DE10000650C2 - Multi-functional additive for fuel oils - Google Patents

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 additized in this way.

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. 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 making them from petroleum Fractions obtained by distillation hydrogenated refined. In the Desulphurization also removes other substances that Fuel oils are natural. Give lubrication. 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. B. the distributor injection pumps from Diesel engines can be expected to eat after a short time got to. The further reduction of the 95%  Distillation point below 370 ° C, sometimes below 350 ° C or below 330 ° C 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 from ethylene / unsaturated ester Copolymers for the synergistic improvement of the lubricating effect of highly desulfurized oils.

EP-A-0 807 676 discloses the use of a mixture of one 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.

WO-97/45507 discloses esterified alkenylsuccinic acid derivatives which are described in Fuel oils improve their lubricity.

US 4,491,455 discloses cold flow improvers for fuel oils, the esters of Nitrogen-containing compounds with several hydroxyl groups with linear contain saturated fatty acids, as well as their mixtures with olefin polymers.  

US 5 891 203 discloses mixtures of diethanolamine derivatives and biodiesel as Lubricity improver for low sulfur diesel oil.

JP-A-10-130 666 discloses mixtures of branched fatty acid esters Nitrogen compounds as lubricity improvers in low sulfur Diesel oil.

DE-40 42 206 discloses terpolymers of ethylene, vinyl acetate and Neoalkanoic acid vinyl esters as cold flow improvers for fuel oils.

JP-A-10-237 468 also discloses terpolymers of ethylene, vinyl acetate and Neoalkanoic acid vinyl esters as cold flow improvers for fuel oils.

EP-A-0 807 642 discloses terpolymers made from ethylene, vinyl acetate and 4- Methylpentene-1 as a cold flow improver for 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 affected. 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, z. B. in the cold season u. a. for diesel engines and combustion plants Clogging of the filters, which prevent safe metering of the fuels and finally result in an interruption of the fuel or heating medium supply. Also conveying mineral oils and mineral oil products through pipelines larger distances can e.g. B. in winter by the precipitation of wax 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 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 prior art synergistic additive combinations, in particular cold blending, which is becoming increasingly important in practice, d. H. the Mixing additives in cold oils to filtration problems above the cloud Lead points of the additive oils. This often results in one Impairment of the lubrication effect by the flow improver and the oils do not show the properties expected from the components. This is e.g. B. in 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 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 has been found that additives which are in addition to lubricating amphiphile terpolymers made of ethylene, vinyl esters and contain certain olefins that have the required properties.  

The invention relates to additives for improving cold flow and Lubricating properties of fuel oils as defined in claim 1.

Another object of the invention are fuel oils that 0.001 to 2 wt .-% of the additives mentioned.

Another object of the invention is the use of the additives in amounts from 0.001 to 2 wt .-% to improve the lubrication and Cold flow properties of fuel oils.

The oil-soluble amphiphile (component A) comprises a radical R ¹ having 8 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, diethylene glycol and higher alkoxylation products, Glycerin, trimethylolpropane, pentaerythritol and sugar derivatives. Others too Polyols containing heteroatoms, such as triethanolamine, are suitable.  

If X is a residue containing nitrogen, 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 Wear groups. Examples include fatty acid monoethanolamides and diethanolamides and called -N-methylethanolamide.

In one embodiment, the multifunctional additive can 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 (3a)

and R ^{42 is} a radical of the formula 3b

- (R ⁴³ -NR ⁴⁴ ) _n -R ⁴⁵ (3b)

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.

Compounds of the formula 3d are also suitable as an amphiphile

wherein
R ^{46 has} the meaning of R ¹ ,
R ⁴⁷ meaning of R ¹ 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, γ-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 while 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 radical R ^{1 is} derived, have 12 to 30 carbon atoms. The carboxylic acid preferably has one or two carboxyl groups. The carbon chain of the carboxylic acids can be straight-chain, branched, saturated or unsaturated. Preferably more than 50% of the carboxylic acids (mixtures) used contain 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 z. B. accessible by oligomerization of unsaturated fatty acids, and alkenyl succinic acids are used.

In a preferred embodiment, ether and amines of the formula 2 are used as component A. These are partial esters of polyols such as. B. glycerol monooctadecyl ether or hydroxyl-bearing amines, such as z. B. 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 Propionate.

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 the neocarboxylic acid vinyl esters are preferably 1 to 8 mol%. The total comonomer content is between 8 and 19, in particular between 9 and 16 mol%.  

Are particularly suitable for use in the additive according to the invention Terpolymers according to the invention with an ISO 3219 (B) at 140 ° C. measured melt viscosity of 50 to 5000 mPa.s, preferably 30 to 1,000 mPa.s and in particular 50 to 500 mPa.s.

For the production of terpolymers from ethylene, the vinyl ester of an aliphatic linear or branched monocarboxylic acid containing 2 to 40 carbon atoms in the Contains molecule, and neocarboxylic acid vinyl esters are believed to be mixtures of Monomers.

The starting materials are copolymerized by known processes (cf. for this z. B. 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 include z. As 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 given Composition of the monomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired. Hydrogen, saturated or unsaturated hydrocarbons, e.g. B. propane, aldehydes, e.g. B. propionaldehyde,  n-butyraldehyde or isobutyraldehyde, ketones, e.g. B. acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. B. 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, monomer mixtures are used which, apart from ethylene and optionally a moderator 5 to 40 wt .-%, preferably 10 to 40 wt .-% short chain vinyl ester and 1 to 40 wt .-% neocarboxylic acid vinyl ester contain.

With that deviating 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 solidify.

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 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. B. 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 be preserved. Other paraffin dispersants are copolymers of  Maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols are implemented can, the reaction products of alkenylspirobislactones 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.

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 remaining 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 z. B. the Nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2- diamine tetraacetic acid by reacting the acids with 0.5 to 1.5 mol Amine, preferably 0.8 to 1.2 moles of amine per carboxyl group. The Reaction temperatures are about 80 to 200 ° C, being used for manufacturing the amides a continuous removal of the water of reaction formed he follows. However, the reaction does not have to be carried out completely to the amide, Rather, 0 to 100 mol% of the amine used in the form of Ammonium salt are present. Under analog conditions, the compounds mentioned under B1) are produced.

As amines of 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 ^⊖ (10)

wherein 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 is halogen, preferably chlorine, or a methosulfate.

Examples of such quaternary ammonium salts are: dihexadecyl dimethylammonium 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-dimethyl diethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleylester chloride, N-methyltriethanolammoniumtrilaurylestermethosulfat, N-methyltriethanolammonium tristearyl ester methosulfate and mixtures thereof.

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 (anhydride). The formulation (anhydride) means that The anhydrides of the acids mentioned are also preferred acid derivatives.

If the compounds of formula (11) are amides or amine salts, they are preferably from a secondary amine which is a hydrogen and Contains carbon-containing group with at least 10 carbon atoms.

It is preferred that R ^{17 is} 10 to 30, especially 10 to 22, e.g. B. contains 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, e.g. B. contain less than 6 carbon atoms, or, if desired, may have at least 10 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl).

Polymers are also suitable which contain at least one amide or ammonium group bonded directly to the backbone of the polymer, the amide or ammonium group carrying at least one alkyl group of at least 8 carbon atoms on the nitrogen atom. Such polymers can be made in various ways. One way is to use a polymer containing multiple carboxylic acid or anhydride groups and react that polymer with an amine of formula NHR ⁶ R ⁷ to obtain the desired polymer.

In general, copolymers of unsaturated esters such as C ₁ -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. B. carboxylic anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride) are suitable.

Carboxylic acids are preferably 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, depending on the reaction conditions, amides, ammonium salts, amide Ammonium salts or imides are formed. So copolymers give the contain unsaturated carboxylic anhydrides when reacting with a secondary amine due to reaction with the anhydride group in half Amide and half amine salts. Heating can form the diamond Water can be split off.

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

5. Copolymers (a) of a dialkyl fumarate, maleate, citraconate or itaconate with Maleic anhydride, or (b) vinyl esters, e.g. B. vinyl acetate or vinyl stearate with maleic anhydride, or (c) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride and vinyl acetate.

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

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

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

The suitable amines can be represented by the formula R ⁶ R ⁷ NH and the polyamines by R ⁶ NH [R ¹⁹ NH] _x R ⁷ , where R ^{19 is} a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is a whole Number, preferably between 1 and 30. Preferably one of the two or both 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 of nC ₁₄ alkyl, 30% by weight of nC ₁₀ alkyl, 60% by weight of nC ₁₈ alkyl, the rest is unsaturated).

Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-coco propylene 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) from 1000 to 500000, for example 10000 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 derive from e.g. B. Maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferred Maleic anhydride. They can be used both in the form of their homopolymers copolymers can also be used. Suitable comonomers are: Styrene and alkylstyrenes, straight-chain and branched olefins with 2 to 40 Carbon atoms and their mixtures with one another. For example 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 is preferred and isobutene, styrene is particularly preferred.

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

The polymers or copolymers are reacted with the amines in Temperatures from 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is polymerized in amounts of approximately one mole per mole Dicarboxylic anhydride, i.e. i. about 0.9 to 1.1 mol / mol applied. The usage Larger or smaller quantities are possible, but have no advantage. Become If larger amounts are used than one mole, some ammonium salts are obtained, since the formation of a second amide group higher temperatures, longer Residence times and water circles required. Are smaller quantities than applied one mole, there is no complete conversion to the monoamide and you get a correspondingly reduced effect.

Instead of the subsequent implementation of the carboxyl groups in the form of  Dicarboxylic anhydride with amines to the corresponding amides can sometimes be advantageous to prepare the monoamides of the monomers and then polymerize directly in the polymerization. Most of the time, however technically much more complex, since the amines on the double bond of can add monomeric mono- and dicarboxylic acid and then none Copolymerization is more 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% from 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. You are preferred straight chain and unbranched. However, up to 20% by weight cyclic and / or branched portions may be included.

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 as well as fumaric acid. Maleic anhydride is preferred.

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

As a rule, it is advantageous to use the dicarboxylic acids in the form of the anhydrides, where available to use in the copolymerization, e.g. B. Maleic anhydride, itaconic anhydride, citraconic anhydride and Tetrahydrophthalic anhydride since the anhydrides are usually better with the Copolymerize (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 up to 200 ° C in the course of 0.3 to 30 hours. The amine is used in quantities from about one to two moles polymerized per mole Dicarboxylic anhydride, i.e. i. about 0.9 to 2.1 mol / mol applied. The usage Larger or smaller quantities are possible, but have no advantage. Become Free amine is used in amounts greater than two moles. Become applied in amounts less than one mole does not take place fully to monoamide instead and you get a correspondingly reduced Effect.

In some cases, it may be beneficial if the Amide / ammonium salt structure made up of two different amines becomes. For example, a copolymer of lauryl acrylate and Maleic anhydride first with a secondary amine such as hydrogenated Ditalgfettamin be converted to the amide, after which the from the anhydride derived free carboxyl group with another amine, e.g. B. 2-ethylhexylamine is neutralized to the ammonium salt. It is exactly the same reverse procedure is conceivable: First, with ethylhexylamine Monoamide, then converted to ammonium salt with ditallow fatty amine. Preferably at least one amine is used, which is at least a straight-chain, unbranched alkyl group with more than 16 carbon atoms has. It is immaterial whether this amine is responsible for the structure of the amide structure or is present as the ammonium salt of dicarboxylic acid.

Instead of the subsequent implementation of the carboxyl groups or Dicarboxylic anhydride with amines to give the corresponding amides or  Amide / ammonium salts, it can sometimes be beneficial to the monoamides or to produce amide / ammonium salts of the monomers and then at Polymerize polymerization directly. However, this is usually technically a lot more complex, since the amines on the double bond of the monomers Can add dicarboxylic acid and then no longer possible copolymerization is.

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} identical 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
1-30 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 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 stands for 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 cocoalkyl, 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 and 15 and 16 and possibly 13. They only contain in itself known manner in the polymerization by initiation, inhibition and End groups.

Structural units of the formulas 12 to 14 are derived in particular 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 formula 15 are derived from the α, β-unsaturated Compounds of formula 19 from.

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 as well as their mixtures. Alpha-olefins having 10 to 24 carbon atoms and styrene are preferred, alpha-olefins having 12 to 20 carbon atoms are particularly preferred.

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 prepared using 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 e.g. B. 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-butene-1-ol. Addition products of ethylene oxide and / or are preferred Propylene oxide on allyl alcohol.

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 methods are e.g. B. from J. March, Advanced Organic Chemistry, 2nd edition, p. 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 (22)

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 manufacturing processes are e.g. B. in J. March, Advanced Organic Chemistry, 2nd edition, pp. 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, d. H. the number of moles of α-olefin, the per mole of formula 20 or 21 be attached.

Suitable primary amines for the preparation of the terpolymers are named for example the following: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n-stearylamine or also N, N-dimethylaminopropylenediamine, cyclohexylamine, Dehydroabietylamine and mixtures thereof.

Secondary amines which are suitable for the preparation of the terpolymers are for example: didecylamine, ditetradecylamine, distearylamine, Dicocos fatty amine, ditallow fatty amine and mixtures thereof.  

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

9. reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic acid 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 are hydrogen or methyl,
a, b is zero or 1 and a + b is 1,
R ³⁷ = -OH, -O- [C ₁ -C ₃₀ alkylkyl], -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 (28)

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.

The structural units of the formulas 25, 26 and 27 are derived in detail from α, β-unsaturated dicarboxylic anhydrides of the formulas 17 and / or 18 from.

The structural units of formula 15 are derived from the α, β-unsaturated Olefins of formula 19. The aforementioned 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 formula 28, amines of the formula NR ⁶ R ⁷ R ⁸ and, if appropriate, from alcohols having 1 to 30 carbon atoms.

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 formula 28 were preferably used to derivatize the structural units of the formulas 17 and 18.

The preparation of the polyetheramines used is, for example, by reductive amination of polyglycols possible. Furthermore, it succeeds Production of polyetheramines with a primary amino group by Addition of polyglycols to acrylonitrile and subsequent catalytic Hydrogenation. In addition, polyetheramines are produced by the reaction of Polyethers with phosgene or thionyl chloride and subsequent amination accessible to polyetheramine. The used according to the invention Polyetheramines are (e.g.) under the name ®Jeffamine (Texaco) commercially available. Their molecular weight is up to 2000 g / mol and the ethylene oxide / propylene oxide ratio is from 1:10 to 6: 1. Another way to derivatize the structural units of the Formulas 17 and 18 is that instead of the polyether amines Alkanolamine of the formula used and then an alkoxylation is subjected.

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

The oxyalkylation is usually carried out at temperatures between 70 and 170 ° C. with the catalysis of bases, such as NaOH or NaOCH ₃ , by gassing up alkylene oxides, such as ethylene oxide (EO) and / or propylene oxide (PO). Usually 1 to 500, preferably 1 to 100, moles of alkylene oxide are added per mole of hydroxyl groups.

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

The following may be mentioned as primary amines: n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine, n- Stearylamine or also N, N-dimethylaminopropylenediamine, cyclohexylamine,  Dehydroabietylamine and mixtures thereof.

Examples of secondary amines are: Didecylamine, Ditetradecylamine, Distearylamine, Dicocosfettamin, Ditalgfettamin and their mixtures.

Examples of alcohols include: Methanol, ethanol, propanol, isopropanol, n-, sec-, tert-butanol, octanol, Tetradecanol, hexadecanol, octadecanol, tallow fatty alcohol, behenyl alcohol and their mixtures. Suitable examples are listed in EP-A-688 796.

10. copolymers and terpolymers of NC ₆ -C ₂₄ alkylmaleimide with C ₁ -C ₃₀ vinyl esters, vinyl ethers and / or olefins having 1 to 30 C atoms, such as. B. 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 alkylmaleimide are preferred.

To optimize the properties as a flow improver and / or lubricity additive, the additives according to the invention can also 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 for C ₄ -C ₅₀ alkyl or alkenyl, [OR ⁵² ] for ethoxy and / or propoxy,
n stands for a number from 5 to 100 and p stands for a number from 0 to 50.

Finally, in a further variant of the invention additives according to the invention used together with comb polymers. This is understood to mean polymers that contain hydrocarbon residues at least 8, especially at least 10 carbon atoms on one Polymer backbone are bound. It is preferably a Homopolymers whose alkyl side chains are at least 8 and in particular contain at least 10 carbon atoms. Show copolymers at least 20%, preferably at least 30%, of the monomer 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 e.g. B. 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.

For example, comb polymers can be represented by the formula

to be discribed. Mean in it
A R ', COOR', OCOR ', R "-COOR' or OR ';
DH, CH ₃ , A or R ";
EH or A;
GH, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
MH, COOR ", OCOR", OR "or COOH;
NH, R ", COOR", OCOR, COOH or an aryl radical;
R 'is a hydrocarbon chain of 8-150 carbon atoms;
R "is a hydrocarbon chain of 1 to 10 carbon atoms;
m is a number between 0.4 and 1.0; and
n is a number between 0 and 0.6.

The mixing ratio (in parts by weight) of the additives according to the invention 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 that contain 0.5 wt% sulfur and less, especially less than 200 ppm sulfur and in special cases contain less than 50 ppm sulfur. It is generally about those middle distillates which have been subjected to hydrogenating refining, and which therefore only contains 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, if the temperature of the oil in the additives is low, i.e. H. below 40 ° C, in particular 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 that are 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. B. 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 Copolymers improved in their lubricating and / or cold flow properties Mineral oils or mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight Copolymer based on the distillate.

The additives can be used alone or together with other additives be, e.g. B. 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

Table 1

Characterization of the test oils

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 storage for 24 hours 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 (i 25 mm; Whatman GFA, Order No. 1820025) filtered. The ADT value is calculated from the three filtration times T ₁ , T ₂ and T ₃ as follows:

An ADT value <15 is considered as an indication that the gas oil is normal cold weather can be used satisfactorily. Products with ADT values <25 are described as not 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. After 24 Hours of storage at + 3 ° C, the oil is stored according to the conditions of the British Rail  Tests 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 given as the coefficient of friction (Friction) and Wear Scar (WSD). On low coefficient of friction and a low wear scar show a good one Lubricating effect.

polymers

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 / neododecanoic acid vinyl ester
Polymer E: ethylene / vinyl propionate / vinyl neodecanoate

Table 2

Properties of the flow improver polymers

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).  

amphiphilic

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 section)

Lubrication effect and cold flow improvement

To carry out the inventive and comparative examples mentioned cold flow improver polymers mixed with the amphiphiles mentioned.  

Claims (9)

1. Containing additives for improving the cold flow and lubrication properties of fuel oils

• A) 20 to 80% by weight of at least one oil-soluble amphiphile of the formula 1
  and / or Formula 2
  wherein R ^{1 is} an alkyl, alkenyl, hydroxyalkyl or aromatic radical with 8 to 35 carbon atoms, X NH, NR ³ , O or S, y = 1, 2, 3 or 4,
  R ² denotes an alkyl radical with 2 to 10 carbon atoms and hydroxyl groups and R ³ denotes an alkyl radical with 2 to 10 carbon atoms or methyl and nitrogen and / or hydroxyl groups,
• B) 20 to 80 wt .-% 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.

2. Additives according to claim 1, characterized in that R ¹ and R ² together contain at least 15 carbon atoms. 3. 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. 4. Additives according to one or more of claims 1 to 3, characterized characterized in that component A) is a fatty acid alkanolamide is. 5. Additives according to one or more of claims 1 to 4, characterized characterized in that the terpolymers of the component legs melt viscosity at 50 to 5000 mPas at 140 ° C. 6. Additives according to one or more of claims 1 to 5, characterized characterized in that the terpolymers of component B) Neocarboxylic acid vinyl esters are the vinyl esters of neononane, neodecane or Contain neoundecanoic acid. 7. Fuel oils containing 0.001 to 2 wt .-% additives according to one or several of claims 1 to 6. 8. Use of 0.001 to 2 wt .-% additives according to one or more of the Claims 1 to 6 for the simultaneous improvement of the lubricating effect and Cold flow properties of fuel oils. 9. Use of additives according to claim 8 together 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 ';
DH, CH ₃ , A or R ";
EH or A;
GH, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
MH, COOR ", OCOR", OR "or COOH;
NH, R ", COOR", OCOR, COOH or an aryl radical;
R 'is a hydrocarbon chain of 8-150 carbon atoms;
R "is a hydrocarbon chain of 1 to 10 carbon atoms;
m is a number between 0.4 and 1.0; and
n is a number between 0 and 0.6, and the mixing ratio between additive according to claims 1 to 6 and paraffin dispersant or comb polymer is 1:10 to 20: 1.