EP1116781B1 - Polyfunctional additive for fuel oils - Google Patents

Description

The present invention relates to an additive for fuel oils containing Ethylene-vinyl ester / olefin terpolymers and amphiphilic lubricants Additives, as well as its use for the improvement of cold flow and Lubricating properties of the so-additive oils.

Mineral oils and mineral oil distillates used as fuel oils generally 0.5 wt .-% and more sulfur, the combustion Formation of sulfur dioxide causes. To the resulting Reducing environmental pollution becomes the sulfur content of fuel oils lowered further and further. The introduction of diesel fuel standards EN 590 currently writes in Germany a maximum sulfur content of 500 ppm before. In Scandinavia, fuel oils are already less than 50 ppm and in exceptional cases less than 10 ppm of sulfur. These Fuel oils are usually prepared by taking the from the petroleum hydrogenated by distillation obtained fractions. In the Desulfurization will also remove other substances that cause the Give fuel oils a natural lubricating effect. To these substances include polyaromatic and polar compounds.

It has now been shown that the friction and wear-reducing Properties of fuel oils with increasing degree of desulfurization become worse. Often, these properties are so poor that the fuel lubricated materials, such as e.g. the distributor injection pumps of Diesel engines can be expected after a short time with eating symptoms got to. The further reduction of the 95% distillation point, which has meanwhile been made in Scandinavia below 370 ° C, sometimes below 350 ° C or below 330 ° C further aggravates this problem.

The prior art therefore describes approaches that provide a solution to this problem Problems (so-called lubricity additives).

EP-A-0 764 198 discloses additives which improve the lubricity of fuel oils improve, and the polar nitrogen compounds based on alkylamines or Alkyl ammonium salts containing 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 having 10 to 25 carbon atoms or Dicarboxylic acids) and flow improvers of ethylene / unsaturated ester copolymers to synergistically improve the lubricity of highly desulfurized oils.

EP-A-0 807 676 discloses the use of a mixture of a Carboxylic acid amide and a cold flow improver and / or an ashless Dispersant for improving the cold flow properties of low sulfur Fuel oil.

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

The use of cold flow improvers in fuel oils is required because Crude oils and middle distillates obtained by the distillation of crude oils, such as gas oil, Diesel oil or heating oil depending on the origin of the crude oils different amounts long-chain paraffins (waxes) dissolved. At low temperatures These paraffins are deposited as platelet-shaped crystals, partly under Inclusion of oil. This will increase the flowability of the crude oils and of them distillates significantly affected. There are solid deposits, which often causes disruptions in the extraction, transport and use of mineral oils and Lead petroleum products. Thus, at low ambient temperatures, e.g. in the cold season u.a. in diesel engines and combustion plants too Blockages of filters that prevent safe metering of fuels and eventually result in an interruption of fuel or Heizmittelzufuhr.

Also conveying the mineral oils and petroleum products through pipelines longer distances may e.g. in winter by the precipitation of paraffin crystals be affected.

It is known that unwanted crystal growth by suitable additives prevent and thus counteract an increase in the viscosity of the oils. Such additives, they are called pour point lower or Flow improvers known, 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 at increasingly important in practice, cold blending, i. the Mixing additives in cold oils to filtration problems above the cloud Points of the additized oils lead. It often comes to a Impairment of the lubricating effect by the flow improver and the oils do not show the expected properties of the components. This is e.g. in the Case of the additives according to EP-A-0 743 974 due to the poor solubility of their Flow improver component causes, causing clogging of Fuel filters can come. Presumably, the lubricants of the it does not absorb any of the sparingly soluble constituents of the flow improver show the expected effectiveness.

Object of the present invention was to find additive combinations that in largely from sulfur and aromatic compounds freed middle distillates lead to an improvement of the lubricating effect. At the same time, these additives Also included as a cold flow improver, in the oils mentioned soluble and effective as such, and the effect of the lubricity additive supported, and vice versa.

Surprisingly, it has been found that additives, in addition to lubricity improving amphiphilic terpolymers of ethylene, vinyl esters and contain certain olefins having the required properties.

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

und/oder 2 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 einen Stickstoff und/oder Hydroxylgruppen tragenden Alkylrest mit 2 bis 10 Kohlenstoffatomen oder einen C₁-C₂₀-Alkylrest bedeutet, und R¹ und R² zusammen mindestens 15 kohlenstoffatome umfassen,

B) 5 bis 95 Gew.-% eines Terpolymers aus Ethylen, dem Vinylester einer oder mehrerer aliphatischer, linearer oder verzweigter Monocarbonsäuren, die 2 bis 20 Kohlenstoffatome im Molekül enthalten, und einem C₅-C₇-Olefin mit einem Anteil von 9 bis 18 mol-% Vinylester und 0,5 bis 5 mol-% Olefin (jeweils bezogen auf das Terpolymer) mit einer bei 140°C gemessenen Schmelzviskosität von 20 bis 10.000 mPas.

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

A) 5 to 95% by weight of at least one oil-soluble amphiphile of the formulas 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 is NH, NR ³ , O or S, y = 1, 2, 3 or 4, R ^{2 is} hydrogen or a hydroxyl-bearing alkyl radical 2 to 10 carbon atoms and R ^{3 is} a nitrogen and / or hydroxyl-carrying alkyl radical having 2 to 10 carbon atoms or a C ₁ -C ₂₀ -alkyl radical, and R ¹ and R ² together comprise at least 15 carbon atoms,

B) 5 to 95 wt .-% of a terpolymer of ethylene, the vinyl ester of one or more aliphatic, linear or branched monocarboxylic acids containing 2 to 20 carbon atoms in the molecule, and a C ₅ -C ₇ olefin in a proportion of 9 to 18 mol% of vinyl ester and 0.5 to 5 mol% of olefin (in each case based on the terpolymer) with a measured at 140 ° C melt viscosity of 20 to 10,000 mPas.

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

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

Preferred proportions of A) and B) are between 10 and 90 wt .-%, 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 may be interrupted by nitrogen and / or oxygen atoms. In another preferred embodiment, component A carries from 2 to 5 hydroxyl groups, each carbon atom carrying no more than one hydroxyl group.

In a preferred embodiment of the invention, X in formula 1 has the Meaning oxygen. These are in particular fatty acids and esters between carboxylic acids and di- 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 Polyols with the carboxylic acid is therefore not complete. Suitable polyols are for example, ethylene glycol, propylene glycol, diethylene glycol and higher Alkoxylation products, glycerol, trimethylolpropane, pentaerythritol, diglycerol and higher condensation products of glycerol and sugar derivatives. Also more Heteroatom-containing polyols such as triethanolamine are suitable.

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

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.

The multifunctional additive may in one embodiment contain compounds of the formula 3 as component A.

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 formula 3b - (R ⁴³ -NR ⁴⁴ ) _n -R ⁴⁵ R ^{43 is} a C ₂ - to C ₁₀ -alkylene group, R ^{44 is} hydrogen, methyl, C ₂ - to C ₂₀ -alkyl, a radical of the formula 3c

or an alkoxy radical, and R ^{45 is} H or a radical of the formula 3c, and m and n are each independently 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 radical. The polyamine from which the structural unit formed from R ⁴¹ , R ⁴² and the nitrogen atom connecting them is derived is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or a higher homologue of the aziridine such as polyethyleneimine, and mixtures thereof. Parts of the amino group may be alkylated. Also suitable are star amines and dendrimers. This refers to polyamines having generally 2-10 nitrogen atoms which are connected to each other via -CH ₂ -CH ₂ groups and which are saturated in marginal position with acyl or alkyl radicals.

R ⁴⁴ is preferably 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.Also suitable as amphiphile are compounds of the formula 3d

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

may have the meaning of R ² and

p

an integer from 1 to 10,

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

The amides are generally obtained by condensation of the polyamines with the Carboxylic acids or their derivatives such as esters or anhydrides produced. It are preferably 0.2 to 1.5 mol, in particular 0.3 to 1.2 mol, especially 1 mol Used acid per base equivalent. The condensation is preferably carried out at Temperatures between 20 and 300 ° C, in particular between 50 and 200 ° C below Distilling off the water of reaction. For this purpose, solvents, preferably aromatic solvents such as benzene, toluene, xylene, trimethylbenzene and / or commercial solvent mixtures such. 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 assumes the values 1 or 2. Examples of preferred compound groups with y = 2 are derivatives of dimer fatty acids and alkenyl succinic 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 carry 2, 3, 4 or 5 hydroxyl groups, but not more than they contain carbon atoms. The Carbon chain of the polyols can be straight-chain, branched, saturated or unsaturated and optionally contain heteroatoms. Preferably, it is saturated.

Preferred carboxylic acids, of which the compounds of formula 1 are derived let or represent the compounds of formula 1 have 5 to 40, in particular 12 to 30 carbon atoms. Preferably, the carboxylic acid has a or two carboxyl groups. The carbon chain of the carboxylic acids can straight chain, branched, saturated or unsaturated. Preferably contain more as 50% of the carboxylic acids used (mixtures) at least one Double bond. Examples of preferred carboxylic acids include caprylic acid, Capric, lauric, myristic, palmitic, stearic, oleic, 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 as Alkenylsuccinic acids are used.

As component A, ethers and amines of the formula 2 are used in a preferred embodiment. These are partial ethers of polyols, for example glycerol monooctadecyl ethers or hydroxyl-bearing amines, as 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. Preference is given to 1-10, in particular 1-5 mol of alkylene oxide per H atom of the nitrogen used.

The vinyl esters contained in the terpolymer of component B) are preferably of monocarboxylic acids having 2 to 16, especially 2 to 12 carbon atoms derived. One or even more vinyl esters may be present at the same time. In a further preferred embodiment, the vinyl esters are vinyl acetate, Vinyl propionate, vinyl 2-ethylhexanoate, vinyl neodecanoate, Vinyl neononanoate, vinyl neoundecanoate, vinyl pivalate or vinyl laurate, in particular vinyl acetate and / or vinyl propionate.

The olefin contained in the terpolymer comprises 5, 6 or 7 carbon atoms. It are, for example, penten-1, hexene-1 or heptene-1. Especially preferred embodiments of the invention are 4-methylpentene-1 or norbomene.

Preferably, the terpolymers contain from 10 to 16 mole percent vinyl ester and from 1 to 3 mole percent olefin. Their degree of branching determined by NMR spectroscopy is between 3 and 15, in particular between 3.5 and 10 CH ₃ / 100CH ₂ groups, which are not derived from the vinyl ester.

For use in the additive according to the invention are particularly suitable Terpolymers according to the invention having an ISO 3219 (B) at 140 ° C. measured melt viscosity of 50 to 5000 mPas, preferably 30 to 1,000 mPas and in particular 50 to 500 mPas.

For the preparation of the terpolymers of ethylene, the vinyl ester of an aliphatic linear or branched monocarboxylic acid containing 2 to 20 carbon atoms in the Molecule contains, and olefins one starts from mixtures of the monomers. The copolymerization of the starting materials by known methods (see. for example, e.g. Ullmanns Encyclopadie der Technischen Chemie, 5th edition, Vol. A21, Pages 305 to 413). The polymerization is suitable in solution, in suspension, in the gas phase and the high-pressure mass polymerization. Preferably one turns the high-pressure mass polymerization, which 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 performed. The reaction of the monomers is by radicals forming initiators (radical chain starter) initiated. To this substance class include e.g. Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxydicarbonate, t-butyl perpivalate, t-butyl per-maleate, t-butyl perbenzoate, Dicumyl peroxide, t-butyl cumyl peroxide, di (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are individually or as a mixture of two or more substances in amounts of 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 given Composition of the monomer mixture by variation of the Reaction parameters pressure and temperature and optionally by adding Moderators set. As moderators have become hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven. In Depending on the desired viscosity, the moderators in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture applied.

To be suitable for use in the additives of the invention To obtain terpolymers, one uses monomer mixtures which except ethylene and optionally a moderator 5 to 40 wt .-%, preferably 10 to 40 wt .-% Vinyl ester and 1 to 40 wt .-% olefin. With the of the composition of the terpolymer deviating composition of the monomer mixture one bears the different polymerization rate of the monomers Bill. The polymers are obtained as colorless melts, which at Solidify room temperature to waxy solids.

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 already by themselves the cold flow properties and / or lubricating action of crude oils, lubricating oils or fuel oils improve. Examples of such co-additives are paraffin dispersants, alkylphenol-aldehyde resins and comb polymers.

Paraffin dispersants reduce the size of the paraffin crystals and cause The paraffin particles do not settle, but colloidly with significantly reduced Sedimentation tendency, remain dispersed. As paraffin dispersants have become oil-soluble polar compounds having ionic or polar groups, e.g. amine salts and / or amides obtained by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic Mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols which can be reacted Reaction products of alkenylspirobislactones with amines and Reaction products of terpolymers based on α, β-unsaturated Dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols. Also alkylphenol-formaldehyde resins are as 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: Dihexadecyl-dimethylammoniumchlorid, 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-Methyltriethanolammoniumdioleylester-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-Alkyl-propylendiamin), 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 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 = 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-ol 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 Carbonsäureestem 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 Propylen

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 Polyethem mit Phosgen bzw. Thionylchlorid und anschließende Aminierung zum Polyetheramine 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, Vinylethem 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.

The following paraffin dispersants are prepared in part 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 may be} identical or different, and at least one of these groups is 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 Is 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 are each independently H, C ₁ -C ₃₀ - Alkyl or - (AO) _x . By acyl group is meant here 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 obtained in the reaction of compounds of formula (4) with the amines amides or amide ammonium salts.

2. Amides or ammonium salts of aminoalkylenepolycarboxylic 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 denote in particular alkyl radicals having 10 to 30, preferably 14 to 24, C atoms, the amide structures also being partly or completely in the form of the ammonium salt structure of the formula 8

may be present. The amides or amide ammonium salts or ammonium salts of, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid are obtained by reacting the acids with from 0.5 to 1.5 mol of amine, preferably from 0.8 to 1.2 mol Amine per carboxyl group. The reaction temperatures are about 80 to 200 ° C, wherein for the preparation of the amides a continuous removal of the resulting water of reaction takes place. However, the reaction does not have to be completely led to the amide, but may be 0 to 100 mol% of the amine used in the form of the ammonium salt. Under analogous conditions, the compounds mentioned under B1) can also be prepared. As amines of the formula 9

Particularly suitable dialkylamines are contemplated in which R ⁶ , R ^{7 is} a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms. Specifically, dioleylamine, dipalmitinamine, dicoco fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned.

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 abovementioned meaning and R ^{11 is} 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 wherein 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 is halogen, preferably chlorine, or a methosulfate. Examples of such quaternary ammonium salts include: 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-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleyl ester chloride, N-methyltriethanolammonium trilauryl ester methosulfate, N-methyltriethanolammonium tristearyl ester methosulfate, and mixtures thereof.

4. Compounds of the formula 11

in which R ^{14 is} CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ , R ¹⁵ and R ^{16 is} 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), trimellit, pyromellitic (dianhydride), isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride). The formula (anhydride) means that the anhydrides of said acids are also preferred acid derivatives. When the compounds of formula (11) are amides or amine salts, they are preferably of a secondary amine containing a hydrogen and carbon containing group of at least 10 carbon atoms It is preferred that R ^{17 contains} 10 to 30, especially 10 to 22, eg 14 to 20, carbon atoms and is preferably straight-chained or branched at the 1- or 2-position. The other hydrogen and carbon containing groups may be shorter, eg containing less than 6 carbon atoms, or may have at least 10 carbon atoms if desired. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl). Further suitable are polymers containing at least one amide or ammonium group bonded directly 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 prepared in various ways. One way is to use a polymer containing several carboxylic acid or anhydride groups and react this polymer with an amine of the formula NHR ⁶ R ⁷ to obtain the desired polymer. Polymers of these are generally copolymers of unsaturated esters such as C ₁ C ₄₀ alkyl (meth) acrylates, dialkyl fumarates, 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 carboxylic acids such as carboxylic acid anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride). Carboxylic acids are preferably used at 0.1 to 1.5 moles, more preferably 0.5 to 1.2 moles of amine per acid group, carboxylic acid anhydrides preferably reacted with 0.1 to 2.5, in particular 0.5 to 2.2 moles of amine per acid anhydride, wherein depending on the reaction conditions amides, ammonium salts, amide ammonium salts or imides e ntstehen. Thus, copolymers containing unsaturated carboxylic acid anhydrides, upon reaction with a secondary amine, yield half amide and half amine salts by reaction with the anhydride group. By heating, water can be split off to form the diamide. Particularly suitable examples of amide group-containing polymers for use according to the invention are:

5. Copolymers of (a) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) vinyl esters, for example vinyl acetate or vinyl stearate with maleic anhydride, or (c) 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 an alcohol when forming an ester amide). When polymers containing an anhydride group are reacted, the resulting amino groups will be ammonium salts and amides. Such polymers may 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 having at least 10 carbon atoms. This long-chain group, which may be a straight-chain or branched alkyl group, may be bonded via the nitrogen atom of the amide group. The suitable amines may be replaced by the formula R ⁶ R ⁷ NH and the polyamines by R ⁶ NH [R ¹⁹ NH] _x R ⁷ wherein R ^{19 is} a divalent hydrocarbon group, preferably an alkylene or hydrocarbyl-substituted alkylene group, and x is an integer, preferably between 1 and 30. Preferably one or both of 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 containing alkyl groups of 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 wt% nC ₁₄ alkyl, 30 wt% nC ₁₀ - Alkyl, 60% by weight of nC ₁₈ alkyl, the remainder is unsaturated). Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-coco propylenediamine (C ₁₂ / C ₁₄ alkyl propylenediamine), N-tallow propylenediamine (C ₁₆ / C ₁₈ alkyl propylenediamine). The amide-containing polymers typically have a number average molecular weight of from 1,000 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 detail, 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 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 which may be mentioned: 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 particularly preferred, and styrene is particularly preferred. Examples of polymers include polymaleic acid, a molar styrene / maleic acid copolymer of alternating design, random 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 is carried out at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is thereby applied in amounts of about one mole per mole of polymerized dicarboxylic anhydride, ie about 0.9 to 1.1 mol / mol. The use of larger or smaller amounts is possible, but brings no advantage. If larger amounts than one mole are used, ammonium salts are sometimes obtained because the formation of a second amide group requires higher temperatures, longer residence times, and water recirculation. If less than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained. Instead of the subsequent conversion of the carboxyl groups in the form of the dicarboxylic acid anhydride with amines to the corresponding amides, it may sometimes be advantageous to use the monoamides of the monomers and then polymerize directly in the polymerization. In most cases, however, this is technically much more complicated because the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then no copolymerization is 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 from 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, wherein the copolymer is largely with a or more primary or secondary amines to the monoamide or amide / ammonium salt of the dicarboxylic acid is reacted. 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 from 10 to 40 mol% of the olefinically unsaturated dicarboxylic acid derivatives. The alkyl groups of the alkyl (meth) acrylates contain 1 to 26, preferably 4 to 22 and more preferably 8 to 18 carbon atoms. They are preferably straight-chain and unbranched. However, it may also contain up to 20 wt .-% cyclic and / or branched portions. 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. Maleinsäureanhydrid.Als amines is preferable are compounds of the formula HNR ⁶ R ⁷ in Betracht.In a rule, it is advantageous, if available, to use the dicarboxylic acids in the form of the anhydrides in the copolymerization, for example, maleic anhydride, itaconic anhydride, citraconic anhydride and tetrahydrophthalic anhydride as the anhydrides usually 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 employed in amounts of about one to two moles per mole of copolymerized dicarboxylic acid anhydride, ie, about 0.9 to 2.1 moles / mole. The use of larger or smaller amounts is possible, but brings no advantage. If amounts greater than two moles are used, free amine is present. When less than one mole is used, complete conversion to the monoamide does not occur and a correspondingly reduced effect is obtained. In some cases, it may be advantageous to synthesize the amide / ammonium salt structure from two different amines. For example, a copolymer of lauryl acrylate and maleic anhydride may first be reacted with a secondary amine such as hydrogenated di-tallow fatty amine to form the amide, after which the free carboxyl group derived from the anhydride is neutralized with another amine, eg 2-ethylhexylamine, to the ammonium salt. Likewise, the reverse procedure is conceivable: first with ethylhexylamine to the monoamide, then reacted with Ditalgfettamin to the ammonium salt. Preferably, at least one amine is used which has at least one straight-chain, unbranched alkyl group having more than 16 carbon atoms. It is not significant whether this amine is present in the structure of the amide structure or as the ammonium salt of the dicarboxylic acid. Instead of the subsequent reaction of the carboxyl groups or of the dicarboxylic acid anhydride with amines to the corresponding amides or amide / ammonium salts, it may sometimes be advantageous to use the monoamides or produce amide / ammonium salts of the monomers and then polymerize directly in the polymerization. However, this is usually technically much more complicated because the amines can attach to the double bond of the monomeric dicarboxylic acid and then no copolymerization is 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 20-80, preferably 40- 60 mol% of bivalent structural units of the formulas 12 and / or 14, and optionally contain 13, wherein the structural units 13 come from unreacted Anhydridresten,

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 for the groups -NHR ⁶ , N (R ⁶ ) ₂ and / or -OR ²⁷ , and R ^{27 is} 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 - 30 mol%, preferably 1 - 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 is} 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 , wherein
R ^{34 is} C ₁ -C ₄₀ -alkyl, C ₅ -C ₁₀ -cycloalkyl or C ₆ -C ₁₈ -aryl,
contain.

The abovementioned alkyl, cycloalkyl and aryl radicals may 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 stands for a straight-chain or branched hydrocarbon radical. Specific examples which may be mentioned are: 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 cocoalkyl , Tallow fatty alkyl and behenyl. Cycloalkyl here stands for a cyclic aliphatic radical having 5 to 20 carbon atoms. Preferred cycloalkyl radicals are cyclopentyl and cyclohexyl. Aryl here stands for an optionally substituted aromatic ring system having 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 optionally 13. They only contain in themselves In known manner, the structural units of the formulas 12 to 14 of α, β-unsaturated dicarboxylic acid anhydrides of the formulas 17 and 18 are derived in the polymerization by initiation, inhibition and chain termination

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

Examples which may be mentioned are the following α, β-unsaturated olefins: 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. Preference is given to α-olefins having 10 to 24 C atoms and styrene, particular preference being given to α-olefins having 12 to 20 C atoms. The structural units of the formula 16 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of the formula

The monomers of formula 20 are etherification products (R ³² = R ³⁴ ) or esterification products (R ³² = -C (O) R ³⁴ ) of polyoxyalkylene ethers (R ³² = H). Allow the polyoxyalkylene ethers (R ³² = H) by known processes by addition of 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-ol or methylbutenols, such as 2-methyl-3-buten-1-ol, 2-methyl-3 -but-2-ol and 3-methyl-3-buten-1-ol. Addition products of ethylene oxide and / or propylene oxide onto allyl alcohol are preferred. A subsequent etherification of these polyoxyalkylene ethers to give compounds of the formula 20 where R ³² = C ₁ -C ₂₄ -alkyl, cycloalkyl or aryl is carried out by processes known per se. Suitable methods are known, for example, from J. March, Advanced Organic Chemistry, 2nd edition, p. 357f (1977). These etherification products of the polyoxyalkylene ethers can also be prepared by reacting α-olefin oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide, with 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 attached and with polymerizable lower unsaturated halides of the formula 23rd

where W is a halogen atom. The halides used are preferably the chlorides and bromides. Suitable production methods are mentioned, for example, in J. March, Advanced Organic Chemistry, 2nd Edition, p. 377f (1977). The esterification of the polyoxyalkylene ethers (R ³² = -C (O) -R ³⁴ ) takes place by reaction with customary esterification agents, such as carboxylic acids, carboxylic acid halides, carboxylic 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 -arylcarboxylic acids are preferably used. The esterification is generally carried out at temperatures of 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 Examples of suitable primary amines for preparing the terpolymers are n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine and also N, N-dimethylaminopropylenediamine, cyclohexylamine, Dehydroabietylamine and mixtures thereof. Examples of secondary amines which are suitable for the preparation of the terpolymers include: didecylamine, ditetradecylamine, distearylamine, dicoco fatty amine, ditallow fatty amine and mixtures thereof. The terpolymers have K values (measured according to Ubbelohde in 5% by weight solution in toluene at 25 ° C) from 8 to 100, preferably 8 to 50, corresponding to average molecular weights (M _w ) between about 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

equal to zero or 1 and a + b equal to 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

x =

1 to 50

E =

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

mean, and
80 to 20 mol%, preferably 60 to 40 mol% of bivalent structural units of the formula 15. In detail, the structural units of formulas 25, 26 and 27 are derived from α, β-unsaturated dicarboxylic acid anhydrides of formulas 17 and / or 18. The structural units of formula 15 are derived from the α, β-unsaturated olefins of 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 or 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, where appropriate, of 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.

For the derivatization of the structural units of the formulas 17 and 18, preference was given to using 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) the polyetheramines used is possible, for example, by reductive amination of polyglycols. Furthermore, it is possible to prepare polyetheramines having a primary amino group by addition of polyglycols to acrylonitrile and subsequent catalytic hydrogenation. In addition, polyetheramines are accessible by reaction of polyethers with phosgene or thionyl chloride and subsequent amination to the polyetheramine. The polyetheramines used according to the invention are commercially available (for example) 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. Another possibility for derivatizing the structural units of the formulas 17 and 18 is that, instead of the polyetheramines, an alkanolamine of the formula is used and subsequently subjected to an alkoxylation. From 0.01 to 2 mol, preferably from 0.01 to 1 mol of alkanolamine are used per mole of anhydride. The reaction temperature is between 50 and 100 ° C (amide formation). In the case of primary amines, the reaction is carried out at temperatures above 100 ° C (imide) .The alkoxylation is usually carried out at temperatures between 70 and 170 ° C with catalysis of bases, such as NaOH or NaOCH ₃ , by gassing of 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. Examples of primary amines which may be mentioned are: n-hexylamine, n-octylamine , n-tetradecylamine, n-hexadecylamine, n-stearylamine or else N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof. Examples of secondary amines which may be mentioned are: didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, di-tallow fatty amine and mixtures thereof for example: 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. Co- and terpolymers of NC ₆ -C ₂₄ -alkylmaleinimid with C ₁ -C ₃₀ vinyl esters, vinyl ethers and / or olefins having 1 to 30 carbon atoms, such as styrene or α-olefins. These are accessible on the one hand by reacting an anhydride-containing polymer with amines of the formula H ₂ NR ⁶ or by imidization 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 -alkylmaleimide are preferred.

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.In order to optimize the properties as flow improver and / or lubricant additive, the additives according to the invention can furthermore be used in a mixture with alkylphenol-formaldehyde resins. In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those of the formula

wherein 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.

Finally, in a further variant of the invention, the inventive Additives used together with comb polymers. By this one understands Polymers in which hydrocarbon radicals having at least 8, in particular at least 10 carbon atoms are attached to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. at Copolymers have at least 20%, preferably at least 30% of the monomers Side chains (see Comb-like Polymers-Structure and Properties; N. A. Platé and V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).

Examples of suitable comb polymers are 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 -alkylmaleimide (cf., EP-A- 0 320 766), further esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

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.

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 of 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 with paraffin dispersants or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
The additives according to the invention are suitable for improving the cold flow and lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of alcoholic fuels and mineral oils. They are particularly well suited for use in middle distillates. As middle distillates are in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil. The additives according to the invention are preferably used in middle distillates which contain not more than 500 ppm, in particular less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur. These are generally those middle distillates that have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds that give them a natural lubricating effect. The additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree. The effectiveness of the mixtures is better than would be expected from the individual components and compared to the mixtures according to the prior art. In particular, the additive combinations according to the invention are distinguished under cold blending conditions when the temperature of the oil during the additization is low, ie below 40 ° C., in particular below 20 ° C. and especially below 10 ° C.

The additive components of the invention may be mineral oils or Mineral oil distillates are added separately or in mixture. When using Mixtures have solutions or dispersions 10 to 90 wt .-%, preferably from 20 to 80 wt .-%, the additive combination contained proven. suitable Solvent or dispersant are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g. Petroleum 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 grades. Due to the additives in their lubricating and / or cold-flow properties improved mineral oils or Mineral oil distillates contain from 0.001 to 2, preferably 0.005 to 0.5 wt .-% additive, based on the distillate.

The additives may be used alone or together with other additives, for example, with other pour point depressants, dewaxing aids, corrosion inhibitors, antioxidants, conductivity improvers, sludge inhibitors, dehazems, and cloud point depressant additives. The addition of these additives to the oil can be carried out together with the additive components according to the invention or separately.
The effectiveness of the additives according to the invention as lubricity enhancers and cold flow improvers is 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) - 2 - 14 - 6 - 6 - 27 Pour point (PP) (° C) - 3 - 12 - 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 18 24.2 19.0 21 Siedeende (FBP) (° C) 332 336 359.6 358.6 320.7 density 0.828 0.831 0.843 0.842 0.819 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 according to ASTM D-86, the determination 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 temperature controlled to 22 ° C dispersion of the additive combination are metered to 200 ml of tempered to 22 ° C test oil (see Table 3) and shaken vigorously for 30 seconds. After 24 hours of storage at + 3 ° C., shake again for 15 seconds and then at 3 ° C. in three portions of 50 ml each over a 1.6 μm glass fiber microfilter (25 mm in diameter, Whatman GFA, Order No. 1820025). filtered. From the three filtration times T ₁ , T ₂ , and T ₃ , the ADT value is calculated as follows: ADT = (T 3 - T 1 ) T 2 · 50

An ADT value <15 is taken as an indication that the gas oil is normal cold weather is satisfactorily usable. Products with ADT values> 25 are referred to as non-filterable.

The lubricity of the additives was measured using an HFRR device from PCS Instruments performed. The tempered at 22 ° C additives are added to the dosed at 22 ° C tempered oil and shaken vigorously for 30 seconds. To 24 hours storage at + 3 ° C will be the oil according to the conditions of the British Rail test filtered and the filtrate on the lubricating effect determined in the HFRR test. Of the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 2, p. 217, 1986 and is carried out at 60 ° C. The Results are known as friction coefficient (friction) and wear scar (WSD) specified. A low coefficient of friction and a low Wear Scar show a good lubricating effect.

polymers:

Polymer B:

Ethylen/Vinylacetat/4-Methylpenten-1

Polymer C:

Ethylen/Vinyl-n-Heptanoat/n-Hexen

Polymer D:

Ethylen/Vinylacetat/n-Hexen

Polymer E:

Ethylen/Vinylacetat/Norbornen

Eigenschaften der Fließverbesserer - Polymere Ethylengehalt mol-% Vinylestergehalt mol-% Olefingehalt mol-% V₁₄₀ (mPas) Polymer A 85,2 14,8 - 125 Polymer B 84,2 14,4 1,4 115 Polymer C 88,1 8,8 3,1 165 Polymer D 78,4 12,7 8,9 195 Polymer E 81,8 12,2 6 100 The flow improvers used were an EVA copolymer (comparison) and the following vinyl ester-olefin terpolymers (according to the invention). Table 2 indicates their properties.

Polymer B:

Ethylene / vinyl acetate / 4-methylpentene-1

Polymer C:

Ethylene / vinyl n-heptanoate / n-hexene

Polymer D:

Ethylene / vinyl acetate / n-hexene

Polymer E:

Ethylene / vinyl acetate / norbornene

Properties of flow improvers - polymers Ethylene content mol% Vinyl ester content mol% Olefin content mol% V ₁₄₀ (mPas) Polymer A 85.2 14.8 - 125 Polymer B 84.2 14.4 1.4 115 Polymer C 88.1 8.8 3.1 165 Polymer D 78.4 12.7 8.9 195 Polymer E 81.8 12.2 6 100

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

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

paraffin:

For use as flow improvers and / or lubricity additives, the additives according to the invention also used in admixture with paraffin dispersants become.

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

For the performance tests both components were 50% in Solvent naphtha set.

amphiphilic

Amphiphil 1:

Glycerinmonooleat

Amphiphil 2:

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

Amphiphil 3:

Ölsäurediethanolamid

Amphiphil4:

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, doubly esterified with diethylene glycol according to Example 1 of WO-97/45507

Amphiphile 3:

oleic acid diethanolamide

Amphiphil4:

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

Amphiphile 5:

oleic acid

Amphiphile 6:

tall oil fatty acid

Lubricating effect and cold flow improvement

To carry out the novel and comparative examples, the cold flow improver polymers mentioned and, if appropriate, additionally the said wax dispersant, are mixed with the abovementioned amphiphiles.

Claims (10)

1. An additive for improving cold-flow and lubricating properties of fuel oils, comprising

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

   

   or R¹ ― X ― R² in which R¹ is an alkyl, alkenyl, hydroxyalkyl or aromatic radical having 1 to 50 carbon atoms, X is NH, NR³, O or S, y is 1, 2, 3 or 4, R² is hydrogen or an alkyl radical carrying hydroxyl groups and having 2 to 10 carbon atoms and R³ is an alkyl radical carrying nitrogen and/or hydroxyl groups and having 2 to 10 carbon atoms or a C₁-C₂₀-alkyl radical, and R¹ and R² together comprise at least 15 carbon atoms, and

   B) 5 to 95% by weight of a terpolymer of ethylene, the vinyl ester of one or more aliphatic, linear or branched monocarboxylic acids which contain 2 to 20 carbon atoms in the molecule and a C₅-C₇-olefin, comprising from 9 to 18 mol% of vinyl ester and from 0.5 to 5 mol% of olefin (based in each case on the terpolymer) and having a melt viscosity, measured at 140°C, of from 20 to 10,000 mPas.
2. The additive as claimed in claim 1, wherein component A) is an ester of a carboxylic acid with a polyol having 2 to 8 carbon atoms.
3. The additive as claimed in claim 1 and/or 2, wherein R¹ comprises 5 to 40 carbon atoms.
4. The additive as claimed in one or more of claims 1 to 3, wherein component A is a fatty acid alkanolamine or fatty acid alkanolamide.
5. The additive as claimed in one or more of claims 1 to 4, wherein the terpolymers of component B have a melt viscosity at 140°C of from 50 to 5000 mPas.
6. The additive as claimed in one or more of claims 1 to 5, wherein the olefin contained in the terpolymer of component B) is 4-methyl-1-pentene or norbomene.
7. The additive as claimed in one or more of claims 1, 3, 5 and 6, wherein component A is a fatty acid having 5 to 30 carbon atoms.
8. A fuel oil containing an additive as claimed in one or more of claims 1 to 7.
9. The use of an additive as claimed in one or more of claims 1 to 7 for the simultaneous improvement of the lubricating activity and cold flow properties of fuel oils.
10. A mixture of additives as claimed in one or more of claims 1 to 7 with alkylphenol/formaldehyde resins or comb polymers of the formula

    

    in which

    A

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

    D

    is H, CH₃, A or R";

    E

    is H or A;

    G

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

    M

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

    N

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

    R'

    is a hydrocarbon chain having 8 to 150 carbon atoms;

    R"

    is a hydrocarbon chain having 1 to 10 carbon atoms;

    m

    is a number from 0.4 to 1.0; and

    n

    is a number from 0 to 0.6, the mixing ratio of additive as claimed in any of claims 1 to 7 to paraffin dispersant or comb polymer being from 1:10 to 20:1.