EP1116781A1 - Polyfunctional additive for fuel oils - Google Patents
Polyfunctional additive for fuel oils Download PDFInfo
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- EP1116781A1 EP1116781A1 EP00128083A EP00128083A EP1116781A1 EP 1116781 A1 EP1116781 A1 EP 1116781A1 EP 00128083 A EP00128083 A EP 00128083A EP 00128083 A EP00128083 A EP 00128083A EP 1116781 A1 EP1116781 A1 EP 1116781A1
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- 0 C*(*)[N+](*(C)*)[O-] Chemical compound C*(*)[N+](*(C)*)[O-] 0.000 description 2
- DANHSNLBSQXAKS-UHFFFAOYSA-N C[N](C)([NH+]([O-])O)[N](C)(N=O)O Chemical compound C[N](C)([NH+]([O-])O)[N](C)(N=O)O DANHSNLBSQXAKS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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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
- 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
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
- C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1981—Condensation polymers of aldehydes or ketones
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
- C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- 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
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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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
Definitions
- the present invention relates to an additive for fuel oils containing Ethylene / vinyl ester / olefin terpolymers and amphiphilic, lubricant-improving Additives, as well as their use to improve cold flow and Lubrication properties of the oils thus added.
- Mineral oils and mineral oil distillates used as fuel oils generally 0.5 wt .-% and more sulfur, which the combustion Causes formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further.
- 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.
- EP-A-0 743 974 discloses the use of mixtures of lubricity additives (Esters of polyhydric alcohols and carboxylic acids with 10 to 25 carbon atoms or Dicarboxylic acids) and flow improvers made from ethylene / unsaturated ester copolymers to synergistically improve the lubricating effect of highly desulfurized oils.
- EP-A-0 807 676 discloses the use of a mixture of one Carboxamide and a cold flow improver and / or an ashless one Dispersant to improve the cold flow properties of low sulfur Fuel oil.
- EP-A-0 680 506 discloses the use of esters of mono- or polyvalent Carboxylic acids with mono- or polyhydric alcohols as Lubricity-improving additive to fuel oils.
- EP-A-0 807 642 discloses cold flow improvers based on terpolymers which Contain structural units of ethylene, vinyl acetate and 4-methylpentene-1, EP-A-807 643 based on ethylene, vinyl acetate and norbornene.
- the object of the present invention was to find additive combinations which are in Middle distillates largely freed from sulfur and aromatic compounds lead to an improvement in the lubricating effect.
- these additives are said to also contain a proportion as a cold flow improver, in the oils mentioned is soluble and effective as such, and the effect of the lubricity additive supports, and vice versa.
- additives which are in addition to lubricating amphiphile terpolymers made of ethylene, vinyl esters and contain certain olefins that have the required properties.
- Another object of the invention are fuel oils, the said Contain additives.
- Another object of the invention is the use of additives for simultaneous improvement of the lubrication and cold flow properties of Fuel oils.
- Preferred proportions of A) and B) are between 10 and 90% by weight, in particular 20 to 80 wt .-% and especially 40 to 60 wt .-%.
- the oil-soluble amphiphile (component A) preferably comprises a radical R 1 having 5 to 40, in particular 12 to 35, carbon atoms.
- R 1 is particularly preferably linear or branched and contains 1 to 3 double bonds in the case of linear radicals.
- the radical R 2 preferably has 2 to 8 carbon atoms and can be interrupted by nitrogen and / or oxygen atoms.
- the sum of the carbon atoms of R 1 and R 2 is at least 10, in particular at least 15.
- component A carries 2 to 5 hydroxyl groups, each carbon atom not carrying more than one hydroxyl group.
- X in formula 1 has the Meaning of oxygen.
- they are fatty acids and esters between carboxylic acids and dihydric or polyhydric alcohols.
- Preferred esters contain at least 10, especially at least 12 carbon atoms.
- Prefers is also that the esters contain free hydroxyl groups, the esterification of the Polyol is not complete with the carboxylic acid.
- Suitable polyols are for example ethylene glycol, propylene glycol, diethylene glycol and higher Alkoxylation products, glycerin, trimethylolpropane, pentaerythritol, diglycerin and higher condensation products of glycerin as well as sugar derivatives. Others too Polyols containing heteroatoms, such as triethanolamine, are suitable.
- reaction products of ethanolamine are Diethanolamine, hydroxypropylamine, dihydroxypropylamine, n-methylethanolamine, Diglycolamine and 2-amino-2-methylpropanol are suitable.
- the implementation takes place preferably by amidation, the resulting amides also containing free OH groups wear. Examples include fatty acid monoethanolamides and diethanolamides and called -N-methylethanolamide.
- R 3 preferably represents a hydroxyl-bearing alkyl radical having 3 to 8 carbon atoms, or preferably C 2 to C 18 alkyl, in particular C 4 to C 12 alkyl.
- R 43 preferably represents a C 2 - to C 8 -, in particular a C 2 - to C 4 -rest.
- the polyamine from which the structural unit formed from R 41 , R 42 and the nitrogen atom connecting them is derived is preferably ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or a higher homologue of aziridine such as polyethyleneimine, and mixtures thereof. Parts of the amino group can be alkylated. Sternamines and dendrimers are also suitable. This is understood to mean polyamines with generally 2-10 nitrogen atoms which are connected to one another via —CH 2 —CH 2 groups and which are saturated in the marginal position with acyl or alkyl radicals.
- R 44 preferably represents hydrogen, an acyl radical or an alkoxy group of the formula - (OCH 2 CH 2 ) n -, where n is an integer between 1 and 10, and mixtures thereof.
- the amides are generally by condensation of the polyamines with the Carboxylic acids or their derivatives such as esters or anhydrides. It are preferably 0.2 to 1.5 mol, in particular 0.3 to 1.2 mol, especially 1 mol Acid used per base equivalent. The condensation is preferably carried out at Temperatures between 20 and 300 ° C, especially between 50 and 200 ° C below Distilling off the water of reaction. Solvents may be preferred aromatic solvents such as benzene, toluene, xylene, trimethylbenzene and / or commercial solvent mixtures such as B. Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200 are added to the reaction mixture.
- the Products according to the invention generally have a titratable Base nitrogen of 0.01 - 5% and an acid number of less than 20 mg KOH / g, preferably less than 10 mg KOH / g.
- y preferably takes the values 1 or 2.
- Preferred polyols have 2 to 8 carbon atoms. They preferably wear 2, 3, 4 or 5 hydroxyl groups, but no more than they contain carbon atoms.
- the carbon chain of the polyols can be straight-chain, branched, saturated or unsaturated be and optionally contain heteroatoms. It is preferably saturated.
- Preferred carboxylic acids from which the compounds of formula 1 are derived let, or represent the compounds of formula 1, have 5 to 40, especially 12 to 30 carbon atoms.
- the carboxylic acid preferably has one or two carboxyl groups.
- the carbon chain of the carboxylic acids can straight chain, branched, saturated or unsaturated.
- carboxylic acids examples include caprylic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Elaidic acid, linoleic acid, linolenic acid and behenic acid, and carboxylic acids with Heteroatoms such as ricinoleic acid.
- dimer and trimer fatty acids such as they e.g. are accessible by oligomerization of unsaturated fatty acids, as well Alkenyl succinic acids are used.
- component A uses ethers and amines of the formula 2.
- ethers and amines of the formula 2 are partial ethers of polyols, such as, for example, glycerol monooctadecyl ether or hydroxyl-bearing amines, as are obtainable, for example, by alkoxylation of amines of the formula R 1 NH 2 or R 1 R 3 NH with alkylene oxides, preferably ethylene oxide and / or propylene oxide. 1-10, in particular 1-5, mol of alkylene oxide are preferably used per H atom of nitrogen.
- the vinyl esters contained in the terpolymer of component B) are preferred of monocarboxylic acids having 2 to 16, in particular 2 to 12, carbon atoms derived.
- One or more vinyl esters can be contained at the same time.
- the vinyl esters are vinyl acetate, Vinyl propionate, 2-ethylhexanoic acid vinyl ester, neodecanoic acid vinyl ester, Vinyl neononanoate, vinyl neoundecanoate, vinyl pivalate or vinyl laurate, in particular vinyl acetate and / or vinyl propionate.
- the olefin contained in the terpolymer contains 5, 6 or 7 carbon atoms. It is, for example, penten-1, hexen-1 or hepten-1. Especially preferred embodiments of the invention are 4-methylpentene-1 or norbornene.
- the terpolymers preferably contain 10 to 16 mol% of vinyl ester and 1 to 3 mol% of olefin. Their degree of branching, determined by means of NMR spectroscopy, is between 3 and 15, in particular between 3.5 and 10 CH 3 / 100CH 2 groups, which do not originate from the vinyl ester.
- Terpolymers according to the invention with an ISO 3219 (B) at 140 ° C. measured melt viscosity of 50 to 5000 mPas, preferably 30 to 1,000 mPas and in particular 50 to 500 mPas.
- the starting materials are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A21, Pages 305 to 413). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization.
- the reaction of the monomers is caused by radicals initiators (radical chain initiators) initiated.
- radicals initiators radiation chain initiators
- Oxygen, hydroperoxides, peroxides and azo compounds such as Cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl perpivalate, t-butyl permaleinate, t-butyl perbenzoate, Dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'-azo-bis (2-methylbutyronitrile).
- the initiators are individual or as a mixture of two or more substances in amounts from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
- the desired melt viscosity of the terpolymers is given Composition of the monomer 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 become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture, applied.
- terpolymers To be suitable for use in the additives of the invention, monomer mixtures are used which, in addition to ethylene and optionally a moderator 5 to 40% by weight, preferably 10 to 40% by weight Vinyl ester and 1 to 40 wt .-% olefin contain. With that of the composition of the terpolymer differing composition of the monomer mixture you bear the different polymerization rate of the monomers Bill.
- the polymers are obtained as colorless melts which Solidify at room temperature to waxy solids.
- additives according to the invention also together with one or more oil-soluble Co-additives are used, which alone have the cold flow properties and / or lubricating effect of crude oils, lubricating oils or fuel oils improve.
- oil-soluble Co-additives are paraffin dispersants, alkylphenol-aldehyde resins and comb polymers.
- Paraffin dispersants reduce the size of the wax crystals and cause the paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed.
- paraffin dispersants oil-soluble polar 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-, tri- or tetracarboxylic acids or their anhydrides can be obtained.
- paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented Reaction products of alkenyl spirobis lactones with amines and Reaction products of terpolymers based on ⁇ , ⁇ -unsaturated Dicarboxylic anhydrides, ⁇ , ⁇ -unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols.
- Alkylphenol-formaldehyde resins are also available Paraffin dispersants suitable. The following are some suitable ones Paraffin dispersants listed.
- the additives according to the invention can also be used in a mixture with alkylphenol-formaldehyde resins.
- these alkylphenol-formaldehyde resins are those of the formula wherein R 51 is C 4 -C 50 alkyl or alkenyl, [OR 52 ] for ethoxy and / or propoxy, n for a number from 5 to 100 and p for a number from 0 to 50.
- the invention Additives used together with comb polymers.
- Suitable comb polymers are 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 -alkylmaleimide (cf. EP-A- 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 -alkylmaleimide cf. EP-A- 0 320 766
- esterified olefin / maleic anhydride copolymers polymers and
- the mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
- the additives according to the invention are suitable for improving the cold flow and lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of alcoholic fuels and mineral oils. They are particularly well suited for use in middle distillates. Middle distillates are mineral oils that are obtained by distilling crude oil and boil in the range of 120 to 450 ° C, such as kerosene, jet fuel, diesel and heating oil.
- the additives according to the invention are preferably used in middle distillates which contain at most 500 ppm, in particular less than 200 ppm, and in special cases less than 50 ppm of sulfur. These are generally middle distillates which have been subjected to hydrogenation refining and which therefore contain only small amounts of polyaromatic and polar compounds which give them a natural lubricating effect.
- the additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370 ° C., in particular 350 ° C. and in special cases below 330 ° C. The effectiveness of the mixtures is better than would be expected from the individual components and compared to the mixtures according to the prior art.
- the additive combinations according to the invention are distinguished under cold blending conditions if the temperature of the oil during the additive is low, ie below 40 ° C., in particular below 20 ° C. and especially below 10 ° C.
- the additive components according to the invention can be mineral oils or Mineral oil distillates can be added separately or in a mixture.
- Mixtures have solutions or dispersions of 10 to 90% by weight, preferably 20-80 wt .-%, the additive combination contain proven.
- Suitable Solvents or dispersing agents are aliphatic and / or aromatic Hydrocarbons or hydrocarbon mixtures, e.g.
- the additives can be used alone or together with other additives, for example with other pour point depressants, dewaxing aids, corrosion inhibitors, antioxidants, conductivity improvers, sludge inhibitors, dehazers and additives for lowering the cloud point. These additives can be added to the oil together with the additive components according to the invention or separately. The effectiveness of the additives according to the invention as a lubricity enhancer and cold flow improver is explained in more detail by the examples below.
- Test oil 1 Test oil 2 Test oil 3 Test oil 4 Test oil 5 Cloud Point (CP) (° C) + 1 - 9.6 - 3.2 - 4.3 - 26.8 Cold Filter Plugging Point (CFPP) (° C) - 2nd - 14 - 6th - 6th - 27 Pour point (PP) (° C) - 3rd - 12th - 9 - 12th - 27 n-paraffin content (% by weight) 23 21.5 18.9 18.2 16.8 Initial boiling point (IBP) (° C) 163 172 187.9 186.9 185.8 Boiling range 90% - 20% (K) 104 76.9 99.8 102.2 89.9 FBP-90% (K) 27 18th 24.2 19.0 21 End of boiling point (FBP) (° C) 332 336 359.6 358.6 320.7 density 0.828 0.831 0.843 0.842 0.819 S content (ppm) 290 35 54.2 478 6 HFRR
- the boiling characteristics were determined in accordance with ASTM D-86 the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
- the solubility behavior of the additives is determined according to the British Rail Test as follows: 400 ppm of a dispersion of the additive combination heated to 22 ° C are metered into 200 ml of the test oil heated to 22 ° C (see Table 3) and shaken vigorously for 30 seconds. After 24 hours of storage at + 3 ° C for 15 seconds and then again shaken mm ml at 3 ° C in three portions of 50 through a 1.6 ⁇ m-glass fiber microfilter (i 25; Whatman GFA, Order No. 1,820,025 ) filtered.
- An ADT value ⁇ 15 is considered as an indication that the gas oil is normal cold weather can be used satisfactorily. Products with ADT values> 25 are described as not filterable.
- the lubricating effect of the additives was determined using an HFRR device from PCS Instruments performed.
- the additives tempered at 22 ° C become the dosed at 22 ° C oil and shaken vigorously for 30 seconds.
- To 24 hours storage at + 3 ° C, the oil is tested according to the conditions of the British Rail filtered and the lubricating effect on the filtrate determined in the HFRR test.
- the High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986 and is carried out at 60 ° C.
- the Results are as a coefficient of friction (Friction) and Wear Scar (WSD) specified. Show a low coefficient of friction and a lower wear scar a good lubricating effect.
- the polymers were 50% in kerosene set.
- the viscosity was determined using a rotary viscometer (Haake RV 20) with plate-cone measuring system at 140 ° C, in accordance with ISO 3219 (B).
- Additives according to the invention are also used in a mixture with paraffin dispersants become.
- the employed Wachsdispergator (F) is a mixture of 2 parts of a reaction product of a terpolymer of C 14/16 - ⁇ -olefin, maleic anhydride and 2 equivalents of di-tallow Allylpolyglkol with and a part of nonylphenol-formaldehyde resin.
- the cold flow improver polymers mentioned and, if appropriate, additionally the wax dispersant mentioned are mixed with the amphiphiles mentioned.
Abstract
Description
Die vorliegende Erfindung betrifft ein Additiv für Brennstofföle, enthaltend Ethylen/Vinylester/Olefin-Terpolymere und amphiphile, schmierverbessernde Zusätze, sowie dessen Verwendung zur Verbesserung von Kaltfließ- und Schmiereigenschaften der so additivierten Öle.The present invention relates to an additive for fuel oils containing Ethylene / vinyl ester / olefin terpolymers and amphiphilic, lubricant-improving Additives, as well as their use to improve cold flow and Lubrication properties of the oils thus added.
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 Einführung der Dieseltreibstoffe betreffenden Norm EN 590 schreibt in Deutschland zur Zeit einen maximalen Schwefelgehalt von 500 ppm vor. In Skandinavien kommen bereits Brennstofföle mit weniger als 50 ppm und in Ausnahmefällen mit weniger als 10 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 0.5 wt .-% and more sulfur, which the combustion Causes formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further. The introduction of the standard relating to diesel fuels EN 590 currently writes a maximum sulfur content of 500 ppm before. In Scandinavia, fuel oils are already coming in at less than 50 ppm and in exceptional cases with less than 10 ppm sulfur. This Fuel oils are usually made by making them from petroleum Fractions obtained by distillation hydrogenated refined. In the Desulphurization also removes other substances that Give fuel oils a natural lubricating effect. About these substances include 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 that has now taken place in Scandinavia to below 370 ° C, partly to below 350 ° C or below 330 ° C 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-0 764 198 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.
EP-A-0 743 974 offenbart die Verwendung von Mischungen aus Lubricity-Additiven (Ester mehrwertiger Alkohole und Carbonsäuren mit 10 bis 25 C-Atomen bzw. Dicarbonsäuren) und Fließverbesserern aus Ethylen/ungesättigte Ester-Copolymeren zur synergistischen Verbesserung der Schmierwirkung von hochentschwefelten Ölen.EP-A-0 743 974 discloses the use of mixtures of lubricity additives (Esters of polyhydric alcohols and carboxylic acids with 10 to 25 carbon atoms or Dicarboxylic acids) and flow improvers made from ethylene / unsaturated ester copolymers to synergistically improve the lubricating effect of highly desulfurized oils.
EP-A-0 807 676 offenbart die Verwendung einer Mischung aus einem Carbonsäureamid und einem Kaltfließverbesserer und/oder einen aschefreien Dispergator zur Verbesserung der Kaltfließeigenschaften von schwefelarmem Brennstofföl.EP-A-0 807 676 discloses the use of a mixture of one Carboxamide and a cold flow improver and / or an ashless one Dispersant to improve the cold flow properties of low sulfur Fuel oil.
EP-A-0 680 506 offenbart die Verwendung von Estern von ein- oder mehrwertigen Carbonsäuren mit ein- oder mehrwertigen Alkoholen als schmierfähigkeitsverbessernden Zusatz zu Brennstoffölen.EP-A-0 680 506 discloses the use of esters of mono- or polyvalent Carboxylic acids with mono- or polyhydric alcohols as Lubricity-improving additive to fuel oils.
Die Verwendung von Kaltfließverbesserern in Brennstoffölen ist erforderlich, da Rohöle und durch Destillation von Rohölen gewonnene Mitteldestillate wie Gasöl, Dieselöl oder Heizöl je nach Herkunft der Rohöle unterschiedliche Mengen langkettiger Paraffine (Wachse) gelöst enthalten. Bei niedrigen Temperaturen scheiden sich diese Paraffine als plättchenförmige Kristalle ab, teilweise unter Einschluß von Öl. Hierdurch wird die Fließfähigkeit der Rohöle und der aus ihnen gewonnenen Destillate erheblich beeinträchtigt. Es treten Feststoffablagerungen auf, die häufig zu Störungen bei Gewinnung, Transport und Einsatz der Mineralöle und Mineralölprodukte führen. So kommt es bei niedrigen Umgebungstemperaturen, z.B. in der kalten Jahreszeit u.a. bei Dieselmotoren und Feuerungsanlagen zu Verstopfungen der Filter, die eine sichere Dosierung der Brennstoffe verhindern und schließlich in einer Unterbrechung der Kraftstoff- bzw. Heizmittelzufuhr resultieren. The use of cold flow improvers in fuel oils is necessary because Crude oils and middle distillates obtained by distilling crude oils such as gas oil, Different amounts of diesel oil or heating oil depending on the origin of the crude oils long-chain paraffins (waxes) contained in solution. At low temperatures these paraffins separate out as platelet-shaped crystals, sometimes under Inclusion of oil. This makes the flowability of the crude oils and that of them distillates obtained significantly impaired. Solid deposits occur, which frequently lead to disruptions in the extraction, transport and use of mineral oils and Lead petroleum products. So it happens at low ambient temperatures, e.g. in the cold season for diesel engines and combustion plants Clogging of the filters, which prevent safe metering of the fuels and finally result in an interruption in the fuel or heating medium supply.
Auch das Fördern der Mineralöle und Mineralölprodukte durch Rohrleitungen über größere Entfernungen kann z.B. im Winter durch das Ausfallen von Paraffinkristallen beeinträchtigt werden.Also conveying mineral oils and mineral oil products through pipelines larger distances can e.g. in winter due to the precipitation of paraffin crystals be affected.
Es ist bekannt, das unerwünschte Kristallwachstum durch geeignete Zusätze zu unterbinden und damit einem Anstieg der Viskosität der Öle entgegenzuwirken. Solche Zusätze, sie sind unter der Bezeichnung Stockpunkterniedriger bzw. Fließverbesserer bekannt, verändern Größe und Form der Wachskristalle und wirken damit einem Anstieg der Viskosität der Öle entgegen.It is known to increase the undesired crystal growth by means of suitable additives prevent and thus counteract an increase in the viscosity of the oils. Such additives, they are known as pour point lower or Flow improvers are known to change the size and shape of the wax crystals and thus counteract an increase in the viscosity of the oils.
EP-A-0 807 642 offenbart Kaltfließverbesserer auf Basis von Terpolymeren, die Struktureinheiten von Ethylen, Vinylacetat und 4-Methylpenten-1 enthalten, EP-A-807 643 solche auf Basis von Ethylen, Vinylacetat und Norbornen.EP-A-0 807 642 discloses cold flow improvers based on terpolymers which Contain structural units of ethylene, vinyl acetate and 4-methylpentene-1, EP-A-807 643 based on ethylene, vinyl acetate and norbornene.
Es hat sich gezeigt, daß in schwefelarmen und paraffinreichen Ölen die synergistischen Additivkombinationen des Standes der Technik insbesondere bei dem in der Praxis zunehmend an Bedeutung gewinnenden Cold Blending, d.h. dem Einmischen von Additiven in kalte Öle zu Filtrationsproblemen oberhalb des Cloud Points der additivierten Öle führen. Dabei kommt es oftmals zu einer Beeinträchtigung der Schmierwirkung durch den Fließverbesserer und die Öle zeigen nicht die von den Komponenten erwarteten Eigenschaften. Dies wird z.B. im Fall der Additive nach EP-A-0 743 974 durch die schlechte Löslichkeit ihrer Fließverbesserer-Komponente verursacht, wodurch es zur Verstopfung von Kraftstoffiltern kommen kann. Vermutlich werden die Schmierstoffe von den schwerer löslichen Bestandteilen des Fließverbesserers absorbiert wodurch sie nicht die erwartete Wirksamkeit zeigen.It has been shown that in low-sulfur and paraffin-rich oils synergistic additive combinations of the prior art in particular cold blending, which is becoming increasingly important in practice, i.e. the Mixing additives in cold oils to filtration problems above the cloud Lead points of the additive oils. This often leads to one Impairment of the lubrication effect by the flow improver and the oils do not show the properties expected from the components. This will e.g. in the Case of the additives according to EP-A-0 743 974 due to their poor solubility Flow improver component causes it to become constipated Fuel filters can come. The lubricants are probably from the less soluble components of the flow improver are absorbed, which means that they do not show the expected effectiveness.
Aufgabe der vorliegenden Erfindung war es, Additivkombinationen zu finden, die in weitgehend von Schwefel und aromatischen Verbindungen befreiten Mitteldestillaten zu einer Verbesserung der Schmierwirkung führen. Gleichzeitig sollen diese Additive auch einen Anteil als Kaltfließverbesserer enthalten, der in den genannten Ölen löslich und als solcher wirksam ist, und der die Wirkung des Lubricity-Additivs unterstützt, und umgekehrt. The object of the present invention was to find additive combinations which are in Middle distillates largely freed from sulfur and aromatic compounds lead to an improvement in the lubricating effect. At the same time, these additives are said to also contain a proportion as a cold flow improver, in the oils mentioned is soluble and effective as such, and the effect of the lubricity additive supports, and vice versa.
Überraschenderweise wurde gefunden, daß Additive, die neben schmierverbessernden Amphiphilen Terpolymere aus Ethylen, Vinylestern und bestimmten Olefinen enthalten, die geforderten Eigenschaften aufweisen.Surprisingly, it has been found that additives which are in addition to lubricating amphiphile terpolymers made of ethylene, vinyl esters and contain certain olefins that have the required properties.
Gegenstand der Erfindung sind Additive zur Verbesserung von Kaltfließ- und
Schmiereigenschaften von Brennstoffölen, bestehend aus
Ein weiterer Gegenstand der Erfindung sind Brennstofföle, die die genannten Additive enthalten. Another object of the invention are fuel oils, the said Contain additives.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der Additive zur gleichzeitigen Verbesserung der Schmier- und Kaltfließeigenschaften von Brennstoffölen.Another object of the invention is the use of additives for simultaneous improvement of the lubrication and cold flow properties of Fuel oils.
Bevorzugte Anteile von A) und B) liegen zwischen 10 und 90 Gew.-%, insbesondere 20 bis 80 Gew.-% und speziell 40 bis 60 Gew.-%.Preferred proportions of A) and B) are between 10 and 90% by weight, in particular 20 to 80 wt .-% and especially 40 to 60 wt .-%.
Das öllösliche Amphiphil (Komponente A) umfaßt vorzugsweise einen Rest R1 mit 5 bis 40, insbesondere 12 bis 35 Kohlenstoffatomen. Besonders bevorzugt ist R1 linear oder verzweigt und enthält bei linearen Resten 1 bis 3 Doppelbindungen. Der Rest R2 weist bevorzugt 2 bis 8 Kohlenstoffatome auf und kann durch Stickstoff- und/oder Sauerstoffatome unterbrochen sein. In einer weiteren bevorzugten Ausführungsform beträgt die Summe der Kohlenstoffatome von R1 und R2 mindestens 10, insbesondere mindestens 15. In einer weiteren bevorzugten Ausführungsform trägt die Komponente A 2 bis 5 Hydroxylgruppen, wobei jedes Kohlenstoffatom nicht mehr als eine Hydroxylgruppe trägt.The oil-soluble amphiphile (component A) preferably comprises a radical R 1 having 5 to 40, in particular 12 to 35, carbon atoms. R 1 is particularly preferably linear or branched and contains 1 to 3 double bonds in the case of linear radicals. The radical R 2 preferably has 2 to 8 carbon atoms and can be interrupted by nitrogen and / or oxygen atoms. In a further preferred embodiment, the sum of the carbon atoms of R 1 and R 2 is at least 10, in particular at least 15. In a further preferred embodiment, component A carries 2 to 5 hydroxyl groups, each carbon atom not carrying more than one hydroxyl group.
In einer bevorzugten Ausführungsform der Erfindung hat X in der Formel 1 die Bedeutung Sauerstoff. Es handelt sich insbesondere um Fettsäuren und Ester zwischen Carbonsäuren und zwei- oder mehrwertigen Alkoholen. Bevorzugte Ester enthalten mindestens 10, insbesondere mindestens 12 Kohlenstoffatome. Bevorzugt ist ebenfalls, daß die Ester freie Hydroxylgruppen enthalten, die Veresterung des Polyols mit der Carbonsäure also nicht vollständig ist. Geeignete Polyole sind beispielsweise Ethylenglykol, Propylenglykol, Diethylenglykol und höhere Alkoxylierungsprodukte, Glycerin, Trimethylolpropan, Pentaerythrit, Diglycerin und höhere Kondensationsprodukte des Glycerins sowie Zuckerderivate. Auch weitere Heteroatome enthaltende Polyole wie Triethanolamin sind geeignet.In a preferred embodiment of the invention, X in formula 1 has the Meaning of oxygen. In particular, they are fatty acids and esters between carboxylic acids and dihydric or polyhydric alcohols. Preferred esters contain at least 10, especially at least 12 carbon atoms. Prefers is also that the esters contain free hydroxyl groups, the esterification of the Polyol is not complete with the carboxylic acid. Suitable polyols are for example ethylene glycol, propylene glycol, diethylene glycol and higher Alkoxylation products, glycerin, trimethylolpropane, pentaerythritol, diglycerin and higher condensation products of glycerin as well as sugar derivatives. Others too Polyols containing heteroatoms, such as triethanolamine, are suitable.
Ist X ein stickstoffhaltiger Rest, so sind Umsetzungsprodukte von Ethanolamin, Diethanolamin, Hydroxypropylamin, Dihydroxypropylamin, n-Methylethanolamin, Diglykolamin und 2-Amino-2-methylpropanol geeignet. Die Umsetzung erfolgt vorzugsweise durch Amidierung, wobei auch die entstandenen Amide freie OH-Gruppen tragen. Als Beispiele seien Fettsäuremonoethanolamide, -diethanolamide und -N-methylethanolamide genannt. If X is a nitrogen-containing residue, reaction products of ethanolamine are Diethanolamine, hydroxypropylamine, dihydroxypropylamine, n-methylethanolamine, Diglycolamine and 2-amino-2-methylpropanol are suitable. The implementation takes place preferably by amidation, the resulting amides also containing free OH groups wear. Examples include fatty acid monoethanolamides and diethanolamides and called -N-methylethanolamide.
R3 steht vorzugsweise für einen Hydroxylgruppen tragenden Alkylrest mit 3 bis 8 Kohlenstoffatomen, oder vorzugsweise für C2- bis C18-Alkyl, insbesondere C4- bis C12-Alkyl.R 3 preferably represents a hydroxyl-bearing alkyl radical having 3 to 8 carbon atoms, or preferably C 2 to C 18 alkyl, in particular C 4 to C 12 alkyl.
Das multifunktionelle Additiv kann in einer Ausführungsform als Komponente A
Verbindungen der Formel 3 enthalten
worin R1 die oben angegebene Bedeutung hat, R41 einen Rest der Formel 3a
R43 steht vorzugsweise für einen C2- bis C8-, insbesondere für einen C2- bis C4-Rest. Das Polyamin, von dem sich die aus R41, R42 und dem sie verbindenden Stickstoffatom gebildete Struktureinheit ableitet, ist vorzugsweise Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin oder ein höheres Homologes des Aziridins wie Polyethylenimin, sowie deren Mischungen. Teile der Aminogruppe können alkyliert sein. Ebenfalls geeignet sind Sternamine und Dendrimere. Darunter versteht man Polyamine mit im allgemeinen 2-10 Stickstoffatomen, die über -CH2-CH2-Gruppen miteinander verbunden sind und die in randständiger Position mit Acyl- oder Alkylresten abgesättigt sind.R 43 preferably represents a C 2 - to C 8 -, in particular a C 2 - to C 4 -rest. The polyamine from which the structural unit formed from R 41 , R 42 and the nitrogen atom connecting them is derived is preferably ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine or a higher homologue of aziridine such as polyethyleneimine, and mixtures thereof. Parts of the amino group can be alkylated. Sternamines and dendrimers are also suitable. This is understood to mean polyamines with generally 2-10 nitrogen atoms which are connected to one another via —CH 2 —CH 2 groups and which are saturated in the marginal position with acyl or alkyl radicals.
R44 steht vorzugsweise für Wasserstoff, einen Acylrest oder für eine Alkoxygruppe der Formel -(OCH2CH2)n-, wobei n eine ganze Zahl zwischen 1 und 10 bedeutet, sowie deren Mischungen.R 44 preferably represents hydrogen, an acyl radical or an alkoxy group of the formula - (OCH 2 CH 2 ) n -, where n is an integer between 1 and 10, and mixtures thereof.
Als Amphiphil ebenfalls geeignet sind Verbindungen der Formel 3d worin
- R46
- die Bedeutung von R1,
- R47
- die Bedeutung von R1 oder H oder -[CH2-CH2-O-]p-H und
- R48
- die Bedeutung von R2 haben können und
- p
- eine ganze Zahl von 1 bis 10 bedeuten,
- R 46
- the meaning of R 1 ,
- R 47
- the meaning of R 1 or H or - [CH 2 -CH 2 -O-] p -H and
- R 48
- can have the meaning of R 2 and
- p
- is an integer from 1 to 10,
Die Amide werden im allgemeinen durch Kondensation der Polyamine mit den Carbonsäuren oder deren Derivaten wie Estern oder Anhydriden hergestellt. Es werden vorzugsweise 0,2 bis 1,5 mol, insbesondere 0,3 bis 1,2 mol, speziell 1 mol Säure pro Basenäquivalent eingesetzt. Die Kondensation erfolgt bevorzugt bei Temperaturen zwischen 20 und 300 °C, insbesondere zwischen 50 und 200 °C unter Abdestillieren des Reaktionswassers. Dazu können Lösemittel, bevorzugt aromatische Lösemittel wie Benzol, Toluol, Xylol, Trimethylbenzol und/oder kommerzielle Lösemittelgemische wie z. B. Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200 dem Reaktionsgemisch zugefügt werden. Die erfindungsgemäßen Produkte haben im allgemeinen einen titrierbaren Basenstickstoff von 0,01 - 5 % und eine Säurezahl von weniger als 20 mg KOH/g, vorzugsweise weniger als 10 mg KOH/g.The amides are generally by condensation of the polyamines with the Carboxylic acids or their derivatives such as esters or anhydrides. It are preferably 0.2 to 1.5 mol, in particular 0.3 to 1.2 mol, especially 1 mol Acid used per base equivalent. The condensation is preferably carried out at Temperatures between 20 and 300 ° C, especially between 50 and 200 ° C below Distilling off the water of reaction. Solvents may be preferred aromatic solvents such as benzene, toluene, xylene, trimethylbenzene and / or commercial solvent mixtures such as B. Solvent Naphtha, ® Shellsol AB, ® Solvesso 150, ® Solvesso 200 are added to the reaction mixture. The Products according to the invention generally have a titratable Base nitrogen of 0.01 - 5% and an acid number of less than 20 mg KOH / g, preferably less than 10 mg KOH / g.
y nimmt vorzugsweise die Werte 1 oder 2 an. Beispiele bevorzugter Verbindungsgruppen mit y=2 sind Derivate von Dimerfettsäuren und Alkenylbernsteinsäureanhydriden. Letztere können lineare wie auch verzweigte Alkylreste tragen, d.h. sie können sich von linearen α-Olefinen und/oder von Oligomeren niederer C3-C5-Olefine wie Poly(propylen) oder Poly(isobutylen) ableiten.y preferably takes the values 1 or 2. Examples of preferred connecting groups with y = 2 are derivatives of dimer fatty acids and alkenylsuccinic anhydrides. The latter can carry linear as well as branched alkyl radicals, ie they can be derived from linear α-olefins and / or from oligomers of lower C 3 -C 5 olefins such as poly (propylene) or poly (isobutylene).
Bevorzugte Polyole haben 2 bis 8 Kohlenstoffatome. Sie tragen vorzugsweise 2, 3, 4 oder 5 Hydroxylgruppen, jedoch nicht mehr als sie Kohlenstoffatome enthalten. Die Kohlenstoffkette der Polyole kann geradkettig, verzweigt, gesättigt oder ungesättigt sein und gegebenenfalls Heteroatome enthalten. Vorzugsweise ist sie gesättigt.Preferred polyols have 2 to 8 carbon atoms. They preferably wear 2, 3, 4 or 5 hydroxyl groups, but no more than they contain carbon atoms. The The carbon chain of the polyols can be straight-chain, branched, saturated or unsaturated be and optionally contain heteroatoms. It is preferably saturated.
Bevorzugte Carbonsäuren, von denen sich die Verbindungen der Formel 1 ableiten lassen, oder die die Verbindungen der Formel 1 darstellen, haben 5 bis 40, insbesondere 12 bis 30 Kohlenstoffatome. Vorzugsweise hat die Carbonsäure eine oder zwei Carboxylgruppen. Die Kohlenstoffkette der Carbonsäuren kann geradkettig, verzweigt, gesättigt oder ungesättigt sein. Vorzugsweise enthalten mehr als 50% der verwendeten Carbonsäuren (Mischungen) mindestens eine Doppelbindung. Beispiele bevorzugter Carbonsäuren umfassen Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Linolsäure, Linolensäure und Behensäure, sowie Carbonsäuren mit Heteroatomen wie Ricinolsäure. Weiterhin können Dimer- und Trimerfettsäuren, wie sie z.B. durch Oligomerisierung von ungesättigten Fettsäuren zugänglich sind, sowie Alkenylbernsteinsäuren eingesetzt werden. Preferred carboxylic acids, from which the compounds of formula 1 are derived let, or represent the compounds of formula 1, have 5 to 40, especially 12 to 30 carbon atoms. The carboxylic acid preferably has one or two carboxyl groups. The carbon chain of the carboxylic acids can straight chain, branched, saturated or unsaturated. Preferably contain more than 50% of the carboxylic acids (mixtures) used at least one Double bond. Examples of preferred carboxylic acids include caprylic acid, Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Elaidic acid, linoleic acid, linolenic acid and behenic acid, and carboxylic acids with Heteroatoms such as ricinoleic acid. Furthermore, dimer and trimer fatty acids, such as they e.g. are accessible by oligomerization of unsaturated fatty acids, as well Alkenyl succinic acids are used.
Als Komponente A werden in einer bevorzugten Ausführungsform Ether und Amine der Formel 2 eingesetzt. Dabei handelt es sich um Partialether von Polyolen wie z.B. Glycerinmonooctadecylether oder Hydroxylgruppen tragende Amine, wie sie z.B. durch Alkoxylierung von Aminen der Formel R1NH2 oder R1R3NH mit Alkylenoxiden, bevorzugt Ethylenoxid und/oder Propylenoxid zugänglich sind. Bevorzugt werden dabei 1-10, insbesondere 1-5 mol Alkylenoxid pro H-Atom des Stickstoffs eingesetzt.In a preferred embodiment, component A uses ethers and amines of the formula 2. These are partial ethers of polyols, such as, for example, glycerol monooctadecyl ether or hydroxyl-bearing amines, as are obtainable, for example, by alkoxylation of amines of the formula R 1 NH 2 or R 1 R 3 NH with alkylene oxides, preferably ethylene oxide and / or propylene oxide. 1-10, in particular 1-5, mol of alkylene oxide are preferably used per H atom of nitrogen.
Die im Terpolymer der Komponente B) enthaltenen Vinylester sind vorzugsweise von Monocarbonsäuren mit 2 bis 16, insbesondere 2 bis 12 Kohlenstoffatomen abgeleitet. Es können ein oder auch mehrere Vinylester gleichzeitig enthalten sein. In einer weiteren bevorzugten Ausführungsform sind die Vinylester Vinylacetat, Vinylpropionat, 2-Ethylhexansäurevinylester, Neodecansäurevinylester, Neononansäurevinylester, Neoundecansäurevinylester, Vinylpivalat oder Vinyllaurat, insbesondere Vinylacetat und/oder Vinylpropionat.The vinyl esters contained in the terpolymer of component B) are preferred of monocarboxylic acids having 2 to 16, in particular 2 to 12, carbon atoms derived. One or more vinyl esters can be contained at the same time. In a further preferred embodiment, the vinyl esters are vinyl acetate, Vinyl propionate, 2-ethylhexanoic acid vinyl ester, neodecanoic acid vinyl ester, Vinyl neononanoate, vinyl neoundecanoate, vinyl pivalate or vinyl laurate, in particular vinyl acetate and / or vinyl propionate.
Das im Terpolymeren enthaltene Olefin umfaßt 5, 6 oder 7 Kohlenstoffatome. Es handelt sich beispielsweise um Penten-1, Hexen-1 oder Hepten-1. In besonders bevorzugten Ausführungsformen der Erfindung handelt es sich um 4-Methylpenten-1 oder Norbornen.The olefin contained in the terpolymer contains 5, 6 or 7 carbon atoms. It is, for example, penten-1, hexen-1 or hepten-1. Especially preferred embodiments of the invention are 4-methylpentene-1 or norbornene.
Vorzugsweise enthalten die Terpolymere 10 bis 16 mol-% Vinylester und 1 bis 3 mol-% Olefin. Ihr mittels NMR-Spektroskopie bestimmter Verzweigungsgrad liegt zwischen 3 und 15, insbesondere zwischen 3,5 und 10 CH3/100CH2-Gruppen, die nicht vom Vinylester stammen.The terpolymers preferably contain 10 to 16 mol% of vinyl ester and 1 to 3 mol% of olefin. Their degree of branching, determined by means of NMR spectroscopy, is between 3 and 15, in particular between 3.5 and 10 CH 3 / 100CH 2 groups, which do not originate from the vinyl ester.
Für den Einsatz im erfindungsgemäßen Additiv besonders geeignet sind Terpolymerisate gemäß der Erfindung mit einer nach ISO 3219 (B) bei 140°C gemessenen Schmelzviskosität von 50 bis 5000 mPas, vorzugsweise 30 bis 1.000 mPas und insbesondere 50 bis 500 mPas.Are particularly suitable for use in the additive according to the invention Terpolymers according to the invention with an ISO 3219 (B) at 140 ° C. measured melt viscosity of 50 to 5000 mPas, preferably 30 to 1,000 mPas and in particular 50 to 500 mPas.
Zur Herstellung der Terpolymerisate aus Ethylen, dem Vinylester einer aliphatischen linearen oder verzweigten Monocarbonsäure, die 2 bis 20 Kohlenstoffatome im Molekül enthält, und Olefinen geht man von Gemischen der Monomeren aus. Die Copolymerisation der Ausgangsstoffe erfolgt nach bekannten Verfahren (vgl. hierzu z.B. Ullmanns Encyclopädie der Technischen Chemie, 5.Auflage, Vol. A21, Seiten 305 bis 413). 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 Monomeren 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-Butylperpivalat, 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 Monomerengemisch, eingesetzt.For the production of terpolymers from ethylene, the vinyl ester of an aliphatic linear or branched monocarboxylic acid containing 2 to 20 carbon atoms in the Contains molecule, and olefins are assumed to be mixtures of the monomers. The starting materials are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 5th edition, Vol. A21, Pages 305 to 413). 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 monomers is caused by radicals initiators (radical chain initiators) initiated. To this class of substance 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 perpivalate, t-butyl permaleinate, t-butyl perbenzoate, Dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azo-bis (2-methylpropanonitrile), 2,2'-azo-bis (2-methylbutyronitrile). The initiators are individual or as a mixture of two or more substances in amounts from 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture used.
Die gewünschte Schmelzviskosität der Terpolymerisate wird bei gegebener Zusammensetzung des Monomerengemisches 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 Monomerengemisch, angewandt.The desired melt viscosity of the terpolymers is given Composition of the monomer 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 The moderators become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Monomer mixture, applied.
Um für die Verwendung in den erfindungsgemäßen Additiven geeignete Terpolymere zu erhalten, setzt man Monomerengemische ein, die außer Ethylen und gegebenenfalls einem Moderator 5 bis 40 Gew.-%, vorzugsweise 10 bis 40 Gew.-% Vinylester und 1 bis 40 Gew.-% Olefin enthalten. Mit der von der Zusammensetzung des Terpolymerisats abweichenden Zusammensetzung des Monomerengemischs trägt man der unterschiedlichen Polymerisationsgeschwindigkeit der Monomeren Rechnung. Die Polymerisate fallen als farblose Schmelzen an, die bei Raumtemperatur zu wachsartigen Feststoffen erstarren.To be suitable for use in the additives of the invention To obtain terpolymers, monomer mixtures are used which, in addition to ethylene and optionally a moderator 5 to 40% by weight, preferably 10 to 40% by weight Vinyl ester and 1 to 40 wt .-% olefin contain. With that of the composition of the terpolymer differing composition of the monomer mixture you bear the different polymerization rate of the monomers Bill. The polymers are obtained as colorless melts which Solidify at room temperature to waxy solids.
Zur Herstellung von Additivpaketen für spezielle Problemlösungen können die erfindungsgemäßen Additive 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 Brennstoffölen verbessern. Beispiele solcher Co-Additive sind Paraffindispergatoren, Alkylphenol-Aldehydharze und Kammpolymere.For the production of additive packages for special problem solutions the additives according to the invention also together with one or more oil-soluble Co-additives are used, which alone have the cold flow properties and / or lubricating effect of crude oils, lubricating oils or fuel oils improve. Examples of such co-additives are paraffin dispersants, alkylphenol-aldehyde resins and comb polymers.
Paraffindispergatoren reduzieren die Größe der Paraffinkristalle und bewirken, daß die Paraffinpartikel sich nicht absetzen, sondern kolloidal mit deutlich reduziertem Sedimentationsbestreben, dispergiert bleiben. 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-, Tri- oder Tetracarbonsäuren oder deren Anhydriden erhalten werden. Andere Paraffindispergatoren sind Copolymere des Maleinsäureanhydrids und α,β-ungesättigten Verbindungen, die gegebenenfalls mit primären Monoalkylaminen und/oder aliphatischen Alkoholen umgesetzt werden können, die Umsetzungsprodukte von Alkenylspirobislactonen mit Aminen und Umsetzungsprodukte von Terpolymerisaten auf Basis α,β-ungesättigter Dicarbonsäureanhydride, α,β-ungesättigter Verbindungen und Polyoxyalkylenether niederer ungesättigter Alkohole. Auch Alkylphenol-Formaldehydharze sind als Paraffindispergatoren geeignet. Im folgenden werden einige geeignete Paraffindispergatoren aufgeführt.Paraffin dispersants reduce the size of the wax crystals and cause the paraffin particles do not settle, but colloidally with significantly reduced Sedimentation efforts, remain dispersed. Have become paraffin dispersants oil-soluble polar 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-, tri- or tetracarboxylic acids or their anhydrides can be obtained. Other paraffin dispersants are copolymers of maleic anhydride and α, β-unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented Reaction products of alkenyl spirobis lactones with amines and Reaction products of terpolymers based on α, β-unsaturated Dicarboxylic anhydrides, α, β-unsaturated compounds and polyoxyalkylene ethers lower unsaturated alcohols. Alkylphenol-formaldehyde resins are also available Paraffin dispersants suitable. The following are some suitable ones Paraffin dispersants listed.
Die nachfolgend genannten Paraffindispergatoren werden zum Teil durch Reaktion
von Verbindungen, die eine Acylgruppe enthalten, mit einem Amin hergestellt. Bei
diesem Amin handelt es sich um eine Verbindung der Formel NR6R7R8, worin R6, R7
und R8 gleich oder verschieden sein können, und wenigstens eine dieser Gruppen
für C8-C36-Alkyl, C6-C36-Cycloalkyl, C8-C36-Alkenyl, insbesondere C12-C24-Alkyl, C12-C24-Alkenyl
oder Cyclohexyl steht, und die übrigen Gruppen entweder Wasserstoff,
C1-C36-Alkyl, C2-C36-Alkenyl, Cyclohexyl, oder eine Gruppe der Formeln -(A-O)x-E
oder -(CH2)n-NYZ bedeuten, worin A für eine Ethylen- oder Propylengruppe steht, x
eine Zahl von 1 bis 50, E = H, C1-C30-Alkyl, C5-C12-Cycloalkyl oder C6-C30-Aryl, und n
2, 3 oder 4 bedeuten, und Y und Z unabhängig voneinander H, C1-C30-Alkyl oder
-(A-O)x bedeuten. Unter Acylgruppe wird hier eine funktionelle Gruppe folgender
Formel verstanden:
R10 einen geradkettigen oder verzweigten Alkylenrest mit 2 bis 6 Kohlenstoffatomen oder den Rest der Formel 7 in der R6 und R7 insbesondere Alkylreste mit 10 bis 30, bevorzugt 14 bis 24 C-Atomen bedeuten, wobei die Amidstrukturen auch zum Teil oder vollständig in Form der Ammoniumsalzstruktur der Formel 8 vorliegen können. Die Amide bzw. Amid-Ammoniumsalze bzw. Ammoniumsalze z.B. der Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure werden durch Umsetzung der Säuren mit 0,5 bis 1,5 Mol Amin, bevorzugt 0,8 bis 1,2 Mol Amin pro Carboxylgruppe erhalten. Die Umsetzungstemperaturen betragen etwa 80 bis 200°C, wobei zur Herstellung der Amide eine kontinuierliche Entfernung des entstandenen Reaktionswasser erfolgt. Die Umsetzung muß jedoch nicht vollständig zum Amid geführt werden, vielmehr können 0 bis 100 Mol-% des eingesetzten Amins in Form des Ammoniumsalzes vorliegen. Unter analogen Bedingungen können auch die unter B1) genannten Verbindungen hergestellt werden.Als Amine der Formel 9 kommen insbesondere Dialkylamine in Betracht, in denen R6, R7 einen geradkettigen Alkylrest mit 10 bis 30 Kohlenstoffatomen, vorzugsweise 14 bis 24 Kohlenstoffatomen, bedeutet. Im einzelnen seien Dioleylamin, Dipalmitinamin, Dikokosfettamin und Dibehenylamin und vorzugsweise Ditalgfettamin genannt.
Besonders geeignete Beispiele für diese Polymere sind Copolymere von Didodecylfumarat, Vinylacetat und Maleinsäureanhydrid; Ditetradecylfumarat, Vinylacetat und Maleinsäureanhydrid; Di-hexadecylfumarat, Vinylacetat und Maleinsäureanhydrid; oder den entsprechenden Copolymeren, bei denen anstelle des Fumarats das Itaconat verwendet wird. In den oben genannten Beispielen geeigneter Polymere wird das gewünschte Amid durch Umsetzung des Polymers, das Anhydridgruppen enthält, mit einem sekundären Amin der Formel HNR6R7 (gegebenenfalls außerdem mit einem Alkohol, wenn ein Esteramid gebildet wird) erhalten. Wenn Polymere, die eine Anhydridgruppe enthalten, umgesetzt werden, werden die resultierenden Aminogruppen Ammoniumsalze und Amide sein. Solche Polymere können verwendet werden, mit der Maßgabe, daß sie mindestens zwei Amidgruppen enthalten.Es ist wesentlich, daß das Polymer, das mindestens zwei Amidgruppen enthält, mindestens eine Alkylgruppe mit mindestens 10 Kohlenstoffatomen enthält. Diese langkettige Gruppe, die eine geradkettige oder verzweigte Alkylgruppe sein kann, kann über das Stickstoffatom der Amidgruppe gebunden vorliegen.Die dafür geeigneten Amine können durch die Formel R6R7NH und die Polyamine durch R6NH[R19NH)xR7 wiedergegeben werden, wobei R19 eine zweiwertige Kohlenwasserstoffgruppe, vorzugsweise eine Alkylen- oder kohlenwasserstoffsubstituierte Alkylengruppe, und x eine ganze Zahl, vorzugsweise zwischen 1 und 30 ist. Vorzugsweise enthalten einer der beiden oder beide Reste R6 und R7 mindestens 10 Kohlenstoffatome, beispielsweise 10 bis 20 Kohlenstoffatome, zum Beispiel Dodecyl, Tetradecyl, Hexadecyl oder Octadecyl.Beispiele geeigneter sekundärer Amine sind Dioctylamin und solche, die Alkylgruppen mit mindestens 10 Kohlenstoffatomen enthalten, beispielsweise Didecylamin, Didodecylamin, Dicocosamin (d.h. gemischte C12-C14-Amine), Dioctadecylamin, Hexadecyloctadecylamin, Di-(hydriertes Talg)-Amin (annähernd 4 Gew.-% n-C14-Alkyl, 30 Gew.-% n-C10-Alkyl, 60 Gew.-% n-C18-Alkyl, der Rest ist ungesättigt). Beispiele geeigneter Polyamine sind N-Octadecylpropandiamin, N,N'-Dioctadecylpropandiamin, N-Tetradecylbutandiamin und N,N'-Dihexadecylhexandiamin. N-Cocospropylendiamin (C12/C14-Alkyl-propylendiamin), N-Talgpropylendiamin (C16/C18-Alkylpropylendiamin).Die amidhaltigen Polymere haben üblicherweise ein durchschnittliches Molekulargewicht (Zahlenmittel) von 1000 bis 500 000, zum Beispiel 10 000 bis 100 000.
- R22 und R23
- unabhängig voneinander Wasserstoff oder Methyl, a, b gleich Null oder 1 und a + b gleich 1,
- R37 =
- -OH, -O-[C1-C30-Alkyl], -NR6R7, -OsNrR6R7H2
- R38 =
- R37 oder NR6R39
- R39 =
- -(A-O)x-E
- A =
- Ethylen oder Propylen
- x =
- 1 bis 50
- E =
- H, C1-C30-Alkyl, C5-C12-Cycloalkyl oder C6-C30-Aryl
80 - 20 Mol-%, bevorzugt 60 - 40 Mol-% an bivalenten Struktureinheiten der Formel 15 enthalten. Im einzelnen leiten sich die Struktureinheiten der Formeln 25, 26 und 27 von α,β-ungesättigten Dicarbonsäureanhydriden der Formeln 17 und/oder 18 ab.Die Struktureinheiten der Formel 15 leiten sich von den α,β-ungesättigten Olefinen der Formel 19 ab. Die vorgenannte Alkyl-, Cycloalkyl- und Arylreste haben die gleichen Bedeutungen wie unter 8.Die Reste R37 und R38 in Formel 25 bzw. R39 in Formel 27 leiten sich von Polyetheraminen oder Alkanolaminen der Formeln 28 a) und b), Aminen der Formel NR6R7R8 sowie gegebenenfalls von Alkoholen mit 1 bis 30 Kohlenstoffatomen ab. Darin bedeuten
- R53
- Wasserstoff, C6-C40-Alkyl oder
- R54
- Wasserstoff, C1-C4-Alkyl
- R55
- Wasserstoff, C1- bis C4-Alkyl, C5- bis C12-Cycloalkyl oder C6- bis C30-Aryl
- R56, R57
- unabhängig voneinander Wasserstoff, C1- bis C22-Alkyl, C2- bis C22-Alkenyl oder Z - OH
- Z
- C2- bis C4-Alkylen
- n
- eine Zahl zwischen 1 und 1000.
R 10 is a straight-chain or branched alkylene radical having 2 to 6 carbon atoms or the radical of the formula 7 in which R 6 and R 7 are in particular alkyl radicals having 10 to 30, preferably 14 to 24, carbon atoms, the amide structures also partially or completely in the form of the ammonium salt structure of the formula 8 can be present. The amides or amide ammonium salts or ammonium salts, for example of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diamine tetraacetic acid, are reacted with 0.5 to 1.5 mol of amine, preferably 0.8 to 1.2 mol, by reacting the acids Amine obtained per carboxyl group. The reaction temperatures are about 80 to 200 ° C., the water of reaction formed being continuously removed to produce the amides. However, the reaction does not have to be carried out completely to give the amide; on the contrary, 0 to 100 mol% of the amine used can be present in the form of the ammonium salt. The compounds mentioned under B1) can also be prepared under analogous conditions, as amines of the formula 9 Dialkylamines are particularly suitable in which R 6 , R 7 is a straight-chain alkyl radical having 10 to 30 carbon atoms, preferably 14 to 24 carbon atoms. Dioleylamine, dipalmitinamine, dicoconut fatty amine and dibehenylamine and preferably ditallow fatty amine may be mentioned in particular.
Particularly suitable examples of these polymers are copolymers of didodecyl fumarate, vinyl acetate and maleic anhydride; Ditetradecyl fumarate, vinyl acetate and maleic anhydride; Di-hexadecyl fumarate, vinyl acetate and maleic anhydride; or the corresponding copolymers, in which the itaconate is used instead of the fumarate. In the above examples of suitable polymers, the desired amide is obtained by reacting the polymer containing anhydride groups with a secondary amine of the formula HNR 6 R 7 (optionally also with an alcohol if an ester amide is formed). If polymers containing an anhydride group are reacted, the resulting amino groups will be ammonium salts and amides. Such polymers can be used provided that they contain at least two amide groups. It is essential that the polymer containing at least two amide groups contain at least one alkyl group with at least 10 carbon atoms. This long-chain group, which can be a straight-chain or branched alkyl group, can be bound via the nitrogen atom of the amide group. The suitable amines can be represented by the formula R 6 R 7 NH and the polyamines by R 6 NH [R 19 NH) x R 7 are represented, wherein R 19 is a divalent hydrocarbon group, preferably an alkylene or hydrocarbon-substituted alkylene group, and x is an integer, preferably between 1 and 30. Preferably one or both of the radicals R 6 and R 7 contain at least 10 carbon atoms, for example 10 to 20 carbon atoms, for example dodecyl, tetradecyl, hexadecyl or octadecyl. Examples of suitable secondary amines are dioctylamine and those which contain alkyl groups with at least 10 carbon atoms, for example didecylamine, didodecylamine, dicocosamine (ie mixed C 12 -C 14 amines), dioctadecylamine, hexadecyloctadecylamine, di (hydrogenated tallow) amine (approximately 4% by weight nC 14 alkyl, 30% by weight nC 10 - Alkyl, 60 wt .-% nC 18 alkyl, the rest is unsaturated). Examples of suitable polyamines are N-octadecylpropanediamine, N, N'-dioctadecylpropanediamine, N-tetradecylbutanediamine and N, N'-dihexadecylhexanediamine. N-Cocospropylenediamine (C 12 / C 14 alkyl propylene diamine), N-tallow propylene diamine (C 16 / C 18 alkyl propylene diamine). The amide-containing polymers usually have an average molecular weight (number average) of 1000 to 500 000, for example 10,000 to 100,000.
- R 22 and R 23
- independently of one another hydrogen or methyl, a, b is zero or 1 and a + b is 1,
- R 37 =
- -OH, -O- [C 1 -C 30 alkyl], -NR 6 R 7 , -O s N r R 6 R 7 H 2
- R 38 =
- R 37 or NR 6 R 39
- R 39 =
- - (AO) x -E
- A =
- Ethylene or propylene
- x =
- 1 to 50
- E =
- H, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or C 6 -C 30 aryl
Contain 80 - 20 mol%, preferably 60 - 40 mol% of bivalent structural units of the formula 15. Specifically, the structural units of the formulas 25, 26 and 27 are derived from α, β-unsaturated dicarboxylic anhydrides of the formulas 17 and / or 18. The structural units of the formula 15 are derived from the α, β-unsaturated olefins of the formula 19. The abovementioned alkyl, cycloalkyl and aryl radicals have the same meanings as under 8. The radicals R 37 and R 38 in formula 25 and R 39 in formula 27 are derived from polyetheramines or alkanolamines of the formulas 28 a) and b), amines of the formula NR 6 R 7 R 8 and optionally from alcohols having 1 to 30 carbon atoms. Mean in it
- R 53
- Hydrogen, C 6 -C 40 alkyl or
- R 54
- Hydrogen, C 1 -C 4 alkyl
- R 55
- Hydrogen, C 1 to C 4 alkyl, C 5 to C 12 cycloalkyl or C6 to C 30 aryl
- R 56 , R 57
- independently of one another hydrogen, C 1 - to C 22 -alkyl, C 2 - to C 22 -alkenyl or Z - OH
- Z.
- C 2 to C 4 alkylene
- n
- a number between 1 and 1000.
Zur Optimierung der Eigenschaften als Fließverbesserer und/oder Lubricity-Additiv können die erfindungsgemäßen Additive ferner in Mischung mit Alkylphenol-Formaldehydharzen eingesetzt werden. In einer bevorzugten Ausführungsform der Erfindung handelt es sich bei diesen Alkylphenol-Formaldehydharzen um solche der Formel worin R51 für C4-C50-Alkyl oder -Alkenyl, [O-R52] für Ethoxy- und/oder Propoxy, n für eine Zahl von 5 bis 100 und p für eine Zahl von 0 bis 50 steht.To optimize the properties as flow improver and / or lubricity additive, the additives according to the invention can also be used in a mixture with alkylphenol-formaldehyde resins. In a preferred embodiment of the invention, these alkylphenol-formaldehyde resins are those of the formula wherein R 51 is C 4 -C 50 alkyl or alkenyl, [OR 52 ] for ethoxy and / or propoxy, n for a number from 5 to 100 and p for a number from 0 to 50.
Schließlich werden in einer weiteren Variante der Erfindung die erfindungsgemäßen Additive 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).Finally, in a further variant of the invention, the invention Additives used together with comb polymers. This means Polymers in which hydrocarbon radicals with at least 8, in particular at least 10 carbon atoms are attached 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 Copolymers have at least 20%, preferably at least 30%, of the monomers Side chains (see 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 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-A-0 320 766), ferner veresterte Olefin/ Maleinsäureanhydrid-Copolymere, Polymere und Copolymere von α-Olefinen und veresterte Copolymere von Styrol und Maleinsäureanhydrid.Examples of suitable comb polymers are 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 -alkylmaleimide (cf. EP-A- 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 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 8-150 Kohlenstoffatomen;
- R"
- xeine Kohlenwasserstoffkette mit 1 bis 10 Kohlenstoffatomen;
- m
- eine Zahl zwischen 0,4 und 1,0; und
- n
- eine Zahl zwischen 0 und 0,6.
- 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 with 8-150 carbon atoms;
- R "
- xa 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) der erfindungsgemäßen Additive mit
Paraffindispergatoren bzw. Kammpolymeren beträgt jeweils 1:10 bis 20:1,
vorzugsweise 1:1 bis 10:1.
Die erfindungsgemäßen Additive sind geeignet, die Kaltfließ- und
Schmiereigenschaften von tierischen, pflanzlichen oder mineralischen Ölen,
alkoholischen Treibstoffen wie Methanol und Ethanol, sowie Mischungen aus
alkoholischen Treibstoffen und mineralischen Ölen zu verbessern. Sie sind für die
Verwendung in 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 werden die erfindungsgemäßen
Additive in solchen Mitteldestillaten verwendet, die höchstens 500 ppm,
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. Die erfindungsgemäßen
Additive werden weiterhin vorzugsweise in solchen Mitteldestillaten verwendet, die
95 %-Destillationspunkte unter 370°C, insbesondere 350°C und in Spezialfällen
unter 330°C aufweisen. Die Wirksamkeit der Mischungen ist dabei besser als aus
den Einzelkomponenten und gegenüber den Mischungen gemäß dem Stand der
Technik zu erwarten wäre. Insbesondere zeichnen sich die erfindungsgemäßen
Additivkombinationen unter Cold Blending-Bedingungen aus, wenn die Temperatur
des Öls bei der Additivierung niedrig, d.h. unter 40°C, insbesondere unter 20°C und
speziell unter 10°C liegt.The mixing ratio (in parts by weight) of the additives according to the invention with paraffin dispersants or comb polymers is in each case 1:10 to 20: 1, preferably 1: 1 to 10: 1.
The additives according to the invention are suitable for improving the cold flow and lubricating properties of animal, vegetable or mineral oils, alcoholic fuels such as methanol and ethanol, as well as mixtures of alcoholic fuels and mineral oils. They are particularly well suited for use in middle distillates. Middle distillates are mineral oils that are obtained by distilling crude oil and boil in the range of 120 to 450 ° C, such as kerosene, jet fuel, diesel and heating oil. The additives according to the invention are preferably used in middle distillates which contain at most 500 ppm, in particular less than 200 ppm, and in special cases less than 50 ppm of sulfur. These are generally middle distillates which have been subjected to hydrogenation refining and which therefore contain only small amounts of polyaromatic and polar compounds which give them a natural lubricating effect. The additives according to the invention are furthermore preferably used in middle distillates which have 95% distillation points below 370 ° C., in particular 350 ° C. and in special cases below 330 ° C. The effectiveness of the mixtures is better than would be expected from the individual components and compared to the mixtures according to the prior art. In particular, the additive combinations according to the invention are distinguished under cold blending conditions if the temperature of the oil during the additive is low, ie below 40 ° C., in particular below 20 ° C. and especially below 10 ° C.
Die erfindungsgemäßen Additivkomponenten können Mineralölen oder Mineralöldestillaten getrennt oder in Mischung zugesetzt werden. Beim Einsatz von Mischungen haben sich Lösungen oder Dispersionen die 10 bis 90 Gew.-%, bevorzugt 20 - 80 Gew.-%, der Additivkombination enthalten bewährt. 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 Additive in ihren Schmier- und/oder Kaltfließeigenschaften verbesserte Mineralöle oder Mineralöldestillate enthalten 0,001 bis 2, vorzugsweise 0,005 bis 0,5 Gew.-% Additiv, bezogen auf das Destillat.The additive components according to the invention can be mineral oils or Mineral oil distillates can be added separately or in a mixture. When using Mixtures have solutions or dispersions of 10 to 90% by weight, preferably 20-80 wt .-%, the additive combination contain proven. 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 additives in their lubricating and / or cold flow properties improved mineral oils or Mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight additive, based on the distillate.
Die Additive können allein oder auch zusammen mit anderen Additiven verwendet
werden, z.B. mit anderen Stockpunkterniedrigern, Entwachsungshilfsmitteln,
Korrosionsinhibitoren, Antioxidantien, Leitfähigkeitsverbesserern,
Schlamminhibitoren, Dehazern und Zusätzen zur Erniedrigung des Cloud-Points. Die
Zugabe dieser Additive zum Öl kann zusammen mit den erfindungsgemäßen
Additivkomponenten oder separat erfolgen.
Die Wirksamkeit der erfindungsgemäßen Additive als Lubricity-Enhancer und
Kaltfließverbesserer wird durch die nachfolgenden Beispiele näher erläutert.The additives can be used alone or together with other additives, for example with other pour point depressants, dewaxing aids, corrosion inhibitors, antioxidants, conductivity improvers, sludge inhibitors, dehazers and additives for lowering the cloud point. These additives can be added to the oil together with the additive components according to the invention or separately.
The effectiveness of the additives according to the invention as a lubricity enhancer and cold flow improver is explained in more detail by the examples below.
Die Bestimmung der Siedekenndaten erfolgte gemäß ASTM D-86, die Bestimmung des CFPP-Werts gemäß EN 116 und die Bestimmung des Cloud Points gemäß ISO 3015.The boiling characteristics were determined in accordance with ASTM D-86 the CFPP value according to EN 116 and the determination of the cloud point according to ISO 3015.
Das Löslichkeitsverhalten der Additive wird entsprechend dem British-Rail Test wie
folgt bestimmt: 400 ppm einer auf 22°C temperierten Dispersion der
Additivkombination werden zu 200 ml des auf 22°C temperierten Testöls
(s. Tabelle 3) dosiert und 30 Sekunden kräftig geschüttelt. Nach 24 Stunden
Lagerung bei +3°C wird erneut 15 Sekunden geschüttelt und anschließend bei 3°C
in drei Portionen von je 50 ml über einen 1,6 µm-Glasfibermicrofilter (i 25 mm;
Whatman GFA, Best.-Nr. 1820025) filtriert. Aus den drei Filtrationszeiten T1, T2, und
T3 wird der ADT-Wert wie folgt berechnet:
Ein ADT-Wert < 15 wird als Anhaltspunkt dafür angesehen, daß das Gasöl in normal kalter Witterung zufriedenstellend verwendbar ist. Produkte mit ADT-Werten > 25 werden als nicht filtrierbar bezeichnet.An ADT value <15 is considered as an indication that the gas oil is normal cold weather can be used satisfactorily. Products with ADT values> 25 are described as not filterable.
Die Schmierwirkung der Additive wurde mittels eines HFRR-Geräts der Firma PCS Instruments durchgeführt. Die auf 22°C temperierten Additive werden dabei zu dem auf 22°C temperierten Öl dosiert und 30 Sekunden kräftig geschüttelt. Nach 24 Stunden Lagerung bei + 3°C wird das Öl gemäß den Bedingungen des British-Rail-Tests filtriert und am Filtrat die Schmierwirkung im HFRR-Test bestimmt. Der High Frequency Reciprocating Rig Test (HFRR) ist beschrieben in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986 und wird bei 60°C durchgeführt. Die Ergebnisse sind als Reibungskoeffizient (Friction) und Wear Scar (WSD) angegeben. Ein niedriger Reibungskoeffizient und ein niedriger Wear Scar zeigen eine gute Schmierwirkung.The lubricating effect of the additives was determined using an HFRR device from PCS Instruments performed. The additives tempered at 22 ° C become the dosed at 22 ° C oil and shaken vigorously for 30 seconds. To 24 hours storage at + 3 ° C, the oil is tested according to the conditions of the British Rail filtered and the lubricating effect on the filtrate determined in the HFRR test. The High Frequency Reciprocating Rig Test (HFRR) is described in D. Wei, H. Spikes, Wear, Vol. 111, No. 2, p. 217, 1986 and is carried out at 60 ° C. The Results are as a coefficient of friction (Friction) and Wear Scar (WSD) specified. Show a low coefficient of friction and a lower wear scar a good lubricating effect.
Bei den eingesetzten Fließverbesserern handelte es sich um ein EVA-Copolymer
(Vergleich) und folgende Vinylester-Olefin-Terpolymere (erfindungsgemäß).
Tabelle 2 gibt deren Eigenschaften an.
Für die anwendungstechnischen Tests wurden die Polymeren 50 %ig in Kerosin eingestellt.For the application tests, the polymers were 50% in kerosene set.
Die Bestimmung der Viskosität erfolgte mittels eines Rotationsviskosimeters (Haake RV 20) mit Platte-Kegel-Meßsystem bei 140°C, in Übereinstimmung mit ISO 3219 (B).The viscosity was determined using a rotary viscometer (Haake RV 20) with plate-cone measuring system at 140 ° C, in accordance with ISO 3219 (B).
Zur Verwendung als Fließverbesserer und/oder Lubricity-Additiv können die erfindungsgemäßen Additive ferner in Mischung mit Paraffindispergatoren eingesetzt werden.For use as a flow improver and / or lubricity additive, the Additives according to the invention are also used in a mixture with paraffin dispersants become.
Bei dem eingesetzten Wachsdispergator (F) handelt es sich um eine Mischung aus 2 Teilen eines Umsetzungsproduktes eines Terpolymers aus C14/16-α-Olefin, Maleinsäureanhydrid und Allylpolyglkol mit 2 Equivalenten Ditalgfettamin und einem Teil Nonylphenol-Formaldehydharz.The employed Wachsdispergator (F) is a mixture of 2 parts of a reaction product of a terpolymer of C 14/16 -α-olefin, maleic anhydride and 2 equivalents of di-tallow Allylpolyglkol with and a part of nonylphenol-formaldehyde resin.
Für die anwendungstechnischen Tests wurden beide Komponenten 50 %ig in Solvent Naphtha eingestellt.For the application tests, both components were 50% in Solvent naphtha discontinued.
Es wurden folgende öllösliche Amphiphile verwendet:
- Amphiphil 1:
- Glycerinmonooleat
- Amphiphil 2:
- Polyisobutenylbernsteinsäureanhydrid, mit Diethylenglykol zweifach verestert gemäß Beispiel 1 aus WO-97/45507
- Amphiphil 3:
- Ölsäurediethanolamid
- Amphiphil 4:
- C18H35-O-CH2-CH(OH)-CH2OH
(C18-Kette ist technischer Schnitt) - Amphiphil 5:
- Ölsäure
- Amphiphil 6:
- Tallölfettsäure
- Amphiphile 1:
- Glycerol monooleate
- Amphiphile 2:
- Polyisobutenyl succinic anhydride, twice esterified with diethylene glycol according to Example 1 from WO-97/45507
- Amphiphile 3:
- Oleic acid diethanolamide
- Amphiphile 4:
- C 18 H 35 -O-CH 2 -CH (OH) -CH 2 OH
(C 18 chain is technical cut) - Amphiphile 5:
- Oleic acid
- Amphiphile 6:
- Tall oil fatty acid
Zur Durchführung der erfindungsgemäßen und Vergleichsbeispiele werden die genannten Kaltfließverbesserer-Polymere und gegebenenfalls zusätzlich der genannte Wachsdispergator mit den genannten Amphiphilen gemischt. To carry out the inventive and comparative examples, the cold flow improver polymers mentioned and, if appropriate, additionally the wax dispersant mentioned are mixed with the amphiphiles mentioned.
Claims (11)
- 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 8-150 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 bedeuten, und wobei das Mischungsverhältnis
- 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 with 8-150 carbon atoms;
- R "
- a hydrocarbon chain of 1 to 10 carbon atoms;
- m
- a number between 0.4 and 1.0; and
- n
- represent a number between 0 and 0.6, and wherein the mixing ratio
Applications Claiming Priority (2)
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DE10000649 | 2000-01-11 | ||
DE10000649A DE10000649C2 (en) | 2000-01-11 | 2000-01-11 | Multi-functional additive for fuel oils |
Publications (2)
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EP1116781A1 true EP1116781A1 (en) | 2001-07-18 |
EP1116781B1 EP1116781B1 (en) | 2005-08-31 |
Family
ID=7627065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP00128083A Expired - Lifetime EP1116781B1 (en) | 2000-01-11 | 2000-12-21 | Polyfunctional additive for fuel oils |
Country Status (5)
Country | Link |
---|---|
US (1) | US6475250B2 (en) |
EP (1) | EP1116781B1 (en) |
JP (1) | JP2001234180A (en) |
CA (1) | CA2331027C (en) |
DE (2) | DE10000649C2 (en) |
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WO2003042338A2 (en) * | 2001-11-14 | 2003-05-22 | Clariant Gmbh | Additives for sulfur-poor mineral oil distillates comprising an ester of an alkoxylated polyol and an alkylphenol-aldehye resin |
EP1380634A1 (en) * | 2002-07-09 | 2004-01-14 | Clariant GmbH | Lubricity additives stabilised against oxidation for highly desulphurised fuel oils. |
EP1690896A1 (en) * | 2005-02-11 | 2006-08-16 | Infineum International Limited | Additives for oil compositions |
WO2011138400A1 (en) * | 2010-05-07 | 2011-11-10 | Basf Se | Terpolymer and use thereof to improve the low-temperature flow properties of middle-distillate fuels |
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JP2003515660A (en) * | 1999-11-30 | 2003-05-07 | インペリアル・ケミカル・インダストリーズ・ピーエルシー | Oil manufacturing additive formulation |
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DE10357880B4 (en) * | 2003-12-11 | 2008-05-29 | Clariant Produkte (Deutschland) Gmbh | Fuel oils from middle distillates and oils of vegetable or animal origin with improved cold properties |
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US20090090047A1 (en) * | 2007-10-04 | 2009-04-09 | Baker Hughes Incorporated | Additive Useful for Stabilizing Fuel Oils |
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US20110271586A1 (en) * | 2010-05-07 | 2011-11-10 | Basf Se | Terpolymer and use thereof for improving the cold flow properties of middle distillate fuels |
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Also Published As
Publication number | Publication date |
---|---|
JP2001234180A (en) | 2001-08-28 |
CA2331027A1 (en) | 2001-07-11 |
US6475250B2 (en) | 2002-11-05 |
DE50011065D1 (en) | 2005-10-06 |
US20010013196A1 (en) | 2001-08-16 |
DE10000649C2 (en) | 2001-11-29 |
CA2331027C (en) | 2009-09-22 |
DE10000649A1 (en) | 2001-07-19 |
EP1116781B1 (en) | 2005-08-31 |
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