EP1803791B1 - Fuel oils with improved lubricity, comprising mixtures of fatty acids and paraffin dispersing agents and an improved lubricity additive - Google Patents

Description

The present invention relates to mixtures of fatty acids and paraffin dispersants having improved low-temperature stability, and to their use for improving the lubricity of middle distillate fuel oils.

Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5% by weight and more sulfur which causes the formation of sulfur dioxide upon combustion. In order to reduce the resulting environmental impact, the sulfur content of fuel oils is lowered further and further. The standard EN 590 relating to diesel fuels currently prescribes a maximum sulfur content of 350 ppm in Germany. In Scandinavia fuel oils of less than 50 ppm and in exceptional cases less than 10 ppm of sulfur are used. These fuel oils are usually prepared by hydrogenating the fractions obtained from the petroleum by distillation. In the desulfurization but other substances are removed, which give the fuel oils a natural lubricating effect. These substances include polyaromatic and polar compounds.

However, it has now been shown that the friction and wear-reducing properties of fuel oils deteriorate with increasing degree of desulfurization. Often, these properties are so poor that on the lubricated by the fuel materials, such as the distributor injection pumps of diesel engines after a short time must be expected with feeding phenomena. The maximum value set for the 95% distillation point of maximum 360 ° C according to EN 590 since 2000 and the further lowering of the 95% distillation point to below 350 ° C, which has meanwhile been carried out in Scandinavia and sometimes below 330 ° C further aggravates this problem.

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

EP-A-0 798 364 discloses salts and amides of mono- to tetracarboxylic acids having 2 to 50 carbon atoms and aliphatic mono- / polyamines having 2 to 50 carbon atoms and 1 to 10 N atoms as lubricity additives for low-sulfur diesel fuel. Preferred amines have 8-20 C-atoms, such as coco fatty amine, tallow fatty amine and oleylamine.

WO 95/33805 discloses the use of cold flow improvers to improve the lubricity of low sulfur middle distillates. Also suitable as suitable substances are polar nitrogen-containing compounds which contain a group NR ¹³ , where R ^{13 is} a hydrocarbon radical having 8 to 40 C atoms and may be present in the form of a cation.

WO-A-96/18706 disclosed in analogy to WO 95/33805 the use of the nitrogen-containing compounds mentioned therein in combination with lubricity additives.

WO-A-96/23855 disclosed in analogy to WO 95/33805 the use of the nitrogen-containing compounds mentioned therein in combination with detergent additives.

The fatty acids used in the prior art have the disadvantage that they solidify when stored at low temperatures, ie often at room temperature, usually at temperatures of 0 ° C at -5 ° C at the latest, or that deposit crystalline particles and problems prepare handling. This problem can only be partially solved by dilution with organic solvents, since components also crystallize out of these solutions or the solution gels and solidifies. For use as lubricity additives, they therefore have to be diluted considerably, or kept in heated storage containers and metered via heated lines.

The effectiveness of cold flow improvers as lubricity additives alone is not sufficient, so that either very high dosage rates or synergists must be used.

The object underlying the present invention was to find lubricity additives which improve the lubricating effect of middle distillates at reduced metering rates, but remain homogeneous, clear and, in particular, free-flowing even in the cold.

It has been found that mixtures of fatty acids with paraffin dispersants in middle distillates effective polar nitrogen-containing compounds even at significantly lower temperatures, sometimes below -20 ° C, in special cases to below -30 ° C and in special cases to below -40 ° C. remain flowable and clear over a longer period of time and moreover improve the lubricating effect of middle distillates more efficiently than pure fatty acids of the prior art.

• A1) 1 bis 99 Gew.-% mindestens einer gesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,
• A2) 1 bis 99 Gew.-% mindestens einer ungesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,
  sowie
• B) mindestens einer als Paraffindispergator in Mitteldestillaten wirksamen polaren stickstoffhaltigen Verbindung in einer Menge von 0,01 bis 90 Gew.-% bezogen auf das Gesamtgewicht von A1), A2) und B), welche eine Verbindung der Formel 11
  
  ist, worin

  R⁶, R⁷

  gleich oder verschieden sein können, und wenigstens eine dieser Gruppen für C₈-C₃₆-Alkyl, C₆-C₃₆-Cycloalkyl oder C₈-C₃₆-Alkenyl steht, und die übrige Gruppe entweder Wasserstoff, C₁-C₃₆-Alkyl, C₂-C₃₆-Alkenyl, Cyclohexyl, oder eine Gruppe der Formeln -(A-O)_x-E oder -(CH₂)_n-NYZ bedeutet, worin A für eine Ethylen- oder Propylengruppe steht, x eine Zahl von 1 bis 50, E = H, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl oder C₆-C₃₀-Aryl, und n 2, 3 oder 4 bedeuten, und Y und Z unabhängig voneinander H, C₁-C₃₀-Alkyl oder -(A-O)_x-H bedeuten,

  R¹⁴

  für CONR⁶R⁷ oder CO₂ ^-+H₂NR⁶R⁷ steht,

  R¹⁵ und R¹⁶

  für H, CONR 17 ₂, CO₂R¹⁷ oder OCOR¹⁷, -OR¹⁷, -R¹⁷ oder -NCOR¹⁷ stehen und

  R¹⁷

  Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl ist und mindestens 10 Kohlenstoffatome aufweist.

The invention thus cold-stabilized additives for fuel oils with up to 0.05 wt .-% sulfur content, containing fatty acid mixtures

• A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid having 6 to 50 carbon atoms,
• A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid having 6 to 50 carbon atoms,
  such as
• B) at least one polar nitrogen-containing compound which acts as paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight, based on the total weight of A1), A2) and B), which is a compound of the formula II
  
  is in which

  R ⁶ , R ⁷

  may be the same or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl or C ₈ -C ₃₆ -alkenyl, and the remainder of the group is 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 of 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 -H,

  R ¹⁴

  stands for CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ ,

  R ¹⁵ and R ¹⁶

  are H, CONR 17 ₂ , CO ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or -NCOR ¹⁷ and

  R ¹⁷

  Alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.

Another object of the invention are cold-stabilized solutions of the additives of the invention in organic solvents, wherein the solutions contain 1 to 90 wt .-% of solvent. Suitable solvents are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures. The additives according to the invention preferably contain 1 to 80%, especially 10 to 70%, in particular 25 to 60%, of solvent. The cold-stabilized solutions according to the invention have an own pour point of less than 40 ° C., preferably -45 ° C., in particular -50 ° C.

• A1) 1 bis 99 Gew.-% mindestens einer gesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,
• A2) 1 bis 99 Gew.-% mindestens einer ungesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,
  sowie
• B) mindestens einer als Paraffindispergator in Mitteldestillaten wirksamen polaren stickstoffhaltigen Verbindung in einer Menge von 0,01 bis 90 Gew.-% bezogen auf das Gesamtgewicht von A1), A2) und B), welche eine Verbindung der Formel 11
  
  ist, worin

  R⁶, R⁷

  gleich oder verschieden sein können, und wenigstens eine dieser Gruppen für C₈-C₃₆-Alkyl, C₆-C₃₆-Cycloalkyl oder C₈-C₃₆-Alkenyl steht, und die übrige Gruppe entweder Wasserstoff, C₁-C₃₆-Alkyl, C₂-C₃₆-Alkenyl, Cyclohexyl, oder eine Gruppe der Formeln -(A-O)_x-E oder -(CH₂)_n-NYZ bedeutet, worin A für eine Ethylen- oder Propylengruppe steht, x eine Zahl von 1 bis 50, E = H, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl oder C₆-C₃₀-Aryl, und n 2, 3 oder 4 bedeuten, und Y und Z unabhängig voneinander H, C₁-C₃₀-Alkyl oder -(A-O)_x-H bedeuten,

  R¹⁴

  für CONR⁶R⁷ oder CO₂ ^-+H₂NR⁶R⁷ steht,

  R¹⁵ und R¹⁶

  für H, CONR¹⁷ ₂, CO₂R¹⁷ oder OCOR¹⁷, -OR¹⁷, -R¹⁷ oder -NCOR¹⁷ stehen und

  R¹⁷

  Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl ist und mindestens 10 Kohlenstoffatome aufweist.

Another object of the invention are cold-stabilized fatty acid mixtures

• A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid having 6 to 50 carbon atoms,
• A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid having 6 to 50 carbon atoms,
  such as
• B) at least one polar nitrogen-containing compound which acts as paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight, based on the total weight of A1), A2) and B), which is a compound of the formula II
  
  is in which

  R ⁶ , R ⁷

  may be the same or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl or C ₈ -C ₃₆ -alkenyl, and the remainder of the group is 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 of 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 -H,

  R ¹⁴

  stands for CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ ,

  R ¹⁵ and R ¹⁶

  are H, CONR ¹⁷ ₂ , CO ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or -NCOR ¹⁷ and

  R ¹⁷

  Alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.

• A1) 1 bis 99 Gew.-% mindestens einer gesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,
• A2) 1 bis 99 Gew.-% mindestens einer ungesättigten Mono- oder Dicarbonsäure mit 6 bis 50 Kohlenstoffatomen,
  sowie
• B) mindestens einer als Paraffindispergator in Mitteldestillaten wirksamen polaren stickstoffhaltigen Verbindung in einer Menge von 0,01 bis 90 Gew.-% bezogen auf das Gesamtgewicht von A1), A2) und B), welche eine Verbindung der Formel 11
  
  ist, worin

  R⁶, R⁷

  gleich oder verschieden sein können, und wenigstens eine dieser Gruppen für C₈-C₃₆-Alkyl, C₆-C₃₆-Cycloalkyl oder C₈-C₃₆-Alkenyl steht, und die übrige Gruppe entweder Wasserstoff, C₁-C₃₆-Alkyl, C₂-C₃₆-Alkenyl, Cyclohexyl, oder eine Gruppe der Formeln -(A-O)_x-E oder -(CH₂)_n-NYZ bedeutet, worin A für eine Ethylen- oder Propylengruppe steht, x eine Zahl von 1 bis 50, E = H, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl oder C₆-C₃₀-Aryl, und n 2, 3 oder 4 bedeuten, und Y und Z unabhängig voneinander H, C₁-C₃₀-Alkyl oder-(A-O)_xH bedeuten,

  R¹⁴

  für CONR⁶R⁷ oder CO₂ ^-+H₂NR⁶R⁷ steht,

  R¹⁵ und R¹⁶

  für H, CONR¹⁷ ₂, CO₂R¹⁷ oder OCOR¹⁷, -OR¹⁷, -R¹⁷ oder -NCOR¹⁷ stehen und

  R¹⁷

  Alkyl, Alkoxyalkyl oder Polyalkoxyalkyl ist und mindestens 10 Kohlenstoffatome aufweist.

Another object of the invention are fuel oils, containing in addition to a middle distillate with up to 0.05 wt .-% sulfur content of fatty acid mixtures

• A1) 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid having 6 to 50 carbon atoms,
• A2) 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid having 6 to 50 carbon atoms,
  such as
• B) at least one polar nitrogen-containing compound which acts as paraffin dispersant in middle distillates in an amount of 0.01 to 90% by weight, based on the total weight of A1), A2) and B), which is a compound of the formula II
  
  is in which

  R ⁶ , R ⁷

  may be the same or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ -C ₃₆ -cycloalkyl or C ₈ -C ₃₆ -alkenyl, and the remainder of the group is 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 of 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 H,

  R ¹⁴

  stands for CONR ⁶ R ⁷ or CO ₂ ^{- +} H ₂ NR ⁶ R ⁷ ,

  R ¹⁵ and R ¹⁶

  are H, CONR ¹⁷ ₂ , CO ₂ R ¹⁷ or OCOR ¹⁷ , -OR ¹⁷ , -R ¹⁷ or -NCOR ¹⁷ and

  R ¹⁷

  Alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.

Another object of the invention is the use of said mixtures of the components A and B to improve the lubricating properties of low-sulfur middle distillates with up to 0.05 wt .-% sulfur content.

Preferred fatty acids (constituent A) are those having 8 to 40 C atoms, in particular 12 to 22 C atoms. The alkyl radicals of the fatty acids consist essentially of carbon and hydrogen. However, they may contain other substituents, e.g. Hydroxyl, halogen, amino or nitro groups, provided they do not affect the predominantly hydrocarbon character.

Component A2) may contain one or more double bonds and be of natural or synthetic origin. In the case of polyunsaturated carboxylic acids, their double bonds may be isolated or else conjugated. The proportion of saturated Fatty acids A1) in the mixture of A1) and A2) is preferably below 20% by weight, in particular below 10% by weight, especially below 5% by weight. In preferred fatty acid mixtures, which is understood here as the combination of A1) and A2), at least 50% by weight, in particular at least 75% by weight, especially at least 90% by weight, of the constituents contain one or more double bonds. These preferred fatty acid (mixtures) have iodine numbers of at least 40 g I / 100 g, preferably at least 80 gl / 100 g, in particular at least 125 g I / 100 g.

Suitable fatty acids are, for example, lauric, tridecane, myristic, pentadecane, palmitic, margarine, stearic, isostearic, arachic and behenic acid, oleic and erucic acid, palmitoleic, myristoleic, linoleic, linolenic, elaeosterol - And arachidonic acid, ricinoleic acid and derived from natural fats and oils fatty acid mixtures, such as Coconut oil, peanut oil, fish, linseed oil, palm oil, rapeseed oil, ricinine, castor oil, rapeseed oil, soybean oil, sunflower oil and tall oil fatty acid.

Also suitable are dicarboxylic acids, such as dimer fatty acids and alkyl- and alkenylsuccinic acids with C ₈ -C ₅₀ -alk (en) yl radicals, preferably with C ₈ -C ₄₀ -, in particular with C ₁₂ -C ₂₂ -alkyl radicals. The alkyl radicals can be linear or branched (oligomerized alkenes, PIB).

The fatty acids may further contain 1-40, especially 1-25% by weight of resin acids, based on the weight of A1) and A2) together.

The additives according to the invention contain as constituent B at least one polar nitrogen-containing compound of the formula II which is active as paraffin dispersant in middle distillates. Preferred. Carboxylic acids or acid derivatives are phthalic acid (anhydride), trimellit, pyromellitic acid (dianhydride), isophthalic acid, terephthalic acid, cyclohexane-dicarboxylic acid (anhydride), maleic acid (anhydride), alkenylsuccinic acid (anhydride). The formulation (anhydride) means that the anhydrides of said acids are also preferred acid derivatives.

When the compounds of formula (11) are amides or amine salts, they are preferably obtained from a secondary amine containing a hydrogen and carbon containing group having at least 10 carbon atoms.

It is preferred that R ^{17 contains from} 10 to 30, in particular from 10 to 22, for example from 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 may be shorter, eg containing less than 6 carbon atoms, or may have at least 10 carbon atoms if desired. Suitable alkyl groups include methyl, ethyl, propyl, hexyl, decyl, dodecyl, tetradecyl, eicosyl and docosyl (behenyl).

Paraffin dispersants reduce the size of paraffin crystals precipitated in the cold and cause the paraffin particles not to settle but to remain colloidally dispersed with significantly reduced sedimentation effort. In addition to compounds of formula 11, oil-soluble polar compounds having ionic or polar groups, for example amine salts and / or amides, which have been prepared by reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, tri - Are obtained or tetracarboxylic acids or their anhydrides. Particularly preferred paraffin dispersants contain reaction products of secondary fatty amines
8 to 36 carbon atoms, especially dicocosfettamine, ditallow fatty amine and distearylamine. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds which can optionally be reacted with primary monoalkylamines and / or aliphatic alcohols, the reaction products of alkenyl spirobislactones with amines and reaction products of terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated alcohols. Alkylphenol-formaldehyde resins are also suitable as paraffin dispersants. In the following, some suitable paraffin dispersants are listed.

1. 1. Umsetzungsprodukte von Alkenyl-spirobislactonen der Formel 4
   
   wobei R jeweils C₈-C₂₀₀-Alkenyl bedeutet, mit Aminen der Formel NR⁶R⁷R⁸. Geeignete Umsetzungsprodukte sind in EP-A-0 413 279 aufgeführt. Je nach Reaktionsbedingung erhält man bei der Umsetzung von Verbindungen der Formel (4) mit den Aminen Amide oder Amid-Ammoniumsalze.
2. 2. Amide bzw. Ammoniumsalze von Aminoalkylenpolycarbonsäuren mit sekundären Aminen der Formeln 5 und 6
   
   
   in denen

   R¹⁰

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

   

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

The following paraffin dispersants become partly by reaction of compounds containing an acyl group, prepared with an amine. This amine is a compound of the formula NR ⁶ R ⁷ R ⁸ , in which R ⁶ , R ⁷ and R ^{8 may be} identical or different, and at least one of these groups is C ₈ -C ₃₆ -alkyl, C ₆ - C ₃₆ -cycloalkyl, C ₈ -C ₃₆ -alkenyl, in particular C ₁₂ -C ₂₄ -alkyl, C ₁₂ -C ₂₄ -alkenyl or cyclohexyl, and the other groups are either hydrogen, C ₁ -C ₃₆ -alkyl, C ₂ -C ₃₆ alkenyl, cyclohexyl, or a group of the formulas - (AO) _x -E or - (CH ₂ ) _n -NYZ, where A is an ethylene or propylene group, x is a number from 1 to 50, E Is H, C ₁ -C ₃₀ -alkyl, C ₅ -C ₁₂ -cycloalkyl or C ₆ -C ₃₀ -aryl, and n is 2, 3 or 4, and Y and Z are each independently H, C ₁ -C ₃₀ - Alkyl or - (AO) _x . By acyl group is meant here a functional group of the following formula:

> C = O

1. 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 in EP-A-0 413 279 listed. Depending on the reaction condition obtained in the reaction of compounds of formula (4) with the amines amides or amide ammonium salts.
2. 2. Amides or ammonium salts of aminoalkylenepolycarboxylic acids with secondary amines of the formulas 5 and 6
   
   
   in which

   R ¹⁰

   a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula 7

   

   in which R ⁶ and R ⁷ denote in particular alkyl radicals having 10 to 30, preferably 14 to 24, C atoms, the amide structures also being partly or completely in the form of the ammonium salt structure of the formula 8
   
   may be present.

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

kommen insbesondere Dialkylamine in Betracht, in denen R⁶, R⁷ einen geradkettigen Alkylrest mit 10 bis 30 Kohlenstoffatomen, vorzugsweise 14 bis 24 Kohlenstoffatomen, bedeutet. Im einzelnen seien Dioleylamin, Dipalmitinamin, Dikokosfettamin und Dibehenylamin und vorzugsweise Ditalgfettamin genannt.As amines of the formula 9

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

Quaternary ammonium salts of formula 10

⁺ NR ⁶ R ⁷ R ⁸ R ¹¹ X ^- (10)

where R ⁶ , R ⁷ , R ^{8 have} the abovementioned meaning and R ^{11 is} C ₁ -C ₃₀ -alkyl, preferably C ₁ -C ₂₂ -alkyl, C ₁ -C ₃₀ -alkenyl, preferably C ₁ -C ₂₂ - Alkenyl, benzyl or a radical of the formula - (CH ₂ -CH ₂ -O) _n -R ¹² wherein R ^{12 is} hydrogen or a fatty acid radical of the formula C (O) -R ¹³ , with R ¹³ = C ₆ -C ₄₀ alkenyl, n is a number from 1 to 30 and X is halogen, preferably chlorine, or a methosulfate.

Examples of such quaternary ammonium salts include: dihexadecyldimethylammonium chloride, distearyldimethylammonium chloride, quaternization products of esters of di- and triethanolamine with long-chain fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid and fatty acid mixtures such as coconut fatty acid, tallow fatty acid, hydrogenated tallow fatty acid, tall oil fatty acid) such as N-methyltriethanolammonium distearyl ester chloride, N-methyltriethanolammonium distearyl ester methosulfate, N, N-dimethyldiethanolammonium distearyl ester chloride, N-methyltriethanolammonium dioleyl ester chloride, N-Methyltriethanolammoniumtrilaurylestermethosulfat, N-Methyltriethanolammoniumtristearylestermethosulfat and mixtures thereof.

Furthermore, polymers are suitable which contain at least one amide or ammonium group bound directly to the skeleton of the polymer, wherein the amide or ammonium group carries at least one alkyl group of at least 8 C atoms on the nitrogen atom. Such polymers can be prepared in various ways. One way is to use a polymer containing several carboxylic acid or anhydride groups and react this polymer with an amine of the formula NHR ⁶ R ⁷ to obtain the desired polymer.

As polymers are generally copolymers of unsaturated esters such as C ₁ -C ₄₀ alkyl (meth) acrylates, fumaric di (C ₁ -C ₄₀ alkyl esters), C ₁ -C ₄₀ alkyl vinyl ethers, C ₁ -C ₄₀ alkyl vinyl esters or C. C ₂ -C ₄₀ -olefins (linear, branched, aromatic) with unsaturated carboxylic acids or their reactive derivatives, such as carboxylic acid anhydrides (acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride) suitable.

Carboxylic acids are preferably reacted with from 0.1 to 1.5 mol, in particular from 0.5 to 1.2 mol of amine per acid group, carboxylic anhydrides, preferably with from 0.1 to 2.5, in particular from 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. Thus, copolymers containing unsaturated carboxylic acid anhydrides, upon reaction with a secondary amine, yield half amide and half amine salts by reaction with the anhydride group. By heating, water can be split off to form the diamide.

• 4. Copolymere (a) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid, oder (b) von Vinylestern, z.B. Vinylacetat oder Vinylstearat mit Maleinsäureanhydrid, oder (c) eines Dialkylfumarats, -maleats, -citraconats oder -itaconats mit Maleinsäureanhydrid und Vinylacetat.

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

• 4. Copolymers of (a) a dialkyl fumarate, maleate, citraconate or itaconate with maleic anhydride, or (b) vinyl esters, for example vinyl acetate or vinyl stearate with maleic anhydride, or (c) a dialkyl fumarate, maleate, citraconate or itaconate Maleic anhydride and vinyl acetate.

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

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

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

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

Examples of suitable secondary amines are dioctylamine and those containing alkyl groups of at least 10 carbon atoms, for example, didecylamine, didodecylamine, dicocosamine (ie, mixed C ₁₂ -C ₁₄ amines), dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approx Wt% nC ₁₄ alkyl, 30 wt% nC ₁₀ alkyl, 60 wt% nC ₁₈ alkyl, the remainder is unsaturated).

Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-Cocospropylenediamine (C ₁₂ / C ₁₄ -alkylpropylenediamine), N-tallowpropylenediamine (C ₁₆ / C ₁₈ -alkylpropylenediamine).

• 5. Copolymere des Styrols, seiner Derivate oder aliphatischer Olefine mit 2 bis 40 C-Atomen, bevorzugt mit 6 bis 20 C-Atomen und olefinisch ungesättigten Carbonsäuren oder Carbonsäureanhydriden, die mit Aminen der Formel HNR⁶R⁷ umgesetzt sind. Die Umsetzung kann vor oder nach der Polymerisation vorgenommen werden.

The amide-containing polymers usually have a number average molecular weight of from 1,000 to 500,000, for example 10,000 to 100,000.

• 5. Copolymers of styrene, its derivatives or aliphatic olefins having 2 to 40 carbon atoms, preferably having 6 to 20 carbon atoms and olefinically unsaturated carboxylic acids or carboxylic anhydrides, which are reacted with amines of the formula HNR ⁶ R ⁷ . The reaction can be carried out before or after the polymerization.

In detail, the structural units of the copolymers are derived from, for example, maleic acid, fumaric acid, tetrahydrophthalic acid, citraconic acid, preferably maleic anhydride. They can be used both in the form of their homopolymers and the copolymers. Suitable comonomers are: styrene and alkylstyrenes, straight-chain and branched olefins having 2 to 40 carbon atoms, and mixtures thereof with one another. Examples include: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, ethylene, propylene, n-butylene, diisobutylene, decene, dodecene, tetradecene, hexadecene, octadecene. Preference is given to styrene and isobutene, particular preference to styrene.

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

The reaction of the polymers or copolymers with the amines is carried out at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is thereby present in amounts of about one mole per mole of polymerized dicarboxylic anhydride, d.i. ca.0.9 to 1.1 mol / mol applied. The use of larger or smaller amounts is possible, but brings no advantage. If larger amounts than one mole are used, ammonium salts are sometimes obtained because the formation of a second amide group requires higher temperatures, longer residence times, and water recirculation. If amounts smaller than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained.

• 6. Copolymere, bestehend aus 10 bis 95 Mol-% eines oder mehrerer Alkylacrylate oder Alkylmethacrylate mit C₁-C₂₆-Alkylketten und aus 5 bis 90 Mol-% einer oder mehrerer ethylenisch ungesättigter Dicarbonsäuren oder deren Anhydriden, wobei das Copolymere weitgehend mit einem oder mehreren primären oder sekundären Aminen zum Monoamid oder Amid/Ammoniumsalz der Dicarbonsäure umgesetzt ist.

Instead of the subsequent reaction of the carboxyl groups in the form of the dicarboxylic anhydride with amines to the corresponding amides, it may sometimes be advantageous to prepare the monoamides of the monomers and then to copolymerize them directly in the polymerization. In most cases, however, this is technically much more complicated because the amines can attach to the double bond of the monomeric mono- and dicarboxylic acid and then no copolymerization is possible.

• 6. Copolymers consisting of 10 to 95 mol% of one or more Alkyl acrylates or alkyl methacrylates with C ₁ -C ₂₆ alkyl chains and from 5 to 90 mol% of one or more ethylenically unsaturated dicarboxylic acids or their anhydrides, wherein the copolymer is largely reacted with one or more primary or secondary amines to the monoamide or amide / ammonium salt of the dicarboxylic acid is.

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

Examples of particularly preferred alkyl (meth) acrylates are n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tetradecyl (meth) acrylate, n-hexadecyl (meth) acrylate and n-octadecyl (meth) acrylate and mixtures thereof.

Examples of ethylenically unsaturated dicarboxylic acids are maleic acid, tetrahydrophthalic acid, citraconic acid and itaconic acid or their anhydrides and fumaric acid. Preference is given to maleic anhydride.

Suitable amines are compounds of the formula HNR ⁶ R ⁷ .

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

The reaction of the polymers with the amines takes place at temperatures of 50 to 200 ° C in the course of 0.3 to 30 hours. The amine is thereby added in amounts of about one to two moles per mole of polymerized dicarboxylic anhydride, d.i. about 0.9 to 2.1 mol / mol applied. The use of larger or smaller amounts is possible, but brings no advantage. If amounts greater than two moles are used, free amine is present. If amounts smaller than one mole are used, complete conversion to the monoamide does not take place and a correspondingly reduced effect is obtained.

In some cases, it may be advantageous for the amide / ammonium salt structure to be built up from two different amines. For example, a copolymer of lauryl acrylate and maleic anhydride may first be reacted with a secondary amine such as hydrogenated di-tallow fatty amine to form the amide, after which the free carboxyl group derived from the anhydride may be reacted with another amine, e.g. 2-ethylhexylamine is neutralized to the ammonium salt. Likewise, the reverse procedure is conceivable: first with ethylhexylamine to the monoamide, then reacted with Ditalgfettamin to the ammonium salt. Preferably, at least one amine is used which has at least one straight-chain, unbranched alkyl group having more than 16 carbon atoms. It is not significant whether this amine is present in the structure of the amide structure or as the ammonium salt of the dicarboxylic acid.

• 7. Terpolymere auf Basis von α,ß-ungesättigten Dicarbonsäureanhydriden, α,β-ungesättigten Verbindungen und Polyoxyalkylenethern von niederen, ungesättigten Alkoholen, die dadurch gekennzeichnet sind, dass sie 20 - 80, bevorzugt 40 - 60 Mol-% an bivalenten Struktureinheiten der Formeln 12 und/oder 14, sowie gegebenenfalls 13 enthalten, wobei die Struktureinheiten 13 von nicht umgesetzten Anhydridresten stammen,
  
  
  
  wobei
  • R²² und R²³ unabhängig voneinander Wasserstoff oder Methyl,
  • a, b gleich Null oder Eins und a + b gleich Eins,
  • R²⁴ und R²⁵ gleich oder verschieden sind und für die Gruppen -NHR⁶, N(R⁶)₂ und/oder -OR²⁷ stehen, und R²⁷ für ein Kation der Formel H₂N(R⁶)₂ oder H₃NR⁶ steht,
  • 19 - 80 Mol-%, bevorzugt 39-60 Mol-% an bivalenten Struktureinheiten der Formel 15
    
    worin
  • R²⁸ Wasserstoff oder C₁-C₄-Alkyl und
  • R²⁹ C₆-C₆₀-Alkyl oder C₆-C₁₈-Aryl bedeuten und
  • 1 - 30 Mol-%, bevorzugt 1 - 20 Mol-% an bivalenten Struktureinheiten der Formel 16
    
    worin
  • R³⁰ Wasserstoff oder Methyl,
  • R³¹ Wasserstoff oder C₁-C₄-Alkyl,
  • R³³ C₁-C₄-Alkylen,
  • m eine Zahl von 1 bis 100,
  • R³² C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl, C₆-C₁₈-Aryl oder -C(O)-R³⁴, wobei
  • R³⁴ C₁-C₄₀-Alkyl, C₅-C₁₀-Cycloalkyl oder C₆-C₁₈-Aryl,
  enthalten.

Instead of the subsequent reaction of the carboxyl groups or of the dicarboxylic anhydride with amines to the corresponding amides or amide / ammonium salts, it may sometimes be advantageous to prepare the monoamides or amide / ammonium salts of the monomers and then to copolymerize them directly in the polymerization. However, this is usually technically much more complicated because the amines can attach to the double bond of the monomeric dicarboxylic acid and then no copolymerization is possible.

• 7. terpolymers based on α, ß-unsaturated dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower, unsaturated alcohols, which are characterized in that they 20-80, preferably 40-60 mol% of bivalent structural units of the formulas 12 and / or 14, and optionally contain 13, wherein the structural units 13 come from unreacted Anhydridresten,
  
  
  
  in which
  • R ²² and R ²³ independently of one another are hydrogen or methyl,
  • a, b is zero or one and a + b is one,
  • R ²⁴ and R ^{25 are the} same or different and are -NHR ⁶ , N (R ⁶ ) ₂ and / or -OR ²⁷ and R ^{27 is} a cation of the formula H ₂ N (R ⁶ ) ₂ or H ₃ NR ⁶ stands,
  • 19-80 mol%, preferably 39-60 mol% of bivalent structural units of the formula 15
    
    wherein
  • R ^{28 is} hydrogen or C ₁ -C ₄ -alkyl and
  • R ^{29 is} C ₆ -C ₆₀ -alkyl or C ₆ -C ₁₈ -aryl and
  • 1 - 30 mol%, preferably 1 - 20 mol% of bivalent structural units of the formula 16
    
    wherein
  • R ^{30 is} hydrogen or methyl,
  • R ^{31 is} hydrogen or C ₁ -C ₄ -alkyl,
  • R ^{33 is} C ₁ -C ₄ -alkylene,
  • m is a number from 1 to 100,
  • R ^{32 is} C ₁ -C ₂₄ -alkyl, C ₅ -C ₂₀ -cycloalkyl, C ₆ -C ₁₈ -aryl or -C (O) -R ³⁴ , wherein
  • R ^{34 is} C ₁ -C ₄₀ -alkyl, C ₅ -C ₁₀ -cycloalkyl or C ₆ -C ₁₈ -aryl,
  contain.

The abovementioned alkyl, cycloalkyl and aryl radicals may optionally be substituted. Suitable substituents of the alkyl and aryl radicals are, for example, (C ₁ -C ₆ ) -alkyl, halogens, such as fluorine, chlorine, bromine and iodine, preferably chlorine and (C ₁ -C ₆ ) -alkoxy

Alkyl here stands for a straight-chain or branched one Hydrocarbon radical. Specific examples which may be mentioned are: n-butyl, tert-butyl, n-hexyl, n-octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, dodecenyl, tetrapropenyl, tetradecenyl, pentapropenyl, hexadecenyl, octadecenyl and eicosanyl or mixtures such as cocoalkyl , Tallow fatty alkyl and behenyl.

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

Aryl here stands for an optionally substituted aromatic ring system having 6 to 18 carbon atoms.

The terpolymers consist of the bivalent structural units of the formulas 12 and 14 and 15 and 16 and optionally 13. They contain only in a conventional manner the end groups formed in the polymerization by initiation, inhibition and chain termination.

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

In detail, structural units of the formulas 12 to 14 are derived from α, β-unsaturated dicarboxylic acid anhydrides of the formulas 17 and 18

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

Examples which may be mentioned are the following α, β-unsaturated olefins: styrene, α-methylstyrene, dimethylstyrene, α-ethylstyrene, diethylstyrene, i-propylstyrene, tert-butylstyrene, diisobutylene and α-olefins, such as decene, dodecene, tetradecene, pentadecene, Hexadecene, octadecene, C ₂₀ -α-olefin, C ₂₄ -α-olefin, C ₃₀ -α-olefin, tripropenyl, tetrapropenyl, pentapropenyl and mixtures thereof. Preference is given to α-olefins having 10 to 24 C atoms and styrene, particular preference being given to α-olefins having 12 to 20 C atoms.

The structural units of formula 16 are derived from polyoxyalkylene ethers of lower, unsaturated alcohols of 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).

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

        R³² - OH     (22)

worin R³² gleich C₁-C₂₄-Alkyl, C₅-C₂₀-Cycloalkyl oder C₆-C₁₈-Aryl, nach bekannten Verfahren anlagert und mit polymerisierbaren niederen, ungesättigten Halogeniden der Formel 23

umsetzt, wobei W für ein Halogenatom steht. Als Halogenide werden bevorzugt die Chloride und Bromide eingesetzt. Geeignete Herstellungsverfahren werden z.B. in J. March, Advanced Organic Chemistry, 2.Auflage, S.357f (1977) genannt. Die Veresterung der Polyoxyalkylenether (R³² = -C(O)-R³⁴) erfolgt durch Umsetzung mit gängigen Veresterungsmitteln, wie Carbonsäuren, Carbonsäurehalogeniden, Carbonsäureanhydriden oder Carbonsäureestern mit C₁-C₄-Alkoholen. Bevorzugt werden die Halogenide und Anhydride von C₁-C₄₀-Alkyl-, C₅-C₁₀-Cycloalkyl- oder C₆-C₁₈-Arylcarbonsäuren verwendet. Die Veresterung wird im allgemeinen bei Temperaturen von 0 bis 200°C, vorzugsweise 10 bis 100°C durchgeführt.The polyoxyalkylene ethers (R ³² = H) can be prepared by known processes by addition of α-olefin oxides, such as ethylene oxide, propylene oxide and / or Butylene oxide to polymerizable lower unsaturated alcohols of the formula 21

produce. Such polymerizable lower unsaturated alcohols are, for example, allyl alcohol, methallyl alcohol, butenols, such as 3-buten-1-ol and 1-buten-3-ol or methylbutenols, such as 2-methyl-3-buten-1-ol, 2-methyl-3 -but-2-ol and 3-methyl-3-buten-1-ol. Preferred are addition products of ethylene oxide and / or propylene oxide with allyl alcohol.
A subsequent etherification of these polyoxyalkylene ethers to give compounds of the formula 20 where R ³² = C ₁ -C ₂₄ -alkyl, cycloalkyl or aryl is carried out by processes known per se. Suitable methods are known, for example, from J. March, Advanced Organic Chemistry, 2nd edition, p. 357f (1977). These etherification products of the polyoxyalkylene ethers can also be prepared by reacting α-olefin oxides, preferably ethylene oxide, propylene oxide and / or butylene oxide, with alcohols of the formula 22

R ³² - OH (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 attached and with polymerizable lower unsaturated halides of the formula 23rd

where W is a halogen atom. The halides used are preferably the chlorides and bromides. Suitable production methods are mentioned, for example, in J. March, Advanced Organic Chemistry, 2nd Edition, p. 377f (1977). The esterification of the polyoxyalkylene ethers (R ³² = -C (O) -R ³⁴ ) takes place by reaction with customary esterification agents, such as carboxylic acids, carboxylic acid halides, carboxylic anhydrides or carboxylic acid esters with C ₁ -C ₄ alcohols. The halides and anhydrides of C ₁ -C ₄₀ -alkyl, C ₅ -C ₁₀ -cycloalkyl or C ₆ -C ₁₈ -arylcarboxylic acids are preferably used. The esterification is generally carried out at temperatures of 0 to 200 ° C, preferably 10 to 100 ° C.

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

• n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin,
• n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.

Examples of suitable primary amines for the preparation of the terpolymers are the following:

• n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine,
• N-stearylamine or N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

Examples of suitable secondary amines for preparing the terpolymers are: didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, ditallow fatty amine and mixtures thereof.

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

  R²² und R²³

  unabhängig voneinander Wasserstoff oder Methyl,

  a, b

  gleich Null oder 1 und a + b gleich 1,

  R³⁷

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

  R³⁸

  = R³⁷ oder NR⁶R³⁹

  R³⁹

  = -(A-O)_x-E

  mit
  • A = Ethylen- oder Propylengruppe
  • x = 1 bis 50
  • E = H, C₁-C₃₀-Alkyl, C₅-C₁₂-Cycloalkyl oder C₆-C₃₀-Aryl
  bedeuten, und
  80 - 20 Mol-%, bevorzugt 60 - 40 Mol-% an bivalenten Struktureinheiten der Formel 15 enthalten.

The terpolymers have K values (measured according to Ubbelohde in 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 about 500 and 100,000. Suitable examples are in EP 606,055 listed.

• 8. Reaction products of alkanolamines and / or polyetheramines with polymers containing dicarboxylic anhydride groups, characterized in that they contain 20-80, preferably 40-60, mol% of bivalent structural units of the formulas 25 and 27 and optionally 26
  
  
  
  in which

  R ²² and R ²³

  independently of one another hydrogen or methyl,

  a, b

  equal to zero or 1 and a + b equal to 1,

  R ³⁷

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

  R ³⁸

  = R ³⁷ or NR ⁶ R ³⁹

  R ³⁹

  = - (AO) _x -E

  With
  • A = ethylene or propylene 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
  80 to 20 mol%, preferably 60 to 40 mol% of bivalent structural units of the formula 15.

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

The structural units of the formula 15 are derived from the α, β-unsaturated olefins of the formula 19. The abovementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 7.

The radicals R ³⁷ and R ³⁸ in formula 25 or R ³⁹ in formula 27 are derived from polyetheramines or alkanolamines of the formulas 28 a) and b), amines of the formula NR ⁶ R ⁷ R ⁸ and optionally of alcohols having 1 to 30 carbon atoms from.

R⁵³

Wasserstoff, C₆-C₄₀-Alkyl oder

R⁵⁴

Wasserstoff, C₁-C₄-Alkyl

R⁵⁵

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

R⁵⁶, R⁵⁷

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

Z

C₂- bis C₄-Alkylen

n

eine Zahl zwischen 1 und 1000.

Zur Derivatisierung der Struktureinheiten der Formeln 17 und 18 wurden vorzugsweise Gemische aus mindestens 50 Gew.-% Alkylaminen der Formel HNR⁶R⁷R⁸ und höchstens 50 Gew.-% Polyetheraminen, Alkanolaminen der Formeln 28 a) und b) verwendet.Mean in it

R ⁵³

Hydrogen, C ₆ -C ₄₀ -alkyl or

R ⁵⁴

Hydrogen, C ₁ -C ₄ -alkyl

R ⁵⁵

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

R ⁵⁶ , R ⁵⁷

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

Z

C ₂ - to C ₄ -alkylene

n

a number between 1 and 1000.

For the derivatization of the structural units of the formulas 17 and 18, preference was given to using mixtures of at least 50% by weight of alkylamines of the formula HNR ⁶ R ⁷ R ⁸ and at most 50% by weight of polyetheramines, alkanolamines of the formulas 28 a) and b).

The preparation of the polyetheramines used is possible, for example, by reductive amination of polyglycols. Furthermore, it is possible to prepare polyetheramines having a primary amino group by addition of polyglycols to acrylonitrile and subsequent catalytic hydrogenation. In addition, polyetheramines are accessible by reaction of polyethers with phosgene or thionyl chloride and subsequent amination to the polyetheramine. The polyetheramines used according to the invention are (for example) commercially available under the name ^® Jeffamine (Texaco). Its molecular weight is up to 2000 g / mol and the ethylene oxide / propylene oxide ratio is from 1:10 to 6: 1.
A further possibility for derivatizing the structural units of the formulas 17 and 18 is that instead of the polyether amines an alkanolamine of the formulas 28a) or 28b) is used and subsequently subjected to alkoxylation.

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

The alkoxylation is usually carried out at temperatures between 70 and 170 ° C with catalysis of bases, such as NaOH or NaOCH ₃ , by gassing of alkylene oxides, such as ethylene oxide (EO) and / or propylene oxide (PO).

Usually, 1 to 500, preferably 1 to 100, moles of alkylene oxide are added per mole of hydroxyl groups.

• Monoethanolamin, Diethanolamin, N-Methylethanolamin, 3-Aminopropanol, Isopropanol, Diglykolamin, 2-Amino-2-methylpropanol und deren Mischungen.

Examples of suitable alkanolamines include:

• Monoethanolamine, diethanolamine, N-methylethanolamine, 3-aminopropanol, isopropanol, diglycolamine, 2-amino-2-methylpropanol and mixtures thereof.

• n-Hexylamin, n-Octylamin, n-Tetradecylamin, n-Hexadecylamin,
• n-Stearylamin oder auch N,N-Dimethylaminopropylendiamin, Cyclohexylamin, Dehydroabietylamin sowie deren Mischungen.

As primary amines, for example, the following may be mentioned:

• n-hexylamine, n-octylamine, n-tetradecylamine, n-hexadecylamine,
• N-stearylamine or N, N-dimethylaminopropylenediamine, cyclohexylamine, dehydroabietylamine and mixtures thereof.

• Didecylamin, Ditetradecylamin, Distearylamin, Dicocosfettamin, Ditalgfettamin und deren Mischungen.

Examples of secondary amines are:

• Didecylamine, ditetradecylamine, distearylamine, dicocosfettamine, ditallow fatty amine and mixtures thereof.

• Das Mischungsverhältnis zwischen A und B kann in weiten Grenzen variieren. So wirken schon geringe Mengen B von 100 ppm bis 50.000 ppm, bevorzugt 1.000 ppm bis 10.000 ppm, in Fettsäurelösungen als Kälteadditiv für A. Sie vermögen dabei die Eigenkristallisation der Fettsäure zu unterbinden, was zu einer Absenkung des Cloud Points führt, bzw. die Sedimentation gebildeter Kristalle zu verhindern und ermöglichen so ein problemloses Handling bei abgesenkten Temperaturen. Für spezielle Problemlösungen können aber auch von 5 % bis zu 50 %, in besonderen Fällen bis zu 90 % des Bestandteils B bezogen auf die Menge des Bestandteils A anwesend sein. Dabei werden insbesondere der Eigenstockpunkt des Additivs abgesenkt und die Schmierfähigkeit des additivierten Öls verbessert. Demzufolge liegt das bevorzugte Mischungsverhältnis von A:B zwischen 1 : 10 und 1 : 0,0001, insbesondere zwischen 1 : 4 und 1 : 0,0005, speziell zwischen 1:1 und 1 : 0,001.

Examples of alcohols which may be mentioned are:
Methanol, ethanol, propanol, isopropanol, n-, sec-, tert-butanol, octanol, tetradecanol, hexadecanol, octadecanol, tallow fatty alcohol, behenyl alcohol and mixtures thereof. Suitable examples are in EP-A-688 796 listed.
9. Co- 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 styrene or α-olefins. These are accessible on the one hand by reacting an anhydride-containing polymer with amines of the formula H ₂ NR ⁶ or by imidization of the dicarboxylic acid and subsequent copolymerization. Preferred dicarboxylic acid is maleic acid or maleic anhydride. Copolymers of 10 to 90% by weight of C ₆ -C ₂₄ -α-olefins and 90 to 10% by weight of NC ₆ -C ₂₂ -alkylmaleimide are preferred.

• The mixing ratio between A and B can vary within wide limits. Even small amounts of B from 100 ppm to 50,000 ppm, preferably from 1,000 ppm to 10,000 ppm, in fatty acid solutions act as a cold additive for A. They are capable of doing so To prevent self-crystallization of the fatty acid, which leads to a lowering of the cloud point, or to prevent the sedimentation of formed crystals and thus allow easy handling at reduced temperatures. However, for specific problem solutions, from 5% up to 50%, in special cases up to 90% of constituent B, based on the amount of constituent A, may also be present. In particular, the self-sticking point of the additive is lowered and the lubricity of the additized oil is improved. Accordingly, the preferred mixing ratio of A: B is between 1:10 and 1: 0.0001, more preferably between 1: 4 and 1: 0.0005, especially between 1: 1 and 1: 0.001.

The additives according to the invention are added to oils in amounts of from 0.001 to 0.5% by weight, preferably from 0.001 to 0.1% by weight. They may be used as such or dissolved in solvents, such as aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures such as toluene, xylene, ethylbenzene, decane, pentadecane, gasoline fractions, kerosene or commercial solvent mixtures such as Solvent Naphtha, ^® Shellsol AB, ^® Solvesso 150 , ^® Solvesso 200, ^® Exxsol, ^® Isopar and ^® Shellsol D types. The additives according to the invention preferably contain 1 to 80%, especially 10 to 70%, in particular 25 to 60%, of solvent. The additives, which can be used without problems even at low temperatures of, for example, -40 ° C and lower, improve the lubricity of the additized oils and their cold and corrosion protection properties.

For the preparation of additive packages for special problem solutions, the additives according to the invention can also be used together with one or more oil-soluble co-additives, which in themselves improve the cold flow properties and / or lubricity of crude oils, lubricating oils or fuel oils. Examples of such co-additives are vinyl acetate-containing copolymers or terpolymers of ethylene, comb polymers, alkylphenol-aldehyde resins and oil-soluble amphiphiles.

Thus, mixtures of the additives according to the invention with copolymers have proven outstandingly, the 10 to 40 wt .-% vinyl acetate and 60 to 90 wt .-% Contain ethylene. According to a further embodiment of the invention, the additives according to the invention are used in admixture with ethylene / vinyl acetate / vinyl neononanoate terpolymers or ethylene / vinyl acetate / vinyl neodecanoate terpolymers to improve the flowability of mineral oils or mineral oil distillates. The terpolymers of vinyl neononanoate or vinyl neodecanoate contain, in addition to ethylene, 10 to 35% by weight of vinyl acetate and 1 to 25% by weight of the respective neo compound. Further preferred copolymers contain, in addition to ethylene and from 10 to 35% by weight of vinyl esters, from 0.5 to 20% by weight of olefin, such as diisobutylene, 4-methylpentene or norbornene. The mixing ratio of the additives according to the invention with the ethylene / vinyl acetate copolymers described above or the terpolymers of ethylene, vinyl acetate and the vinyl esters of neononanic or neodecanoic acid is (in parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10.

worin R⁵⁰ für C₄-C₅₀-Alkyl oder -Alkenyl, R⁵¹ für Ethoxy- und/oder Propoxy, n für eine Zahl von 5 bis 100 und p für eine Zahl von 0 bis 50 steht.Thus, the additives according to the invention can be used together with alkylphenol-formaldehyde resins be used. In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those of the formula

wherein R ^{50 is} C ₄ -C ₅₀ alkyl or alkenyl, R ^{51 is} ethoxy and / or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50.

Finally, in a further embodiment of the invention, the additives according to the invention are used together with comb polymers. This term refers to polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. Preferably, they are homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30% of the monomers have side chains (cf., Comb-like Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff ). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1 ), Copolymers of a C ₆ -C ₂₄ -α-olefin and a NC ₆ -C ₂₂ -alkylmaleimide (cf. EP 0 320 766 Further, esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

beschrieben werden. Darin bedeuten

A

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

D

H, CH₃, A oder R;

E

H oder A;

G

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

M

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

N

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

R'

eine Kohlenwasserstoffkette mit 8-150 Kohlenstoffatomen;

R"

eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;

m

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

n

eine Zahl zwischen 0 und 0,6.

Comb polymers may, for example, be represented by the formula

to be discribed. Mean in it

A

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

D

H, CH _3, A or R;

e

H or A;

G

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

M

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

N

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

R '

a hydrocarbon chain of 8-150 carbon atoms;

R "

a hydrocarbon chain of 1 to 10 carbon atoms;

m

a number between 0.4 and 1.0; and

n

a number between 0 and 0.6.

The mixing ratio (in parts by weight) of the inventive additives with resins or comb polymers is 1:10 to 20: 1, preferably 1: 1 to 10: 1.

The additives according to the invention are suitable for improving the lubricating properties of animal, vegetable, mineral or synthetic fuel oils with only low dosing rates. Due to their improved cold properties can be dispensed with storage and application to a warming and / or dilution. In addition, they simultaneously improve the cold and corrosion protection properties of the additized oils. The emulsifying properties of the additized oils are less affected than is the case with the lubricating additives of the prior art. The additives of the invention are particularly well suited for use in middle distillates. As middle distillates are in particular those mineral oils which are obtained by distillation of crude oil and boil in the range of 120 to 450 ° C, for example kerosene, jet fuel, diesel and fuel oil. The oils can also be alcohols such as methanol and / or contain or consist of ethanol. Preferably, the additives of the invention are used in middle distillates containing 0.05% by weight of sulfur and less, more preferably less than 350 ppm of sulfur, more preferably less than 200 ppm of sulfur and in special cases less than 50 ppm of sulfur. These are generally those middle distillates that have been subjected to a hydrogenating refining, and therefore contain only small amounts of polyaromatic and polar compounds that give them a natural lubricating effect. The additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370.degree. C., in particular 350.degree. C. and in special cases below 330.degree. They can also be used as components in lubricating oils.

The mixtures can be used alone or together with other additives, e.g. with other pour point depressants or dewaxing aids, with corrosion inhibitors, antioxidants, sludge inhibitors, dehazers, conductivity improvers, lubricity additives, and cloud point depressant additives. Furthermore, they are successfully used in conjunction with additive packages, which i.a. known ashless dispersing additives, detergents, defoamers and corrosion inhibitors.

The improved low-temperature stability and the effectiveness of the additives according to the invention as lubricity additives is further illustrated by the following examples.

Examples

• A1) Tallölfettsäure, enthaltend als Hauptbestandteile 30 % Ölsäure, 60 % Linol- und andere mehrfach ungesättigte Fettsäuren und 4% gesättigte Fettsäuren. Jodzahl 155 gJ/100 g.
• A2) Ölsäure (technisch) enthaltend als Hauptbestandteile 69 % Ölsäure, 12% Linolsäure, 5 % Hexadecensäure und 10 % gesättigte Fettsäuren. Jodzahl 90 gJ /100 g.
• B1) Umsetzungsprodukt eines Terpolymers aus C₁₄/₁₆-α-Olefin, Maleinsäureanhydrid und Allylpolyglykol mit 2 Equivalenten Ditalgfettamin, 50 %ig in Solvent Naphtha
• B2) Umsetzungsprodukt eines Dodecenyl-Spirobislactons mit einer Mischung aus primärem und sekundärem Talgfettamin 60 %ig in Solvent Naphtha
• B3) Nonylphenol-Formaldehydharz, 50 %ig in Solvent Naphtha
• B4) Mischung aus 2 Teilen B1 und 1 Teil B2
• B5) Amid-Ammoniumsalz auf Basis Ethylendiamintetraessigsäure mit 3 Equivalenten Ditalgfettamin gemäß EP 0597278 .
• B6) Mischung aus Amid-Ammoniumsalz auf Basis Ethylendiamintetraessigsäure mit 4 Equivalenten Ditalgfettamin und Copolymer aus gleichen Teilen Maleinsäureanhydrid und C₂₀/₂₄-Olefin, imidiert mit N-Talgfettpropylendiamin gemäß EP-0 909 307
• B7) Amid-Ammoniumsalz aus 1 mol Phthalsäureanhydrid und 2 mol einer Mischung gleicher Teile Ditalg- und Dicocosfettamin
• B8) Mischung aus gleichen Teilen
  1. a) Amid-Ammoniumsalz aus 1 mol Phthalsäureanhydrid und 2 mol Ditalgfettamin und
  2. b) Copolymer aus Fumarsäuredi(tetradecylester), 50 %ig in Solvent Naphtha.

The following substances were used:

• A1) Tall oil fatty acid containing as main constituents 30% oleic acid, 60% linoleic and other polyunsaturated fatty acids and 4% saturated fatty acids. Iodine value 155 gJ / 100 g.
• A2) Oleic acid (technical) containing as main constituents 69% oleic acid, 12% linoleic acid, 5% hexadecenoic acid and 10% saturated fatty acids. Iodine number 90 gJ / 100 g.
• B1) Reaction product of a terpolymer of C _14/16 -α-olefin, Maleic anhydride and allyl polyglycol with 2 equivalents of ditallow fatty amine, 50% in solvent naphtha
• B2) Reaction product of a dodecenyl spirobislactone with a mixture of primary and secondary tallow fatty amine 60% in solvent naphtha
• B3) Nonylphenol-formaldehyde resin, 50% in solvent naphtha
• B4) Mixture of 2 parts B1 and 1 part B2
• B5) amide ammonium salt based on ethylenediaminetetraacetic acid with 3 equivalents of ditallow fatty amine according to EP 0597278 ,
• B6) mixture of amide-ammonium salt based on ethylenediaminetetraacetic acid with 4 equivalents of ditallow fatty amine and copolymer of equal parts of maleic anhydride and C _20- / _24-olefin, imidized with N-tallowpropylenediamine according EP-0 909 307
• B7) Amide ammonium salt of 1 mol of phthalic anhydride and 2 mol of a mixture of equal parts Ditalg- and Dicocosfettamin
• B8) Mixture of equal parts
  1. a) amide ammonium salt of 1 mol of phthalic anhydride and 2 mol Ditalgfettamin and
  2. b) Copolymer of fumaric di (tetradecyl ester), 50% in solvent naphtha.

To assess the cold properties, the pour point was measured according to ISO 3016 (Table 1) and the cloud point according to ISO 3015 (Table 2) of the mixtures according to the invention. Thereafter, the additive mixtures according to the invention were stored for several days at different temperatures and then assessed visually (Table 3 to 5). V denotes comparative examples. Table 1: Own point (pour point) of the additives of the invention Composition (parts by weight) Pour point example A1 A2 B1 B2 B3 B4 V1 80 20 -9 V2 50 50 -24 V3 20 80 0 V4 80 20 -9 V5 50 50 -24 V6 20 80 -6 V7 80 20 0 V8 50 50 -15 V9 20 80 -48 V10 80 20 -9 V11 50 50 -18 V12 20 80 -15 V13 80 20 -27 V14 50 50 -27 V15 20 80 -6 V16 80 20 -27 V17 50 50 -54 V18 20 80 -45 V19 80 20 -21 V20 50 50 -30 V21 20 80 -21 V22 80 20 -21 V23 50 50 -21 V24 20 80 -9 V25 * 99.95 0.05 -36 V26 * 99.95 0.05 -36 V27 99.95 0.05 -15 V28 100 -9 V29 100 6 V30 100 9 V31 100 -12 V32 100 0 V33 100 -6 V34 * 100 -36 * These examples are obtained with a 50% by weight setting of the fatty acid in solvent naphtha. Composition (parts by weight) Cloud point example A1 A2 B1 B2 B3 B4 V35 * 100 -27.0 V36 * 99.9995 0.0005 -33.0 V37 * 99.9995 0.0005 -30.5 V38 * 99,998 0,002 -33.5 V39 * 99,998 0,002 -33.5 V40 * 99.995 0.005 -31.0 V41 * 99.995 0.005 -32.2 V42 ** (B5) 99,998 0,002 -29.0 V43 ** (B6) 99,998 0,002 -31.0 1 ** (B7) 99,998 0,002 -35.5 2 ** (B8) 99,998 0,002 -37.0 * These examples were obtained with a 50% by weight adjustment of the fatty acid in solvent naphtha.
** These examples relate to mixtures of A1 with 2000 ppm B5 to B8, respectively, and were obtained with a 50% by weight adjustment of the fatty acid in solvent naphtha. example Composition (parts by weight) evaluation A2 B1 B2 B3 V44 50 50 viscous V45 80 20 liquid V46 20 80 liquid V47 50 50 liquid V48 20 80 liquid V49 100 firm, waxy V50 100 firmly V51 100 firmly V52 100 viscous example Component A Component B Amount ppm after 1 day after 3 days after 5 days after 7 days then 1 day at -28 ° C V54 A1 (50% in SN) without addition clear, sediment (crystalline) clear, sediment (crystalline) clear, sediment (crystalline) clear, sediment (crystalline) clear, sediment (crystalline) V55 " B1 100 Clear, few crystals on the ground Clear, few crystals on the ground Clear, few crystals on the ground Clear, few crystals on the ground clear, sediment (crystalline) V56 " " 500 clear, no sediment Clear, few crystals on the ground Clear, few crystals on the ground Clear, few crystals on the ground clear, sediment (crystalline) V57 " " 1000 clear, no sediment clear, no sediment clear, no sediment clear, no sediment cloudy, no sediment V58 " " 5000 clear, no sediment clear, no sediment clear, no sediment clear, no sediment clear, no sediment V59 " " 10,000 clear, no sediment clear no sediment clear, no sediment clear, no sediment clear, no sediment V60 " " 50,000 cloudy, no sediment cloudy, no sediment cloudy, no sediment cloudy, no sediment cloudy, no sediment V61 " B4 100 Clear, few crystals on the ground Clear, few crystals on the ground Clear, few crystals on the ground Clear, few crystals on the ground clear, sediment (crystalline) V62 " " 500 clear, no sediment clear, no sediment Clear, few crystals on the ground Clear, few crystals on the ground clear, sediment (crystalline) V63 " " 1000 clear, no sediment clear, no sediment clear, no sediment clear, no sediment clear, no sediment V64 " " 5000 clear, no sediment clear, no sediment clear, no sediment clear, no sediment clear, no sediment V65 " " 10,000 clear, no sediment clear, no sediment clear, no sediment clear, no sediment clear, no sediment V66 " " 50,000 clear, no sediment clear, no sediment clear, no sediment clear, no sediment slightly cloudy, no sediment V67 " B3 5000 clear, crystalline precipitations in suspension clear, crystalline precipitations in suspension clear, crystalline precipitations in suspension clear, crystalline precipitations in suspension cloudy, crystalline precipitations in suspension SN = solvent naphtha example Component A Component B Amount ppm after 3 days after 7 days then 1 day at -28 ° C V68 A1 (50% in MS) without addition clear, sediment (crystalline) clear, sediment (crystalline) clear, sediment (crystalline), solid V69 " B1 1000 clear, no sediment clear, no sediment cloudy, sediment V70 " " 5000 cloudy, no sediment cloudy, no sediment cloudy, no sediment V71 " " 10,000 cloudy, no sediment cloudy, no sediment cloudy, no sediment V72 " B4 1000 Sure, no sediment clear, little sediment slightly cloudy, sediment V73 " " 5000 clear, no sediment clear, no sediment cloudy, no sediment V74 " " 10,000 clear, slight cloudiness on the ground, no sediment cloudy, no sediment cloudy, no sediment V75 " " 50,000 cloudy, no sediment cloudy, no sediment drifted, no sediment

MS is a mixture of a number of aliphatic and cyclic non-aromatic hydrocarbons. The main components of MS can be found in the following table: Table 6: Components of MS component Concentration range (wt%) Di-2-ethylhexyl 10 - 25 2-ethylhexyl acid-2-ethylhexyl 10 - 25 C ₁₆ lactones 4 - 20 2-Ethylhexylbutyrat 3 - 10 2-ethylhexanediol- (1,3) glycol mono-n-butyrate 5 - 15 2-ethylhexanol 4 - 10 C ₄ to C ₈ acetates 2 - 10 2-ethylhexanediol- (1,3) 2 - 5 Ethers and esters ≥ C ₂₀ 0 - 20

Lubricating effect in middle distillates

The lubricating effect of the additives was carried out using an HFRR instrument from PCS Instruments on additized oils at 60 ° C. The High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No.2, p.217, 1986 , The results are given as coefficient of friction and Wear Scar (WS1.4). A low coefficient of friction and a low Wear Scar show a good lubricating effect. Table 7: Characterization of the test oils: To test the lubricity, test oils having the following characteristics were used: Test oil 1 Test oil 2 boiling range: 170 - 344 ° C 182-304 ° C density 0.830 g / cm ³ 0.821 g / cm ³ Cloud point -9 ° C -33 ° C sulfur content 45 ppm 6 ppm

The boiling characteristics are determined according to ASTM D-86 and the determination of the cloud point according to ISO 3015. Table 8: Wear Scar in Test Oil 1 example additive Wear Scar Friction V76 Without 555 μm 0.33 3 100 ppm according to Ex. 1 385 μm 0.18 V77 100 ppm A1 + 150 ppm B4 381 μm 0.18 V78 100 ppm A1 421 μm 0.18 V79 150 ppm B4 549 μm 0.34 example additive Wear Scar Friction V80 without 637 μm 0.30 V81 200 ppm according to Ex. 48 386 0.18 V82 200 ppm according to Ex. 60 395 0.18 V83 200 ppm according to Ex.54 405th 0.19

Claims (11)

1. A low-temperature-stabilized additive for fuel oils having a sulfur content of up 0.05% by weight, comprising fatty acid mixtures of

   A1 ) from 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid having from 6 to 50 carbon atoms,

   A2) from 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid having from 6 to 50 carbon atoms,
   and

   B) at least one polar nitrogen-containing compound which is effective as paraffin dispersant in middle distillates, in an amount of from 0.01 to 90% by weight, based on the total weight of A1), A2) and B), which is a compound of the formula 11

   

   in which

   R⁶, R⁷ may be identical or different, and at least one of these groups is C₈-C₃₆-alkyl, C₆-C₃₆-cycloalkyl or C₈-C₃₆-alkenyl, and the other group is either hydrogen, C₁-C₃₆-alkyl, C₂-C₃₆-alkenyl, cyclohexyl, or a group of the formula -(A-O)_x-E or -(CH₂)_n-NYZ, in which A is an ethylene or propylene group, x is a number from 1 to 50, E = H, C₁-C₃₀-alkyl, C₅-C₁₂-cycloalkyl or C₆-C₃₀-aryl, and n is 2, 3 or 4, and Y and Z, independently of one another, are H, C₁-C₃₀-alkyl or-(A-O)_x-H,

   R¹⁴ is CONR⁶R⁷ or CO₂ ^{- +}H₂NR⁶R⁷,

   R¹⁵ and R¹⁶ are H, CONR¹⁷ ₂, CO₂R¹⁷ or OCOR¹⁷, -OR¹⁷, -R¹⁷ or -NCOR¹⁷, and

   R¹⁷ is alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.
2. An additive as claimed in claim 1, in which constituent A is a carboxylic acid having from 12 to 22 carbon atoms.
3. An additive as claimed in claim 1 and/or 2, comprising from 1 to less than 20% by weight of A1 ) and from greater than 80 to 99% by weight of A2).
4. An additive as claimed in one or more of claims 1 to 3, in which the mixture of A1) and A2) has an iodine number of at least 40 g of I/100 g.
5. An additive as claimed in one or more of claims 1 to 4, in which the mixture of A1) and A2) comprises from 1 to 40% by weight of resin acids.
6. An additive as claimed in one or more of claims 1 to 5, in which the compounds of the formula (11) are amides or amine salts of a secondary amine which contains a hydrogen- and carbon-containing group having at least 10 carbon atoms.
7. A low-temperature-stabilized solution of an additive as claimed in one or more of claims 1 to 6 in an organic solvent, where the solution comprises from 1 to 80% by weight of solvent.
8. A low-temperature-stabilized solution as claimed in claim 7, where the solvent employed is an aliphatic and/or aromatic and/or oxygen-containing hydrocarbon.
9. A low-temperature-stabilized fatty acid mixture comprising

   A1) from 1 to 99% by weight of at least one saturated mono- or dicarboxylic acid having from 6 to 50 carbon atoms,

   A2) from 1 to 99% by weight of at least one unsaturated mono- or dicarboxylic acid having from 6 to 50 carbon atoms,
   and

   B) at least one polar nitrogen-containing compound which is effective as paraffin dispersant in middle distillates, in an amount of from 0.01 to 90% by weight, based on the total weight of A1), A2) and B), which is a compound of the formula 11

   

   in which

   R⁶, R⁷ may be identical or different, and at least one of these groups is C₈-C₃₆-alkyl, C₆-C₃₆-cycloalkyl or C₈-C₃₆-alkenyl, and the other group is either hydrogen, C₁-C₃₆-alkyl, C₂-C₃₆-alkenyl, cyclohexyl, or a group of the formula -(A-O)_x-E or -(CH₂)_n-NYZ, in which A is an ethylene or propylene group, x is a number from 1 to 50, E = H, C₁-C₃₀-alkyl, C₅-C₁₂-cycloalkyl or C₆-C₃₀-aryl, and n is 2, 3 or 4, and Y and Z, independently of one another, are H, C₁-C₃₀-alkyl or -(A-O)_x-H,

   R¹⁴ is CONR⁶R⁷ or CO₂ ^{- +}H₂NR⁶R⁷,

   R¹⁵ and R¹⁶ are H, CONR¹⁷ ₂, CO₂R¹⁷ or OCOR¹⁷, -OR¹⁷, -R¹⁷ or -NCOR¹⁷ and

   R¹⁷ is alkyl, alkoxyalkyl or polyalkoxyalkyl and has at least 10 carbon atoms.
10. A fuel oil comprising, besides a middle distillate having a sulfur content of up to 0.05% by weight, an additive as claimed in one or more of claims 1 to 9.
11. The use of an additive as claimed in one or more of claims 1 to 9 for improving the lubrication properties of low-sulfur middle distillates having a sulfur content of up to 0.05% by weight.