DE10349860B4 - Additive mixtures as a component of mineral oil formulations - Google Patents

Abstract

Additive mixtures as a constituent of mineral oil formulations with small proportions of an additive mixture contain the additive components DOLLAR A a) ethylene-vinyl ester copolymers having molecular weight average molecular weights of 3,000 to 50,000 and an ethylene content of 50 to 90% by mass and DOLLAR A b) partially and / or completely imidized copolymers from maleic anhydride and alpha-methylstyrene having a number average molecular weight of 4000 to 15000 and at least one end group based on dimeric alpha-methylstyrene, DOLLAR A where the content of the additive mixture in the mineral oil is 0.005 to 1% by mass and the mass ratio of the additive components a / b is 10 : 90 to 90: 10. DOLLAR A The mineral oil formulations containing additive mixtures are suitable as flowable media to be transported at low temperatures and as a mineral oil fuel of high flowability.

Description

The The invention relates to additive mixtures as a constituent of mineral oil formulations and a method for producing the additive mixtures containing Mineral oil formulations.

Mineral oil recipes comprising ethylene / vinyl acetate copolymers, hydrocarbon polymers, esterified maleic anhydride / olefin copolymers, polar nitrogen compounds, such as amine salts of polybasic carboxylic acids and esterified polyoxyalkylenes, which are known from additive mixtures, are known (WO 94/10267 A1, WO 95/33 012 A1, US Pat. EP 0 921 183 A1 , WO 93/14178 A1, EP 0 889 323 A1 ).

From Disadvantages are the insufficient flow behavior and the storage stability of these formulations at low temperatures when the mineral oil component has a sulfur content below 0.005% by mass.

task the invention are additive mixtures as part of mineral oil formulations, the improved flow behavior and improved shelf life at low temperatures. Due to the improved flow behavior should an energy saving be achieved with the pump sets, through which the transport of the mineral oil formulations takes place. The development the additive mixtures should from the point of view of use of mineral oils with very low sulfur content to improve fuels environmental in terms of pollutant emissions from vehicles.

• a) Ethylen-Vinylester-Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Masse%, und
• b) partiell und/oder vollständig imidisierte Copolymere aus Maleinsäureanhydrid und α-Methylstyren mit Molmassen-Zahlenmitteln von 1500 bis 15000 und mindestens einer Endgruppe auf Basis von dimerem α-Methylstyren enthält, und wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse%, und das Masseverhältnis der Additivkomponenten a/b 10 : 90 bis 90 : 10 beträgt.

The object of the invention was achieved by an additive mixture as a constituent of mineral oil formulations with small proportions of an additive mixture, wherein the additive mixture according to the invention, the additive components

• a) ethylene-vinyl ester copolymers having a molecular weight of from 3,000 to 50,000 and an ethylene content of from 50 to 90% by weight, and
• b) partially and / or fully imidized copolymers of maleic anhydride and α-methylstyrene with molecular weight numbers of from 1500 to 15000 and at least one end group based on dimeric α-methylstyrene, and wherein the content of the additive mixture in the mineral oil 0.005 to 1 mass%, and the mass ratio of the additive components a / b is 10: 90 to 90:10.

Examples for the Vinylester components, which in the ethylene-vinyl ester copolymers of the additive mixture can be included are vinyl acetate, vinyl propionate, 2-ethylhexyl vinyl ester, vinyl laurate, 2-hydroxyethyl vinyl ester and 4-hydroxybutyl vinyl ester.

The Ethylene-vinyl ester copolymers in which the additive mixture is preferred Ethylene-vinyl acetate copolymers having a vinyl acetate content of 12 to 50% by weight.

The Ethylene-vinyl ester copolymers can as further unsaturated Ester components 1 to 30% by weight, based on the vinyl ester, of (meth) acrylic esters such as methyl methacrylate, ethyl methacrylate, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, ethylene glycol diacrylate or Hydroxyethyl methacrylate and / or vinyl ethers such as octyl vinyl ether or hexanediol monovinyl ether.

A further preferred variant for the ethylene-vinyl ester copolymers in the additive mixture are mixtures of 10 to 90% by mass unmodified Ethylene-vinyl ester copolymers and 90 to 10% by mass of polar Group modified ethylene-vinyl ester copolymers.

Prefers the modified ethylene-vinyl ester copolymers are oxidized ethylene-vinyl ester copolymers, partially hydrolyzed ethylene-vinyl ester copolymers, semiacetals of partially hydrolyzed Ethylene vinyl ester copolymers and / or polar unsaturated monomers of the type vinyl ester, (meth) acrylic ester and / or vinyl ether grafted Vinylester-ethylene copolymers.

When oxidized ethylene-vinyl ester copolymers become oxidized ethylene-vinyl acetate copolymers with molecular weight numbers of 800 to 5000, acid numbers of 2 to 40 mg KOH / g and OH numbers of 20 to 150 mg KOH / g are preferred.

The partially saponified ethylene-vinyl ester copolymers are preferably partially hydrolyzed Ethylene-vinyl acetate copolymers having number average molecular weights of 800 to 5000 in which 5 to 30 mol% of vinyl acetate units are saponified are.

Another preferred variant is that the modified ethylene-vinyl ester copolymers are hemiacetals of partially hydrolyzed ethylene-vinyl ester copolymers with butyraldehyde. Examples of hemiacetals of ethylene-vinyl ester-vinyl alcohol copolymers with butyraldehyde are hemiacetals of ethylene-vinyl acetate-vinyl alcohol copolymers, which DD 295 507 A7 have been reacted in heterogeneous phase with butyraldehyde.

Other preferred modified ethylene-vinyl ester copolymers are copolymers which have been grafted with from 6 to 20% by weight of unsaturated vinyl ester monomers, (meth) acrylic esters and / or vinyl ethers. The graft modification of these copolymers can be carried out by reaction with the unsaturated monomers in the extruder ( DD 282 462 B5 ) or in the stirred reactor ( DD 293 125 B5 ) in the presence of thermally decomposing radical formers. It is also possible to carry out the modification in the preparation of the copolymer by the high-pressure process by metering the monomers into the polymer melt in the low-pressure separator or in the discharge extruder.

Especially are preferred as modified ethylene-vinyl ester copolymers in the additive mixture vinyl acetate grafted ethylene-vinyl acetate copolymers with molecular weight indexing agents from 800 to 5000 and a total vinyl acetate content of 20 to 60 Mass%, wherein the vinyl acetate content of the copolymer backbone 10 to 40% by weight and the proportion of grafted vinyl acetate side chains 10 to 20% by mass.

Examples of partially imidized copolymers of maleic anhydride and α-methylstyrene are copolymers having an approximately equimolar ratio of both monomers, in which the partial and / or complete imidization with ammonia, C ₁ -C ₂₄ -monoalkylamines, C ₆ -C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ - Monoaminoalkoholen, monoaminated poly (C ₂ -C ₄ alkylene) oxides, and / or mono-etherified poly (C ₂ -C ₄ alkylene) oxides is carried out, wherein the molar ratio of anhydride copolymer / ammonia, amino groups C ₁ -C ₂₄ -monoalkylamines, C ₆ -C ₁₈ -aromatic monoamines, C ₂ -C ₁₈ -monoamino alcohols or monoaminated poly (C ₂ -C ₄ -alkylene) oxide 1: 1 to 20: 1.

The partially imidized copolymers of maleic anhydride and α-methylstyrene in the additive mixture are preferably partially imidized with C ₆ -C ₂₄ monoalkylamines maleic anhydride-α-methylstyrene copolymers in which the molar ratio of anhydride groups in the copolymer / bound C ₆ -C ₂₄ - Monoalkylamine in the copolymer 8: 1 to 1.3: 1.

Examples of C ₁₂ -C ₂₄ -monoalkylamines with which the partially imidized maleic anhydride-α-methylstyrene copolymers present in the additive mixture can be imidized are dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, oleylamine or eicosylamine.

Examples for mineral oils, the The main components in mineral oil formulations are crude oils and petroleum distillates with a boiling range of 100 to 500 ° C such as lubricating oils, kerosene, Diesel, fuel oil, heavy heating oils, Petroleum, tractor fuel and cracked gasoline. The mineral oils can also up to 30 mass% of synthesis hydrocarbons from the Fischer-Tropsch synthesis, up to 20 Mass% modified vegetable oils based on sunflower oil, Soybean oil, Rapeseed oil, or oils animal origin, biodiesel and / or up to 10% by mass of alcohol such as methanol or ethanol.

Prefers are mineral oil formulations containing the additive mixtures the mineral oils Crude oils or fuel oils from a middle distillate with a sulfur content below 0,05% by weight, preferably fuel oils, gas oils or Diesels.

The mineral oil formulations may contain a total of up to 200% by weight, based on the additive components a) and b), of further additive components of the fatty acid mixture type, polar nitrogen compounds, preferably polyamines, ether amines, amino alcohols, amine salts, amides or imides of polybasic carboxylic acids; C ₇ -C ₃₀ -alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ -monocarboxylic acids, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds having C ₈ -C ₁₀₀ -alkyl substituents , carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane improvers, defoamers and / or cosolvents.

Examples of fatty acids contained in the mineral oil formulations as further additive components mixtures are mixtures of saturated and / or unsaturated C ₆ -C ₄₀ -carboxylic acids such as lauric acid, palmitic acid, oleic acid, linolenic acid, dimer fatty acids and alkenylsuccinic acids.

Examples for the in the mineral oil formulations as further additive components contained polar nitrogen compounds polyamines are N-hexa-decyl-1,3-diaminopropane, N-octadecyldipropylenetriamine, N-dodecyl-1,3-diamino-propane, N, N'-didodecyl-1,3-diaminopropane and N, N'-dioctadecyldipropylenetriamine.

Examples for the in the mineral oil formulations as further additive components contained polar nitrogen compounds of the etheramine type are 3-methoxy-propylamine, 3-N-octyloxypropyl-1,3-diaminopropane and 3-N- (2,4,6-trimethyl-decyloxypropyl) -1,3-diaminopropane.

Examples for the in the mineral oil formulations as further additive components contained polar nitrogen compounds Amino-pentan-5-ol, aminoundecan-11-ol are of the amino-alcohol type and 2-amino-2-methylpropanol.

Examples of the amines used in polar nitrogen compounds of the amine salt type, amides or imides of polybasic carboxylic acids are C ₈ -C ₄₀ -amines such as hydrogenated tallamine, tetradecylamine, eicosylamine, dioctadecylamine, methylbehenylamine, N-oleyl-1,3-diaminopropane, N Stearyl-1-methyl-1,3-diaminopropane or N-Oleyldipropylentriamin.

Examples for the in polar nitrogen compounds of the amine salt or amide type polybasic carboxylic acids phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediaminetetraacetic acid and Cyclohexane.

Specific examples for the in the mineral oil formulations as further additive components contained polar nitrogen compounds Amine salts are N-methyltriethanolammonium distearyl ester chloride and N-methyltriethanolammonium distearyl ester methosulfate.

Examples of C ₇ -C ₃₀ -alcohols which may be contained as further additive components in the mineral oil formulations are dodecanol, stearyl alcohol and ceryl alcohol.

Examples for polyalkylene glycols, as additional additive components in the mineral oil formulations can be included are polyethylene glycols, polypropylene glycols and ethylene oxide-propylene oxide copolymers with Molar masses from 500 to 5000.

Examples of esters of polyoxyalkylene compounds which may be included as further additive components in the mineral oil formulations are C ₁₀ -C ₂₄ monoalkyl ester or dialkyl esters of polyalkylene glycols such as polyethylene glycol monostearyl ester or polypropylene glycol dioleate.

Examples of ethers of polyoxyalkylene compounds which may be contained as further additive components in the mineral oil formulations are C ₁ -C ₄ monoalkyl ether or dialkyl ethers of polyalkylene glycols such as polyethylene glycol monomethyl ether or polypropylene glycol dibutyl ether.

Examples of polyhydric alcohols which may be present as the alcohol component in the C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids are ethylene glycol, polyalkylene glycols, glycerol, 1,1,1-tris- (hydroxy-methyl ) propane, pentaerythritol and sorbitol.

Examples of C ₁₂ -C ₄₀ monocarboxylic acids which may be present as the carboxylic acid component in the C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids are lauric acid, palmitic acid, stearic acid, oleic acid, elaidic acid, ricinoleic acid, eleostearic acid, linoleic acid, Linolenic acid and erucic acid or dimer acids based on oleic acid or linolenic acid.

Also preferred as C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids are mixed esters of polyalcohols in which the polyalcohols are esterified by mixtures of C ₁₂ -C ₄₀ monocarboxylic acids. Specific examples of C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ monocarboxylic acids are the monoesters of ethylene glycol with dilinolenic acid, a C ₃₆ -dimeric acid, the diester of propylene glycol with oleic acid and the triester of pentaerythritol with stearic acid.

Particularly preferred as C ₂ -C ₆ -oxyalkylverbrückte C ₁₂ -C ₄₀ monocarboxylic acids are esters of unge saturated C ₁₆ -C ₂₄ monocarboxylic acids with C ₃ -C ₄ polyalcohols, wherein the proportion of C ₂₂ monocarboxylic acids, based on the total mass of C ₁₆ -C ₂₄ monocarboxylic acids, 45 to 52 mass%.

Examples of unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids which may be present in the preferred esters of unsaturated C ₁₆ -C ₂₄ -monocarboxylic acids with C ₃ -C ₄ -polyalcohols are oleic acid, linoleic acid, linolenic acid and erucic acid.

Examples of hydrocarbon polymers which may be other additive components in the mineral oil formulations are copolymers of ethylene and C ₃ -C ₂₂ alpha-olefins such as ethylene-propylene copolymers or ethylene-dodecene copolymers or hydrogenated polymers of hydrogenated polyunsaturated monomers Diene copolymers such as hydrogenated polybutadiene or hydrogenated polyisoprene with molecular weight numbers up to 30,000.

Examples for alkylphenol-aldehyde copolymers, as additional additive components in the mineral oil formulations can be included are copolymers formed by the reaction of alkylated phenols such as phenol-propylene oligomer adducts can be prepared with paraformaldehyde.

Examples of aromatic compounds having C ₈ -C ₁₀₀ alkyl substituents, which may be included as further additive components in the mineral oil formulations, are compounds prepared by Friedel-Kraft condensation of halogenated hydrocarbons such as halogenated polyethylene wax with aromatic hydrocarbons such as benzene or naphthalene can.

Examples of carboxylated polyamines as defoamers are reaction products of C ₈ -C ₂₄ -fatty acids and amines such as ethylenediamine, butylenediamine, diethylenetriamine and pentaethylenehexamine-1,2-diaminobutanol.

Examples of detergents which may be present as further additive components in the mineral oil formulations are aliphatic sulfonic acids such as C ₈ -C ₃₀ -alkanesulfonates or aromatic-aliphatic alkanesulfonates, in particular nonylbenzenesulfonic acid, dodecylbenzenesulfonic acid, didodecylbenzenesulfonic acid and nonylnaphthalenesulfonic acid.

Examples for demulsifiers, as additional additive components in the mineral oil formulations can be included are oxalkylated phenol-formaldehyde condensates, polyalkylene glycol-modified diglycidyl ethers, polyesteramines or alkoxylated fatty acids.

Examples for cetane improvers, as additional additive components in the mineral oil formulations can be included are organic nitric acid esters such as ethylhexyl nitrate, cyclohexyl nitrate or ethoxyethyl nitrate, or soluble organic peroxides, hydroperoxides or peresters.

preferred defoamers, as additional additive components in the mineral oil formulations can be included are polyalkylene oxide-siloxane block copolymers and carboxylated polyamines.

Examples for polyalkylene oxide-siloxane block copolymers are block copolymers containing a combination of trifunctional siloxane blocks such as Monomethylsiloxane groups, difunctional siloxane groups such as dimethylsiloxane groups and monofunctional siloxane groups such as trimethylsiloxane groups included, a preferred length the siloxane blocks is 5 to 20 monomer units. For the polyalkylene oxide blocks is the preferred length 2 to 40 monomer units, polyoxyalkylene blocks are preferred Ethylene oxide and / or propylene oxide units.

Examples for co-solvents, as additional additive components in the mineral oil formulations can be included are gasoline fractions, toluene, xylene, ethylbenzene, isononanol, 2-ethylhexanol. Dodecylphenol, epoxidized soybean oil and epoxidized rapeseed oil.

• a) Ethylen-Vinylester-Copolymere mit Molmassengewichtsmitteln von 3000 bis 50000 und einem Ethylenanteil von 50 bis 90 Masse%, und
• b) partiell und/oder vollständig imidisierte Copolymere aus Maleinsäureanhydrid und α-Methylstyren mit Molmassen-Zahlenmitteln von 4000 bis 15000 und mindestens einer Endgruppe auf Basis von dimerem α-Methylstyren enthalten, wobei der Gehalt der Additivmischung im Mineralöl 0,005 bis 1 Masse% und das Masseverhältnis der Additivkomponenten a/b 10 : 90 bis 90 : 10 beträgt,

nach einem Vorhomogenisierungsverfahren hergestellt werden, bei dem

• – in der ersten Verfahrensstufe 1 bis 60 Masse% Additivkomponenten enthaltende Lösungen in Mineralöl-Mitteldestillaten bei 20 bis 90°C hergestellt werden, und
• – in der zweiten Verfahrensstufe die Additivkomponenten enthaltenden Lösungen mit dem Mineralöl als Hauptkomponente homogenisiert werden,

wobei dem Mineralöl insgesamt bis 200 Masse%, bezogen auf die Additivkomponenten a) und b), weitere Additivkomponenten in der ersten oder zweiten Verfahrensstufe zugesetzt werden können.Mineral oil formulations containing additive mixtures are prepared by a process according to the invention in which the mineral oil formulations contain the additive components in the additive mixture

• a) ethylene-vinyl ester copolymers having a molecular weight of from 3,000 to 50,000 and an ethylene content of from 50 to 90% by weight, and
• b) partially and / or fully imidized copolymers of maleic anhydride and α-methylstyrene having a number average molecular weight of 4000 to 15000 and at least one end group based on dimeric α-methylstyrene, wherein the content of the additive mixture in the mineral oil 0.005 to 1 mass% and the Mass ratio of the additive components a / b is 10: 90 to 90: 10,

be prepared by a Vorhomogenisierungsverfahren in which

• - In the first process stage 1 to 60% by weight of additive components containing solutions are prepared in mineral oil middle distillates at 20 to 90 ° C, and
• In the second process stage, the solutions containing the additive components are homogenized with the mineral oil as main component,

wherein the mineral oil in total up to 200% by weight, based on the additive components a) and b), of further additive components in the first or second process stage can be added.

The In particular, mineral oil formulations containing additive mixtures are as flowable media to be transported at low temperatures and as mineral oil fuel high flowability suitable.

Examples for the Flowable media to be transported at low temperatures are the transport of crude oil formulations from the funding body of crude oil through pipelines for loading, storage and transport of diesel or heating oil formulations in pipelines.

The invention is illustrated by the following examples, the ratios were determined by the following test methods
Cloud Point (CP): DIN EN 23 015
Cold Filter Plugging Point (CFPP): EN 116
Boiling analysis: EN ISO 3405, ASTM D 86
IBP: Initial Boiling Point FBP: Final Boiling Point

Vinyl acetate content: modified Method according to ISO 8995, DIN 16778 part 2

E = Einwaage in g
F = Faktor der ethanolischen 0,5 n KOH
V = Verbrauch in ml an 0,5 n ethanolischer KOH für die Probe
B = Verbrauch in ml an 0,5 n ethanolischer KOH für den Blindwert2 g sample are weighed to the nearest 0.001 g and rd in a 300 ml Erlenmeyer flask with 70 ml of distilled xylene and 2 Siedeperlen. Dissolved for 15 minutes under reflux at the reflux condenser. Subsequently, approx. Slowly add 30 ml of ethanol through the reflux condenser, remove the Erlenmeyer flask from the hot plate, add 30 ml of ethanol, 0.5 n KOH from the burette and 2 boiling beads, and boil the sample for 1 h at reflux. Thereafter, the sample is again taken from the reflux, mixed with 30 ml of methanolic-aqueous 0.5 N HCl and 2 Siedeperlen and further boiled for 15 min at reflux. The sample is then after addition of 2 to 3 drops of phenolphthalein solution (1% by weight in ethanol) with ethanolic 0.5 N KOH titrated dropwise with shaking until the color changes to red. In parallel, a blank value has to be determined.

E = weight in g
F = factor of ethanolic 0.5 n KOH
V = consumption in ml of 0.5 N ethanolic KOH for the sample
B = consumption in ml of 0.5 N ethanolic KOH for the blank value

Short-time sedimentation test:

To check the Sedimentation tendency of crystallized paraffins in mineral oil becomes a 500 ml - sample Stored for 16 h in a graduated cylinder and then the above 80 vol% sucked the sample and discarded. The remaining 20% by volume of Sample (100 ml) at 40 ° C homogenized and of which the Cloud Point (CP) according to DIN EN 23 015 certainly.

SEDAB filtration test:

A 500 ml mineral oil sample is shaken 20 × vertically, tempered for 16 h at 10 ° C, shaken 10 × vertically, and the entire sample is passed through a filter made of cellulose nitrate (diameter 50 mm, pore size 0.8 μm) at once a suction cup with a vacuum of approx. 200 hPa is added, filtered. The time (s) in which the sample passes through the filter is determined. The SEDAB filtration test is considered passed if the Sample in a period <120 s the filter passes.

example 1

1.1 Starting products

1.1.1 Unadditized diesel

• Batch: 16080601 Test DK 1
• Characterization:
• Cloud Point (CP): + 6 ° C
• Cold Filter Plugging Point (CFPP): + 2 ° C

boiling analysis:

1.1.2 Additive component a)

Ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, molecular weight weight average 2300 g / mol).

Additive component b)

α-methylstyrene-maleic anhydride copolymer partially-imidated with C ₁₆ -C ₁₈ fatty amine, number average molecular weight 12800 g / mol, acid number 35

Preparation of the additive component b)

In a 500 l stirred reactor 81 l of α-methylstyrene, 7 l of α-methylstyrene dimer and 20 liters of acetone and heated the stirred reactor to 59 ° C. Within 6 hours, a solution will be released of 52 kg of maleic anhydride and 2.4 kg azoisobutyrodinitrile in 150 l of acetone evenly in the stirred reactor metered and the reaction mixture for a further 6 h at 70 to 73 ° C stirred.

One Analytical pattern of the copolymer has an acid number of 445 mg / KOH per Gram of copolymer. NMR studies yield 1.3 α-methylstyrene dimer end groups / mole.

The still 54 to 56 ° C warm polymer solution is now continuously fed to a two-roll vacuum dryer and in a powdery Copolymer with about 1.1% by mass residual volatile content and in Acetone separated.

For partial imidization of the copolymer, a C ₈ -C ₉ -diesel aromatic fraction boiling above 160 ° C. in an amount of 382 kg and 122 kg of C ₁₆ -C ₁₈ -fatty amine is initially charged in a 500 l stirred reactor and heated to 130 ° C. 135.5 kg of the copolymer are continuously metered into this solution within 4 hours. The internal temperature in the stirred reactor rises to 180 to 185 ° C, and it forms water, which is distilled off azeotropically with an approximately equal amount of C ₈ -C ₉ -Dieselaromatenfraktion. After a total of 6 hours of reaction time at 160 to 190 ° C, 8.5 kg of water and 10.2 kg of solvent are distilled off. This gives a 40% solution of the partially imidized copolymer having an acid number of 35 and a molecular weight average of 12800 g / mol.

1.1.4 Further additive components

Additive component c)

Mixture of C ₃ -oxyalkyl-bridged unsaturated C ₁₈ -C ₂₄ -carboxylic acids, degree of esterification 92 mol%, content of C ₁₈ -unsaturated fatty acids 32 mass%, content of C ₂₂ -unsaturated fatty acids 48 mass%, iodine value 96

Additive component d)

Ethyl acrylate-ethylhexyl acrylate copolymer (molar ratio 3: 2, number average molecular weight 13500)

1.2 Preparation of the additive components containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of a 40% solution of the additive component b) in C ₈ -C ₉ -Dieselaromatenfraktion, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso), 20 kg of the additive component c) and 19 kg of a 20% solution of the additive component d) toluene mixed for 90 min at 65 ° C, and transferred the mixture into a storage tank.

1.3 Preparation of the mineral oil formulation

In a product stream of non-additive diesel batch 16080601 at At 800 kg / min, the additive solution according to 1.2 is injected at 0.48 kg / min and transferred to a storage tank.

The Testing the cold resistance the mineral oil recipe gives a CFPP value of -16 ° C. The CP value of the short-term sediment test + 5 ° C. Of the SEDAB filtration test is passed (500 ml in 76 s).

Becomes produced under the same conditions a mineral oil formulation, the exclusively contains the copolymer wax as an additive, the CFPP value is -3 ° C. The CP value of the short-term sediment test + 10 ° C. Of the SEDAB filtration test is considered failed (468 ml in> 120 s).

Example 2

2.1 Starting products

2.1.1 Unadditized diesel

• Batch: 030210 test DK 2
• Characterization:
• Cloud Point (CP): + 7 ° C;
• Cold Filter Plugging Point (CFPP): + 2 ° C

boiling analysis:

2.1.2 Additive component a)

mixture from 10% by weight of a partially hydrolyzed ethylene-vinyl acetate copolymer wax (molecular weight weight average 1600 g / mol, vinyl acetate content of the non-saponified ethylene-vinyl acetate copolymer wax 32 Mass%, saponification degree 15 mol%) and 90 mass% of an ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, molecular weight weight average 2300 g / mol).

2.1.3 Additive component b)

α-methylstyrene-maleic anhydride copolymer, partially diallylized with dodecylamine, number average molecular weight 14200 g / mol, acid number 56

Preparation of the additive component b)

In a 500 l stirred reactor 83 l of α-methylstyrene, 5 l of α-methylstyrene dimer 62 kg of maleic anhydride and 110 l of 2-butanone submitted and the stirred reactor to 70 ° C heated. Within 2 h, a solution of 1.9 kg of dibenzoyl peroxide in 52 l of 2-butanone uniformly in the stirred reactor metered and the reaction mixture for a further 10 h at 72 to 73 ° C stirred.

One Analysis pattern of the copolymer has an acid number of 452 mg / KOH per Gram of copolymer. NMR studies reveal 1.1 α-methylstyrene dimer end groups / mole.

The about 70 ° C warm polymer solution is then continuously in a 500 l stirred reactor containing 280 l of 2-ethylhexanol and heated to a temperature of 150 ° C, while distilling off 2-butanone-2 metered. Now within 4 hours 104 kg of a C ₁₆ -C ₁₈ fatty amine are metered in, wherein the temperature is raised to 165 to 185 ° C to distill off water together with a small amount of 2-ethylhexanol.

you receives a 40% solution of the partially imidized copolymer in 2-ethylhexanol having an acid number of 56 and a molecular weight average of 14200 g / mol.

2.1.4 Further additive components

Additive component c)

triester of pentaerythritol with oleic acid

Additive component d)

Diethylenglycolmonolauroylester

2.2 Production of additive components containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of a 40% solution of the additive component b) in 2-ethylhexanol, 50 kg of a 60% solution of the additive component a) in C ₈ -C ₉ -Dieselaromatenfraktion, 20 kg of the additive component c) and 1 kg of Additive component d), stirred for 90 min at 65 ° C, and transferred the mixture into a storage tank.

2.3 Preparation of the mineral oil formulation

In a product stream of non-additive diesel lot 030210 at 800 kg / min is injected with 0.24 kg / min, the additive solution according to 2.2 and transferred to a storage tank.

The Testing the cold resistance the mineral oil recipe gives a CFPP value of -7 ° C. The CP value of the short-term sediment test + 7 ° C. Of the SEDAB filtration test is passed (500 ml in 82 s).

Becomes produced under the same conditions a mineral oil formulation, the exclusively contains the copolymer wax as an additive, the CFPP value is -5 ° C. The CP value of the short-term sediment test + 12 ° C. Of the SEDAB filtration test is considered failed (468 ml in> 120 s).

Example 3

3.1 Starting products

3.1.1 Unadditized heating oil

• Lot: 030225 test HEL 1
• Characterization:
• Cloud Point (CP): + 1 ° C;
• Cold Filter Plugging Point (CFPP): -1 ° C

boiling analysis:

3.1.2 additive component a)

mixture of 15% by weight of an oxidized ethylene-vinyl acetate copolymer wax (Weight average molecular weight 950 g / mol, acid number 18 mg KOH / g, OH number 70 mg KOH / g) and 85% by weight of a non-oxidized ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, weight average molecular weight 2300 g / mol).

3.1.3 Additive component b)

α-methylstyrene-maleic anhydride copolymer, partially imidized with C ₁₂ -C ₁₄ fatty amine mixture, molecular weight weight average 7000 g / mol, acid number 25

Preparation of the additive component b)

In a 500 l stirred autoclave 83 l of α-methylstyrene, 12 l of α-methylstyrene dimer, 62 kg of maleic anhydride and 140 liters of 1,2-dichloroethane submitted and at 90 ° C. heated. Within 2 h, a solution of 2.5 kg of tert-butyl peroxy-2-ethylhexanoate in 55 l of 1,2-dichloroethane evenly into the stirred autoclave metered and the reaction mixture for a further 10 h at 90 to 93 ° C stirred.

One Analytical pattern of the copolymer has an acid value of 430 mg KOH per Gram of copolymer. NMR studies reveal 1.4 α-methylstyrene dimer end groups / mole.

The about 90 ° C warm polymer solution is now continuously in a 500 l stirred reactor containing 280 l of a C ₈ -C ₉ -Dieselaromatenfraktion and 122 kg of a C ₁₂ -C ₁₄ fatty amine mixture and heated to a temperature of 160 ° C. , Metered with distilling off of 1,2-dichloroethane and the water of reaction of the imidization.

This gives a 40% solution of the partially imidized copolymer in a C ₈ -C ₉ -diesel aromatic fraction having an acid number of 25 and a molecular weight weight average 7000 g / mol

3.1.4 Further additive components

Additive component c)

diester of ethylene glycol with erucic acid

Additive component d)

N- (2-hydroxyethyl) oleylamine

3.2 Production of additive components containing solutions in mineral oil middle distillates

In a stirred tank containing 25 kg of a 40% solution of the additive component b) in C ₈ -C ₉ -Dieselaromatenfraktion at 65 ° C, 50 kg of a 60% solution of the additive component a) in C ₈ -C ₉ -Dieselaromatenfraktion , 20 kg of the additive component c) and 3 kg of the additive component d), stirred for 90 min at 65 ° C, and the mixture is transferred to a storage tank.

3.3 Preparation of the mineral oil formulation

In a product stream of non-additive fuel oil charge 030225 at 800 kg / min the additive solution according to 3.2 is injected at 0.24 kg / min and transferred to a storage tank.

The Testing the cold resistance the mineral oil recipe gives a CFPP value of -15 ° C.

Becomes produced under the same conditions a mineral oil formulation, the exclusively contains the copolymer wax as an additive, the CFPP value is -13 ° C.

Example 4

4.1 Starting products

4.1.1 Unadditized diesel

• Batch: 16080601 Test DK 1
• Characterization:
• Cloud Point (CP): + 6 ° C;
• Cold Filter Plugging Point (CFPP): + 2 ° C

boiling analysis:

4.1.2 Additive component a)

Ethylene-vinyl acetate copolymer wax (Manufacturer LEUNA Polymer GmbH, vinyl acetate content 32% by weight, molecular weight weight average 2300 g / mol).

4.1.3 Additive component b)

α-methylstyrene-maleic anhydride copolymer, partially staged with stearylamine, weight average molecular weight 13750 g / mol, acid number 51

Preparation of the additive component b)

In a 500 l stirred reactor 81 l of α-methylstyrene, 7 l of α-methylstyrene dimer and 20 liters of acetone and heated the stirred reactor to 59 ° C. Within 6 h will be a solution of 52 kg of maleic anhydride and 2.4 kg azoisobutyrodinitrile in 150 l of acetone evenly in the stirred reactor metered and the reaction mixture for a further 6 h at 70 to 73 ° C stirred.

An analysis pattern of the copolymer has an acid number of 445 mg / KOH per gram of copolymer. NMR studies yield 1.3 α-methylstyrene dimer end groups / mole.

The still 54 to 56 ° C warm polymer solution is now continuously fed to a two-roll vacuum dryer and in a powdery Copolymer with about 1.1% residual volatile content and in Acetone separated.

For partial imidization of the copolymer, a C ₈ -C ₉ -diesel aromatic fraction boiling above 160 ° C. in an amount of 382 kg and 135 kg of stearylamine is introduced into a 500 l stirred reactor and heated to 130 ° C. 135.5 kg of the copolymer are continuously metered into this solution within 4 hours. The internal temperature rises in the stirred reactor at 180 to 185 ° C, and it forms water which is distilled off azeotropically with an approximately equal amount of C ₈ -C ₉ -Dieselaro matenfraktion. After a total of 6 hours of reaction time at 160 to 190 ° C, 8.5 kg of water and 10.2 kg of solvent are distilled off.

you receives a 40% solution of stearylamine partially imidized copolymer having an acid number of 51 and a molecular weight of 13750 g / mol.

4.1.4 Further additive components

Additive component c)

Mixture of C ₃ -oxyalkyl-bridged unsaturated C ₁₈ -C ₂₄ -carboxylic acids, degree of esterification 92 mol%, content of C ₁₈ -unsaturated fatty acids 32 mass%, content of C ₂₂ -unsaturated fatty acids 48 mass%, iodine value 96

Additive component d)

Ethyl acrylate octadecyl acrylate copolymer (molar ratio 4: 1, number average molecular weight 8400)

4.2 Production of additive components containing solutions in mineral oil middle distillates

In a stirred tank 25 kg of a 40% solution of the additive component b) in C ₈ -C ₉ -Dieselaromatenfraktion, 50 kg of a 50% solution of the additive component a) in an aromatic hydrocarbon mixture (Solvesso), 20 kg of the additive component c) and 19 kg of a 20% solution of the additive component d) in toluene for 90 min at 65 ° C mixed, and transferred the mixture into a storage tank.

4.3 Preparation of the mineral oil formulation

In a product stream of non-additive diesel batch 16080601 at At 800 kg / min, the additive solution according to 4.2 is injected at 0.48 kg / min and transferred to a storage tank. The Testing the cold resistance the mineral oil recipe gives a CFPP value of -17 ° C.

Becomes produced under the same conditions a mineral oil formulation, the exclusively contains the copolymer wax as an additive, the CFPP value is -3 ° C.

Claims (10)

Additive mixtures as a constituent of mineral oil formulations with small proportions of an additive mixture, characterized in that the additive mixture, the additive components a) ethylene-vinyl ester copolymers having molecular weight of from 3,000 to 50,000 and an ethylene content of 50 to 90% by weight, and b) partially and / or completely imidized copolymers of maleic anhydride and α-methylstyrene having molecular weight numbers of from 1500 to 15000 and at least one end group based on dimeric α-methylstyrene, the content of the additive mixture in the mineral oil being 0.005 to 1% by weight, and the mass ratio of the additive components a / b is 10: 90 to 90: 10. Additive mixture according to claim 1, characterized in that that the ethylene-vinyl ester copolymers ethylene-vinyl acetate copolymers having a vinyl acetate content from 12 to 50% by mass. Additive mixture according to claim 1 or 2, characterized that the ethylene-vinyl ester copolymers mixtures of 10 to 90 Mass% of unmodified ethylene-vinyl ester copolymers and 90 to 10% by mass of polar group-modified ethylene-vinyl ester copolymers. Additive mixture according to claim 3, characterized in that in that the modified ethylene-vinyl ester copolymers comprise oxidized ethylene-vinyl ester copolymers, partially hydrolyzed ethylene-vinyl ester copolymers, semiacetals of partially hydrolyzed Ethylene vinyl ester copolymers and / or polar unsaturated monomers of the type vinyl ester, (meth) acrylic ester and / or vinyl ether grafted Vinylester-ethylene copolymers are. An additive mixture according to one or more of claims 1 to 4, characterized in that the partially imidized copolymers of maleic anhydride and α-methylstyrene are partially imidized with C ₆ -C ₂₄ monoalkylamines maleic anhydride-α-methylstyrene copolymers in which the molar ratio of anhydride in the Copolymer / bound C ₆ -C ₂₄ monoalkylamine in the copolymer 8 is 1 to 1.3: 1. Mineral oil formulations containing additive mixtures according to one or more of claims 1 to 5, characterized that the mineral oils crude oils or fuel oils from a middle distillate with a sulfur content below 0,05% by weight, preferably heating oils, gas oils or diesel oils, are. Mineral oil formulations containing additive mixtures according to one or more of claims 1 to 6, characterized in that the mineral oil formulations total 0 to 200% by weight, based on the additive components a) and b), further additive components of the fatty acid mixture type, polar nitrogen compounds, preferably polyamines, ether amines, Amino alcohols, amine salts, amides or imides of polybasic carboxylic acids; C ₇ -C ₃₀ -alcohols, polyalkylene glycols, esters or ethers of polyoxyalkylene compounds, C ₂ -C ₆ -oxyalkyl-bridged C ₁₂ -C ₄₀ -monocarboxylic acids, hydrocarbon polymers, alkylphenol-aldehyde copolymers, aromatic compounds having C ₈ -C ₁₀₀ -alkyl substituents, carboxylated polyamines, detergents, corrosion inhibitors, demulsifiers, metal deactivators, cetane improvers, defoamers and / or cosolvents. Mineral oil recipes containing additive mixtures according to claim 7, characterized in that the C ₂ -C ₆ -oxyalkylverbrückten C ₁₂ -C ₄₀ monocarboxylic acids are esters of unsaturated C ₁₆ -C ₂₄ monocarboxylic acids with C ₃ -C ₄ polyalcohols, wherein the Proportion of C ₂₂ monocarboxylic acids, based on the total mass of C ₁₆ -C ₂₄ monocarboxylic acids, 45 to 52% by mass. Process for the preparation of additive mixtures containing Mineral oil formulations, characterized in that mineral oil formulations that in the additive mixture the additive components a) ethylene-vinyl ester copolymers with Molar mass of 3000 to 50,000 and an ethylene content of 50 to 90% by mass, and b) partially and / or completely imidized Copolymers of maleic anhydride and α-methylstyrene with molecular weight numbers of 4000 to 15000 and at least one Containing end group based on dimeric α-methylstyrene in which the content of the additive mixture in mineral oil 0.005 to 1 mass%, and that mass ratio the additive component a / b is 10: 90 to 90: 10, to a Vorhomogenisierungsverfahren be prepared, in which - in the first process stage 1 to 60% by weight of additive components containing solutions in mineral oil middle distillates at 20 to 90 ° C be prepared, and - in the second process stage containing the additive components solutions with the mineral oil be homogenised as the main component, wherein the mineral oil in total 0 to 200% by weight, based on the additive components a) and b), further additive components in the first and / or second process stage be added. Use of mineral oil formulations containing additive mixtures according to one or more of claims 1 to 8 than at low Temperatures to be transported flowable media and as mineral oil fuel high flowability.