Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen

Definitions

• the present invention relates to an additive which is a long-chain carboxylic acid and / or their derivatives, and one or more polymers containing hydroxyl groups includes, fuel oils containing such additives, and the use of such Additives to improve the lubricity of middle distillates.
• Mineral oils and mineral oil distillates used as fuel oils generally contain 0.5 wt .-% and more sulfur, when burning causes the formation of sulfur dioxide. To the resulting To reduce environmental pollution, the sulfur content of fuel oils lowered further and further.
• 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 based on copolymers of ethylene and unsaturated esters to synergistically improve the lubricating effect of highly desulfurized oils.
• EP-A-0 802 961 discloses fuel oils which improve their lubricating effect contain at least one hydroxyamine.
• WO-99/36 489 discloses the use of mixtures of monomeric and polymeric fatty acids to improve the lubricating effect of low sulfur Middle distillates.
• EP-A-0 807 676 discloses an additive to fuel oil, the Lubricity increases and that in addition to a carboxylic acid amide Cold flow improver and an ashless dispersant.
• 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.
• the lubricity additives of the prior art are the disadvantage that they improve their viscosity due to their high viscosity Handling used as a solution or dispersion in suitable solvents Need to become.
• the use of solvents requires increased Dosing rates and thus the transport of large quantities of substances.
• the non-polymeric Due to their amphiphilic character, additives often show a pronounced character Tendency to emulsify. As a result, the residual water in storage tanks becomes stable Emulsions brought with the middle distillates, which are then regarding corrosivity and Cold flow properties can cause problems.
• the object underlying the present invention was therefore to Find additive compositions that also in low emulsification tendency small amounts of additive are effective.
• additive combinations consist of oil-soluble Amphiphiles and copolymers containing hydroxyl groups are the state of the art show their own disadvantages in a significantly reduced manner.
• Another object of the invention are fuel oils, the said Contain additives.
• Another object of the invention is the use of additives for Improve the lubricating properties of fuel oils.
• Another object of the invention is a method for improving the Lubricity of fuel oils.
• the oil-soluble amphiphile (component A) preferably comprises a radical R 1 having 5 to 40, in particular 12 to 26, 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, in particular 2 to 6, 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 and at most 35, in particular at most 28 C atoms.
• 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, diethylene glycol and higher alkoxylation products, Glycerin, trimethylolpropane, pentaerythritol and sugar derivatives. Others too Polyols containing heteroatoms, such as triethanolamine, are suitable.
• the compounds that form component A of the additive to form fatty acids 10 to 22 carbon atoms can be saturated or unsaturated.
• Preferred components A are straight-chain saturated fatty acids with up to 18 carbon atoms such as caprylic acid (octanoic acid), capric acid (decanoic acid), Lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (Hexadecanoic acid), stearic acid (octadecanoic acid) and especially unsaturated Fatty acids such as oleic acid (octadecenoic acid), linoleic acid, linolenic acid and their Mixtures such as Rapeseed acid, soy fatty acid, sunflower fatty acid, Peanut fatty acid and tall oil fatty acid.
• caprylic acid octanoic acid
• capric acid decanoic acid
• Lauric acid diodecanoic acid
• myristic acid tetradecanoic acid
• palmitic acid Heexadecanoic acid
• stearic acid octadecano
• dimer and Oligomeric fatty acids such as those used in the oligomerization of unsaturated fatty acids arise, be present.
• oil-soluble partial esters of these fatty acids with polyols such as ethylene glycol, diethylene glycol and higher oligomers of alkylene oxides and glycerol, pentaerythritol, sorbitol, diethanolamine, triethanolamine and alkoxylated polyamines.
• Glycerol monooleate is particularly preferred.
• Esters which have at least two free OH groups and an alkyl radical having at least 8 C atoms are particularly preferred.
• the esters preferably have OH numbers between 10 and 200 mg KOH / g, preferably 20 to 150 mg KOH / g.
• R 3 preferably represents methyl or ethyl.
• 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 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 radical R 1 is derived, have 5 to 40, in particular 12 to 30, carbon atoms.
• the carboxylic acid preferably has one or two carboxyl groups.
• the carbon chain of the carboxylic acids can be straight-chain, branched, saturated or unsaturated.
• 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.
• Dimeric and trimer fatty acids such as those obtainable, for example, by oligomerizing unsaturated fatty acids, and alkenyl succinic acids can also be 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 copolymer which forms component B of the additive according to the invention contains free OH groups.
• the proportion of Structural units (B1) between 1 and 15, in particular 3 to 12 mol%.
• the copolymer has an OH number of 10 up to 300, in particular 20 to 200 mg KOH / g.
• the copolymer has an average molecular weight Mw of 700 up to 10,000 g / mol.
• the olefinically unsaturated compounds which the comonomers (B1) make up it is preferably vinyl esters, acrylic esters, mono- and Diesters of ethylenically unsaturated carboxylic acids, methacrylic esters, alkyl vinyl ethers and / or alkenes which are hydroxyalkyl, hydroxyalkenyl, hydroxycycloalkyl or Wear hydroxyaryl residues. These residues contain at least one hydroxyl group, which can be anywhere on the rest, but preferably on Chain end ( ⁇ position) or in para position for ring systems.
• Suitable vinyl esters include 2-hydroxyethyl vinyl esters, ⁇ -hydroxypropyl vinyl esters, 3-hydroxypropyl vinyl esters and 4-hydroxybutyl vinyl esters.
• Suitable acrylic esters include hydroxyethyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, hydroxyisopropyl acrylate, 4-hydroxybutyl acrylate and glycerol monoacrylate.
• the corresponding esters of methacrylic acid and also esters of ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with diols are equally suitable.
• Suitable alkyl vinyl ethers include 2-hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hexanediol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and cyclohexanedimethanol monovinyl ether.
• the alkenes are preferably monounsaturated Hydroxy hydrocarbons with 3 to 30 carbon atoms, especially 4 to 16 carbon atoms and especially 5 to 12 carbon atoms.
• Suitable Comonomers are, for example, acrylic acid or methacrylic acid, acrylic acid esters of alcohols with 1 to 20 carbon atoms, in particular methyl acrylate, ethyl acrylate, Propyl acrylate, butyl acrylate and ethylhexyl acrylate, as well as the corresponding Methacrylic acid esters, vinyl esters such as vinyl acetate, vinyl propionate, hexyl vinyl ester and Vinyl esters of neocarboxylic acids with 8, 9, 10, 11 or 12 carbon atoms, Vinyl ethers and olefins with 3 to 20 carbon atoms such as propene, butene, isobutene, Penten, hexene, 4-methylpentene, diisobutylene, norbornene are copolymerized.
• acrylic acid or methacrylic acid acrylic acid esters of alcohols with 1 to 20 carbon atoms, in particular methyl acrylate, ethyl acrylate,
• the melt viscosities of the copolymers at 140 ° C. are preferably below 10,000 mPas, especially between 10 and 2000 mPas and especially between 15 and 1000 mPas.
• Oil-soluble in the sense of the invention means that at least 10% by weight, preferably at least 1% by weight, in particular at least 0.1% by weight of the Additive is clearly soluble in the middle distillate to be added.
• copolymers which form component B of the additive according to the invention can be obtained by direct polymerization of compounds that are specified Structural units are obtained. It is also possible to use a to produce polymer-analogous implementation.
• the comonomers are copolymerized by known processes (cf. for this e.g. Ullmann's Encyclopedia of Technical Chemistry, 4th Edition, Vol. 19, Pages 169 to 178). Polymerization in solution, in suspension, in the gas phase and high pressure bulk polymerization. Preferably one turns high-pressure bulk polymerization, which is carried out at pressures of 50 to 400 MPa, preferably 100 to 300 MPa and temperatures of 50 to 350 ° C, preferably 100 to 300 ° C, is carried out.
• the reaction of the comonomers is determined by Radical initiators (radical chain initiators) initiated. To this Substance classes belong e.g.
• Oxygen, hydroperoxides, peroxides and Azo compounds such as cumene hydroperoxide, t-butyl hydroperoxide, dilauroyl peroxide, Dibenzoyl peroxide, bis (2-ethylhexyl) peroxidicarbonate, t-butyl permaleinate, t-butyl perbenzoate, dicumyl peroxide, t-butylcumyl peroxide, di- (t-butyl) peroxide, 2,2'-azobis (2-methylpropanonitrile), 2,2'-azobis (2-methylbutyronitrile).
• the initiators are used individually or as a mixture of two or more substances in quantities of 0.01 to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
• the desired melt viscosity of the copolymers is given Composition of the comonomer mixture by varying the Reaction parameters pressure and temperature and optionally by adding Moderators hired.
• Hydrogen, saturated or unsaturated hydrocarbons e.g. Propane, aldehydes, e.g. Propionaldehyde, n-butyraldehyde or isobutyraldehyde, ketones, e.g. Acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone or alcohols, e.g. Butanol, proven.
• the moderators become dependent on the desired viscosity in quantities up to 20 wt .-%, preferably 0.05 to 10 wt .-%, based on the Comonomer mixture used.
• High pressure bulk polymerization is carried out in known high pressure reactors, e.g. Autoclaves or tube reactors are carried out batchwise or continuously, Tube reactors have proven particularly useful. Solvents such as aliphatic Hydrocarbons or hydrocarbon mixtures, benzene or toluene, can be contained in the reaction mixture, although the solvent-free Working method has proven particularly successful.
• the Polymerization is the mixture of the comonomers, the initiator and, if provided used, the moderator, a tubular reactor via the reactor inlet and via one or more side branches fed.
• the comonomer streams be composed differently (EP-B-0 271 738).
• the lubricating effect of oils can be improved in the manner according to the invention by adding copolymers which are obtained by copolymers containing acid groups by oxalkylation.
• Suitable ethylene copolymers are, for example, those of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride.
• these copolymers containing acid groups are oxalkylated on the acid groups with C 1 -C 10 -alkylene oxides.
• Preferred alkylene oxides are ethylene oxide, propylene oxide and butylene oxide.
• the oxyalkylation is preferably carried out using 0.5 to 10 mol, in particular 1 to 5 mol and especially 1 to 2 mol of alkylene oxide per mol of acid group.
• the polymeric acid groups can also be reacted with at least bifunctional reagents which carry at least one OH function. Binding to the polymer can take place via hydroxyl groups as esters and / or via primary or secondary amino groups in the form of amides, imides and / or ammonium salts. To avoid crosslinking reactions, for example, an excess of bifunctional reagent and / or a high dilution can be used. The esterification, amidation or imidation generally takes place with the removal of water of reaction (azeotropic distillation, stripping with a gas stream such as N 2 ).
• the residual acid number is set to values ⁇ 150, preferably ⁇ 20, in particular ⁇ 10 mg KOH / g.
• Suitable reagents are, for example: ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, mixed alkoxylates of ethylene oxide, propylene oxide and / or butylene oxide with up to 50, in particular up to 10 units derived from ethylene oxide, propylene oxide and / or butylene oxide, glycerol, pentaerythritol, sorbitol, Ethanolamine, diethanolamine, triethanolamine, butyldiethanolamine, methyldiisopropylamine, aminopropanediol and alkoxylated polyamines.
• the latter can be derived, for example, from ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and their higher homologues, which are alkoxylated with 0.5 to 50, in particular 10 mol, ethylene oxide, propylene oxide and / or butylene oxide per H atom bound to an N atom .
• the reaction with the polymer can take place either via an OH group to form the ester or via a primary or secondary amino group to form the amide or imide.
• the conversion of the copolymers containing acid groups takes place between 30 and 250 ° C over the course of 0.5 to 20 hours.
• the hydroxy-functional reagent will with amounts of about 1 to about 2 moles per mole of polymerized Acid (derivative) implemented.
• the additives of the invention are mineral oils or mineral oil distillates preferably added as a mixture, the oil-soluble amphiphile A as a solvent for the copolymer B.
• Preferred mixtures are at temperatures flowable below 40 ° C, i.e. at this temperature they have a viscosity of less than 10 Pas, especially ⁇ 1Pas. If one is too high for processing
• the viscosity and / or intrinsic pour point of the mixture can be up to 50% by weight, in particular up to 20% by weight, based on the additive of a solvent be added.
• Solvents can be aliphatic and / or aromatic Be hydrocarbons.
• Mineral oils or mineral oil distillates contain 0.001 to 2, preferably 0.005 to 0.5% by weight additive, based on the distillate.
• the additives according to the invention can also be in the form of mixtures are used, which consist of additives of the claimed type, however differ in qualitative and / or quantitative composition.
• the mixing ratio (in parts by weight) of the additive components can be via a wide range and e.g. 20: 1 to 1:20, preferably 10: 1 to 1:10 be. In this way, the additives can be individually tailored Adjust requirements.
• 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 improve the lubricating effect of crude oils, lubricating oils or fuel oils.
• oil-soluble Co-additives are copolymers containing vinyl acetate or Terpolymers of ethylene, polar compounds that have a paraffin dispersion effect (paraffin dispersants), comb polymers, alkylphenol-aldehyde resins and oil-soluble amphiphiles.
• additives with copolymers have proven to be excellent, which contain 10 to 40% by weight of vinyl acetate and 60 to 90% by weight of ethylene.
• the terpolymers of vinyl neononanoate or In addition to ethylene, neodecanoic acid vinyl esters contain 10 to 35% by weight of vinyl acetate and 1 to 25% by weight of the respective new compound.
• copolymers contain in addition to ethylene and 10 to 35% by weight vinyl esters also 0.5 to 20% by weight Olefin such as diisobutylene, 4-methylpentene or norbornene.
• Olefin such as diisobutylene, 4-methylpentene or norbornene.
• the mixing ratio of the additives according to the invention with those described above Ethylene / vinyl acetate copolymers or the terpolymers of ethylene, Vinyl acetate and the vinyl esters of neononanoic or neodecanoic acid is (in Parts by weight) 20: 1 to 1:20, preferably 10: 1 to 1:10.
• the additives according to the invention furthermore in a mixture with paraffin dispersants be used.
• Paraffin dispersants reduce the size of the paraffin crystals and cause the paraffin particles not to settle, but colloidally with them significantly reduced sedimentation efforts, remain dispersed. Farther they increase the lubricating effect of the additives according to the invention.
• Paraffin dispersants have become oil-soluble polar compounds with ionic or polar groups, e.g.
• Amine salts and / or amides proven by reaction aliphatic or aromatic amines, preferably long-chain aliphatic Amines, with aliphatic or aromatic mono-, di-, tri- or tetracarboxylic acids or their anhydrides are obtained (cf. US Pat. No. 4,211,534).
• Other Paraffin dispersants are copolymers of maleic anhydride and ⁇ , ⁇ -unsaturated compounds, optionally with primary monoalkylamines and / or aliphatic alcohols can be implemented (cf. EP 0 154 177) Reaction products of alkenyl spirobis lactones with amines (cf.
• EP 0 413 279 B1 and according to EP 0 606 055 A2 reaction products of terpolymers based ⁇ , ⁇ -unsaturated dicarboxylic acid anhydrides, ⁇ , ⁇ -unsaturated compounds and Polyoxyalkylene ethers of lower unsaturated alcohols. Also alkylphenol aldehyde resins are suitable as paraffin dispersants.
• the copolymers according to the invention can be used in a mixture with alkylphenol-formaldehyde resins.
• these alkylphenol-formaldehyde resins are those of the formula 7 wherein R 6 is C 4 -C 50 alkyl or alkenyl, R 7 is ethoxy and / or propoxy, n is a number from 5 to 100 and p is a number from 0 to 50.
• the additives according to the invention are used together with comb polymers.
• comb polymers This is understood to mean polymers in which hydrocarbon radicals having at least 8, in particular at least 10, carbon atoms are bonded to a polymer backbone. They are preferably homopolymers whose alkyl side chains contain at least 8 and in particular at least 10 carbon atoms. In the case of copolymers, at least 20%, preferably at least 30%, of the monomers have side chains (cf. Comb-like Polymers-Structure and Properties; NA Plate and VP Shibaev, J. Polym. Sci. Macromolecular Revs. 1974, 8, 117 ff).
• Suitable comb polymers are, for example, fumara / vinyl acetate copolymers (cf. EP 0 153 176 A1), copolymers of a C 6 to C 24 ⁇ -olefin and an NC 6 to C 22 alkyl maleimide (cf. EP 0 320 766), also esterified olefin / maleic anhydride copolymers, polymers and copolymers of ⁇ -olefins and esterified copolymers of styrene and maleic anhydride.
• Comb polymers can be represented, for example, by Formula 8
• Paraffin dispersants, resins or comb polymers are each 1:10 to 20: 1, preferably 1: 1 to 10: 1.
• the additives according to the invention are suitable for the lubricating properties of animal, vegetable or mineral oils with only low dosage rates improve. In addition, they improve the cold properties of the additive oils.
• the emulsifying properties of the additive oils less impaired than with the lubricating additives of the prior art Case is.
• the additives of the invention are for use in middle distillates particularly well suited. Middle distillates are particularly those Mineral oils obtained from crude oil distillation and in the range of Boil 120 to 450 ° C, for example kerosene, jet fuel, diesel and heating oil.
• the additives according to the invention are preferably used in such middle distillates used, the 0.05 wt .-% sulfur and less, particularly preferably less than 350 ppm sulfur, especially less than 200 ppm sulfur and in in special cases contain less than 50 ppm sulfur. It is in the general to those middle distillates that are hydrogenated refining were subjected, and therefore only small proportions of polyaromatic and contain polar compounds that give them a natural lubricating effect to lend.
• the additives of the invention are also preferably in such middle distillates, the 95% distillation points below 370 ° C, in particular 350 ° C and in special cases below 330 ° C. You can also can be used as components in lubricating oils.
• the additives can be used alone or together with other additives e.g. with other pour point depressants or dewaxing aids, with Corrosion inhibitors, antioxidants, sludge inhibitors, dehazers and additives to lower the cloud point.
• other additives e.g. with other pour point depressants or dewaxing aids, with Corrosion inhibitors, antioxidants, sludge inhibitors, dehazers and additives to lower the cloud point.
• the polymers A1-A4 were obtained by high-pressure bulk polymerization from ethylene, Vinyl acetate and hydroxy-functional comonomers according to DE-A-197 57 830 manufactured.
• the hydroxy-functional comonomers are determined by determination the OH number by reacting the polymer with excess acetic anhydride and subsequent titration of the acetic acid formed with KOH.
• the viscosity is determined in accordance with ISO 3219 (B) using a rotary viscometer (Haake RV 20) with a plate and cone measuring system at 140 or 160 C. Characterization of the hydroxy-functional copolymers Example No. Comonomer (s) A1 Terpolymer of ethylene, 24% by weight vinyl acetate and 9% by weight hydroxyethyl methacrylate with a melt viscosity at 140 ° C of 200 mPas and an OH number of 43 mg KOH / g A2 Terpolymer of ethylene, 24% by weight of vinyl acetate and 12% by weight of hydroxyethyl vinyl ether with a melt viscosity at 140 ° C.
• the boiling data are determined in accordance with ASTM D-86, the CFPP value in accordance with EN 116 and the cloud point in accordance with ISO 3015. Characterization of the test oils Test oil 1 Test oil 2 Test oil 3 Initial boiling point [° C] 182 171 188 20% [° C] 202 227 220 30% [° C] 208 243 228 90% [° C] 286 322 270 95% [° C] 302 338 278 Cloud Point [° C] -29 -9.4 -29 CFPP [° C] -32 -11 -33 S content [ppm] 3rd 38 6 Density [g / cm 3 ] 0.819 0.830 0.810 WS 1.4 [ ⁇ m] 679 555 626
• HFRR High Frequency Reciprocating Rig Test
• a low coefficient of friction and a low wear scar show a good lubricating effect Wear Scar in Test Oil 1 example
• Additive Wear scar Friction Movie 1 150 ppm A1 50% in B1 437 0.21 49 2 200 ppm A1 50% in B1 375 0.16 69 3rd 400 ppm A1 50% in B1 310 0.13 67 4th 100 ppm A1 50% in B3 406 0.17 67 5 300 ppm A1 50% in B3 193 0.13 94 6 250 ppm A2 50% in B2 276 0.14 73 7 200 ppm A3 50% in B4 318 0.15 69 8th 200 ppm A2 50% in B5 290 0.14 75 9 200 ppm A3 50% in B6 370 0.16 71 10 (see) 600 ppm A1 (50% in SN) 484 0.29 14 11 (see) 600 ppm A2 (50% in SN) 473 0.26 19th 12 (See) 150 ppm B1 435 0.18 51 13 (see)
• the tendency to emulsify is determined in accordance with ASTM D-1094-85. For this, 80 ml of the diesel fuel in a 100 ml cylinder with the additive to be tested offset and 15 min. tempered at 60 ° C and shaken. After cooling down Room temperature, 20 ml of buffer solution pH 7.0 are added and 2 minutes shaken. After 5 minutes the sample is assessed optically.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Combustion & Propulsion (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Lubricants (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2000
  • 2000-03-16 DE DE10012946A patent/DE10012946B4/de not_active Expired - Fee Related
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