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WO2004087789A2 - Procede de fabrication d'une composition de polyether - Google Patents

Procede de fabrication d'une composition de polyether Download PDF

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Publication number
WO2004087789A2
WO2004087789A2 PCT/EP2004/003365 EP2004003365W WO2004087789A2 WO 2004087789 A2 WO2004087789 A2 WO 2004087789A2 EP 2004003365 W EP2004003365 W EP 2004003365W WO 2004087789 A2 WO2004087789 A2 WO 2004087789A2
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polyether
oxide
polyether composition
alkylene oxides
mol
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German (de)
English (en)
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WO2004087789A3 (fr
Inventor
Hans Peter Rath
Ulrich Treuling
Marc Walter
Arno Lange
Helmut Mach
Ernst Langer
Georg Heinrich Grosch
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BASF SE
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BASF SE
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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 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
    • 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
    • C10L1/1985—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 polyethers, e.g. di- polygylcols and derivatives; ethers - esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C08G65/3255—Ammonia
    • 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
    • C10L1/22—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)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M133/08—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/30—Polyoxyalkylenes of alkylene oxides containing 3 carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/32—Polyoxyalkylenes of alkylene oxides containing 4 or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
    • C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/24—Polyethers
    • C10M145/26—Polyoxyalkylenes
    • C10M145/36—Polyoxyalkylenes etherified
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/106—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing four carbon atoms only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof

Definitions

  • the present invention relates to a process for the preparation of a polyether composition
  • a polyether composition comprising polyethers having a polyether chain which contains a higher proportion of alkylene oxide repeating units of oxides which are not derived from linear ⁇ -olefins but from branched olefins and / or olefins Derive ⁇ -permanent double bond.
  • the invention further relates to the polyether compositions obtained by this process and their use in the additization of fuels and lubricants.
  • EP-A-0 862 947 describes a process for the preparation of double metal cyanide catalysts and their use for the production of polyether alcohols.
  • WO 99/16775 describes crystalline multimetal cyanide complexes and their use as catalysts for the preparation of polyether polyols by reacting diols or polyols with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.
  • WO 00/14045 describes a process for the preparation of fatty alcohol alkoxylates by alkoxylation of monohydric aliphatic alcohols with ethylene oxide, propylene oxide and / or butylene oxide in the presence of a double metal cyanide catalyst. None of these documents contains an indication of the suitability of multimetal cyanide catalysts for the production of polyether compounds which contain relatively large amounts of alkylene oxides which are not derived from oxides of linear I-01efins.
  • WO 00/74843 and WO 00/75845 describe platelet-shaped multimetal cyanide compounds and their use for the production of polyether alcohols.
  • suitable alkylene oxides for the preparation of the polyether alcohols are also those which are not derived from 1,2-olefins.
  • the catalysts used are suitable for the preparation of polyether compounds which contain a larger proportion of repeating units of alkylene oxides which are not derived from oxides of linear I-01efins.
  • Carburetors and intake systems of gasoline engines, but also injection systems for fuel metering are increasingly contaminated with 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.
  • detergents are added to the fuel to keep valves and carburettors or injection systems clean.
  • Such detergents are generally used in combination with one or more so-called carrier oils.
  • the carrier oils generally serve not only as a formulation basis, but also perform an additional "washing function", i. H. they often support and promote the detergents in their cleansing and purely preserving action and can thus help to reduce the amount of detergents required.
  • Viscous, high-boiling and in particular thermostable liquids are usually used as carrier oils. They coat the hot metal surfaces, e.g. B. the inlet valves, with a thin film of liquid and thereby prevent or delay the formation and deposition of decomposition products on the metal surfaces.
  • carrier oils are, for example, high-boiling refined mineral oil fractions, but also synthetic liquids such as oil-soluble polyethers from alkylene oxides or adducts of alkylene oxides with alcohols.
  • Adducts of alkylene oxides with alcohols are known, for example, from DE-A-21 29 461.
  • carrier oils based on polyethers or adducts of alkylene oxides with short-chain alcohols as starters can be obtained simply and inexpensively, but as a rule show an insufficient compatibility with modern detergent additives, in particular detergent additives based on polyisobutenes, so that they separate can come.
  • EP-A-0 277 345 describes adducts of ethylene oxide, propylene oxide and / or butylene oxide with polybutyl or polyisobutyl alcohols as carrier oils for fuel and lubricant compositions.
  • the adducts are prepared in the presence of basic catalysts.
  • EP-A-0 398 100 describes fuel compositions for internal combustion engines which contain alkoxylation products which can be obtained by reacting mixtures of oxo alcohols with more than 8 C atoms and alkylene oxides with 2 to 4 C atoms.
  • the only alkylene oxides used are linear 1,2-olefins derived alkylene oxides such as ethylene oxide, propylene oxide and 1,2-butylene oxide are used.
  • WO 00/50543 describes polyalkylene alcohol polyalkoxylates and their use in fuels and lubricants.
  • suitable alkylene oxides are also cis and trans-2,3-butylene oxide and 1,3-propylene oxide, 1,4-butylene oxide, 1,6-hexylene oxide and 1,8-octylene oxide.
  • propylene oxide and 1,2-butylene oxide are used in the exemplary embodiments.
  • alkoxylates of alkylene oxides which are not based on 1,2-olefins cannot be prepared.
  • All of the aforementioned carrier oils have at least one of the following disadvantages. They require the use of expensive starting materials, such as propene or 1-butene; their preparation requires long polymerization times; their compatibility with modern detergent additives, such as polyisobutene and polyisobutene derivatives, is still in need of improvement, especially pure propene derivatives are incompatible.
  • the last aspect concerns above all the viscosity properties of the polymer portion contained in the additive.
  • the lowest possible viscosity of the polymer component used is particularly important in order to avoid the undesirable effect of the so-called "valve plug".
  • "Valve plugging” means the complete loss of compression on one or more cylinders of the internal combustion engine if - caused by deposits, e.g. B. polymeric deposits on the valve stem - the spring forces are no longer sufficient to close the valves properly.
  • Polyether compounds are not only suitable as carrier oils, but e.g. B. in the form of polyetheramines and polyetheramine derivatives also as detergents for fuels and lubricants.
  • WO 85/01956 describes fuel and lubricant additives which contain polyether polyamines.
  • EP-A-0 244 616 describes fuel and lubricant compositions which contain polybutyl or polyisobutyl amines.
  • EP-A-0 356 725 describes fuels for gasoline engines which contain a polyetheramine and / or polyetheramine derivative as an additive.
  • WO 00/61708 describes polyalkylene alcohol polyether amines and their use in fuels and lubricants.
  • EP-A-0 687 699 describes the preparation of hydroxy-functionalized polybutylene oxide ether compositions by polymerizing Cj epoxides in the presence of acid-activated clays, such as montmorillonite, as catalysts. Among other things, these are said to be suitable as intermediates for the production of fuel and lubricant additives. This process is still in need of improvement.
  • the object of the present invention is to provide an improved process for the production of polyether compositions for further processing into fuel and lubricant additives.
  • the polyether composition obtained is additionally subjected to an amino functionalization to obtain a polyether composition which contains amino- and / or polyamino-terminated polyethers.
  • Ci-C ß -alkyl includes straight-chain and branched Ci-Cg-alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3, 3- Dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1,2,2-tri
  • Suitable longer-chain C 8 -C 20 -alkyl groups are straight-chain and branched alkyl groups. These are preferably alkyl residues such as those found in natural fatty alcohols or alcohols which are commercially available, e.g. B. oxo alcohols occur. These include e.g. B. octyl, nonyl, decyl ⁇ undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecy1, heptadecy1, octadecyl, motoronecyl etc.
  • Cycloalkyl is preferably Cs-Cs-cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • heterocycloalkyl for the purposes of the present invention encompasses saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur, and can optionally be substituted.
  • heterocycloaliphatic groups examples include pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, Morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydro- furanyl, Tetrahydropyrany1, dioxanyl.
  • Aryl comprises unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl, tolyl, xylyl or mesityl.
  • Hetaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
  • Alkylene oxides or alkylene oxide mixtures are preferably used to prepare the polyether compositions according to the invention, so that the polyethers contained therein contain at least 10 mol% of repeating units of alkylene oxides of the general formula I, based on the total proportion of repeating ether units.
  • the polyethers particularly preferably contain 10 to 90 mol%, particularly preferably 20 to 80 mol%, in particular 25 to 70 mol% and especially 30 to 65 mol% of repeating units of alkylene oxides of the general formula I incorporated.
  • alkylene oxides of the general formula I are preferably selected from 2,3-butene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 2,3-pentene oxide, 2-meth 1,2-1,2-butene oxide and 3-methyl 1,2-butene oxide, 2, 3-hexene oxide, 3, 4-hexene oxide,
  • These also preferably include mixtures obtainable by oxidation of olefin streams which are commercially available and which may contain further alkylene oxides and / or olefins and / or inerts (alkanes) not covered by the oxidation.
  • the alkylene oxides of the formula I are preferably selected from ice-2,3-butene oxide, trans-2,3-butene oxide, 2-methyl-1,2-propene oxide and mixtures thereof. This also includes mixtures which contain further alkylene oxides and / or saturated and unsaturated hydrocarbons.
  • the polyethers of the polyether composition according to the invention preferably contain at most 70 mol%, particularly preferably at most 60 mol% and in particular at most 50 mol% of repeating units of alkyl-1,2-alkene oxides, such as 2-methyl-1,2-pro- built in penoxid.
  • alkyl-1,2-alkene oxide repeating units in particular of 2-methyl-1,2-propene oxide repeating units in the polyether compositions according to the invention can be advantageous for setting the desired product properties.
  • polyether compounds based on 2-methyl-1,2-propene oxide generally have a good effect as a carrier oil for detergents and dispersants in fuel and lubricant compositions even at lower molecular weights than polyether compounds which do not contain isobutene oxide
  • polyethers can contain further, different alkylene oxide repeating units incorporated therein.
  • polyethers in which the polyether chain additionally contains repeating units of alkylene oxides which are selected from compounds of the general formula II
  • R 5 represents hydrogen or Ci-C ⁇ -alkyl.
  • the compounds of the formula II are preferably selected from ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,2-pentylene oxide, 1,2-hexylene oxide and mixtures thereof.
  • the alkylene oxides of the formula II are particularly preferably selected from 1,2-propene oxide, 1,2-butene oxide and mixtures thereof.
  • the compounds of formula II can preferably also be used in the form of mixtures obtained by oxidation of olefin streams which are commercially available. These can additionally contain alkylene oxides of the general formula I, other alkylene oxides different from alkylene oxides of the formulas I and II, olefins and / or inerts (alkanes) not affected by the oxidation.
  • Alkylene oxide mixtures which are derived from industrially available olefin mixtures are preferably used for the production of the polyether chains.
  • examples of such mixtures of alkylene oxides are the oxidation or epoxidation products of olefin-rich hydrocarbon streams in which the proportion of alkylene oxides of the formula I is in the ranges given above.
  • Preferred olefin mixtures which are available on an industrial scale result from the hydrocarbon splitting in petroleum processing, for example by cat cracking, such as fluid catalytic cracking (FCC), thermal cracking or hydrocracking.
  • a preferred technical olefin mixture is the C 4 cut .
  • C 4 cuts are available, for example, by fluid catalytic cracking of gas oil, steam cracking from ethane to gas oil and in particular by steam cracking from naphtha or LPG (liquefied petroleum gas) for the production of ethene and propene.
  • LPG liquefied petroleum gas
  • a distinction is made between the total C 4 cut the so-called raffinate I obtained after the separation of 1,3-butadiene and the raffinate II obtained after the isobutene separation.
  • the HC 4 fraction is also suitable, ie a total C 4 cut , the butadiene portion of which has been hydrogenated to a mixture of 1-butene and ice and trans-2-butene.
  • the C 4 cuts obtained may also contain saturated and unsaturated hydrocarbons with a lower or higher number of carbon atoms than 4, such as propane, propene, pentanes, pentenes, hexanes, hexenes etc. These olefin mixtures can also be used use advantageously for the production of polyether compounds.
  • a mixture of alkylene oxides obtained from raffinate I and having the following composition is suitable for the process according to the invention: about 3.4 mol% of isobutane; approximately
  • a mixture of alkylene oxides which was obtained from raffinate II and has the following composition, is also suitable: approximately 6.2 mol% of isobutane; about 13.3 mole percent n-butane; about 55.6 mole percent 1,2-butene oxide; about 14.6 mol% 2,3-trans-butene oxide; approximately
  • the number of alkylene oxide repetition units is preferably in a range from 2 to 200, particularly preferably 4 to 150 and in particular 6 to 100.
  • polyether compositions obtained by the process according to the invention comprise polyether chains which contain repeating units of two or more than two different alkylene oxides of the general formula I and, if appropriate, of the general formula II, these can be arranged statistically or in the form of blocks in the polyether chain, statistical sections can also alternate with sections made up of (chemically uniform) blocks.
  • a minimum degree of alkoxylation of the polyethers is achieved such that the oxygen content in the at least one polyether chain is at least 16.5% by weight, particularly preferably at least 17.5% by weight and in particular at least 18.5% by weight of the number average molecular weight of the polyether.
  • Suitable radicals R 6 of the compounds R 6 -0H are straight-chain or branched hydrocarbon radicals having preferably 9 to 18 carbon atoms, preferably 10 to 16 carbon atoms and in particular 12 to 15 carbon atoms.
  • Suitable hydrocarbon residues are those obtained from alcohols, e.g. B.
  • fatty alcohols such as 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, cetyl alcohol or stearyl alcohol, or oxo alcohols, as is usually done by hydroformylation of linear or branched olefins with 7 up to 19 carbons are obtained, or from alcohols such as those starting from olefins having 8 to 20 carbon atoms either by ozonolysis and subsequent reduction or by epoxidation and subsequent reduction or by hydroboration and subsequent oxidative cleavage with H 2 0 2 or by halogenation with Chlorine or bromine and subsequent alkaline hydrolysis are obtained.
  • oxo alcohols such as 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, cetyl alcohol or stearyl alcohol, or o
  • radicals R 6 are also suitable as radicals R 6 , for example those which are derived from the abovementioned alcohols or are obtained during their preparation, such as, for example, B. raw products and individual fractions, such as those obtained in the distillative processing of the raw products.
  • suitable mixtures from which the radical R 6 can be derived are so-called oxo oils or oxo oil fractions, as are regularly obtained in the production of oxo alcohols.
  • tridecanol N An alcohol mixture which is obtained by trimerization of butene and subsequent hydroformylation and hydrogenation and is referred to as tridecanol N is advantageously suitable as starter R 6 -0H.
  • Suitable starters R 6 -0H are furthermore alicyclic and aromatic hydroxy compounds, preferably compounds of the formulas
  • R 9 , R 10 and R 11 independently of one another represent hydrogen or C 1 -C 3 o-alkyl.
  • Preferred alicyclic and aromatic hydroxy compounds as starters are cyelohexanol, phenol, the cresol isomers, isobutylphenol, isobutylcresol, diisobutylphenol, diisobutylcresol tert.-butylphenol, tert.-butylcresol, di-tert.-butylphenyl di-tert.-but. , Isooctylphenol, diisooctylphenol, isononylphenol, diisononylphenol, isododecylphenol, diisododecylphenol and mixtures thereof.
  • the polyether composition obtained by the process according to the invention preferably contains at least one compound of the general formula III
  • the order of the alkylene oxide units is arbitrary, two of the radicals R 1 to R 4 are Ci-Cg-alkyl and the rest are hydrogen or Ci-C ⁇ -alkyl,
  • R 5 represents hydrogen or -CC 6 alkyl
  • R 6 represents C 8 -C 2 o-alkyl, optionally alkylated cyclohexyl or optionally alkylated aryl,
  • X represents OH or NR 7 R 8 , where R 7 and R 8 independently of one another are hydrogen, alkyl, cycloalkyl, heterocycloalkyl, aryl, hetaryl, aminoalkylene, polyaminoalkylene, polyoxyalkylene or R 7 and R 8 together with the nitrogen atom to which they are attached are a 5- to 8-membered heterocycle,
  • n for an integer from 1 to 200 and
  • n an integer from 0 to 200
  • n / (n + m) is at least 0.1.
  • starters compounds having active hydrogen atoms
  • alkylene oxides which are do not derive from linear ⁇ -olefins, do not react or react only if uneconomically long reaction times are used.
  • multimetal cyanide catalysts When using alkylene oxide mixtures which contain alkylene oxides based on linear ⁇ -olefins and those based on different olefins (more highly branched or with internal double bonds), essentially only the alkylene oxides derived from linear ⁇ -olefins react. If, on the other hand, acid-activated clays are used as catalysts, generally only an incomplete implementation of the starter used results. Surprisingly, it has now been found that these disadvantages are avoided if a so-called double metal or multimetal cyanide catalyst (hereinafter referred to as multimetal cyanide catalysts) is used for the alkoxylation.
  • multimetal cyanide catalysts so-called double metal or multimetal cyanide catalyst
  • a polyether composition containing polyethers which contain at least one block with repeating units of alkylene oxides of the general formula I and at least one block with repeating units of alkylene oxides of the general formula II only the build-up of blocks of alkylene oxides I in the presence of a Multimetal cyanide catalyst take place.
  • a conventional catalyst can be used to build blocks of alkylene oxides II. So you can z.
  • B. polymerize a 1-butene oxide-containing mixture for block formation first in the presence of a conventional basic catalyst and, after removing the basic catalyst, continue the polymerization in the presence of a multimetal cyanide catalyst.
  • Multimetal cyanide catalysts which are suitable for the preparation of the alkanol-polyalkoxylate compounds according to the invention are known to the person skilled in the art, eg. B. from EP-A-0 654 302, EP-A-0 700 949, EP-A-0 743 093, EP-A-0 755 716, EP-A-0 862 947, WO 97/40086, WO 98/16310, WO 99/16775, WO 00/14045, WO 00/74843 and WO 00/74845. These documents are expressly and fully referred to.
  • multimetal cyanide catalysts containing a multimetal cyanide complex compound of the general formula IV are suitable
  • M 1 at least one metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Co 3+ , Ni + , Mn 2+ , Co 2+ , Sn 2+ , Pb 2+ , Mo + , Mo6 +, Al 3+ , V + , V 5+ , Sr + , W + , W6 +, Cr 2+ , Cr 3+ , Cd 2+ ,
  • M 2 at least one metal ion selected from the group consisting of Fe + , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , Ir 3+
  • A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
  • X is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate or nitrate,
  • L is a water miscible ligand selected from the
  • a, b, c, d, g and n are selected so that the electro-neutrality of the connection is ensured, e is the coordination number of the ligand,
  • f is a fractional or whole number greater than 0 or 0 and
  • Preferred multimetal cyanide catalysts of the formula IV are those which have one or more of the following features:
  • the multimetal cyanide complex compounds of the formula IV are preferably applied to solid, inert, non-foamed supports or introduced into them or shaped into shaped bodies.
  • Multimetal cyanide catalysts which are produced in the presence of surface-active substances, are particularly suitable for the preparation of the alkanol-polyalkoxylate compounds according to the invention, for example by the following process steps:
  • M 1 contains at least one metal ion selected from the group comprising Zn 2+ , Fe 2+ , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Pb 2+ , Fe 3+ , Mo + , Mo6 +, Al 3+ , V 5+ , Sr + , W 4+ , W 6+ , Cu 2 +, Cr 2+ , Cr 3+ , Cd 2+ , Hg 2+ , Pd 2 +, Pt 2+ , V 2+ , Mg 2+ , Ca 2+ , Ba 2+ and mixtures thereof,
  • X at least one anion, selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, carboxylate, especially formate, acetylene, tat, propionate, oxalate, nitrate and m and n are integers that satisfy the valences of M 1 and X,
  • M 2 is at least one metal ion selected from the group comprising Fe 2+ , Fe 3+ , Co 3+ , Cr 3+ , Mn 2+ , Mn 3+ , Rh 3+ , Ru 2+ , Ru 3+ , V + , V 5+ , Co 2+ , Ir 3+ and Cr 2+ means and M 2 can be the same or different M 1 ,
  • H is hydrogen or a metal ion, usually an alkali metal, alkaline earth metal or ammonium ion
  • A is at least one anion selected from the group comprising halide, hydroxide, sulfate, carbonate, cyanate, thiocyanate, isocyanate, carboxylate or nitrate, in particular whose cyanide means, where A can be the same or different X, and ß are an integer greater than zero and ⁇ and ⁇ are integers greater than or equal to zero, which are selected so that the electroneutrality of the cyanide compound is ensured,
  • one or both solutions may optionally contain at least one water-miscible, heteroatom-containing ligand which is selected from the group consisting of alcohols, ethers, esters, ketones, aldehydes, carboxylic acids, amides, sulfides or mixtures of at least two of the compounds mentioned,
  • step b) optionally combining the aqueous suspension formed in step a) with a ligand containing water-miscible heteroatoms, selected from the group described, which may be the same or different from the ligand from step a),
  • the platelet-shaped multimetal cyanide compounds obtained in this way are preferably crystalline and can have a cubic, tetragonal, trigonal, orthorobic, hexagonal, monoclinic or triclinic crystal system.
  • cyanometalate hydrogen acids which can preferably be used, are stable and easy to handle in aqueous solution. Their production can, for example, as in W. Klemm, W. Brandt, R. Hoppe, Z. Anorg. Gen. Che. 308, 179 (1961), starting from the alkali metal cyanometalate via the silver oxyanometalate to cyanometalate hydrogen acid.
  • Another possibility is to convert an alkali metal or alkaline earth metal cyanometalate into a cyanometalate hydrogen acid using an acidic ion exchanger, as described, for example, in F. Hein, H. Lilie, Z. Anorg. Gen. Chem. 270, 45 (1952), or A. Ludi, H.U. Güdel, V.
  • the proportion of acid in the solution should be greater than 80% by weight, preferably greater than 90% by weight, in particular greater than 95% by weight, based on the total mass of cyanometalate complexes.
  • the organic substances described above are used as ligands containing heteroatoms.
  • the ligand containing no hetero atom-containing ligand is added to the solutions, and step b), the addition of ligand containing hetero atoms to the precipitation suspension, is also omitted.
  • only at least one surface-active compound is added to one or the two solutions in step a).
  • the surface-active compounds to be used in the production of the multimetal cyanide catalysts can be anionic, cationic, nonionic and / or polymeric surfactants.
  • nonionic and / or polymeric surfactants are used.
  • fatty alcohol alkoxylates, block copolymers of various epoxies with different hydrophilicity, castor oil alkoxylates or block copolymers of epoxides and other monomers, such as acrylic acid or methacrylic acid, are selected from this group.
  • Preferred fatty alcohol alkoxylates are based on a fatty alcohol with 8 to 36 carbon atoms, in particular with 10 to 18 carbon atoms. This is preferably with ethylene oxide, propylene lenoxide and / or butylene oxide alkoxylated.
  • the polyether part of the fatty alcohol alkoxylate according to the invention can consist of pure ethylene oxide, propylene oxide or butylene oxide polyethers. Furthermore, copolymers of two or three different alkylene oxides or block copolymers of two or three different alkylene oxides are also possible as the polyether part.
  • the polyether part preferably consists of 2 to 50, in particular 3 to 15, alkylene oxide units.
  • Pure polyether compounds or polyalkylene oxides are also suitable as surfactants, in particular block copolymers of two or more alkylene oxides.
  • block copolymers generally contain two or more, preferably two, different polyether blocks which differ in their hydrophilicity, for example
  • the water solubility is controlled by the lengths of the different blocks.
  • the molecular weights of such block copolymers are preferably in the range from 500 Da to 20,000 Da, particularly preferably 1000 Da to 6000 Da and in particular 1500 to 4000 Da.
  • the ethylene oxide content is preferably 5 to 50% by weight and the propylene oxide content is preferably 50 to 95% by weight.
  • surfactants are copolymers or block copolymers of alkylene oxides, preferably ethylene oxide, with other monomers such as butyl methacrylate, methyl methacrylate or methacrylic acid.
  • the surface-active substances are already introduced in at least one of the two solutions.
  • the surface-active substances are preferably added to the solution which is initially introduced during the precipitation.
  • the proportion of surfactant in the reaction mixture is preferably 0.01 to 70% by weight, particularly preferably 0.1 to 50% by weight, very particularly preferably 0.2 to 35 40% by weight and in particular 0.5 to 30 % By weight, based on the total mass of the two solutions used in the preparation.
  • 45 component worked from 1.1 to 7.0, preferably 1.2 to 5.0 and particularly preferably from 1.3 to 3.0. In many cases, it may be advantageous to submit the metal salt solution and the cyanome add talla compound, but the reverse can also be used. Thorough mixing, for example by stirring, is advantageous during and after the combination of the educt solutions.
  • the content of the cyanometalate compound in the cyanometalate reactant solution is preferably 0.1 to 30% by weight, preferably 0.1 to 20% by weight and in particular 0.2 to 10 wt .-%.
  • the content of metal salt component in the metal salt solution is preferably 0.1 to 50% by weight, particularly preferably 0.2 to 40% by weight and in particular 0.5 to 30% by weight, based on the mass of metal salt solution ,
  • the ligands containing heteroatoms are preferably added to the resulting suspension after the two educt solutions have been combined, care being taken to ensure thorough mixing. However, it is also possible to add all or part of the ligands to one of the two reactant solutions. Due to the change in the salt solubility, the ligand should preferably be added to the solution of the cyanometalate compound.
  • the multimetal cyanide compounds produced by precipitation by the process described above can then be separated from the liquid constituents of the precipitation suspension by filtration or centrifugation. The separation can be followed by several cleaning steps, e.g. B. Wash with water or other suitable solvents.
  • the multimetal cyanide compound can then be dried, eg. B. at temperatures from 30 ° C to 180 ° C and pressures from 0.001 bar to 2 bar, preferably at temperatures between 30 ° C and 100 ° C and pressures from 0.01 bar to 1 bar.
  • the use of the multimetal cyanide catalysts in the preparation of the polyether compounds according to the invention leads to a high conversion, generally greater than 90%, preferably greater than 95% and in particular greater than 98%, even with a high proportion of alkylene oxides of the formula I.
  • the use of these catalysts contributes to advantageous molecular weight distributions and thus to advantageous viscosity properties of the polyether compounds according to the invention.
  • the multimetal cyanide catalysts are preferably used in an amount of 0.001 to 5% by weight, particularly preferably 0.1 to 2% by weight and in particular 0.3 to 1% by weight, based on the amount of all alkylene oxides used.
  • Typical reaction temperatures for the reaction of the alcohols R 6 -OH with alkylene oxides are 70 to 200 ° C., preferably 80 to 180 ° C. and particularly preferably 90 to 150 ° C.
  • the pressure is usually 0.1 to 30 bar, preferably 0.2 to 20 bar and in particular 0.5 to 15 bar.
  • the reaction is usually carried out with the substantial exclusion of oxygen, e.g. B. under inert gases such as nitrogen or argon.
  • the reaction product can be worked up by degassing volatile constituents in vacuo and, if appropriate, by filtration.
  • the alcohols can be reacted with alkylene oxides in a continuous process or in a batch or semi-batch process. Batch and semi-batch processes are preferred because of the ease with which they can be carried out and the lower outlay on equipment.
  • a semi-batch process is understood to mean a process in which only a subset of the alkylene oxides to be reacted, generally less than 50% by weight, preferably less than 30% by weight and in particular less than 15% by weight .-% is added directly to the catalyst and starter (ie alcohol) at the start of the reaction and the remaining portion is added over a period of time.
  • the period of addition is generally at least one sixth, preferably at least one fifth, particularly preferably at least one third of the total reaction time.
  • the total reaction time is generally in the range from about 10 minutes to 10 hours, such as 30 minutes to 7 hours.
  • OH-terminated polyether compounds resulting from the process according to the invention for example compounds of the formula III in which X represents OH, can subsequently be converted into amino- or polyamino-terminated compounds, for example compounds of the formula III in which X is NR 7 R 8 stands in which the radicals R 7 and R 8 are as defined above.
  • X is NR 7 R 8 stands in which the radicals R 7 and R 8 are as defined above.
  • the amino functionalization by reductive amination is preferred.
  • Hydrogen is particularly suitable as a reducing agent.
  • Suitable catalysts are copper, nickel, cobalt, iron or else platinum or palladium catalysts, as are usually used for hydrogenation reactions. Palladium-activated carbon, Raney nickel or Raney copper is preferably used as the catalyst.
  • Particularly preferred as a catalyst are Ni contacts (catalysts), i. H. Nickel on inorganic substrates.
  • Suitable amines are ammonia, primary amines and secondary amines and oligo- and polyamines which have at least one primary and / or secondary amino group.
  • Examples of such amines are compounds of the formula HNR 7 R 8 , in which the radicals R 7 and R 8 are selected from hydrogen,
  • C 1 -C 20 alkyl, C 3 -C 8 cycloalkyl and C 1 -C 20 alkoxy radicals which can be interrupted and / or substituted by heteroatoms selected from N and 0, the heteroatoms in turn being substitutes , preferably selected from H, Ci-Cg-alkyl, aryl and heteroaryl, can wear; or R 7 and R 8 together with the N atom to which they are attached form a 5- to 8-membered cycle which has one or two further heteroatoms selected from N and 0 and with one, two or three Ci -C ⁇ alkyl radicals can be substituted.
  • R 7 and R 8 can also represent C 6 -C 1 -aryl and heteroaryl radicals.
  • the aryl and heteroaryl radicals optionally have one to three substituents, selected for. B. under hydroxy and the aforementioned alkyl, cycloalkyl or alkoxy radicals and polyisobutene radicals.
  • Suitable radicals R 7 , R 8 are, for example, hydrogen, methyl, ethyl, n-propyl, sec-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl and n- Hexyl, 5-, 6- and 7-membered saturated, unsaturated or aromatic carbocycles and heterocycles, such as cyclopentyl, cyclohexyl, phenyl, toloyl, xylyl, cycloheptanyl, naphthyl, tetrahydrofuranyl, tetrahydropyranyl, dinaxanyl, Pyrrolidyl, piperidyl, pyridyl and pyrimidyl.
  • Examples of compounds of the formula HNR 7 R 8 which have only a primary amino function are, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine . Hexylamine, cyclopentylamine, cyclohexylamine, aniline and benzylamine.
  • Examples of compounds of the formula HNR 7 R 8 'which have only a primary amino function and in which the radical R 7 or R 8 are alkyl radicals which are interrupted and / or substituted by the heteroatom 0 are, for example, CH 3 -0-C 2 H 4 -NH 2 , C 2 H 5 -0-C 2 H 4 -NH 2 , CH 3 -0-C 3 H 6 -NH 2 , C 2 H 5 -0-C 3 H 6 -NH 2 , nC 4 H 9 -0-C 4 H 8 -NH 2 , HO-C 2 H 4 -NH 2 , H0-C 3 H 7 -NH 2 and H0-C 4 H 8 -NH 2 .
  • Examples of compounds of the formula HNR 7 R 8 'which have only a secondary amino function are, for example, dimethylamine, diethylamine, methylethylamine, di-n-propylamine, diisopropylamine, diisobutylamine, di-sec-butylamine, di-tert. -butylamine, dipentylamine, dihexylamine, dicyclopentylamine, dicyclohexylamine and diphenylamine.
  • Examples of compounds of the formula HNR 7 R 8 'which have only a secondary amino function and in which the radicals R 7 and R 8 are alkyl radicals which are interrupted and / or substituted by the heteroatom O are, for example (CH 3 -0-C 2 H 4 ) 2 NH, (C 2 H 5 -0-C 2 H 4 ) 2 NH, (CH 3 -0-C 3 H 6 ) 2 NH, (C 2 H 5 -0-C 3 H 6 ) 2 NH , (nC 4 H 9 - 0-C 4 H 8 ) 2 NH, (H0-C 2 H 4 ) 2 NH, (HO-C 3 H 6 ) 2 NH and (HO-C 4 H 8 ) 2 NH.
  • Examples of compounds of the formula HNR 7 R 8 'in which R 7 and R 8 together with the N atom to which they are attached form a 5-, 6- or 7-membered cycle, the one or two heteroatoms selected below N and 0, and can be substituted with one, two or three Ci-C ö alkyl radicals j are, for example, pyrrolidine, piperidine, morpholine and piperazine and their substituted derivatives, such as N-Ci-C ß -alkylpiperazines and Dimethylmorpholine.
  • Examples of compounds of the formula HNR 7 R 8 ' which have N-interrupted and / or substituted alkyl radicals are alkylene diamines, dialkylene triamines, trialkylene tetramines, tetraalkylene pentaamines and polyalkylene polyamines with a degree of polymerization of 5 to 100, such as oligo- or polyalkyleneimines , in particular oligo- or polyethyleneimines, preferably oligoethyleneimines, consisting of 2 to 20, preferably 2 to 10 and particularly preferably 2 to 6 ethyleneimine units.
  • Suitable compounds of this type are in particular ethylenediamine, n-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine, triethylenetetamine, tetraethylenepentamine and the above-mentioned polyethyleneimines, and also their alkylation products which have at least one primary or secondary amino function, z.
  • Ethylene diamine is also suitable.
  • compounds of the formula HNR 7 R 8 are the reaction products of alkylene oxides, in particular ethylene oxide, with primary amines, and copolymers of ethylene oxide with ethyleneimine and / or primary or secondary Ci-Cg-alkylamines.
  • Preferred compounds of the formula HNR 7 R 8 are 3- (dimethylamino) -n-propylamine, di [3- (dimethylamino) -n-propyl] amine, di [3- (diethylamino) -n-propyl] amine, di [2- (dimethylamino) ethyl] amine, ammonia, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, pyrrolidine, piperidine, morpholine, dimethylmorpholine, N-methylpiperazine, HO-CH 4 -NH 2j , (HO-C 2 H 4 ) 2 NH, H 3 C-0- (CH 2 ) 2 -NH 2 , H 3 C-0- (CH 2 ) 3 -NH 2f diethylenetriamine, triethylenetetramine, N, N- Diethylethylenediamine, N, N, N ',
  • Particularly preferred compounds of the formula HNR 7 R 8 are 3- (dimethylamino) -n-propylamine, di [3- (dimethylamino) -n-propyl] amine, dimethylamine, diethylamine, tetraethylene pentamine and morpholine.
  • the reductive amination is generally carried out at a temperature in the range from about 50 to 300 ° C., preferably 80 to 200 ° C.
  • the reductive amination is preferably carried out at a pressure in the. Range from 50 to 500 bar, preferably 80 to 300 bar.
  • a suitable solvent which is inert under the reaction conditions in order to reduce the viscosity of the reaction mixture.
  • polar solvents such as aliphatic, cycloaliphatic and aromatic hydrocarbons, are suitable as solvents.
  • These hydrocarbons should preferably be low in sulfur. Suitable hydrocarbons are e.g. B. linear or branched Cs-Ci ß alkanes and in particular dodecane, 2,4,4-trimethylpentane, and cyclohexane and toluene.
  • the polyethers contained in the polyether compositions obtained by the process according to the invention preferably have a weight-average molecular weight M w of at least 450 g / mol, particularly preferably of at least 550 g / mol and in particular of at least 600 g / mol.
  • the weight-average molecular weight is preferably at most 3500 g / mol, particularly preferably at most 2500 g / mol.
  • the viscosity of the polyether compositions according to the invention is 40 ° C., preferably in the range from 30 to 500 mPa-s, particularly preferably from 50 to 300 mPa-s.
  • the polyether compositions obtained by the process according to the invention advantageously generally contain a significant proportion of unsaturated components. These can result, for example, from rearrangement of alkylene oxides to allyl compounds and subsequent alkoxylation of these allyl compounds. Furthermore, unsaturated components can also arise during the cleavage of polyether chains in the course of the process.
  • the method according to which he polyether compositions obtained indungshacken an iodine number determined according to Hanus is from 1 to 20, particularly preferably 3 to 18 g I 2/100 g polyether on.
  • using alkylene oxide mixtures of 1-butene oxide with isobutene oxide and / or 2,3-butene oxide results in higher proportions of unsaturated components than in the homopolymerization of 1-butene oxide.
  • the polyether compositions obtained by the process according to the invention preferably have a residual content of monohydroxy compounds used as starters of at most 5% by weight, particularly preferably at most 1% by weight and in particular at most 0.2% by weight, based on the originally used Amount, on.
  • the residual content of monohydroxy compounds is around 0% (ie below the detection limit).
  • the polydispersity (PD) of the polyether compositions obtained by the process according to the invention is preferably in a range from 1.03 to 1.70, particularly preferably 1.04 to 1.60 and especially from 1.05 to 1.50.
  • the polydispersity can be determined by means of gel permeation chromatography (GPC).
  • the invention further relates to the polyether compositions obtained by the process according to the invention.
  • polyether compositions according to the invention preferably those which contain OH-terminated polyether compounds, in particular those of the formula III in which X represents OH, are outstandingly suitable as carrier oils for detergents and dispersants in fuel and lubricant compositions. They are particularly preferably used in fuel compositions, in particular in gasoline fuel compositions with direct injection performance.
  • the present invention therefore also relates to the use of polyether compositions as carrier oils for detergents and dispersants in fuel and lubricant compositions.
  • polyether compositions according to the invention preferably those which contain amine- or polyamine-terminated polyether compounds, in particular those of the formula III in which X represents NR 7 R 8 , are outstandingly suitable as detergents and / or dispersants in fuel and lubricant compositions They are particularly preferably used in fuel compositions, in particular in gasoline fuel compositions.
  • the present invention therefore also relates to the use of polyether compositions as detergents and / or dispersants in fuel and lubricant compositions.
  • Typical detergents and / or dispersants which are known from the prior art are, for example:
  • Polyisobutenamines which are obtainable by hydroformylation of highly reactive polyisobutene and subsequent reductive amination with ammonia, monoamines or polyamines such as dimethyleneaminopropylamine, ethylene diamine, diethylene triamine, triethylene tetraamine or tetraethylene pentamine, for. B. those described in EP-A 244 616,
  • poly (iso) butenamines which are obtainable by chlorination of polybutenes or polyisobutenes with double bonds predominantly in the ⁇ and ⁇ position and subsequent amination with ammonia, monoamines or the above-mentioned polyamines,
  • poly (iso) butenamines which can be obtained by oxidation of double bonds in poly (iso) butenes with air or ozone to give carbonyl or carboxyl compounds and subsequent amination under reducing (hydrogenating) conditions
  • Polyetheramines which are obtained by reacting C 2 -C 30 alkanols, C 6 -C 3 o-alkanediols, mono- or di-C 2 -C 3 o-alkylamines, -C-C 30 -alkylcyclohexanols or C ⁇ -C 3 o-alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl or amino group and subsequent reductive amination with ammonia, monoamines or the above-mentioned polyamines are available, polyetheramines with a carbamate structure can also be used,
  • Typical dispersants are, for example, imides, amides, esters and ammonium and alkali metal salts of polyisobutene succinic anhydrides, which are used in particular in lubricating oils, but are also sometimes used as detergents in fuel compositions.
  • gasoline fuel additives that can be used to prevent valve seat wear can be used together with the polyether compounds according to the invention;
  • carboxyl groups or additives containing their alkali metal or alkaline earth metal salts such as, for example, copolymers of C 2 -C 4 o-olefins with maleic anhydride with a total molar mass of 500 to 20,000, the carboxyl groups of which are wholly or partly to the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines, as described in EP-A 307 815, or sulfonic acid groups or their additives containing alkali metal or alkaline earth metal salts, such as, for example, alkali metal or alkaline earth metal salts of sulfosuccinic acid alkyl esters, as described in US Pat EP-A 639 632 are of interest.
  • Such valve seat wear-resistant gasoline fuel additives can with Advantage also in combination
  • the present invention also relates to fuel and lubricant additive concentrates which contain the polyether compositions according to the invention in amounts of 0.1 to 80, in particular 0.5 to 60% by weight, based on the total amount of the concentrates. These concentrates usually also contain the detergents or dispersants listed above, as well as other components and auxiliaries customary for this purpose, as well as solvents or diluents, for. B. aliphatic and aromatic hydrocarbons such as solvent naphtha.
  • base oils mineral carrier oils
  • SN Solvent Neutral
  • the present invention furthermore relates to fuel and lubricant compositions, in particular fuel compositions, especially gasoline compositions, which contain the polyether compositions according to the invention in effective amounts.
  • Effective amounts are generally 10 to 5000 ppm by weight in fuel compositions, preferably 30 to 3500 ppm by weight and in particular 50 to 1000 ppm by weight and at
  • Lubricant compositions 0.1 to 10% by weight, in particular 0.5 to 5% by weight, in each case based on the total amount of the compositions to understand.
  • the fuel and lubricant compositions usually contain the compounds according to the invention as carrier oils and the above-mentioned detergents or dispersants as well as the other components and auxiliaries and solvents or diluents customary for this purpose.
  • the fuel compositions according to the invention can also be in the form of combinations of a petrol with a mixture of polyether compounds, polyisobutenamine detergents, in particular those from the aforementioned groups (a), (b), (c) or (d), and corrosion inhibitors and / or lubrication improvers Basis of carboxylic acids or fatty acids, which can be present as monomeric and / or dimeric species.
  • polyether compounds according to the invention are able to effectively avoid the undesired "valve plugging", particularly in gasoline engines. As a rule, they are still sufficiently compatible with the other additives so that no segregation effects occur. Their viscosity behavior also does not cause formulation problems.
  • the OH-terminated polyether compounds which can primarily be used as carrier oils, also show activity as detergents. They therefore make a large contribution to the overall performance of an additive package or a fuel or lubricant composition with regard to the detergent action, even with low dosing, and therefore enable at least a partial saving of the more expensive detergents.
  • the amino-terminated polyether compounds which can be used primarily as detergents and / or dispersants show good compatibility with carrier oils, in particular with the abovementioned, good activity, in particular with regard to preventing and removing deposits in internal combustion engines, and are also notable for advantageous viscosity behavior.
  • the polydispersities were determined by GPC. The calibration was carried out with polystyrene. The internal standard was toluene, solvent tetrahydrofuran. The flow was 1 ml / min. The following columns were used: guard column: PSS, SDV 8 x 50 mm, 5 ⁇ m; Separation columns: SDV 100 ⁇ , 10 3 i, 10 5 A, every 8 x 300 mm, 5 ⁇ m. The detection was carried out using RI detectors.
  • a mixture consisting of tridekanol N (alcohol mixture of trimerized butene) as starter and the catalyst DMC GrG494K is placed in a steel autoclave with a usable volume of 250 ml 5. After closing the autoclave, the reaction mixture is homogenized by stirring with a magnetic stirrer.
  • reaction mixture is heated to 100 ° C. and evacuated to a pressure of less than 5 bar for 2 hours. Subsequently, the autoclave was charged with N 2 and is filled bar absolute purged three times with N 2 at a pressure of. 4 Then 5 the reactor is depressurized to a pressure of 1.5 bar absolute and the respective reaction temperature is set.
  • the alkylene oxides are added via a storage vessel.
  • the corresponding amount of alkylene oxide is added in a controlled manner. For safety reasons, after the first small amount of alkylene oxide has been added, it is awaited whether the reaction has started. The onset of the reaction is detected by changes in pressure and / or temperature. When the reaction has started 5, the remaining amount of alkylene oxide is metered in within the specified periods. The temperature and pressure curve are measured and recorded.
  • a post-reaction time 30 of 1 hour is observed.
  • the autoclave is then released and evacuated for 15 minutes (less than or equal to 5 mbar). Any unreacted alkylene oxide is collected using a low-temperature cold trap. After cooling to about room temperature, the autoclave is opened and the reaction product is separated from the solid catalyst via a pressure filter (depth filter with 5 ⁇ m).
  • polyether compounds of Examples 4 to 9 were prepared analogously to Examples 1 to 3 according to general procedure A.
  • the amounts of isobutene oxide and propene oxide were chosen as required by the calculated number-average molecular weights. The results are shown in Table 1.
  • a mixture of tridecanol N and the DMC GrG494K catalyst is placed in a 250 ml three-necked flask with reflux condenser, inert gas connection (N 2 ) and storage vessel for the alkylene oxides.
  • N 2 inert gas connection
  • the reaction mixture is generally heated to about 100 ° C. and evacuated for 2 hours to a pressure of less than 5 mbar.
  • the flask with N 2 is gassed and purged three times with N 2.
  • the subsequent reaction was carried out under a nitrogen atmosphere.
  • the alkylene oxides were added via the storage vessel.
  • the corresponding amount of alkylene oxide is added in a controlled manner. For safety reasons, it is waited after adding a first small amount of alkylene oxide whether the reaction has started. The onset of the reaction is due to changes in pressure and / or Temperature detected. When the reaction has started, the remaining amount of alkylene oxide is metered in within the stated time periods in such a way that the reaction mixture remains at the boil with gentle reflux.
  • the polyether compounds of Examples 11 to 15 were prepared analogously to Example 10 according to the general procedure B.
  • the amounts of isobutene oxide and butene oxide were chosen as required by the calculated number-average molecular weights.
  • the results are shown in Table 1.
  • the polyether composition obtained in Example 13 contained 4.7 mmol / kg of unsaturated components.
  • the Hanus iodine number was 12 g iodine / 100 g.
  • the OH number was 74 mg KOH / g.
  • the polydispersity was 1.21.
  • Example 16 was carried out analogously to Example 11, but instead of the equimolar mixture of isobutylene oxide and 1,2-butylene oxide, a mixture of alkylene oxides was used which was obtained by oxidation or epoxidation of raffinate I and had the following composition:
  • Example 17 was carried out analogously to Example 11, but instead of the equimolar mixture of isobutylene oxide and 1,2-butylene oxide, a mixture of alkylene oxides was used which was obtained by oxidation or epoxidation of raffinate II and had the following composition:
  • 1,2-butene oxide 55.6 mol%
  • 2,3-trans-butene oxide 14.6 mol%
  • the OH-terminated polyether compounds prepared according to the invention can be subjected to reductive amination with ammonia or a primary or secondary amine without further pretreatment.
  • the alkoxylates have a higher viscosity, it may be advantageous to dilute them with a suitable inert solvent, for example branched aliphatic hydrocarbons such as isododecane, in such a way that a viscosity of the solution of 50 to 200 mm 2 / s at 20 ° C. results.
  • Ammonia or amine are usually used in excess, based on the alkoxylate, z. B. in 2 to 100 times, preferably 10 to 80 times molar excess in ammonia and 1.5 to 50 times, preferably 2 to 20 times excess in primary or secondary amines.
  • the mixture of alkoxylate and amine is in the presence of a commercially available hydrogenation catalyst, such as Raney nickel, Raney cobalt or a nickel contact, at elevated pressure, for. B. in the range of 10 to 300 bar, preferably 50 to 250 bar, in a pressure reactor, for. B. a rolling autoclave, at elevated temperatures, eg. B. 80 to 300 ° C, preferably 20 to 250 ° C, treated with hydrogen.
  • the catalyst is separated off by filtration, excess amine, e.g. B. by distilling off in vacuo, and optionally distilling water of reaction still contained azeotropically or under an inert gas stream.
  • a commercially available hydrogenation catalyst such as Raney nickel, Raney cobalt or a nickel contact
  • 500 g of the polyether compound obtained according to Example 11 were, without further purification and without the addition of a solvent, in a roller autoclave in the presence of 100 g of nickel on Zr0 as catalyst at a pressure of 200 bar and a temperature of 100 ° C with 400 g of ammonia (43, 3-fold molar excess) implemented.
  • the pressure is set with H 2 .
  • the reaction time was 20 minutes. After cooling to room temperature, the catalyst was separated off by filtration, the excess ammonia was removed in vacuo (less than 5 mbar) and the water of reaction was distilled off azeotropically. 498 g of a clear liquid with a viscosity of 64 mm 2 / s at 40 ° C. were obtained, which had an amine number of 57 mg KOH per g polyetheramine.
  • Example 20 was carried out analogously to Example 19, but a commercially available Eurosuper base fuel in accordance with EN 228 was used as the additive, which contains 200 mg of the polyether obtained from Example 14 and 100 mg of one in accordance with EP 244 616, Example 1 per kg of base fuel , 3: 1 mixture of polyisobutenamine and polyisobutene obtained. At the end of the test, the deposits had decreased from 368 mg to 4 mg in total across all inlet valves.
  • Example 21
  • Example 21 was carried out analogously to Example 19, but a commercially available Eurosuper 5 base fuel according to EN 228 was used as the additive, which contains 200 mg of the polyether obtained from Example 14 and 100 mg of one according to WO 01/25295 as additives per kg of base fuel.
  • Example 6, obtained polyisobutene phenol Mannich adduct. At the end of the test, the deposits had decreased from 368 mg to 6 mg in total over 10 of all intake valves.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une composition de polyéther contenant du polyéther pourvu d'une chaîne polyéther présentant une teneur supérieure en unités répétées d'oxyde d'alkylène d'oxydes intégrées, dérivées d'oléfines ramifiées et/ou d'oléfines ne possédant pas de double liaison α, et non d'α-oléfines linéaires. L'invention concerne également les compositions de polyéther obtenues au moyen du procédé selon l'invention, ainsi que leur utilisation lors de l'addition de carburants ou de lubrifiants.
PCT/EP2004/003365 2003-03-31 2004-03-30 Procede de fabrication d'une composition de polyether Ceased WO2004087789A2 (fr)

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US20120108482A1 (en) * 2009-07-23 2012-05-03 Greaves Martin R Polyakylene glycols useful as lubricant additives for groups i-iv hydrocarbon oils
WO2013062682A1 (fr) * 2011-10-28 2013-05-02 Dow Global Technologies Llc Compositions d'huiles hydrocarbonées et de pags solubles dans l'huile obtenus par catalyse par dmc
CN103249821A (zh) * 2010-11-26 2013-08-14 道达尔炼油与销售部 发动机润滑剂组合物
US9328364B2 (en) 2004-03-31 2016-05-03 Cargill Incorporated Process for fermenting sugars containing oligomeric saccharides
US9850447B2 (en) 2013-05-23 2017-12-26 Dow Global Technologies Llc Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils
CN112608465A (zh) * 2020-11-27 2021-04-06 广东石油化工学院 一种抗氧剂及其制备方法

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US3941849A (en) * 1972-07-07 1976-03-02 The General Tire & Rubber Company Polyethers and method for making the same
JP3231090B2 (ja) * 1992-07-15 2001-11-19 旭硝子株式会社 イソブチレンオキシド共重合体の製造方法
US5426174A (en) * 1992-12-08 1995-06-20 Arco Chemical Technology, L.P. Hydroxy-functionalized polyoxyalkylene ether compositions derived from mixtures of C4 epoxides
US6821308B2 (en) * 1997-04-02 2004-11-23 Bayer Antwerp N.V. Polyoxyalkylene monoethers with reduced water affinity
DE19840846A1 (de) * 1998-09-07 2000-03-09 Basf Ag Verfahren zur Herstellung von Fettalkoholalkoxylaten
DE10205086A1 (de) * 2002-02-07 2003-08-21 Basf Ag Verfahren zur Aktivierung von Doppelmetallcyanid-Verbindungen

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US9328364B2 (en) 2004-03-31 2016-05-03 Cargill Incorporated Process for fermenting sugars containing oligomeric saccharides
US9714438B2 (en) 2004-03-31 2017-07-25 Cargill, Incorporated Process for fermenting sugars containing oligomeric saccharides
US20120108482A1 (en) * 2009-07-23 2012-05-03 Greaves Martin R Polyakylene glycols useful as lubricant additives for groups i-iv hydrocarbon oils
US8969271B2 (en) * 2009-07-23 2015-03-03 Dow Global Technologies Llc Polyakylene glycols useful as lubricant additives for groups I-IV hydrocarbon oils
CN103249821A (zh) * 2010-11-26 2013-08-14 道达尔炼油与销售部 发动机润滑剂组合物
CN103249821B (zh) * 2010-11-26 2015-04-08 道达尔销售服务公司 发动机润滑剂组合物
CN103890152A (zh) * 2011-10-28 2014-06-25 陶氏环球技术有限责任公司 烃油和通过dmc催化产生的油溶性pag的组合物
CN103890152B (zh) * 2011-10-28 2016-01-20 陶氏环球技术有限责任公司 烃油和通过dmc催化产生的油溶性pag的组合物
US9650588B2 (en) 2011-10-28 2017-05-16 Dow Global Technologies Llc Compositions of hydrocarbon oils and oil soluble PAGS produced by DMC catalysts
WO2013062682A1 (fr) * 2011-10-28 2013-05-02 Dow Global Technologies Llc Compositions d'huiles hydrocarbonées et de pags solubles dans l'huile obtenus par catalyse par dmc
US9850447B2 (en) 2013-05-23 2017-12-26 Dow Global Technologies Llc Polyalkylene glycols useful as lubricant additives for hydrocarbon base oils
CN112608465A (zh) * 2020-11-27 2021-04-06 广东石油化工学院 一种抗氧剂及其制备方法
CN112608465B (zh) * 2020-11-27 2023-04-28 广东石油化工学院 一种抗氧剂及其制备方法

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