Additive formulation suited for anti-static finishing and improvement of the electrical conductivity of inanimate organic material

Translation of description of equivalent WO 2008107371 A2

p0001For antistatic modification and improving the electrical conductivity of inanimate organic material suitable additive formulation

p0002description

p0003The present invention relates to a new and improved additive formulation suitable for antistatic modification and improving the electrical conductivity of inanimate organic material and for preventing electrostatic charge in chemical and physical processes. Furthermore, the present invention relates to a method for de production of this additive formulation. Furthermore, the present invention relates to the use of this additive formulation and hereby antistatic equipped inanimate organic material. Furthermore, the present invention relates to a process for preparing olefin-sulfur dioxide copolymers with a low olefin mers residual content, which can be used advantageously as a component in this additive formulation.

p0004Inanimate organic material, such as a fuel is usually a very poor conductor of electricity. Therefore, electric charges tend to like to accumulate locally in such organic material and an uncontrolled discharge as sparks, which can cause an explosion or fire on contact of this organic material, which is usually combustible and often highly flammable, with air or oxygen. By suitable antistatic additives, the electrical conductivity of inanimate organic material can be increased, so that no static electricity can form more and the risk of explosions and fires is reduced.

p0005From US-A 3,917,466 (1) additive formulations for antistatic modification and improving the electrical conductivity are known, consisting of olefin-sulfur dioxide copolymers, polymeric polyamines which by reacting epichlorohydrin with aliphatic monoamines or polyamines, such as N-tallow-1 , 3-diamino propane, available are, oil-soluble sulfonic acids and low-boiling solvents such as toluene and / or isopropanol are made.

p0006In US-A 4,416,668 (2) mixtures of α-olefin-maleimide copolymers and olefin-sulfur dioxide mers are copolymers as an antistatic agent for organic liquids as described fuels. These mixtures may comprise solvents such as benzene, toluene or xylenes.

p0007However, the effect of the antistatic agents described in the prior art is not yet satisfactory. There is a need for a more effective and sustainable increase the electrical conductivity in inanimate organic material. Furthermore, the antistatic agent should have an even higher thermal stability. From toxicity ity and environmental reasons, they shall be as heavy metals and halogens. Not least, they should have a very high flash point, so that they in their preparation Position, their transport and their storage prior to use in the inanimate organic material safely, ie, can be handled without explosion and fire risk.

p0008It was therefore an object to provide acceptable antistatic agent to increase the electrical conductivity in inanimate organic material, especially in fuels and mineral oil products, with effective action, a high thermal stability and a very high flash point lower toxicity and environmental viewpoints.

p0009Accordingly, an additive formulation has been found which is suitable for antistatic modification and improving the electrical conductivity of inanimate organic material and consists essentially of

p0010(A) 1 to 50 wt .-% of an olefin-sulfur dioxide copolymer,

p0011(B) 1 to 50 wt .-% of a compound one or more basic nitrogen atom-containing containing at least one long-chain linear or branched hydrocarbon radical having at least 4 carbon atoms or a equiv- TES structural element which the solubility of component (B) in the inanimate organic material guarantees which

p0012(C) 0.1 to 30 wt .-% of an oil soluble acid and

p0013(D) 1 to 80 wt .-% of a high-boiling organic solvent which consists of one or more molecule types, where at least 80 wt .-% of these molecule types have a boiling point of more than 150⁰have C at atmospheric pressure,

p0014, wherein the sum of all components (including secondary components may of existing and / or non-interfering impurities) 100 wt .-% results.

p0015The additive formulation according to the invention can - mostly due to manufacturing - as secondary components and / or non-interfering impurities still to 10 wt .-%, in particular up to 5 wt .-%, especially up to 2 wt .-%, contain other ingredients.

p0016In a preferred embodiment, the additive formulation according to the invention consists essentially of (A) 10 to 30 wt .-%, in particular from 13 to 25 wt .-%, the component (A),

p0017(B) 10 to 30 wt .-%, in particular from 13 to 25 wt .-%, component (B),

p0018(C) 2 to 15 wt .-%, in particular 4 to 10 wt .-%, component (C) and

p0019(D) 40 to 78 wt .-%, in particular 50 to 70 wt .-%, the component (D).

p0020The Addivformulierung invention described represents a concentrate of the actual active components (A), (B) and (C) in high boiling organic solvent (D), which is ideally suited for the safe transportation and the safe storage of the goods.

p0021The structure and the known processes for preparing the olefin-sulfur dioxide-Copolymer component (A) are described in the documents (1) and (2). The component (A) is preferably a copolymer of sulfur dioxide with one or more linear or branched 1-olefins having 2 to 24 carbon atoms. Üblicherwei- se is in the copolymers (polysulfones) of component (A) to alternating 1: 1 copolymers, where usually a sulfone unit follows an olefin unit; small amounts of sequences of two or more olefin units may occur. A part of the olefin monomers can be prepared by ethylenically unsaturated carboxylic acids (eg acrylic acid, methacrylic acid or vinylacetic acid) or ethylenically unsaturated dicarboxylic acids (such as maleic acid or fumaric acid) or derivatives thereof (eg, maleic anhydride) can be replaced, so that the copolymer of component (A), especially from 50 mol -% Schwefeid ioxid-or. Sulfone units, from 40 to 50 mol% of olefin units, and 0 to 10 mol% of units from said ethylenically unsaturated carboxylic acids, ethylenically unsaturated dicarboxylic acids or derivatives thereof is constructed.

p0022Suitable branched and especially linear 1-olefins having 2 to 24 carbon atoms for preparing component (A) are, for example ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-nonene, 1-decene, 1-accident decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-hepta-decene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene or mixtures thereof into consideration. Particularly preferred are linear 1-olefins having from 6 to 16, in particular having 8 to 14 carbon atoms, or linear 1-olefins having from 12 to 22, in particular 14 to 20 carbon atoms, and mixtures thereof, for example a mixture of 1-dodecene and 1-tetradecene , It may also be advantageous to use mixtures of low and high molecular weight 1-olefins, ie 1-olefin use with a bimodal distribution, to prepare component (A), for example mixtures of 1-olefins having 6 to 13 carbon atoms and 1-olefins 14 to 20 carbon atoms or mixtures of 1-olefins having 6 to 10 carbon atoms and 1-olefins having from 1 1 to 15 carbon atoms or mixtures of 1-olefins having 2 to 24 carbon atoms and a single 1-olefin having 4 to 10 carbon atoms. When technical or other 1-olefin Mixtures are used, the indication of the carbon atoms in the above areas to the average carbon atom number of these mixtures relates, wherein the average carbon atom number of the sum over the mathematical products of weight fraction and associated carbon atom number of all mixing existing in fiscal 1 represents olefins.

p0023The olefin-sulfur dioxide copolymer of component (A) typically has a number average molecular weight M_n 2000-1000000, in particular from 4000 to 100,000, especially from 6000 to 25,000, on. The polydispersity (PDI = Mw / Mn) is generally in the range of 1, 1 to 30, especially from 1, 5 to 20, especially from 2 to 10, very particularly preferably from 2.3 to 5.

p0024In the document (1), the preparation of the olefin-sulfur dioxide copolymers by a suitable free radical polymerization process in the temperature range of 0 to 50⁰C recommended as solvent to be mentioned benzene, toluene or xylene; it is carried out with only a small molar excess of sulfur dioxide (a maximum of 1, 5 times the molar quantity); it is recommended radical initiators such as peroxides or azo compounds and the additional irradiation with actinic light. According to Scripture (2) one can prepare the olefin-sulfur dioxide copolymers by emulsion polymerization in an aqueous medium. However, both preparation methods need to be improved and the use of the obtained olefin copolymers sulfur dioxide in the additive formulation according to the invention leads to disadvantages in their handling and effect. In particular, the content of volatile and combustible starting olefins is still too high, so that the flash point of the resulting antistatic additive formulation is too low. There was therefore the need for an improved preparation process for the olefin-sulfur dioxide copolymers in order to make their use in the additive formulation according to the invention easily.

p0025Accordingly, it was within the scope of the present invention, a method for preparing olefin-sulfur dioxide copolymers which contain less than 15 mol%, preferably less than 10 mol%, especially less than 7 mol%, especially less than 5 mol% , not included in the copolymerization reacted with the sulfur dioxide olefin found which is characterized in that the sulfur dioxide in a minimum of 1, 4-fold molar excess, especially 1, 6-fold molar excess, is used, and the polymerization in a high boiling inert organic solvent is carried out, which consists of one or more molecule types, where at least 50 wt .-% of these molecule types have more than 8 carbon atoms. Preference is given to the sulfur dioxide in an at least one 8-fold molar excess, especially in a 1, 8- to 2.5-fold molar excess, and carrying out the polymerization in a high boiling inert organic solvent which consists of one or more molecular species exists wherein at least 80 wt .-% of these molecule types have from 9 to 30 carbon atoms. Is advantageously used here, a high boiling organic solvent, especially a high-boiling aromatic hydrocarbon having from 9 to 30 carbon atoms or a mixture of such high-boiling aromatic hydrocarbons, as defined for the present invention as component (D). Preferably the reaction is conducted at 10 to 40⁰C, in particular at 15 to 29 ° C, over a period of 0.5 to 24 hours.

p0026Accordingly, it was within the scope of the present invention, another process for preparing olefin-sulfur dioxide copolymers which contain less than 15 mol%, preferably less than 10 mol%, especially less than 7 mol%, especially less than 5 mol %, not included in the copolymerization reacted with the sulfur dioxide olefin found which is characterized in that the sulfur dioxide in an at least 1, 1 -fold molar excess employed and polymerization at 15 to 38 ° C, in particular at 20 to 30⁰C, performs under its own pressure. Preference is given to sulfur dioxide in this case in a minimum of 1, 4-fold molar excess, especially in an at least 1, 6-fold molar excess, especially in an at least one 8-fold molar excess, particularly preferably in a 1, 8- to 2.5-fold or a 1, 4- to 2.5-fold molar excess, and carrying out the polymerization in a high boiling inert organic solvent which consists of one or more molecule types, where at least 80 wt .-% of these have molecule types from 9 to 30 carbon atoms. Is advantageously used here too a high boiling organic solvent, especially a high-boiling aromatic hydrocarbon having from 9 to 30 carbon atoms or a mixture of such high-boiling aromatic hydrocarbons, as defined for the present invention as component (D).

p0027In a preferred embodiment of the latter process for preparing olefin-sulfur dioxide copolymers, the polymerization is conducted in a first stage over a period of 0.5 to 5 hours at 30 to 38 ° C under autogenous pressure, and thereafter in a second stage over a period 1-5 hours at 20 to 29 ° C under autogenous pressure by.

p0028In many cases, the alternative implementation of the first-mentioned or of the latter process for preparing olefin-sulfur dioxide copolymers is sufficient to achieve the desired improvement in the process, in particular in regard to increasing the flash point of the resulting anti-static additive formulation. But you can combine both methods also, that you can use the sulfur dioxide in a minimum of 1, 6-fold molar excess and the polymerization in a high boiling inert organic solvent which consists of one or more types of molecules, wherein at least 50 wt .-% of Types of molecules having more than 8 carbon atoms, and perform at 15 to 38 ° C under autogenous pressure. In all the above alternatives can be dispensed with the irradiation with actinic light, which would be carried out only at great expense in an industrial scale mainly.

p0029The polymerization described of the sulfur dioxide with the olefin proceeds generally by a free radical mechanism. Such free-radical polymerization is carried out by the customary methods. Used for this purpose, the customary free-radical initiators, in particular those based on peroxides or azo compounds, for example di-tert-butyl peroxide, tert-butyl peroxypivalate or azobisisobutyronitrile. One can for controlling the molecular weight to be achieved concomitantly regulators, for example mercaptans, such as dodecylmercaptan.

p0030The described improved process for preparing olefin-sulfur dioxide copolymer, a practically complete conversion of the olefin is obtained.

p0031The one or more basic nitrogen atom-containing compound of component (B) must be in with the inventive additive formulation to be treated inanimate organic material is soluble, but at least homogeneously distributable, his. The component (B) is in many cases likewise a polymer. It has at least one long-chain branched or especially linear hydrocarbon radical having at least 4, preferably at least 8, especially at least 12, especially having 12 to 30 carbon atoms, on, unless an equivalent structural element ensuring the solubility in the inanimate organic material. The connection fertil the component (B) preferably contains no free hydroxyl groups, because this may affect the effectiveness of the additive formulation according to the invention may.

p0032In the compound of component (B), the said long-chain branched or linear hydrocarbon radical at the or one of the basic nitrogen atoms or on a carbon atom, in polymeric structures, sitting in particular to a carbon atom of the polymer backbone. Typical long-branched or linear hydrocarbon radicals are, for example, linear alkyl groups such as occur in fatty acids, and polyisobutyl, particularly those having 20 to 150, especially 35 to 100 carbon atoms.

p0033Suitable oligomeric or polymeric structure types for component (B) with such relatively long-hydrocarbon radicals are for example reaction products of Oligoethylenaminen or oligoethyleneimines with alkyl halides, polyethyleneimine mines with polyisobutenylsuccinic, ethylene-amino (meth) - acrylate terpolymers and in particular with amines or polyamines derivatized-ized Olefin-maleic anhydride copolymers, especially α-olefin-maleimide copolymers having at least one basic nitrogen atom.

p0034A typical example of a reaction product of Oligoethylenamins with an alkyl halide is the reaction product comb, from Decaethylenun- decamin and a multiple molar excess of n-hexadecyl chloride.

p0035Suitable non-polymeric structure types for component (B) with such relatively long-chain hydrocarbon radicals are, for example salts trialkylammonium fatty acid, for example Trialkylammoniumoleate and Polyisobutenylbernsteinsäureimide.

p0036Suitable structure types for component (B) no longer chain hydrocarbon radicals are, for example, polyethyleneimines and polyvinylamines in which the special, usually crosslinked polymer backbone provides properties for the desired Löslichkeitsei-.

p0037The structure and the preparation process for the particularly preferred α-olefin-maleic acid imide copolymers having at least one basic nitrogen atom of component (B) are described in principle in document (2). In a preferred embodiment of this α-olefin-maleimide copolymers are obtainable by free-radical polymerization of one or more linear or branched α-olefins having 6 to 50 carbon atoms with maleic anhydride and subsequent reaction with one or more aliphatic polyamines. The α-olefin-maleic anhydride copolymers, and the produced therefrom α-olefin-maleimide copolymers are usually present in the main polymer chain alternating 1: 1 copolymers in which one maleic acid unit always follows one α-olefin unit. Through the longer linear or branched hydrocarbon radicals arise normally comb structures.

p0038Suitable branched and especially linear 1-olefins having 6 to 50 carbon atoms for preparing the α-olefin-maleimide copolymers of component (B) include, for example, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecyl CEN, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexa-decene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-triacontene, 1-tetracontene, 1-pentacontene or mixtures thereof into consideration. linear 1-olefins having from 12 to 30, especially having 16 to 24 carbon atoms, and mixtures thereof are particularly preferred.

p0039The free radical polymerization of 1-olefins with maleic anhydride is carried out by the customary methods. Used for this purpose, the customary free-radical initiators, in particular those based on peroxides or azo compounds, for example di-tert-butyl peroxide, tert-butyl peroxypivalate or azobisisobutyronitrile, works in the conventional temperature and pressure ranges, for example, at 50 to 150⁰C at atmospheric pressure, and performs the conversions in the usual solvents, for example aromatic hydrocarbons, by. Preferably used as the solvent, a high boiling organic solvent of component (D) of the present invention.

p0040After the polymerization, the obtained α-olefin-maleic anhydride copolymers with one or more aliphatic polyamines to give the corresponding imide. There are polyamines having a primary amino group for the imide formation, and at least one further primary, secondary or tertiary amino group for the basic nitrogen atom is required. There are here, for example kürzerket- term diamines such as ethylene diamine, 1, 3-propylenediamine, 3- (N, N-dimethylamino) propyl amine ( "DMAPA") or bis [3- (N, N-dimethylamino) propyl] amine ( "bis-DMAPA") or longer-chain diamines such as N-tallow-1, 3-diaminopropane. The usual reaction conditions for this imide formation are known to those Mannn. If solvents are used for this imide formation, it is preferred to a high-boiling organic solvent of the component (D) of the present invention.

p0041Typical examples of aliphatic polyamines reacted with α-olefin-maleic anhydride copolymers are the reaction products of comblike construction C2o / 24-α-olefin-maleic anhydride copolymers and 3- (N, N-dimethylamino) -Pro- pylamin ( "DMAPA ") or bis [3- (N, N-dimethylamino) propyl] amine (" bis-DMAPA ").

p0042The described α-olefin-maleimide copolymers with at least one Basidiomycetes see nitrogen atom of the component (B) typically have a molecular weight M TES gewichtsgemittel-_w from 500 to 50,000, particularly from 1,000 to 10,000 on. A typical α-olefin-maleimide copolymer is an N-tallow-1, 3-diaminopropane to the imide unreacted α-olefin-maleic anhydride copolymer having a weight average molecular weight M_w in the range of 1,000 to 10,000.

p0043The oil-soluble acid of component (C) is preferably an organic sulfonic acid, which to achieve the oil solubility advantageously a long-chain or bulky hydrocarbyl radical, in particular with 6 to 40, especially 8 to 32, particularly preferably having 10 to 24 carbon atoms, which. Suitable such hydrocarbyl radicals are linear or branched alkyl or alkenyl radicals, such as n-hexyl, n-Hep tyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n- tricosyl, n-tetra- cosyl, oleyl, linolyl or linolenyl, cycloalkyl radicals, eg, cyclohexyl, methylcyclohexyl, or dimethylcyclohexyl, aryl radicals, such as phenyl or naphthyl, aralkyl radicals such as benzyl or 2-phenylethyl, or more preferably alkaryl radicals, in particular with linear or branched C to C alkyl substituted phenyl or naphthyl, for example, tolyl, xylyl, n-nonylphenyl, n-decylphenyl, n-dodecylphenyl, iso-Tridecylphenyl, n-Nonylnapthyl, di-n-nonylnaphthyl, n-Decylnaphthyl, di-n-decylnaphthyl, n-dodecyl, naphthyl, di-n -dodecylnaphthyl, iso-Tridecylnaphthyl or di-iso-tridecylnaphthyl. In the latter monosubstituted phenyl radicals, the alkyl groups can be ortho, meta or para position to the sulfonic acid group, wherein para-permanence is preferred. Typical examples of the component (C) are therefore n-nonylbenzenesulfonic acid, n-decylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, iso-Tridecylbenzolsulfon- acid, n-Nonylnaphthylsulfon-acid, di-n-nonylnaphthylsulfonsäure, n-Decylnaphthyl- sulfonic acid, di-n- decylnaphthyl-sulfonic acid, n-dodecylnaphthylsulfonsäure, di-n-dodecylnaphthylsulfonsäure, iso-tri-decylnaphthylsulfonsäure and di-iso-tridecyl naphthylsulfonic.

p0044In addition to these organic sulfonic acids may in principle be used as component (C), for example, oil-soluble organic sulfinic or organic phosphonic be used acids, which also advantageously have a relatively long or bulky hydrocarbyl, in particular one having 6 to 40, especially 8 to 32, particularly preferably having 10 to 24 carbon atoms.

p0045The high-boiling organic solvents of component (D), although no one gentliche active component in the additive formulation of the invention for antistatic modification and improving the conductivity of inanimate organic material, supports and reinforces However, through its interaction with components (A), (B) and ( C) whose action contributes to the thermal stability of the formulation and ensures a high flashpoint. Furthermore, the component (D) also for better adjustability of the desired viscosity of the additive formulation according to the invention, which is an important factor for the applicability of this formulation is used.

p0046In a preferred embodiment, component (D) consists of at least 80 wt .-%, especially at least 90 wt .-%, of a high-boiling aromatic hydrocarbon having from 9 to 30 carbon atoms or a mixture of such high-boiling aromatic hydrocarbons. the component is very particularly preferably (D) at least 80 wt .-%, in particular at least 90 wt .-%, especially up to 100 wt .-%, a mixture of high boiling aromatic hydrocarbons see with 9 to 20 carbon atoms, in particular 9 to 14 carbon atoms. Such aromatic hydrocarbons are in particular di-, tri- or polynuclear aromatics, such as naphthalene, biphenyl, anthracene or phenanthrene, or mono-, di-, tri- or polynuclear aromatics with aliphatic side chains, for example substituted benzenes with C₇- To C₄Alkyl side chains, in particular C₇- To Ci2-alkyl side chains, such as n-dodecyl or n-tetradecylbenzene, but above all, with d- to Cβ-alkyl side chains, for example, n-propyl, isopropyl benzene, Ethylmethylbenzole, trimethyl benzenes, ethyl dimethyl benzenes, Diethylbenzenes n-butyl benzene, iso-butylbenzene, sec-butylbenzene, tert-butylbenzene, n-pentylbenzene, tert-pentylbenzene, n-hexyl benzene, methylnaphthalene, dimethylnaphthalenes or C2-Cβ-alkylnaphthalenes. All mentioned aromatic hydrocarbons have boiling points above 150⁰C at atmospheric pressure, typically in the range of more than 150⁰C to 330 ° C at atmospheric pressure.

p0047Mixtures of said aromatic hydrocarbons with 9 or more carbon atoms are commercially available as technical solvent cuts, for example, from ExxonMobil Chemical under the names Solvesso® 100 (Cg to Cio-Aromatenschnitt), Solvesso® 150 (C10 to Cn-Aromatenschnitt) and Solvesso® 200 (C10 to Cu Aromatenschnitt); such C10 to Cn-aromatics cut is also referred to as "solvent naphtha Heavy" ( "solvent naphtha heavy").

p0048can atoms addition to the aforementioned aromatic hydrocarbons having 9 or more carbon component (D) in the preferred embodiment described

p00490 to less than 20 wt .-% non-aromatic organic solvent components (for example long-chain paraffins and / or alicyclic compounds and / or heterocyclic compounds with boiling points of more than 100 each⁰C, in particular more than 130 ° C) and / or aromatic solvent components having less than 9 carbon atoms (for example, toluene or xylenes) included.

p0050The additive formulation according to the invention is advantageously of the following components (A), (B), (C) and (D) by mixing. In principle, any conceivable sequence of mixing allows the preservation of the additive formulation according to the invention. However, it has been found in relation to the practicality of mixing together as preferred that first in the presence of at least a portion of the high boiling organic solvent (D), the components (A) and (C) are homogeneously mixed together and then the component (B) incorporated. Furthermore, it may be advantageous schens perform the operations of Zusammenmi- at ​​slightly elevated temperatures, eg at 20 to 8O⁰C, particularly at 25 to 50⁰C. In a particularly preferred embodiment, first mixed in the presence of at least a portion of the high boiling organic solvent (D), the components (A) and (C) homogeneously with one another at 30 to 6O⁰C, in particular at 40 to 55 ° C, and then operates a component (B), whereby the mixture of components (A) and (C) and a part of the high boiling organic solvent (D) is preferably at least 1 minute, especially

p0051is maintained for 1 to 120 minutes, especially 1 to 30 minutes, in the aforementioned temperature range, before the component (B) is incorporated. It may also be advantageous to the processes of mixing together completely or partly in a vacuum, expediently at 100 mbar to less than 1 bar, in particular from 10 mbar to less than 1 bar to perform. All common mixing techniques and mixing elements are applicable. The additive formulation according to the invention is used in the sense of the present invention for antistatic modification and improving the electrical conductivity of inanimate organic material and for preventing electrostatic charge in chemical and physical processes.

p0052For this purpose, the additive formulation according to the invention is incorporated in the antistatic properties and thus to better electrically conductive to be made inanimate organic material during or after its preparation or mixed and distributed as homogeneously as possible. The concentration of the additive formulation according to the invention in the inanimate organic material is generally from 0.01 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight, especially 0.5 to 500 ppm by weight, particularly 1 to 350 ppm by weight, based on the inanimate organic material. Specifically, when used in fuels, the concentration of the additive formulation according to the invention can be lower, conventional dosages there are 0.01 to 1000 ppm by weight, preferably 0.1 to 500 ppm by weight, especially 0.5 to 100 parts by weight ppm, especially 1 to 10 ppm by weight, based on the fuel.

p0053Inanimate organic material are in particular cosmetic preparations such as ointments and lotions, drug formulations such as pills and suppositories, photogra- phic recording materials such as photographic emulsions, paints, plastics, waxes, solvents and petroleum products and fuels, especially diesel fuel, heating oil, gasoline, aviation gasoline and jet fuel, and lubricants, ie engine oils, lubricating oils, hydraulic oils, turbine oils, regulator oils, transmission, manual and automatic oils, Kalanderöle, heat transfer oils, metalworking oils, shock absorbers to understand, oil and lubricants.

p0054Examples of plastics which can be antistatic with the additive formulation according to the invention, which may be mentioned:

p0055Polymers of mono- or diolefins, such as polyethylene of low or high density polyethylene, polypropylene, linear polybutene-1, polyisoprene, polybutadiene and copolymers of mono- or diolefins or mixtures of said polymers;

p0056Polystyrene and copolymers of styrene or alpha-methylstyrene with dienes and / or acrylic derivatives, for example styrene-butadiene, styrene-acrylonitrile (SAN), styrene-ethyl methacrylate, styrene-butadiene-ethyl acrylate, styrene-acrylonitrile methacrylate, acrylonitrile-butadiene-styrene ( ABS) or methyl methacrylate butadiene styrene (MBS); halogen-containing polymers, for example polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof;

p0057Polymers derived from α, ß-unsaturated acids and derivatives thereof such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles; Polymers derivatives from unsaturated alcohols and amines or from their acyl derivatives or acetals, for example polyvinyl alcohol and polyvinyl acetate;

p0058Polyurethanes (for example, as a material for shoe soles), especially thermoplastic carbonate plasma-tables polyurethanes, polyamides, polyureas, polyphenylene ether, polyester, polyethylene, polysulfones, polyethersulfones, polyether ketones and ethylene-vinyl acetate copolymers (for example, as a material for shoe soles).

p0059The paints that can be antistatic with the additive formulation according to the invention, among other coatings such as alkyd paints, dispersion paints, epoxy, polyurethane coatings, acrylic resin coatings and Cellulosenitratla- blocks, or glazes such as wood protection varnishes.

p0060The waxes which can be equipped antistatic off with the additive formulation of the invention, include the ethylene-vinyl acetate copolymer waxes.

p0061As solvents that may be antistatic with the additive formulation of the invention and thus made more conductive, which may be mentioned: alkanes such as n-pentane, n-hexane or n-heptane, alkenes such as hexene, heptene,

p0062Octene, nonene, decene, undecene or dodecene, aromatics such as toluene or xylene, naphthalene thene, alcohols such as methanol, ethanol, isopropanol or tert-butanol, aldehydes such as acetaldehyde, propionaldehyde or Butryaldehyd, ketones such as acetone or butanone, carboxylic acids such as formic acid , acetic acid or propionic acid, carboxylic esters such as methyl acetate or ethyl acetate, carboxamides such as N, N-dimethylformamide, and mixtures thereof.

p0063The additive formulation according to the invention is suitable in a particularly advantageous manner for antistatic modification and improving the conductivity of turbine fuels (jet fuels). Turbine fuels are used for the operation of aircraft turbines especially.

p0064The usual turbine fuel composition comprises a majority of a liquid turbine fuel, which is, for example, is a common way in civil or mili- tary aviation turbine fuel. These include, for example, fuels the designation Jet Fuel A, Jet Fuel A-1, Jet Fuel B, Jet Fuel JP-4, JP-5, JP-7, JP-8 and JP-8 + 100th Jet A and Jet A-1 are commercially available turbine fuel specifications based on kerosene. The corresponding standards are ASTM D 1655 and DEF STAN 91-91. Jet B is a more cut fuel based on naphtha and kerosene fractions. JP-4 is equivalent to Jet B. JP-5, JP-7, JP-8 and JP-8 + 100 are military turbine fuels, as they are for example used by the Navy and Air Force. Some of these standards designate formulations which already comprise further additives such as corrosion inhibitors, icing inhibitors, other antistatic agents such as static dissipators, etc. included.

p0065The additive formulation according to the invention may the turbine fuel or the turbine binenkraftstoffzusammensetzung in combination with other known additives may be added. Suitable additives which may be included in the Turbinenkraftstoff- composition comprise typically detergents, corrosion inhibitors, antioxidants such as sterically hindered tert-butylphenols, N-butyl phenylenediamines or N, N'-diphenylamine and derivatives thereof, metal deactivators such as N, N ' -Disalicyliden-1, 2-diaminopropane, solubilizers, more marketable as antistatic agents Stadis® 450, biocides, anti-icing agents such as diethylene glycol methyl ether, and mixtures of said additives.

p0066Preferred additives for a turbine fuel or a Turbinenkraftstoffzu- are composition the specific compound classes (E), (F) and (G):

p0067Preferred additives (E) are derived from succinic anhydride compounds with long-chain hydrocarbon radicals having generally from 15 to 700, especially 30 to 200 carbon atoms. These compounds may have further functional groups which are preferably selected from hydroxy, amino, amido and / or imido groups. Preferred additives are the corresponding derivatives of polyalkenyl which z. B. by reacting polyalkenes with maleic anhydride by a thermal route or via the chlorinated hydrocarbons are available. The number average molecular weight of the long chain hydrocarbon radicals is preferably in a range of about 200 to 10,000, more preferably 400 to 5000, especially 600 to 3000 and especially from 650 to 2000. Preferably, these long-chain hydrocarbon radicals of conventional and particularly reactive by the aforementioned polyisobutenes derive , Of particular interest as additives (E) are the derivatives of Polyalkenylbernstein- anhydrides with ammonia, monoamines, polyamines, monoalcohols and polyols,. For the derivatization preferred polyamines include ethylene diamine, amine-diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, etc. Suitable alcohols comprise monohydric alcohols such as ethanol, allyl alcohol, dodecanol and benzyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1, 2- butanediol, neopentyl glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, mannitol and sorbitol.

p0068Additives suitable succinic acid derivatives (E) US 4,234,435, US 4,849,572, US 4,904,401, US 5,569,644 and US 6,165,235 for example, in US 3,522,179, the disclosures of which are hereby fully respect is taken. Preferred additives (F) are polyalkenylthiophosphonate esters. The polyalkenyl these esters preferably has a number average molecular weight in the range of about 300 to 5000, particularly preferably 400 to 2000 and preferably 500 to 1,500. The polyalkenyl is preferably derived from polyolefins, as previously described in connection with component (E) as a long chain hydrocarbon radical. This is especially polyalkenyl radicals which derive from conventional or reactive polyisobutenes. Suitable processes for preparing suitable polyalkenylthiophosphonate esters by reacting a polyolefin with a Thiophospho- z. B. US 5,725,611 are rylierungsmittel described, to which reference is taken GE.

p0069Preferred additives (G) are Mannich adducts. Such adducts are obtained in principle by Mannich reaction of aromatic hydroxyl compounds, especially phenol and phenol derivatives, with aldehydes and mono- or polyamines. Preferably, the reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, etc. Suitable Mannich adducts and processes for their preparation are, for. B. US 5,876,468, EP-A 831 141, EP-A 1,233,990 and EP-A 1,226,188, been on here in its entirety by reference.

p0070Further possible additives for a turbine fuel or a Turbinenkraft- are material composition as described in WO 2007/012580 tetrahydro- benzoxazin-stabilizers and / or the polycyclic phenolic stabilizers described in international patent application PCT / EP2007 / 051632, hereby incorporated herein in its entirety by reference becomes.

p0071The additives (E) to (G) and optionally further the above-mentioned additives may usually respectively in amounts of 0.0001 to 1 wt .-%, preferably 0.001 to 0.6 wt .-% and especially 0.0015 to 0 , 4 wt .-% are based on the total amount of the turbine fuel composition.

p0072The additive formulation according to the invention may be part of an additive concentrate for turbine fuels (jet fuels) be, which contains in addition to the inventive additive formulation at least one diluent and at least one further additive which is preferably selected from those described above. Preferably, this additive concentrate, as then, the thus additized turbine fuel composition, one or more additives from the group (E), (F) and (G), in particular mixtures containing thereof as (E) + (F), (E) + ( G), (F) + (G) and (e) + (F) + (G). Suitable diluents are fractions obtained as kerosene, naphtha or mineral base oils, for example, in crude oil processing. Also suitable are aromatic and aliphatic hydrocarbons such as Solvent Naphtha heavy, Solvesso®^® or Shellsol^® and mixtures of these solvents and diluents.

p0073The additive formulation according to the invention is described in the additive concentrate for turbine fuels, preferably in an amount of 0.01 to 70 wt .-%, particularly preferably from 0.05 to 25 wt .-% and in particular from 0.1 to 5 wt .-%, based on the total weight of the concentrate.

p0074The additive formulation according to the invention described is also suitable in an advantageous manner for antistatic modification and improving the conductivity of aviation fuel, gasoline and middle distillate fuels, especially diesel fuel and heating oil.

p0075Aviation fuel is a especially for aviation engines, especially gasoline engines for propeller aircraft, developed fuel commercially available gasoline is similar to the operation of ground vehicles.

p0076As gasoline fuels are all commercial gasoline fuel compositions contemplated. A typical representative of the normal market Euro Super should be mentioned base fuel according to EN 228 here. In addition, gasoline fuel compositions of the specification according to WO 00/47698 are possible applications for the present invention. The gasoline fuels mentioned may continue th bioethanol contained.

p0077As middle distillate fuels include all commercial diesel and heating oil compositions come into consideration. A typical representative of the normal market European diesel fuel is to be disclosed in accordance with EN 590 here. Diesel fuels trade it delt usually mineral oil raffinates which generally have a boiling range from 100 to 400⁰C have. These are usually distillates having a 95% point up to 360⁰C or even higher. But this may also be "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by one nen 95% point for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to the obtainable by refining diesel fuels, whose main constituents are relatively long paraffins, are those obtained by coal gasification [ "coal to liquid" (CTL) fuels] or gas liquefaction [ "gas to liquid" (GTL) fuels] available are suitable. Also suitable are mixtures of the aforementioned diesel fuels with renewable fuels such as biodiesel are. Furthermore, diesel fuels produced from biomass [ "biomass to liquid" (BTL) fuels] suitable. Of particular interest are currently diesel fuels with low Sulfur content, i.e. with a sulfur content of less than 0.05 wt .-%, preferably of less than 0.02 wt .-%, in particular less than 0.005 wt .-% and especially of less than 0.001 wt .-% sulfur , Diesel fuels may also comprise water, for example in an amount up to 20 wt .-%, containing, for example, in the form of diesel-water microemulsions or as so-called "White Diesel".

p0078Heating oils are, for example, low or sulfur-rich crude oil raffinates or coal or brown coal distillates which typically have a boiling range from 150 to 400⁰C. Heating oils may be standard heating oil according to DIN 51603-1 which has a sulfur content of 0.005 to

p00790.2 wt .-% has, or is low-sulfur fuel oil with a sulfur content from 0 to 0.005 wt .-%. Examples of heating oil in particular heating oil for domestic oil-fired boilers or fuel oil may be mentioned.

p0080The additive formulation according to the invention can be either the particular base fuel, especially the gasoline or diesel fuel, alone or in the form of fuel additive packages, for example the so-called gasoline- or diesel performance packages are added. Such packages are fuel additive concentrates and usually contain in addition to solvents, also a series of other components as co-additives, for example carrier oils, cold flow improvers, corrosion inhibitors, demulsifiers, Dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, further antistats, metallocenes, metal talldeaktivatoren, solubilizers, markers and / or dyes.

p0081In a preferred embodiment, the additized gasoline or diesel fuel includes not only the additive formulation of the invention as further fuel additives, in particular at least one detergent, referred to as component (H), respectively.

p0082Detergents or detergent additives (H) usually Ablagerungsinhibi- be factors referred for fuels. Preferably, The detergents are amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number average molecular weight (M_n) 85-20000, in particular from 300 to 5000, especially from 500 to 2500, and at least one polar moiety, which is selected from

p0083(Ha) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom has basic properties;

p0084(Hb) nitro groups, optionally in combination with hydroxyl groups;

p0085(Hc) hydroxyl groups in combination with mono- or polyamino groups, at least one nitrogen atom has basic properties; (Hd) carboxyl groups or their alkali metal or alkaline earth metal;

p0086(He) sulfonic acid groups or their alkali metal or alkaline earth metal;

p0087(Hf) polyoxy-C 2 -C 4 -alkylene, by hydroxyl groups, mono- or

p0088Polyamino groups, at least one nitrogen atom has basic properties, or by carbamate groups;

p0089(Hg) carboxylic ester groups;

p0090(Hh) of succinic anhydride derived moieties having hydroxyl and / or amino and / or amido and / or imido groups; and or

p0091(Hi) moieties no- by Mannich reaction of substituted phenols with aldehydes and Mo or polyamines produced.

p0092The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate solubility in the fuel oil composition has a number-lengemitteltes molecular weight (M_n) 85-20000, in particular from 300 to 5000, especially from 500 to 2500. Typical hydrophobic hydrocarbon radicals, especially in conjunction with the polar moieties (Ha), (Hc), (Hh) and (Hi), come longer chain alkyl - or alkenyl groups, especially the polypropenyl, polybutenyl and polyisobutenyl each M_n = 300 to 5000, especially 500 to 2500, especially from 700 to 2300, into consideration.

p0093Examples of the above groups of detergent additives include the following may be mentioned:

p0094containing mono- or polyamino groups (Ha) are preferably polyalkylene kenmono- or polyalkenepolyamines based on polypropene or conventional (ie having predominantly internal double bonds) polybutene or polyisobutene having M_n = 300 to 5000. Such additives based on highly reactive polyisobutene, which from the polyisobutene which may contain wt .-% n-butene units up to 20, by hydroformylation and reductive amination with ammonia, monoamines or polyamines, such as 3- (N , N-dimethylamino) propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are disclosed in particular in EP-A 244 616th If one performs the preparation of the additives polybutene or polyisobutene having predominantly internal double bonds (usually in the ß and γ-positions), the preparative route provides by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give carbonyl or carboxyl compound and subsequent amination under reductive to (hydrogenating) conditions. The amination can here amines, such as. For example, ammonia, monoamines or polyamines, such as dimethylaminopropylamine, ethylenediamine amine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are used. Corresponding additives based on polypropene are described in particular in WO-A-94 / 24,231th

p0095Further preferred monoamino groups (Ha) containing are the hydrogenation of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 described with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97 / 03946th

p0096Further preferred monoamino groups (Ha) containing additives are selected from polyimide sobutenepoxiden by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A-196 20 262nd

p0097Nitro groups (Hb), optionally in combination with hydroxyl-containing additives are preferably reaction products of polyisobutenes having an average degree of polymerization P of from 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-96/03367 and WO-A-96 / are described 03,479th These reaction products are generally mixtures of pure nitropolyisobutenes (z. B. α, ß-dinitropolyisobutene) and mixed Hydroxynitropolyisobutenen (z. B. α-nitro-.beta.-hydroxypolyisobutene).

p0098Hydroxyl particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds and having polyisobutylene in combination with mono- or polyamino groups (Hc) Additives containing butene having M_n = 300 to 5000, with ammonia, mono- or polyamines, as described in particular in EP-A-476 485 interface.

p0099containing carboxyl groups or their alkali metal or alkaline earth metal salts (Hd) are preferably copolymers of C2-C4o-olefins with maleic anhydride having a total molar mass of 500 to 20,000, the carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining rest of the carboxyl are reacted with alcohols or amines. Such additives are disclosed in particular in EP-A-307 815th Such additives serve mainly to prevent valve seat wear and can, as described in WO-A-87/01126, advantageously in combination with customary fuel detergents such as poly (iso) - butenamines or polyetheramines.

p0100Sulfonic acid groups or their alkali metal or alkaline earth metal salts (He) enthalten- de additives are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate steinsäurealkylesters, as described in particular in EP-A-639 632nd Such additives serve mainly to prevent valve seat wear and can NEN amines or polyetheramines used advantageously in combination with customary fuel detergents such as poly (iso) butene-.

p0101Polyoxy-C2-C4-moieties (Hf) containing additives are preferably polyethers or polyetheramines which are prepared by reacting C2-C6o alkanols, C6-C30-AI kandiolen, mono- or di-C2-C3o-alkylamines, Ci -C3o-alkylcyclohexanols or C C3o-alkylphenols with from 1 to 30 mol ethylene oxide and / or propylene and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines are available. Such products are described in particular in EP-A-310 875,

p0102EP-A-356 725, EP-A-700 985 and US-A-4877416 described. In the case of polyethylene ethers, such products also have carrier oil properties. Typical examples thereof are tridecanol, isotridecanol, isononylphenol and polyisobutylene butenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

p0103Carboxylic ester groups (Hg) containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mm²/ S at 100⁰C, as described in particular in DE-A-38 38 918th The mono-, di- or tri-carboxylic acids can be used aliphatic or aromatic acids, and ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, iso-phthalates, terephthalates and tri- mellitates of isooctanol, iso-nonanol, iso-decanol and isotridecanol. Derar- term products also have carrier oil properties.

p0104Moieties derived from succinic anhydride and having hydroxyl and / or amino and / or amido and / or imido groups (Hh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and especially the corresponding derivatives of polyisobutenylsuccinic anhydride which by reacting conventional or highly reactive polyisobutene having M_n = 300 to 5000 are available with maleic anhydride by a thermal route or via the chlorinated polyisobutene. Of particular interest here are derivatives with aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The moieties having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines, which also have in addition to the amide function free amine groups, succinic acid derivatives having a acid and an amide function, carboximides NEN with monoamines, carboximides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which by the reaction of di- or polyamines NEN are formed with two succinic acid derivatives. Such fuel additives are described in particular in US-A-4849572.

p0105In the detergent additives from group (Hh) are preferably the reaction products of alkyl- or alkenyl-substituted succinic anhydrides, especially of polyisobutenylsuccinic anhydrides, with amines and / or alcohols. It is thus of alkyl, alkenyl or polyisobutenyl succinic anhydride derived derivatives with amino and / or amido and / or imido and / or hydroxyl groups. It goes without saying that these reaction products not only when substituted succinic anhydride, but also when substituted succinic acid or suitable acid derivatives, such as succinic acid or ester, and text.

p0106Includes the additized fuel a detergent based on a polyisobutenyl-substituted succinimide, are especially the imides with aliphatic polyamines of interest. Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine and especially Tetraethylenpenta- min. The polyisobutenyl group has a number average molecular weight M_n of preferably 500 to 5000, particularly preferably from 500 to 2000 and especially from about 1000th

p0107By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines produced groupings (Hi) containing additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols may stem from conventional or highly reactive polyisobutene having M_n = From 300 to 5000.. Such "polyisobutene Mannich bases" are described in particular in EP-A-831 141st

p0108Delay, the said detergent additives (H) together with the additive formulation according to the invention used in combination with at least one carrier oil.

p0109Suitable mineral carrier oils are the crude oil processing fractions such as bright stock or base oils having viscosities, for example, from the SN 500 class - 2000; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxy alkanols. Likewise useful is a as "hydrocrack oil" and known in the refining of mineral oil fraction which is obtained (vacuum distillate cut having a boiling range of about 360-500⁰C obtainable from high pressure catalytically hydrogenated and isomerized and also deparaffinized natural mineral). Also suitable are mixtures of abovementioned mineral carrier oils. Examples of suitable synthetic carrier oils are selected from: polyolefins (polyalphaolefins or Polyinternalolefinen), (poly) esters, (poly) alkoxylates, poly ethers, aliphatic polyether amines, alkylphenol polyethers, alkylphenol nolgestarteten polyether amines and carboxylic esters of long-chain alkanols.

p0110Examples of suitable polyolefins are olefin polymers having M_n = 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated).

p0111Examples of suitable polyethers or polyetheramines are preferably compounds comprising polyoxy-C 2 -C 4 -alkylene moieties which are obtainable by reacting C2-C6o alkanols, Cβ-Cso-alkanediols, mono- or di-C2-C3o-alkylamines, Ci-C3o-alkyl -cyclohexanolen or C C3o-alkylphenols with from 1 to 30 mol ethylene oxide and / or propylene and / or butylene oxide per hydroxyl group or amino group and, in the case of the polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416 described in particular in EP-A. For example, can be used as polyether poly-C2-C6-alkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecanol, isotridecanol, isononylphenol and polyisobutenol nolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

p0112Examples of carboxylic esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as special in particular are described in DE-A 38 38 918th The mono-, di- or tri-carboxylic acids, aliphatic or aromatic acids can be used as ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, iso-phthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol such. B. phthalate di- (n- or iso-tridecyl).

p0113Further suitable carrier oil systems are, for example, in DE-A 38 26 608

p0114DE-A 41 42 241, DE-A 43 09 074, EP-A 0452328 and EP-A 0 548 617..

p0115Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having from about 5 to 35, such as. For example, about 5 to 30, Cs-Cβ-alkylene, such. As selected from propylene oxide, n-butylene oxide and isobutylene-butylene units, or mixtures thereof. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl, long-chain alkyl radical is in particular wherein the straight-chain or branched Cβ-Cis-alkyl radical. Preferred examples include tridecanol and nonylphenol. Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 101 02 913th

p0116Preferred carrier oils are synthetic carrier oils, which polyethers are particularly preferred.

p0117The additized fuel is the detergent additive (H) or a mixture of different such detergent additives in a total amount of preferably 10 to 2000 ppm by weight, particularly preferably from 20 to 1000 ppm by weight, more preferably from 50 to 500 wt .-ppm and in particular from 50 to 200 ppm by weight, for example from 70 to 150 ppm by weight, is added.

p0118When a carrier oil is used, then this is the inventive additized fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight, is added.

p0119Cold flow improvers suitable as further coadditives are, for example copolymers of ethylene with at least another unsaturated monomer, such as ethylene-vinyl acetate copolymers.

p0120Other co-additives suitable corrosion inhibitors are, for example, succinic acid ester, in particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids and substituted ethanolamines te.

p0121Other co-additives suitable demulsifiers include the alkali and alkaline earth metal salts of alkyl-substituted phenol and naphthalene and the alkali and alkaline earth metal salts of fatty acid, further alcohol alkoxylates, eg alcohol ethoxylates, phenol alkoxylates, eg tertiary Butylphenolethoxylate or t-pentyl phenol ethoxylates, fatty acid, alkylphenols, condensation products of ethylene oxide and propylene oxide, including ethylene oxide-propylene oxide block copolymers, polyethyleneimines and polysiloxanes.

p0122Other co-additives Dehazers suitable example, alkoxylated phenol-formaldehyde condensates are.

p0123Other co-additives suitable anti-foaming agents, for example, polyether modified polysiloxanes are.

p0124Other co-additives suitable cetane number and combustion improvers are for example alkyl nitrates, eg cyclohexyl nitrate and especially 2-ethylhexyl nitrate, and peroxides such as di-tert-butyl peroxide. Suitable as further coadditives are, for example antioxidants, substituted phenols, for example 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, and phenylene lendiamine, for example N, N'-di- sec-butyl-p-phenylenediamine.

p0125Other co-additives suitable Metalldeakivatoren example, salicylic acid derivatives, for example N, N'-disalicylidene-1, 2-propane.

p0126Suitable solvents, especially for fuel additive packages, for example, nonpolar organic solvents, especially aromatic and aliphatic hydrocarbons such as toluene, xylenes, "white spirit" and the technical solvent mixtures of the designations Shellsol.RTM (manufacturer: Royal Dutch / Shell Group) , Exxol® (manufacturer: ExxonMobil) and Solvent naphtha. Furthermore, polar organic solvents, especially alcohols, such as 2-ethylhexanol, 2-Propylhep- come here, especially in a blend with the nonpolar organic solvents, Tanol, decanol and isotridecanol.

p0127If the mentioned co-additives and / or solvents are used in gasoline or diesel fuel, they are used in the amounts customary therefor.

p0128The additive formulation according to the invention described is also suitable in an advantageous manner for antistatic modification and improving the conductivity of lubricants. As lubricants or lubricant compositions are here motor oils, lubricating oils, hydraulic oils, turbine oils, regulator oils, transmission, manual and automatic oils, Kalanderöle, heat transfer oils, metalworking oils, shock absorber oils and related liquid compositions which lubricate mechanically moving parts - mostly as metal - serve, are designated. Furthermore, greases are among the lubricants.

p0129The economically most significant lubricant compositions are motor oils and transmission, manual and automatic oils. Motor oils consist typically of mineral base oils which comprise predominantly paraffinic constituents and are produced by complicated processing and purification processes in the refinery, with a proportion of about 2 to 10 wt .-% of additives (based on the active substance contents). For special applications, such as high-temperature operations, the mineral base oils may be partially or completely replaced by synthetic components such as organic esters, synthetic hydrocarbons such noligomere olefins, poly-α-olefins or polyolefins or hydrocracking oils. Motor oils must also at high temperatures sufficiently high viscosities aufwei- sen to ensure impeccable lubrication effect and good sealing between cylinder and piston. Furthermore, engine oils must be designed, the flow properties and so that prob- at low temperatures of the engine can be started lemlos. Motor oils must be stable to oxidation and may even under difficult working conditions little decomposition products produce in liquid or solid form and deposits. Motor oils disperse solids (dispersant behavior), prevent deposits (detergent behavior), neutralize acidic reaction products and form a wear protective film on the metal surfaces in the engine. Motor oils are typically characterized (SAE classes) by viscosity classes.

p0130Transmission, manual and automatic oils have regard to their base components and ad- ditive similar composition to motor oils. The power transmission in the gear system of gearboxes is performed to a high degree through the liquid pressure in the transmission oil between the teeth. The transmission oil accordingly has to be such that it withstands high pressures in the long term, without decomposing. In addition to the viscosity properties, wear, pressure resistance, friction, shear stability, traction and running-in behavior are the crucial parameters.

p0131Motor oils and transmission, manual and automatic oils in addition to the use in accordance with the present invention, the inventive additive formulation is usually at least one, but usually some or all of the following list of additives in the amounts for this purpose generally usual (which in weight .-%, based on the total lubricant composition, are shown in parentheses):

p0132(A) antioxidants (from 0.1 to 5%):

p0133oils sulfur compounds, for example reaction products of terpenes (α-pinene) resin or low molecular weight polybutenes with sulfur, dialkyl sulfides, Dialkyltri- sulfides, polysulfides, diaryl sulfides, modified thiols, mercaptobenzimidazoles, mercaptotriazines, thiophene derivatives, xanthates, zinc dialkyldithiocarbamates, thionyl oglykole, thioaldehydes, dibenzyl, alkyl phenol, Dialkylphenolsulfide or sulfur-containing carboxylic acids

p0134Phosphorus compounds, for example triaryl and trialkyl phosphites, 3,5-di-tert-butyl-4-hy- droxybenzyl phosphonic dialkyl or Phosphonsäurepiperazide

p0135Sulfur-phosphorus compounds, for example zinc dialkyldithiophosphates (Metalldial- kyldithiophosphate act in lubricating oils as corrosion inhibitors and

p0136Extreme pressure additives), or reaction products of phosphorus pentasulfide with terpenes (α-pinene, dipentene), polybutenes, olefins or unsaturated esters

p0137Phenol derivatives, for example sterically hindered mono-, bis- or trisphenols, sterically hindered polycyclic phenols, polyalkylphenols, 2,6-di-tert-butyl-4-methylphenol or methylene-4,4'-bis (2, 6-di-tert-butylphenol) (phenol derivatives often used in combination with antioxidants, sulfur-based or amine-based)

p0138Amines, for example arylamines such as diphenylamine, phenyl-α-naphthylamine or 4,4'-tetra-diphenylmethane methyldiamino

p0139Metal deactivators in the narrower sense, for example N-salicylidene-ethylamine, N, N'-dis- alicyliden-ethylenediamine, N, N'-disalicylidene-1, 2-propanediamine, triethylenediamine, ethylenediaminetetraacetic acid, phosphoric acid, citric acid, glycolic acid, lecithin, thiadiazole, imidazole or pyrazole derivatives

p0140(B) viscosity index improvers (from 0.05 to 10%), for example: polyisobutenes having a molecular weight of usually 10,000 to 45,000, polymethacrylates having a molecular weight of 5,000 to 100,000 Üblicherweisel, homo- and copolymerization sowed of 1, 3-dienes, such as butadiene or isoprene having a molecular weight of usually 80,000 to 100,000, 1, 3-diene-styrene copolymers having a molecular weight of usually 80,000 to 100,000, maleic anhydride-styrene polymers in esterified form having a molecular weight of usually 60000-120000, star-shaped polymers with block-structure by units of conjugated dienes and aromatic monomers having a molecular weight of usually 200,000 to 500,000, polyalkylstyrenes having a molecular weight of usually 80,000 to 150,000, polyolefins of ethylene and propylene or styrene-cyclopentadiene-norbornene terpolymers having a molecular weight of usually 60,000 to 140,000

p0141(C) pour point depressants (cold flow improvers) (from 0.03 to 1%), for example bicyclic aromatics such as naphthalene with different long-chain alkyl radicals, poly- methyacrylate having 12 to 18 carbon atoms in the alcohol radical, a degree of branching between 10 to 30 mol% and a average molecular weight from 5,000 to 500,000, and long-chain alkylphenols Phthalsäuredialkyl- aryl esters or copolymers of different olefins

p0142(D) detergents (HD additives) (from 0.2 to 4%), for example, calcium, lead, zinc and manganese naphthenates, calcium Dichlorostearate, calcium Phenylstearate, calcium Chloro-phenylstearate, sulfonation products of alkylaromatics such as dodecyl - benzene, petroleum sulfonates, sodium, calcium, barium or magnesium sulfonates, neutral, basic and overbased sulfonates, phenates and carboxylates carbonyl, salicylates, metal salts of alkylphenols and alkylphenol sulfides, phosphates, thiophosphates or alkenyl phosphonic acid derivatives

p0143(E) Ashless dispersants (0.5 to 10%), for example, Mannich condensates of alkyl phenol, formaldehyde and polyalkylenepolyamines, reaction products of polyethylene lyisobutenylsuccinanhydriden with polyhydroxy compounds or polyamines, copolymers of alkyl methacrylates with diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-Vinylpryridin or 2-hydroxyethyl methacrylate or vinyl acetate-fumarate copolymerized-sate

p0144(F) high-pressure additives (extreme pressure additives) (from 0.2 to 2.5%), for example chlorinated paraffins with 40 to 70 wt .-% chlorine, chlorinated fatty acid (especially having trichloromethyl end groups), dialkyl hydrogen phosphites, triaryl phosphites, aryl phosphates such as tricresyl phosphate , dialkyl, trialkyl such as tributyl phosphate, trialkyl, diesters, nitroaromatics, amino nophenol derivatives of naphthenic acid, carbamic, Dithiocarbaminsäu- acid derivatives, substituted 1, 2,3-triazoles, mixtures of benzotriazole and alkyl succinic anhydride or Alkylmaleinsäureanhydrid, 1, 2,4-thiadiazole polymers, Morpholinobenzothiadiazol disulfide, chlorinated alkyl sulfides, sulfurized olefins, sulfurized chloronaphthalenes, chlorinated Alkylthiocarbonate, organic sulfides and polysulfides such as bis (4-chlorobenzyl) disulfide and Tetrachlordiphenylsulfid, Trichloracrolein mercaptals or especially zinc -dialkyldithiophosphate (ZDDP)

p0145(G) friction modifiers (Friction Modifier) ​​(0.05 to 1%), especially polar oil-soluble compounds which generate a thin layer on the frictional surface by adsorption, for example fatty alcohols, fatty amides, fatty acid salts, fatty acid alkyl esters or fatty acid glycerides

p0146(H) anti-foam additives (0.0001 to 0.2%), for example, liquid silicones such Polydimethylsi- Loxane or Polhethylenglykolether and sulfides

p0147(I) demulsifiers (from 0.1 to 1%), for example Dinonylnaphthalinsulfonate in form of their alkali and alkaline earth metal salts

p0148(J) corrosion inhibitors (also known as metal deactivators) (from 0.01 to 2%), for example tertiary amines and salts thereof, imino esters, amide oximes, diaminomethanes, derivatives of saturated or unsaturated fatty acids with alkanolamines, alkylamines mine, Sarcosine, imidazolines, alkylbenzotriazoles , dimercaptothiadiazole derivatives thereof, diaryl phosphates, thiophosphates, neutral salts of primary n-Cs-ds-alkylamines or cycloalkylamines with dialkyl branched C5-Ci2-alkyl groups, neutral or basic alkaline earth metal, zinc naphthenates, mono- and Dialkylarylsulfonate, Bariumdinonylnaphthalin- sulfonate, lanolin (wool fat ), heavy metal salts of naphthenic acid, dicarboxylic acid, unsaturated fatty acids, hydroxy fatty acids, fatty acid esters, and sorbitan monooleate Pentaerythri- tol-, O-Stearoylalkanolamine, Polyisobutenylbernstein- acid derivatives or zinc dialkyldithiophosphates and zinc dialkyldithiocarbamates- (K) emulsifiers (0.01 to 1%), including long chain unsaturated, natural occurrences mende carboxylic acid, naphthenic acids, synthetic carboxylic acid, sulfonamides, N-oleylsarcosine, Alkansulfamidoessigsäure, dodecylbenzenesulfonate, long-chain alkylated ammonium salts such Dimethyldodecylbenzylammonium chloride, imidazole zolinium- salts, alkyl, alkylaryl, acyl, alkylamino and Acylaminopolyglykole or long-chain acylated mono- and diethanolamine

p0149(I) dyes and fluorescence additives (from 0.001 to 0.2%)

p0150(M) preservatives (from 0.001 to 0.5%)

p0151(N) odor (0.001 to 0.2%)

p0152Typical ready engine oil and transmission, switching and Automatiköl-

p0153Compositions within the scope of the present invention comprises the following items, where the figures of the additives on the Wirksubstanz- related contents and the entirety of the components always being 100 wt .-% yields:

p0154• 80 to 99.3 wt .-%, more preferably 90 to 98 wt .-% engine oil or transmission, manual and automatic oil-based (mineral base oils and / or synthetic components), including shares in solvents and diluents for the additives

p0155• 0.01 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight, especially 0.5 to 500 ppm by weight, in particular 1 to 350 ppm by weight, of the additive formulation according to the invention

p0156• 0.2 to 4 wt .-%, in particular 1, 3 to 2.5 wt .-% detergents of group (d)

p0157• 0.5 to 10 wt .-%, in particular 1, 3 to 6.5 wt .-% dispersants of group (e)

p0158• 0.1 to 5 wt .-%, preferably 0.4 to 2.0 wt .-% antioxidants of group (a) and / or high-pressure additives of group (f) and / or friction modifiers of group (g)

p0159• 0.05 to 10 wt .-%, in particular 0.2 to 1, 0 wt .-% viscosity index improvers of group (b)

p0160• 0 to 2 wt .-% of other additives of groups (c) and (h) to (n) As an example of chemical and physical processes in which the additive formulation of the invention may be used to prevent electrostatic charging, the polyethylene gas phase fluidized bed process is mentioned. In this case, ethylene or a mixture of ethylene and comonomers such as 1-butene, 1-hexene or 1-octene is polymerized coordinately. The density of the resulting poly- ethylene depends largely on the amount and the type of built-comonomers. So high-density HDPE is obtained preferably from ethylene without comonomers and low-density LLDPE in the presence of significant amounts of the abovementioned comonomers. The catalyst preferably used silica supported Ziegler or metallocene catalysts. The polymerization is carried out in each case in a fluidized bed at a temperature below the melting point of the polyethylene, which is why solid product particles rub against the inner wall of the tower-shaped fluidized bed reactor. The additive formulation according to the invention serves to prevent the electrostatic charge in the entire reactor system and therefore counteracts the polymer deposit formation on the inner reactor wall and in the heat exchangers.

p0161The present invention is also anti-static equipped inanimate organic material having improved electrical conductivity, selected from cosmetic preparations, medicament formulations, photographic recording materials, paints, plastics, waxes, solvents, mineral oil products and fuels, and which from 0.01 to 2000 ppm by weight , preferably 0.1 to 1000 ppm by weight, especially 0.5 to 500 ppm by weight, in particular 1 to 350 ppm by weight, of the additive formulation of the invention contains.

p0162The additive formulation according to the invention allows in comparison to the known means an even more effective and sustainable increase in electrical conductivity in inanimate organic material, especially in petroleum products and fuels, especially in turbine, gasoline and diesel fuel as well as lubricants. In many cases, the electrical conductivity remains even after storage at a high level, whereas a distinct drop of the values ​​can be observed with appropriate additive formulations of the prior art during storage. Even with very small amounts in the range of a few ppm by weight is obtained in fuels generally electrical conductivities of at least 50 to 100 pS / m.

p0163The additive formulation according to the invention has a high thermal stability. It is heavy metals and halogens. She also has a high flash point, so it is in their preparation, their transport and their storage prior to use in the inanimate organic material safely, ie they can without explosion and fire risk can be handled. The invention will be illustrated by the following non-limiting examples.

p0164Example 1: Preparation of I-decene-sulfur dioxide copolymer at 25 ° C

p0165In a 5 liter autoclave 1 122g (7.90 mol) of 1-decene and 28 g dodecyl mercaptan in 350 g solvent naphtha Heavy (Solvesso® 150) submitted. 10 to 20⁰C, 950 g (14.84 mol) of sulfur dioxide introduced. Thereafter, the reaction mixture turned a to 25 ° C and continued at this temperature for 3 hours a solution of 72 g tert-butyl peroxypivalate (75 wt .-%) in 700 g of Solvent Naphtha Heavy at. Followed by 5 hours at 20⁰C stirred. For workup, the autoclave was depressurized and it was first at normal pressure and then degassed under vacuum (200 to 10 mbar). To afford 2.4 kg of a clear, viscous polymer solution. The conversion was 95% (¹H-NMR spectroscopy of the 3 olefin protons of Restolefins at 5.8 ppm / 4.9 ppm to the 3 protons in the main polymer chain at 4.3 to 3.0 ppm) due to the integral ratio. The resulting 1-decene-sulfur dioxide copolymer had a number average molecular weight M_n of 19,600 and a polydispersity PDI of 3.2.

p0166Example 2: Preparation of a 1-decene-sulfur dioxide copolymer at 35 ° C

p0167In a 5 liter autoclave 1 122g (7.90 mol) of 1-decene and 28 g dodecyl mercaptan in 350 g solvent naphtha Heavy (Solvesso® 150) submitted. 10 to 20⁰C, 950 g (14.84 mol) of sulfur dioxide introduced. After this there were the reaction onsmischung at 35 ° C and drove for 2 hours at this temperature, a

p0168Solution of 72 g of tert-butyl peroxypivalate (75 wt .-%) in 700 g of solvent naphtha Heavy to. Followed by 4 hours at 20⁰C stirred. For workup, the autoclave was depressurized and it was first at normal pressure and then degassed under vacuum (200 to 10 mbar). This gave 2.5 kg of a clear viscous polymer solution. The conversion was 97% (¹H-NMR spectroscopy due to the integral ratio of the 3 olefin protons of Restolefins at 5.8 ppm / 4.9 ppm to the 3 protons in the main polymer chain at 4.3 to 3.0 ppm). The resulting 1-decene-sulfur dioxide copolymer had a number average molecular weight M_n of 13,400 and a polydispersity PDI of 2.9.

p0169Example 3: Preparation of a 1-decene-sulfur dioxide copolymer at 33 ° C.

p0170In a 5 liter autoclave 1 122g (7.90 mol) of 1-decene and 28 g dodecyl mercaptan to 630 g solvent naphtha Heavy (Solvesso® 150) submitted. At 10 to 20 ° C 720 g (1 1, 25 mol) of sulfur dioxide were introduced. Thereafter, provided the reaction mixture a at 33 ° C and continued at this temperature for 2 hours, a solution of 88 g of tert-butyl peroxypivalate (75 wt .-%) in 420 g of Solvent Naphtha Heavy to. Followed by 4 hours at 20⁰C stirred. For workup, the autoclave was depressurized and it was first at normal pressure and then degassed under vacuum (200 to 10 mbar). This gave 2.5 kg of a clear viscous polymer solution. The conversion was 92% (¹H-NMR spectroscopy due to the integral rela- tionship of the 3 olefin protons of Restolefins at 5.8 ppm / 4.9 ppm to the 3 protons in the main polymer chain at 4.3 to 3.0 ppm). The resulting 1-decene-sulfur dioxide copolymer had a number average molecular weight M_n of 12,500 and a polydispersity PDI of 2.5.

p0171Example 4 Preparation of an Additive Formulation from a 1-decene-sulfur dioxide copolymer, a C2o / 24-olefin-maleimide copolymer, dodecylbenzenesulfonic acid and solvent naphtha heavy

p01721 kg of the 1-decene-sulfur dioxide copolymer solution (50 wt .-% in Solvent Naphtha Heavy) from example 2 [component (A)] were mixed with stirring at 25 to 35 ° C with further 1, 1 kg of solvent naphtha Heavy , Thereafter, 160 g of dodecyl benzene sulfonic acid [component (C)] were added under stirring at the same temperature, and mixed homogeneously. This mixture was 10 minutes at 40 to 50⁰C stirred. Subsequently, 1 kg of a solution of N-tallow-1, 3-diaminopropane to the imide unset C2o / 24-α-olefin-maleic anhydride copolymer of molecular weight M gewichtsgemit- termined_w in the range from 2000 to 5000 [component (B)] in Solvent Naphtha Heavy (50 wt .-%) at the temperature of 40 to 50⁰C was added and mixed homogeneously. The additive formulation had obtained a composition of 15.3 wt .-% of (A), 15.3 wt .-% (B), 4.9 wt .-% (C) and 64.4 wt .-% of solvent naphtha Heavy [component (D)].

p0173Example 5: Preparation of an Additive Formulation from a 1-decene-sulfur dioxide copolymer, a C2o / 24-olefin-maleimide copolymer, Dodecylben- zolsulfonsäure and Sovent Naphtha Heavy

p0174The same components (A), (B), (C) and (D) were mixed in analogy to the formulation in example 4 in such ratios that an additive formulation of the composition of 21 wt .-% of (A), 18 parts by weight % (B), 7 wt .-% (C) and 54 wt .-% (D) resulted.

p0175Example 6 Preparation of an Additive Formulation from a 1-decene-sulfur dioxide copolymer, a C2o / 24-olefin-maleimide copolymer, Dodecylben- zolsulfonsäure and Sovent Naphtha Heavy

p0176The same components (A), (B), (C) and (D) were mixed in analogy to the formulation in

p0177Example 4 mixed in proportions such that an additive formulation of Composition of 14 wt .-% of (A), 13 wt .-% (B), 5 wt .-% (C) and 68 wt .-% (D) resulted.

p0178Example 7 (comparative) Preparation of an Additive Formulation from a 1-decene sulfur dioxide copolymer, an N-tallow fatty-1, 3-diaminopropan-

p0179Epichlorohydrin reaction product, dodecylbenzenesulfonic acid and solvent naphtha heavy

p0180An analogous in the ratios of the four components to the formulation of example game 6 formulation was prepared with the only difference that instead of 50 wt .-% strength C2o 50/24-olefin-maleimide copolymer solution, the same amount of a commercially available wt .-% solution of the polymeric condensation product of N-tallow fatty-1, 3-diaminopropane and epichlorohydrin in a mixture of aromatic Kohlenwassserstoffen - according to the teaching of document (1) - was used.

p0181Example 8: Measurement of conductivities of the additive formulations

p0182Electrical conductivity measurements were (pass field tests) according to DIN 51412-2 performed. For this purpose, an immersion test cell was immersed into the liquids to be measured. The conductivity values ​​in pS / m were each at the same temperature of liquids, namely 25 ° C, read on the display of the immersion measuring cell. As liquid to be measured commercial petroleum, commercial diesel fuel, commercial fuel oil, commercially available turbine fuel and commercial hydraulic oil were used in the above a defined amount of the additive formulation was metered as conductivity. The following table shows the results of measurements.

p0183a) in commercial paraffin oil (dosage: each 3 mg per liter):

p0184the additive formulation from example 5 (inventive) gave 890 pS / m; the additive formulation from example 6 (inventive) gave 750 pS / m; the additive formulation from Example 7 (for comparison) gave 540 pS / m; A commercial anti-static formulation (AF1) gave 760 pS / m;

p0185b) in commercial diesel fuel (dosage: each 3 mg per liter):

p0186the additive formulation from example 5 (inventive) gave 670 pS / m; the additive formulation from example 6 (inventive) gave 440 pS / m; A commercial anti-static formulation (AF1) gave 415 pS / m; c) in commercial heating oil (dosage: each 3 mg per liter):

p0187the additive formulation from example 5 (inventive) gave 690 pS / m; the additive formulation from example 6 (inventive) gave 520 pS / m; A commercial anti-static formulation (AF1) gave 505 pS / m;

p0188d) in commercial jet fuel (dosage: each 1, 3 or 5 mg per liter):

p0189the additive formulation from example 5 (inventive) gave 1 mg per liter of 174 pS / m at 3 mg per liter of 750 pS / m at 5 mg per liter, and 1275 pS / m; every 4 days of storage, the conductivity measurements were repeated to thereby give values ​​of 230 pS / m (at 1 mg per liter), 735 pS / m (at 3 mg per liter) and 1205 pS / m (at 5 mg per liter);

p0190a commercially available anti-static formulation (AF2) gave 1 mg per liter of 205 pS / m at 3 mg per liter of 723 pS / m at 5 mg per liter, and 1230 pS / m; every 4 days of storage, the conductivity measurements were repeated to thereby give values ​​of 150 pS / m (at 1 mg per liter), 677 pS / m (at 3 mg per liter) and 1034 pS / m (at 5 mg per liter);

p0191e) in commercial hydraulic oil (dosage: each 130 mg per liter):

p0192the additive formulation from example 5 (inventive) gave 167 pS / m; A commercial anti-static formulation (AF1) gave 120 pS / m.

p0193For the commercially available antistatic formulations for improving the electrical conductivity in organic liquids (AF1 and AF2), a composition according to the teaching of document (1) was adopted.

p0194The measurement results show that additive formulations according to the invention the corresponding additive formulations of the prior art - within the measurement accuracy of experience, about ± 10-20 pS / m - are at least equivalent; in most cases they exceed these, however, and provide the desired significantly higher electrical conductivities, especially also in direct comparison with comparative example 7. This is also true of inventive example 6, which has a comparatively high content of solvent (D), so is relatively highly diluted, but still provides the sufficiently high electrical conductivities as are also achieved with a commercially available anti-static formulation. In the measurements in jet fuel is to be noted as a further advantage of the additive formulation according to the invention that remains constant, the electrical conductivity of the turbine fuel at a high level even after a certain storage time - in contrast to treated with standard anti-static formulation turbine fuel, its conductivity after said storage time decreases significantly.

p0195Example 9: gene testing of storage stability and flashpoint Additivformulierun-

p0196The storage stabilities of the additive formulations according to the invention of Example 5 and 6 and of commercial antistatic formulations (AF1 and AF2) were after prolonged storage at constant 40⁰C rated visually for turbidity and possibly precipitate formation. In all cases, the samples had after 3 months of storage, no turbidity or precipitation. The flash points of the specimens employed were previously in accordance with the EN ISO 2719: determined 2002 (measurement in closed Pensky-Martens): in the case of the samples of the invention were those at 62 ° C (Example 5) and 63 ° C ( example 6), in the commercially available antistatic formulation but significantly lower at 21⁰C (AF1) or <20 ° C (AF2).