DE102007028305A1 - Detergent additives containing mineral oils with improved cold flowability - Google Patents

Abstract

The invention relates to the use of at least one oil-soluble, acting as nucleator for Paraffinkristalisation compound B) selected from comb polymers carrying alkyl side chains with a length of at least 18 C-atoms in the molar average, to improve the response of Mineralölaltfließverbesserern C), which of B) are in middle distillates containing at least one ashless, nitrogen-containing detergent additive A) which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical attached to a polar group, wherein the alkyl or Alkenyl radical 10 to 500 carbon atoms and the polar group comprises 2 or more nitrogen atoms.

Description

The The present invention relates to the use of nucleating agents to improve the cold flowability of detergent additives containing mineral oil distillates, as well as the additivierten Petroleum distillates.

always stricter environmental laws require one always more sophisticated engine technology to comply with the specified Emission limits. An assignment of engine parts such as the valves with combustion residues changed However, the characteristics of the engine and leads to increased Emissions as well as increased consumption. Therefore, be Motor fuels added detergent additives, such deposits remove or prevent their formation. It is in the Generally oil-soluble amphiphiles, in addition to an oil-soluble, temperature-stable hydrophobic Rest contain a polar headgroup.

on the other hand become heavier in the course of decreasing world oil reserves and thus promoted paraffin-rich crude oils and which consequently also leads to paraffin-rich fuel oils to lead. The contained in particular in middle distillates Paraffins can lower the temperature of the oil crystallize out and partially including oil agglomerate. Through this crystallization and agglomeration can It is especially in winter to block the filters in engines and Firing systems come, ensuring a safe metering of the fuels prevented and possibly a complete Interruption of fuel supply may occur. The paraffin problem is also due to environmental reasons for the purpose of lowering of the sulfur content increasing hydrodesulfurization of fuel oils aggravated, which leads to an increased proportion of cold-critical Paraffins in the fuel oil leads.

to Improvement of the cold flow properties become middle distillates often chemical additives, so-called cold flow improvers or flow improver added, the crystal structure and Modify agglomeration tendency of the precipitated paraffins, see above that the so-additive oils still pump at temperatures or use, which are often more than 20 ° C lower than non-additized oils. As a cold flow improver usually become oil-soluble copolymers of ethylene and unsaturated esters, oil-soluble polar Nitrogen compounds and / or comb polymers used. About that but also other additions have been proposed.

in the In the wake of increasingly sophisticated engine technology as well Increasing demands on the environmental compatibility of Fuel oils and their combustion products are detergent additives with evolved ever higher effectiveness. In addition, they will often used in very high dosage rates. It is reported, that, for example, for diesel fuels, the specific Consumption reduced or increased the power of the engines becomes. However, these additives often have negative effects on the cold flowability of middle distillates and in particular the effectiveness of known cold flow improvers. Especially with middle distillates with low boiling end and at the same time low aromatic content, it is often difficult or even impossible, in the presence of modern detergent additives by means of conventional flow improvers a satisfactory Adjust cold flow behavior. This is often done through Addition of detergent additives an antagonistic effect on the Effectiveness of the added cold flow improvers observed. In the process, the paraffin dispersion set by paraffin dispersants becomes the middle distillate impaired without increased Dosage can be restored to paraffin dispersant. Often, the measured as CFPP filterability with Cold flow improvers of additized oils in the Cold is significantly reduced and can only be controlled by greatly increased dosage of the flow improver compensate.

Especially In particular, such detergent additives are problematic, derived from higher polyamines as well as those for example due to multiple alkylation and / or acylation of these Polyamines have very high molecular weights. Also special problematic are those detergent additives whose hydrophobic radical of sterically hindered olefins and / or of higher molecular weight and / or polyfunctionalized poly (olefins).

task Thus, it was the response of cold flow improvers to improve in detergent additives containing middle distillates. Another object of the invention was to be opposite to provide the prior art improved detergent additive, this does not affect the response of cold flow improvers impaired.

Surprisingly, it has now been found that certain oil-soluble compounds acting as nucleators for paraffin crystallization impair the effectiveness of conventional cold flow improvers counteract by nitrogen-containing detergent additives or cancel this impairment.

object The invention thus relates to the use of at least one oil-soluble, acting as nucleator for paraffin crystallization Compound B) selected from comb polymers, the alkyl side chains with a length of at least 20 carbon atoms, to Improvement of the response of mineral oil flow improvers C), which are different from B), in middle distillates, which are at least an ashless, nitrogen-containing detergent additive A), which is an oil-soluble, amphiphilic compound which comprises at least one alkyl or alkenyl radical attached to a polar group is attached, wherein the alkyl or alkenyl radical 10 to 500 C atoms and the polar group 2 or more nitrogen atoms includes.

Another object of the invention is a process for improving the response of mineral oil flow improvers C) in middle distillates containing ashless nitrogen-containing detergent additives A),
and wherein the ashless nitrogen-containing detergent additives A) are oil-soluble, amphiphilic compounds comprising at least one alkyl or alkenyl group attached to a polar group, wherein the alkyl or alkenyl group is 10 to 500 carbon atoms and the polar group is 2 or more Includes nitrogen atoms,
by adding to the oil at least one oil-soluble compound B), which acts as a nucleator for paraffin crystallization, selected from comb polymers carrying alkyl side chains of at least 20 carbon atoms, different from C;

• a) mindestens ein aschefreies, stickstoffhaltiges Detergenzadditiv A), welches eine öllösliche, amphiphile Verbindung ist, die mindestens einen Alkyl- oder Alkenylrest umfasst, der an eine polare Gruppe gebunden ist, wobei der Alkyl- oder Alkenylrest 10 bis 500 C-Atome und die polare Gruppe 2 oder mehr Stickstoffatome umfasst, und
• b) mindestens eine öllösliche, als Nucleator für die Paraffinkristallisation wirkende Verbindung B), ausgewählt aus Kammpolymeren, die Alkylseitenketten mit einer Länge von mindestens 20 C-Atomen tragen sowie gegebenenfalls
• c) einen von B) verschiedenen Mineralölkaltfließverbesserer C).

Another object of the invention are additives containing

• a) at least one ashless, nitrogen-containing detergent additive A), which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical bonded to a polar group, wherein the alkyl or alkenyl radical has 10 to 500 carbon atoms and the polar group comprises 2 or more nitrogen atoms, and
• b) at least one oil-soluble compound B) acting as nucleator for the paraffin crystallization, selected from comb polymers carrying alkyl side chains with a length of at least 20 carbon atoms and optionally
• c) a mineral oil flow improver C) other than B).

The Combination of A) and B) is hereinafter also referred to as "inventive Additive ".

• a) mindestens ein aschefreies, stickstoffhaltiges Detergenzadditiv A), welches eine öllösliche, amphiphile Verbindung ist, die mindestens einen Alkyl- oder Alkenylrest umfasst, der an eine polare Gruppe gebunden ist, wobei der Alkyl- oder Alkenylrest 10 bis 500 C-Atome und die polare Gruppe 2 oder mehr Stickstoffatome umfasst,
• b) mindestens eine öllösliche, als Nucleator für die Paraffinkristallisation wirkende Verbindung B), ausgewählt aus Kammpolymeren, die Alkylseitenketten mit einer Länge von mindestens 20 C-Atomen tragen, sowie
• c) mindestens einen von B) verschiedenen Mineralölkaltfließverbesserer C).

Another object of the invention are middle distillates having a sulfur content of less than 100 ppm and a 90% distillation point of below 360 ° C, containing

• a) at least one ashless, nitrogen-containing detergent additive A), which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical bonded to a polar group, wherein the alkyl or alkenyl radical has 10 to 500 carbon atoms and the polar group comprises 2 or more nitrogen atoms,
• b) at least one oil-soluble compound B) acting as nucleator for paraffin crystallization, selected from comb polymers bearing alkyl side chains of at least 20 carbon atoms in length, and
• c) at least one mineral oil flow improver C) other than B).

Under improving the response of cold flow improvers C) is understood according to the invention that at least a set or adjustable by cold flow improver C) and impaired by the addition of a detergent additive A) Cold property of middle distillates by adding one as Nucleating agent for paraffin crystallization acting Compound B) is improved. Specifically, by adding the Nucleating agent B) without the presence of the detergent additive A) by the cold flow improver C) set or adjustable cold property achieved. Under cold conditions individually or in combination, the solidification point (Pour Point), the cold filterability (Gold Filter Plugging Point), the Cold flow (low temperature flow) as well as understood the paraffin dispersion of middle distillates.

Especially impaired is the response of flow improvers in middle distillates containing more than 10 ppm of a nitrogenous Detergent additive A), in particular more than 20 ppm and especially more as 40 ppm such as 50 to 2,000 ppm nitrogen-containing Detergent additive A) included.

The additives according to the invention preferably contain from 0.01 to 10 parts by weight, and in particular from 0.05 to 5 parts by weight, as in one part by weight of the nitrogen-containing detergent additive A) For example, 0.1 to 3 parts by weight of the oil-soluble, acting as Nucleator for paraffin crystallization compound B).

ash free means that the relevant additives are essentially just off Consist of elements that are gaseous during combustion Form reaction products. Preferably, the additives are essentially only from the elements carbon, hydrogen, oxygen and nitrogen. In particular, ashless additives are substantially free of metals and metal salts.

Under Nucleators are understood to mean compounds that cool off of a paraffinic oil, the crystallization of paraffins initiate. They postpone the beginning of paraffin crystallization of the additivated with them oil, for example, by Measuring the Cloud Point or Wax Appearance Temperature (WAT) can be determined to higher temperatures. It deals These are connections that are above the cloud point in the oil are soluble and just above the temperature of paraffin saturation begin to crystallize then as seed for to serve the crystallization of the paraffins. Thus they prevent a supersaturation of the oil with paraffins and lead to crystallization near the saturation concentration. This leads to the formation of a multiplicity of equally small ones Wax crystals. In the presence of a nucleator, paraffin crystallization begins ie at a higher temperature than in non-additivated oil. This is for example by measuring the WAT by means of differential thermal analysis (Differential Scanning Calorimetry, DSC) at a slow cooling of the oil can be determined with, for example, -2 K / min.

Prefers middle distillates are 10 to 10,000 ppm and especially 50 to 3,000 ppm of the nitrogen-containing detergent additives A) added.

Preferably For example, the alkyl or alkenyl group imparts oil solubility to the detergent additives.

Particularly problematic are those detergent additives whose alkyl radical has 15 to 500 carbon atoms and in particular 20 to 350 carbon atoms, for example 50 to 200 carbon atoms. This alkyl radical can be linear or branched, in particular it is branched. In a preferred embodiment, the alkyl radical is derived from oligomers of lower olefins having 3 to 6 C atoms such as propene, butene, pentene or hexene and mixtures thereof. Preferred isomers of these olefins are isobutene, 2-butene, 1-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1-pentene, 2-pentene and iso-pentene and mixtures thereof. Particular preference is given to propene, isobutene, 2-butene, 2-methyl-2-butene, 2,3-dimethyl-2-butene and mixtures thereof. Particular preference is given to olefin mixtures containing more than 70 mol%, especially more than 80 mol%, for example more than 90 mol% or more than 95 mol% of 2-methyl-2-butene, 2,3-dimethyl 2-butene and / or isobutene. Particularly suitable for the preparation of such detergent additives are highly reactive low molecular weight polyolefins having a proportion of terminal double bonds of at least 75%, especially at least 85% and in particular at least 90% such as at least 95%. Particularly preferred low molecular weight polyolefins are poly (isobutylene), poly (2-butene), poly (2-methyl-2-butene), poly (2,3-dimethyl-2-butene), poly (ethylene-co-isobutylene) and atactic poly (propylene). The molecular weight of particularly preferred polyolefins is between 500 and 3000 g / mol. Such oligomers of lower olefins are accessible for example by polymerization by means of Lewis acids such as BF ₃ and AlCl ₃ , by means of Ziegler catalysts and in particular by means of metallocene catalysts.

The polar component of the detergent additives which are particularly problematic for the response of known cold additives is derived from polyamines having 2 to 20 N atoms. Such polyamines correspond for example to the formula (R ⁹ ) ₂ N- [AN (R ⁹ ) _q - (R ⁹ ) wherein each R ^{9 is} independently hydrogen, an alkyl or hydroxyalkyl radical of up to 24 carbon atoms, a polyoxyalkylene radical - (AO) _r - or polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ) but wherein at least one R ^{9 is} hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, r and s independently of one another are from 1 to 50. Usually these are mixtures of polyamines and in particular mixtures of poly (ethylene amines) and / or poly (propyleneamines). For example:
Ethylenediamine, 1,2-propylenediamine, dimethylaminopropylamine, diethylenetriamine (DETA), dipropylenetriamine, triethylenetetramine (TETA), tripropylenetetramine, tetraethylenepentamine (TEPA), tetrapropylenepentamine, pentaethylenehexamine (PEHA), pentapropylenehexamine and heavy polyamines. Heavy polyamines are generally understood as meaning mixtures of polyalkylenepolyamines which, in addition to small amounts of TEPA and PEHA, are mainly oligomers having 7 or more nitrogen atoms, of which two or more are in the form of primary amines nogruppen present.

often These polyamines also contain tertiary amino groups branched structural elements.

Other suitable amines include those which comprise cyclic structural units derived from piperazine. The piperazine units may preferably carry hydrogen at one or both nitrogen atoms, an alkyl or hydroxyalkyl radical having up to 24 carbon atoms or a polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ), where A, R ⁹ and s have the meanings given above.

Further suitable amines include alicyclic diamines such as 1,4-di (aminomethyl) cyclohexane and heterocyclic nitrogen compounds such as imidazolines and N-aminoalkylpiperazines such as N- (2-aminoethyl) piperazine.

Also, detergent additives whose polar portion is derived from hydroxyl-bearing polyamines, heterocycle-substituted polyamines, and aromatic polyamines are problematic. For example:
N- (2-hydroxyethyl) ethylenediamine, N, N ¹ -bis (2-hydroxyethyl) ethylenediamine,
N- (3-hydroxybutyl) tetra (methylene) diamine, N-2-aminoethylpiperazine, N-2 and
N-3-aminopropylmorpholine, N-3- (dimethylamino) propylpiperazine,
2-heptyl-3- (2-aminopropyl) imidazoline, 1,4-bis (2-aminoethyl) piperazine,
1- (2-hydroxyethyl) piperazine, various isomers of phenylenediamine and naphthalenediamine and mixtures of these amines.

Detergent additives based on heavy polyamines, in which R ^{9 is} hydrogen in the above formula and q has values of at least 3, in particular at least 4, such as 5, 6 or 7, are particularly critical for the cold additization of middle distillates. For mixtures of various polyamines, a proportion of more than 10 wt .-%, in particular more than 20 wt .-% and especially of more than 50 wt .-% of amines having q-values of 4 or higher and especially with q Values of 5 or higher and in particular with q values of 6 or higher on the total amount of amines used have proven particularly critical.

The oil-soluble Alkyl radical and the polar head group of the detergent additives can either directly over a C-N or over one Ester, amide or imide bond linked together. Accordingly, preferred detergent additives are alkylpolyamines, Mannich reaction products, hydrocarbyl-substituted succinic acid amides and imides and mixtures of these classes of substances.

at the detergent additives linked via C-N bonds they are preferably alkylpoly (amines), for example by reaction of polyisobutylenes with polyamines, for example by hydroformylation and subsequent reductive amination are accessible with the above polyamines. there For example, one or more alkyl radicals can be bound to the polyamine be. Particularly critical for the cold additivation are detergent additives based on higher polyamines with more than 4 N atoms such as those with 5, 6 or 7 N atoms.

amide or imide-containing detergent additives are, for example by reaction of Alkenylbernsteinsäureanhydriden with Polyamines accessible. alkenylsuccinic and polyamine are preferably in molar ratio from about 1: 0.5 to about 1: 1 reacted. The production of the basis lying Alkenylbernsteinsäureanhydride is usually carried out by addition of ethylenically unsaturated polyolefins or chlorinated polyolefins to ethylenically unsaturated Dicarboxylic acids.

For example, alkenyl succinic anhydrides can be prepared by reaction of chlorinated polyolefins with maleic anhydride. Alternatively, the preparation can also be achieved by thermal addition of polyolefins to maleic anhydride in an "ene reaction." Highly reactive olefins having a high content of, for example, more than 75% and especially more than 85 mol%, based on the total number of polyolefin molecules, are present The terminal double bonds can be both vinylidene double bonds [-CH ₂ -C (= CH ₂ ) -CH ₃ ] and vinyl double bonds [-CH = C (CH ₃ ) ₂ ]. act.

For the preparation of alkenylsuccinic anhydrides, the molar ratio of the two reactants in the reaction between maleic anhydride and polyolefin can vary within wide limits. Preferably, it may be between 10: 1 and 1: 5, with molar ratios of 6: 1 to 1: 1 being particularly preferred are. Maleic anhydride is preferably used in stoichiometric excess, for example 1.1 to 3 moles of maleic anhydride per mole of polyolefin. Excess maleic anhydride can be removed from the reaction by, for example, distillation.

There the adducts primarily formed by ene reaction in turn contain an olefinic double bond is suitable Reaction a further addition of unsaturated Dicarboxylic acids to form so-called bis-maleinates possible. The thereby accessible reaction products have based on those with unsaturated carboxylic acids converted amounts of poly (olefins) on average a Maleinierungsgrad of more than 1, preferably about 1.01 to 2.0, and in particular 1.1 to 1.8 dicarboxylic acid units per alkyl radical. By Implementation with the amines mentioned above results in products with significantly increased efficacy as detergent additives. on the other hand increases with Maleinierungsgrad the degree of deterioration the effectiveness of cold flow improvers.

The Reaction of alkenylsuccinic anhydrides with polyamines leads to products containing one or more amide and / or Imide bonds per polyamine and depending on the Maleinierungsgrad one or two polyamines per alkyl radical can carry. Prefers be for the implementation of 1.0 to 1.7 and in particular 1.1 to 1.5 mol alkenyl succinic anhydride per mole of polyamine used, leaving free primary amino groups in the product remain. In a further preferred embodiment Alkenylsuccinic anhydride and polyamine become equimolar implemented. In the reaction of polyamines with alkenylsuccinic anhydrides with a high degree of acylation of 1.1 or more anhydride groups per Alkyl radical such as 1.3 or more anhydride groups per alkyl radical also arise polymers that are particularly problematic for the response of cold additives are.

typical and particularly preferred acylated nitrogen compounds are Reaction of poly (isobutylene) -, poly (2-butenyl) -, poly (2-methyl-2-butenyl) -, Poly (2,3-dimethyl-2-butenyl) - or poly (propenyl) succinic anhydrides with an average of about 1.2 to 1.5 anhydride groups per alkyl radical, whose Carry alkylene radicals between 50 and 400 carbon atoms, with a mixture of poly (ethylene amines) having about 3 to 7 nitrogen atoms and about 1 to 6 ethylene units available.

Also oil-soluble Mannich reaction products based on polyolefin-substituted Phenols and polyamines affect the effectiveness conventional cold flow improvers. such Mannich bases are by known methods, for example by alkylation of phenol and / or salicylic acid with those described above Polyolefins such as poly (isobutylene), poly (2-butene), Poly (2-methyl-2-butene), poly (2,3-dimethyl-2-butene) or atactic Poly (propylene) and subsequent condensation of the alkylphenol with Aldehydes having 1 to 6 carbon atoms such as formaldehyde or its reactive equivalents such as formalin or paraformaldehyde and the above-described polyamines such as TEPA, PEHA or heavy polyamines produced.

The average molecular weight determined by vapor pressure osmometry especially efficient, but at the same time also for the cold additivation of middle distillates of particularly critical detergent additives above 800 g / mol and in particular above 2,000 g / mol such as above 3,000 g / mol. The average molecular weight of those described above Detergent additives can also be increased via crosslinking reagents and the purpose of use.

suitable Crosslinking reagents are for example dialdehydes such as glutaraldehyde, Bisepoxides derived, for example, from bisphenol A, dicarboxylic acids and their reactive derivatives such as maleic anhydride and alkenyl succinic anhydrides, and higher polybasic carboxylic acids and their derivatives such as Trimellitic acid, trimellitic anhydride and pyromellitic dianhydride.

preferred acting as nucleator for paraffin crystallization Comb polymers B) are polymers attached to the polymer backbone bound alkyl side chains with a length of at least Wear 20 C atoms. Particularly preferred are those polymers which Side chains with 22 to 60 such as 24 to 45 carbon atoms wear. The proportion of these alkyl side chains in the total amount of Alkyl side chains of the polymer is at least 10 mol%, preferably at least 25 mole% and especially at least 50 mole% such as for example at least 80 mol%. Preferably, the side chains are linear or have at least correspondingly long linear segments.

The polymer backbone may for example be composed of ethylenically unsaturated mono- and / or polycarboxylic acids such as, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid. In addition, it may contain other monomers such as olefins, vinyl esters and / or vinyl ethers. Be Particularly preferred are copolymers based on fumaric acid and vinyl acetate and those based on maleic acid and α-olefins.

The Polymer backbone carries long-chain alkyl radicals in molar average at least 18, preferably at least 20 such as at least 24 C atoms. The alkyl radicals can be as in the case of α-olefins directly via a C-C bond be tied to the backbone or via an ester, Amide, imide or ammonium group bonded to the polymer backbone be. Furthermore, the alkyl radicals via spacer such as polyoxyalkylene or polyalkyleneamine groups with in each case 1 to 200 and in particular 2 to 50 oxyalkyl or Alkylenamineinheiten be bound to the polymer backbone.

As nucleator suitable for the paraffin crystallization comb polymers B) are, for example, polymers of the formula (1)

A

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

D

H, CH₃, A oder R'';

E

H, A;

G

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

M

H, COOR'', OCOR'', OR'', COOH;

N

H, R'', COOR'', OCOR, einen Arylrest;

R'

eine Kohlenwasserstoffkette mit mindestens 20 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.

Mean in it

A

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

D

H, CH _3, A or R '';

e

H, A;

G

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

M

H, COOR '', OCOR '', OR '', COOH;

N

H, R ", COOR", OCOR, an aryl radical;

R '

a hydrocarbon chain having at least 20 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.

Preferred comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters. Particularly preferred olefins are α-olefins having at least 22 and especially 24 to 60 carbon atoms such as C ₂₀ -α-olefin, C ₂₄ -α-olefin, C ₂₆ -α-olefin and mixtures thereof such as C _20-24 -α-olefin, C _26-28 -α-olefin or C _24-28 -α-olefin and technical chain cuts in the range C ₃₀₊ . By α-olefins are meant linear alkenes with terminal double bond. A particularly preferred comonomer vinyl ester is vinyl acetate. Usually, the copolymers of unsaturated carboxylic acids are essentially alternating copolymers.

Usually These are copolymers of ethylenically unsaturated carboxylic acids at least 50%, preferably 60-100% and in particular to 70-98% such as 80-95% with alcohols esterified. Preference is given to alcohols with at least 20 and preferably used with at least 22 C atoms. It can however, also shorter-chain alcohols, for example with 10 to 18 and especially 12 to 16 carbon atoms used for the esterification if the polymer already has a sufficient amount of long Carries side chains with at least 20 carbon atoms.

Further preferred comb polymers are homo- and copolymers of alkyl acrylates, Alkyl methacrylates and alkyl vinyl ethers derived from alcohols with at least 20 and especially 22 to 60 carbon atoms such as Derive 24 to 40 carbon atoms as well as homopolymers and copolymers of alkyl vinyl esters, which differ from fatty acids with at least 20 and specifically Derive 22 to 40 carbon atoms. In a further preferred embodiment be with long-chain fatty alcohols with at least 20 C-atoms esterified copolymers of dicarboxylic acids such as Maleic or fumaric acid and vinyl acetate as comb polymers used. In the case of copolymers contain at least 10 mol%, preferably at least 25 mol% and in particular at least 50 mol% such as at least 80 mole percent of the monomers are alkyl chains having at least 20 carbon atoms, and preferably 22 to 60 such as 24 to 45 C atoms.

Further preferred comb polymers are structural units derived from alkylaromatics Polycondensates. These are in particular alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in ortho and / or para position to the OH group. Particularly preferred as starting materials are alkylphenols which carry at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols. Particularly preferably, the alkyl radical is in the para position to the phenolic OH group. The alkyl radicals may be the same or different in the case of the alkylphenol-aldehyde resins which can be used in the process according to the invention; they may be saturated or, preferably, unsaturated

At least 10 mol%, preferably at least 25 mol% and in particular at least 50 mol%, for example at least 80 mol% of the alkyl radicals of the alkylphenol resins suitable according to the invention as nucleator B) have alkyl chains with at least 20 carbon atoms and preferably between 22 and 60 such as 24 to 45 carbon atoms. On a molar average, the alkyl radicals have at least 18, preferably 20 to 60, such as 24 to 45 carbon atoms. In a preferred embodiment, mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins. Thus, for example, resins based on mixtures of C _20/22/24 -alkylphenols, C _24/25/28 -alkylphenols and of alkylphenols with chain lengths of C ₃₀ and higher have proven particularly useful.

suitable Alkylphenol resins can also structural units more Phenol analogs such as salicylic acid, hydroxybenzoic acid and their derivatives such as esters, amides and salts or contain insist on them. That is, the alkyl radicals can directly via a C-C bond or via a Ester or ether group to be bound to the phenol.

preferred Polycondensates are by reaction of alkylphenols with aldehydes and / or ketones accessible. Suitable aldehydes for the alkylphenol-aldehyde resins are those having 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as Formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, Benzaldehyde, glyoxylic acid and their reactive equivalents such Paraformaldehyde and trioxane. Particularly preferred is formaldehyde in the form of paraformaldehyde and especially formalin. The polycondensation may also be in the presence of aldehydes and amines in the form of a Mannich reaction be performed.

worin R¹¹ für C₂₀-C₂₀₀-Alkyl oder -Alkenyl, O-R¹⁰ oder O-C(O)-R¹⁰, R¹⁰ für C₂₀-C₂₀₀-Alkyl oder -Alkenyl und n für eine Zahl von 5 bis 200 steht, enthalten. R¹⁰ steht bevorzugt für C₂₂-C₁₀₀-Alkyl oder -Alkenyl und insbesondere für C₂₄-C₅₀-Alkyl oder -Alkenyl. Besonders bevorzugt steht R¹¹ für C₂₂-C₁₀₀-Alkyl oder -Alkenyl und insbesondere für C₂₄-C₅₀-Alkyl oder -Alkenyl. Bevorzugt steht n für eine Zahl von 7 bis 100 und speziell für eine Zahl von 10 bis 50.In a preferred embodiment of the invention, the compounds suitable as nucleator B) are alkylphenol-formaldehyde resins which contain oligomers or polymers having a repeating structural unit of the formula (2)

wherein R ^{11 is} C ₂₀ -C ₂₀₀ -alkyl or -alkenyl, OR ¹⁰ or OC (O) -R ¹⁰ , R ^{10 is} C ₂₀ -C ₂₀₀ -alkyl or -alkenyl and n is a number from 5 to 200, contain. R ¹⁰ preferably represents C ₂₂ -C ₁₀₀ -alkyl or -alkenyl and in particular C ₂₄ -C ₅₀ -alkyl or -alkenyl. R ¹¹ particularly preferably represents C ₂₂ -C ₁₀₀ -alkyl or -alkenyl and in particular C ₂₄ -C ₅₀ -alkyl or -alkenyl. Preferably n is a number from 7 to 100 and especially for a number from 10 to 50.

These alkylphenol-aldehyde resins are accessible by known methods, for. B. by condensation of the corresponding alkylphenols with formaldehyde, ie with 0.5 to 1.5 moles, preferably 0.8 to 1.2 moles of formaldehyde per mole of alkylphenol. The condensation can be carried out solvent-free, but preferably it is carried out in the presence of an inert or only partially water-miscible inert organic solvent such as mineral oils, alcohols, ethers and the like. Particularly preferred are solvents which can form azeotropes with water. As such solvents in particular aromatics such as toluene, xylene diethylbenzene and higher-boiling commercial solvent mixtures such as ^® Shellsol AB, and solvent naphtha are used. Also, fatty acids and their derivatives such as esters with lower alcohols having 1 to 5 carbon atoms such as ethanol and especially methanol are suitable as solvents. The condensation is preferably carried out between 70 and 200 ° C such as between 90 and 160 ° C.

It is usually catalysed by 0.05 to 5 wt .-% bases or preferably by 0.05 to 5 wt .-% acids. As acidic catalysts in addition to carboxylic acids such as acetic acid and oxalic acid in particular strong mineral acids such as hydrochloric acid, phosphoric acid and sulfuric acid and sulfonic acids are common catalysts. Particularly suitable catalysts are sulfonic acids which contain at least one sulfonic acid group and at least one saturated or unsaturated, linear, branched and / or cyclic hydrocarbon radical having 1 to 40 C atoms and preferably having 3 to 24 C atoms. Particularly preferred are aromatic sulfonic acids, especially alkylaromatic mono-sulfonic acids having one or more C ₁ -C ₂₃ -alkyl radicals and in particular those having C ₃ -C ₂₂ -alkyl radicals. Suitable examples are methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 2-mesitylenesulfonic acid, 4-ethylbenzenesulfonic acid, isopropylbenzenesulfonic acid, 4-butylbenzenesulfonic acid, 4-octylbenzenesulfonic acid; Dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid, naphthalenesulfonic acid. Mixtures of these sulfonic acids are suitable. Usually, these remain after completion of the reaction as such or in neutralized form in the product. For neutralization, amines and / or aromatic bases are preferably used, since they can remain in the product; Metal ions containing and thus ash-forming salts are usually separated.

The by gel permeation chromatography against poly (styrene) standards molecular weight measured in THF as nucleators for the paraffin crystallization is preferred comb polymers B) preferably 1,000-100,000 g / mol, more preferably 2,000-50,000 g / mol and especially 2,500-25,000 g / mol such as 3,000-20,000 g / mol. Prerequisite here is that the Comb polymers at least in application-relevant concentrations of 0.001 to 1 wt .-% are oil-soluble.

The Amount ratio between detergent additive A) and nucleators B) in the additized oil can vary within wide limits. A use of 0.01 to 10 has proven particularly useful Parts by weight, in particular 0.05 to 5 parts by weight such as 0.1 to 3 parts by weight of nucleator per part by weight of detergent additive, in each case based on the active ingredient.

When Flow improver C), which in the inventive Middle distillates are used, in particular one or several of the following substance classes III to VII into consideration, wherein preferably ethylene copolymers (component III) or mixtures thereof with one or more of the constituents IV to VII are used. Mixtures of ethylene copolymers have proved to be particularly useful (Component III) and Alkylphenol-Aldehyde Resins (Component V) and ethylene copolymers (component III) and comb polymers (Component VI). For the paraffin dispersion have in particular mixtures of ethylene copolymers (component III) with constituents IV and V or constituents IV and VI proven.

preferred Cold flow improvers as constituent III are copolymers of ethylene and olefinically unsaturated compounds. Suitable ethylene copolymers are, in particular, those which are used in addition Ethylene 8 to 21 mol%, in particular 10 to 18 mol% olefinic unsaturated compounds as comonomers.

at the olefinically unsaturated compounds are preferably vinyl esters, acrylic esters, methacrylic esters, alkyl vinyl ethers and / or alkenes, wherein said compounds substituted with hydroxyl groups could be. There may be one or more comonomers be contained in the polymer.

The vinyl esters are preferably those of the formula 1 CH ₂ = CH-OCOR ¹ (1) wherein R ^{1 is} C ₁ to C ₃₀ alkyl, preferably C ₄ to C ₁₆ alkyl, especially C ₈ - to C ₁₂ alkyl. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

In a further preferred embodiment, R ^{1 is} a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms, in particular having 8, 9 or 10 carbon atoms. Particularly preferred vinyl esters are derived from secondary and especially tertiary carboxylic acids whose branching is in the alpha position to the carbonyl group. Suitable vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate, vinyl stearate and versatic acid esters such as vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate.

In a further preferred embodiment, these ethylene copolymers contain vinyl acetate and at least one further vinyl ester of the formula 1 in which R ^{1 is} C ₄ to C ₃₀ -alkyl, preferably C ₄ to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl ,

The acrylic esters are preferably those of the formula 2 CH ₂ = CR ² -COOR ³ (2) wherein R ^{2 is} hydrogen or methyl and R ^{3 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Suitable acrylic esters include, for. Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n- and iso-butyl (meth) acrylate, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl , Hexadecyl, octadecyl (meth) acrylate and mixtures of these comonomers. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups. An example of such an acrylic ester is hydroxyethyl methacrylate.

The alkyl vinyl ethers are preferably compounds of the formula 3 CH ₂ = CH-OR ⁴ (3) wherein R ^{4 is} C ₁ - to C ₃₀ -alkyl, preferably C ₄ - to C ₁₆ -alkyl, especially C ₆ - to C ₁₂ -alkyl. Examples which may be mentioned are methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether. In a further embodiment, said alkyl groups may be substituted with one or more hydroxyl groups.

at the alkenes are preferably monounsaturated Hydrocarbons having 3 to 30 carbon atoms, in particular 4 to 16 carbon atoms and especially 5 to 12 carbon atoms. Suitable alkenes include propene, butene, isobutylene, pentene, hexene, 4-methylpentene, octene, diisobutylene and norbornene and its derivatives such as methylnorbornene and vinylnorbornene. In a further embodiment the alkyl groups mentioned may be substituted by one or more Be substituted hydroxyl groups.

Particular preference is given to terpolymers which, apart from ethylene, have from 3.5 to 20 mol%, in particular from 8 to 15 mol% of vinyl acetate and from 0.1 to 12 mol%, in particular from 0.2 to 5 mol%, of at least one longer-chain and preferably branched one Vinyl esters such as vinyl 2-ethylhexanoate, vinyl neononanoate or vinyl neodecanoate, the total comonomer content of the terpolymers preferably being between 8 and 21 mol%, in particular between 12 and 18 mol%. In addition to ethylene and 8 to 18 mol% of vinyl esters of C ₂ -C ₁₂ -carboxylic acids, further particularly preferred copolymers still contain from 0.5 to 10 mol% of olefins such as propene, butene, isobutylene, hexene, 4-methylpentene, octene, diisobutylene and / or norbornene.

Preferably, these ethylene-co- and terpolymers have melt viscosities at 140 ° C of 20 to 10,000 m · Pas, in particular from 30 to 5,000 m · Pas, especially from 50 to 2,000 m · Pas. The means of ¹ H-NMR spectroscopy, certain degrees of branching are preferably between 1 and 9 CH _3/100 CH ₂ groups, especially between 2 and 6 CH _3/100 CH ₂ groups, which do not stem from the comonomers.

Prefers are mixtures of two or more of the above-mentioned ethylene copolymers used. Particularly preferably, the mixtures differ underlying polymers in at least one characteristic. For example, they can contain different comonomers, different comonomer contents, molecular weights and / or degrees of branching exhibit.

The Mixing ratio between the invention Additives and ethylene copolymers as component III may vary depending on Use case vary within wide limits, the ethylene copolymers III often represent the larger share. Prefers contain such additive and oil mixtures 0.1 to 25, preferably 0.5 to 10 parts by weight of ethylene copolymers per part by weight the additive combination according to the invention.

Other cold flow improvers which are suitable are oil-soluble polar nitrogen compounds (constituent IV). These are preferably reaction products of fatty amines with compounds containing an acyl group. The preferred amines are compounds 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 ₃₅ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A is a 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 = 2, 3 or 4 and Y and Z independently of one another are H, C ₁ -C ₃₀ -alkyl or - (AO) _x . Also polyamines of the formula - [N- (CH ₂ ) _n ] _m -NR ⁶ R ⁷ , in which m is a number between 1 and 20 and n, R ⁶ and R ^{7 have} the meanings given above, are suitable as fatty amines , The alkyl and alkenyl radicals can be linear or branched and contain up to two double bonds. They are preferably linear and substantially saturated, ie they have iodine numbers of less than 75 gl ₂ / g, preferably less than 60 gl ₂ / g and in particular between 1 and 10 gl ₂ / g. Particularly preferred are secondary fatty amines in which two of the groups R ⁶ , R ⁷ and R ^{8 are} C ₈ -C ₃₅ -alkyl, C ₆ -C ₃₆ -cycloalkyl, C ₈ -C ₃₈ -alkenyl, in particular C ₁₂ -C ₂₄ alkyl, C ₁₂ -C ₂₄ alkenyl or cyclohexyl. Suitable fatty amines are, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, behenylamine, didecylamine, didodecylamine, ditetradecylamine, dihexadecylamine, dioctadecylamine, dieicosylamine, dibehenylamine and mixtures thereof. Specifically, the amines contain chain cuts based on natural raw materials such. Cocosfettamine, tallow fatty amine, hydrogenated tallow fatty amine, dicocosfettamine, ditallow fatty amine and di (hydrogenated tallow fatty amine). Particularly preferred amine derivatives are amine salts, imides and / or amines such as, for example, amide ammonium salts of secondary fatty amines, especially dicocosfettamine, ditallow fatty amine and distearylamine.

By acyl group is meant here a functional group of the following formula: > C = O

Suitable carbonyl compounds for the reaction with amines are both monomeric and polymeric compounds having one or more carboxyl groups. In the case of the monomeric carbonyl compounds, preference is given to those having 2, 3 or 4 carbonyl groups. They can also contain heteroatoms such as oxygen, sulfur and nitrogen. Examples of suitable carboxylic acids are maleic, fumaric, crotonic, itaconic, succinic, C ₁ -C ₄₀ -alkenylsuccinic, adipic, glutaric, sebacic, and malonic acids and benzoic, phthalic, trimellitic and pyromellitic acid, nitrilotriacetic acid , Ethylenediaminetetraacetic acid and their reactive derivatives such as esters, anhydrides and acid halides. Copolymers of ethylenically unsaturated acids, such as, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, have proven particularly suitable as polymeric carbonyl compounds, particular preference is given to copolymers of maleic anhydride. Suitable comonomers are those which impart oil solubility to the copolymer. Oil-soluble means here that the copolymer dissolves without residue in the middle distillate to be additive after reaction with the fatty amine in practice-relevant metering rates. Suitable comonomers are, for example, olefins, alkyl esters of acrylic acid and methacrylic acid, alkyl vinyl esters and alkyl vinyl ethers having 2 to 75, preferably 4 to 40 and in particular 8 to 20 carbon atoms in the alkyl radical. In the case of olefins, the carbon number refers to the alkyl radical attached to the double bond. The molecular weights of the polymeric carbonyl compounds are preferably between 400 and 20,000, more preferably between 500 and 10,000, for example between 1,000 and 5,000.

Oil-soluble polar nitrogen compounds which have been 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 have proved particularly suitable (cf. US 4 211 534 ). Similarly, amides and ammonium salts of aminoalkylene polycarboxylic acids such as nitrilotriacetic acid or ethylenediaminetetraacetic acid with secondary amines are suitable as oil-soluble polar nitrogen compounds (cf. EP 0 398 101 ). Other oil-soluble polar nitrogen compounds are copolymers of maleic anhydride with α, β-unsaturated compounds, which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols (cf. EP-A-0 154 177 . EP-0 777 712 ), the reaction products of Alkenylspirobislactonen with amines (see. EP-A-0 413 279 B1 ) and after EP-A-0 606 055 A2 Reaction products of terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. The mixing ratio between the inventive ethylene copolymers III and oil-soluble polar nitrogen compounds as constituent IV may vary depending on the application. Such additive mixtures preferably contain 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on the active compounds, of at least one oil-soluble polar nitrogen compound per part by weight of the additive combination according to the invention.

Also suitable as flow improvers are alkylphenol-aldehyde resins as constituent V. These are, in particular, those alkylphenol-aldehyde resins which are derived from alkylphenols having one or two alkyl radicals in ortho and / or para position to the OH group. Particularly preferred starting materials are alkylphenols which contain at least two hydrogen atoms capable of condensation with aldehydes on the aromatic and in particular monoalkylated phenols. Particularly preferably, the alkyl radical is in the para position to the phenolic OH group. The alkyl radicals (which are generally understood to mean hydrocarbon radicals as defined below for the constituent V) may be the same or different in the alkylphenol-aldehyde resins which can be used in the process according to the invention, they may be saturated or unsaturated and have preferably 1-20, in particular 4-16 such as 6-12 carbon atoms; it is preferably n-, iso- and tert-butyl, n- and iso-pentyl, n- and iso-hexyl, n- and iso-octyl, n- and iso-nonyl-, n - and iso-decyl, n- and iso-dodecyl, tetradecyl, hexadecyl, octadecyl, tripropenyl, tetrapropenyl, poly (propenyl) - and poly (isobutenyl) radicals. In a preferred embodiment, mixtures of alkylphenols having different alkyl radicals are used for the preparation of the alkylphenol resins. For example, resins based on butyphenol on the one hand and octyl, nonyl and / or dodecylphenol in a molar ratio of 1:10 to 10: 1 on the other hand have proven particularly useful.

suitable Alkylphenol resins can also structural units more Phenol analogs such as salicylic acid, hydroxybenzoic acid and their derivatives such as esters, amides and salts or contain insist on them.

suitable Aldehydes for the alkylphenol-aldehyde resins are those with 1 to 12 carbon atoms and preferably those having 1 to 4 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-ethylhexanal, benzaldehyde, glyoxylic acid and their reactive Equivalents such as paraformaldehyde and trioxane. Especially preferred is formaldehyde in the form of paraformaldehyde and especially formalin.

The by gel permeation chromatography against poly (styrene) standards in THF measured molecular weight of the alkylphenol-aldehyde resins is preferably 500-25,000 g / mol, especially preferably 800-10,000 g / mol and especially 1,000-5,000 g / mol such as 1500-3000 g / mol. requirement is here that the alkylphenol-aldehyde resins at least in application-relevant Concentrations of 0.001 to 1 wt% oil-soluble are.

worin R¹² für C₁-C₁₈-Alkyl oder -Alkenyl, O-R¹³ oder O-C(O)-R¹³, R¹³ für C₁-C₁₈-Alkyl oder -Alkenyl und n für eine Zahl von 2 bis 100 steht, enthalten. R¹³ steht bevorzugt für C₁-C₁₈-Alkyl oder -Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder -Alkenyl wie beispielsweise für C₆-C₁₂-Alkyl oder -Alkenyl. Besonders bevorzugt steht R¹² für C₁-C₁₈-Alkyl oder -Alkenyl und insbesondere für C₄-C₁₆-Alkyl oder -Alkenyl wie beispielsweise für C₅-C₁₂-Alkyl oder -Alkenyl. Bevorzugt steht n für eine Zahl von 2 bis 50 und speziell für eine Zahl von 3 bis 25 wie beispielsweise eine Zahl von 5 bis 15.In a preferred embodiment of the invention, these are alkylphenol-formaldehyde resins which contain oligomers or polymers having a repeating structural unit of the formula (3)

wherein R ^{12 is} C ₁ -C ₁₈ alkyl or alkenyl, OR ¹³ or OC (O) -R ¹³ , R ^{13 is} C ₁ -C ₁₈ alkyl or alkenyl and n is a number from 2 to 100, contain. R ¹³ is preferably C ₁ -C ₁₈ -alkyl or -alkenyl and in particular C ₄ -C ₁₆ -alkyl or -alkenyl, for example C ₆ -C ₁₂ -alkyl or -alkenyl. R ^{12 is} particularly preferably C ₁ -C ₁₈ -alkyl or -alkenyl and in particular C ₄ -C ₁₆ -alkyl or -alkenyl, for example C ₅ -C ₁₂ -alkyl or -alkenyl. Preferably, n is a number from 2 to 50 and especially a number from 3 to 25, such as a number from 5 to 15.

These Alkylphenol-aldehyde resins are also according to the above for the compounds B) described methods accessible

beschrieben werden. Darin bedeuten

Q

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

D

H, CH₃, A oder R'';

E

H, A;

G

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

M

H, COOR'', OCOR'', OR'', COOH;

N

H, R'', COOR'', OCOR, einen Arylrest;

R''

eine Kohlenwasserstoffkette mit 8 bis 18, bevorzugt 10 bis 16 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.

Also suitable as flow improvers comb polymers (component VI), for example, by the formula (4)

to be discribed. Mean in it

Q

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

D

H, CH _3, A or R '';

e

H, A;

G

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

M

H, COOR '', OCOR '', OR '', COOH;

N

H, R ", COOR", OCOR, an aryl radical;

R ''

a hydrocarbon chain having 8 to 18, preferably 10 to 16 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.

Suitable comb polymers are, for example, copolymers of ethylenically unsaturated dicarboxylic acids such as maleic or fumaric acid with other ethylenically unsaturated monomers such as olefins or vinyl esters. Particularly suitable olefins are α-olefins having 10 to 18 and especially 12 to 16 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and mixtures thereof. Even longer-chain olefins based on oligomerized C ₂ -C ₅ -olefins such as poly (isobutylene) with a high proportion of terminal double bonds are suitable as comonomers. A particularly suitable vinyl ester is, for example, vinyl acetate. Usually, these copolymers are at least 50% esterified with alcohols having 10 to 18 and especially 12 to 16 carbon atoms. Suitable alcohols include n-decan-1-ol, n-dodecan-1-ol, n-tetradecan-1-ol, n-hexadecan-1-ol, n-octadecan-1-ol and mixtures thereof. Particular preference is given to mixtures of n-tetradecan-1-ol and n-hexadecan-1-ol. Also suitable as comb polymers are poly (alkyl acrylates), poly (alkyl methacrylates) and poly (alkyl vinyl ethers) derived from alcohols having 10 to 18 and especially 12 to 16 carbon atoms, and poly (vinyl esters) derived from fatty acids having 10 to Derive 18 and especially 12 to 16 carbon atoms.

Farther suitable as flow improvers are oil-soluble Polyoxyalkylene compounds (component VII) such as Esters, ethers and ether / esters of polyols containing at least one Carry alkyl radical having 12 to 30 carbon atoms. In a preferred embodiment For example, the oil-soluble polyoxyalkylene compounds have at least 2, such as 3, 4 or 5 aliphatic hydrocarbon radicals. These radicals preferably have 16 independently of one another to 26 C atoms, such as 17 to 24 C atoms. Preferred are these residues of the oil-soluble polyoxyalkylene compounds linear. Further preferably, they are largely saturated, in particular, these are alkyl radicals. Esters are special prefers.

Particularly according to the invention suitable polyols are polyethylene glycols, polypropylene glycols, Polybutylene glycols and their copolymers having a molecular weight from about 100 to about 5,000 g / mol, preferably from 200 to 2,000 g / mol. In a particularly preferred embodiment are derived the oil-soluble polyoxyalkylene compounds of Polyols with 3 or more OH groups, preferably of polyols with From 3 to about 50 OH groups such as 4 to 10 OH groups in particular of neopentyl glycol, glycerol, trimethylolethane, Trimethylolpropane, sorbitan, pentaerythritol, as well as the resulting Condensation accessible oligomers having 2 to 10 monomer units such as As polyglycerol. Also higher polyols such as Sorbitol, sucrose, glucose, fructose and their oligomers such as For example, cyclodextrin are suitable as polyols, if their esterified or etherified alkoxylates at least in application-relevant Quantities are oil-soluble.

preferred Polyoxyalkylene compounds thus have a branched polyoxyalkylene nucleus, at the multiple oil solubility conferring alkyl radicals are bound.

The Polyols are generally preferred with 3 to 70 moles of alkylene oxide 4 to 50, especially 5 to 20 moles of alkylene oxide per hydroxyl group reacted of the polyol. Preferred alkylene oxides are ethylene oxide, propylene oxide and / or butylene oxide. The alkoxylation is carried out by known methods.

The fatty acids which are suitable for the esterification of the alkoxylated polyols preferably have 12 to 30 and in particular 16 to 26 C atoms. Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic, oleic and erucic acid, palmitoleic, myristoleic, ricinoleic acid and natural fats and oils derived fatty acid mixtures. Preferred fatty acid mixtures contain more than 50 mol% of fatty acids having at least 20 carbon atoms. Preferably, less than 50 mol% of the fatty acids used for the esterification contain double bonds, in particular less than 10 mol%; specifically, they are largely saturated. The esterification can also take off proceeding from reactive derivatives of the fatty acids such as esters with lower alcohols (for example methyl or ethyl esters) or anhydrides.

Under is largely saturated in the sense of the present Invention, an iodine value of the fatty acid or the used used fatty alcohol of up to 5 g I per 100 g fatty acid or fatty alcohol understood.

Examples of suitable polybasic carboxylic acids are dimer fatty acids, alkenylsuccinic acids and aromatic polycarboxylic acids and derivatives thereof such as anhydrides and C ₁ - to C ₅ -esters. Alkenylsuccinic acid and its derivatives with alkyl radicals having 8 to 200, in particular 10 to 50, carbon atoms are preferred. Examples are dodecenyl, octadecenyl and poly (isobutenyl) succinic anhydride. The polybasic carboxylic acids are preferably used here to lower levels of up to 30 mol%, preferably 1 to 20 mol%, in particular 2 to 10 mol%.

ester and fatty acid are used for the esterification on the content of hydroxyl groups on the one hand and carboxyl groups on the other hand in a ratio of 1.5: 1 to 1: 1.5, preferably in the ratio 1.1: 1 to 1: 1.1 and in particular equimolar. The acid number of the esters formed is in Generally below 15 mg KOH / g, preferably below 10 mg KOH / g especially below 5 mg KOH / g. The OH number of the esters is preferably less than 20 mg KOH / g and especially below 10 mg KOH / g.

In A preferred embodiment is after the alkoxylation of the polyol, the terminal hydroxyl groups, for example by oxidation or by reaction with dicarboxylic acids converted into terminal carboxyl groups. By reaction with fatty alcohols with 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms are also inventive Polyoxyalkylenester obtained. Preferred fatty alcohols or fatty alcohol mixtures contain more than 50 mol% of fatty alcohols with at least 20 C atoms. Preferably, less than 50 mol% of those used for esterification Fatty alcohols double bonds, in particular less than 10 mol%; specifically, they are largely saturated. Also esters alkoxylated Fatty alcohols with fatty acids, the above proportions containing poly (alkylene oxides) and their fatty alcohol and fatty acid above alkyl chain lengths and saturation levels own, are suitable according to the invention.

Of others may be the alkoxylated polyols described above by etherification with fatty alcohols with 8 to 50, in particular 12 to 30, especially 16 to 26 carbon atoms in accordance with the invention Polyoxyalkylenverbindungen be transferred. The For this preferred fatty alcohols are linear and largely saturated. Preferably, the etherification is complete or at least largely complete. The etherification becomes known Procedure performed.

Particularly preferred polyoxyalkylene compounds are derived from polyols having 3, 4 and 5 OH groups, which carry about 5 to 10 mol of structural units derived from ethylene oxide per hydroxyl group of the polyol and are largely completely esterified with largely saturated C ₁₇ -C ₂₄ fatty acids. Further particularly preferred polyoxyalkylene compounds are polyethylene glycols which have been esterified with largely saturated C ₁₇ -C ₂₄ -fatty acids and have molecular weights of about 350 to 1,000 g / mol. Examples of particularly suitable polyoxyalkylene compounds are stearic and especially behenic acid esterified polyethylene glycols having molecular weights between 350 and 800 g / mol; Neopentyl glycol 14-ethylene oxide distearate (neopentyl glycol alkoxylated with 14 moles of ethylene oxide and then esterified with 2 moles of stearic acid), and especially neopentyl glycol 14-ethylene oxide dibehenate; Glycerol 20-ethylene oxide tristearate, glycerol 20-ethylene oxide dibehenate, and especially glycerol 20-ethylene oxide tribehenate; Trimethylolpropane-22-ethylenoxidtribehenat; Sorbitan 25-ethylene oxide tristearate, sorbitan 25-ethylene oxide tetrastearate, sorbitan 25 ethylene oxide tribehenate, and especially sorbitan 25 ethylene oxide tetrabehenate; Pentaerythritol-30-ethylene oxide tribehenate, pentaerythritol-30-ethylene oxide tetrastearate and especially pentaerythritol-30-ethylene oxide tetrabehenate and pentaerythritol-20-ethylene oxide-10-propylene oxide tetrabehenate.

The Mixing ratio between the invention Additives and the other ingredients V, VI and VII is in general in each case between 1:10 and 10: 1, preferably between 1: 5 and 5: 1.

Just Detergent additive A) and Nucleator B) containing inventive Additives preferably contain 10-90 wt .-% and in particular 20-80% by weight, such as 30-70% by weight of detergent additive A) and 10-90% by weight and in particular 20-80% by weight such as 30-70% by weight of Nucleator B). If so another cold flow improver C) is present the additives preferably 15-80 wt .-%, preferably 20-70 % By weight of detergent additive A), 2-40% by weight, preferably 5-25 Wt .-% Nucleator B) and 15-80 wt .-%, preferably 20-70 % By weight of cold flow improver C).

The Additives of the invention are for the purpose of simpler Handling preferably used as concentrates containing 10 to 95 wt .-% and preferably from 20 to 80% by weight, for example from 25 to 60% by weight. Containing solvents. Preferred solvents are higher-boiling aliphatic, aromatic hydrocarbons, Alcohols, esters, ethers and mixtures thereof. Preferably contain such Concentrates 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight such as 0.1 to 3 parts by weight of the comb polymer B) per Part by weight of detergent additive A).

The Nucleators B) according to the invention improve this Response of detergent-containing middle distillates such as kerosene, jet fuel, diesel and fuel oil for conventional Flow improver with regard to the lowering of pour point and CFPP value as well as the improvement of the paraffin dispersion.

Particularly preferred mineral oil distillates are middle distillates. The middle distillate is in particular those mineral oils which are obtained by distillation of crude oil, boiling in the range of about 150 to 450 ° C and in particular in the range of about 170 to 390 ° C, for example kerosene, jet fuel, diesel and fuel oil. Typically, middle distillates contain about 5 to 50 wt .-%, such as about 10 to 35 wt .-% n-paraffins, of which the longer-chain crystallize on cooling and can affect the flowability of the middle distillate. Particularly advantageous are the compositions of the invention in middle aromatics with low aromatic content of less than 21 wt .-%, such as less than 19 wt .-%. The compositions according to the invention are furthermore particularly advantageous in low boiling end middle distillates, ie in middle distillates which have 90% distillation points below 360 ° C., in particular 350 ° C. and in special cases below 340 ° C. and further in such middle distillates, the boiling ranges have between 20 and 90% distillation volume of less than 120 ° C and in particular of less than 110 ° C. By aromatic compounds is meant the sum of mono-, di- and polycyclic aromatic compounds as determined by HPLC according to DIN EN 12916 (Edition 2001) is determinable. The middle distillates may also contain minor amounts, for example up to 40% by volume, preferably 1 to 20% by volume, especially 2 to 15, for example 3 to 10% by volume of the oils of animal and / or vegetable origin described in more detail below such as fatty acid methyl esters.

The Compositions of the invention are also for improving the cold properties of detergent additives containing fuels based on renewable raw materials (biofuels) suitable. Biofuels are oils, from animal and preferably from vegetable material or Both are obtained as well as derivatives thereof, which as fuel and in particular be used as diesel or fuel oil can. These are in particular triglycerides of fatty acids with 10 to 24 C atoms as well as those from them lower fatty acid esters accessible by transesterification Alcohols such as methanol or ethanol.

Examples suitable biofuels are rapeseed oil, coriander oil, Soybean oil, cottonseed oil, sunflower oil, Castor oil, olive oil, peanut oil, corn oil, Almond oil, palm kernel oil, coconut oil, mustard seed oil, Beef tallow, bone oil, fish oils and used Edible oils. Other examples include oils one that is made of wheat, jute, sesame, shea nut, arachis oil and derive linseed oil. Also called biodiesel Fatty acid alkyl esters can be made from these oils be derived by methods known in the art. Rapeseed oil containing a mixture of glycerol esterified Fatty acids is preferred as it is in large quantities Quantities is available and in a simple manner by squeezing of rapeseed is available. Furthermore, they are also widespread oils of sunflowers, palm trees and soybeans and their mixtures with rapeseed oil preferred.

Especially suitable as biofuels are lower alkyl esters of fatty acids. Here come, for example, commercial mixtures of Ethyl, propyl, butyl and especially methyl esters of fatty acids with 14 to 22 carbon atoms, for example of lauric acid, Myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, Elaidic acid, petroselinic acid, ricinoleic acid, Elaeostearic acid, linoleic acid, linolenic acid, Eicosanoic acid, gadoleic acid, docosanoic acid or erucic acid. Preferred esters have one Iodine number from 50 to 150 and in particular from 90 to 125. Mixtures with particularly advantageous properties are those which are mainly d. H. at least 50% by weight of methyl esters of fatty acids with 16 to 22 carbon atoms and 1, 2 or 3 double bonds contain. The preferred lower alkyl esters of fatty acids are the methyl esters of oleic acid, linoleic acid, Linolenic acid and erucic acid.

The additives can be used alone or together with other additives, for. With other pour point depressants or dewaxing aids, with other detergents, with antioxidants, cetane number improvers, dehazers, demulsifiers, dispersants, defoamers, dyes, corrosion inhibitors, lubricity additives, sludge inhibitors, odorants and / or additives for lowering the Cloud point.

Examples

Improvement of the cold flowability of middle distillates

to Assessment of the effect of the invention Additives to the cold flow properties of middle distillates were detergent additives (A) with different nucleators (B) and further flow improvers (C) with the below Characteristics used.

The suppression of the negative effect of the detergent additives A) on known cold flow improvers for mineral oils and mineral oil distillates by nucleators is firstly determined by the CFPP test (cold filter plugging test according to US Pat EN 116 ).

Furthermore, the paraffin dispersion in middle distillates is determined in the short sediment test as follows:
150 ml of the middle distillates mixed with the additive components indicated in the table were cooled to -13 ° C. in a cold cabinet at -2 ° C./hour in 200 ml graduated cylinders and stored at this temperature for 16 hours. Subsequently, the volume and appearance of both the sedimented paraffin phase and the oil phase above are visually determined and assessed. A small amount of sediment and a cloudy oil phase show a good paraffin dispersion.

In addition, immediately after cold storage, the lower 20 vol .-% isolated and the cloud point according to IP 3015 certainly. Only a small deviation of the cloud point of the lower phase (CP _KS ) from the blank value of the oil shows a good paraffin dispersion.

Table 1: Characterization of the test oils:

The test oils used were current middle distillates from European refineries. The determination of the CFPP value was carried out according to EN 116 and the determination of the cloud point according to ISO 3015 , The determination of the aromatic hydrocarbon groups was carried out according to DIN EN 12916 (Issue November 2001) Test oil 1 Test oil 2 Test oil 3 distillation IBP [° C] 20% [° C] 90% [° C] (90-20)% [° C] FBP [° C] 192 250 322 72 347 186 222 324 102 352 165 228 335 107 359 Cloud Point [° C] -8.0 -8.9 -4.4 CFPP [° C] -10 -10 -5 Density @ 15 ° C [g / cm ³ ] 0.835 .8307 .8273 Sulfur content [ppm] <10 <10 15 Aromatic content [wt%] thereof mono [wt%] di [wt%] poly [wt%] 19.6 18.0 1.6 <0.1 18.8 18.2 0.6 <0.1 22.8 20.6 2.1 0.1

The following additives were used:

(A) Characterization of the used detergent additives

When Detergent additives A were various listed in Table 2 Reaction products of alkenylsuccinic anhydrides (ASA) based on highly reactive polyolefins (proportion of terminal Double bonds> 90%; Maleinierungsgrad about 1.2 to 1.3) used with polyamines.

Alkenyl succinic anhydride and polyamine were reacted thereto in a molar ratio of 1.0 to 1.5 moles alkenyl succinic anhydride per mole of polyamine (see Table 2). For better meterability, the detergent additives were used as 33% solutions in higher boiling aromatic solvent. The dosage rates given in Tables 2 to 4 for the detergent additives A) and nucleators B) relate to the active ingredients used.

(B) Characterization of the used nucleators

• B1) Alternating copolymer of maleic anhydride and a mixture of equal parts C ₂₂ - and C ₂₄ -α-olefin, esterified with 1.5 moles per mole of anhydride groups of a mixture of equal parts eicosanol and docosanol, 50% in higher boiling aromatic solvent
• B2) C _20-24 alkylphenol-formaldehyde resin, 50% in higher boiling aromatic solvent
• (C) Characterization of the further flow improvers used
• C1) terpolymer of ethylene, 13 mol% vinyl acetate and 2 mol% Neodecanoic acid vinyl ester with a measured at 140 ° C. Melt viscosity V140 of 95 mPas, 65% in kerosene
• C2) mixture of equal parts of C1) and a copolymer of Ethylene and 13.5 mol% vinyl acetate with one at 140 ° C measured melt viscosity V140 of 125 m · Pas, 56% in kerosene.
• C3) Mixture of 2 parts of reaction product of a copolymer from C14 / C16 α-olefin and maleic anhydride with 2 equivalents of hydrogenated ditallow fatty amine with one part of nonylphenol-formaldehyde resin, 50% in higher boiling aromatic solvent.
• C4) Reaction product of ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine to the amide ammonium salt prepared according to EP 0 398 101 , 50% in higher boiling aromatic solvent.
• C5) mixture of equal parts of a reaction product of phthalic anhydride and 2 equivalents of di (hydrogenated tallow fat) amine with a copolymer from fumaric acid ditetradecyl ester, 50% in higher boiling aromatic solvent.

The Determination of CFPP values in test oil 1 was carried out after addition of the oil with 200 ppm C2 and 150 ppm C3.

Tabelle 3: Kaltfließverbesserung in Testöl 2 Beispiel Additive Testöl 2 CFPP [°C] A B C 14 (Vgl.) - - 75 ppm C2 - –14 15 (Vgl.) - - 100 ppm C2 - –19 16 (Vgl.) - - 150 ppm C1 - –20 17 (Vgl.) - - 75 ppm C1 150 ppm C3 –21 18 (Vgl.) - - 100 ppmC1 150 ppm C3 –29 19 (Vgl.) - - 150 ppm C1 150 ppm C3 –31 20 (Vgl.) 50 ppm A1 - 75 ppm C1 150 ppm C3 –14 21 (Vgl.) 50 ppm A1 - 100 ppm C1 150 ppm C3 –19 22 (Vgl.) 50 ppm A1 - 150 ppm C1 150 ppm C3 –20 23 (Vgl.) 50 ppm A1 - 150 ppm C1 250 ppm C3 –20 24 50 ppm A1 30 ppm B1 75 ppm C1 150 ppm C3 –20 25 50 ppm A1 40 ppm B1 100 ppm C1 150 ppm C3 –30 26 50 ppm A1 40 ppm B1 100 ppm C1 150 ppm C3 –31 27 (Vgl.) 50 ppm A2 - 75 ppm C1 150 ppm C4 –15 28 (Vgl.) 50 ppm A2 - 100 ppm C1 150 ppm C4 –12 29 (Vgl.) 50 ppm A2 - 150 ppm C1 150 ppm C4 –20 30 (Vgl.) 50 ppm A2 - 150 ppm C1 250 ppm C4 –21 31 50 ppm A2 30 ppm B1 75 ppm C1 150 ppm C4 –22 32 50 ppm A2 30 ppm B1 100 ppm C1 150 ppm C4 –29 33 50 ppm A2 30 ppm B2 75 ppm C1 150 ppm C4 –21 Tabelle 4: Kaltfließverbesserung in Testöl 3 Beispiel Additive [ppm] Testöl 3 (CP –4,4°C) A B C D CFPP [°C] Sediment [Vol.-%] Aussehen Ölphase CP_KS [°C] 34 (Vgl.) - - 400 C2 200 C3 –20 2 trüb –3,1 35 (Vgl.) - - 535 C2 265 C3 –22 2 trüb –3,2 36 (Vgl.) 40 A2 - 400 C2 200 C3 –17 20 wolkig 0,2 37 (Vgl.) 40 A2 - 535 C2 265 C3 –18 10 wolkig –1,2 38 40 A2 25 B1 400 C2 200 C3 –21 0 trüb –2,9 39 40 A2 25 B1 535 C2 265 C3 –22 0 trüb –3,1 41 40 A2 25 B2 400 C2 200 C3 –19 2 trüb –2,8 42 40 A2 25 B2 535 C2 265 C3 –22 2 trüb –3,1 43 (Vgl.) - - 400 C3 200 C5 –19 4 trüb –2,8 44 (Vgl.) 50 A1 - 400 C3 200 C5 –15 30 fast klar 0,8 45 50 A1 30 B1 400 C3 200 C5 –19 2 trüb –2,7 In the examples of Tables 3 and 4, the reaction product of poly (isobutenyl) -succinic anhydride and pentaethylenehexamine according to Table 2, Example 4 was used as detergent additive A1 and the reaction product of poly (isobutenyl) succinic anhydride and pentaethylenehexamine according to Table 2, Example 13 as detergent additive A2 ,

Table 3: Cold Flow Improvement in Test Oil 2 example additives Test Oil 2 CFPP [° C] A B C 14 (Cf.) - - 75 ppm C2 - -14 15 (Cf.) - - 100 ppm C2 - -19 16 (Cf.) - - 150 ppm C1 - -20 17 (Cf.) - - 75 ppm C1 150 ppm C3 -21 18 (Cf.) - - 100 ppm C1 150 ppm C3 -29 19 (See) - - 150 ppm C1 150 ppm C3 -31 20 (Cf.) 50 ppm A1 - 75 ppm C1 150 ppm C3 -14 21 (Cf.) 50 ppm A1 - 100 ppm C1 150 ppm C3 -19 22 (See) 50 ppm A1 - 150 ppm C1 150 ppm C3 -20 23 (Cf.) 50 ppm A1 - 150 ppm C1 250 ppm C3 -20 24 50 ppm A1 30 ppm B1 75 ppm C1 150 ppm C3 -20 25 50 ppm A1 40 ppm B1 100 ppm C1 150 ppm C3 -30 26 50 ppm A1 40 ppm B1 100 ppm C1 150 ppm C3 -31 27 (Cf.) 50 ppm A2 - 75 ppm C1 150 ppm C4 -15 28 (Cf.) 50 ppm A2 - 100 ppm C1 150 ppm C4 -12 29 (Cf.) 50 ppm A2 - 150 ppm C1 150 ppm C4 -20 30 (Cf.) 50 ppm A2 - 150 ppm C1 250 ppm C4 -21 31 50 ppm A2 30 ppm B1 75 ppm C1 150 ppm C4 -22 32 50 ppm A2 30 ppm B1 100 ppm C1 150 ppm C4 -29 33 50 ppm A2 30 ppm B2 75 ppm C1 150 ppm C4 -21 Table 4: Cold flow improvement in test oil 3 example Additives [ppm] Test oil 3 (CP -4.4 ° C) A B C D CFPP [° C] Sediment [vol.%] Appearance oil phase CP _KS [° C] 34 (Cf.) - - 400 C2 200 C3 -20 2 cloudy -3.1 35 (Cf.) - - 535 C2 265 C3 -22 2 cloudy -3.2 36 (See) 40 A2 - 400 C2 200 C3 -17 20 cloudy 0.2 37 (Cf.) 40 A2 - 535 C2 265 C3 -18 10 cloudy -1.2 38 40 A2 25 B1 400 C2 200 C3 -21 0 cloudy -2.9 39 40 A2 25 B1 535 C2 265 C3 -22 0 cloudy -3.1 41 40 A2 25 B2 400 C2 200 C3 -19 2 cloudy -2.8 42 40 A2 25 B2 535 C2 265 C3 -22 2 cloudy -3.1 43 (Cf.) - - 400 C3 200 C5 -19 4 cloudy -2.8 44 (Cf.) 50 A1 - 400 C3 200 C5 -15 30 almost clear 0.8 45 50 A1 30 B1 400 C3 200 C5 -19 2 cloudy -2.7

The experiments show that the impairment of the cold flow properties such as the CF PP value and the paraffin dispersion of additized with flow improver middle distillates can be compensated only by adding the Nucleatoren invention. By higher dosage of the flow improver alone, this result can not be achieved.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• US 4211534 [0072]
• EP 0398101 [0072, 0107]
• EP 0154177A [0072]
• EP 0777712 [0072]
• - EP 0413279 B1 [0072]
• EP 0606055 A2 [0072]

Cited non-patent literature

• - DIN EN 12916 [0096]
• - EN 116 [0102]
• - IP 3015 [0104]
• - EN 116 [0105]
• - ISO 3015 [0105]
• - DIN EN 12916 [0105]

Claims (29)

Use of at least one oil-soluble, acting as nucleator for paraffin crystallization Compound B) selected from comb polymers, the alkyl side chains with a length of at least 20 carbon atoms, to Improvement of the response of mineral oil flow improvers C), which are different from B), in middle distillates, which are at least an ashless, nitrogen-containing detergent additive A), which is an oil-soluble, amphiphilic compound which comprises at least one alkyl or alkenyl radical attached to a polar group is attached, wherein the alkyl or alkenyl radical 10 to 500 C atoms and the polar group 2 or more nitrogen atoms includes. Use according to claim 1, wherein, based on a Part by weight of the nitrogen-containing detergent additive A), 0.01 to 10 parts by weight of the oil-soluble, as Nucleator paraffin crystallization compound B) be used. Use according to claim 1 and / or 2, wherein the Middle distillate 10 to 10,000 ppm of an ashless nitrogen-containing Detergent additive A) contains. Use according to one or more of the claims 1-3, wherein the ashless nitrogen-containing detergent additive A) has an alkyl radical having 15 to 500 carbon atoms. Use according to claim 4, wherein the alkyl radical of Oligomeric lower olefins having 3 to 6 carbon atoms or mixtures thereof is derived. Use according to claim 5, wherein a mixture of Oligomeric lower olefins having 3 to 6 carbon atoms is used, to more than 70 mol% of 2-methyl-2-butene, 2,3-dimethyl-2-butene and / or isobutene. Use according to one or more of the claims 1-6, wherein the ashless nitrogen-containing detergent additive A) using highly reactive low molecular weight polyolefins with a proportion of terminal double bonds of at least 75 mol% is produced. Use according to one or more of claims 1 to 7, wherein the ashless nitrogen-containing detergent additive A) comprises a polar moiety derived from polyamines of the formula (R ⁹ ) ₂ N- [AN (R ⁹ )] _q - (R ⁹ ) wherein each R ⁹ independently of one another represents hydrogen, an alkyl or hydroxyalkyl radical having up to 24 C atoms, a polyoxyalkylene radical - (AO) _r - or polyiminoalkylene radical - [AN (R ⁹ )] _s - (R ⁹ ) but wherein at least one R ^{9 is} hydrogen, q is an integer from 1 to 19, A is an alkylene radical having 1 to 6 C atoms, and r and s independently of one another are integers from 1 to 50. Use according to claim 8, wherein R ^{9 is} hydrogen and q assumes values of at least 3. Use according to one or more of the claims 1-9, wherein the ashless nitrogen-containing detergent additive A) an oil-soluble alkyl radical and a polar Head group comprises, and the oil-soluble alkyl radical and the polar head group via a C-N or over an ester, amide or imide bond linked together are. Use according to one or more of the claims 1-10, wherein the ashless nitrogen-containing detergent additive A) a mean molecular weight determined by means of vapor pressure osmometry of above 800 g / mol. Use according to one or more of the claims 1 to 11, wherein as cold flow improver C) copolymers of ethylene and 8 to 21 mol% of olefinically unsaturated Compounds selected from vinyl esters, acrylic esters, Methacrylic esters, alkyl vinyl ethers and / or alkenes, for use come, said compounds substituted with hydroxyl groups and one or more of these comonomers in the polymer may be included. Use according to claim 12, wherein as cold flow improver C) copolymers of ethylene and 8 to 21 mol% vinyl esters of formula 1 are used CH ₂ = CH-OCOR ¹ (1) wherein R ^{1 is} C ₁ to C ₃₀ alkyl, and said alkyl groups may be substituted with one or more hydroxyl groups. Use according to claim 13, wherein R ^{1 represents} a branched alkyl radical or a neoalkyl radical having 7 to 11 carbon atoms. Use according to claim 13 and / or 14, wherein the ethylene copolymers contain vinyl acetate and at least one further vinyl ester of formula 1, wherein R ^{1 is} C ₄ to C ₃₀ alkyl. Use according to one or more of claims 1 to 15, wherein as cold flow improver C) oil-soluble polar nitrogen compounds are used, which reaction products of compounds of formula NR ⁶ R ⁷ R ⁸ , wherein R ⁶ , R ⁷ and R ^{8 may be the} same 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, especially 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, in which A is an ethyl or propyl 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 = 2, 3 or 4, and Y and Z independently of one another are H, C ₁ -C ₃₀ -alkyl or - (AO) _x , with compounds which contain at least one acyl group. Use according to one or more of claims 1 to 16, wherein as cold flow improver C) alkylphenol-aldehyde resins are used, which condensation products of alkylphenols with one or two C ₁ -C ₁₈ alkyl or alkenyl in the ortho and / or para position to the OH group with aldehydes having 1 to 12 carbon atoms. Use according to one or more of the claims 1 to 17, which are used as nucleator for paraffin crystallization acting comb polymers a proportion of the alkyl side chains with at least 20 C atoms on the total of the alkyl side chains of the comb polymer of at least 10 mol%. Use according to one or more of the claims 1 to 18, which are used as nucleator for paraffin crystallization acting comb polymers carry side chains with 22 to 60 carbon atoms. Use according to one or more of the claims 1 to 19, wherein the alkyl side chains of the comb polymers are linear. Use according to one or more of the claims 1 to 20, which are used as Nucleator for paraffin crystallization acting comb polymers a backbone of ethylenically unsaturated Monocarboxylic acids, polycarboxylic acids or a Mixture of it contained. Use according to one or more of the claims 1 to 21, wherein the alkyl side chains of the comb polymers via an ester, amide, imide or ammonium group on the polymer backbone are bound. Use according to one or more of the claims 1 to 20 and 22, wherein as Nucleator for paraffin crystallization acting comb polymers derived from alkylaromatic structural units containing polycondensates, the alkyl radicals having at least 20 C atoms have. Use according to claim 23, wherein the alkyl radicals are over a C-C bond or via an ester or ether group are bound to the aromatics. Use according to one or more of the claims 1 to 24, wherein the ratio between detergent additive A) and acting as Nucleator for Paraffinkristallisation Comb polymer B) in the additized oil at 0.01 to 10 parts by weight on nucleator per part by weight of detergent additive, in each case based on the active ingredient, lies. Additives comprising a) at least one ashless nitrogen-containing detergent additive A) which is an oil-soluble, amphiphilic compound comprising at least one alkyl or alkenyl radical attached to a polar group, the alkyl or alkenyl radical being from 10 to 500 carbon atoms. Atoms and the polar group comprises 2 or more nitrogen atoms, and b) at least one oil-soluble compound B) acting as nucleator for paraffin crystallization, selected from comb polymers carrying molar average alkyl side chains of at least 18 carbon atoms in length. Additives according to claim 26, containing one of B) various mineral oil flow improvers C). Additives according to claim 27, wherein the mineral oil flow improver C) from those in one or more of claims 12 to 17 described compounds is selected. Middle distillates with a sulfur content of less than 100 ppm and a 90% distillation point of below 360 ° C, containing a) at least one ash-free, nitrogen-containing Detergent additive A), which is an oil-soluble, amphiphilic compound which has at least one alkyl or alkenyl radical which is bound to a polar group, wherein the alkyl or Alkenylrest 10 to 500 C-atoms and the polar group 2 or comprises more nitrogen atoms, b) at least one oil-soluble, acting as nucleator for paraffin crystallization Compound B) selected from comb polymers, the alkyl side chains with a length of at least 18 carbon atoms in the molar mean, such as c) at least one mineral oil flow improver other than B) C).