.0; and

n

represent a number between 0 and 0.6, and wherein the mixing ratio

between additive according to claims 1 to 7 and paraffin dispersant or comb polymer is 1:10 to 20: 1.