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

[0001] The present invention relates to a new improved additive formulation suitable for antistatic finishing and improving the electrical conductivity of inanimate organic material and for preventing the formation of electrostatic charge in chemical and physical processes. In addition, the present invention relates to a method for producing such an additive formulation. The present invention also relates to the use of this additive formulation and thus the inanimate organic material finished antistatic.

[0002] Inanimate organic material, for example motor fuel, is generally a very poor conductor of electricity. Therefore, electric charges tend to accumulate locally in such organic material and discharge uncontrollably in the form of a spark, which can lead to explosions and fires when this organic material, which is most often flammable and often easily flammable, comes into contact with air or oxygen. Thanks to the appropriate anti-static additives, the electrical conductivity of inanimate organic material can be increased, so that electrostatic charge can no longer form and thus the risk of explosions and fires is reduced.

[0003] From US-A 3 917 466 (1), preparations for antistatic finishing and improvement of electrical conductivity are known, consisting of copolymers of sulfur olefinadoxide, polymeric polyamines which can be obtained by reaction of epichlorohydrin with aliphatic monoamines or polyamines, for example N tallow-1,3-diaminopropane, oil soluble sulfonic acids and low boiling solvents such as toluene and / or isopropanol.

[0004] US-A 4 416 668 (2) describes mixtures of α-olefin-maleimide copolymers and olefin-sulfur dioxide copolymers as antistatic agents for organic liquids such as motor fuels. These mixtures may contain solvents such as benzene, toluene or xylenes.

[0005] EP-A 1 568 756 describes an additive preparation for improving the conductivity of propellants under the trade name Stadis 450, which contains 13.3% 1-decene-polysulfone, 13.3% reaction product N-tallow-1,3- propylenediamine with epichlorohydrin, 7.4% dodecylbenzensulfonic acid and 66% toluene.

[0006] EP-B 1 274 819 describes an antistatic formulation for propellants containing 1-decene sulfur dioxide copolymer, tetramine T, dodecylbenzenesulfonic acid and Solvent 14.

[0007] EP-A 1 749 874 describes an antistatic formulation for propellants containing polysulfones and alkylphenol-aldehyde resins.

[0008] However, the effectiveness of the antistatic agents described in the prior art is not satisfactory. There is a need for a more effective and long-lasting increase in electrical conductivity in inanimate organic material. In addition, antistatic agents should show greater thermal stability. Due to toxicity and the environment, they should not contain metals and halogens, if possible. It is also important that they have as high a flash point as possible so that they can be handled safely, i.e. without risk of explosion and fire, during their manufacture, transport and storage before use in inanimate organic material.

[0009] The object of the invention was therefore to provide an anti-static agent, which raises no objections, for increasing the electrical conductivity in inanimate organic material, especially in motor fuels and petroleum products, having effective operation, high thermostability and possibly high flash point.

Accordingly, an additive formulation suitable for antistatic finishing and improving the electrical conductivity of inanimate organic material and consisting of (A) 1 to 50% olefin-sulfur dioxide copolymer, (B) 1 to 50% compound containing one or more compounds was developed basic nitrogen atoms and having at least one linear or branched chain hydrocarbon group with a relatively long chain of at least 4 carbon atoms, or an equivalent structural element, ensuring solubility of component (B) in inanimate organic material, which is an α-olefin-maleimide copolymer with at least one basic nitrogen atom, (C) 0.1 to 30 wt. oil-soluble acid, and (D) 1 to 80% high boiling solvent, consisting of one or more types of molecules, at least 80 wt. these types of particles have a boiling point greater than 154 ° C at normal pressure, with all components (optionally including any by-products and / or non-interfering impurities present) giving a total of 100 wt.

[0011] The additive formulation according to the invention may still contain - usually depending on the production conditions - as other by-products and / or non-obstructing impurities in an amount of up to 10% by weight, especially up to 5% by weight, in particular up to 2% by weight. other ingredients.

[0012] In a preferred embodiment, the additive formulation consists of (A) 10 to 30% by weight, in particular 13 to 25% by weight. component (A), (B) 10 to 30% by weight, in particular 13 to 25% by weight component (B), (C) 2 to 15% by weight, especially 4 to 10% by weight component (C) and (D) 40 to 78% by weight, especially 50 to 70% by weight component (D).

[0013] The additive formulation according to the invention described is a concentrate of the active ingredients (A), (B) and (C) in the high boiling solvent (D) which is most suitable for the safe transport and safe storage of the product.

[0014] The structure and known methods for preparing the olefin-sulfur dioxide copolymer or component (A) are described in publications (1) and (2). Component (A) is preferably a copolymer of sulfur dioxide with one or more linear or branched 1-olefins with 2 to 24 carbon atoms. Typically, the copolymers (polysulfones) of component (A) are 1: 1 alternating copolymers in which the sulfone unit generally follows the olefin unit; sequences of two or more olefin units may also be present in small amounts. Some olefin monomers can be replaced by ethylenically unsaturated carboxylic acids (e.g. acrylic acid, methacrylic acid or vinylacetic acid), or ethylenically unsaturated dicarboxylic acids (e.g. maleic acid or fumaric acid), or their derivatives (e.g. maleic anhydride), such that the copolymer of component (A) is composed in particular of 50 mole% sulfur or sulfonic dioxide units, 40 to 50 mole% olefinic units and 0 to 10 mole% units of said ethylenically unsaturated carboxylic acids, ethylenically unsaturated dicarboxylic acids or their derivatives.

As branched and especially linear 1-olefins with 2 to 24 atoms for the production of component (A) carbon, for example, ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,

1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene or mixtures thereof . Particularly preferred are linear 1-olefins with 6 to 16, especially 8 to 14 carbon atoms, or linear 1-olefins with 12 to 22, especially 14 to 20 carbon atoms, as well as mixtures thereof, for example a mixture of 1-dodecene and 1-tetradecene . It may also be advantageous to use for the preparation of component (A) mixtures of low molecular weight 1-olefins and higher molecular weight, i.e. mixtures of 1-olefins with bimodal distribution, for example mixtures of 1-olefins with 6 to 13 carbon atoms and 1-olefins with 14 up to 20 carbon atoms or mixtures of 1-olefins with 6 to 10 carbon atoms and 1-olefins with 11 to 15 carbon atoms, or mixtures of 1-olefins with 2 to 24 carbon atoms and a single 1-olefin with 4 to 10 carbon atoms. If technical or other mixtures of 1-olefins are used, the number of carbon atoms given above refers to the average number of carbon atoms of this mixture, the average number of carbon atoms being the sum of mathematical products of the weight fraction and the corresponding number of carbon atoms of all 1-olefins present in a mixture.

[0016] The olefin-sulfur dioxide copolymer component (A) usually has a number average molecular weight M_n from 2000 to 1,000,000, especially from 4,000 to 100,000, primarily from 6,000 to 25,000. Polydispersity (PDI = M_in/ M_n) generally ranges from 1.1 to 30, especially from 1.5 to 20, especially from 2 to 10, particularly preferably from 2.3 to 5.

[0017] Publication (1) recommends the preparation of olefin-sulfur dioxide copolymers in a suitable radical polymerization process at a temperature in the range of 0 to 50 ° C; benzene, toluene or xylene are mentioned as the solvents used, only a small molar excess of sulfur dioxide is used (maximum 1.5 times the molar amount); it is recommended to use radical initiators such as peroxides or azo compounds and additional exposure to actinic light. According to publication (2), sulfur olefin peroxide copolymers can be prepared by emulsion polymerization in an aqueous medium. [0018] The compound of component (B) containing one or more basic nitrogen atoms must be soluble or at least capable of being homogeneously dispersed in inanimate organic material treated with the additive formulation of the invention. Component (B) is also a polymer. It has at least one branched, especially linear, long-chain hydrocarbon group with at least 4, preferably at least 8, especially at least 12, especially with 12 to 30 carbon atoms, provided that the solubility in inanimate organic material is not is provided by an equivalent structural element. The compound of component (B) preferably does not contain free hydroxyl groups, because under certain circumstances they may adversely affect the effectiveness of the additive formulation of this invention.

[0019] In the compound of component (B), said branched or linear hydrocarbon group with a relatively long chain may be on a basic nitrogen atom or on one of the basic nitrogen atoms or on a carbon atom, especially on the carbon atom of the main polymer chain. Typical branched or linear, long chain, hydrocarbon groups are, for example, linear alkyl groups that occur in fatty acids and polysobutyl groups, especially 20 to 150, especially 35 to 100 carbon atoms.

[0020] The structure and method of producing α-olefma-maleimide copolymers with at least one basic nitrogen atom as component (B) are generally described in publication (2). In a preferred embodiment, such α-olefm-maleimide copolymers are obtained by free radical polymerization of one or more linear or branched α-olefins with 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 α-olefin-maleimide copolymers produced from them are 1: 1 alternating copolymers in the polymer backbone, in which the maleic acid unit always follows the α-olefin unit. Combined structures are generally formed due to branched or linear hydrocarbon groups with a relatively long chain.

[0021] As branched and especially linear 1-olefins with 6 to 50 carbon atoms used in the preparation of α-olefin-maleimide copolymers of component (B), for example, 1-hexene, 1-heptene, 1-octene, 1-nonene , 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene. 1-nonadecene, 1-eicosene, 1-heneicosene, 1-docosene, 1-tricosene, 1-tetracozen, 1-triacontene, 1-tetracontene, 1-pentacontene or mixtures thereof. Linear 1-olefins of 12 to 30, especially 16 to 24 carbon atoms, and mixtures thereof are particularly preferred.

[0022] Radical polymerization of 1-olefin with maleic anhydride is carried out by conventional methods. For this purpose, conventional radical initiators are used, especially those based on peroxides or azo compounds, for example di-tert-butyl peroxide, tert-butyl peroxypivalate or azobisisobutyronitrile, using usual temperature and pressure ranges, e.g. 50 to 150 ° C at normal pressure and by carrying out the reaction in conventional solvents, for example aromatic hydrocarbons. Preferably, high boiling organic solvents of component (D) of the present invention are used.

[0023] After polymerization, the resulting α-olefin-maleic anhydride copolymer is reacted with one or more aliphatic polyamines leading to the corresponding imide. Polyamines with a primary amine group and at least one other primary, secondary or tertiary amino group providing a basic nitrogen are needed to form the imide. Examples of shorter chain diamines such as ethylenediamine, 1,3-propylenediamine, (N, N-dimethylamino) propylamine ("DMAPA") or bis [3- (N, N-dimethylamino) propyl] amine (suitable) "Bis-DMAPA") or relatively long chain diamines such as N-tallow 1,3-diaminopropane. Common reaction conditions for imide formation are known to those skilled in the art. If a solvent is additionally used for this imide preparation, preferably high boiling organic solvents of component (D) of the present invention are used.

[0024] Typical examples of α-olefin-maleic anhydride copolymers reacted with aliphatic polyamines are products with a comb structure formed by reacting C20 / 24-α-olefm-maleic anhydride copolymers with 3- (N, N-dimethylamino) propylamine ("DMAPA "Or bis [3- (N, N-dimethylamino) propyl] amine (" bisDMAPA ").

[0025] The α-olefin-maleimide copolymers described with at least one basic nitrogen atom of component (B) typically have a weight average molecular weight M_in from 500 to 50,000, especially from 1,000 to 10,000. A typical α-olefin-maleimide copolymer is an α-olefin-maleic anhydride copolymer reacted with N-tallow-1,3-diaminopropane to form an imide having a weight average molecular weight of M_in in the range of

1000 up to 10,000.

[0026] The oil-soluble acid component (C) is preferably an organic sulfonic acid which, in order to achieve oil solubility, preferably has a relatively long chain or large volume hydrocarbon group, especially 6 to 40, especially 8 to 32, especially preferably 10 to 24 carbon atoms. Suitable hydrocarbon groups of this type are linear or branched alkyl or alkenyl groups, e.g. n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, nhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, oleyl, linolyl or linolenyl, cycloalkyl groups, e.g. cyclohexyl, methylcyclohexyl or dimethylcyclo groups aryl, e.g. phenyl or naphthyl, aralkyl groups e.g. benzyl or 2-phenylethyl and particularly preferably alkaryl groups, especially those substituted with linear or branched C groups₁ to C.₁₈-alkyl phenyl or naphthyl, e.g. tolyl, xylyl, n-nonylphenyl, n-decylphenyl, n-dodecylphenyl, isotridecylphenyl, n-nonylnaphthyl, di-n-nonylnaphthyl, n-decylnaphthyl, di-n-decylnaphthyl, n-dodecyl7 naphthyl , di-n- dodecylnaphthyl , and zotridecylnaphthyl or di-isotridecylnaphthyl. In the last-mentioned monosubstituted phenol groups, the alkyl groups may be in ortho, meta or para positions relative to the sulfonic acid group, with the para position being preferred. Typical examples of component (C) are therefore n-nonylbenzenesulfonic acid, n-decylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, isotridecylbenzenesulfonic acid, n-nonylnaphthylsulfonic acid, di-n-nonylnaphthylsulfonic acid, n-decylnaphthylsulfonic acid, di-n-decylnaphthylsulfonic acid, n-dodecylnaphthylsulfonic acid, di-n-dodecylnaphthylsulfonic acid, isotridecylnaphthylsulfonic acid and diisotridecylnaphthylsulfonic acid.

In addition to the said organic sulfonic acids, as a component (C), it is also possible in principle also to use, for example, oil-soluble organic sulfonic acids or organic phosphonic acids, which also preferably have a relatively long chain or larger volume hydrocarbon group, in particular 6 to 40, in particular all 8 to 32, particularly preferably 10 to 24 carbon atoms.

[0028] The high-boiling organic solvent component (D) is not the actual active ingredient of the additive formulation according to the invention for antistatic finishing and improvement of the electrical conductivity of inanimate organic material, however, by its interaction with components (A), (B) and (C) supports and increases their actions and contributes to the thermostability of the preparation and ensures a high flash point. Furthermore, component (D) serves to better set the desired viscosity of the additive formulation according to the invention, which is an important criterion for the usefulness of this formulation.

[0029] In a preferred embodiment, component (D) consists of at least 80% by weight, in particular at least 90% by weight. a high-boiling aromatic hydrocarbon with 9 to 30 carbon atoms or a mixture of such high-boiling aromatic hydrocarbons. Particularly preferably component (D) at least 80% by weight, especially at least 90% by weight, in particular 100% by weight is a mixture of high-boiling aromatic hydrocarbons with 9 to 20 carbon atoms, especially 9 to 14 carbon atoms. Such aromatic hydrocarbons are especially bicyclic, tricyclic or polycyclic aromatic compounds, e.g. naphthalene, diphenyl, anthracene or phenanthrene, or bicyclic, tricyclic or polycyclic aromatic compounds with aliphatic side chains, for example substituted benzenes with C side chains₇- to C.₁₄- alkyl, especially with C side chains₇- to C.₁₂-alkyl, such as n-dodecylbenzene or n-tetradecylbenzene, but primarily with C side chains₁- to C.₆-alkyl, e.g., such as n-propylbenzene, iso-propylbenzenes, ethylmethylbenzenes, trimethylbenzenes, ethyldimethylbenzenes, diethylbenzenes, n-butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, npentylbenzene, tenzylbenzene, tenzenebenzene, C₂- to C.₆-alkilonaftaleny. All of these aromatic hydrocarbons have a boiling point above 150 ° C at normal pressure, generally in the range of over 150 ° C to 330 ° C at normal pressure.

[0030] Mixtures of the said aromatic hydrocarbons with 9 or more carbon atoms are commercially available as technical solvent fractions, for example from Exxon Mobil Chemical under the name Solvesso® 100 (aromatic fraction C₉- to C.₁₀-), Solvesso® 150 (aromatic fraction C₁₀- to C.₁₁-) and Solvesso® 200 (aromatic fraction C₁₀- to C.₁₄-); this type of aromatic fraction C₁₀- to C.₁₁- also referred to as "Solvent Naphta Heavy".

[0031] In addition to the said aromatic hydrocarbons with 9 or more carbon atoms, component (D) in the preferred embodiment described may contain from 0 to less than 20 wt. non-aromatic organic solvent components (e.g. long chain paraffins and / or alicyclic compounds and / or heterocyclic compounds with a boiling point in each case higher than 100 ° C, especially higher than 130 ° C) and / or aromatic solvent components with less than 9 numbers carbon atoms (for example toluene or xylenes).

[0032] The additive formulation according to the invention is preferably prepared from components (A), (B), (C) and (D) by mixing them. In principle, any possible sequence of mixing the ingredients is allowed to obtain the additive formulation of the invention. However, it has proved that from the point of view of practical feasibility, it is advantageous to first mix the components (A) and (C) homogeneously in the presence of at least part of the high boiling organic solvent (D) and then to introduce the component (B). In addition, it may be advantageous to carry out the mixing operation at a slightly elevated temperature, about 20 to 80 ° C, especially at 25 to 50 ° C. In a particularly preferred embodiment, the components (A) and (C) are first homogeneously mixed together in the presence of at least part of the high boiling organic solvent (D) at 30 to 60 ° C, especially at 40 to 55 ° C, and then the component is introduced (B), wherein before the introduction of component (B), the mixture of components (A) and (C) and at least a portion of the high boiling organic solvent (D) is kept in the above-mentioned temperature range, preferably for at least 1 minute, especially for 1 to 120 m and 9 notes, especially for 1 to 30 minutes. It may also be advantageous to carry out the mixing operation completely or partly under vacuum, preferably at a pressure of 100 mbar to less than 1 bar, especially 10 mbar to less than 1 bar. All commonly known mixing techniques and mixing devices can be used.

[0033] According to the present invention, the additive formulation according to the invention is used for antistatic finishing and improving the electrical conductivity of inanimate organic material and for preventing the formation of electrostatic charge in chemical and physical processes.

[0034] To this end, the additive formulation according to the invention is introduced or mixed with the subjected to anti-electrostatic finishing and thus the improvement of the electrical conductivity of inanimate organic material, during or after its production, and distributed as uniformly as possible. The concentration of the additive preparation according to the invention in inanimate organic material is generally 0.01 to 2000 ppm by weight, preferably 0.1 to 1000 ppm by weight, especially 0.5 to 500 ppm by weight, especially 1 to 350 ppm by weight, calculated as inanimate organic material. In particular when used in motor fuels, the concentration of the additive formulation according to the invention may be lower, typical dosages are then 0.01 to 1000 ppm by weight, preferably 0.1 to 500 ppm by weight, especially 0.5 to 100 ppm by weight. , especially 1 to 10 ppm by weight, calculated on motor fuel.

[0035] Inanimate organic material is primarily understood to mean cosmetic preparations such as ointments and lotions, medicinal preparations such as pills and suppositories, photographic registration materials such as photographic emulsions, painting materials, plastics, waxes, solvents and products from petroleum and motor fuels, in particular diesel, heating oil, carburettor fuel, aviation gasoline and turbine fuel as well as lubricants, i.e. motor oils, lubricating oils, hydraulic oils, turbine oils, regulator oils, gear oils, switching and automation oils, calender oils, heat transfer oils, metalworking oils, shock absorber oils and greases.

[0036] As plastics that can be antistatically finished with the preparation according to the invention, for example:

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

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

polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates, polymethacrylates, polyacrylamides and polyacrylonitriles; polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, e.g. polyvinyl alcohol and polyvinyl acetate;

polyurethanes (for example as a material for shoe soles), especially thermoplastic polyurethanes, polyamides, polyureas, phenylene polyethers, polyesters, polycarbonates, polysulfones, polyethersulfones, polyetherketones and ethylene vinyl acetate (for example also as shoe soles).

[0037] Painting materials that can be anti-electrostatically finished with the formulation of the invention include, but are not limited to, varnishes, such as alkyd varnishes, suspension varnishes, epoxy varnishes, polyurethane varnishes, acrylic varnishes, nitrocellulose varnishes, or translucent varnishes, such as protective translucent varnishes wood.

[0038] Waxes that can be anti-electrostatically finished with the formulation of the invention are, inter alia, ethylene-vinyl acetate copolymer waxes.

[0039] As solvents which can be anti-electrostatically finished with the preparation according to the invention and thus can have an improved electrical conductivity, for example: alkanes such as n-pentane, n-hexane or n-heptane, alkenes such as hexene, heptene, octene, nonene, decene, undecene or dodecene, aromatic compounds such as toluene or xylene, naphthenes, alcohols such as methanol , ethanol, isopropanol or tert-butanol, aldehydes such as acetaldehyde, propionic aldehyde or butyl aldehyde, ketones such as acetone or butanone, carboxylic acids such as formic acid, acetic acid or propionic acid, carboxylic acid esters, such as methyl acetate or ethyl acetate, carboxylic acid amides such as N, N-dimethylformamide, and mixtures thereof.

[0040] The additive formulation according to the invention is particularly advantageous for anti-electrostatic finishing and improvement of the electrical conductivity of jet fuel fuels. Turbine engine fuels are used primarily for the operation of aircraft turbines.

[0041] A conventional turbine engine fuel composition comprises a major amount of liquid turbine engine fuel, for example, conventional turbine engine fuel used in civil or military aviation. These include, for example, motor fuels with the designations Jet Fuel A, Jet Fuel A-1, Jet Fuel B, Jet Fuel JP4, JP-5, JP-7, JP-8 and JP-8 + 100. Jet A and Jet A-1 are commercially available kerosene-based turbine fuel grades. The relevant standards are ASTM D 1655 and DEF STAN 91-91. Jet B is a narrower fraction of motor fuel based on kerosene and kerosene. JP-4 is the equivalent of Jet B. JP-5, JP-7, JP-8 and JP-8 + 100 are military fuels for turbine engines, which are used by the navy and air forces. Some of these standards specify preparations that already contain other additives, such as corrosion inhibitors, ice inhibitors, other antistatic agents, such as static charge dispersants, etc.

[0042] The additive formulation according to the invention may be added to turbine engine fuels or to turbine engine fuel compositions in combination with other known additives. Suitable additives that may be present in turbine fuel compositions are usually detergents, corrosion inhibitors, and antioxidants such as hindered tert-butylphenols, N-butylphenylenediamines or N, N'diphenylamine and their derivatives, metal deactivators, such as N, N'-disalicylidene-1,2-diaminopropane, solubilizing agents, other antistatic agents commonly known on the market, such as Stadis® 450, biocides, anti-icing agents, such as diethylene glycol methyl ether as well as mixtures of the listed additives.

[0043] Preferred additives for turbine fuel or turbine fuel compositions are the following special classes of compounds (E), (F) and (G):

[0044] Preferred additives (E) are those derived from succinic anhydride having long chain hydrocarbon groups having generally 15 to 700, primarily 30 to 200 carbon atoms. These compounds may have further functional groups, preferably selected from hydroxyl, amino, amide and / or imide groups. Preferred additives are the corresponding polyalkenyl succinic anhydride derivatives which can be obtained e.g. by reaction of polyalkenes with maleic anhydride by thermal means or by chlorinated hydrocarbons. The number average molecular weight of the long chain hydrocarbon groups is preferably in the range from about 200 to 10,000, particularly preferably 400 to 5,000, especially 600 to 3,000 and especially 650 to 2,000. These long chain hydrocarbon groups are preferably derived from ordinary, especially from previously mentioned reactive polyisobutenes. Particularly important additives (E) are derivatives of polyalkenyl succinic anhydride with ammonia, monoamines, polyamines, monohydric alcohols and polyols. Preferred polyamines for the preparation of derivatives are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylene diamine, etc. Suitable alcohols are 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, glycerin, trimethylolpropane, erythritol, pentane and sorbitol.

[0045] Suitable as additive derivatives of (E) succinic anhydride are described, for example, in US 3 522 179, US 4 234 435, US 4 849 572, US 4 904 401, US 5 569 644 and US 6 165 235, which are hereby incorporated by vocation.

[0046] Preferred additives (F) are polyalkenyl thiophosphonate esters. The polyalkenyl group of these esters preferably has a number average molecular weight in the range of about 300 to 5000, particularly preferably 400 to 2000, especially 500 to 1500. The polyalkenyl group is preferably derived from polyolefins as previously described with component (E) as the hydrocarbon group long chain. In particular, these are polyalkenyl groups derived from ordinary or reactive polyisobutenes. Suitable methods for preparing polyalkenylthio phosphonate esters by reacting a polyolefin with a thiophosphorylating agent are described, e.g., in US 5,725,611, which is incorporated herein by reference.

[0047] Preferred additives (G) are Mannich addition compounds. Such addition compounds are generally obtained by Mannich reaction of aromatic hydroxyl compounds, especially phenol and phenol derivatives, with aldehydes and monoamines or polyamines. Preferably they are reaction products of polyisobuten substituted phenols with formaldehyde and monoamines or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, etc. Suitable Mannich addition compounds and methods for their preparation are described, e.g., in US 5 876 ​​468, EP-A 831 141, EP-A 1 233 990 and EP-A 1 226 188, which are hereby incorporated by reference.

[0048] Other possible fuel additives for turbine engines or for turbine fuel compositions are tetrahydrobenzoxazine stabilizing agents and / or polycyclic phenolic stabilizing agents described in WO 2007/012580 described in international patent application PCT / EP2007 / 051632, which is incorporated herein by calling.

[0049] Additives (E) to (G) and optionally other previously mentioned additives can usually be used in each case in an amount of 0.0001 to 1% by weight, preferably 0.001 to 0.6% by weight. , in particular 0.0015 to 0.4% by weight, based on the total amount of fuel positions for turbine engines.

[0050] The additive formulation according to the invention may be a component of a concentrate for turbine fuel additives (jet fuels) which, in addition to the additive formulation according to the invention, contains at least one diluent and at least one other additive, preferably selected from those previously described. This additive concentrate, and thus the fuel composition for turbine engines with this additive concentrate, preferably contains one or more additives from the groups (E), (F) and (G), especially also mixtures of these additives, such as (E) + (F), (E) + (G), (F) + (G) and (E) + (F) + (G).

[0051] Suitable diluents are, for example, fractions obtained in the processing of petroleum, such as kerosene, naphtha or mineral base oils. Aromatic and aliphatic hydrocarbons such as heavy kerosene solvent, Solvesso® or Shellsol® and mixtures of these solvents and diluents are also suitable.

[0052] The additive formulation according to the invention is present in the described fuel additive concentrate for turbine engines in an amount of from 0.01 to 70% by weight, particularly preferably from 0.05 to 25% by weight, in particular from 0.1 to 5 % by weight, based on the total weight of the concentrate.

[0053] The described additive formulation according to the invention is advantageously suitable for anti-electrostatic finishing and improvement of the electrical conductivity of aviation gasoline, carburettor fuels and middle distillate fuel, in this case, in particular, diesel and heating oil.

[0054] Aviation gasoline is a motor fuel specially developed for aircraft engines, especially spark-ignition engines for propeller-driven aircraft, which is similar to commercially available carburettor fuels for propulsion of ground operated vehicles.

[0055] All commercial carburetor fuel compositions are included as carburettor fuels. As a typical example, Eurosuper basic motor fuel, compliant with EN228, which is commonly available on the market, can be mentioned here. In addition, carburetor fuel compositions with specifications in accordance with WO 00/47698 are also a possible field of application of the present invention. These carburetor fuels may additionally contain bioethanol.

[0056] All commercial diesel and fuel oil compositions are considered as middle fuel distillate. A typical example that may be mentioned here is the European diesel fuel that is widely available on the market in accordance with EN 590. Diesel fuels are usually petroleum raffinates, generally having a boiling point in the range from 100 to 400 ° C. These are usually distillates that distil 95% to a temperature of 360 ° C or even higher. They may also be so-called "ultra low sulfur diesel" or "city diesel", characterized in that 95% of their volume distils, for example, to a temperature not exceeding 345 ° C, and that the sulfur content is a maximum of 0.005% by weight, or in that 95% of their volume is distilled, for example, to a temperature not higher than 285 ° C, and that the sulfur content is a maximum of 0.001% by weight. In addition to gas oils obtained by refining, the main components of which are relatively long chain paraffins, suitable gas oils are those obtained by gasification of coal ["coal to liquid" (CTL) motor fuels) or by liquefaction of gas ["gas to liquid" motor fuel (GTL)]. Mixtures of the abovementioned diesel fuels with renewable motor fuels such as biodiesel are also suitable. Furthermore, diesel fuels produced from biomass [biomass to liquid (BTL) motor fuels] are suitable. Diesel oils with a low sulfur content, i.e. with a content of less than 0.05 wt.%, More preferably less than 0.02 wt.%, Especially less than 0.005 wt.%, Especially less than 0.001 wt. sulfur. Diesel fuels may also contain water, e.g. in an amount of up to 20% by weight, for example in the form of a diesel oil-water emulsion or as so-called "White Diesel".

[0057] Fuel oils are, for example, low or high sulfur petroleum refinates, or distillates of hard coal or lignite, usually having a boiling range from 150 to 400 ° C. Heating oils may be standard heating oils according to DIN 51603-1, which have a sulfur content of 0.005 to 0.2% by weight, or are low-sulfur heating oils with a sulfur content of 0 to 0.005% by weight. Examples of heating oils include in particular heating oil for domestic oil-fired appliances or EL heating oil.

[0058] The additive formulation according to the invention may be added to a given basic motor fuel, in particular to carburettor fuel or diesel fuel, either alone or in the form of a fuel additive package, e.g. so-called gasoline additive packages or diesel additive packages. These types of packages are concentrates of engine fuel additives and generally contain, as co-additives, in addition to the solvent, a number of other components used together as additives, such as carrier oils, cold flow improvers, corrosion inhibitors, demulsifiers, anti-fog additives, antifoaming additives, and increasing agents cetane number, combustion enhancers, antioxidants or stabilizers, other anti-static agents, metallocenes, metal deactivators, solubilizing additives, markers and / or dyes.

[0059] In a preferred embodiment, the carburettor fuel or diesel fuel in addition to the additive formulation according to the invention contains, as other motor fuel additives, at least one detergent, hereinafter referred to as component (H).

[0060] Detergents or detergent additives (H) are usually referred to as sediment inhibitors for motor fuels. The detergents are preferably amphiphilic substances having at least one hydrophobic hydrocarbon group with number average molecular weight (M_n) from 85 to 20,000, especially from 300 to 5000, especially from 500 to 2500, and at least one polar moiety selected from (Ha) mono- or polyamino groups having up to 6 nitrogen atoms, where at least one nitrogen has alkaline properties;

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

(Hc) hydroxyl groups, in combination with mono- or polyamino groups, at least one nitrogen atom having basic properties;

(Hd) carboxyl groups or their alkali metal or alkaline earth metal salts;

(He) sulfone groups or their salts with alkali or alkaline earth metals;

(Hf) polyoxy-C moieties₂-C₄-alkylene, terminated with hydroxyl, mono- or polyamino groups, at least one nitrogen atom having basic properties, or carbamate groups;

(Hg) carboxyl ester groups;

(Hh) moieties derived from succinic anhydride having hydroxyl and / or amino and / or amide and / or imide groups; and / or (Hi) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines.

[0061] The hydrophobic hydrocarbon group in the above detergent additives, which provides sufficient solubility in the fuel composition, has a number average molecular weight (M_n) from 85 to 20,000, especially from 300 to 5000, especially from 500 to 2500. As typical hydrophobic hydrocarbon groups, especially in compounds with polar moieties (Ha), (Hc), (Hh) and (Hi), attention of alkyl or alkenyl groups with a relatively long chain, especially polypropenyl, polybutenyl and polyisobutenyl, in each case with M_n = 300 to 5000, especially 500 to 2500, especially 700 to 2300.

As examples of the above groups in detergent additives, mention may be made of: [0063] Additives containing mono- or polyamino groups (Ha) are preferably polyalkenone mono- or polyalkenol polyamines based on polypropene or ordinary (i.e. usually with middle double bonds) polybutene or polysobutene with M_n = 300 to 5000. These types of additives based on highly reactive polyisobutene, which can be made from polysobutenes, containing up to 20 wt. n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as 3- (N, N-dimethylamino) propylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known in particular from EP-A 244 616. If polybutene or polyisobutene is predominantly produced in the production of additives with predominantly middle double bonds (usually in the β and γ positions), the proposed production route is chlorination and subsequent amination, or oxidation of the double bond with air or ozone to a carbonyl or carboxylic compound followed by amination under reducing (hydrogenating) conditions. For amination, amines such as ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine may be used. Suitable propane-based additives are described in particular in WO-A94 / 24231.

[0064] Other preferred additives containing monoamino groups (Ha) are hydrogenation products of reaction products of polysobutenes with an average degree of polymerization of P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A-97/03946.

[0065] Other preferred additives containing monoamino (Ha) groups are compounds obtained from polyisobutenoepoxides by reaction with amines and subsequent dehydration and reduction of amino alcohols, as described in particular in DE-A-196 20 262. [0066] Additives containing nitro (Hb) groups, optionally in combination with hydroxyl groups, are preferably reaction products of polysobutenes with an average degree of polymerization of P = 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-96/03479. These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. α, β-dinitropolyisobutene) and various hydroxynitropolyisobutenes (e.g. α-nitro-e-hydroxypolyisobutene).

[0067] Additives containing hydroxyl groups in combination with mono- or polyamino (Hc) groups are, in particular, reaction products of polyisobutenoepoxides obtained from polyisobuten having predominantly double double bonds and M_n = 300 to

5000, with ammonia, mono- or polyamines, as described in particular in EP-A-476 485. [0068] Additives containing carboxyl groups or their salts with alkali or alkaline earth metal (Hd) are preferably copolymers of C₂-C₄₀-olefin with maleic anhydride with a total molecular weight of 500 to 20,000 whose carboxyl groups have partially or completely reacted to alkali or alkaline earth metal salts and the remaining carboxyl groups have reacted with alcohols or amines. Such additives are known in particular from EP-A-307 815. These additives mainly serve to prevent valve seat wear and can be, as described in WOA-87/01126, preferably used in combination with conventional detergents for motor fuels such as poly (iso) -butenamines or polyetheramines.

[0069] Additives containing sulfone groups or their alkali metal or alkaline earth metal (He) salts are preferably the alkali metal or alkaline earth metal salts of the alkyl sulfosuccinate as described in particular in EP-A-639 632. Such additives mainly serve to prevent abrasion valve seats and can preferably be used in combination with conventional fuel detergents such as poly (iso) butenoamine or polyetheramine.

[0070] Additives containing polyoxy-C moieties₂-C₄-alkylene are preferably polyethers or polyetheramines which can be obtained by reaction of C₂-C₆₀-alkanols, C.₆C₃₀-alkanediols, mono- or di-C₂-C₃₀-alkylamines, C.₁-C₃₀-alkylcyclohexanols or C₁C₃₀-alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, followed by reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416. In the case of polyethers, such products also have the properties of carrier oils. Typical examples of such products are oxybutylenated tridecanol or oxybutylenated isotridecanol, oxybutylated isononylphenol and oxybutylated and propoxylated polyisobutenol, as well as the corresponding reaction products with ammonia.

[0071] Additives containing carboxyl ester (Hg) groups are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those with the lowest viscosity being 2 mm²/ s at 100 ° C, as described in particular in DE-A-38 38 918. As mono-, di- or tricarboxylic acids, aliphatic or aromatic acids can be used, suitable alcohol esters or polyol esters are representative of their long chain compounds, for example with 6 to 24 carbon atoms. Typical examples of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. These types of products also have the properties of carrier oils.

[0072] Additives containing moieties derived from succinic anhydride, having hydroxyl and / or amine and / or amide and / or imide (Hh) are preferably corresponding succinic anhydride derivatives substituted with alkyl or alkenyl groups, and especially suitable derivatives of polyisobutenyl succinic anhydride, which can obtain by reaction ordinary or highly reactive polyisobutene with M_n = 300 to 5000 with maleic anhydride by thermal route or via chlorinated hydrocarbons. Derivatives with aliphatic polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine are particularly important. The moieties having hydroxyl and / or amino and / or amide and / or imide groups are, for example, carboxylic acid groups, monoamine acid amides, di- or polyamine acid amides, which, in addition to the amide function, also have free amino groups, succinic acid derivatives having an acid function and amide, carboxylic acid imides with monoamines, carboxylic acid imides with di- or polyamines, which in addition to imide functions have free amino groups or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Motor fuel additives of this kind are described in particular in US-A-4 849 572.

[0073] Detergent additives from group (Hh) are preferably reaction products of alkyl or alkenyl substituted succinic anhydrides, especially polyisobutenyl succinic anhydrides, with amines and / or alcohols. They are therefore derivatives derived from alkyl, alkenyl or polyisobutenyl succinic anhydrides with amino and / or amide and / or imide and / or hydroxyl groups. It is understood that these reaction products are obtained not only using substituted succinic anhydride, but also using substituted succinic acid or appropriate acid derivatives such as succinic acid halides or succinic acid esters.

[0074] If the motor fuel with additives contains a detergent based on polyisobutenyl substituted succinic imide, imides with aliphatic polyamines are particularly important. Particularly preferred polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine and above all tetraethylenepentamine. The polyisobutenyl group has a number average molecular weight M_n preferably 500 to 5000, particularly preferably from 500 to 2000, especially about 1000.

[0075] Additives containing moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines ((Hi) are preferably reaction products of polyisobuten substituted phenols with formaldehyde and mono- or polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropyl The polyisobutenyl substituted phenols can be derived from ordinary or highly reactive polyisobuten with M_n = 300 to 5000. Such "Mannich polysobuten bases" are described in particular in EP-A-831 141.

[0076] Preferably, said detergent additives (H) are used together with the additive formulation of the invention in combination with at least one carrier oil.

[0077] Suitable mineral carrier oils are the fractions obtained in the processing of crude oil, such as Brightstock, or base oils with viscosity, for example, from the SN class 500 - 2000, as well as aromatic hydrocarbons, paraffin hydrocarbons and alkoxyalkanols. Also useful is the fraction obtained during refining mineral oil and known as "hydrocrack oil" (fraction of vacuum distillate with a boiling range from about 360 to 500 ° C, obtainable from catalytically hydrogenated under high pressure and isomerized and dewaxed natural mineral oil) . Mixtures of the aforementioned mineral carrier oils are also suitable. Selected examples of suitable synthetic carrier oils are: polyolefins (poly-alpha-olefins or poly-internal olefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and long-chain alkanol carboxylic esters.

[0078] Examples of suitable polyolefins are olefin polymers with M_n = 400 to 1800, primarily based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

[0079] Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C moieties₂-C₄-alkylene which is obtained by reaction of C₂C₆₀-alkanols, C.₆-C₃₀-alkanediols, mono- or di-C₂-C₃₀-alkylamines, C.₁-C₃₀-alkylcyclohexanols or C₁-C₃₀-alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, followed by reductive amination with ammonia, monoamines or polyamines. Such products are described in particular in EP-A-310 875, EP-A-356 725, EP-A-700 985 and US-A-4 877 416. For example, polyC can be used₂-C₆-etheramines or their functional derivatives. Typical examples of such products are oxybutylenated tridecanol or oxybutylenated isotridecanol, oxybutylated isononylphenol and oxybutylated and propoxylated polyisobutenol, as well as the corresponding reaction products with ammonia.

[0080] Examples of carboxylic acid esters with long chain alkanols are especially esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols as described in particular in DE-A-38 38 918. As mono-, di- or tricarboxylic acids aliphatic or aromatic acids may be used, suitable alcohol esters or polyol esters are representative of their long chain compounds having for example 6 to 24 carbon atoms. Typical examples of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, such as di- (n- or isotridecyl) phthalate.

[0081] Other suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 0 452 328 and EP-A 0 548 61.

[0082] Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers having about 3 to 35, e.g. about 5 to 30 C oxide units₃C₆-alkylene, selected e.g. from propylene oxide, n-butylene oxide and i-butylene oxide units or mixtures thereof. Non-limiting examples of suitable starter alcohols are long chain alkanols or phenols substituted with long chain alkyls, wherein the long chain alkyl group is especially the C group₆-C₁₈straight or branched chain alkyl. As a preferred example, tridecanol and nonylphenol can be mentioned.

[0083] Other suitable synthetic carrier oils are alkoxylated alkylphenols as described in DE-A 101 02 913.

[0084] Preferred carrier oils are synthetic carrier oils, with polyethers being particularly preferred.

[0085] To the fuel with additives, a detergent additive (H) or a mixture of various such detergent additives is added in a total amount of preferably from 10 to 2000 wt. ppm, particularly preferably from 20 to 1000 wt. ppm, even more preferably from 50 to 500 wt. ppm and especially from 50 to 200 wt. ppm, e.g. from 70 to 150 wt. ppm.

[0086] If a carrier oil is also used in addition, it is added to the motor fuel with the additives according to the invention in an amount of preferably from 1 to 1000 wt. ppm, particularly preferably from 10 to 500 wt. ppm, especially from 20 to 100 wt. ppm.

[0087] Suitable co-additives for improving low temperature fluidity are, for example, copolymers of ethylene with at least one other unsaturated monomer, e.g. ethylene-vinyl acetate copolymers.

[0088] Corrosion inhibitors suitable as other co-additives are, for example, succinic acid esters, primarily with polyols, fatty acid derivatives, e.g. oleic acid esters, oligomerized fatty acids and substituted ethanolamines.

[0089] Suitable demulsifiers as, for example, alkali metal and alkaline earth metal salts of alkyl substituted phenolsulfonates and naphthalene sulfonates, as well as alkali metal and alkaline earth metal salts of fatty acid, as well as alkoxylated alcohols, e.g. ethoxylated alcohols, alkoxylated phenols, e.g. ethoxylated tert-butylphenols or ethoxylated tert-pentylphenols, fatty acid, alkylphenols, condensation products of ethylene oxide and propylene oxide, e.g. ethylene oxide-propylene oxide block polymers, polyethyleneimines and polysiloxanes. [0090] Suitable anti-fog additives as co-additives are, for example, alkoxylated phenol-formaldehyde condensates.

[0091] Antifoaming additives suitable as co-additives are, for example, polyether modified polysiloxanes.

[0092] Cetane number improvers and combustion improvers suitable as other co-additives are, for example, alkyl nitrates, e.g. cyclohexyl nitrate and especially nitrate

2-ethylhexyl, and peroxides, e.g. di-tert-butyl peroxide.

[0093] Suitable antioxidants as co-additives are, for example, substituted phenols, e.g., 2,6-di-tert-butylphenol and 2,6-di-tert-butyl-3-methylphenol, as well as phenylenediamines, e.g. N, N'- di-sec-butyl-p-phenylenediamine.

[0094] Suitable metal deactivators as co-additives are, for example, salicylic acid derivatives, e.g. N, N'-disalicylidene-1,2-propanediamine.

[0095] Suitable solvents, especially for motor fuel additive packages, are, for example, non-polar organic solvents, especially aromatic and aliphatic hydrocarbons, e.g. toluene, xylenes, "white spilit", as well as technical solvent mixtures with Shellsol® designations (manufacturer: Royal Dutch / Shell Group), Exxol® (producer. ExxonMobil) and kerosene solvent. In addition, polar mixtures of organic polar solvents, especially alcohols such as 2-ethylhexanol, 2-propylheptanol, decanol and isotridecanol, are also taken into account, especially when mixed with the non-polar organic solvents mentioned.

[0096] If the co-additives and solvents mentioned are additionally used in carburettor fuels and diesel fuels, they are used in the usual amounts for this purpose.

[0097] The additive formulation according to the invention described is furthermore also suitable in an antistatic way for finishing and improving the electrical conductivity of lubricants. Lubricants and lubricating compositions are here referred to as engine oils, lubricating oils, hydraulic oils, turbine oils, regulator oils, transmission oils, switching and automation elements, calender oils, heat transfer oils, metalworking oils, shock absorber oils and related compositions liquid, used to lubricate moving mechanical parts - usually as metal. Lubricants also include greases.

[0098] The most economically important lubricating compositions are engine oils and gear oils, for switching elements and automation. Engine oils usually consist of mineral base oils, usually containing paraffinic components and produced in refineries by expensive processing and purification processes, with a proportion of 2 to 10% by weight. additives (based on the content of active substances). For specific applications, for example high temperature applications, mineral base oils may be partially or completely replaced by synthetic components such as organic esters, synthetic hydrocarbons such as olefinoligomers, poly-α-olefins or polyolefins or hydrocracked oils. Engine oils must have sufficiently high viscosity also at high temperatures to ensure impeccable lubrication and good seal between the cylinder and piston. In addition, the flow properties of engine oils must be such that the engine can be started without problems at low temperatures. Engine oils must be resistant to oxidation and can create only small amounts of liquid or solid decomposition products and sediments, even under difficult operating conditions. Engine oils disperse solids (dispersive behavior), prevent deposits (detergent action), neutralize acidic reaction products, and form a film that protects against abrasion on metal surfaces in the engine. Engine oils are usually characterized by viscosity classes (SAE classes).

[0099] Oils for transmissions, switching elements and automation in their basic components and additives have a similar composition as engine oils. The transmission of force in the gears of the gears is largely due to the fluid pressure in the gear oil between the teeth. Accordingly, gear oil must be able to withstand high pressure for a long time without decomposing. In addition to viscosity properties, the decisive parameters here are wear, pressure, friction, shear, running and break-in behavior.

[0100] Engine oils and oils for gearboxes, switching elements and automation, in addition to the additive formulation according to the invention used in accordance with the invention, generally contain at least one, but usually several or all of the additives listed below, in the amounts usually used for this purpose (which in brackets in weight%, based on the total composition of the grease):

(a) Antioxidants (0.1 to 5%):

sulfur compounds, e.g. reaction products of terpenes (α-pinene), resin oils or low molecular weight polybutenes with sulfur, dialkyl sulfides, polysulfides, diaryl sulfides, modified thiols, mercaptobenzimidazoles, mercaptotriazines, thiophene derivatives, xanthogenates, dialkyltankylcyclodinates thioaldehydes, dibenzyl disulfides, alkylphenol sulfides, dialkylphenol sulfides or sulfur-containing carboxylic acids, phosphorus compounds, e.g. triaryl and trialkyl phosphites, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dialkyl phosphates or piperazide phosphonates sulfur-phosphorus compounds, e.g. zinc dialkyldithiophosphates (metal dialkyldithiophosphates also act in lubricating oils as corrosion inhibitors and high pressure fluoride products) (V) with terpenes (αpinene, dipentene), polybutenes, olefins or unsaturated phenol derivatives, e.g. hindered mono-, bis- or trisphenols, hindered polycyclic phenols, polyalkylphenols, 2,6-di-tert-butyl4-methylphenol or methylene-4,4'-bis (2,6-di-tert-butylphenol) (phenol derivatives are often used in combination with sulfur or amine based antioxidants) amines, e.g. arylamines such as diphenylamine, phenyl-α-naphthylamine or 4,4'-tetramethyldiamine-diphenylmethane metal deactivators in the strict sense, e.g. N-salicylideneethylamine, N, N'disalicylidene-ethylenediamine, N, N'-disalicylidene-1,2-propanediamine, triethylenediamine, ethylenediaminetetraacetic acid, phosphoric acid, citric acid, glycolic acid, lecithin, thiadiazole, imidazole or derivatives viscosity index improvers (0.05 to 10%), e.g. polyisobutens with a molecular weight usually from 10,000 to 45,000, polymethacrylates with a molecular weight usually from 15,000 to 100,000, homopolymers and copolymers of 1,3-diene such as butadiene or isoprene with a molecular weight usually from 80,000 to 100,000, copolymers

1,3-diene styrene with a molecular weight usually from 80,000 to 100,000, polymers maleic anhydride-styrene in esterified form with a molecular weight usually from 60,000 to 120,000, blocky star polymers consisting of conjugated diene units and aromatic monomers, weighing molecular weight, usually from 200,000 to 500,000, polyalkylstyrene, usually from 80,000 to 150,000, polyolefins consisting of ethylene and propylene or styrene-cyclopentadiene-norbornene terpolymers with a molecular weight usually from 60,000 to 140,000 (c) freezing point additives (improving low temperature fluidity) (0.03 to 1%), e.g. bicyclic aromatics, such as naphthalene with various long chain alkyl groups, polymethacrylates with 12 to 18 carbon atoms in the alcohol group, branching between 10 to 30 mole% and average molecular weight from 5000 to 500000, long chain alkylphenols and dialkylaryl phthalates or copolymers various olefins (d) detergents (HD additives) (0.2 to 4%), e.g. calcium, lead, zinc and manganese naphthenates, calcium dichlorostearates, calcium phenyl stearates, calcium chlorophenyl stearates, sulfonation products of alkylaromatic compounds such as dodecylbenzene, sulfonation products for oil refining, sodium, calcium, barium or magnesium sulfonates, neutral, basic and overbased sulfonates, phenol sulfonates carboxylates, salicinates, metal salts with alkylphenols and alkylphenol sulfides, phosphates, phosphorothioates or alkenylphosphonic acid derivatives (e) ashless dispersants (0.5 to 10%), e.g. Mannich condensates of alkylphenol, formaldehyde and polyalkylene polyamines, reaction products of polyisobutenylsuccinic anhydrides with polyhydroxy compounds or polyamines, copolymers of alkyl methacrylates with diethylaminoethyl methacrylate, N-vinylpyrrolidone, N-vinylpyridine or 2-hydroxy ethyl methoxy acrylate Pressure Additives) (0.2 to 2.5%), e.g. chlorinated paraffins with 40 to 70 wt. chlorine, chlorinated fatty acid (especially with trichloromethyl end groups), dialkyl hydrogen phosphites, triaryl phosphites, aryl phosphates such as tricresyl phosphate, dialkyl phosphates, trialkyl phosphates such as tributyl phosphate, trialkyl phosphines, diphosphoric esters, phosphate derivatives naphthenic acid, carbamic acid esters, thiocarbamic acid derivatives, substituted 1,2,3-triazoles, mixtures of benzotriazole and alkyl succinic anhydride or alkylmaline anhydride, 1,2,4-thiadiazole polymers, morpholinobenzothiadiazole disulfide, chlorinated alkyl sulfides, sulfurized olefins, sulfurized chlorinaphthalenes, chlorinated alkylthiocarbonates, organic sulfides and polysulfides, such as bisislide (4-chloris) tetrachlordifenylosulfid, thioacetal trichloroacrolein or especially zinc dialkildithiophosphate (ZDDP) (g) Friction Modifier (0.05 to 1%), especially polar oil-soluble compounds, due to adsorption producing a thin film on the surface exposed to friction, e.g. fatty alcohols , fatty amides, fatty acid salts, fatty acid alkyl esters or fatty acid glycerides (h) antifoaming additives (0.0001 to 0.2%), e.g. liquid silicones such as polydimethylsiloxanes or polyethylene glycol ethers and polyethylene glycol sulfides.

(i) demulsifiers (0.1 to 1%), e.g. dinonylnaphthalene sulfonates, in the form of alkali and alkaline earth metal salts (j) corrosion inhibitors (also known as metal deactivators) (0.01 to 2%), e.g. tertiary amines and their salts, iminoesters, amide oximes, diaminomethanes, derivatives of saturated and unsaturated fatty acids with alkanolamines, alkylamines, sarcosines, imidazolines, alkylbenzotriazoles, dimercaptothiadiazole derivatives, diaryl phosphates, thiophosphorus primary esters, neutral salts₈-C₁₈-alkylamines or cycloalkylamines with dialkyl phosphates having branched C groups₅-C₁₂-alkyl, neutral or basic alkaline earth metal sulfonates, zinc naphthenates, mono- and dialkylarylsulfonates, barium dinonylnaphthalenesulfonates, lanolin (wool grease), heavy metal salts of naphthenic acid, dicarboxylic acid, unsaturated fatty acids, hydroxy fatty acids, fatty acid ester and monooleates of sorbitan, O-stearoylalkanolamine, derivatives of polyisobutenyl succinic acid or zinc dialkyldithiophosphates and zinc dialkyldithiocarbamates (k) emulsifying additives (0.01 to 1%), e.g. long-chain, naturally occurring carboxylic acid, naphthenic acids, synthetic carboxylic acid, sulfonamides, N-oleylsarcosine, alkanesulfamidoacetic acid, dodecylbenzenesulfonate, long-chain alkylated ammonium salts, such as dimethyldecylbenzylammonium acyl, alkyl imiglene, and polyglycolyl, or long chain acylated mono- and diethanolamines (1) dyes and fluorescent additives (0.001 to 0.2%) (m) preservatives (0.001 to 0.5%) (n) odor enhancers (0.001 to 0.2%) [0101 ] Typical ready-to-use engine oils and compositions of oils for transmissions, switching elements and automation according to the invention are summarized as follows, where the data on the additives refer to the active substance content, and the sum of all ingredients is always 100%:

- 80 to 99.3% by weight, in particular 90 to 98% by weight basic engine oil or basic oils for gears, switching elements and automation (mineral basic oils and / or synthetic components), including solvent and thinner fractions for additives

- 0.01 to 2000 weight ppm, preferably 0.1 to 1000 wt. ppm, primarily 0.5 to 500 wt. ppm, especially 1 to 350 wt. ppm, the additive preparation according to the invention

- 0.2 to 4% by weight, in particular 1.3 to 2.5% by weight detergents from group (d)

0.5 to 10% by weight, in particular 1.3 to 6.5% by weight dispersants of group (e)

0.1 to 5% by weight, in particular 0.4 to 2.0% by weight antioxidants from group (a) and / or high pressure additives from group (f) and / or friction reducing additives from group (g)

- 0.05 to 10% by weight, in particular 0.2 to 1.0% by weight viscosity index improvers of group (b)

- 0 to 2 wt. other additives from groups (c) and (h) to (n) [0102] As an example of a chemical and physical process in which the additive formulation according to the invention can be used to prevent the formation of electrostatic charge, mention may be made of the polyethylene-gas phase-bed process bed. In this process, ethylene or a mixture of ethylene and comonomers such as 1-butene, 1-hexene or 1 octene undergoes coordination polymerization. The density of polyethylene formed depends decisively on the amount and type of comonomers incorporated. For example, high density HDPE is preferably obtained from ethylene without comonomers, and low density LLDPE is obtained in the presence of significant amounts of the aforementioned comonomers. The catalysts used are preferably Ziegler or metallocene catalysts deposited on silicon dioxide. The polymerization is in each case carried out in a fluidized bed at a temperature below the melting point of the polyethylene, as a result of which the solid product particles rub against the inner wall of the fluidized bed column rector. The additive formulation according to the invention serves to prevent the formation of electrostatic charge throughout the entire reactor system and thus counteracts the formation of polymer deposits on the inner wall of the reactor and in heat exchangers.

[0103] The present invention also relates to an antistatic finished inanimate organic material with improved electrical conductivity, selected from cosmetic preparations, medical preparations, photographic registration materials, painting materials, plastics, waxes, solvents, petroleum products and motor fuels containing 0.01 to 2000 weight ppm, preferably 0.1 to 1000 wt. ppm, primarily 0.5 to 500 wt. ppm, especially 1 to 350 wt. ppm of the additive formulation according to the invention.

[0104] Compared to known compositions, the additive formulation according to the invention allows an even more effective and long-lasting increase in electrical conductivity in inanimate organic material, especially in mineral oil products and motor fuels, especially in turbine fuel, carburettor fuel and oil propulsion and in lubricants. In many cases, the electrical conductivity, even after storage, remains constantly high, while in the corresponding additive formulations known from the prior art a clear decrease in this value can be observed during storage. Already with very small quantities in the range of several weights. ppm, generally a fuel conductivity of at least 50 to 100 pS / m is achieved.

[0105] The additive formulation according to the invention has high thermostability. It does not contain metals and halogens. In addition, it has a high flash point and is therefore safe during its manufacture, transport and storage, before use in inanimate organic material, i.e. it can be handled without risk of explosion and fire.

[0106] The invention is further elucidated based on the following non-limiting examples.

Example 1: Preparation of 1-decene-sulfur dioxide copolymer at 25 ° C [0107] 1122g (7.90 mol) of 1-decene and 28 g dodecylmercaptan in 350 g Solvent Naphta Heavy (Solvesso® 150) were placed in a 5-liter autoclave. At 10 to 20 ° C, 950 g (14.84 moles) of sulfur dioxide were introduced. Then the temperature of the reaction mixture was adjusted to 25 ° C and at this temperature a solution of 72 g of tert-butyl peroxypivalate (75% by weight) in 700 g of Solvent Naphta Heavy was introduced over 3 hours. The mixture was then further stirred at 20 ° C for 5 hours. For finishing, the pressure was evacuated and the autoclave was degassed first under normal pressure and then under vacuum (200 to 10 mbar). 2.4 kg of a clear, viscous polymer solution were obtained. The conversion was 95% (determined by spectroscopy)¹H-NMR, based on the ratio of integral 3 olefin protons of residual olefin at 5.8 ppm / 4.9 ppm to 3 protons in the polymer backbone at 4.3-3.0 ppm). The 1-decene sulfur dioxide copolymer thus obtained had a number average molecular weight M_n 19,600 and PDI polydispersity 3.2.

Example 2: Preparation of 1-decene-sulfur dioxide copolymer at 35 ° C [0108] 1122g (7.90 mol) of 1-decene and 28 g dodecylmercaptan in 350 g Solvent Naphta Heavy (Solvesso® 150) were placed in a 5-liter autoclave. At 10 to 20 ° C, 950 g (14.84 moles) of sulfur dioxide were introduced. Then the temperature of the reaction mixture was adjusted to 35 ° C, and at this temperature a solution of 72 g of tert-butyl peroxypivalate (75% by weight) in 700 g of Solvent Naphta Heavy was introduced over 2 hours. The mixture was then stirred further at 20 ° C for 4 hours. For finishing, the pressure was evacuated and the autoclave was degassed first under normal pressure and then under vacuum (200 to 10 mbar). 2.5 kg of a clear, viscous polymer solution was obtained. The conversion rate was 97% (determined by spectroscopy)¹H-NMR, based on the ratio of the integral 3 olefin protons of residual olefin at 5.8 ppm / 4.9 ppm to 3 protons in the polymer backbone at 4.3-3.0 ppm). The 1-decene sulfur dioxide copolymer thus obtained had a number average molecular weight M_n 13,400 and PDI polydispersity 2.9.

Example 3: Preparation of 1-decene-sulfur dioxide copolymer at 33 ° C [0109] In a 5-liter autoclave, 1122g (7.90 mol) of 1-decene and 28 g dodecylmercaptan in 630 g Solvent Naphta Heavy (Solvesso® 150) were placed. 720 g (11.25 moles) of sulfur dioxide were introduced at 10 to 20 ° C. Then the temperature of the reaction mixture was adjusted to 33 ° C and at this temperature a solution of 88 g of tert-butyl peroxypivalate (75% by weight) in 420 g of Solvent Naphta Heavy was introduced over 2 hours. The mixture was then stirred further at 20 ° C for 4 hours. For finishing, the pressure was reduced and the autoclave was degassed first under normal pressure and then under vacuum (200 to 10 mbar). 2.5 kg of a clear, viscous polymer solution was obtained. The conversion was 92% (determined by spectroscopy)¹H-NMR, based on the ratio of the integral 3 olefin protons of residual olefin at 5.8 ppm / 4.9 ppm to 3 protons in the polymer backbone at 4.3-3.0 ppm). The 1-decene sulfur dioxide copolymer thus obtained had a number average molecular weight M_n 12,500 and polydispersity PDI 2.5.

Example 4: Preparation of an additive formulation from 1-decene-sulfur dioxide copolymer C_20-24-olefin-maleimide, dodecylbenzenesulfonic acid and Solvent Naphta Heavy [0110] 1 kg solution of 1-decene sulfur dioxide copolymer (50% by weight in Solvent Naphta

Heavy) of example 2 [component (A)] was mixed while mixing at 25 to 35 ° C with another 1.1 kg portion of Solvent Naphta Heavy. Then 160 g of dodecylbenzenesulfonic acid [component (C)] was added while stirring at the same temperature and mixed for homogeneity. This mixture was stirred 10 minutes at 40 to 50 ° C. Then, at a temperature of 40 to 50 ° C, 1 kg of a solution in Solvent Naphta Heavy (50% by weight) converted into imide by reaction with N-tallow-1,3-diamionopropane of copolymer C_20/24olefin-maleimide, weight average molecular weight M_in in the range of 2000 to 5000 [component (B)] and mixed until homogeneous. The resulting additive formulation had a composition of 15.3 wt. (A), 15.3 wt. (B), 4.9% by weight (C) and 64.4% by weight Solvent Naphta He10 avy [component (D)].

Example 5: Preparation of an additive formulation from 1-decene sulfur dioxide copolymer C_20/24-olefin-maleimide, dodecylbenzenesulfonic acid and Solvent Naphta Heavy [0111] The same ingredients (A), (B), (C) and (D) analogously to the recipe in Example 4 were mixed in such quantitative proportions that an additive formulation was obtained

21 wt. (A), 18 wt. (B), 7 wt. (C) and 54 wt. (D).

Example 6: Preparation of an additive formulation from 1-decene-sulfur dioxide copolymer C_20/24-olefin-maleimide, dodecylbenzenesulfonic acid and Solvent Naphta Heavy [0112] The same ingredients (A), (B), (C) and (D) analogously to the recipe in Example 4 were mixed in such quantitative proportions that an additive formulation was obtained

14 wt. (A), 13 wt. (B), 5 wt. (C) and 68 wt. (D).

Example 7: (for comparison) Preparation of an additive formulation from a 1-decendoxide sulfur copolymer, a reaction product of N-tallowamino-1,3-diaminopropane-epichlorohydrin, dodecylbenzenesulfonic acid and Solvent Naphta Heavy [0113] A preparation analogous to the ratio of four components to of the preparation of Example up to 6, with one difference that instead of 50 wt. copolymer solution C_20/24-olefin-maleimide used the same amount of commercially available 50 wt. a solution of a polymeric condensation product of N-tallowamine-1,3-diaminopropane and epi chlorohydrin in a mixture of aromatic hydrocarbons - as disclosed in document (1 ).

Example 8: Measurement of the conductivity of additive formulations [0114] Electrical conductivity measurements were carried out in accordance with DIN 514122 (field method). To this end, the immersion measuring cell was immersed in the liquid to be measured. The conductivity value in pS / m was read on the display of the immersion measuring cell, in each case at the same liquid temperature, namely 25 ° C. The liquids to be measured were commercial petroleum, commercial diesel oil, commercial heating oil, commercial turbine fuel and commercial hydraulic oil, to which in each case a specific amount of the additive preparation was first added as a conductivity improver. The following set shows the measurement results.

a) in commercial petroleum (dose: in each case 3 mg per liter):

the additive formulation of example 5 (according to the invention) showed 890 pS / m; the additive formulation from example 6 (according to the invention) showed 750 pS / m; the additive formulation from Example 7 (for comparison) showed 540 pS / m; a commercial antistatic preparation (AF1) showed 760 pS / m;

(b) in commercial diesel (dose: in each case 3 mg per liter):

the additive formulation of example 5 (according to the invention) showed 670 pS / m; the additive formulation of example 6 (according to the invention) showed 440 pS / m; a commercial antistatic preparation (AF1) showed 415 pS / m;

c) in commercial heating oil (dose: in each case 3 mg per liter):

the additive formulation of example 5 (according to the invention) showed 690 pS / m; the additive formulation of example 6 (according to the invention) showed 520 pS / m; a commercial antistatic preparation (AF1) showed 505 pS / m;

(d) in commercial fuel for turbine engines (dose: in each case 1, 3 or 5 mg per liter):

the additive formulation of example 5 (according to the invention) at 1 mg per liter showed 174 pS / m, at 3 mg per liter showed 750 pS / m and at 5 mg per liter showed 1275 pS / m; after 4 days of storage, conductivity measurements were repeated which showed 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); commercial antistatic preparation (AF2) at 1 mg per liter showed 205 pS / m, at 3 mg per liter showed 723 pS / m and at 5 mg per liter showed 1230 pS / m; after 4 days of storage, conductivity measurements were repeated which showed 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);

e) in commercial hydraulic oil (dose: in each case 130 mg per liter):

the additive formulation of example 5 (according to the invention) showed 167 pS / m; a commercial antistatic preparation (AF1) showed 120 pS / m;

[0115] For commercial antistatic preparations, a composition according to the disclosure in document (1) was adapted to improve the electrical conductivity in organic liquids (AF1 and AF2).

[0116] The results of the measurements showed that the additive formulations according to the invention at least match the corresponding additive formulations known in the art - within the accuracy of measurements, as demonstrated by experience of + 10-20 pS / m - but in most cases they are superior and provide clearly higher electrical conductivity desired, especially also in direct comparison with comparative example 7. This also applies to example 6 according to the invention, in which the formulation has a relatively high solvent content (D), and thus is relatively highly diluted, but nevertheless provides a sufficiently high electrical conductivity, which is also achieved with a commercial antistatic preparation. When measuring in fuel for turbine engines, it should be noted that another advantage of the additive formulation according to the invention is that the electrical conductivity of fuel for turbine engines, even after a certain storage time, remains constant at a high level - in contrast to turbine fuel treated with a commercial preparation antistatic, whose conductivity clearly decreases after the said storage time.

Example 9: Storage stability and flash point testing of additive formulations [0117] Storage stability of the additive formulations of Examples 5 and 6 and commercial antistatic formulations (AF1 and AF2), after prolonged storage at a constant temperature of 40 ° C, were evaluated by visual examination, under relative to turbidity and possible sediment formation. In all cases, after 3 months of storage, the samples did not cloud or precipitate formed. The flashpoints of the samples used were previously determined according to EN ISO 2719: 2002 (measurements in a closed crucible by the Pensky-Martens method): for the samples of the invention, the flashpoints were 62 ° C (Example 5) or 63 ° C (Example 6), but however, the flash point of the commercial antistatic preparation was significantly lower and was 21 ° C (AF1) or <20 ° C (AF2).