US20160130514A1 - Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants - Google Patents

Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants Download PDF

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Publication number
US20160130514A1
US20160130514A1 US14/896,598 US201414896598A US2016130514A1 US 20160130514 A1 US20160130514 A1 US 20160130514A1 US 201414896598 A US201414896598 A US 201414896598A US 2016130514 A1 US2016130514 A1 US 2016130514A1
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Prior art keywords
hydrocarbyl
fuel
substituted
quaternizable
acid
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US14/896,598
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English (en)
Inventor
Markus Hansch
Harald Boehnke
Wolfgang Grabarse
Ludwig Voelkel
Maxim Peretolchin
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BASF SE
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BASF SE
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=50928102&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20160130514(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP13171057.6A external-priority patent/EP2811007A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of US20160130514A1 publication Critical patent/US20160130514A1/en
Priority to US15/678,974 priority Critical patent/US10407634B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • C—CHEMISTRY; METALLURGY
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    • 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
    • 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
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    • 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
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    • 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)
    • C—CHEMISTRY; METALLURGY
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • 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
    • 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
    • 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
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C10M133/14—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring 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
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/54—Amines
    • 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
    • C10M133/52—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of 30 or more atoms
    • C10M133/56—Amides; Imides
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0259—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • C—CHEMISTRY; METALLURGY
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043—Kerosene, jet fuel
    • C—CHEMISTRY; METALLURGY
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • C—CHEMISTRY; METALLURGY
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • C—CHEMISTRY; METALLURGY
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
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    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/24—Mixing, stirring of fuel components
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/127—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids polycarboxylic
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
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    • 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
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26—Amines
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines
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    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/255—Gasoline engines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to the use of nitrogen compounds quaternized in a specific manner as a fuel additive and lubricant additive or kerosene additive, such as, more particularly, as a detergent additive; for reducing the level of or preventing deposits in the injection systems of direct injection diesel engines, especially in common rail injection systems, for reducing the fuel consumption of direct injection diesel engines, especially of diesel engines with common rail injection systems, and for minimizing power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems; and as an additive for gasoline fuels, especially for operation of DISI engines.
  • a fuel additive and lubricant additive or kerosene additive such as, more particularly, as a detergent additive
  • direct injection diesel engines the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber of the engine, instead of being introduced into a prechamber or swirl chamber as in the case of the conventional (chamber) diesel engine.
  • the advantage of direct injection diesel engines lies in their high performance for diesel engines and nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds.
  • the diesel fuel is conveyed by a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Proceeding from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The full pressure is always applied to the common rail, which enables multiple injection or a specific injection form. In the other injection systems, in contrast, only a smaller variation in the injection is possible.
  • Injection in the common rail is divided essentially into three groups: (1.) pre-injection, by which essentially softer combustion is achieved, such that harsh combustion noises (“nailing”) are reduced and the engine seems to run quietly; (2.) main injection, which is responsible especially for a good torque profile; and (3.) post-injection, which especially ensures a low NO x value.
  • the fuel is generally not combusted, but instead vaporized by residual heat in the cylinder.
  • the exhaust gas/fuel mixture formed is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides NO x .
  • variable, cylinder-individual injection in the common rail injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and especially of particulates (soot). This makes it possible, for example, for engines equipped with common rail injection systems to meet the Euro 4 standard theoretically even without additional particulate filters.
  • NO x nitrogen oxides
  • CO carbon monoxide
  • particulates particulates
  • deposits can form on the injector orifices, which adversely affect the injection performance of the fuel and hence impair the performance of the engine, i.e. especially reduce the power, but in some cases also worsen the combustion.
  • the formation of deposits is enhanced further by further developments in the injector construction, especially by the change in the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting optimal functioning of engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives.
  • IDID internal diesel injector deposits
  • U.S. Pat. No. 4,248,719 describes quaternized ammonium salts which are prepared by reacting an alkenylsuccinimide with a monocarboxylic ester and find use as dispersants in lubricant oils for prevention of sludge formation. More particularly, for example, the reaction of polyisobutylsuccinic anhydride (PIBSA) with N,N-dimethylaminopropylamine (DMAPA) and quaternization with methyl salicylate is described.
  • PIBSA polyisobutylsuccinic anhydride
  • DMAPA N,N-dimethylaminopropylamine
  • use in fuels, more particularly diesel fuels is not proposed therein.
  • the use of PIBSA with low bismaleation levels of ⁇ 20% is not described therein.
  • U.S. Pat. No. 4,171,959 describes quaternized ammonium salts of hydrocarbyl-substituted succinimides, which are suitable as detergent additives for gasoline fuel compositions. Quaternization is preferably accomplished using alkyl halides. Also mentioned are organic C 2 -C 8 -hydrocarbyl carboxylates and sulfonates. Consequently, the quaternized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a C 2 -C 8 -hydrocarbyl carboxylate or a C 2 -C 8 -hydrocarbyl sulfonate group. The use of PIBSA with low bismaleation levels of ⁇ 20% is likewise not described therein.
  • EP-A-2 033 945 discloses cold flow improvers which are prepared by quaternizing specific tertiary monoamines bearing at least one C 8 -C 40 -alkyl radical with a C 1 -C 4 -alkyl ester of specific carboxylic acids. Examples of such carboxylic esters are dimethyl oxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Uses other than that for improvement of the CFPP value of middle distillates are not demonstrated in EP-A-2 033 945.
  • WO 2006/135881 describes quaternized ammonium salts prepared by condensation of a hydrocarbyl-substituted acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amino group, and subsequent quaternization by means of hydrocarbyl epoxide in combination with stoichiometric amounts of an acid such as, more particularly, acetic acid.
  • Further quaternizing agents claimed in WO 2006/135881 are dialkyl sulfates, benzyl halides and hydrocarbyl-substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally.
  • quaternizing agents used with preference in WO 2006/135881 have serious disadvantages such as: toxicity or carcinogenicity (for example in the case of dimethyl sulfate and benzyl halides), no residue-free combustion (for example in the case of dimethyl sulfate and alkyl halides), and inadequate reactivity which leads to incomplete quaternization or uneconomic reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent; for example in the case of dimethyl carbonate).
  • EP-A-2 033 945 describes the preparation of halogen- and sulfur-free quaternary ammonium salts of organic carboxylic acids (for example oxalic acid, phthalic acid, salicylic acid, malonic acid and maleic acid, and the alkyl esters thereof) and the use thereof for improvement of the CFPP value of diesel fuels.
  • organic carboxylic acids for example oxalic acid, phthalic acid, salicylic acid, malonic acid and maleic acid, and the alkyl esters thereof
  • Quaternary ammonium salts of alpha-hydroxycarboxylic acids are proposed in EP-A-1 254 889 as cleaning agents for electronic components.
  • Japanese patent application, application number 61-012197 describes the use of quaternary ammonium salts of organic carboxylic acids as surfactants or raw materials for medicaments or cosmetics.
  • inventive additives are surprisingly effective in common rail diesel engines and are notable for their particular suitability as an additive for reducing power loss resulting from external deposits and cold start problems resulting from internal deposits.
  • FIG. 1 shows the running of a one-hour engine test cycle according to CEC F-098-08.
  • FIG. 2A to D shows photographs of injectors of a DISI gasoline engine operated with fuel either in unadditized form (A) or additized with various additives of the invention (B, C, D).
  • “Quaternizable” nitrogen groups or amino groups comprise especially primary, secondary and, in particular, tertiary amino groups.
  • Hydrocarbyl should be interpreted broadly and comprises both long-chain and short-chain, straight-chain and branched hydrocarbyl radicals having 1 to 50 carbon atoms, which may optionally additionally comprise heteroatoms, for example O, N, NH, S, in the chain thereof.
  • a specific group of hydrocarbyl radicals comprises both long-chain and short-chain, straight-chain or branched alkyl radicals having 1 to 1000, 3 to 500 4 to 400 carbon atoms.
  • “Long-chain” or “high molecular weight” hydrocarbyl radicals are straight-chain or branched hydrocarbyl radicals and have 7 to 50 or 8 to 50 or 8 to 40 or 10 to 20 carbon atoms, which may optionally additionally comprise heteroatoms, for example O, N, NH, S, in the chain thereof.
  • the radicals may be mono- or polyunsaturated and have one or more noncumulated, for example 1 to 5, such as 1, 2 or 3, C—C double bonds or C—C triple bonds, especially 1, 2 or 3 double bonds. They may be of natural or synthetic origin.
  • M n number-average molecular weight
  • M n number-average molecular weight
  • They are more particularly formed essentially from C 2-6 , especially C 2-4 , monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof, where the different monomers may be copolymerized in random distribution or as blocks.
  • Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-C 2-6 - or poly-C 2-4 -alkylene radicals. Suitable long-chain hydrocarbyl radicals and the preparation thereof are also described, for example, in WO 2006/135881 and the literature cited therein.
  • polyalkylene radicals examples include polyisobutenyl radicals derived from what are called “high-reactivity” polyisobutenes which feature a high content of terminal double bonds. Terminal double bonds are alpha-olefinic double bonds of the type
  • Suitable high-reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol %, especially greater than 80 mol % or greater than 85 mol %. Preference is given especially to polyisobutenes which have homogeneous polymer skeletons. Homogeneous polymer skeletons are possessed especially by those polyisobutenes formed from isobutene units to an extent of at least 85% by weight, preferably to an extent of at least 90% by weight and more preferably to an extent of at least 95% by weight.
  • Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementioned range.
  • the high-reactivity polyisobutenes may have a polydispersity in the range from 1.05 to 7, especially of about 1.1 to 2.5, for example of less than 1.9 or less than 1.5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn.
  • Other number-average molecular weights can be established in a manner known in principle by mixing polyisobutenes of different number-average molecular weights or by extractive enrichment of polyisobutenes of particular molecular weight ranges.
  • a specific group of long-chain hydrocarbyl radicals comprises straight-chain or branched alkyl radicals (“long-chain alkyl radicals”) having 8 to 50, for example 8 to 40 or 8 to 30 or 10 to 20, carbon atoms.
  • a further group of specific long-chain hydrocarbyl radicals comprises polyalkylene radicals which are formed essentially from C 2-6 , especially C 2-4 , monomer units, such as ethylene, propylene, n- or isobutylene or mixtures thereof and have a degree of polymerization of 2 to 100, or 3 to 50 or 4 to 25.
  • Short-chain hydrocarbyl or “low molecular weight hydrocarbyl” is especially straight-chain or branched alkyl or alkenyl, optionally interrupted by one or more, for example 2, 3 or 4, heteroatom groups such as —O— or —NH—, or optionally mono- or polysubstituted, for example di-, tri- or tetrasubstituted.
  • “Hydrocarbylene” represents straight-chain or singly or multiply branched bridge groups having 1 to 10 carbon atoms, optionally interrupted by one or more, for example 2, 3 or 4, heteroatom groups such as —O— or —NH—, or optionally mono- or polysubstituted, for example di-, tri- or tetrasubstituted.
  • “Hydroxyalkyl” represents, in particular, the mono- or polyhydroxylated, for example the monohydroxylated, analogs of the above alkyl radicals, for example the linear hydroxyalkyl groups, for example those having a primary (terminal) hydroxyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those having nonterminal hydroxyl groups, such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3-hydroxybutyl.
  • Alkyl or “lower alkyl” represents especially saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 5, 1 to 6, or 1 to 7, carbon atoms, for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-didi
  • “Long-chain alkyl” represents, for example, saturated straight-chain or branched hydrocarbyl radicals having 8 to 50, for example 8 to 40 or 8 to 30 or 10 to 20, carbon atoms, such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, constitutional isomers, especially singly or multiply branched isomers and higher homologs thereof.
  • “Hydroxyalkyl” represents, in particular, the mono- or polyhydroxylated, for example the monohydroxylated, analogs of the above alkyl radicals, for example the linear hydroxyalkyl groups, for example those having a primary (terminal) hydroxyl group, such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, or those having nonterminal hydroxyl groups, such as 1-hydroxyethyl, 1- or 2-hydroxypropyl, 1- or 2-hydroxybutyl or 1-, 2- or 3-hydroxybutyl.
  • Alkenyl represents mono- or polyunsaturated, especially monounsaturated, straight-chain or branched hydrocarbyl radicals having 2 to 4, 2 to 6, or 2 to 7 carbon atoms and one double bond in any position, e.g.
  • C 2 -C 6 -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl
  • Haldroxyalkenyl represents, in particular, the mono- or polyhydroxylated, especially monohydroxylated, analogs of the above alkenyl radicals.
  • aminoalkyl and aminoalkenyl represent, in particular, the mono- or polyaminated, especially monoaminated, analogs of the above alkyl and alkenyl radicals respectively, or analogs of the above hydroxyalkyl where the OH group has been replaced by an amino group.
  • Alkylene represents straight-chain or singly or multiply branched hydrocarbyl bridging groups having 1 to 10 carbon atoms, for example C 1 -C 7 -alkylene groups selected from —CH 2 —, —(CH 2 ) 2 —, —(CH 2 ) 3 —, —(CH 2 ) 4 —, —(CH 2 ) 2 —CH(CH 3 )—, —CH 2 —CH(CH 3 )—CH 2 —, (CH 2 ) 4 —, —(CH 2 ) 5 —, —(CH 2 ) 6 , —(CH 2 ) 7 —, —CH(CH 3 )—CH 2 —CH 2 —CH(CH 3 )— or —CH(CH 3 )—CH 2 —CH 2 —CH 2 —CH(CH 3 )—, or C 1 -C 4 -alkylene groups selected from —CH 2 —, —(CH 2 ) 2 —, —
  • C 2 -C 6 -alkylene groups for example —CH 2 —CH(CH 3 )—, —CH(CH 3 )—CH 2 —, —CH(CH 3 )—CH(CH 3 )—, —C(CH 3 ) 2 —CH 2 —, —CH 2 —C(CH 3 ) 2 —, —C(CH 3 ) 2 —CH(CH 3 )—, —CH(CH 3 )—C(CH 3 ) 2 —, —CH 2 —CH(Et)-, —CH(CH 2 CH 3 )—CH 2 —, —CH(CH 2 CH 3 )—CH(CH 2 CH 3 )—, —C(CH 2 CH 3 ) 2 —CH 2 —, —CH 2 —C(CH 2 CH 3 ) 2 —CH 2 —, —CH 2 —C(CH 2 CH 3 ) 2 —CH 2 —, —CH 2 —C(CH 2 CH 3
  • Oxyalkylene radicals correspond to the definition of the above straight-chain or singly or multiply branched alkylene radicals having 2 to 10 carbon atoms, where the carbon chain is interrupted once or more than once, especially once, by an oxygen heteroatom.
  • Nonlimiting examples include: —CH 2 —O—CH 2 —, —(CH 2 ) 2 —O—(CH 2 ) 2 —, —(CH 2 ) 3 —O—(CH 2 ) 3 —, or —CH 2 —O—(CH 2 ) 2 —, —(CH 2 ) 2 —O—(CH 2 ) 3 —, —CH 2 —O—(CH 2 ) 3
  • “Aminoalkylene” corresponds to the definition of the above straight-chain or singly or multiply branched alkylene radicals having 2 to 10 carbon atoms, where the carbon chain is interrupted once or more than once, especially once, by a nitrogen group (especially —NH group).
  • Nonlimiting examples include: —CH 2 —NH—CH 2 —, —(CH 2 ) 2 —NH—(CH 2 ) 2 —, —(CH 2 ) 3 —NH—(CH 2 ) 3 —, or —CH 2 —NH—(CH 2 ) 2 —, —(CH 2 ) 2 —NH—(CH 2 ) 3 —, —CH 2 —NH—(CH 2 ) 3 .
  • Alkenylene represents the mono- or polyunsaturated, especially monounsaturated, analogs of the above alkylene groups having 2 to 10 carbon atoms, especially C 2 -C 7 -alkenylenes or C 2 -C 4 -alkenylene, such as —CH ⁇ CH—, —CH ⁇ CH—CH 2 —, —CH 2 —CH ⁇ CH—, —CH ⁇ CH—CH 2 —CH 2 —, —CH 2 —CH ⁇ CH—CH 2 —, —CH 2 —CH ⁇ CH—CH 2 —, —CH(CH 3 )—CH ⁇ CH—, —CH 2 —C(CH 3 ) ⁇ CH—.
  • Cycloalkyl represents carbocyclic radicals having 3 to 20 carbon atoms, for example C 3 -C 12 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl, cycloheptyl, and also cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, or C 3 -C 7 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl
  • Cycloalkenyl or “mono- or polyunsaturated cycloalkyl” represents, in particular, monocyclic, mono- or polyunsaturated hydrocarbyl groups having 5 to 8, preferably up to 6, carbon ring members, for example monounsaturated cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl radicals.
  • Aryl represents mono- or polycyclic, preferably mono- or bicyclic, optionally substituted aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for example phenyl, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyl, fluorenyl, indenyl and phenanthrenyl. These aryl radicals may optionally bear 1, 2, 3, 4, 5 or 6 identical or different substituents.
  • Alkylaryl represents the alkyl-substituted analogs of the above aryl radicals with mono- or polysubstitution, especially mono- or disubstitution, in any ring position, where aryl likewise has the definitions given above, for example C 1 -C 4 -alkylphenyl, where the C 1 -C 4 -alkyl radicals may be in any ring position.
  • Substituents for radicals specified herein are especially, unless stated otherwise, selected from keto groups, —COOH, —COO-alkyl, —OH, —SH, —CN, amino, —NO 2 , alkyl, or alkenyl groups.
  • Mn represents the number-average molecular weight and is determined in a conventional manner; more particularly, such figures relate to Mn values determined by relative methods, such as gel permeation chromatography with THF as the eluent and polystyrene standards, or absolute methods, such as vapor phase osmometry using toluene as the solvent.
  • Mw represents the weight-average molecular weight and is determined in a conventional manner; more particularly, such figures relate to Mw values determined by relative methods, such as gel permeation chromatography with THF as the eluent and polystyrene standards, or absolute methods, such as light scattering.
  • the “degree of polymerization” usually refers to the numerical mean degree of polymerization (determination method: gel permeation chromatography with THF as the eluent and polystyrene standards; or GC-MS coupling).
  • Quaternizable nitrogen compounds are especially:
  • Tertiary amines are especially compounds of the above formula (3) and are compounds known per se, as described, for example, in EP-A-2 033 945.
  • the tertiary amine reactant (3) preferably bears a segment of the formula NR a R b where one of the radicals has an alkyl group having 8 to 40 carbon atoms and the other an alkyl group having up to 40 and more preferably 8 to 40 carbon atoms.
  • the R c radical is especially a short-chain C 1 -C 6 -alkyl radical, such as a methyl, ethyl or propyl group.
  • R a and R b may be straight-chain or branched, and/or may be the same or different.
  • R a and R b may be a straight-chain C 12 -C 24 -alkyl group.
  • only one of the two radicals may be long-chain (for example having 8 to 40 carbon atoms), and the other may be a methyl, ethyl or propyl group.
  • the NR a R b segment is derived from a secondary amine, such as dioctadecylamine, dicocoamine, hydrogenated ditallowamine and methylbehenylamine.
  • Amine mixtures as obtainable from natural materials are likewise suitable.
  • One example is a secondary hydrogenated tallowamine where the alkyl groups are derived from hydrogenated tallow fat, and contain about 4% by weight of C 14 , 31% by weight of C 16 and 59% by weight of C 18 -alkyl groups.
  • Corresponding tertiary amines of the formula (3) are sold, for example, by Akzo Nobel under the Armeen® M2HT or Armeen® M2C name.
  • the tertiary amine adduct (3) may also be one where the R a , R b and R c radicals have identical or different long-chain alkyl radicals, especially straight-chain or branched alkyl groups having 8 to 40 carbon atoms.
  • the tertiary amine adduct (3) may also be one where the R a , R b and R c radicals have identical or different short-chain alkyl radicals, especially straight-chain or branched alkyl groups having 1 to 7 or especially 1 to 4 carbon atoms.
  • Suitable amines are:
  • Nonlimiting examples of short-chain tertiary amines are: trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, ethyldimethylamine, dimethylethylamine, n-propyldimethylamine, isopropyldimethylamine, n-propyldiethylamine, isopropyldiethylamine, n-butyldimethylamine, n-butyldiethylamine, n-butyldipropylamine.
  • Short-chain triamines are also appropriate especially when the quaternizing agent (see below) bears one or more alkyl radicals R d having more than one carbon atom or one or more aromatic radicals R d .
  • Substituted amines of this kind especially have at least one, especially one, polyether substituent having monomer units of the general formula Ic
  • R 3 and R 4 are the same or different and are each H, alkyl, alkylaryl or aryl.
  • the polyether-substituted amine may have a number-average molecular weight in the range from 500 to 5000, especially 800 to 3000 or 900 to 1500.
  • the quaternizable, polyether-substituted amines are especially nitrogen compounds of the general formula Ia-1 or Ib-2
  • R 1 and R 2 are the same or different and are each alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together are alkylene, oxyalkylene or aminoalkylene;
  • R 3 and R 4 are the same or different and are each H, alkyl, alkylaryl or aryl;
  • R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example by at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom;
  • A is a straight-chain or branched alkylene radical optionally interrupted by one or more heteroatoms such as N, O and S; and
  • n is an integer value from 1 to 50.
  • R 1 and R 2 are the same or different and are each C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkenyl, or amino-C 1 -C 6 -alkyl, or R 1 and R 2 together form a C 2 -C 6 -alkylene, C 2 -C 6 -oxyalkylene or C 2 -C 6 -aminoalkylene radical; R 3 and R 4 are the same or different and are each H, C 1 -C 6 -alkyl or phenyl; R 6 is C 1 -C 20 -alkyl, for example C 10 -C 20 -, C 11 -C 20 - or C 12 -C 20 -alkyl or aryl or alkylaryl, where alkyl is especially for C 1 -C 20 —; A is a straight-chain or branched C 2 -C 6 -alkylene radical optionally interrupted by one
  • reaction products of N,N-dimethylethanolamine and propylene oxide as described in Synthesis example 1 of WO 2013/064689.
  • This reaction can also be performed without catalysis or with an amine (for example imidazole) as a catalyst, as described, for example, in M. Ionescu, Chemistry and Technology of Polyols for Polyurethanes, 2005, ISBN 978-85957-501-7.
  • Nitrogen compounds of the general formula Ia-1 are preparable by alkoxylating an aminoalkanol of the general formula II
  • R 1 to R 4 , A and n are each as defined above.
  • Nitrogen compounds of the general formula Ia-2 are preparable by
  • R 6 is alkyl, alkenyl, optionally mono- or polyunsaturated cycloalkyl, aryl, in each case optionally substituted, for example by at least one hydroxyl radical or alkyl radical, or interrupted by at least one heteroatom; and 2) amino alkanols, for example of the general formula II
  • R 1 and R 2 are the same or different and are each alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aminoalkyl or aminoalkenyl, or R 1 and R 2 together are alkylene, oxyalkylene or aminoalkylene; and A is a straight-chain or branched alkylene or alkenylene radical optionally interrupted by one or more heteroatoms such as N, O and S.
  • a further suitable group of quaternizable amino alcohols that should be mentioned is that of compounds selected from hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable, primary, secondary or tertiary amino group and at least one hydroxyl group which can be joined to a polyether radical.
  • the quaternizable nitrogen compound is especially selected from hydroxyalkyl-substituted primary, secondary and especially tertiary monoamines, and hydroxyalkyl-substituted primary, secondary and especially tertiary diamines.
  • Suitable “hydroxyalkyl-substituted mono- or polyamines” are those which have been provided with at least one hydroxyalkyl substituent, for example 1, 2, 3, 4, 5 or 6 hydroxyalkyl substituents.
  • hydroxyalkyl-substituted monoamines include: N-hydroxyalkylmonoamines, N,N-dihydroxyalkylmonoamines and N,N,N-trihydroxyalkyl-monoamines, where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl here represents especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
  • Examples include the following “hydroxyalkyl-substituted polyamines” and especially “hydroxyalkyl-substituted diamines”: (N-hydroxyalkyl)alkylenediamines, N,N-dihydroxyalkyl-alkylenediamines, where the hydroxyalkyl groups are the same or different and are also as defined above.
  • Hydroxyalkyl here represents especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl
  • alkylene here represents especially ethylene, propylene or butylene.
  • the amino alcohols of the general formula II can be alkoxylated in a manner known in principle to obtain alkoxylated amines of the general formula Ia-1.
  • C 2 -C 16 -alkylene oxides are used, for example ethylene oxide, propylene oxide or butylene oxide. Preference is given to the 1,2-alkylene oxides in each case.
  • the alkoxylation may be a base-catalyzed alkoxylation.
  • the amino alcohols (II) can be admixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide, or with alkali metal alkoxides, for example sodium methoxide.
  • alkali metal hydroxides preferably potassium hydroxide
  • alkali metal alkoxides for example sodium methoxide.
  • the catalyst can be neutralized by addition of acid (e.g. acetic acid or phosphoric acid) and can be filtered off if required.
  • acid e.g. acetic acid or phosphoric acid
  • the basic catalyst can also be neutralized by addition of commercial magnesium silicates, which are subsequently filtered off.
  • the alkoxylation can also be performed in the presence of a solvent. This may be, for example, toluene, xylene, dimethylformamide or ethylene carbonate.
  • the alkoxylation of the amino alcohols can also be undertaken by means of other methods, for example by acid-catalyzed alkoxylation.
  • DMC catalysts are disclosed, for example, in DE 102 43 361 A1, especially paragraphs [0029] to [0041] and the literature cited therein.
  • the amino alcohol can be admixed with the catalyst, and the mixture can be dewatered as described above and reacted with the alkylene oxides as described.
  • not more than 1000 ppm of catalyst is used, based on the mixture, and the catalyst can remain in the product because of this small amount.
  • the amount of catalyst may generally be less than 1000 ppm, for example 250 ppm or less.
  • the alkoxylation can alternatively also be undertaken by reaction of the compounds (IV) and (V) with cyclic carbonates, for example ethylene carbonate.
  • polyethers As described in the above paragraph a1) for amino alcohols (II), it is analogously also possible to alkoxylate alkanols R 6 OH in a manner known in principle to polyethers (Ib-1).
  • the polyethers thus obtained can subsequently be converted to the corresponding polyether amines (Ib-2) by reductive amination with ammonia, primary amines or secondary amines (VII) by customary methods, in continuous or batchwise processes using hydrogenation or amination catalysts customary therefor, for example those comprising catalytically active constituents based on the elements Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Re, A1, Si, Ti, Zr, Nb, Mg, Zn, Ag, Au, Os, Ir, Cr, Mo, W or combinations of these elements with one another, in customary amounts.
  • the conversion can be performed without solvent or, in the case of high polyether viscosities, in the presence of a solvent, preferably in the presence of branched aliphatics, for example isododecane.
  • the amine component (VII) is generally used here in excess, for example in a 2- to 100-fold excess, preferably a 10- to 80-fold excess.
  • the reaction is conducted at pressures of 10 to 600 bar over a period of 10 minutes to 10 hours. After cooling, the catalyst is removed by filtering, excess amine component (VII) is evaporated and the water of reaction is distilled off azeotropically or under a gentle nitrogen stream.
  • the resulting polyether amine (Ib-2) can subsequently be converted to a polyether amine having a tertiary amine function (R 1 and R 2 not H).
  • the alkylation can be effected in a manner known in principle by reaction with alkylating agents.
  • Any alkylating agents are suitable in principle, for example alkyl halides, alkylaryl halides, dialkyl sulfates, alkylene oxides, optionally in combination with acid; aliphatic or aromatic carboxylic esters, such as dialkyl carboxylates in particular; alkanoates; cyclic nonaromatic or aromatic carboxylic esters; dialkyl carbonates; and mixtures thereof.
  • the conversions to the tertiary polyether amine can also take place through reductive amination by reaction with a carbonyl compound, for example formaldehyde, in the presence of a reducing agent.
  • Suitable reducing agents are formic acid or hydrogen in the presence of a suitable heterogeneous or homogeneous hydrogenation catalyst. The reactions can be performed without solvent or in the presence of solvents.
  • Suitable solvents are, for example, H 2 O, alkanols such as methanol or ethanol, or 2-ethylhexanol, aromatic solvents such as toluene, xylene or solvent mixtures from the Solvesso series, or aliphatic solvents, especially mixtures of branched aliphatic solvents.
  • the reactions are conducted at temperatures of 10° C. to 300° C. at pressures of 1 to 600 bar over a period of 10 minutes to 10 h.
  • the reducing agent is used here at least stoichiometrically, preferably in excess, especially in a 2- to 10-fold excess.
  • reaction product thus formed (polyether amine Ib-1 or Ib-2) can theoretically be purified further, or the solvent can be removed. Usually, however, this is not absolutely necessary, and so the reaction product can be transferred without further purification to the next synthesis step, the quaternization.
  • suitable quaternizable nitrogen compounds are polyalkene-substituted amines having at least one tertiary nitrogen group. This group of compounds is likewise known and is described, for example, in WO 2008/060888 or US 2008/0113890 and the further prior art cited therein, which is hereby explicitly incorporated by reference.
  • Such polyalkene-substituted amines having at least one tertiary amino group are derivable from an olefin polymer and an amine such as ammonia, monoamines, polyamines or mixtures thereof. They can be prepared by a multitude of processes, for example the following processes cited by way of example:
  • a process for preparing a polyalkene-substituted amine comprises the reaction of a halogenated olefin polymer with an amine, as described in U.S. Pat. Nos. 3,275,554, 3,438,757, 3,454,555, 3,565,804, 3,755,433 and 3,822,289.
  • a further process for preparing a polyalkene-substituted amine comprises the reaction of a hydroformylated olefin with a polyamine and hydrogenation of the reaction product, as described in U.S. Pat. Nos. 5,567,845 and 5,496,383.
  • a further process for preparing a polyalkene-substituted amine comprises the conversion of a polyalkene with the aid of a conventional epoxidizing reagent with or without catalyst to the corresponding epoxide and the conversion of the epoxide to the polyalkene-substituted amine by reaction with ammonia or an amine under the conditions of reductive amination, as described in U.S. Pat. No. 5,350,429.
  • a further process for preparing a polyalkene-substituted amine comprises the hydrogenation of a ⁇ -amino nitrile which has been prepared by reaction of an amine with a nitrile, as described in U.S. Pat. No. 5,492,641.
  • a further process for preparing a polyalkene-substituted amine comprises hydroformylation of a polybutene or polyisobutylene with a catalyst, such as rhodium or cobalt, in the presence of CO and hydrogen at elevated pressures and temperatures, as described in U.S. Pat. No. 4,832,702.
  • a catalyst such as rhodium or cobalt
  • the polyalkenes used for the preparation are derived from olefin polymers.
  • the olefin polymers may comprise homopolymers and copolymers of polymerizable olefin monomers having 2 to about 16 carbon atoms, 2 to about 6 carbon atoms or 2 to about 4 carbon atoms.
  • Interpolymers are those in which two or more olefin monomers are interpolymerized by known conventional methods, giving polyalkenes having units derived from each of the the two or more olefin monomers within their structure.
  • interpolymers comprise copolymers, terpolymers and tetrapolymers.
  • Polyalkenes from which the polyalkene-substituted amines are derived, are conventionally frequently also referred to as “polyolefins”.
  • the olefin monomers from which the olefin polymers are derived are polymerizable olefin monomers having one or more ethylenically unsaturated groups (i.e. >C ⁇ C ⁇ ). In other words, they are monoolefinic monomers such as ethylene, propylene, 1-butene, isobutene (2-methyl-1-butene), 1-octene, or polyolefinic monomers (usually diolefinic monomers) such as 1,3-butadiene and isoprene.
  • the olefin monomers are usually polymerizable terminal olefins, i.e. olefins having the >C ⁇ CH 2 group in their structure.
  • polymerizable internal olefin monomers characterized by groups of the formula >C—C ⁇ C—C ⁇ .
  • terminal and internal olefin monomers which can be used to prepare the polyalkenes by conventional methods are: ethylene, propylene, the butenes (butylene), especially 1-butene, 2-butene and isobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 2-pentene, propylene tetramer, diisobutylene, isobutylene trimer, 1,2-butadiene, 1,3-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,5-hexadiene, 2-methyl-5-propyl-1-hexene, 3-pentene, 4-octene and 3,3-dimethyl-1-pentene.
  • the olefin polymer is preparable by polymerization of a C 4 refinery stream having a butene content of about 35 to about 75 percent by weight and an isobutene content of about 30 to about 60 percent by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride.
  • a Lewis acid catalyst such as aluminum trichloride or boron trifluoride.
  • These polybutenes typically comprise predominantly (more than about 80% of all the repeat units) repeat isobutene units of the (—CH 2 —C(CH 3 ) 2 —) type.
  • the polyalkene substituent of the polyalkene-substituted amine is derived from a polyisobutylene.
  • the amines which can be used to form the polyalkene-substituted amine comprise ammonia, monoamines, polyamines or mixtures thereof, including mixtures of various monoamines, mixtures of various polyamines and mixtures of monoamines and polyamines (the diamines).
  • the amines comprise aliphatic, aromatic, heterocyclic and carbocyclic amines.
  • Monoamines and polyamines are characterized by the presence in their structure of at least one HN ⁇ group.
  • the amines may be aliphatic, cycloaliphatic, aromatic or heterocyclic.
  • the monoamines are generally substituted by a hydrocarbyl group having 1 to 50 carbon atoms.
  • hydrocarbyl groups may especially be aliphatic and free of acetylenically unsaturated groups and have 1 to about 30 carbon atoms.
  • the monoamines may have the formula HNR 1 R 2 where R 1 is a hydrocarbyl group having up to 30 carbon atoms and R 2 is hydrogen or a hydrocarbyl group having up to about 30 carbon atoms.
  • suitable monoamines are methylamine, ethylamine, diethylamine, 2-ethylhexylamine, di(2-ethylhexyl)amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamines and oleylamine.
  • Aromatic monoamines are those monoamines in which a carbon atom in the aromatic ring structure is bonded directly to the amine nitrogen atom.
  • the aromatic ring will usually be a monocyclic aromatic ring (i.e. derived from benzene), but may include fused aromatic rings, especially those derived from naphthalene.
  • Examples of aromatic monoamines are aniline, di(para-methylphenyl)amine, naphthylamine, N-(n-butyl)aniline.
  • aliphatic-substituted, cycloaliphatic-substituted and heterocyclic-substituted aromatic monoamines are: para-dodecylaniline, cyclohexyl-substituted naphthylamine and thienyl-substituted aniline.
  • Hydroxylamines are likewise suitable monoamines.
  • Compounds of this kind are the hydroxyhydrocarbyl-substituted analogs of the aforementioned monoamines.
  • the hydroxymonoamines of the formula HNR 3 R 4 where R 3 is a hydroxyl-substituted alkyl group having up to about 30 carbon atoms, and in one embodiment up to about 10 carbon atoms; and R 4 is a hydroxyl-substituted alkyl group having up to about 30 carbon atoms, hydrogen or a hydrocarbyl group having up to about 10 carbon atoms.
  • Examples of hydroxyl-substituted monoamines include: ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine and N-methyl-2-hydroxypropylamine.
  • the amine of the polyalkene-substituted amines may be a polyamine.
  • the polyamine may be aliphatic, cycloaliphatic, heterocyclic or aromatic.
  • Examples of the polyamines include: alkylenepolyamines, hydroxyl group-comprising polyamines, aryl polyamines and heterocyclic polyamines.
  • alkylenepolyamines comprise those of the following formula:
  • n is in the range from 1 to about 10 and, for example, in the range from 2 to about 7, or from 2 to about 5, and the “alkylene” group has 1 to about 10 carbon atoms, for example 2 to about 6, or 2 to about 4 carbon atoms;
  • the R 5 radicals are each independently hydrogen, an aliphatic group, a hydroxyl- or amine-substituted aliphatic group of up to about 30 carbon atoms in each case.
  • R 5 is H or lower alkyl (an alkyl group having 1 to about 5 carbon atoms), especially H.
  • Alkylenepolyamines of this kind include: methylenepolyamines, ethylenepolyamines, butylenepolyamines, propylenepolyamines, pentylenepolyamines, hexylenepolyamines and heptylenepolyamines. The higher homologs of such amines and related aminoalkyl-substituted piperazines are likewise included.
  • alkylenepolyamines for preparation of the polyalkene-substituted amines are the following: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, 3-dimethylaminopropylamine, trimethylenediamine, hexamethylene-diamine, decamethylenediamine, octamethylenediamine, di(heptamethylene)triamine, tripropylenetetramine, pentaethylenehexamine, di(trimethylenetriamine), N-(2-aminoethyl)piperazine and 1,4-bis(2-aminoethyl)piperazine.
  • Ethylenepolyamines such as those mentioned above, are particularly suitable for reasons of cost and effectiveness.
  • Polyamines of this kind are described in detail in the chapter “Diamine und pli Amine” [Diamines and higher amines] in Encyclopedia of Chemical Technology, second edition, Kirk-Othmer, volume 7, pages 27-39, Interscience Publishers, division of John Wiley & Sons, 1965.
  • Compounds of this kind are most conveniently prepared by the reaction of an alkylene chloride with ammonia or by reaction of an ethyleneimine with a ring-opening reagent such as ammonia. These reactions lead to preparation of complex mixtures of alkylenepolyamines, including cyclic condensation products such as piperazines.
  • polyamine bottoms Other suitable types of polyamine mixtures are the products which are formed as residue by stripping the above-described polyamine mixtures and are frequently referred to as “polyamine bottoms”.
  • alkylenepolyamine bottom products those which comprise less than two, usually less than 1%, by weight of material that boils below about 200° C.
  • a typical example of such ethylenepolyamine bottoms is that of the products designated “E-100” from Dow Chemical Company in Freeport, Tex.
  • These alkylenepolyamine bottoms comprise cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramines and the like.
  • Hydroxyl group-comprising polyamines comprise: hydroxyalkylalkylenepolyamines having one or more hydroxyalkyl substituents on the nitrogen atoms.
  • Polyamines of this kind can be prepared by reacting the above-described alkylenepolyamines with one or more alkylene oxides (e.g. ethylene oxide, propylene oxide and butylene oxide).
  • alkylene oxides e.g. ethylene oxide, propylene oxide and butylene oxide
  • Similar alkylene oxide-alkanolamine reaction products may also, for example, be the products of the reaction of primary, secondary or tertiary alkanolamines with ethylene, propylene or higher epoxides in a molar ratio of 1:1 to 1:2. Reactant ratios and temperatures for performance of such reactions are known to those skilled in the art.
  • the hydroxyalkyl-substituted alkylenepolyamine may be a compound in which the hydroxyalkyl group is a hydroxy-lower alkyl group, i.e. has fewer than eight carbon atoms.
  • hydroxyalkyl-substituted polyamines examples include N-(2-hydroxyethyl)ethylenediamine (also known as 2-(2-aminoethylamino)ethanol), N,N-bis(2-hydroxyethyl)ethylenediamine, 1-(2-hydroxyethyl)piperazine, monohydroxypropyl-substituted diethylenetriamine, dihydroxypropyl-substituted tetraethylenepentamine and N-(3-hydroxybutyl)tetramethylenediamine.
  • N-(2-hydroxyethyl)ethylenediamine also known as 2-(2-aminoethylamino)ethanol
  • N,N-bis(2-hydroxyethyl)ethylenediamine 1-(2-hydroxyethyl)piperazine
  • monohydroxypropyl-substituted diethylenetriamine dihydroxypropyl-substituted tetraethylenepentamine
  • N-(3-hydroxybutyl)tetramethylenediamine examples
  • Aryl polyamines are analogs of the abovementioned aromatic monoamines.
  • aryl polyamines include: N,N′-di-n-butyl-para-phenylenediamine and bis(para-aminophenyl)methane.
  • Heterocyclic mono- and polyamines may comprise: aziridines, azetidines, azolidines, pyridines, pyrroles, indoles, piperidines, imidazoles, piperazines, isoindoles, purines, morpholines, thiomorpholines, N-aminoalkylmorpholines, N-aminoalkylthiomorpholines, N-aminoalkylpiperazines, N,N′-diaminoalkylpiperazines, azepines, azocines, azonines, anovanes and tetra-, di- and perhydro derivatives of each of the above compounds and mixtures of two or more of these heterocyclic amines.
  • Typical heterocyclic amines are saturated 5- and 6-membered heterocyclic amines having only nitrogen, oxygen and/or sulfur in the heterocycle, especially piperidines, piperazines, thiomorpholines, morpholines, pyrrolidines and the like.
  • Piperidine, aminoalkyl-substituted piperidines, piperazine, aminoalkyl-substituted piperazines, morpholine, aminoalkyl-substituted morpholines, pyrrolidine and aminoalkyl-substituted pyrrolidines are particularly preferred.
  • the aminoalkyl substituents are bonded to a nitrogen atom which is part of the heterocycle.
  • heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine and N,N′-diaminoethylpiperazine.
  • Hydroxyheterocyclic polyamines are also suitable. Examples include: N-(2-hydroxyethyl)cyclohexylamine, 3-hydroxycyclopentylamine, para-hydroxyaniline and N-hydroxyethylpiperazine.
  • polyalkene-substituted amines are as follows: poly(propylene)amine, poly(butene)amine, N,N-dimethylpolyisobutyleneamines; polybutenemorpholines, N,N-poly(butene)ethylenediamine, N-poly(propylene)trimethylenediamine, N-poly(butene), diethylenetriamine, N′,N′-poly(butene)tetraethylenepentamine and N,N-dimethyl-N′-poly(propylene)-1,3-propylenediamine.
  • the number-average molecular weight of such polyalkene-substituted amines is about 500 to about 5000, for example 1000 to about 1500 or about 500 to about 3000.
  • any of the abovementioned polyalkene-substituted amines which are secondary or primary amines can be alkylated to tertiary amines with alkylating agents which are also known as quaternizing agents, such as dialkyl sulfates, alkyl halides, hydrocarbyl-substituted carbonates; hydrocarbyl epoxides in combination with an acid and mixtures thereof. If particular quaternizing agents, such as alkyl halides or dialkyl sulfates, are used, it may be necessary to provide a base or basic compositions, such as sodium carbonate or sodium hydroxide, to give the free tertiary amine form.
  • alkylating agents which are also known as quaternizing agents, such as dialkyl sulfates, alkyl halides, hydrocarbyl-substituted carbonates; hydrocarbyl epoxides in combination with an acid and mixtures thereof.
  • Primary amines require two equivalents of alkylating agent and two equivalents of base to obtain a tertiary amine.
  • the alkylation of primary amines can frequently be conducted in four successive steps, first a treatment with the alkylating agent and second treatment with a base and then repetition of the two steps.
  • the alkylation of a primary amine will be effected in one step, for example using two moles of alkyl halide in the presence of an excess of heterogeneous base, such as sodium carbonate.
  • the polyamine can be exhaustively or partially alkylated in a manner known per se.
  • the alkylation of primary amines and secondary amines to tertiary amines can be effected with epoxides.
  • no treatment with base is required in the case of use of an epoxide to obtain the free amine.
  • at least one mole of epoxide is used for each hydrogen atom in the amine.
  • neither additional acid nor base is required.
  • polyisobutenedimethylamine obtainable by hydroformylating polyisobutene (Mn 1000) and subsequent reductive amination with dimethylamine; see Example B of WO 2008/060888.
  • Suitable hydrocarbyl-substituted polycarboxylic acid compounds, or hydrocarbyl-substituted acylating agents include:
  • the polycarboxylic acid compounds used are aliphatic di- or polybasic (for example tri- or tetrabasic), especially from di-, tri- or tetracarboxylic acids and analogs thereof, such as anhydrides or lower alkyl esters (partially or completely esterified), and are optionally substituted by one or more (for example 2 or 3), especially one long-chain alkyl radical and/or one high molecular weight hydrocarbyl radical, especially one polyalkylene radical.
  • di- or polybasic for example tri- or tetrabasic
  • di-, tri- or tetracarboxylic acids and analogs thereof such as anhydrides or lower alkyl esters (partially or completely esterified)
  • one or more for example 2 or 3
  • especially one long-chain alkyl radical and/or one high molecular weight hydrocarbyl radical especially one polyalkylene radical.
  • Examples are C 3 -C 10 polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and the branched analogs thereof; and the tricarboxylic acid citric acid; and anhydrides or lower alkyl esters thereof of.
  • the polycarboxylic acid compounds can also be obtained from the corresponding monounsaturated acids and addition of at least one long-chain alkyl radical and/or high molecular weight hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric acid, maleic acid, itaconic acid.
  • the hydrophobic “long-chain” or “high molecular weight” hydrocarbyl radical which ensures sufficient solubility of the quaternized product in the fuel has a number-average molecular weight (M n ) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500.
  • Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and polyisobutenyl radicals, for example with a number-average molecular weight M n of 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500.
  • Suitable hydrocarbyl-substituted compounds are described, for example, in DE 43 19 672 and WO2008/138836.
  • Suitable hydrocarbyl-substituted polycarboxylic acid compounds also comprise polymeric, especially dimeric, forms of such hydrocarbyl-substituted polycarboxylic acid compounds.
  • Dimeric forms comprise, for example, two acid anhydride groups which can be reacted independently with the quaternizable nitrogen compound in the preparation process according to the invention.
  • the quaternizable nitrogen compounds reactive with the above polycarboxylic acid compound are selected from
  • the quaternizable nitrogen compounds are especially selected from
  • Suitable “hydroxyalkyl-substituted mono- or polyamines” are those provided with at least one hydroxyalkyl substituent, for example 1, 2, 3, 4, 5 or 6 hydroxyalkyl substituent.
  • hydroxyalkyl-substituted monoamines include: N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl monoamines and N,N,N-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl.
  • hydroxyalkyl-substituted polyamines and especially “hydroxyalkyl-substituted diamines” may be mentioned: (N-hydroxyalkyl)alkylenediamines, N,N-dihydroxyalkylalkylenediamines, where the hydroxyalkyl groups are the same or different and are also as defined above.
  • Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl; alkylene is especially ethylene, propylene or butylene.
  • Suitable “diamines” are alkylenediamines, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated alkylenediamines and the N,N- or N,N′-dialkylated alkylenediamines.
  • Alkylene is especially straight-chain or branched C 1-7 - or C 1-4 -alkylene as defined above.
  • Alkyl is especially C 1-4 -alkyl as defined above.
  • Examples are especially ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and singly or multiply, for example singly or doubly, C 1 -C 4 -alkylated, for example methylated, derivatives of the aforementioned diamine compounds such as 3-dimethylamino-1-propylamine (DMAPA), N,N-diethylaminopropylamine and N,N-dimethylamino-ethylamine.
  • DMAPA 3-dimethylamino-1-propylamine
  • N,N-diethylaminopropylamine N,N-dimethylamino-ethylamine.
  • Suitable straight-chain “polyamines” are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkylenepentamine, pentaalkylenehexamine, and the N-alkyl-substituted analogs thereof, such as N-monoalkylated and the N,N- or N,N′-dialkylated alkylenepolyamines.
  • Alkylene is especially straight-chain or branched C 1-7 - or C 1-4 -alkylene as defined above.
  • Alkyl is especially C 1-4 -alkyl as defined above.
  • Examples are especially diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, dibutylenetriamine, tributylenetetramine, tetrabutylenepentamine, pentabutylenehexamine; and the N,N-dialkyl derivatives thereof, especially the N,N-di-C 1-4 -alkyl derivatives thereof.
  • Examples include: N,N-dimethyldimethylenetriamine, N,N-diethyldimethylenetriamine, N,N-dipropyldimethylenetriamine, N,N-dimethyldiethylene-1,2-triamine, N,N-diethyldiethylene-1,2-triamine, N,N-dipropyldiethylene-1,2-triamine, N,N-dimethyldipropylene-1,3-triamine (i.e.
  • DMAPAPA N,N-diethyldipropylene-1,3-triamine, N,N-dipropyldipropylene-1,3-triamine, N,N-dimethyldibutylene-1,4-triamine, N,N-diethyldibutylene-1,4-triamine, N,N-dipropyldibutylene-1,4-triamine, N, N-dimethyldipentylene-1,5-triamine, N,N-diethyldipentylene-1,5-triamine, N, N-dipropyldipentylene-1,5-triamine, N,N-dimethyldihexylene-1,6-triamine, N, N-diethyldihexylene-1,6-triamine and N,N-dipropyldihexylene-1,6-triamine.
  • “Aromatic carbocyclic diamines” having two primary amino groups are the diamino-substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, fluorene, indene and phenanthrene.
  • “Aromatic or nonaromatic heterocyclic polyamines” having two primary amino groups are the derivatives, substituted by two amino groups, of the following heterocycles:
  • “Aromatic or nonaromatic heterocycles having one primary and one tertiary amino group” are, for example, the abovementioned N-heterocycles which are aminoalkylated on at least one ring nitrogen atom, and especially bear an amino-C 1-4 -alkyl group.
  • “Aromatic or nonaromatic heterocycles having a tertiary amino group and a hydroxyalkyl group” are, for example, the abovementioned N-heterocycles which are hydroxyalkylated on at least one ring nitrogen atom, and especially bear a hydroxy-C 1-4 -alkyl group.
  • Group 2 NAME FORMULA Heterocycles 1-(3-Aminopropyl)imidazole 4-(3-Aminopropyl)morpholine 1-(2-Aminoethylpiperidine) 2-(1-Piperazinyl)ethylamine (AEP) N-Methylpiperazine Amines with a tertiary second nitrogen atom 3,3-Diamino-N-methyldipropylamine 3-Dimethylamino-1-propylamine (DMAPA) N,N-Diethylaminopropylamine N,N-Dimethylaminoethylamine
  • Group 3 NAME FORMULA Alcohols with a primary and secondary amine Ethanolamine 3-Hydroxy-1-propylamine Diethanolamine Diisopropanolamine N-(2-Hydroxyethyl)ethylenediamine Alcohols with a tertiary amine Triethanolamine, (2,2′,2′′-nitrilotriethanol) 1-(3-Hydroxypropyl)imidazole Tris(hydroxymethyl)amine 3-Dimethylamino-1-propanol 3-Diethylamino-1-propanol 2-Dimethylamino-1-ethanol 4-Diethylamino-1-butanol
  • the hydrocarbyl-substituted polycarboxylic acid compound can be reacted with the quaternizable nitrogen compound under thermally controlled conditions, such that there is essentially no condensation reaction. More particularly, no formation of water of reaction is observed in that case. More particularly, such a reaction is effected at a temperature in the range from 10 to 80° C., especially 20 to 60° C. or 30 to 50° C.
  • the reaction time may be in the range from a few minutes or a few hours, for example about 1 minute up to about 10 hours.
  • the reaction can be effected at a pressure of about 0.1 to 2 atm, but especially at approximately standard pressure. For example, an inert gas atmosphere, for example nitrogen, is appropriate.
  • the reaction can also be effected at elevated temperatures which promote condensation, for example in the range from 90 to 100° C. or 100 to 170° C.
  • the reaction time may be in the region of a few minutes or a few hours, for example about 1 minute up to about 10 hours.
  • the reaction can be effected at pressure at about 0.1 to 2 atm, but especially at about standard pressure.
  • the reactants are initially charged especially in about equimolar amounts; optionally, a small molar excess of the polycarboxylic acid compound, for example a 0.05- to 0.5-fold, for example a 0.1- to 0.3-fold, excess, is desirable.
  • the reactants can be initially charged in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are, for example, solvents of the Solvesso series, toluene or xylene.
  • the solvent can also serve, for example, to remove water of condensation azeotropically from the reaction mixture. More particularly, however, the reactions are performed without solvent.
  • reaction product thus formed can theoretically be purified further, or the solvent can be removed. Usually, however, this is not absolutely necessary, such that the reaction product can be transferred without further purification into the next synthesis step, the quaternization.
  • the at least one quaternizable tertiary nitrogen atom is quaternized with at least one quaternizing agent selected from epoxides, especially hydrocarbyl epoxides.
  • R d radicals present therein are the same or different and are each H or a hydrocarbyl radical, where the hydrocarbyl radical has at least 1 to 10 carbon atoms. More particularly, these are aliphatic or aromatic radicals, for example linear or branched C 1-10 -alkyl radicals, or aromatic radicals, such as phenyl or C 1-4 -alkylphenyl.
  • hydrocarbyl epoxides include aliphatic and aromatic alkylene oxides such as, more particularly, C 2-12 -alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propene oxide (isobutene oxide), 1,2-pentene oxide, 2,3-pentene oxide, 2-methyl-1,2-butene oxide, 3-methyl-1,2-butene oxide, 1,2-hexene oxide, 2,3-hexene oxide, 3,4-hexene oxide, 2-methyl-1,2-pentene oxide, 2-ethyl-1,2-butene oxide, 3-methyl-1,2-pentene oxide, 1,2-decene oxide, 1,2-dodecene oxide or 4-methyl-1,2-pentene oxide; and aromatic-substituted ethylene oxides such as optionally substituted styrene oxide, especially styrene oxide or 4-methylstyrene oxide.
  • epoxides as quaternizing agents, these are used in the presence of free acids, especially in the presence of free hydrocarbyl-substituted unsaturated, especially saturated, optionally substituted, especially unsubstituted, protic acids, such as particularly with hydrocarbyl-substituted dicarboxylic acids, especially hydrocarbyl-substituted C 3 -C 28 or C 3 -C 12 -dicarboxylic acids, especially unsubstituted saturated C 3 -C 6 -dicarboxylic acid.
  • Suitable dicarboxylic acids here are saturated acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid, or higher molecular weight acids, such as tetra-, hexa- or octadecanedioic acid; substituted acids, such as malic acid, ⁇ -ketoglutaric acid, oxaloacetic acid; glutamic acid; aspartic acid; and unsaturated acids, such as maleic acid and fumaric acid; such as, more particularly, malonic acid, succinic acid, glutaric acid, adipic acid and pimelic acid.
  • saturated acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid
  • aromatic dicarboxylic acids for example phthalic acid.
  • hydrocarbyl-substituted dicarboxylic acids in their anhydride form.
  • the ring opening of the anhydride is then brought about by addition of water.
  • the hydrocarbyl-substituted dicarboxylic acids can be prepared by hydrolysis of the corresponding hydrocarbyl-substituted dicarboxylic anhydrides in a manner known in principle, as described, for example, in DE 2443537.
  • the hydrolysis is preferably conducted with stoichiometric amounts of water at temperatures of 50 to 150° C., but it is also possible to use an excess of water.
  • the hydrolysis can be conducted without solvent or in the presence of an inert solvent. Typical examples are, for example, solvents from the Solvesso series, toluene, xylene or straight-chain and branched saturated hydrocarbons such as paraffins or naphthenes.
  • the solvent can be removed after the hydrolysis, but preferably remains, and is used as solvent or cosolvent for the subsequent quaternization.
  • hydrocarbyl-substituted dicarboxylic anhydrides are hydrocarbyl-substituted succinic anhydrides, as sold, for example, by Pentagon: n-dodecenylsuccinic anhydride CAS 19780-11-1, n-octadecenylsuccinic anhydride CAS 28777-98-2, i-octadecenylsuccinic anhydride CAS 28777-98-2, i-hexadecenylsuccinic anhydride/i-octadecenylsuccinic anhydride CAS 32072-96-1 & 28777-98-2, n-octenylsuccinic anhydride CAS 26680-54-6, tetrapropenylsuccinic anhydride CAS 26544-38-7.
  • polyisobutenesuccinic anhydride PIBSA
  • PIB polyisobutene
  • MA maleic anhydride
  • BML bismaleation level
  • PIBSA having a bismaleation level of up to 30%, preferably up to 25% and more preferably up to 20%.
  • the bismaleation level is at least 2%, preferably at least 5% and more preferably at least 10%.
  • Controlled preparation is described, for example, in U.S. Pat. No. 5,883,196.
  • HR-PIB high-reactivity PIB
  • Mn is determined by means of GPC as described in U.S. Pat. No. 5,883,196.
  • Such an alcoholysis is preferably conducted with stoichiometric amounts of alcohol or amine at temperatures of 50 to 150° C., but it is also possible to use an excess of alcohol or amine, preferably alcohol. In that case, the latter appropriately remains in the reaction mixture and serves as solvent in the subsequent quaternization.
  • the quaternization with an epoxide of the formula (4) is likewise based on known processes.
  • the boiling temperature of one component of the reaction mixture, especially of the epoxide, at standard pressure is above the reaction temperature, the reaction is appropriately performed in an autoclave.
  • a solution of the tertiary amine is admixed with the organic hydrocarbyl-substituted dicarboxylic acid (for example polyisobutenesuccinic acid) in the required, approximately stoichiometric amounts.
  • the organic hydrocarbyl-substituted dicarboxylic acid for example polyisobutenesuccinic acid
  • propylene oxide in the stoichiometric amounts required at a temperature between 20° C. and 180° C. It is possible to use, for example, 0.1 to 4.0, 0.2 to 3 or 0.5 to 2 equivalents of epoxide per equivalent of quaternizable tertiary nitrogen atom. More particularly, however, about 1 to 2 equivalents of epoxide are used in relation to the tertiary amine, in order to fully quaternize the tertiary amine group. More particularly, it is also possible to use a molar excess of alkylene oxide, as a result of which the free carboxyl group of the dicarboxylic acid is partly or fully esterified.
  • the reaction can be effected at a pressure of about 0.1 to 20 bar, for example 1 to 10 or 1.5 to 5 bar. However, the reaction can also be effected at standard pressure.
  • An inert gas atmosphere is particularly appropriate, for example nitrogen.
  • the reactants can be initially charged for the quaternization in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof.
  • suitable inert organic aliphatic or aromatic solvent or a mixture thereof are, for example, solvents from the Solvesso series, toluene or xylene or 2-ethylhexanol, or 2-propylheptanol, and also butyldiglycol, butylglycol, methoxypropoxypropanol, butoxydipropanol or straight-chain or branched saturated hydrocarbons such as paraffins or naphthenes.
  • the quaternization can also be performed in the absence of a solvent.
  • the quaternization can be performed in the presence of a protic solvent, optionally also in combination with an aliphatic or aromatic solvent.
  • Suitable protic solvents especially have a dielectric constant (at 20° C.) of greater than 7.
  • the protic solvent may comprise one or more OH groups and may also be water.
  • Suitable solvents may also be alcohols, glycols and glycol ethers. More particularly, suitable protic solvents may be those specified in WO 2010132259.
  • Especially suitable solvents are methanol, ethanol, n-propanol, isopropanol, all isomers of butanol, all isomers of pentanol, all isomers of hexanol, 2-ethylhexanol, 2-propylheptanol, and also mixtures of various alcohols.
  • the presence of a protic solvent can have a positive effect on the conversion and the reaction rate of the quaternization.
  • reaction end product thus formed can theoretically be purified further, or the solvent can be removed.
  • excess reagent for example excess epoxide
  • solvents after the reaction for example solvents of the Solvesso series, 2-ethylhexanol, or essentially aliphatic solvents.
  • solvents for example solvents of the Solvesso series, 2-ethylhexanol, or essentially aliphatic solvents.
  • the quaternized ammonium compounds have a weight loss in a thermogravimetric analysis (TGA) at 350° C. of less than 50% by weight, for example less than 40%, less than 35%, less than 30%, less than 20% or less than 15%, for example down to 0% to 5% weight loss.
  • TGA thermogravimetric analysis
  • thermogravimetric analysis is conducted in accordance with standard ISO-4154. Specifically, in the test, a run from 50° to 900° C. is conducted at a rate of temperature rise of 20° C. per minute under a nitrogen atmosphere at a flow rate of 60 mL per minute.
  • the fuel additized with the inventive quaternized additive is a gasoline fuel or especially a middle distillate fuel, in particular a diesel fuel.
  • the fuel may comprise further customary additives to improve efficacy and/or suppress wear.
  • lubricity improvers in particular lubricity improvers (friction modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistats, metallocenes, metal deactivators, dyes and/or solvents.
  • the customary detergent additives are preferably amphiphilic substances which possess at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M n ) of 85 to 20 000 and at least one polar moiety selected from:
  • the hydrophobic hydrocarbon radical in the above detergent additives which ensures adequate solubility in the fuel, has a number-average molecular weight (M n ) of 85 to 20 000, preferably of 113 to 10 000, more preferably of 300 to 5000, even more preferably of 300 to 3000, even more especially preferably of 500 to 2500 and especially of 700 to 2500, in particular of 800 to 1500.
  • M n number-average molecular weight
  • hydrophobic hydrocarbon radicals especially in conjunction with the polar, especially polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight M n of preferably in each case 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500 into consideration.
  • detergent additives examples include the following:
  • Such additives based on high-reactivity polyisobutene which can be prepared from the polyisobutene which may comprise up to 20% by weight of n-butene units by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known especially from EP-A 244 616.
  • additives comprising monoamino groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described more particularly in DE-A 196 20 262.
  • These reaction products are generally mixtures of pure nitropolyisobutenes (e.g. ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g. ⁇ -nitro- ⁇ -hydroxypolyisobutene).
  • Additives comprising carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to C 40 -olefins with maleic anhydride which have a total molar mass of 500 to 20 000 and wherein some or all of the carboxyl groups have been converted to the alkali metal or alkaline earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines.
  • Such additives are disclosed more particularly by EP-A 307 815.
  • Such additives serve mainly to prevent valve seat wear and can, as described in WO-A 87/01126, advantageously be used in combination with customary fuel detergents such as poly(iso)buteneamines or polyetheramines.
  • Additives comprising sulfonic acid groups or their alkali metal or alkaline earth metal salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as described more particularly in EP-A 639 632.
  • Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as poly(iso)buteneamines or polyetheramines.
  • Additives comprising polyoxy-C 2 -C 4 -alkylene moieties are preferably polyethers or polyetheramines which are obtainable by reaction of C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are described more particularly in EP-A 310 875, EP-A 356 725, EP-A 700 985 and U.S. Pat. No. 4,877,416.
  • polyethers such products also have carrier oil properties. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.
  • Additives comprising carboxylic ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 /s at 100° C., as described more particularly in DE-A 38 38 918.
  • the mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, of isononanol, of isodecanol and of isotridecanol. Such products also satisfy carrier oil properties.
  • the moieties having hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • the further detergent additive in the context of the present invention is, however, used only up to a maximum of 100% of the weight of compounds with betaine structure.
  • Such fuel additives are common knowledge and are described, for example, in documents (1) and (2). They are preferably the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and more preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
  • reaction products with aliphatic polyamines such as especially ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
  • Additives comprising moieties (Di) obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • Such “polyisobutene Mannich bases” are described more particularly in EP-A 831 141.
  • One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm by weight.
  • Carrier oils additionally used may be of mineral or synthetic nature. Suitable mineral carrier oils are fractions obtained in crude oil processing, such as brightstock or base oils having viscosities, for example, from the SN 500-2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. Likewise useful is a fraction which is obtained in the refining of mineral oil and is known as “hydrocrack oil” (vacuum distillate cut having a boiling range of from about 360 to 500° C., obtainable from natural mineral oil which has been catalytically hydrogenated under high pressure and isomerized and also deparaffinized). Likewise suitable are mixtures of the abovementioned mineral carrier oils.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternalolefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably compounds comprising polyoxy-C 2 - to C 4 -alkylene moieties obtainable by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines.
  • the polyetheramines used may be poly-C 2 - to C 6 -alkylene oxide amines or functional derivatives thereof. Typical examples thereof are tridecanol butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also polyisobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia.
  • carboxylic esters of long-chain alkanols are more particularly esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described more particularly in DE-A 38 38 918.
  • the mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids; particularly suitable ester alcohols or ester polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyl) phthalate.
  • suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 C 3 - to C 6 -alkylene oxide units, for example propylene oxide, n-butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule.
  • suitable starter alcohols are long-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is especially a straight-chain or branched C 6 - to C 18 -alkyl radical.
  • Particular examples include tridecanol and nonylphenol.
  • Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides.
  • monohydric aliphatic C 6 -C 15 -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and the constitutional and positional isomers thereof.
  • the alcohols can be used either in the form of the pure isomers or in the form of technical grade mixtures.
  • a particularly preferred alcohol is tridecanol.
  • C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Particular preference among these is given to C 3 - to C 4 -alkylene oxides, i.e. propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide. Especially butylene oxide is used.
  • suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
  • Particular carrier oils are synthetic carrier oils, particular preference being given to the above-described alcohol-started polyethers.
  • the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, more preferably of 10 to 500 ppm by weight and especially of 20 to 100 ppm by weight.
  • Suitable cold flow improvers are in principle all organic compounds which are capable of improving the flow performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. More particularly, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flow improvers, MDFIs) typically used in the case of middle distillates of fossil origin, i.e. in the case of customary mineral diesel fuels. However, it is also possible to use organic compounds which partly or predominantly have the properties of a wax antisettling additive (WASA) when used in customary diesel fuels. They can also act partly or predominantly as nucleators. It is also possible to use mixtures of organic compounds effective as MDFIs and/or effective as WASAs and/or effective as nucleators.
  • WASA wax antisettling additive
  • the cold flow improver is typically selected from
  • Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20 and especially 2 to 10 carbon atoms, and 1 to 3 and preferably 1 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond.
  • the carbon-carbon double bond may be arranged either terminally ( ⁇ -olefins) or internally.
  • ⁇ -olefins preference is given to ⁇ -olefins, particular preference to ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and in particular ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters and further olefins.
  • further olefins are also copolymerized, they are preferably higher in molecular weight than the abovementioned C 2 - to C 40 -olefin base monomer.
  • the olefin base monomer used is ethylene or propene
  • suitable further olefins are especially C 10 - to C 40 - ⁇ -olefins. Further olefins are in most cases only additionally copolymerized when monomers with carboxylic ester functions are also used.
  • Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, especially C 1 - to C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, and structural isomers thereof.
  • Suitable alkenyl carboxylates are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbyl radical may be linear or branched.
  • preference is given to the vinyl esters.
  • carboxylic acids with a branched hydrocarbyl radical preference is given to those whose branch is in the ⁇ position to the carboxyl group, and the ⁇ -carbon atom is more preferably tertiary, i.e. the carboxylic acid is what is called a neocarboxylic acid.
  • the hydrocarbyl radical of the carboxylic acid is preferably linear.
  • alkenyl carboxylates examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference being given to the vinyl esters.
  • a particularly preferred alkenyl carboxylate is vinyl acetate; typical copolymers of group (K1) resulting therefrom are ethylene-vinyl acetate copolymers (“EVAs”), which are some of the most frequently used.
  • Ethylene-vinyl acetate copolymers usable particularly advantageously and the preparation thereof are described in WO 99/29748.
  • Suitable copolymers of class (K1) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group.
  • copolymers which, as well as the alkenyl carboxylate(s), comprise at least one olefin and/or at least one (meth)acrylic ester in copolymerized form.
  • Terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable as copolymers of class (K1).
  • Terpolymers of this kind are described in WO 2005/054314.
  • a typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate.
  • the at least one or the further ethylenically unsaturated monomer(s) are copolymerized in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer.
  • the main proportion in terms of weight of the monomer units in the copolymers of class (K1) therefore originates generally from the C 2 - to C 40 base olefins.
  • the copolymers of class (K1) preferably have a number-average molecular weight Mn of 1000 to 20 000, more preferably of 1000 to 10 000 and especially of 1000 to 8000.
  • Typical comb polymers of component (K2) are, for example, obtainable by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol having at least 10 carbon atoms.
  • Further suitable comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid.
  • Suitable comb polymers may also be polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers.
  • Comb polymers suitable as components of class (K2) are, for example, also those described in WO 2004/035715 and in “Comb-Like Polymers. Structure and Properties”, N. A. Plate and V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pages 117 to 253 (1974). Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as components of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, preferably at least two linear alkyl groups, each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are described, for example, in EP A 061 895 and also in U.S. Pat. No. 4,491,455. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000. Additionally suitable are polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
  • Polar nitrogen compounds suitable as components of class (K4) may be either ionic or nonionic and preferably have at least one substituent, especially at least two substituents, in the form of a tertiary nitrogen atom of the general formula >NR 7 in which R 7 is a C 8 - to C 40 -hydrocarbyl radical.
  • the nitrogen substituents may also be quaternized, i.e. be in cationic form.
  • An example of such nitrogen compounds is that of ammonium salts and/or amides which are obtainable by the reaction of at least one amine substituted by at least one hydrocarbyl radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines preferably comprise at least one linear C 8 - to C 40 -alkyl radical.
  • Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures especially amine mixtures obtainable on the industrial scale, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th Edition, “Amines, aliphatic” chapter.
  • Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and succinic acids substituted by long-chain hydrocarbyl radicals.
  • the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group with primary or secondary amines.
  • the poly(C 2 - to —C 20 -carboxylic acids) which have at least one tertiary amino group and form the basis of this reaction product comprise preferably at least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids have preferably 2 to 10 carbon atoms, and are especially acetic acid units.
  • the carboxylic acid units are suitably bonded to the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of a plurality of nitrogen atoms, are bonded via hydrocarbon chains.
  • the component of class (K4) is preferably an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are of the general formula IIa or IIb
  • variable A represents a straight-chain or branched C 2 - to C 6 -alkylene group or the moiety of the formula III
  • variable B denotes a C 1 - to C 19 -alkylene group.
  • the compounds of the general formulae IIa and IIb especially have the properties of a WASA.
  • the preferred oil-soluble reaction product of component (K4) is an amide, an amide-ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups have been converted to amide groups.
  • Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1,2-ethylene.
  • the variable A comprises preferably 2 to 4 and especially 2 or 3 carbon atoms.
  • C 1 - to C 19 -alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene.
  • the variable B comprises preferably 1 to 10 and especially 1 to 4 carbon atoms.
  • the primary and secondary amines as a reaction partner for the polycarboxylic acids to form component (K4) are typically monoamines, especially aliphatic monoamines. These primary and secondary amines may be selected from a multitude of amines which bear hydrocarbyl radicals which may optionally be bonded to one another.
  • These parent amines of the oil-soluble reaction products of component (K4) are usually 10 secondary amines and have the general formula HN(R 8 ) 2 in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, especially C 14 - to C 24 -alkyl radicals.
  • These relatively long-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals derive from naturally occurring fatty acids and from derivatives thereof.
  • the two R 8 radicals are preferably the same.
  • the secondary amines mentioned may be bonded to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; it is also possible for only a portion to be present as amide structures and another portion as ammonium salts. Preferably only few, if any, free acid groups are present.
  • the oil-soluble reaction products of component (K4) are preferably present completely in the form of the amide structures.
  • Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, of ethylenediaminetetraacetic acid or of propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, especially 0.8 to 1.2 mol per carboxyl group, of dioleylamine, dipalmitamine, dicocoamine, distearylamine, dibehenylamine or especially ditallowamine.
  • a particularly preferred component (K4) is the reaction product of 1 mol of ethylenediaminetetraacetic acid and 4 mol of hydrogenated ditallowamine.
  • component (K4) include the N,N-dialkylammonium salts of 2-N′,N′-dialkylamidobenzoates, for example the reaction product of 1 mol of phthalic anhydride and 2 mol of ditallowamine, the latter being hydrogenated or unhydrogenated, and the reaction product of 1 mol of an alkenylspirobislactone with 2 mol of a dialkylamine, for example ditallowamine and/or tallowamine, the latter two being hydrogenated or unhydrogenated.
  • component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/18115.
  • Sulfocarboxylic acids, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic esters of ortho-sulfobenzoic acid, in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957.
  • Poly(meth)acrylic esters suitable as cold flow improvers of the component of class (K6) are either homo- or copolymers of acrylic and methacrylic esters. Preference is given to copolymers of at least two different (meth)acrylic esters which differ with regard to the esterified alcohol.
  • the copolymer optionally comprises another different olefinically unsaturated monomer in copolymerized form.
  • the weight-average molecular weight of the polymer is preferably 50 000 to 500 000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated C 14 - and C 15 -alcohols, the acid groups having been neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic esters are described, for example, in WO 00/44857.
  • the cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, more preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm by weight and especially of 100 to 700 ppm by weight, for example of 200 to 500 ppm by weight.
  • Suitable lubricity improvers or friction modifiers are based typically on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described, for example, in WO 98/004656, and glyceryl monooleate.
  • the reaction products, described in U.S. Pat. No. 6,743,266 B2, of natural or synthetic oils, for example triglycerides, and alkanolamines are also suitable as such lubricity improvers.
  • Suitable corrosion inhibitors are, for example, succinic esters, in particular with polyols, fatty acid derivatives, for example oleic esters, oligomerized fatty acids, substituted ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Afton Corporation).
  • Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth metal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e.g.
  • tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EO/PO block copolymers, polyethyleneimines or else polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
  • Suitable antifoams are, for example, polyether-modified polysiloxanes, for example the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
  • Suitable cetane number improvers are, for example, aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
  • Suitable antioxidants are, for example, substituted phenols, such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol, and also phenylenediamines such as N,N′-di-sec-butyl-p-phenylenediamine.
  • Suitable metal deactivators are, for example, salicylic acid derivatives such as N,N′-disalicylidene-1,2-propanediamine.
  • Suitable solvents are, for example, nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, white spirit and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • solvents are usually added to the diesel fuel together with the aforementioned additives and coadditives, which they are intended to dissolve or dilute for better handling.
  • the compounds of the invention are combined with further auxiliaries to counteract internal and external deposits in injectors in diesel engines.
  • These may preferably be olefin-polymerizable carboxylic acid copolymers, where the copolymer comprises at least one free carboxylic acid side group, or a nitrogen compound quaternized with epoxide in the presence of an olefin-polymerizable carboxylic acid copolymer, where the copolymer comprises at least one free carboxylic acid side group, where the polymerizable carboxylic acid is a polymerizable mono- or polycarboxylic acid.
  • copolymers may be copolymers, copolymer-containing reaction products or a copolymer-containing component fraction thereof, where the copolymer is obtainable by
  • copolymerizing a) at least one ethylenically unsaturated, polymerizable polycarboxylic anhydride with b) at least one polymerizable olefin; (2) then derivatizing the copolymer from step (1) by partial or complete reaction of the anhydride radicals of the copolymer from step (1) with water, at least one hydroxyl compound, at least one primary or secondary amine; or mixtures thereof, to form a carboxyl-containing copolymer derivative; and optionally (3) quaternizing a quaternizable (especially tertiary) nitrogen compound with an epoxide and the copolymer derivative from step (2).
  • copolymers may be copolymers, copolymer-containing reaction products or a copolymer-containing component fraction thereof, where the copolymer is obtainable by
  • copolymerizing a) at least one ethylenically unsaturated, polymerizable mono- or polycarboxylic acid with b) at least one polymerizable olefin; (2) then derivatizing the copolymer from step (1) by partial reaction of the carboxyl radicals of the copolymer with at least one hydroxyl compound, at least one primary or 25 secondary amine; or mixtures thereof, to form a copolymer derivative having a reduced content of free carboxyl groups; and optionally (3) quaternizing a quaternizable nitrogen compound with an epoxide and the copolymer derivative from step (2).
  • copolymers may be copolymers, copolymer-containing reaction products or a copolymer-containing component fraction thereof, where the copolymer is obtainable by
  • Copolymer compounds of this kind are described, for example, in European patent application EP application number 14152991.7 to the present applicant.
  • the inventive additive is outstandingly suitable as a fuel additive and can be used in principle in any fuels. It brings about a whole series of advantageous effects in the operation of internal combustion engines with fuels. Preference is given to using the inventive quaternized additive in middle distillate fuels, especially diesel fuels.
  • the present invention therefore also provides fuels, especially middle distillate fuels, with a content of the inventive quaternized additive which is effective as an additive for achieving advantageous effects in the operation of internal combustion engines, for example of diesel engines, especially of direct injection diesel engines, in particular of diesel engines with common rail injection systems.
  • This effective content is generally 10 to 5000 ppm by weight, preferably 20 to 1500 ppm by weight, especially 25 to 1000 ppm by weight, in particular 30 to 750 ppm by weight, based in each case on the total amount of fuel.
  • Middle distillate fuels such as diesel fuels or heating oils are preferably mineral oil raffinates which typically have a boiling range from 100 to 400° C. These are usually distillates having a 95% point up to 360° C. or even higher. These may also be what is called “ultra low sulfur diesel” or “city diesel”, characterized by a 95% point of, for example, not more than 345° C. and a sulfur content of not more than 0.005% by weight or by a 95% point of, for example, 285° C. and a sulfur content of not more than 0.001% by weight.
  • mineral middle distillate fuels or diesel fuels obtainable by refining
  • those obtainable by coal gasification or gas liquefaction [“gas to liquid” (GTL) fuels] or by biomass liquefaction [“biomass to liquid” (BTL) fuels] are also suitable.
  • renewable fuels such as biodiesel or bioethanol.
  • biodiesel or bioethanol such as biodiesel or bioethanol.
  • HVO hydrogenated vegetable oils
  • UKO used kitchen oil
  • the inventive quaternized additive can also be used in mixtures of such middle distillates with biofuel oils (biodiesel).
  • biofuel oils biodiesel
  • Such mixtures are also encompassed by the term “middle distillate fuel” in the context of the present invention. They are commercially available and usually comprise the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, especially of 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
  • Biofuel oils are generally based on fatty acid esters, preferably essentially on alkyl esters of fatty acids which derive from vegetable and/or animal oils and/or fats.
  • Alkyl esters are typically understood to mean lower alkyl esters, especially C 1 - to C 4 -alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and/or animal oils and/or fats, especially triglycerides, by means of lower alcohols, for example ethanol or in particular methanol (“FAME”).
  • Typical lower alkyl esters based on vegetable and/or animal oils and/or fats which find use as a biofuel oil or components thereof, are, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soya oil methyl ester (“SME”) and especially rapeseed oil methyl ester (“RME”). Also conceivable are hydrogenated vegetable oils (HVO) or used kitchen oil (UKO).
  • HVO hydrogenated vegetable oils
  • UKO used kitchen oil
  • the middle distillate fuels or diesel fuels are more preferably those having a low sulfur content, i.e. having a sulfur content of less than 0.05% by weight, preferably of less than 0.02% by weight, more particularly of less than 0.005% by weight and especially of less than 0.001% by weight of sulfur.
  • Useful gasoline fuels include all commercial gasoline fuel compositions.
  • One typical representative which shall be mentioned here is the Eurosuper base fuel to EN 228, which is customary on the market.
  • gasoline fuel compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention.
  • the inventive quaternized additive is especially suitable as a fuel additive in fuel compositions, especially in diesel fuels, for overcoming the problems outlined at the outset in direct injection diesel engines, in particular in those with common rail injection systems.
  • Preferred additives in fuels of this kind are the following specific compound classes (A) and (C):
  • Preferred additives (A) are compounds which are derived from succinic anhydride and have long-chain hydrocarbyl radicals having generally 15 to 700 and particularly 30 to 200 carbon atoms. These compounds may have further functional groups which are preferably selected from hydroxyl, amino, amido and/or imido groups.
  • Preferred additives are the corresponding derivatives of polyalkenylsuccinic anhydride, which are obtainable, for example, by reaction of polyalkenes with maleic anhydride by a thermal route or via the chlorinated hydrocarbons.
  • the number-average molecular weight of the long-chain hydrocarbyl radicals is preferably within a range from about 200 to 10 000, more preferably 400 to 5000, particularly 600 to 3000 and especially 650 to 2000.
  • long-chain hydrocarbyl radicals preferably derive from conventional polyisobutenes and especially from the aforementioned reactive polyisobutenes.
  • additives (A) are the derivatives of polyalkenylsuccinic anhydrides with ammonia, monoamines, polyamines, monoalcohols and polyols.
  • Polyamines preferred for derivatization comprise ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, propylenediamine, etc.
  • Suitable alcohols comprise monohydric alcohols, such as ethanol, allyl alcohol, dodecanol and benzyl alcohol, polyhydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-butanediol, neopentyl glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, mannitol and sorbitol.
  • monohydric alcohols such as ethanol, allyl alcohol, dodecanol and benzyl alcohol
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, 1,2-butanediol, neopentyl glycol, glycerol, trimethylolpropane, erythritol, pentaerythritol, mannitol and sorbitol.
  • Succinic anhydride derivatives (A) suitable as additives are described, for example, in U.S. Pat. No. 3,522,179, U.S. Pat. No. 4,234,435, U.S. Pat. No. 4,849,572, U.S. Pat. No. 4,904,401, U.S. Pat. No. 5,569,644 and U.S. Pat. No. 6,165,235, which are fully incorporated by reference.
  • Preferred additives (C) are Mannich adducts.
  • Such adducts are obtained in principle by Mannich reaction of aromatic hydroxyl compounds, especially phenol and phenol derivatives, with aldehydes and mono- or polyamines. These are preferably the reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, etc.
  • Suitable Mannich adducts and processes for preparation thereof are described, for example, in U.S. Pat. No. 5,876,468, EP-A 831 141, EP-A 1 233 990 and EP-A 1 226 188, which are fully incorporated by reference.
  • additives (A) and (C) and any further additives from those mentioned above may typically each be present in amounts of in each case 0.0001 to 1% by weight, preferably 0.001 to 0.6% by weight and especially 0.0015 to 0.4% by weight, based on the total amount of the fuel composition.
  • the keep-clean test is based on CEC test procedure F-098-08 Issue 5. This is done using the same test setup and engine type (PEUGEOT DW10) as in the CEC procedure.
  • test run time was 12 h without shutdown phases.
  • the one-hour test cycle from CEC F-098-08, shown in FIG. 1 was run through 12 times.
  • the final performance (Pend,KC) is determined in the 12th cycle in stage 12 (see table, FIG. 2 ).
  • the operation point is full load 4000/min.
  • Pend,KC [kW] is calculated from the torque measured.
  • the power loss in the KC test is calculated as follows:
  • the DU-CU test is based on CEC test procedure F-098-08 Issue 5.
  • the procedure is described in Issue 5 of the test procedure (CEC F-98-08). This is done using the same test setup and the PEUGEOT DW10 engine type.
  • the DU-CU test consists of two individual tests which are run in succession.
  • the first test serves to form deposits (DU), the second to remove the deposits (CU).
  • the power loss is determined.
  • the engine is not operated for at least 8 hours and is cooled to ambient temperature. Thereafter, the CU fuel is used to start the CU without deinstalling and cleaning the injectors.
  • the deposits and power loss ideally decline over the course of the CU test.
  • test run time was 4.28 h for the DU and 8 h or 12 h for the CU.
  • the engine was operated in the DU and CU tests without shutdown phases.
  • the initial power P0,du [kW] is calculated from the measured torque at full load 4000/min directly after the test has started and the engine has run hot. The procedure is likewise described in Issue 5 of the test procedure.
  • the final performance (Pend,du) is determined in the 12th cycle in stage 12 (see table above).
  • the operation point is full load 4000/min.
  • Pend,du [kW] is calculated from the torque measured.
  • the power loss in the DU is calculated as follows:
  • the initial power P0,cu [kW] is calculated from the measured torque at full load 4000/min directly after the test has started and the engine has run hot in the CU. The procedure is likewise described in Issue 5 of the test procedure.
  • the final performance (Pend,cu) is determined in the 12th cycle in stage 12 (see table, FIG. 2 ).
  • the operation point is full load 4000/min.
  • Pend,cu [kW] is calculated from the torque measured.
  • the power loss in the CU test is calculated as follows (negative number for the power loss in the cu test means an increase in performance)
  • the fuel used was a commercial diesel fuel from Craigrmann (RF-06-03). To artificially induce the formation of deposits at the injectors, 1 ppm by weight of zinc in the form of a zinc didodecanoate solution was added thereto.
  • IDID Test Determination of Additive Effect on Internal Injector Deposits The formation of deposits within the injector was characterized by the deviations in the exhaust gas temperatures of the cylinders at the cylinder outlet on cold starting of the DW10 engine.
  • the test is conducted as a dirty-up clean-up test (DU-CU).
  • DU-CU is based on CEC test procedure F-098-08 Issue 5.
  • the DU-CU test consists of two individual tests which are run in succession. The first test serves to form deposits (DU), the second to remove the deposits (CU).
  • the CU fuel is used to start the CU without deinstalling and cleaning the injectors.
  • a cold start of the engine is conducted, followed by idling for 10 minutes.
  • the evaluation is effected by the comparison of the temperature profiles for the individual cylinders after the cold start in the DU and CU runs.
  • the IDID test indicates the formation of internal deposits in the injector.
  • the characteristic used in this test is the exhaust gas temperature of the individual cylinders.
  • the exhaust gas temperatures of the cylinders increase homogeneously.
  • the exhaust gas temperatures of the individual cylinders do not increase homogeneously and deviate from one another.
  • the temperature sensors are beyond the cylinder head outlet in the exhaust gas manifold. Significant deviation of the individual cylinder temperatures (e.g. >20° C.) indicates the presence of internal injector deposits (IDIDs).
  • the tests (DU and CU) are each conducted with run time 8 h.
  • the one-hour test cycle from CEC F-098-08 (see FIG. 3 ) is run through 8 times in each case. In the event of deviations of the individual cylinder temperatures of greater than 45° C. from the mean for all 4 cylinders, the test is stopped early.
  • R 1 here represents long-chain hydrocarbyl
  • R 2 , R 3 and R 4 correspond to R a , R b and R c as defined above
  • R 5 corresponds to R d as defined above
  • R is H or a radical obtained by esterification with the epoxide, for example —CH 2 CH(R 5 )OH
  • Polyisobutylenesuccinic anhydride (PIBSA, Glissopal® SA, from BASF): Prepared from maleic anhydride and Polyisobutene 1000 in a known manner. Unless stated otherwise, for the inventive preparation examples, qualities having a bismaleation level of 10% to 20% and hydrolysis numbers in the range of 84-95 mg KOH/g were used.
  • polyisobutylenesuccinic acid polyisobutylenesuccinic anhydride was admixed with the equimolar amount of water in accordance with the hydrolysis number and hydrolyzed at a temperature of 80° C.
  • Cocoyldimethylamine (N,N-dimethyl-N—C12/14-amine, CAS 68439-70-3 and 112-18-5) having a total amine value of 246 mg KOH/g.
  • N-Methyl-N,N-ditallowamine Armeen® M2HT from Akzo Nobel, CAS 61788-63-4, having a total amine value of 108 mg KOH/g.
  • N,N-Dimethylhexadecylamine (n-C 16 H 33 NMe 2 , CAS 112-69-6, Aldrich) Tridecylamine (branched; isomer mixture, CAS 86089-17-0) from BASF.
  • N,N-Dimethyl-1,3-diaminopropane (DMAPA, CAS 109-55-7) from BASF.
  • 2-Ethylhexanol and 2-propylheptanol from BASF.
  • a 2 l autoclave is initially charged with a solution of the tertiary amine (1 eq. according to the total amine number) and of the alkylenesuccinic acid derivative (1 eq. according to the acid number) in the given solvent (2-ethylhexanol, unless stated otherwise).
  • the amount of solvent and the batch size are selected such that the end product has an active content of 50% and the reactor a fill level of about 70%.
  • This is followed by purging three times with N 2 , establishment of a supply pressure of approx. 2 bar of N 2 and an increase in the temperature to 50° C.
  • the given alkylene oxide, propylene oxide unless stated otherwise, (2 eq.) is metered in within 1 h. This is followed by stirring at 50° C.
  • Tridecylamine (140.2 g) is initially charged at room temperature and formic acid (166.7 g) is added while stirring within 15 min.
  • the reaction mixture is heated to 45° C. and aqueous formaldehyde solution (37%; 132.7 g) is added dropwise with evolution of CO 2 within 25 min. Subsequently, stirring is continued at 80° C. for 23 h.
  • hydrochloric acid (32%; 121.5 g) is added while stirring.
  • the mixture is stirred at room temperature for 3 h and the water is removed on a rotary evaporator under reduced pressure. 500 mL of water are added to the product mixture, and 50% sodium hydroxide solution is used to release the amine.
  • the mixture was extracted twice with methyl tert-butyl ether, the combined organic phases were dried over sodium sulfate and the solvent was removed on a rotary evaporator.
  • the product (143.5 g) exhibited a total amine number of 228 mg KOH/g with 94% tertiary amine.
  • Dimethyloctadecyl(2-hydroxyhexyl)ammonium acetatefrag is obtained by quaternizing n-C 18 H 37 NMe 2 with hexene oxide/acetic acid.
  • this product as a 50% solution in 2-ethylhexanol turns cloudy when stored at room temperature over a period of 1 week.
  • a 2 L autoclave is initially charged with a solution of cocoyldimethylamine (1 eq.) and oleic acid (1 eq.) in 2-ethylhexanol.
  • the amount of 2-ethylhexanol and the batch size are chosen such that the end product has an active content of 50% and the reactor a fill level of about 70%.
  • This is followed by purging three times with N 2 , establishment of a supply pressure of about 2 bar of N 2 and an increase in the temperature to 50° C.
  • Propylene oxide (2 eq.) is metered in within 1 h. This is followed by stirring at 50° C.
  • a 2 L autoclave is initially charged with a solution of cocoyldimethylamine (1 eq.) and oleic acid (2 eq.) in 2-ethylhexanol.
  • the amount of 2-ethylhexanol and the batch size are chosen such that the end product has an active content of 50% and the reactor a fill level of about 70%.
  • This is followed by purging three times with N 2 , establishment of a supply pressure of about 2 bar of N 2 and an increase in the temperature to 50° C.
  • Propylene oxide (2 eq.) is metered in within 1 h. This is followed by stirring at 50° C.
  • Thermogravimetry was measured from 30° C. to 900° C. with a temperature rise of 20° C./min. under a nitrogen atmosphere at a flow rate of 60 mL/min.
  • the following changes in mass (TG) at 350° C. were determined:
  • the additives are used either as a pure substance (as synthesized in the above preparation examples) or in the form of an additive package.
  • the test was conducted with a Peugeot DW10 engine which is used according to the standard CEC F-98-08 procedure, except modified by more severe conditions in the dirty-up part and a run under full load rather than the CEC F-98-08 procedure.
  • the test consisted of two parts:
  • Power loss in the CU test is calculated as follows (negative number for power loss in the CU test means performance increase)
  • the compounds described in accordance with the invention are effective against the formation of deposits in direct injection engines such as Peugeot DW10, when tested in accordance with CEC F-98-08, and are capable of removing the deposits formed at an earlier stage.
  • test was conducted according to the standard procedure CEC F-023-01 with a Peugeot engine XUD9 with diesel base fuel according to EN590 B7, without performance additives.
  • the compounds described by the invention are effective against the formation of deposits in indirect injection engines such as Peugeot XUD9, when tested in accordance with CEC F-023-01, and are capable of removing the deposits formed at an earlier stage.
  • test was conducted according to the DIN EN 116 standard method for determining the cold flow characteristics (cold flow filter plugging point, CFPP) with winter diesel base fuel according to EN590 B7, without performance additives.
  • CFPP cold flow filter plugging point
  • the compounds described in this invention do not cause a deterioration in the cold flow properties nor any deterioration in the CFPP measured according to the EN116 standard.
  • the test was conducted in accordance with standard DGMK 531 1-A with base fuel according to EN590 B7 without performance additives and Wintershall Multi-Rekord Top 15W-40 motor oil.
  • the product to be tested was mixed with motor oil and heated to 90° C. for 3 days. This was followed by cooling and dilution with diesel fuel to a volume of 500 ml. Then the mixture was filtered through a filter described in the method. A filtration time exceeding 120 seconds was regarded as a fail.
  • the compounds described by the invention do not cause any deterioration in motor oil compatibility measured by the DGMK 531 1-A standard and do not lead to any deterioration in motor oil properties.
  • test was conducted according to standard ASTM D665 B (modified) with water (synthetic seawater) in a mixture with diesel base fuel according to EN590 B7, without performance additives.
  • the compounds described by the invention show very significant anticorrosive action, as shown by ASTM D 665 B (using synthetic seawater).
  • the test was conducted with a Peugeot DW10 engine, by the standard 44-hour CEC F-98-08 procedure.
  • a base fuel according to EN590 B7 was used, without performance additives. Fuels both with and without additions were examined. The results are compiled in the table below.
  • the compounds described in this invention are effective against the formation of deposits in direct injection engines such as the Peugeot DW10 as used in the test procedure according to CEC F-98-08 and are capable of removing deposits formed beforehand.
  • the test was conducted to the standard DIN ISO 12156-1 test for determination of the lubricity of diesel fuels.
  • the fuel was tested with and without additions. In the measurement, abrasion was determined. The higher the abrasion, the poorer the lubricity properties of the fuel. Coryton B0 fuel having low lubricity was used in this test.
  • the compounds described in accordance with the invention can improve lubricity of diesel fuels and prevent malfunction of fuel pumps as measured in the DIN ISO 12156-1 test.
  • the IDID engine test in which the exhaust gas temperatures in the cylinders at the cylinder outlet were determined on cold starting of the DW10 engine.
  • the fuel used was a commercial B7 diesel fuel according to EN 590.
  • 1 mg/L of Na in the form of sodium naphthenate and 20 mg/L of dodecenylsuccinic acid were added in each case.
  • the engine power is measured during the test.
  • the test was conducted without addition of compounds according to this invention.
  • the test was shortened to 8 hours; the CEC F-98-08 method was conducted without addition of Zn, but with addition of sodium naphthenate and dodecylsuccinic acid (DDS). If significant deviations in exhaust gas temperatures were observed, the test was stopped before the 8-hour mark was reached, in order to avoid engine damage.
  • the engine was left to cool and then restarted and operated in idling mode for 5 minutes. During these 5 minutes, the engine was warmed up. The exhaust gas temperature of each cylinder was recorded. The smaller the differences between the exhaust gas temperatures found, the smaller the amount of IDIDs formed.
  • the test was shortened to 8 hours; the CEC F-98-08 method was conducted without addition of Zn. However, 1 mg/L of Na in the form of sodium naphthenate and 20 mg/L of dodecenylsuccinic acid, and also an inventive compound, were added in each case, and the engine power was determined.
  • the compounds described by the invention are very effective against the formation of IDIDs in direct injection engines, as can be seen by the example of the Peugeot DW10, which is used in the test in a similar manner to the CEC F-98-08 procedure, but in the presence of 1 mg/L of Na in the form of sodium naphthenate and 20 mg/L of dodecenylsuccinic acid.
  • Power loss in the CU test is calculated as follows (negative number for power loss in the CU test means performance increase):
  • the compounds described in this invention are effective against the formation of deposits which are caused by metals other than Zn, such as Na, K, Ca, as shown by the above Na power loss test.
  • the FR value is a parameter detected by the engine management system, which correlates with the duration of the injection operation of the fuel into the combustion chamber. The more marked the formation of deposits in the injector nozzles, the longer the injection time and the higher the FR value. Conversely, the FR value remains constant or has a slightly decreasing tendency when the injector nozzles remain free of deposits. 2) Change in the FR value in % compared to the FR value at the start of the test (the greater the positive values, the more deposits are formed in the injector and the greater the contamination of the injector)

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US14/896,598 2013-06-07 2014-06-06 Use of nitrogen compounds quaternised with alkylene oxide and hydrocarbyl-substituted polycarboxylic acid as additives in fuels and lubricants Abandoned US20160130514A1 (en)

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EP13171057.6A EP2811007A1 (de) 2013-06-07 2013-06-07 Verwendung mit Alkylenoxid und Hydrocarbyl-substituierter Polycarbonsäure quaternisierter Alkylamine als Additive in Kraft- und Schmierstoffen
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PCT/EP2014/061834 WO2014195464A1 (de) 2013-06-07 2014-06-06 Verwendung mit alkylenoxid und hydrocarbyl-substituierter polycarbonsäure quaternisierter stickstoffverbindungen als additive in kraft- und schmierstoffen

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WO2014195464A1 (de) 2014-12-11
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US20170342340A1 (en) 2017-11-30
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