RU2388795C9 - Turbine fuel compositions with improved low-temperature characteristics - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: polymers contain polymerisable α-olefin, ester of α,β-saturated carboxylic acid and, if necessary, alkenyl ester of carboxylic acid, as an additive to turbine fuel and in particular as an additive for improving cold flow properties of turbine fuel; to turbine fuel containing such polymers; as well as to a set of additives containing such copolymers.

EFFECT: improved cold flow properties of turbine fuel, lower freezing point, cloud point and in particular set point.

15 cl, 2 tbl

Description

The invention relates to the use of polymers that contain a polymerizable α-olefin, an ester of α, β-unsaturated carboxylic acid and, if necessary, an alkenyl ester of a carboxylic acid, as an additive for turbine fuel and in particular as an additive to improve cold flow properties for turbine fuel; to turbine fuels supplemented with such polymers, as well as to a kit of additives containing such copolymers.

State of the art

Turbine fuel, which is also referred to as aviation fuel, jet fuel, Jet Fuel, Aviation Fuel or Turbo Fuel, based on its use in aviation and at the same time related temperature conditions must meet high requirements for their low temperature characteristics. Thus, the freezing temperature of turbine fuel should be so low that the fluidity of the fuel under the temperature conditions prevailing at high altitudes does not deteriorate and, moreover, the fuel filter passes without problems. The freezing temperature for turbine fuel refers to the temperature at which previously formed and precipitated hydrocarbon crystals are completely dissolved again by cooling. Depending on the application in civil and military aviation, the freezing temperature cannot exceed -40 ° C or, for example, -50 ° C. If the freezing temperature is exceeded, then long-chain paraffins recrystallize and form large scaly wax crystals. Such wax crystals have a spongy structure and lead to the inclusion of other fuel components in the crystalline compound.

The appearance of such crystals leads to the fact that the fuel can only slowly pass through small holes and filters. In addition, increases the viscosity of the fuel, resulting in deteriorating fluidity of the fuel. At temperatures below the yield point (PP), finally no more fuel flow occurs.

Currently, the freezing temperature of turbine fuels is controlled primarily by distillation measures in the raffinates, for example, by reducing a portion of the high boiling fractions, which also include wax fractions. However, this drawback is the resulting increase in the cost of turbine fuel.

Chemical measures to lower the freezing point are also known. Thus, in European patent application EP-A 1357168, a turbine fuel composition is described which, in addition to turbine fuel, contains at least one of the following additives: ethylene copolymers with at least one unsaturated ester selected from vinyl esters with at least 5 carbon atoms, alkyl (meth) acrylates, dialkyl fumarates and dialkyl maleates; ethylene / alkene copolymers; ethylene / vinyl acetate copolymers with less than 15 wt.% vinyl acetate; crystallization centers (nucleating agents); waxes; alkyl phenol / formaldehyde condensates; comb polymers; and organic nitrogen compounds. Such additives should cause the thus added turbine fuel to remain fluid also below the freezing temperature specified in its specification.

International patent application WO 01/62874 describes a composition which, along with turbine fuel, contains additives that are selected from the reaction products of alkanolamines with long-chain aromatic acylation agents; phenol / aldehyde condensates; special aromatic systems; and ethylene / vinyl acetate copolymers. Such additives should lower the freezing point of the thus added turbine fuel.

The German patent application DE 1250188 describes copolymers of ethylene and an ester of acrylic acid with a maximum of 7 carbon atoms in the molecule of the ester, which should lower the pour point of fuel oil, diesel fuel and jet fuel. However, the examples do not use jet fuel.

In addition, there is a need for additives that further improve the low temperature characteristics of turbine fuels.

A brief description of the invention.

In accordance with the foregoing, the objective of the proposed invention is the provision of such new additives.

Unexpectedly, this problem can be solved by unexpected observation that polymers that contain polymerizable α-olefin, ester of α, β-unsaturated carboxylic acid and, if necessary, alkenyl ester of carboxylic acid, improve low-temperature characteristics, in particular cold flow properties, turbine fuel and furthermore have better characteristics than the ethylene / vinyl acetate copolymers described in the prior art.

In accordance with the foregoing, the first subject of the present invention relates to the use of a polymer which contains a polymerizable α-olefin, an ester of an α, β-unsaturated carboxylic acid and, if necessary, an alkenyl ester of a carboxylic acid, as an additive for turbine fuel. Especially used are those polymers which contain polymerizable esters of α, β-unsaturated carboxylic acid and, if necessary, the alkenyl ester present in the statistical distribution. Preferably, the polymer is a binary polymer, which is mainly constructed from an α-olefin and an ester of α, β-unsaturated carboxylic acid, or alternatively, it is a terpolymer which is mainly constructed from the above monomers.

Preferably, polymers are used which are constructed from monomers, including monomers M1, M2 and, if necessary, M3, wherein M1, M2 and M3 have the following general formulas:

in which R ¹ means hydrogen or hydrocarbyl having from 1 to 40 carbon atoms;

R ² , R ³ and R ⁴ independently from each other mean hydrogen or alkyl having from 1 to 4 carbon atoms;

R ⁵ means hydrocarbyl having from 1 to 20 carbon atoms;

R ⁶ , R ⁷ and R ⁸ independently from each other mean hydrogen or alkyl having from 1 to 4 carbon atoms; and

R ⁹ means hydrocarbyl having from 1 to 19 carbon atoms.

DETAILED DESCRIPTION OF THE INVENTION

If you do not make any other instructions, then in the framework of the proposed invention, the following general definitions apply:

hydrocarbyl having from 1 to 40 carbon atoms means a hydrocarbon residue having from 1 to 40 carbon atoms. Preferably, it is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. Especially hydrocarbyl having from 1 to 40 carbon atoms means alkyl having from 1 to 40 carbon atoms. Alkyl having from 1 to 40 carbon atoms means a linear or branched alkyl residue having from 1 to 40 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, nencosyl, docosyl, hetacosyl, hecacosyl isomers, higher homologues, as well as related structural isomers.

The same applies for hydrocarbyl residues having from 1 to 20 carbon atoms, that is, we are talking about a hydrocarbon residue having from 1 to 20 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 1 to 20 carbon atoms means alkyl having from 1 to 20 carbon atoms. Alkyl having from 1 to 20 carbon atoms means a linear or branched residue of alkyl having from 1 to 20 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and their structural isomers.

Hydrocarbyl having from 1 to 19 carbon atoms means a hydrocarbon residue having from 1 to 19 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 1 to 19 carbon atoms means alkyl having from 1 to 19 carbon atoms. Alkyl having from 1 to 19 carbon atoms means a linear or branched residue of alkyl having from 1 to 19 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and their structural isomers.

Hydrocarbyl having from 1 to 10 carbon atoms means a hydrocarbon residue having from 1 to 10 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 1 to 10 carbon atoms means alkyl having from 1 to 10 carbon atoms. Alkyl having from 1 to 10 carbon atoms means a linear or branched residue of alkyl having from 1 to 10 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl and their structural isomers.

Hydrocarbyl having from 1 to 9 carbon atoms means a hydrocarbon residue having from 1 to 9 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 1 to 9 carbon atoms means alkyl having from 1 to 9 carbon atoms. Alkyl having from 1 to 9 carbon atoms means a linear or branched residue of alkyl having from 1 to 9 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl and their structural isomers.

Hydrocarbyl having from 5 to 16 carbon atoms means a hydrocarbon residue having from 5 to 16 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 5 to 16 carbon atoms means alkyl having from 5 to 16 carbon atoms. Alkyl having from 5 to 16 carbon atoms means a linear or branched residue of alkyl having from 5 to 16 carbon atoms. Examples include pentyl, neopentyl, isopentyl, hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl, isononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neodecyl, dodecyl, tridecyl, as well as their structural isomers.

Hydrocarbyl having from 8 to 12 carbon atoms means a hydrocarbon residue having from 8 to 12 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 8 to 12 carbon atoms means alkyl having from 8 to 12 carbon atoms. Alkyl having from 8 to 12 carbon atoms means a linear or branched residue of alkyl having from 8 to 12 carbon atoms. Examples include octyl, 2-ethylhexyl, neoctyl, nonyl, neononyl, isononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neo-undecyl, dodecyl, as well as their structural isomers.

Hydrocarbyl having from 8 to 14 carbon atoms means a hydrocarbon residue having from 8 to 14 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 8 to 14 carbon atoms means alkyl having from 8 to 14 carbon atoms. Alkyl having from 8 to 14 carbon atoms means a linear or branched residue of alkyl having from 8 to 14 carbon atoms. As examples, along with the previously mentioned for alkyl having from 8 to 12 carbon atoms, the alkyl radicals are called tridecyl and tetradecyl, as well as their structural isomers.

Hydrocarbyl having from 8 to 16 carbon atoms means a hydrocarbon residue having from 8 to 16 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 8 to 16 carbon atoms means alkyl having from 8 to 16 carbon atoms. Alkyl having from 8 to 16 carbon atoms means a linear or branched residue of alkyl having from 8 to 16 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 8 to 14 carbon atoms, alkyl radicals include pentadecyl and hexadecyl, as well as their structural isomers.

Hydrocarbyl having from 8 to 20 carbon atoms means a hydrocarbon residue having from 8 to 20 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 8 to 20 carbon atoms means alkyl having from 8 to 20 carbon atoms. Alkyl having from 8 to 20 carbon atoms means a linear or branched alkyl residue having from 8 to 20 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 8 to 16 carbon atoms, alkyl radicals include heptadecyl, octadecyl, nonadecyl and eicosanil, as well as their structural isomers.

Hydrocarbyl having from 6 to 14 carbon atoms means a hydrocarbon residue having from 6 to 14 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 6 to 14 carbon atoms means alkyl having from 6 to 14 carbon atoms. Alkyl having from 6 to 14 carbon atoms means a linear or branched alkyl residue having from 6 to 14 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 8 to 14 carbon atoms, hexyl and heptyl, as well as their structural isomers, are referred to as alkyl radicals.

Hydrocarbyl having from 6 to 16 carbon atoms means a hydrocarbon residue having from 6 to 16 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 6 to 16 carbon atoms means alkyl having from 6 to 16 carbon atoms. Alkyl having from 6 to 16 carbon atoms means a linear or branched alkyl residue having from 6 to 14 carbon atoms. As examples, along with the previously mentioned for alkyl having from 8 to 16 carbon atoms, the alkyl radicals are named hexyl and heptyl, as well as their structural isomers.

Hydrocarbyl having from 6 to 20 carbon atoms means a hydrocarbon residue having from 6 to 20 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 6 to 20 carbon atoms means alkyl having from 6 to 20 carbon atoms. Alkyl having from 6 to 20 carbon atoms means a linear or branched alkyl residue having from 6 to 20 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 8 to 20 carbon atoms, alkyl residues are hexyl and heptyl, as well as their structural isomers.

Hydrocarbyl having from 5 to 20 carbon atoms means a hydrocarbon residue having from 5 to 20 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 5 to 20 carbon atoms means alkyl having from 5 to 20 carbon atoms. Alkyl having 5 to 20 carbon atoms means a linear or branched alkyl residue having 5 to 20 carbon atoms. As examples, along with the previously mentioned for alkyl having from 6 to 20 carbon atoms, pentyl and its structural isomers are called alkyl residues.

Hydrocarbyl having from 4 to 14 carbon atoms means a hydrocarbon residue having from 4 to 14 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 4 to 14 carbon atoms means alkyl having from 4 to 14 carbon atoms. Alkyl having 4 to 14 carbon atoms means a linear or branched alkyl residue having 4 to 14 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 6 to 14 carbon atoms, the alkyl radicals include pentyl and its structural isomers, as well as n-butyl, sec-butyl, isobutyl and tert-butyl.

Hydrocarbyl having from 4 to 16 carbon atoms means a hydrocarbon residue having from 4 to 16 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 4 to 16 carbon atoms means alkyl having from 4 to 16 carbon atoms. Alkyl having from 4 to 16 carbon atoms means a linear or branched alkyl residue having from 4 to 16 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 6 to 16 carbon atoms, the alkyl radicals include pentyl and its structural isomers, as well as n-butyl, sec-butyl, isobutyl and tert-butyl.

Hydrocarbyl having from 4 to 20 carbon atoms means a hydrocarbon residue having from 4 to 20 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 4 to 20 carbon atoms means alkyl having from 4 to 20 carbon atoms. Alkyl having from 4 to 20 carbon atoms means a linear or branched alkyl residue having from 4 to 20 carbon atoms. As examples, in addition to those previously mentioned for alkyl having from 5 to 20 carbon atoms, n-butyl, sec-butyl, isobutyl and tert-butyl are referred to as alkyl radicals.

Hydrocarbyl having from 1 to 4 carbon atoms means a hydrocarbon residue having from 1 to 4 carbon atoms. Preferably, this is an aliphatic hydrocarbon residue such as alkyl, alkenyl, alkadienyl or alkynyl. In particular, hydrocarbyl having from 1 to 4 carbon atoms means alkyl having from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.

Hydrocarbyl residues, for example, alkyl residues, may be unsubstituted or once or repeatedly substituted. Suitable substituents are, for example, OH, alkoxy having from 1 to 4 carbon atoms, NR ¹¹ R ¹² (R ¹¹ and R ^{12 are} independently hydrogen or alkyl having from 1 to 4 carbon atoms) or carbonyl (COR ¹¹ ) However, they are preferably unsubstituted.

Alkoxy having 1 to 4 carbon atoms is an alkyl residue having 1 to 4 carbon atoms bonded through an oxygen atom. Examples are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.

Alkanol having from 1 to 4 carbon atoms means an alkyl residue having from 1 to 4 carbon atoms, which is substituted by 1 to 3 hydroxy groups on different carbon atoms. Alkanol having from 1 to 10 carbon atoms means an alkyl residue having from 1 to 10 carbon atoms, which is substituted by 1 to 6 hydroxy groups on different carbon atoms. Alkanol having from 1 to 40 carbon atoms means an alkyl residue having from 1 to 40 carbon atoms, which is substituted by 1 to 6 hydroxy groups on different carbon atoms. As examples of an alkanol having from 1 to 4 carbon atoms, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, ethylene glycol, propylene glycol and glycerol are mentioned.

Moreover, alkanol having from 1 to 10 carbon atoms means pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, their structural isomers, in addition, erythritol, pentaerythritol and sorbitol.

Moreover, alkanol having from 1 to 20 carbon atoms means undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol and eicosanol, as well as their structural isomers.

a) polymers used according to the invention

The following carried out preferred embodiments of the polymers and monomers used according to the invention from which they are built are used both for themselves and in combination.

In the polymers used according to the invention, the monomers M1, M2 and M3 can be present in the polymer in the following molar parts (Mx / (M1 + M2 + M3)):

M1: preferably 0.60 to 0.99;

M2: preferably from 0.01 to 0.40;

M3: preferably from 0 to 0.20.

For the case when the polymers used according to the invention contain the non-polymerizable monomer M3:

M1: preferably from 0.60 to 0.99, particularly preferably from 0.7 to 0.95, in particular from 0.75 to 0.85;

M2: preferably from 0.01 to 0.6, particularly preferably from 0.05 to 0.3, in particular from 0.05 to 0.25.

For the case when the polymers used according to the invention contain a polymerizable monomer M3:

M1: preferably from 0.60 to 0.98, particularly preferably from 0.7 to 0.95, in particular from 0.75 to 0.9;

M2: preferably from 0.01 to 0.20, particularly preferably from 0.01 to 0.17, in particular from 0.015 to 0.16;

M3: preferably from 0.01 to 0.20, particularly preferably from 0.02 to 0.15, in particular from 0.03 to 0.12, especially from 0.03 to 0.11.

With the monomers M1, it is preferably a monoalkene with a terminal double bond, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, their structural isomers , as well as higher once unsaturated homologues having up to 40 carbon atoms.

In the monomers M1, R ¹ preferably means hydrogen or hydrocarbyl having from 1 to 20 carbon atoms, particularly preferably hydrogen or hydrocarbyl having from 1 to 10 carbon atoms, and even more preferably hydrogen or hydrocarbyl having from 1 to 4 carbon atoms. Moreover, preferably hydrocarbyl means alkyl. In particular, R ¹ is hydrogen, methyl or ethyl. In accordance with the foregoing, the monomer M1 is in particular ethylene, propylene or 1-butene. Specifically, R ¹ means hydrogen, that is, M1 specifically means ethylene.

In the monomer M2, the residues R ² , R ³ and R ^{4 are} preferably hydrogen or methyl. Particularly preferably, two of the residues R ² , R ³ and R ^{4 are} hydrogen and the other residue is hydrogen or methyl. In particular, all three residues R ² , R ³ and R ^{4 are} hydrogen.

In accordance with the foregoing, the monomer M2 is preferably an ester of an α, β-unsaturated carboxylic acid which is selected from acrylic acid, methacrylic acid, crotonic acid and isocrotonic acid, particularly preferably from acrylic acid and methacrylic acid and in particular acrylic acid.

Examples of such a preferably α, β-unsaturated carboxylic acid ester M2 are: alkanol esters based on alkanols having 1 to 20 carbon atoms, such as methyl acrylic acid ester, ethyl acrylic ester, propyl ester acrylic acid, isopropyl ester of acrylic acid, n-butyl ester of acrylic acid, isobutyl ester of acrylic acid, tert-butyl ester of acrylic acid, n-pentyl ester of acrylic acid slots, neopentyl ester of acrylic acid, isopentyl ester of acrylic acid, hexyl ester of acrylic acid, isohexyl ester of acrylic acid, heptyl ester of acrylic acid, octyl ester of acrylic acid, neo-octyl ester of acrylic acid, 2-ethylhexyl ester acids, acrylic acid nonyl ester, acrylic acid neonyl ester, decyl ester of acrylic acid, non-decyl ester of acrylic acid ota, 2-propylheptyl acrylic acid, lauryl ester of acrylic acid, palmityl ester of acrylic acid and stearyl ester of acrylic acid; in addition, the corresponding esters of methacrylic acid, crotonic acid and isocrotonic acid, with acrylates (esters of acrylic acid) being preferred.

R ⁵ means hydrocarbyl having from 1 to 20 carbon atoms, preferably alkyl having from 1 to 20 carbon atoms.

In the case where the polymer used according to the invention does not include any alkenyl ester and specifically no M3 monomer, in a preferred embodiment of the invention, R ⁵ means a hydrocarbyl residue having at least 5 carbon atoms, for example hydrocarbyl having from 5 to 20 carbon atoms. Particularly preferably, R ⁵ means a hydrocarbyl residue having at least 6 carbon atoms, for example, hydrocarbyl having 6 to 20 carbon atoms, preferably hydrocarbyl having 6 to 16 carbon atoms, or particularly preferably hydrocarbyl having 6 to 14 atoms carbon. In particular, R ⁵ means a hydrocarbyl residue having at least 8 carbon atoms, for example a hydrocarbyl having 8 to 20 carbon atoms, preferably a hydrocarbyl having 8 to 16 carbon atoms and particularly preferably a hydrocarbyl having 8 to 14 carbon atoms. Specifically, R ⁵ means a hydrocarbyl residue having from 8 to 12 carbon atoms. Moreover, hydrocarbyl preferably means alkyl. In accordance with the foregoing, in this case, R ⁵ means an alkyl residue having at least 5 carbon atoms, for example, alkyl having from 5 to 20 carbon atoms. Particularly preferably, R ⁵ means an alkyl residue having at least 6 carbon atoms, for example, alkyl having from 6 to 20 carbon atoms, preferably alkyl having from 6 to 16 carbon atoms, or particularly preferably alkyl having from 6 to 14 atoms carbon. In particular, R ⁵ means an alkyl residue having at least 8 carbon atoms, for example, alkyl having from 8 to 20 carbon atoms, preferably alkyl having from 8 to 16 carbon atoms, or particularly preferably alkyl having from 8 to 14 carbon atoms. Specially means an alkyl residue having from 8 to 12 carbon atoms.

In the case where the polymer used according to the invention contains a polymerizable alkenyl ester and specifically M3 monomer, in a preferred embodiment of the present invention, R ⁵ means hydrocarbyl having from 4 to 20 carbon atoms, for example hydrocarbyl having from 4 to 18 carbon atoms, or hydrocarbyl having 4 to 16 carbon atoms or hydrocarbyl having 4 to 14 carbon atoms or hydrocarbyl having 4 to 12 carbon atoms, particularly preferably hydrocarbyl having 5 to 20 carbon atoms, for example Drocarbyl having 5 to 18 carbon atoms, or hydrocarbyl having 5 to 16 carbon atoms or hydrocarbyl having 5 to 14 carbon atoms, or hydrocarbyl having 5 to 12 carbon atoms, even more preferably hydrocarbyl having 6 up to 20 carbon atoms, for example hydrocarbyl having 6 to 18 carbon atoms, or hydrocarbyl having 6 to 16 carbon atoms or hydrocarbyl having 6 to 14 carbon atoms, or hydrocarbyl having 6 to 12 carbon atoms, and in particular hydrocarbyl having from 8 to 20 carbon atoms, for example rokarbil having from 8 to 18 carbon atoms or a hydrocarbyl having from 8 to 16 carbon atoms or a hydrocarbyl having from 8 to 14 carbon atoms or a hydrocarbyl having from 8 to 12 carbon atoms. Moreover, hydrocarbyl preferably means alkyl. In accordance with the foregoing, in this case, R ⁵ preferably means alkyl having from 4 to 20 carbon atoms, for example, alkyl having from 4 to 18 carbon atoms, or alkyl having from 4 to 16 carbon atoms, or alkyl having from 4 up to 14 carbon atoms, or alkyl having from 4 to 12 carbon atoms, particularly preferably alkyl having from 5 to 20 carbon atoms, for example alkyl having from 5 to 18 carbon atoms, or alkyl having from 5 to 16 carbon atoms, or alkyl having from 5 to 14 carbon atoms, or alkyl having from 5 to 12 carbon atoms, more preferably alkyl having from 6 to 20 carbon atoms, for example, alkyl having from 6 to 18 carbon atoms, or alkyl having from 6 to 16 carbon atoms, or alkyl having from 6 to 14 carbon atoms, or alkyl having from 6 to 12 carbon atoms, and in particular alkyl having from 8 to 20 carbon atoms, for example, alkyl having from 8 to 18 carbon atoms, or alkyl having from 8 to 16 carbon atoms, or alkyl having from 8 to 14 atoms carbon, or alkyl having from 8 to 12 carbon atoms. Specifically, R ⁵ means an alkyl residue having from 8 to 12 carbon atoms.

Preferred R ⁵ alkyl residues are independent of their chain length and independent of whether or not the polymer contains a polymerizable alkenyl ester, especially M3 monomer, preferably linear or slightly branched. Slightly branched means that at n carbon atoms in the longest carbon chain of the alkyl residue there are maximum (n-3) branches. As examples of such slightly branched alkyl radicals, isopentyl (- (CH ₂ ) ₂ -CH (CH ₃ ) ₂ ), isohexyl (- (CH ₂ ) ₃ -CH (CH ₃ ) ₂ ), 2-ethylhexyl, isononyl (3 , 5,5-dimethylhexyl), 2-propylheptyl and the like. Particularly preferably, the alkyl radical R ⁵ is linear or contains a maximum of 2 branches. In particular, it is linear or contains one branch.

Regardless of whether or not the polymer contains the polymerizable alkenyl ester and specifically the monomer M3, R ⁵ means n-octyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, 2-propylheptyl, n-undecyl, lauryl (= n-dodecyl) or n-tridecyl and especially 2-ethylhexyl or lauryl.

Particularly preferably, the monomer M2 is selected from octyl ester of acrylic acid, 2-ethylhexyl ester of acrylic acid, n-nonyl ester of acrylic acid, isononyl ester of acrylic acid, n-decyl ester of acrylic acid, 2-propylheptyl ester of acrylic acid, n-undecyl ester of acrylic acid, lauryl ester of acrylic acid and n-tridecyl ester of acrylic acid. In particular, the M2 monomer is selected from acrylic acid 2-ethylhexyl ester and acrylic acid lauryl ester. Specifically, it is a 2-ethylhexyl ester of acrylic acid.

With the monomers M3, we are talking about an alkenyl ester, for example a vinyl or propenyl ester, an aliphatic carboxylic acid, which may be unsaturated or preferably saturated.

As examples of alkenyl esters, in particular aliphatic carboxylic acid vinyl or propenyl ester, which may be unsaturated or preferably saturated, aliphatic carboxylic acid vinyl or propenyl ester having from 2 to 20 carbon atoms, such as acetic acid, propionic acid, butyric acid, valerianic acid, isovaleric acid, pivalic acid, neopentanoic acid, caproic acid, enanthic acid, caprylic acid, ne argon acid, 2-ethylhexanoic acid, acid "versatic (Versatic ^TM acid), in particular neononanovaya acid and neodecanoic acid (for example, VeaVa ^TM = vinyl ester acid" versatic "), capric acid neoundekanovaya acid, lauric acid, stearic acid nonadecanoic acid and arachinic acid. Vinyl esters of the named carboxylic acids are preferred.

In the monomer M3, R ⁶ , R ⁷ and R ^8, independently of one another, are preferably hydrogen or methyl, and particularly preferably hydrogen.

R ⁹ preferably means hydrocarbyl having from 1 to 9 carbon atoms. Moreover, hydrocarbyl preferably means alkyl. Particularly preferably, R ⁹ is ethyl or methyl, and in particular methyl.

With the monomer M3, it is particularly preferably vinyl acetate.

In a special embodiment of the invention, the copolymer used according to the invention comprises a polymerizable monomer M3 and is thus constructed from monomers including monomers M1, M2 and M3.

The polymers used according to the invention are preferably constructed mainly from the above defined monomers M1, M2 and, if necessary, M3. Due to production, minor portions of the compound used as a regulator (chain terminating agent) may be contained.

The polymers used according to the invention also have a number average molecular weight M _n in the range from, for example, 1000 to 20,000, particularly preferably from 1000 to 10,000, in particular from 1,500 to 6,000 and especially from 1,500 to 5,000.

The polymers can also have a weight average molecular weight M _w from 1000 to 30000, in particular from 2000 to 20,000 and / or a ratio M _w / M _n from 1.5 to 5.0, preferably from 1.8 to 4.0, and in particular from 1.9 to 3.5.

The number average weight average molecular weight M _w and M _n refer to values obtained by gel permeation chromatography (GPC).

The viscosity of such polymers (determined according to Ubbelohde DIN 51562) is, for example, from 5 to 25,000 mm ² / s, preferably, for example, from 10 to 1000 mm ² / s, in particular, for example, from 50 to 700 mm ² / s , respectively, at a temperature of, for example, 120 ° C.

Preferably, the polymers used are selected from copolymers of ethylene and alkyl acrylates having 5 to 20 carbon atoms, for example alkyl acrylates having 5 to 18 carbon atoms, or alkyl acrylates having 5 to 16 carbon atoms, or alkyl acrylates having 5 to 14 carbon atoms and copolymers of ethylene, vinyl acetate and alkyl acrylates having from 5 to 20 carbon atoms, for example alkyl acrylates having from 5 to 18 carbon atoms, or alkyl acrylates having from 5 to 16 carbon atoms, or alkyl acrylates having from 5 to 14 carbon atoms. Particularly preferably, the polymers used are selected from copolymers of ethylene and alkyl acrylates having from 6 to 20 carbon atoms, for example alkyl acrylates having from 6 to 18 carbon atoms, or alkyl acrylates having from 6 to 16 carbon atoms, or alkyl acrylates having from 6 to 14 atoms carbon and copolymers of ethylene, vinyl acetate and alkyl acrylates having from 6 to 20 carbon atoms, for example alkyl acrylates having from 6 to 18 carbon atoms, or alkyl acrylates having from 6 to 16 carbon atoms, or alkyl acrylates having from 6 to 14 carbon atoms kind of. Even more preferably, the polymers used are selected from copolymers of ethylene and alkyl acrylates having from 8 to 20 carbon atoms, for example, alkyl acrylates having from 8 to 18 carbon atoms, or alkyl acrylates having from 8 to 16 carbon atoms, or alkyl acrylates having from 8 to 14 carbon atoms or alkyl acrylates having from 8 to 12 carbon atoms and copolymers of ethylene, vinyl acetate and alkyl acrylates having from 8 to 20 carbon atoms, for example alkyl acrylates having from 8 to 18 carbon atoms, or alkyl acrylates having from 8 to 16 carbon atoms genus, or alkyl acrylates having from 8 to 14 carbon atoms or alkyl acrylates having from 8 to 12 carbon atoms.

In particular, polymers are used which are selected from polymers of ethylene / 2-ethylhexyl ester of acrylic acid, polymers of ethylene / complex 2-ethylhexyl ester of acrylic acid / vinyl acetate and polymers of ethylene / complex lauryl ester of acrylic acid / vinyl acetate.

Based on the polymer of ethylene, 2-ethylhexyl ester of acrylic acid (AEN) and vinyl acetate (VAC), the mass part of the monomer is:

AEN: from 4 to 80 wt.%, Preferably from 5 to 62 wt.%, In particular, for example, from 7 to 47 wt.%.

VAC: from 1 to 42 wt.%, Preferably from 1 to 30 wt.%, In particular, for example, from 1 to 25 wt.%, Especially from 1 to 20 wt.%

The difference up to 100 wt.% Corresponds to part of ethylene.

Preferably, the polymers are used as additives to improve cold flow properties. They are particularly preferably used to lower the pour point (yield point; PP) of the turbine fuel thus supplemented.

The above polymers are used alone or in combination with other such polymers in quantities that are sufficient to affect the low temperature characteristics, in particular the cold flow properties of the thus-added turbine fuel.

The polymers used according to the invention can also be used in combination with other conventional additives to improve cold flow properties and / or the following additives for turbine fuels.

b) obtaining polymers

The polymers used according to the invention can be obtained in a known manner. Preferably, they are obtained by radical polymerization, in particular high pressure polymerization, of monomers M1, M2 and, if necessary, M3. Such methods of direct radical copolymerization under high pressure of unsaturated compounds are known from the prior art (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, brief abstracts: Waxes, Bd. A 28, p. 146 et al., VCH Weinheim, Basel Cambridge, New York, Tokyo, 1996; in addition, US patent 3,627,838; German patent application DE-A 2515805; DE-A 3141507; European patent application EP-A 0007590).

The copolymers obtained by the polymerization processes used according to the invention are preferably mainly constructed from the above-defined monomers M1, M2 and, if necessary, M3. Due to production, minor portions of the compound used as a regulator (chain terminating agent) may be contained.

The preparation of the polymers takes place preferably in stirred autoclaves operating under high pressure or in reactors operating under high pressure, or in combinations of both. They preferably have a length / diameter ratio that remains in the range from 5: 1 to 30: 1, preferably from 10: 1 to 20: 1.

Suitable pressure conditions for polymerization are from 1000 to 3000 bar, preferably from 1500 to 2000 bar. Reaction temperatures are, for example, in the range of 160 to 320 ° C., preferably in the range of 200 to 280 ° C.

As a regulator for determining the molecular weight of the copolymers, for example, an aliphatic aldehyde or an aliphatic ketone of the general formula

or mixtures thereof.

Moreover, the residues R ^a and R ^b are the same or different and are selected from

- hydrogen;

- alkyl having from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso-hexyl, sec-hexyl; particularly preferably alkyl having from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

- cycloalkyl having from 3 to 12 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred.

Residues R ^a and R ^b can also be covalently linked together to form a 4-13 membered ring. Thus, R ^a and R ^b together form, for example, the following alkylene groups: - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ , - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH ( CH ₃ ) —CH ₂ —CH ₂ —CH (CH ₃ ) - or —CH (CH ₃ ) —CH ₂ —CH ₂ —CH ₂ —CH (CH ₃ ) -.

Preferred is the use of propionaldehyde or ethyl methyl ketone as a regulator.

Further well-suited regulators are unbranched aliphatic hydrocarbons, such as, for example, propane or branched aliphatic hydrocarbons with tertiary hydrogen atoms, such as, for example, isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-pentamethylheptane). Higher olefins, such as, for example, propylene, can be used as further additional regulators.

Mixtures of both regulators with hydrogen or hydrogen alone are also preferred.

The amount of regulator used corresponds to the quantities conventional for high pressure polymerization processes.

Conventional radical initiators, such as, for example, organic peroxides, oxygen or azo compounds, can be used as an initiator for radical polymerization. Mixtures of several radical initiators are also suitable. As radical initiators, for example, one or more peroxides selected from the following commercially available substances can be used:

- didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoyl peroxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyethyl acetate, tert-butyl peroxide diethyl -di- (tert-butylperoxycarbo) -cyclohexane as an isomeric mixture, tert-butylperisononanoate, 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (tert-butylperoxy) β-cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxy isopropyl carbonate, 2,2-di-tert-butyl peroxy) butane or tert-butyl peroxy acetate;

tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, isomeric di- (tert-butyl peroxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane, tert-butyl cumyl peroxide, 2,5-dimethyl-2, 5-di (tert-butyl peroxy) -hex-3-yn, di-tert-butyl peroxide, 1,3-diisopropyl monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide;

or

- dimeric or trimeric ketone peroxides, such as those known from European patent application EP-A 0813550.

Particularly suitable as peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof. As the azo compound, for example, azobisisobutyronitrile (“AIBN”) is called. The radical initiator is added in amounts conventional for polymerization.

In a preferred mode of action, the polymers used according to the invention are obtained by the fact that the mixture of monomers M1, M2 and, optionally, M3 in the presence of a regulator at a temperature in the range from, for example, 20 to 50 ° C, such as, for example, 30 ° C preferably continuously passed through a stirred autoclave, which is kept under pressure in the range from, for example, 1500 to 2000 bar, such as, for example, 1700 bar. Due to the preferably continuous supply of initiator, which is usually dissolved in a suitable solvent, such as, for example, isododecane, the temperature is kept in the reactor at the desired reaction temperature, such as, for example, 200-250 ° C. The polymer formed after degassing the reaction mixture is then isolated in the usual manner.

Variations of this method of action, of course, are possible and can be carried out by a specialist in this field without unacceptable costs. Thus, comonomers and regulators can be added separately to the reaction mixture, the reaction temperature during the process can be varied, to name just a few examples.

c) turbine fuel compositions

A further subject of the invention relates to turbine fuel compositions containing large mass parts of turbine fuel and small mass parts of at least one polymer used according to the invention according to the above definition.

In the framework of the proposed invention, the polymers used according to the invention can be used in combination with the following conventional additives to improve cold flow properties and / or the following additives for turbine fuel.

The composition of turbine fuel contains the bulk of liquid turbine fuel, and we can talk about turbine fuel, which is common for civil or military aviation. To it belongs, for example, a fuel called Jet A, Jet A-1, Jet B, JP-4, JP-5, JP-7, JP-8 and JP-8 + 100. Jet A and Jet A-1 are commercially available kerosene-based turbine fuel specifications. Related standards are ASTM D 1655, as well as DEF STAN 91-91. Jet A and Jet A-1, according to their respective specifications, have a freezing point of -40 ° C or -47 ° C. Jet B is further chopped fuel based on fractions of heavy naphtha and kerosene. JP-4 is equivalent to Jet B. JP-4, JP-5, JP-7, JP-8 and JP-8 + 100 are military turbine fuels, which, for example, are used in the navy and military aviation. Partially, such standards indicate formulations that already contain the following additives, such as corrosion inhibitors, deicers, static dissipators, etc. Preferred turbine fuels are Jet A, Jet A-1 and JP-8.

The polymer used according to the invention is preferably used in quantitative terms, based on the total amount of the composition of the turbine fuel, which when considered has mainly a sufficient effect on the cold flow properties of the composition of the turbine fuel. The polymer is preferably used in an amount of from 10 to 10,000 mg / L, particularly preferably from 50 to 7,000 mg / L, in particular from 100 to 5,000 mg / L, based on 1 liter of turbine fuel composition.

d) additives

The polymers used according to the invention can be added to the turbine fuel compositions individually or as a mixture of such polymers and, if necessary, in combination with the following known additives.

Suitable additives that may be present in the turbine fuel compositions of the invention include the following additives that improve the low temperature characteristics of the fuel (additives to improve cold flow properties), detergents, corrosion inhibitors, antioxidants such as spatially hindered tert-butylphenols or N-butylphenylenediamines, deactivators such as N, N'-disalicylidene-1,2-diaminopropane, solvents, anti-static agents such as Stadis 450, biocides, anti-icers such as diethylene glycol yl ester and mixtures thereof.

As conventional additives for improving the properties of cold flow are called, in particular:

(a) copolymers of ethylene with at least one of the following ethylenically unsaturated monomers, which differ from the polymers used according to the invention;

(b) comb polymers;

(c) crystallization centers;

(d) polar nitrogen compounds:

(e) sulfocarboxylic acids or sulfonic acids or their derivatives;

(f) poly (meth) acrylic acid ester;

(g) Alkanolamine conversion products with acylation agents;

(h) condensation products of hydroxyaromatic compounds with aldehydes; and

(i) waxes.

For ethylene copolymers with at least one of the following ethylenically unsaturated monomers (a), the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters, fumaric esters, maleic esters and olefins.

Suitable olefins are, for example, olefins having from 3 to 20 carbon atoms, as well as from 1 to 3, preferably 1 or 2, in particular one carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be located both at the end (α-olefins) and inside. However, α-olefins are preferred, particularly preferably α-olefins having from 3 to 20, particularly preferably from 3 to 10 and in particular from 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene .

Suitable esters of (meth) acrylic acid are, for example, esters of (meth) acrylic acid with alkanols having from 1 to 10 carbon atoms, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol , tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol. The style of “(meth) acrylic acid” should express that includes both acrylic acid and methacrylic acid.

Suitable alkenyl carboxylic esters are, for example, vinyl and propenyl esters of carboxylic acids having from 2 to 20 carbon atoms, whose hydrocarbon residues may be linear or branched. Here, vinyl ester is preferred under this. Among branched-chain carboxylic acids, preferred are those whose branches are in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, i.e. the carboxylic acid is the so-called neocarboxylic acid.

Suitable alkenylcarboxylic acid esters are vinyl acetate, vinyl propionate, vinyl butyrate, neopentanoic acid vinyl ester, hexalic acid vinyl ester, octanoic acid vinyl ester, vinyl 2-ethylhexanoate, neononanoic acid vinyl ester and non-vinyl ester corresponding non-complex propenyl esters, with vinyl esters being preferred. A particularly preferred alkenylcarboxylic acid ester is vinyl acetate.

Particularly preferably, the ethylenically unsaturated monomer is selected from alkenylcarboxylic acid esters.

Also suitable are copolymers that contain polymerizable two or more different alkenylcarboxylic acid esters, which may differ in the function of alkenyl and / or in the carboxylic acid group. Also suitable are copolymers which, along with the alkenyl carboxylic ester (esters), contain the polymerizable at least one olefin and / or at least one (meth) acrylic acid ester.

The ethylenically unsaturated monomer is a copolymer in an amount of from preferably 1 to 50 wt.%, Particularly preferably from 10 to 50 wt.% And in particular from 5 to 20 wt.%, Based on the entire copolymer.

The copolymer (a) preferably has a number average molecular weight M _{n of} from 1000 to 10000 and in particular from 1000 to 6000.

Such ethylene copolymers (a) are described in international patent application WO 01/62874 or in European patent application EP-A 1357168, to which reference is hereby made in full.

Comb polymers (b) are described, for example, in Comb-Like Polymers. Structure and Properties ”, N.A. Platé und V.P.Shibaev, J.Poly. Sci. Macromolecular Revs. 8, pp. 117-253 (1974). Of the described there are suitable, for example, comb polymers of the formula II

wherein

D is R ¹⁷ , COOR ¹⁷ , OCOR ¹⁷ , R ¹⁸ , OCOR ¹⁷ or OR ¹⁷ , E is hydrogen, CH ₃ , D or R ¹⁸ , G is hydrogen or D,

J is hydrogen, R ¹⁸ , R ^{18 is} COOR ¹⁷ , aryl or heterocycle, K is hydrogen, COOR ¹⁸ , OCOR ¹⁸ , OR ¹⁸ or COOH, L is hydrogen, R ¹⁸ , COOR ¹⁸ , OCOR ¹⁸ , COOH or aryl, where R ¹⁷ means a hydrocarbon residue having at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, R ¹⁸ means a hydrocarbon residue having at least one carbon atom, preferably from 1 to 30 carbon atoms, m means molar a proportion in the region of 1.0 to 0.4 and n means a molar fraction in the region of 0 to 0.6.

Preferred comb polymers are prepared, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example, an α-olefin or an unsaturated ester such as vinyl acetate, and then esterifying the anhydride or acid function with an alcohol having at least at least 10 carbon atoms. Further preferred comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Mixtures of comb polymers are also suitable. Comb polymers can also be polyfumarates or polymaleinates. Further suitable comb polymers are homopolymers and copolymers of vinyl ethers.

Suitable crystallization centers (c) are, in particular, polyoxyalkylenes, for example polyoxyalkylene ester, polyoxyalkylene ether, polyoxyalkylene ester / simple, and mixtures thereof. Preferably, the polyoxyalkylene compounds contain at least one, particularly preferably at least two linear alkyl groups having from 10 to 30 carbon atoms, and at least one polyoxyalkylene group having a molecular weight of up to 5000. Moreover, the alkyl group polyoxyalkylene residues preferably contains from 1 to 4 carbon atoms. Such polyoxyalkylene compounds are described, for example, in European patent application EP-A 0061895, EP-A 1357168, as well as in US patent 4491455, to which reference is hereby made in full. Preferred polyoxyalkylene esters, polyoxyalkylene ethers, polyoxyalkylene esters / ethers have the general formula III

R ¹⁹ - [O- (CH ₂ ) _y -] - _x OR ²⁰ (III)

wherein

R ¹⁹ and R ^20, respectively, independently of one another, are R ²¹ , R ²¹ —CO—, R ²¹ —O — CO (CH ₂ ) _z — or R ²¹ —O — CO (CH ₂ ) _z —CO—, wherein R ²¹ means alkyl having from 1 to 30 carbon atoms,

y means a number from 1 to 4,

x is a number from 2 to 200, and

z means a number from 1 to 4.

Preferred polyoxyalkylene compounds of formula III in which both R ¹⁹ and R ^{20 are} R ²¹ are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Preferred polyoxyalkylene compounds of formula III in which one of the radicals R ^{19 are} R ²¹ and the other means R ²¹ —CO—, are polyoxyalkylene esters of fatty acids having from 10 to 30 carbon atoms, such as stearic acid or behenic acid. Preferred polyoxyalkylene compounds in which both R ¹⁹ and R ^{20 are} R ²¹ —CO— are diesters of fatty acids having from 10 to 30 carbon atoms, preferably stearic or behenic acid.

The following suitable crystallization centers (c) are block copolymers, such as those described in European patent application EP-A 1357168, the contents of which are hereby incorporated by reference in their entirety. Suitable block copolymers include at least one crystallizable block and at least one non-crystallizable block. With copolymers, we can talk about diblock copolymers, tribloxopolymers or higher block copolymers. Preferred triblock copolymers at the ends of both polymers have one crystallizable block.

Preferably, such block copolymers are constructed from elements of butadiene and isoprene.

Polar nitrogen compounds (d) are also referred to as additives that inhibit the growth of paraffin crystals in diesel fuel (WASA). They are suitably oil soluble, can be either ionic or non-ionic, and preferably have at least one, particularly preferably at least 2 substituents of the formula> NR ²² , in which R ²² is a hydrocarbon residue having from 8 up to 40 carbon atoms. Nitrogen substituents can also be quaternized, which means in cationic form. An example of such nitrogen compounds are ammonium salts and / or amides, which are obtained by converting at least one amine substituted by at least one hydrocarbon residue with a carboxylic acid having 1 to 4 carboxyl groups or a suitable derivative thereof. Preferably, the amines contain at least one linear alkyl residue having from 8 to 40 carbon atoms. Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and higher linear homologs. Suitable secondary amines are, for example, dioctadecylamine and methyl begenylamine. Also suitable are amine mixture, in particular industrially produced mixture of amines such as fatty amines or hydrogenated tallaminy such as, for example, described in Ullmann's Encydopedia of Industrial Chemistry, 6 ^th edition, 2000 electronic release, Kapitel «Amines, aliphatic ». Acids suitable for conversion are, for example, cyclohexane-1, 2-dicarboxylic acid, cyclohexene-1, 2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long chain hydrocarbon residues.

A further example of polar nitrogen compounds are ring systems which carry at least two substituents of the formula —A — NR ²³ R ²⁴ , in which A represents a linear or branched aliphatic hydrocarbon group which, if necessary, is interrupted by one or more groups which selected from O, S, NR ³⁵ and CO, and R ²³ and R ²⁴ mean a hydrocarbon residue having from 9 to 40 carbon atoms, which, if necessary, is interrupted by one or more groups selected from O, S, NR ³⁵ and CO, and / or substituted with one or more substitutes styrenes that are selected from OH, SH and NR ³⁵ R ³⁶ , wherein R ³⁵ is alkyl having from 1 to 40 carbon atoms, which is optionally interrupted by one or more moieties selected from CO, NR ³⁵ , O and S, and / or substituted by one or more residues selected from NR ³⁷ N ³⁸ , OR ³⁷ , SR ³⁷ , COR ³⁷ , COOR ³⁷ , CONR ³⁷ R ³⁸ , aryl or heterocycle, and R ³⁷ and R ^{38 are} respectively independently selected from hydrogen or alkyl having from 1 to 4 carbon atoms; and R ³⁶ means hydrogen or R ³⁵ .

Preferably, A is a methylene or polymethylene group having from 2 to 20 methylene elements. As examples of suitable radicals R ²³ and R ²⁴ are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl. In a cyclic system, it can be a homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic system. Preferably, the ring system is carboaromatic or heteroaromatic, in particular carboaromatic. Examples of such polycyclic ring systems are condensed benzoid structures such as naphthalene, anthracene, phenanthrene and pyrene, condensed non-benzoid structures such as azulene, indene, hydrindene and fluorene, non-condensed polycycles such as diphenyl, heterocycles such as quinoline , indole, dihydroindole, benzofuran, coumarin, isocumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems such as decalin, and three-dimensional structures, t Kie like Apin, camphene, bornylene, norbonan, norbonen, bicyclooctane and bicyclooctene.

A further example of suitable polar nitrogen compounds is the condensation of long chain primary or secondary amines with polymers containing carboxyl groups.

The polar nitrogen compounds referred to here are described in international patent application WO 00/44857, as well as in the references therein, to which reference is made in full.

Suitable polar nitrogen compounds are also described, for example, in German patent applications DE-A 19848621, DE-A 19622052, European patent applications EP-A 1357168 or EP-B 398101, referred to.

Suitable sulfocarboxylic acids / sulfonic acids or their derivatives (e) are, for example, such general formulas IV

wherein

Y is SO ₃ ^- (NR ²⁵ ₃ R ²⁶ ) ⁺ , SO ₃ ^- (NHR ²⁵ ₂ R ²⁶ ) ⁺ , SO ₃ - (NR ₂ R ²⁵ R ²⁶ ), SO ₃ ^- (NH ₃ R ²⁶ ) or SO ₂ NR ²⁵ R ²⁶ ,

X is Y, CONR ²⁵ R ²⁷ , CO ₂ ^- (NR ²⁵ ₃ R ²⁷ ) ⁺ , CO ₂ ^- (NHR ²⁵ ₂ R ²⁷ ) ⁺ , R ²⁸ -COOR ²⁷ , NR ²⁵ COR ²⁷ , R ²⁸ OR ²⁷ , R ²⁸ OCOR ²⁷ , R ²⁸ R ²⁷ , N (COR ²⁵ ) ²⁷ or Z- (NR ²⁵ ₃ R ²⁷ ) ⁺ , moreover

R ²⁵ means a hydrocarbon residue,

R ²⁶ and R ²⁷ mean alkyl, alkoxyalkyl or polyalkoxyalkyl having at least 10 carbon atoms in the main chain, R ²⁵ means alkylene having from 2 to 5 carbon atoms, Z means the equivalent of anions and

A and B are alkyl, alkenyl or two substituted hydrocarbon residues, or together with the hydrocarbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.

Such sulfocarboxylic acids or sulfonic acids and their derivatives are described in European patent application EP-A 0261957, to which reference is made in full.

Suitable poly (meth) acrylic acid esters are both homopolymers and copolymers of acrylic acid esters and methacrylic acid, and homopolymers of acrylic acid esters which are derived from alcohols having from 1 to 40 carbon atoms are preferred. Also preferred are copolymers of at least two different (meth) acrylic acid esters, which differ with respect to the condensed alcohol. The copolymer, if necessary, contains another next, different olefinically unsaturated monomer. The weight average molecular weight of the polymer is preferably from 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated alcohols having 14 and 15 carbon atoms, the acid groups being neutralized with hydrogenated thallamine. Suitable esters of poly (meth) acrylic acid are described in international patent application WO 00/44857, which is hereby incorporated by reference in its entirety.

In order to obtain suitable alkanolamine conversion products with acylation agents (g), those which contain a hydrocarbon residue having from 8 to 50 carbon atoms are preferably used as acylation agents. As examples, succinic acids or derivatives of succinic acids are mentioned, substituted with an alkyl or alkenyl radical having from 8 to 50 carbon atoms, preferably from 12 to 35 carbon atoms. When alkanolamines are, for example, diethanolamine, dipropanolamine, dibutanolamine, N-methylethanolamine or N-ethylethanolamine. Such compounds are described, for example, in international patent application WO 01/62874, to which reference is made here.

When heteroaromatic compounds used to obtain condensation products of hydroxyaromatic compounds with aldehydes (h), we are talking about those that are substituted by a linear or branched hydrocarbon residue. The hydroxyaromatic compound can be either a substituted phenol or any other aromatic compound containing a hydroxy group, such as naphthol. As the aldehyde component, both aldehydes alone and suitable sources of aldehydes can be used. Suitable aldehydes are, for example, formaldehyde (which can be used, for example, as paraldehyde or trioxane), acetaldehyde, propanal, butanal, isobutyraldehyde, heptanal, 2-ethylhexanal and glyoxalic acid. Such condensation products are described, for example, in international patent application WO 01/62874 or in European patent application EP-A 1357168, referred to here.

Suitable waxes (i) are both linear and non-linear paraffins. With H-paraffins, it is preferably an alkane having from 8 to 35 carbon atoms, particularly preferably from 8 to 30 carbon atoms and in particular from 8 to 25 carbon atoms. Non-linear paraffins include preferably an amorphous solid with a melting point of 10 to 60 ° C and a molecular weight of 150 to 500. Such waxes are described, for example, in European patent application EP-A 1357168, referred to here.

e) a set of additives

The last subject of the invention relates, in addition, to a set of additives comprising at least one polymer used according to the invention according to the above definition and at least one of the following conventional additives for turbine fuel, and, if necessary, at least one thinner.

Suitable conventional turbine fuel additives are the additives described above. Preferred additives are anti-icing additives; in addition, the aforementioned conventional cold flow improvers, with such groups (a) being preferred; corrosion inhibitors; detergents; antioxidants; antistatic agents and deactivators. In particular, the additive package contains, along with at least one of the above-described polymer, at least one anti-icing agent and, if necessary, at least one of the following additives: a conventional additive that improves cold flow properties, and such groups are preferred ( but); corrosion inhibitors; detergents; antioxidants; antistatic agents and deactivators.

The amount of polymer used according to the invention in the additive kits is preferably from 0.1 to 99 wt.%, Particularly preferably from 1 to 95 wt.% And in particular from 5 to 90 wt.%.

In addition, the additive kit may optionally contain at least one diluent. Suitable diluents are, for example, fractions from oil refining, such as kerosene, heavy naphtha or residual cylinder oil. Moreover, aromatic hydrocarbons such as a solvent: heavy naphtha, Solvesso® or Shellsol®, and aliphatic hydrocarbons are suitable.

If the kit contains a diluent, the polymer used according to the invention is preferably in a concentration of from 0.1 to 90 wt.%, Particularly preferably from 1 to 80 wt.% And in particular from 10 to 70 wt.%, Based on the total mass of concentrate.

Thanks to the use of the described polymers according to the invention, the cold flow properties of the turbine fuel thus supplemented are improved. First of all, the freezing point, cloud point (CP) and, in particular, the pour point (PP) are reduced.

Now the invention is explained in more detail below with the help of examples, in no way limiting its scope.

Experimental part:

1. Examples of obtaining 1-28

In total, 28 different polymers used according to the invention are obtained by high pressure polymerization of ethylene and 2-ethylhexyl ester of acrylic acid (AEN) or ethylene, of 2-ethylhexyl ester of acrylic acid (AEN) or lauryl ester of acrylic acid (AL) and vinyl acetate (VAC).

Table 1 summarizes the characteristics of the polymers used in the following test examples.

The content of ethylene, AEN or AL and VAC in the obtained polymers is determined using NMR spectroscopy. Viscosities are determined according to Ubbelohde DIN 51562 at a temperature of 120 ° C.

Table 1 Polymer No. E (wt.%) VAC (wt.%) Acrylate (wt.%) Viscosity (mm ² / s) M _n M _w M _w / M _n one 79.9 - 20.1 ¹ 150 3197 8499 2.66 2 88.0 4.2 7.8 ¹ 60 2088 4189 2.01 3 88.0 4.4 7.6 ¹ 150 2959 6666 2.25 four 88.1 4.4 7.5 ¹ 605 4635 12811 2.76 5 86.6 3.9 9.5 ¹ 60 2124 4285 2.02 6 86.4 4.3 9.3 ¹ 150 3022 6754 2.23 7 86.4 4.1 9.5 ¹ 595 4797 13238 2.76 8 83.8 4.1 12.1 ¹ 60 2064 4280 2.07 9 83,2 4.4 12.4 ¹ 150 2994 7203 2.41 10 83.1 4.4 12.5 ¹ 600 4744 14503 3.06 eleven 80.2 4,5 15.3 ¹ 150 3038 7279 2.40 12 80,4 4.1 15,5 ¹ 600 4681 15697 3.35 13 89.6 8.0 2.4 ¹ 60 1977 3910 1.98 fourteen 89.8 7.9 2,3 ¹ 150 2831 6212 2.19 fifteen 89.2 8.2 2.6 ¹ 605 3862 11098 2.87 16 89.8 8.4 4.8 ¹ 60 1928 3902 2.02 17 86.5 8.4 5.1 ¹ 150 2926 6337 2.17 eighteen 86.3 8.5 5.2 ¹ 620 4613 12019 2.61 19 84.2 8.1 7.7 ¹ 60 2003 4025 2.01 twenty 83.1 8.7 8.2 ¹ 150 2855 6382 2.24 21 84.3 8.0 7.7 ¹ 615 4858 13061 2.69 22 81.1 7.9 11.0 ¹ 60 2100 4276 2.04 23 80.8 8.0 11.2 ¹ 150 2878 6634 2,31 24 81.1 7.6 11.3 ¹ 630 4774 14263 2.99 25 77.6 8.7 13.7 ¹ 150 3134 7195 2,30 26 86.8 4.8 8.4 ¹ 60 1928 3902 2.02 27 86.3 5.2 8.5 ¹ 620 4613 12019 2.61 28 87.9 10.5 1.6 ² 153 3100 7301 2,36

E: ethylene

VAC: Vinyl Acetate

1. A complex of 2-ethylhexyl ester of acrylic acid.

2. Lauryl ester of acrylic acid.

2. Test Examples

The following tests are carried out with the obtained polymers 1-28. For comparison purposes, a common ethylene / vinyl acetate copolymer is tested together.

Jet A turbine fuel with a pour point (PP) of -48 ° C, firstly, is supplemented with a conventional ethylene / vinyl acetate copolymer and, secondly, with copolymers of examples 1, 17 and 25-28 in the amount of respectively 1000 mg / l and determined the PP value of the added turbine fuel, respectively, according to ISO 3016. The PP value of the turbine fuel supplemented with the usual ethylene / vinyl acetate copolymer is -48 ° C, that is, it could not go down. The PP values of the turbine fuel, respectively supplemented with the copolymers used according to the invention, are given in table 2.

table 2 Polymer No. PP (° C) - -48 EVA * -48 one <-68 17 -63 25 <-70 26 -63 27 -51 28 -51

EVA * = conventional ethylene / vinyl acetate copolymer (comparative example).

As shown in the examples, turbine fuel supplemented with the copolymers used according to the invention exhibits a distinctly lower pour point than a non-supplemented fuel, while a conventional ethylene / vinyl acetate copolymer had no effect on the pour point.

Claims (15)

1. The use of a polymer that is built of monomers containing M1, M2 and optionally M3, moreover, M1, M2 and M3 have the following general formulas

in which R ¹ means hydrogen or hydrocarbyl having from 1 to 40 atoms
carbon;
R ² , R ³ and R ⁴ independently from each other mean hydrogen or alkyl having from 1 to 4 carbon atoms;
R ⁵ means unsubstituted alkyl having from 1 to 20 carbon atoms, or for the case when the polymer does not contain any polymerizable monomer M3, means unsubstituted alkyl having from 8 to 20 carbon atoms;
R ⁶ , R ⁷ and R ⁸ independently from each other mean hydrogen or alkyl having from 1 to 4 carbon atoms; and
R ⁹ means methyl or ethyl;
as an additive for turbine fuel. 2. The use according to claim 1, wherein the polymer contains polymerizable monomers M1, M2 and optionally M3 in a statistical distribution. 3. The use according to claim 1, wherein the monomers M1, M2 and M3 are present in the polymer in the following molar parts:
M1: 0.60 to 0.99;
M2: from 0.01 to 0.40;
M3: 0 to 0.20. 4. The use according to claim 1, wherein the monomer M1 is ethylene. 5. The use according to claim 1, wherein R ² , R ³ and R ^{4 are} hydrogen or two of the residues R ² , R ³ and R ^{4 are} hydrogen and the other residue is methyl. 6. The use according to claim 1, wherein R ⁵ is alkyl having from 8 to 12 carbon atoms. 7. The use according to claim 6, wherein R ⁵ is 2-ethylhexyl or lauryl. 8. The use according to claim 1, wherein M2 is an acrylic acid 2-ethylhexyl ester or an acrylic acid lauryl ester. 9. The use according to claim 1, wherein M3 is vinyl acetate. 10. The use according to one of claims 1 to 9, wherein the polymer is used as an additive to improve cold flow properties. 11. The use of claim 10, wherein the polymer lowers the pour point of the thus supplemented turbine fuel. 12. The use according to one of claims 1 to 9, wherein the polymer is used in combination with other additives for turbine fuel. 13. The composition of the turbine fuel containing a large mass part of the turbine fuel and a smaller mass part of at least one polymer according to the definition of one of claims 1 to 9. 14. The composition of the turbine fuel according to item 13, further containing additives for turbine fuel. 15. A set of additives containing at least one polymer as defined by one of claims 1 to 9 in combination with at least one other turbine fuel additive and, if necessary, at least one diluent.