EP0964052B1 - Use of nitrogen-containing ethylene copolymers for producing fuel oils with improved lubricating activity - Google Patents

Use of nitrogen-containing ethylene copolymers for producing fuel oils with improved lubricating activity Download PDF

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Publication number
EP0964052B1
EP0964052B1 EP99106980A EP99106980A EP0964052B1 EP 0964052 B1 EP0964052 B1 EP 0964052B1 EP 99106980 A EP99106980 A EP 99106980A EP 99106980 A EP99106980 A EP 99106980A EP 0964052 B1 EP0964052 B1 EP 0964052B1
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EP
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Prior art keywords
nitrogen
vinyl
acrylate
copolymers
use according
Prior art date
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EP99106980A
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German (de)
French (fr)
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EP0964052A1 (en
Inventor
Matthias Dr. Krull
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
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    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
    • C—CHEMISTRY; METALLURGY
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    • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
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    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
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    • C10L1/188—Carboxylic acids; metal salts thereof
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    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1966—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof poly-carboxylic
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Definitions

  • the present invention relates to the use of nitrogenous Ethylene copolymers to improve the lubricating effect of fuel oils.
  • Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5 wt .-% and more sulfur, when burning causes the formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further.
  • the diesel fuel standard EN 590 writes in Germany currently has a maximum sulfur content of 500 ppm. In Scandinavia already comes in with fuel oils with less than 200 ppm Exceptional cases with less than 50 ppm sulfur.
  • This Fuel oils are usually made by making them from petroleum Fractions obtained by distillation hydrogenated refined. Desulfurization however, other substances are removed that give the fuel oils a impart a natural lubricating effect. These substances include, among others polyaromatic and polar compounds.
  • EP-A-0 680 506 discloses esters from carboxylic acids having 2 to 50 carbon atoms as additives to improve the lubricating effect of low sulfur Middle distillates with less than 0.5 wt% S.
  • DD-126 090 discloses lubricant-improving additives from copolymers of Ethylene and unsaturated carboxylic acid esters, preferably vinyl acetate, which the Fuels in amounts of 0.01 to 0.5 wt .-% are added.
  • DE-A-15 94 417 discloses additives for improving the lubricating effect of oleophilic Liquids containing esters of glycols and dicarboxylic acids with at least Contain 11 carbon atoms.
  • EP-A-0 635 558 discloses diesel oils with sulfur contents below 0.2% by weight and aromatic contents below 30% by weight containing 100 to 10,000 ppm C 1 -C 5 alkyl esters of unsaturated straight-chain C 12 -C 22 - Fatty acids derived from oilseeds are added, which improves their lubricating effect.
  • EP-A-0 764 198 discloses additives which improve the lubricating effect of fuel oils improve, and the polar nitrogen compounds based on alkylamines or Contain alkylammonium salts with alkyl radicals of 8 to 40 carbon atoms.
  • the object of the present invention was to find a method which Middle distillates largely freed from sulfur and aromatic compounds helps to improve the lubricating effect. At the same time, with this Process also affects the cold flow properties of these middle distillates favorably become.
  • the invention relates to the use of 0.001 to 2% by weight (based on the fuel oil) of an additive which contains at least one copolymer which in addition to structural units derived from ethylene, such structural units has, which are derived from an ethylenically unsaturated compound, the at least one aromatic or aliphatic nitrogen atom Exception of nitrogen atoms in imide bond has to improve the Lubricating effect of middle distillates with a maximum sulfur content of 200 ppm.
  • the process is particularly well suited for the additivation of oils that are less than Contain 0.05, in particular less than 0.035 wt .-% sulfur.
  • the monomers are commercially available or by known methods produced.
  • the various aminoalkylene (meth) acrylates are e.g. according to EP-A-0 188 639 by transesterification of (meth) acrylic esters with amino alcohols accessible in the presence of a titanium catalyst.
  • the production of Aminoalkyl vinyl ethers are e.g. in Liebigs Ann. Chem. 601 (1956), 81.
  • Those for use in the process according to the invention are preferably Copolymers suitable, the 0.1 to 15; in particular 1 to 10 mol% of one or contain several of the nitrogen-containing comonomers. Furthermore, in Processes according to the invention can also be used in mixtures of such copolymers.
  • the melt viscosities of the copolymers that can be used are 140 ° C. preferably below 10,000 mPas, in particular between 10 and 1000 mPas and especially between 20 and 500 mPas.
  • the copolymers which can be used in the process according to the invention contain in addition Ethylene at least one comonomer with nitrogen atoms. You can still more, for example one, two or three more olefinically unsaturated Comonomers included.
  • Such olefinically unsaturated comonomers are for example vinyl esters, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, Vinyl ethers or olefins.
  • Particularly preferred vinyl esters are vinyl acetate, Vinyl propionate and vinyl ester of neocarboxylic acids with 8, 9, 10, 11 or 12 Carbon atoms.
  • acrylic and methacrylic esters are those with Alcohols with 1 to 20 carbon atoms, especially of methanol, ethanol, Propanol, n-butanol, iso-butanol and tert-butanol.
  • Particularly preferred olefins are those with 3 to 10 carbon atoms, especially propene, isobutylene, diisobutylene, 4-methylpentene-1 and hexene. If the copolymers contain another comonomer, its molar fraction is preferably up to 15 mol%, in particular up to 12 mol%.
  • the comonomers are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 19, Pages 169 to 178). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably one turns high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out.
  • the reaction of the comonomers is determined by Radical initiators (radical chain initiators) initiated. To this Substance classes belong e.g.
  • Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
  • the initiators are used individually or as a mixture of two or more substances in quantities of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
  • the desired melt viscosity of the copolymers is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
  • Hydrogen, saturated or unsaturated hydrocarbons e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
  • the moderators in quantities up to to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
  • High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene can in Reaction mixture may be included, although the solvent-free Working method has proven particularly successful.
  • the Polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed.
  • the comonomer streams be composed differently (EP-B-0 271 738).
  • oils can be improved in the manner according to the invention by adding to them ethylene copolymers which contain acid groups reacted with compounds bearing amino groups.
  • ethylene copolymers and ethylene terpolymers are, for example, those which contain acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride.
  • these copolymers containing acid groups are attached to the acid groups with primary or secondary amines such as methylamine, dimethylamine, ethylamine, propylamine, butylamine, or alkanolamines such as ethanolamine, propanolamine, which carry C 1 -C 10 -alkyl radicals.
  • primary or secondary amines such as methylamine, dimethylamine, ethylamine, propylamine, butylamine, or alkanolamines such as ethanolamine, propanolamine, which carry C 1 -C 10 -alkyl radicals.
  • Diethanolamine, N-ethylethanolamine, diglycolamine, 2-amino-2-methylpropanolamine and mixtures thereof. 0.1 to 1.2 mol, preferably equimolar amounts, of amine per mol of acid are used.
  • the reaction with hydroxyamines can take place either via the OH group to form esters or via an NH 2 group to form amides.
  • Copolymers mineral oils or mineral oil distillates in the form of solutions or Dispersions containing 10 to 90% by weight, preferably 20 to 80% by weight, of the polymers included, added.
  • Suitable solvents or dispersing agents are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and Shellsol D types.
  • Mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight Copolymer based on the distillate.
  • Mixtures can also be used in the process according to the invention, those of copolymers of the claimed type, but of different quality and / or quantitative composition and / or different (at 140 ° C measured) viscosity exist.
  • the mixing ratio (in parts by weight) of the Copolymers can be varied over a wide range and e.g. 20: 1 to 1:20, preferably 10: 1 to 1:10. In this way, the additives specifically adapt to individual requirements.
  • the copolymers together with one or several oil-soluble co-additives can be used, which alone Cold flow properties and / or lubricating effect of crude oils, lubricating oils or Improve fuel oils.
  • oil-soluble co-additives are those containing vinyl acetate Copolymers or terpolymers of ethylene, polar compounds, the one Paraffin dispersion effects (paraffin dispersants), comb polymers and oil-soluble amphiphiles.
  • paraffin dispersants can also be used. These additives reduce the size of the paraffin crystals and cause the paraffin particles to separate not settle, but colloidally with significantly reduced sedimentation efforts, stay dispersed. Furthermore, they increase the lubricating effect of the nitrogen-containing copolymers. Oil-soluble polar dispersants have been found as paraffin dispersants Compounds with ionic or polar groups, e.g.
  • Amine salts and / or amides proven by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, trioder Tetracarboxylic acids or their anhydrides are obtained (cf. US 4 211 534).
  • Other paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf. EP 0 154 177) Reaction products of alkenylspirobislactones with amines (cf.
  • EP 0 413 279 B1 and according to EP 0 606 055 A2 reaction products of Terpolymers based on ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers of lower unsaturated Alcohols.
  • Alkylphenol-aldehyde resins are also suitable as paraffin dispersants.
  • the nitrogen-containing copolymers are used together with comb polymers.
  • This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms.
  • at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).
  • Suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C 6 to C 24 ⁇ -olefin and an NC 6 to C 22 alkyl maleimide (cf. EP 0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
  • fumarate / vinyl acetate copolymers cf. EP 0 153 176 A1
  • copolymers of a C 6 to C 24 ⁇ -olefin and an NC 6 to C 22 alkyl maleimide cf. EP 0 320 766
  • esterified olefin / maleic anhydride copolymers polymers and copolymers of ⁇ -olefins and ester
  • the mixing ratio (in parts by weight) of nitrogen-containing copolymers with Paraffin dispersants or comb polymers are 1:10 to 20: 1, preferably 1: 1 to 10: 1.
  • lubricity additives have become preferably fatty alcohols, fatty acids and dimer fatty acids and their esters and Partial esters with glycols (according to DE-A-15 94 417), polyols such as glycerin (according to EP-A-0 680 506, EP-A-0 739 970) or hydroxyamines (according to EP-A-0 802 961) proven.
  • the method according to the invention is suitable for the lubricating properties of to improve animal, vegetable or mineral oils. It is for them Particularly well suited for use with middle distillates.
  • middle distillates One particularly refers to those mineral oils which are obtained by distilling crude oil be obtained and boil in the range from 120 to 450 ° C., for example kerosene, Jet fuel, diesel and heating oil.
  • the method according to the invention is preferably used for such middle distillates, which contain 0.5 wt .-% sulfur and less, in particular less than 200 ppm sulfur and in special cases less than Contain 50 ppm sulfur.
  • Middle distillates that have been subjected to hydrogenating refining and therefore contain only small amounts of polyaromatic and polar compounds that give them a natural lubricating effect.
  • the method according to the invention is still preferably used in such middle distillates, the 95% distillation points below 370 ° C, especially 350 ° C and in special cases below Have 330 ° C.
  • additives can also be used in the process according to the invention, e.g. Pour point depressants or dewaxing aids, corrosion inhibitors, Antioxidants, sludge inhibitors, dehazers and additives to lower the Cloud point.
  • the lubricating effect of the additives was carried out using an HFRR device from PCS Instruments on additive oils at 6 ° C.
  • the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986. The results are reported as the coefficient of friction and wear scar. A low coefficient of friction and a low wear scar show a good lubricating effect. All additives were used as a 50% dispersion in solvent naphtha.
  • a commercially available flow improver based on a copolymer of ethylene and 30% by weight of vinyl acetate and a melt viscosity V140 of 105 mPas is used.

Description

Die vorliegende Erfindung betrifft die Verwendung von stickstoffhaltigen Ethylencopolymeren zur Verbesserung der Schmierwirkung von Brennstoffölen.The present invention relates to the use of nitrogenous Ethylene copolymers to improve the lubricating effect of fuel oils.

Mineralöle und Mineralöldestillate, die als Brennstofföle verwendet werden, enthalten im allgemeinen 0,5 Gew.-% und mehr Schwefel, der bei der Verbrennung die Bildung von Schwefeldioxid verursacht. Um die daraus resultierenden Umweltbelastungen zu vermindern, wird der Schwefelgehalt von Brennstoffölen immer weiter abgesenkt. Die Dieseltreibstoffe betreffende Norm EN 590 schreibt in Deutschland zur Zeit einen maximalen Schwefelgehalt von 500 ppm vor. In Skandinavien kommen bereits Brennstofföle mit weniger als 200 ppm und in Ausnahmefällen mit weniger als 50 ppm Schwefel zur Anwendung. Diese Brennstofföle werden in der Regel dadurch hergestellt, daß man die aus dem Erdöl durch Destillation erhaltenen Fraktionen hydrierend raffiniert. Bei der Entschwefelung werden aber auch andere Substanzen entfernt, die den Brennstoffölen eine natürliche Schmierwirkung verleihen. Zu diesen Substanzen zählen unter anderem polyaromatische und polare Verbindungen.Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5 wt .-% and more sulfur, when burning causes the formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further. The diesel fuel standard EN 590 writes in Germany currently has a maximum sulfur content of 500 ppm. In Scandinavia already comes in with fuel oils with less than 200 ppm Exceptional cases with less than 50 ppm sulfur. This Fuel oils are usually made by making them from petroleum Fractions obtained by distillation hydrogenated refined. Desulfurization however, other substances are removed that give the fuel oils a impart a natural lubricating effect. These substances include, among others polyaromatic and polar compounds.

Es hat sich nun aber gezeigt, daß die reibungs- und verschleißmindernden Eigenschaften von Brennstoffölen mit zunehmendem Entschwefelungsgrad schlechter werden. Oftmals sind diese Eigenschaften so mangelhaft, daß an den vom Kraftstoff geschmierten Materialien wie z.B. den Verteiler-Einspritzpumpen von Dieselmotoren schon nach kurzer Zeit mit Fraßerscheinungen gerechnet werden muß. Die mittlerweile in Skandinavien vorgenommene weitere Absenkung des 95 %-Destillationspunkts auf unter 370°C, teilweise auf unter 350°C oder unter 330°C verschärft diese Problematik weiter. However, it has now been shown that the friction and wear reducing Properties of fuel oils with increasing desulfurization become worse. Often these properties are so poor that the materials lubricated by fuel, e.g. the distributor injection pumps from Diesel engines can be expected to eat after a short time got to. The further lowering of the 95% distillation point below 370 ° C, partly below 350 ° C or below 330 ° C further exacerbates this problem.

Im Stand der Technik sind daher Ansätze beschrieben, die eine Lösung dieses Problems darstellen sollen (sogenannte Lubricity-Additive).Approaches are therefore described in the prior art which provide a solution to this Problems (so-called lubricity additives).

EP-A-0 680 506 offenbart Ester aus Carbonsäuren mit 2 bis 50 Kohlenstoffatomen als Additive zur Verbesserung der Schmierwirkung von schwefelarmen Mitteldestillaten mit unter 0,5 Gew.-% S.EP-A-0 680 506 discloses esters from carboxylic acids having 2 to 50 carbon atoms as additives to improve the lubricating effect of low sulfur Middle distillates with less than 0.5 wt% S.

DD-126 090 offenbart schmierverbessernde Additive aus Copolymerisaten von Ethylen und ungesättigten Carbonsäureestern, vorzugsweise Vinylacetat, die den Kraftstoffen in Mengen von 0,01 bis 0,5 Gew.-% zugesetzt werden.DD-126 090 discloses lubricant-improving additives from copolymers of Ethylene and unsaturated carboxylic acid esters, preferably vinyl acetate, which the Fuels in amounts of 0.01 to 0.5 wt .-% are added.

DE-A-15 94 417 offenbart Zusätze zur Verbesserung der Schmierwirkung oleophiler Flüssigkeiten, die Ester aus Glykolen und Dicarbonsäuren mit mindestens 11 Kohlenstoffatomen enthalten.DE-A-15 94 417 discloses additives for improving the lubricating effect of oleophilic Liquids containing esters of glycols and dicarboxylic acids with at least Contain 11 carbon atoms.

EP-A-0 635 558 offenbart Dieselöle mit Schwefelgehalten unter 0,2 Gew.-% und Aromatengehalten unter 30 Gew.-%, die mit 100 bis 10.000 ppm C1-C5-Alkylestern von ungesättigten geradkettigen C12-C22-Fettsäuren, die von Ölsaaten abstammen, additiviert werden, wodurch ihre Schmierwirkung verbessert wird.EP-A-0 635 558 discloses diesel oils with sulfur contents below 0.2% by weight and aromatic contents below 30% by weight containing 100 to 10,000 ppm C 1 -C 5 alkyl esters of unsaturated straight-chain C 12 -C 22 - Fatty acids derived from oilseeds are added, which improves their lubricating effect.

EP-A-0 764 198 offenbart Additive, die die Schmierwirkung von Brennstoffölen verbessern, und die polare Stickstoffverbindungen auf Basis von Alkylaminen oder Alkylammoniumsalzen mit Alkylresten von 8 bis 40 Kohlenstoffatomen enthalten.EP-A-0 764 198 discloses additives which improve the lubricating effect of fuel oils improve, and the polar nitrogen compounds based on alkylamines or Contain alkylammonium salts with alkyl radicals of 8 to 40 carbon atoms.

Aufgabe der vorliegenden Erfindung war es, ein Verfahren zu finden, das weitgehend von Schwefel und aromatischen Verbindungen befreiten Mitteldestillaten zu einer Verbesserung der Schmierwirkung verhilft. Gleichzeitig sollen mit diesem Verfahren auch die Kaltfließeigenschaften dieser Mitteldestillate günstig beeinflußt werden.The object of the present invention was to find a method which Middle distillates largely freed from sulfur and aromatic compounds helps to improve the lubricating effect. At the same time, with this Process also affects the cold flow properties of these middle distillates favorably become.

Überraschenderweise wurde gefunden, daß Copolymere aus Ethylen und stickstoffhaltigen ethylenisch ungesättigten Verbindungen den mit ihnen additivierten Brennstoffölen die geforderten Eigenschaften verleihen. Surprisingly, it was found that copolymers of ethylene and nitrogen-containing ethylenically unsaturated compounds that are additized with them Give fuel oils the required properties.

Gegenstand der Erfindung ist die Verwendung von 0,001 bis 2 Gew.-% (bezogen auf das Brennstofföl) eines Additivs, welches wenigstens ein Copolymer enthält, das neben Struktureinheiten, die sich vom Ethylen ableiten auch solche Struktureinheiten aufweist, die sich von einer ethylenisch ungesättigten Verbindung ableiten, die mindestens ein aromatisch oder aliphatisch gebundenes Stickstoffatom mit Ausnahme von Stickstoffatomen in Imidbindung aufweist, zur Verbesserung der Schmierwirkung von Mitteldestillaten mit maximal 200 ppm Schwefelgehalt.The invention relates to the use of 0.001 to 2% by weight (based on the fuel oil) of an additive which contains at least one copolymer which in addition to structural units derived from ethylene, such structural units has, which are derived from an ethylenically unsaturated compound, the at least one aromatic or aliphatic nitrogen atom Exception of nitrogen atoms in imide bond has to improve the Lubricating effect of middle distillates with a maximum sulfur content of 200 ppm.

Besonders gut geeignet ist das Verfahren zur Additivierung von Ölen, die weniger als 0,05, insbesondere weniger als 0,035 Gew.-% Schwefel enthalten.The process is particularly well suited for the additivation of oils that are less than Contain 0.05, in particular less than 0.035 wt .-% sulfur.

Bei den ethylenisch ungesättigten Comonomeren, die neben Ethylen Bestandteil des im erfindungsgemäßen Verfahren verwendeten Copolymeren sind, handelt es sich vorzugsweise um stickstoffhaltige Verbindungen, die eine zur radikalischen Polymerisation befähigte ethylenische Doppelbindung enthalten. Als geeignete Comonomere seien genannt:

  • a) Alkylaminoacrylate bzw. -methacrylate, wie z.B. Aminoethylacrylat, Aminopropylacrylat, Amino-n-butylacrylat, N-Methylaminoethylacrylat, N,N-Dimethylaminoethylacrylat, N,N-Diethylaminoethylacrylat, N,N-Dimethylaminopropylacrylat, N,N-Diethylaminopropylacrylat sowie die entsprechenden Methacrylate,
  • b) Alkylacrylamide und -methacrylamide, wie z.B. Ethylacrylamid, Butylacrylamid, N-Octylacrylamid, N-Propyl-N-methoxyethylacrylamid, N-Acryloylphthalimid, N-Acryloylsuccinimid, N-Methylolacrylamid, sowie die entsprechenden Methacrylamide,
  • c) Vinylamide, wie z.B. N-Vinyl-N-methylacetamid, N-Vinylsuccinimid,
  • d) Aminoalkylvinylether, wie z.B. Aminopropylvinylether, Diethylaminoethylvinylether, Dimethylaminopropylvinylether,
  • e) Allylamin, N-Allyl-N-methylamin, N-Allyl-N-ethylamin,
  • f) eine Vinylgruppe tragende Heterozyklen, wie z.B. N-Vinylpyrrolidon, Methylvinylimidazol, 2-Vinylpyridin, 4-Vinylpyridin, 2-Methyl-5-vinylpyridin, Vinylcarbazol, Vinylimidazol, N-Vinyl-2-piperidon, N-Vinylcaprolactam.
    • The ethylenically unsaturated comonomers which, in addition to ethylene, are a component of the copolymer used in the process according to the invention, are preferably nitrogen-containing compounds which contain an ethylenic double bond which is capable of free-radical polymerization. Suitable comonomers are:
  • a) Alkylaminoacrylates or methacrylates, such as aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, N-methylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, and N, N-corresponding methacrylates,
  • b) alkyl acrylamides and methacrylamides, such as, for example, ethyl acrylamide, butyl acrylamide, N-octylacrylamide, N-propyl-N-methoxyethylacrylamide, N-acryloylphthalimide, N-acryloylsuccinimide, N-methylolacrylamide, and the corresponding methacrylamides,
  • c) vinylamides, such as, for example, N-vinyl-N-methylacetamide, N-vinylsuccinimide,
  • d) aminoalkyl vinyl ethers, such as, for example, aminopropyl vinyl ether, diethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether,
  • e) allylamine, N-allyl-N-methylamine, N-allyl-N-ethylamine,
  • f) heterocycles bearing a vinyl group, such as, for example, N-vinylpyrrolidone, methylvinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, vinylcarbazole, vinylimidazole, N-vinyl-2-piperidone, N-vinylcaprolactam.

    • Die Monomeren sind kommerziell verfügbar oder nach bekannten Methoden herstellbar. So sind die verschiedenen Aminoalkylen(meth)acrylate z.B. gemäß EP-A-0 188 639 durch Umesterung von (Meth)acrylsäureestem mit Aminoalkoholen in Gegenwart eines Titankatalysators zugänglich. Die Herstellung von Aminoalkylvinylethern ist z.B. in Liebigs Ann. Chem. 601 (1956), 81 beschrieben.The monomers are commercially available or by known methods produced. The various aminoalkylene (meth) acrylates are e.g. according to EP-A-0 188 639 by transesterification of (meth) acrylic esters with amino alcohols accessible in the presence of a titanium catalyst. The production of Aminoalkyl vinyl ethers are e.g. in Liebigs Ann. Chem. 601 (1956), 81.

    Für die Verwendung im erfindungsgemäßen Verfahren sind vorzugsweise solche Copolymere geeignet, die 0,1 bis 15; insbesondere 1 bis 10 mol-% eines oder mehrerer der stickstoffhaltigen Comonomere enthalten. Weiterhin sind im erfindungsgemäßen Verfahren auch Mischungen solcher Copolymere verwendbar. Die Schmelzviskositäten der verwendbaren Copolymere liegen bei 140°C vorzugsweise unterhalb von 10 000 mPas, insbesondere zwischen 10 und 1000 mPas und speziell zwischen 20 und 500 mPas.Those for use in the process according to the invention are preferably Copolymers suitable, the 0.1 to 15; in particular 1 to 10 mol% of one or contain several of the nitrogen-containing comonomers. Furthermore, in Processes according to the invention can also be used in mixtures of such copolymers. The melt viscosities of the copolymers that can be used are 140 ° C. preferably below 10,000 mPas, in particular between 10 and 1000 mPas and especially between 20 and 500 mPas.

    Die im erfindungsgemäßen Verfahren verwendbaren Copolymere enthalten neben Ethylen mindestens ein Comonomeres mit Stickstoffatomen. Sie können noch weitere, beispielsweise ein, zwei oder drei weitere olefinisch ungesättigte Comonomere enthalten. Solche olefinisch ungesättigten Comonomere sind beispielsweise Vinylester, Acrylsäure, Methacrylsäure, Acrylester, Methacrylester, Vinylether oder Olefine. Besonders bevorzugte Vinylester sind Vinylacetat, Vinylpropionat und Vinylester von Neocarbonsäuren mit 8, 9, 10, 11 oder 12 Kohlenstoffatomen. Besonders bevorzugte Acryl- und Methacrylester sind solche mit Alkoholen mit 1 bis 20 Kohlenstoffatomen, insbesondere von Methanol, Ethanol, Propanol, n-Butanol, iso-Butanol und tert.-Butanol. Besonders bevorzugte Olefine sind solche mit 3 bis 10 Kohlenstoffatomen, speziell Propen, Isobutylen, Diisobutylen, 4-Methylpenten-1 und Hexen. Enthalten die Copolymeren ein weiteres Comonomer, so beträgt dessen molarer Anteil vorzugsweise bis zu 15 mol-%, insbesondere bis zu 12 mol-%. The copolymers which can be used in the process according to the invention contain in addition Ethylene at least one comonomer with nitrogen atoms. You can still more, for example one, two or three more olefinically unsaturated Comonomers included. Such olefinically unsaturated comonomers are for example vinyl esters, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, Vinyl ethers or olefins. Particularly preferred vinyl esters are vinyl acetate, Vinyl propionate and vinyl ester of neocarboxylic acids with 8, 9, 10, 11 or 12 Carbon atoms. Particularly preferred acrylic and methacrylic esters are those with Alcohols with 1 to 20 carbon atoms, especially of methanol, ethanol, Propanol, n-butanol, iso-butanol and tert-butanol. Particularly preferred olefins are those with 3 to 10 carbon atoms, especially propene, isobutylene, diisobutylene, 4-methylpentene-1 and hexene. If the copolymers contain another comonomer, its molar fraction is preferably up to 15 mol%, in particular up to 12 mol%.

    Die Copolymerisation der Comonomeren erfolgt nach bekannten Verfahren (vgl. hierzu z.B. Ullmanns Encyclopädie der Technischen Chemie, 4. Auflage, Bd. 19, Seiten 169 bis 178). Geeignet sind die Polymerisation in Lösung, in Suspension, in der Gasphase und die Hochdruckmassepolymerisation. Vorzugsweise wendet man die Hochdruckmassepolymerisation an, die bei Drücken von 50 bis 400 MPa, vorzugsweise 100 bis 300 MPa und Temperaturen von 50 bis 350°C, vorzugsweise 100 bis 300°C, durchgeführt wird. Die Reaktion der Comonomeren wird durch Radikale bildende Initiatoren (Radikalkettenstarter) eingeleitet. Zu dieser Substanzklasse gehören z.B. Sauerstoff, Hydroperoxide, Peroxide und Azoverbindungen wie Cumolhydroperoxid, t-Butylhydroperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(2-ethylhexyl)-peroxidicarbonat, t-Butylpermaleinat, t-Butylperbenzoat, Dicumylperoxid, t-Butylcumylperoxid, Di-(t-butyl)peroxid, 2,2'-Azo-bis(2-methylpropanonitril), 2,2'-Azo-bis(2-methylbutyronitril). Die Initiatoren werden einzeln oder als Gemisch aus zwei oder mehr Substanzen in Mengen von 0,01 bis 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Comonomerengemisch, eingesetzt.The comonomers are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 19, Pages 169 to 178). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably one turns high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out. The reaction of the comonomers is determined by Radical initiators (radical chain initiators) initiated. To this Substance classes belong e.g. Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile). The initiators are used individually or as a mixture of two or more substances in quantities of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.

    Die gewünschte Schmelzviskosität der Copolymerisate wird bei gegebener Zusammensetzung des Comonomerengemisches durch Variation der Reaktionsparameter Druck und Temperatur und gegebenenfalls durch Zusatz von Moderatoren eingestellt. Als Moderatoren haben sich Wasserstoff, gesättigte oder ungesättigte Kohlenwasserstoffe, z.B. Propan, Aldehyde, z.B. Propionaldehyd, n-Butyraldehyd oder Isobutyraldehyd, Ketone, z.B. Aceton, Methylethylketon, Methylisobutylketon, Cyclohexanon oder Alkohole, z.B. Butanol, bewährt. In Abhängigkeit von der angestrebten Viskosität werden die Moderatoren in Mengen bis zu 20 Gew.-%, vorzugsweise 0,05 bis 10 Gew.-%, bezogen auf das Comonomerengemisch, angewandt.The desired melt viscosity of the copolymers is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired. Hydrogen, saturated or unsaturated hydrocarbons, e.g. Propane, aldehydes, e.g. propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven. In Depending on the desired viscosity, the moderators in quantities up to to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.

    Die Hochdruckmassepolymerisation wird in bekannten Hochdruckreaktoren, z.B. Autoklaven oder Rohrreaktoren diskontinuierlich oder kontinuierlich durchgeführt, besonders bewährt haben sich Rohrreaktoren. Lösungsmittel wie aliphatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, Benzol oder Toluol, können im Reaktionsgemisch enthalten sein, wenngleich sich die lösungsmittelfreie Arbeitsweise besonders bewährt hat. Nach einer bevorzugten Ausführungsform der Polymerisation wird das Gemisch aus den Comonomeren, dem Initiator und, sofern eingesetzt, dem Moderator, einem Rohrreaktor über den Reaktoreingang sowie über einen oder mehrere Seitenäste zugeführt. Hierbei können die Comonomerenströme unterschiedlich zusammengesetzt sein (EP-B-0 271 738).High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene can in Reaction mixture may be included, although the solvent-free Working method has proven particularly successful. According to a preferred embodiment of the Polymerization is the mixture of the comonomers, the initiator and, if used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed. Here, the comonomer streams be composed differently (EP-B-0 271 738).

    Weiterhin läßt sich die Schmierwirkung von Ölen in erfindungsgemäßer Weise dadurch verbessern, daß man ihnen Ethylencopolymere zusetzt, die mit Aminogruppen tragenden Verbindungen umgesetzte Säuregruppen enthalten. Dazu geeignete Ethylencopolymere und Ethylenterpolymere sind beispielsweise solche, die Acrylsäure, Methacrylsäure, Itaconsäure, Fumarsäure, Maleinsäure oder Maleinsäureanhydrid enthalten. Zur Herstellung eines die Schmierwirkung von Ölen verbessernden Additivs werden diese säuregruppenhaltigen Copolymere an den Säuregruppen mit Ammoniak, C1- bis C10-Alkylresten tragenden primären oder sekundären Aminen wie Methylamin, Dimethylamin, Ethylamin, Propylamin, Butylamin, oder Alkanolaminen wie Ethanolamin, Propanolamin, Diethanolamin, N-Ethylethanolamin, Diglykolamin, 2-Amino-2-methylpropanolamin sowie deren Mischungen umgesetzt. Es werden 0,1 bis 1,2 mol, vorzugsweise äquimolare Mengen, Amin pro mol Säure verwendet. Die Umsetzung mit Hydroxyaminen kann sowohl über die OH-Gruppe zu Estern als auch über eine NH2-Gruppe zu Amiden erfolgen.Furthermore, the lubricating effect of oils can be improved in the manner according to the invention by adding to them ethylene copolymers which contain acid groups reacted with compounds bearing amino groups. Suitable ethylene copolymers and ethylene terpolymers are, for example, those which contain acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride. To produce an additive that improves the lubricating effect of oils, these copolymers containing acid groups are attached to the acid groups with primary or secondary amines such as methylamine, dimethylamine, ethylamine, propylamine, butylamine, or alkanolamines such as ethanolamine, propanolamine, which carry C 1 -C 10 -alkyl radicals. Diethanolamine, N-ethylethanolamine, diglycolamine, 2-amino-2-methylpropanolamine and mixtures thereof. 0.1 to 1.2 mol, preferably equimolar amounts, of amine per mol of acid are used. The reaction with hydroxyamines can take place either via the OH group to form esters or via an NH 2 group to form amides.

    Zur erfindungsgemäßen Verbesserung der Schmierwirkung werden die Copolymerisate Mineralölen oder Mineralöldestillaten in Form von Lösungen oder Dispersionen die 10 bis 90 Gew.-%, bevorzugt 20 - 80 Gew.-%, der Polymerisate enthalten, zugesetzt. Geeignete Lösungs- oder Dispersionsmittel sind aliphatische und/oder aromatische Kohlenwasserstoffe oder Kohlenwasserstoffgemische, z.B. Benzinfraktionen, Kerosin, Decan, Pentadecan, Toluol, Xylol, Ethylbenzol oder kommerzielle Lösungsmittelgemische wie Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol-, ®ISOPAR- und Shellsol D-Typen. Durch die Copolymerisate in ihren Schmiereigenschaften verbesserte Mineralöle oder Mineralöldestillate enthalten 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% Copolymerisat, bezogen auf das Destillat. To improve the lubricating effect according to the invention Copolymers mineral oils or mineral oil distillates in the form of solutions or Dispersions containing 10 to 90% by weight, preferably 20 to 80% by weight, of the polymers included, added. Suitable solvents or dispersing agents are aliphatic and / or aromatic hydrocarbons or hydrocarbon mixtures, e.g. Gasoline fractions, kerosene, decane, pentadecane, toluene, xylene, ethylbenzene or commercial solvent mixtures such as Solvent Naphtha, ®Shellsol AB, ®Solvesso 150, ®Solvesso 200, ®Exxsol, ®ISOPAR and Shellsol D types. Through the Copolymers with improved lubricating properties or mineral oils Mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight Copolymer based on the distillate.

    Im erfindungsgemäßen Verfahren können weiterhin Mischungen verwendet werden, die aus Copolymeren der beanspruchten Art, jedoch unterschiedlicher qualitativer und/oder quantitativer Zusammensetzung und/oder unterschiedlicher (bei 140°C gemessener) Viskosität bestehen. Das Mischungsverhältnis (in Gewichtsteilen) der Copolymeren kann über einen weiten Bereich variiert werden und z.B. 20:1 bis 1:20, vorzugsweise 10:1 bis 1:10 betragen. Auf diesem Wege lassen sich die Additive gezielt individuellen Anforderungen anpassen.Mixtures can also be used in the process according to the invention, those of copolymers of the claimed type, but of different quality and / or quantitative composition and / or different (at 140 ° C measured) viscosity exist. The mixing ratio (in parts by weight) of the Copolymers can be varied over a wide range and e.g. 20: 1 to 1:20, preferably 10: 1 to 1:10. In this way, the additives specifically adapt to individual requirements.

    Zur Herstellung von Additivpaketen für spezielle Problemlösungen können im erfindungsgemäßen Verfahren die Copolymere auch zusammen mit einem oder mehreren öllöslichen Co-Additiven eingesetzt werden, die bereits für sich allein die Kaltfließeigenschaften und/oder Schmierwirkung von Rohölen, Schmierölen oder Brennölen verbessern. Beispiele solcher Co-Additive sind Vinylacetat enthaltende Copolymerisate oder Terpolymerisate des Ethylens, polare Verbindungen, die eine Paraffindispergierung bewirken (Paraffindispergatoren), Kammpolymere sowie öllösliche Amphiphile.For the production of additive packages for special solutions to problems in process according to the invention the copolymers together with one or several oil-soluble co-additives can be used, which alone Cold flow properties and / or lubricating effect of crude oils, lubricating oils or Improve fuel oils. Examples of such co-additives are those containing vinyl acetate Copolymers or terpolymers of ethylene, polar compounds, the one Paraffin dispersion effects (paraffin dispersants), comb polymers and oil-soluble amphiphiles.

    So hat sich die Verwendung stickstoffhaltiger Copolymere mit Copolymerisaten hervorragend bewährt, die 10 bis 40 Gew.-% Vinylacetat und 60 bis 90 Gew.-% Ethylen enthalten.So has the use of nitrogen-containing copolymers with copolymers excellent proven, the 10 to 40 wt .-% vinyl acetate and 60 to 90 wt .-% Contain ethylene.

    Zur Verbesserung der Schmierwirkung können im erfindungsgemäßen Verfahren auch Mischungen mit Paraffindispergatoren eingesetzt werden. Diese Additive reduzieren die Größe der Paraffinkristalle und bewirken, daß die Paraffinpartikel sich nicht absetzen, sondern kolloidal mit deutlich reduziertem Sedimentationsbestreben, dispergiert bleiben. Weiterhin verstärken sie die Schmierwirkung der stickstoffhaltigen Copolymere. Als Paraffindispergatoren haben sich öllösliche polare Verbindungen mit ionischen oder polaren Gruppen, z.B. Aminsalze und/oder Amide bewährt, die durch Reaktion aliphatischer oder aromatischer Amine, vorzugsweise langkettiger aliphatischer Amine, mit aliphatischen oder aromatischen Mono-, Di-, Trioder Tetracarbonsäuren oder deren Anhydriden erhalten werden (vgl. US 4 211 534). Andere Paraffindispergatoren sind Copolymere des Maleinsäureanhydrids und α,β-ungesättigter Verbindungen, die gegebenenfalls mit primären Monoalkylaminen und/oder aliphatischen Alkoholen umgesetzt werden können (vgl. EP 0 154 177), die Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen (vgl. EP 0 413 279 B1) und nach EP 0 606 055 A2 Umsetzungsprodukte von Terpolymeren auf Basis α,β-ungesättigter Dicarbonsäureanhydride, α,β-ungesättigter Verbindungen und Polyoxyalkylenether niederer ungesättigter Alkohole. Auch Alkylphenol-Aldehydharze sind als Paraffindispergatoren geeignet.To improve the lubricating effect in the process according to the invention mixtures with paraffin dispersants can also be used. These additives reduce the size of the paraffin crystals and cause the paraffin particles to separate not settle, but colloidally with significantly reduced sedimentation efforts, stay dispersed. Furthermore, they increase the lubricating effect of the nitrogen-containing copolymers. Oil-soluble polar dispersants have been found as paraffin dispersants Compounds with ionic or polar groups, e.g. Amine salts and / or amides proven by the reaction of aliphatic or aromatic amines, preferably long-chain aliphatic amines, with aliphatic or aromatic mono-, di-, trioder Tetracarboxylic acids or their anhydrides are obtained (cf. US 4 211 534). Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf. EP 0 154 177) Reaction products of alkenylspirobislactones with amines (cf. EP 0 413 279 B1) and according to EP 0 606 055 A2 reaction products of Terpolymers based on α, β-unsaturated dicarboxylic acid anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers of lower unsaturated Alcohols. Alkylphenol-aldehyde resins are also suitable as paraffin dispersants.

    Schließlich werden in einer weiteren bewährten Variante des Verfahrens die stickstoffhaltigen Copolymerisate zusammen mit Kammpolymeren verwendet. Hierunter versteht man Polymere, bei denen Kohlenwasserstoffreste mit mindestens 8, insbesondere mindestens 10 Kohlenstoffatomen an einem Polymerrückgrat gebunden sind. Vorzugsweise handelt es sich um Homopolymere, deren Alkylseitenketten mindestens 8 und insbesondere mindestens 10 Kohlenstoffatome enthalten. Bei Copolymeren weisen mindestens 20 %, bevorzugt mindestens 30 % der Monomeren Seitenketten auf (vgl. Comb-like Polymers-Structure and Properties; N.A. Platé and V. P. Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Beispiele für geeignete Kammpolymere sind z.B. Fumarat/Vinylacetat-Copolymere (vgl. EP 0 153 176 A1), Copolymere aus einem C6- bis C24- α-Olefin und einem N-C6- bis C22-Alkylmaleinsäureimid (vgl. EP 0 320 766), ferner veresterte Olefin/ Maleinsäureanhydrid-Copolymere, Polymere und Copolymere von α-Olefinen und veresterte Copolymere von Styrol und Maleinsäureanhydrid.Finally, in a further tried and tested variant of the process, the nitrogen-containing copolymers are used together with comb polymers. This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Platé and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff). Examples of suitable comb polymers are, for example, fumarate / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C 6 to C 24 α-olefin and an NC 6 to C 22 alkyl maleimide (cf. EP 0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of α-olefins and esterified copolymers of styrene and maleic anhydride.

    Beispielsweise können Kammpolymere durch die Formel

    Figure 00080001
    beschrieben werden. Darin bedeuten

    A
    R', COOR', OCOR', R"-COOR' oder OR';
    D
    H, CH3, A oder R";
    E
    H oder A;
    G
    H, R", R"-COOR', einen Arylrest oder einen heterocyclischen Rest;
    M
    H, COOR", OCOR", OR" oder COOH;
    N
    H, R", COOR", OCOR, COOH oder einen Arylrest;
    R'
    eine Kohlenwasserstoffkette mit 8-50 Kohlenstoffatomen;
    R"
    eine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;
    m
    eine Zahl zwischen 0,4 und 1,0; und
    n
    eine Zahl zwischen 0 und 0,6.
    For example, comb polymers can be represented by the formula
    Figure 00080001
    to be discribed. Mean in it
    A
    R ', COOR', OCOR ', R "-COOR' or OR ';
    D
    H, CH 3 , A or R ";
    e
    H or A;
    G
    H, R ", R" -COOR ', an aryl radical or a heterocyclic radical;
    M
    H, COOR ", OCOR", OR "or COOH;
    N
    H, R ", COOR", OCOR, COOH or an aryl radical;
    R '
    a hydrocarbon chain of 8-50 carbon atoms;
    R "
    a hydrocarbon chain of 1 to 10 carbon atoms;
    m
    a number between 0.4 and 1.0; and
    n
    a number between 0 and 0.6.

    Das Mischungsverhältnis (in Gewichtsteilen) von stickstoffhaltigen Copolymeren mit Paraffindispergatoren bzw. Kammpolymeren beträgt jeweils 1:10 bis 20:1, vorzugsweise 1:1 bis 10:1.The mixing ratio (in parts by weight) of nitrogen-containing copolymers with Paraffin dispersants or comb polymers are 1:10 to 20: 1, preferably 1: 1 to 10: 1.

    Zur Optimierung der Schmierwirkung können im erfindungsgemäßen Verfahren weitere Lubricity-Additive eingesetzt werden. Als Lubricity-Additive haben sich vorzugsweise Fettalkohole, Fettsäuren und Dimerfettsäuren sowie deren Ester und Partialester mit Glykolen (gemäß DE-A-15 94 417), Polyolen wie Glycerin (gemäß EP-A-0 680 506, EP-A-0 739 970) oder Hydroxyaminen (gemäß EP-A-0 802 961) bewährt.In order to optimize the lubricating effect, the process according to the invention can additional lubricity additives are used. As lubricity additives have become preferably fatty alcohols, fatty acids and dimer fatty acids and their esters and Partial esters with glycols (according to DE-A-15 94 417), polyols such as glycerin (according to EP-A-0 680 506, EP-A-0 739 970) or hydroxyamines (according to EP-A-0 802 961) proven.

    Das erfindungsgemäße Verfahren ist geeignet, die Schmiereigenschaften von tierischen, pflanzlichen oder mineralischen Ölen zu verbessern. Es ist für die Anwendung bei Mitteldestillaten besonders gut geeignet. Als Mitteldestillate bezeichnet man insbesondere solche Mineralöle, die durch Destillation von Rohöl gewonnen werden und im Bereich von 120 bis 450°C sieden, beispielsweise Kerosin, Jet-Fuel, Diesel und Heizöl. Vorzugsweise wird das erfindungsgemäße Verfahren bei solchen Mitteldestillaten angewendet, die 0,5 Gew.-% Schwefel und weniger, insbesondere weniger als 200 ppm Schwefel und in speziellen Fällen weniger als 50 ppm Schwefel enthalten. Es handelt sich dabei im allgemeinen um solche Mitteldestillate, die einer hydrierenden Raffination unterworfen wurden, und die daher nur geringe Anteile an polyaromatischen und polaren Verbindungen enthalten, die ihnen eine natürliche Schmierwirkung verleihen. Das erfindungsgemäße Verfahren wird weiterhin vorzugsweise in solchen Mitteldestillaten angewendet, die 95 %-Destillationspunkte unter 370°C, insbesondere 350°C und in Spezialfällen unter 330°C aufweisen.The method according to the invention is suitable for the lubricating properties of to improve animal, vegetable or mineral oils. It is for them Particularly well suited for use with middle distillates. As middle distillates One particularly refers to those mineral oils which are obtained by distilling crude oil be obtained and boil in the range from 120 to 450 ° C., for example kerosene, Jet fuel, diesel and heating oil. The method according to the invention is preferably used for such middle distillates, which contain 0.5 wt .-% sulfur and less, in particular less than 200 ppm sulfur and in special cases less than Contain 50 ppm sulfur. These are generally such Middle distillates that have been subjected to hydrogenating refining and therefore contain only small amounts of polyaromatic and polar compounds that give them a natural lubricating effect. The method according to the invention is still preferably used in such middle distillates, the 95% distillation points below 370 ° C, especially 350 ° C and in special cases below Have 330 ° C.

    Im erfindungsgemäßen Verfahren können auch andere Additive verwendet werden, z.B. Stockpunkterniedriger oder Entwachsungshilfsmittel, Korrosionsinhibitoren, Antioxidantien, Schlamminhibitoren, Dehazer und Zusätze zur Erniedrigung des Cloud-Points.Other additives can also be used in the process according to the invention, e.g. Pour point depressants or dewaxing aids, corrosion inhibitors, Antioxidants, sludge inhibitors, dehazers and additives to lower the Cloud point.

    BeispieleExamples Additiveadditives

    Additiv 1:Additive 1:
    Terpolymer aus Ethylen, 15 Gew.-% Vinylacetat und 8 Gew.-% 1-Vinyl-2-pyrrolidon. Die bei 140°C gemessene Schmelzviskosität beträgt 150 mPas.Terpolymer made of ethylene, 15% by weight vinyl acetate and 8% by weight 1-vinyl-2-pyrrolidone. The melt viscosity measured at 140 ° C is 150 mPas.
    Additiv 2:Additive 2:
    Terpolymer aus 22 Gew.-% Vinylacetat und 2,5 Gew.-% 1-Vinyl-2-pyrrolidon und einer Viskosität von 240 mPas bei 140°C.Terpolymer of 22% by weight vinyl acetate and 2.5% by weight 1-vinyl-2-pyrrolidone and a viscosity of 240 mPas at 140 ° C.
    Additiv 3:Additive 3:
    Copolymer aus Ethylen und 15 Gew.-% 1-Vinyl-2-pyrrolidon und einer Viskosität von 205 mPas bei 140°C.Copolymer of ethylene and 15 wt .-% 1-vinyl-2-pyrrolidone and one Viscosity of 205 mPas at 140 ° C.
    Additiv 4:Additive 4:
    Terpolymer aus Ethylen, 27 Gew.-% Vinylacetat und 20 Gew.-% N-Vinyl-N-Methyl-Acetamid und einer Schmelzviskosität von 143 mPas bei 140°C.Terpolymer made of ethylene, 27% by weight vinyl acetate and 20% by weight N-vinyl-N-methyl-acetamide and a melt viscosity of 143 mPas at 140 ° C.
    Additiv 5:Additive 5:
    Copolymer aus Ethylen, 18 Gew.-% N-Vinyl-N-Methyl-Acetamid und einer Schmelzviskosität von 143 mPas bei 140°C.Copolymer of ethylene, 18 wt .-% N-vinyl-N-methyl-acetamide and a melt viscosity of 143 mPas at 140 ° C.
    Additiv 6:Additive 6:
    Terpolymer aus Ethylen, 25 Gew.-% Vinylpropionat und 7 Gew.-% Vinylimidazol und einer Schmelzviskosität von 260 mPas bei 140°C.Terpolymer of ethylene, 25% by weight vinyl propionate and 7% by weight Vinylimidazole and a melt viscosity of 260 mPas at 140 ° C.
    Additiv 7:Additive 7:
    Terpolymer aus Ethylen, 13 Gew.-% Vinylpropionat und 10 Gew.-% Dimethylaminoethylmethacrylat und einer Schmelzviskosität von 105 mPas bei 140°C.Terpolymer of ethylene, 13% by weight vinyl propionate and 10% by weight Dimethylaminoethyl methacrylate and a melt viscosity of 105 mPas at 140 ° C.
    Additiv 8:Additive 8:
    Terpolymer aus Ethylen, 24 Gew.-% Vinylacetat und 8 Gew.-% Dimethylaminoethylmethacrylat und einer Viskosität von 93 mPas be 140°C.Terpolymer made of ethylene, 24% by weight vinyl acetate and 8% by weight Dimethylaminoethyl methacrylate and a viscosity of 93 mPas be 140 ° C.
    Charakterisierung der Testöle:Characterization of the test oils: Die Bestimmung der Siedekenndaten erfolgt gemäß ASTM D-86, die Bestimmung des CFPP-Werts gemäß EN 116 und die Bestimmung des Cloud Points gemäß ISO 3015.The boiling data are determined in accordance with ASTM D-86, the CFPP value in accordance with EN 116 and the cloud point in accordance with ISO 3015. Testöl 1Test oil 1 Testöl 2Test oil 2 Siedebeginn [°C]Initial boiling point [° C] 195195 169169 20 % [°C]20% [° C] 226226 240240 30 % [°C]30% [° C] 232232 259259 90 % [°C]90% [° C] 281281 359359 95 % [°C]95% [° C] 300300 377377 Cloud Point [°C]Cloud Point [° C] - 30,5- 30.5 00 CFPP [°C]CFPP [° C] - 31- 31 - 2- 2nd S-Gehalt [ppm]S content [ppm] 1414 171171 Schmierwirkung in MitteldestillatenLubricating effect in middle distillates

    Die Schmierwirkung der Additive wurde mittels eines HFRR-Geräts der Firma PCS Instruments an additivierten Ölen bei 6°C durchgeführt. Der High Frequency Reciprocating Rig Test (HFRR) ist beschrieben in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986. Die Ergebnisse sind als Reibungskoeffizient und Wear Scar angegeben. Ein niedriger Reibungskoeffizient und ein niedriger Wear Scar zeigen eine gute Schmierwirkung. Alle Additive wurden als 50 %ige Dispersion in Solvent Naphtha eingesetzt. Als Vergleich wird ein handelsüblicher Fließverbesserer auf Basis eines Copolymerisats aus Ethylen und 30 Gew.-% Vinylacetat und einer Schmelzviskosität V140 von 105 mPas eingesetzt. Wear Scar in Testöl 1 Beispiel Additiv Reibung Av. Film [%] Wear Scar [µm] 1 - 0,62 19 620 2 250 ppm Additiv 1 0,19 53 470 3 400 ppm Additiv 2 0,17 88 305 4 500 ppm Additiv 2 0,19 57 430 5 300 ppm Additiv 3 0,17 92 265 6 500 ppm Additiv 4 0,20 68 441 7 500 ppm Additiv 5 0,16 85 293 8 250 ppm Additiv 5 0,18 61 375 9 250 ppm Additiv 6 0,17 95 265 10 125 ppm Additiv 6 0,19 58 443 11 300 ppm Additiv 7 0,21 55 441 12 200 ppm Additiv 8 0,19 65 380 13 500 ppm Ethylen-Vinylacetat-Copolymer (Vergleich) 0,31 9 619 CFPP-Wirksamkeit in Testöl 1 100 ppm 200 ppm Additiv 4 - 38 - 40 Additiv 8 - 37 - 39 Wear scar in Testöl 2 Beispiel Additiv Reibung Av. Film [%] Wear Scar [µm] 14 - 0,45 25 590 15 300 ppm Additiv 1 0,14 88 302 16 300 ppm Additiv 2 0,13 92 275 17 250 ppm Additiv 8 0,16 78 420 18 300 ppm Ethylen-Vinylacetat Copolymer (Vergleich) 0,42 23 585 CFPP-Wirksamkeit in Testöl 2 50 ppm 100 ppm 200 ppm Additiv 4 -5 - 8 -12 Additiv 6 - 6 - 9 - 11 Additiv 8 - 8 - 10 -13 The lubricating effect of the additives was carried out using an HFRR device from PCS Instruments on additive oils at 6 ° C. The High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986. The results are reported as the coefficient of friction and wear scar. A low coefficient of friction and a low wear scar show a good lubricating effect. All additives were used as a 50% dispersion in solvent naphtha. For comparison, a commercially available flow improver based on a copolymer of ethylene and 30% by weight of vinyl acetate and a melt viscosity V140 of 105 mPas is used. Wear Scar in Test Oil 1 example additive friction Av. Movie [%] Wear Scar [µm] 1 - 0.62 19 620 2 250 ppm additive 1 0.19 53 470 3 400 ppm additive 2 0.17 88 305 4 500 ppm additive 2 0.19 57 430 5 300 ppm additive 3 0.17 92 265 6 500 ppm additive 4 0.20 68 441 7 500 ppm additive 5 0.16 85 293 8th 250 ppm additive 5 0.18 61 375 9 250 ppm additive 6 0.17 95 265 10 125 ppm additive 6 0.19 58 443 11 300 ppm additive 7 0.21 55 441 12 200 ppm additive 8 0.19 65 380 13 500 ppm ethylene-vinyl acetate copolymer (comparison) 0.31 9 619 CFPP effectiveness in test oil 1 100 ppm 200 ppm Additive 4 - 38 - 40 Additive 8 - 37 - 39 Wear scar in test oil 2 example additive friction Av. Movie [%] Wear Scar [µm] 14 - 0.45 25 590 15 300 ppm additive 1 0.14 88 302 16 300 ppm additive 2 0.13 92 275 17 250 ppm additive 8 0.16 78 420 18 300 ppm ethylene vinyl acetate copolymer (comparison) 0.42 23 585 CFPP effectiveness in test oil 2 50 ppm 100 ppm 200 ppm Additive 4 -5 - 8th -12 Additive 6 - 6th - 9 - 11 Additive 8 - 8th - 10th -13

    Liste der verwendeten HandelsbezeichnungenList of trade names used

    Solvent Naphtha ®Shellsol AB ®Solvesso 150Solvent naphtha ®Shellsol AB ® Solvesso 150
    aromatische Lösemittelgemische mit Siedebereich 180 bis 210°Caromatic solvent mixtures with boiling range 180 up to 210 ° C
    ®Solvesso 200®Solvesso 200
    aromatisches Lösemittelgemisch mit Siedebereich 230 bis 287°Caromatic solvent mixture with boiling range 230 up to 287 ° C
    ®Exxsol®Exxsol
    Dearomatisierte Lösemittel in verschiedenen Siedebereichen, beispielsweise ®Exxsol D60: 187 bis 215°C Dearomatized solvents in various Boiling ranges, for example ®Exxsol D60: 187 bis 215 ° C
    ®ISOPAR (Exxon)®ISOPAR (Exxon)
    isoparaffinische Lösemittelgemische in verschiedenen Siedebereichen, beispielsweise ®ISOPAR L: 190 bis 210°Cisoparaffinic solvent mixtures in different Boiling ranges, for example ®ISOPAR L: 190 to 210 ° C
    ®Shellsol D®Shellsol D
    hauptsächlich aliphatische Lösemittelgemische in verschiedenen Siedebereichenmainly aliphatic solvent mixtures in different boiling ranges

    Claims (6)

    1. Use of from 0.001 to 2% by weight (based on the fuel oil) of an additive containing at least one copolymer which, besides structural units derived from ethylene, also contains structural units derived from an ethylenically unsaturated compound having at least one aromatically or aliphatically bonded nitrogen atom, with the exception of nitrogen atoms in an imide bond, for improving the lubricity of middle distillates containing at most 200 ppm of sulphur.
    2. Use according to Claim 1, characterized in that the nitrogen-containing comonomer is a derivative of acrylic acid or is a nitrogen-containing organic compound carrying a vinyl radical.
    3. Use according to Claim 1 and/or 2, characterized in that the nitrogen-containing comonomer is
      a) aminoethyl acrylate, aminopropyl acrylate, amino-n-butyl acrylate, N-methylaminoethyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate, N,N-diethylaminopropyl acrylate and the corresponding methacrylates,
      b) ethylacrylamide, butylacrylamide, N-octylacrylamide, N-propyl-N-methoxyethylacrylamide, N-methylolacrylamide and the corresponding methacrylamides,
      c) N-vinyl-N-methylacetamide,
      d) aminopropyl vinyl ether, diethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether,
      e) allylamine, N-allyl-N-methylamine, N-allyl-N-ethylamine,
      f) N-vinylpyrrolidone, methylvinylimidazole, 2-vinylpyridine, 4-vinylpyridine, 2-methyl-5-vinylpyridine, vinylcarbazole, vinylimidazole, N-vinyl-2-piperidone or N-vinylcaprolactam.
    4. Use according to one or more of Claims 1 to 3, characterized in that the molar proportion of the nitrogen-containing comonomer in the copolymer is from 0.1 to 15%, in particular from 1 to 10%.
    5. Use according to one or more of Claims 1 to 4, characterized in that the melt viscosities of the copolymers are less than 10,000 mPas, preferably from 10 to 1000 mPas.
    6. Use according to one or more of Claims 1 to 5, characterized in that, besides ethylene and nitrogen-containing comonomers, the copolymers comprise one, two or three further comonomers selected from the group consisting of vinyl esters, acrylic acid, acrylates, vinyl ethers and/or alkenes.
    EP99106980A 1998-04-16 1999-04-09 Use of nitrogen-containing ethylene copolymers for producing fuel oils with improved lubricating activity Expired - Lifetime EP0964052B1 (en)

    Applications Claiming Priority (2)

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    DE19816797A DE19816797C2 (en) 1998-04-16 1998-04-16 Use of nitrogen-containing ethylene copolymers for the production of fuel oils with improved lubrication
    DE19816797 1998-04-16

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    EP0964052A1 EP0964052A1 (en) 1999-12-15
    EP0964052B1 true EP0964052B1 (en) 2004-02-04

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    Publication number Priority date Publication date Assignee Title
    DE19927560C2 (en) * 1999-06-17 2002-03-14 Clariant Gmbh Fuel oil composition
    DE102005035276B4 (en) 2005-07-28 2007-10-11 Clariant Produkte (Deutschland) Gmbh Mineral oils with improved conductivity and cold flowability
    DE102005035275B4 (en) 2005-07-28 2007-10-11 Clariant Produkte (Deutschland) Gmbh Mineral oils with improved conductivity and cold flowability

    Family Cites Families (11)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3112456A1 (en) * 1981-03-28 1982-10-07 Hoechst Ag, 6000 Frankfurt "METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS"
    JPS6245692A (en) * 1985-08-22 1987-02-27 Mitsubishi Petrochem Co Ltd Additive for fuel oil and fuel oil with improved flowability
    GB8706369D0 (en) * 1987-03-18 1987-04-23 Exxon Chemical Patents Inc Crude oil
    ES2032318T3 (en) * 1987-09-15 1993-02-01 Basf Aktiengesellschaft FUELS FOR OTTO ENGINES.
    DE3921279A1 (en) * 1989-06-29 1991-01-03 Hoechst Ag METHOD FOR IMPROVING THE FLOWABILITY OF MINERAL OILS AND MINERAL OIL DISTILLATES
    DE3941561A1 (en) * 1989-12-16 1991-06-20 Basf Ag REFRIGERABLE STABLE PETROLEUM DISTILLATES, CONTAINING POLYMERS AS PARAFFIN DISPERSATORS
    DE4333680A1 (en) * 1993-10-02 1995-04-06 Basf Ag Copolymers based on ethylene, and the use thereof as flow improvers in petroleum middle distillates
    ES2100743T3 (en) * 1993-10-02 1997-06-16 Basf Ag ETHYLENE BASED COPOLYMERS AND THEIR USE AS FLUENCE IMPROVERS IN OIL DISTILLATES.
    GB9411614D0 (en) * 1994-06-09 1994-08-03 Exxon Chemical Patents Inc Fuel oil compositions
    CA2182995C (en) * 1994-12-13 2003-04-08 Brian William Davies Fuel oil compositions
    JPH09208973A (en) * 1996-02-01 1997-08-12 Nof Corp Fuel oil composition

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    EP0964052A1 (en) 1999-12-15
    DE59908446D1 (en) 2004-03-11
    DE19816797A1 (en) 1999-10-21
    DE19816797C2 (en) 2001-08-02

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