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, 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
• • 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
• • 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
  • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
  • C10L1/2387—Polyoxyalkyleneamines (poly)oxyalkylene amines and derivatives thereof (substituted by a macromolecular group containing 30C)
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B1/00—Engines characterised by fuel-air mixture compression
  • F02B1/02—Engines characterised by fuel-air mixture compression with positive ignition
  • F02B1/04—Engines characterised by fuel-air mixture compression with positive ignition with fuel-air mixture admission into cylinder
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
  • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
  • F02B3/00—Engines characterised by air compression and subsequent fuel addition
  • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

• the invention relates to fuels for gasoline engines or diesel engines which contain small amounts of esters of alkylalkanolamines or alkylaminopolyalkylene glycols with monocarboxylic acids and / or polycarboxylic acids as additives.
• Carburetors and intake systems of gasoline engines are increasingly contaminated by contaminants caused by dust particles from the air, unburned hydrocarbon residues from the combustion chamber and the crankcase ventilation gases that are led into the carburetor.
• the first additive generation could only prevent the formation of deposits in the intake system, but not remove existing deposits, whereas the modern additives of the second generation can do both ("keep-clean” and "clean-up effect"), in particular due to their improved thermal stability at zones of higher temperatures, namely at the inlet valves.
• Esters of such, especially higher, carboxylic acids with aliphatic alcohols are used less frequently because of their often difficult preparative accessibility.
• thermostable solvent components e.g. mineral oils or synthetic oils
• the formulations must contain higher-boiling, thermostable solvent components (e.g. mineral oils or synthetic oils) that facilitate the drainage of the products from the inlet valves.
• the amount of the ester according to the invention contained in the fuels is generally 10 to 5000 mg, preferably 50 to 2000 mg, in particular 100 to 1000 mg, of the ester per kg of fuel.
• the ester additives to be used according to the invention are generally synthesized in several stages.
• a first step it is expedient to prepare by alkoxylation with alkylene oxides having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, in particular 2 to 4 carbon atoms, or mixtures of these alkylene oxides of primary or secondary amines of the general formula III in which R 1 is a C 6 to C 30 alkyl radical, preferably a C 6 to C 24 alkyl radical, in particular a C 6 to C 2o alkyl radical, and R 5 is a C 6 to C 3o alkyl radical, preferably is a C 6 - to C 24 -alkyl radical, in particular a C 6 - to C 2o-alkyl radical, or hydrogen, where R 1 and R 5 as alkyl radicals can be the same or different, the alkylalkanolamines or alkylaminopolyalkylene glycol in a manner known per se general formula 1 ago.
• the alkoxylation is optionally carried out in the presence of alkali such as potassium hydroxide solution, sodium hydroxide solution, sodium methylate, advantageously at elevated temperatures, for example at temperatures from 80 to 160 ° C., preferably 100 to 160 ° C.
• alkali such as potassium hydroxide solution, sodium hydroxide solution, sodium methylate
• Suitable alkylene oxides are, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, isobutylene oxide, 1,2-pentene oxide, ethylene oxide being preferred.
• amines III which may be mentioned are hexylamine, dihexylamine, cyclohexylamine, dicyclohexylamine, octylamine, dioctylamine, decylamine, didecylamine, isotridecylamine, diisotridecylamine, cetylamine, dicetylamine, stearylamine, distearylamine, cerylamine, dicerylamine.
• the secondary amines are preferably used.
• the amine is prepared in a manner known per se, e.g. in the presence of water, reacted with 1 mol of alkylene oxide or a mixture of alkylene oxides per 1 mol of secondary amine III or with 2 mol of alkylene oxide or a mixture of alkylene oxides per 1 mol of primary amine III (see, for example, SP McManus et al. Synth. Commun 1973, 177).
• the alkylalkanolamines thus obtained are expediently reacted with an amount of alkylene oxides such that m in the hydroxyalkyl radicals of the alkylaminopolyalkylene glycols obtained is 1 to 100, preferably 1 to 50, in particular 1 to 30.
• the compounds of formula I obtained are then in a further step to the esters of carboxylic acids and / or polycarboxylic acids according to methods of ester formation known per se, e.g. implemented by esterification processes or transesterification processes.
• the methods of ester formation are e.g. in Houben-Weyl, Methods of Organic Chemistry, Volume VIII, Oxygen Compounds III (1952), pages 516 to 555.
• the ester formation is generally carried out at temperatures from 40 to 220 ° C., preferably 50 to 200 ° C., in particular 60 to 180 ° C.
• the esterification can be carried out with and without a catalyst.
• the esterification is preferably carried out in the presence of acidic catalysts, for example mineral acids such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid, and Lewis acids such as BF 3 , dibutyltin dilaurate.
• a volatile, water-insoluble diluent such as benzene, toluene, xylene or else chloroform and carbon tetrachloride.
• esters are conveniently prepared via transesterification, starting from the esters of carboxylic acids and / or polycarboxylic acids with lower alcohols such as methanol, ethanol, propanol, by their reaction with the compounds of the general formula I in the presence of basic or acidic catalysts, preferably Lewis acidic catalysts with expedient removal of the lower alcohol released by distillation.
• lower alcohols such as methanol, ethanol, propanol
• the carboxylic acids on which the esters are based include, for example, aliphatic, cycloaliphatic and aromatic monocarboxylic acids and polycarboxylic acids, which may still be substituted, for example as hydroxymonocarboxylic acids and hydroxypolycarboxylic acids or amino, imino and nitrilomonocarboxylic acids and polycarboxylic acids.
• the carboxylic acids have 4 to 26, preferably 5 to 20 C atoms.
• the polycarboxylic acids which are preferably used are generally those having 2 to 6, preferably 2 to 4, carboxyl groups.
• aliphatic monocarboxylic acids examples include Caproic acid, n-heptylic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid.
• Suitable aromatic monocarboxylic acids are e.g. Benzoic acid and substituted benzoic acids such as toluic acids.
• Suitable aliphatic polycarboxylic acids are e.g. Dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and citric acid.
• Aromatic polycarboxylic acids include e.g. Phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, mellitic acid into consideration.
• polycarboxylic acids are nitrilotriacetic acid and ethylenediaminetetraacetic acid.
• esters according to the invention are generally obtained as colorless to light yellow, in some cases. viscous, oily products, which are often similar to lubricants in their physical properties.
• esters according to the invention are their excellent thermal stability, which results from the results of thermogravimetric or differential thermal analysis measurements.
• esters according to the invention can be prepared in a simple manner in good yield from the higher carboxylic acids and the aminoalkanol compounds I, since it was known that esters of such carboxylic acids with aliphatic alcohols, i.e. Alcohols that do not contain amino groups are often difficult to obtain from a preparative perspective.
• the carrier oils have an additional washing function, often also a synergistic effect in combination with the detergents.
• the carrier oils are usually high-boiling, viscous, thermostable liquids. They coat the hot metal surface (e.g. the inlet valves) with a thin liquid film and thereby prevent or delay the formation or deposition of decomposition products on the metal surfaces.
• high-boiling, refined mineral oil fractions mostly vacuum distillates
• a particularly good carrier oil is Brightstock in combination with low-boiling, highly refined lubricating oil fractions.
• Synthetic components have also been used as carrier oils.
• Esters in particular have been described as suitable carrier oils (e.g. DE 10 62 484, DE 21 29 461 and DE 23 04 086).
• the carrier oils are generally added to the fuels in an amount of 50 to 5000 mg, preferably 100 to 2000 mg, of carrier oil per kg of fuel.
• the ester is tested as an additive, especially for its suitability as a valve and carburetor cleaner, by means of an engine test according to CEC-F-02-T 79 in an Opel Kadett 1.2-1 engine.
• the alkylene oxide is introduced in a 10 mol% excess, based on the N-H bonds of the amine to be reacted, at a pressure of 10 to 30 bar.
• Primary amines are alkoxylated twice.
• the ⁇ -aminoalkanols thus obtained are used for the esterification.
• a dewatered mixture of the ⁇ -aminoalkanol from Example 1 and KOH used as starter is placed in a pressure vessel, the amount of KOH used being approximately 0.1% of the total weight of the reaction product to be expected. It is purged several times with nitrogen, preheated to the temperatures given in Example 1 and then, with stirring at constant temperature and a pressure between 10 and 30 bar, the alkylene oxide is fed in continuously or batchwise, via an immersion tube or onto the surface until the desired viscosity is reached is.
• the solvent is removed by distillation, lastly by applying a water jet vacuum; if necessary, filter.
• the adipic acid diester is obtained as a yellow oil.
• trimellitic acid triester is obtained from 1 mol of trimellitic anhydride and 3.1 mol of diisotridecylethanolamine.
• the corresponding tetraester is obtained from 1 mol of ethylenediaminetetraacetic acid and 4.2 mol of diisotridecylethanolamine.
• the following table shows the results of the application tests.
• the effect of known detergents and the carboxylic acid alkanolamine esters used according to the invention, in combination with synthetic carrier oils in gasoline for internal combustion engines, are compared here.
• the amounts of detergents and carrier oils specified in the table were added to premium gasoline (unleaded, RON 95) according to DIN 51607, which was used in test bench tests with a 1.2-1 Opel Kadett engine according to CEC-F-02-T-79 were.
• the reference oil RL 51 was used as engine oil.

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• 1990
  • 1990-06-29 DE DE4020664A patent/DE4020664A1/de not_active Withdrawn
• 1991
  • 1991-06-20 DE DE91110146T patent/DE59100880D1/de not_active Expired - Lifetime
  • 1991-06-20 EP EP91110146A patent/EP0464489B1/fr not_active Expired - Lifetime
  • 1991-06-24 US US07/720,066 patent/US5194068A/en not_active Expired - Fee Related
  • 1991-06-28 CA CA002046004A patent/CA2046004C/fr not_active Expired - Fee Related

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