EP0499282B1 - Aqueous concentrate of at least one alkyl- or alkenyl substituted ammonium compound - Google Patents

Aqueous concentrate of at least one alkyl- or alkenyl substituted ammonium compound Download PDF

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Publication number
EP0499282B1
EP0499282B1 EP92102533A EP92102533A EP0499282B1 EP 0499282 B1 EP0499282 B1 EP 0499282B1 EP 92102533 A EP92102533 A EP 92102533A EP 92102533 A EP92102533 A EP 92102533A EP 0499282 B1 EP0499282 B1 EP 0499282B1
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carbon atoms
straight
water
radical
weight
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German (de)
French (fr)
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EP0499282A1 (en
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Heinz Prof. Dr. Hoffmann
Günther Dr. Hertel
Hubert Dr. Seitz
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Clariant Produkte Deutschland GmbH
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/645—Mixtures of compounds all of which are cationic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines

Definitions

  • the invention relates to a water-containing concentrate of one or more alkyl- or alkenyl-substituted ammonium compounds which contain an N atom with up to two H atoms or up to two short-chain alkyl substituents, furthermore a medium-chain and a long-chain alkyl or alkenyl substituent.
  • Water-soluble ammonium compounds which have one or two medium to long-chain alkyl or alkenyl substituents on the nitrogen atom are widely used, for example in the detergent and textile auxiliaries industry, where they are generally used as dilute aqueous solutions.
  • efforts are being made to use the water-soluble ammonium compounds in liquid form, as concentrated solutions as possible in water or water-miscible solvents.
  • the disadvantages here are that the solvents generally make the concentrated solutions highly flammable and flammable, and make it more difficult to dispose of the dilute aqueous solutions produced by the user by increasing their chemical oxygen demand (COD value).
  • GB-A-1 165 007 discloses a mixture of two ammonium compounds, one of which has two long-chain and two short-chain, the other one long-chain and three short-chain or one long-chain, one arylalkyl substituent and two short-chain alkyl substituents on the nitrogen atom.
  • the two ammonium compounds should be used in a mixing ratio of 10: 1 to 1: 1.
  • these mixtures are said not to result in slimy and thread-pulling solutions containing 3 to 6% by weight of active substance.
  • a liquid, low-viscosity concentrate which can be easily diluted with water and which, in addition to a portion of water, consists of two ammonium salts substituted with organic radicals is known from CA-A-1 186 619.
  • One of these two ammonium salts contains a long-chain and two short-chain alkyl substituents
  • the other ammonium salt, which serves as a solubilizer contains two long-chain and one short-chain alkyl substituent
  • both ammonium compounds each contain a benzyl substituent, the most aromatic Core can in turn be substituted.
  • US Pat. No. 4,654,152 describes pumpable concentrate mixtures which contain two nitrogen compounds which have been prepared in situ and are substituted with organic radicals, dissolved in an alcohol which has 1 to 3 C atoms.
  • One of these N compounds is an imidazolinium salt, the other an ammonium salt which carries two long-chain and two short-chain alkyl substituents on the N atom.
  • the solution in alcohol makes the mixtures more expensive and increases their flammability considerably.
  • the alcohol content of aqueous dilutions of these mixtures further increases their chemical oxygen demand (COD value) and thereby makes it difficult to dispose of such dilutions after use.
  • ammonium compounds are described in particular as auxiliaries in the dyeing of fiber materials with cationic dyes, two substituents on the N atom being -CH3, a further substituent including a C8 to C30 alkyl radical, which is via a secondary Carbon atom is attached to the nitrogen atom, and the fourth substituent is, inter alia, a C1 to C20 alkyl radical or a C2 to C20 alkenyl radical.
  • ammonium compounds for the antistatic finishing of polymers are known, among the substituents R, R1, R2 and R3 on the N atom R, inter alia, a C2 to C22-alkyl, R1 a C1 to C3-alkyl or C8 to C18 alkyl, R2 is a C1 to C3 alkyl and R3 is an alkyleneoxy radical.
  • R1, R2 and R3 on the N atom R inter alia, a C2 to C22-alkyl, R1 a C1 to C3-alkyl or C8 to C18 alkyl, R2 is a C1 to C3 alkyl and R3 is an alkyleneoxy radical.
  • the object of the invention is to provide a water-containing concentrate of one or more alkyl- or alkenyl-substituted ammonium compounds which has low viscosity over a wide concentration range in the temperature range of 15 to 40 ° C. which is important for easy handling and with water without substantial viscosity increase can be diluted as desired, which can also be made thin and easily dilutable at very high concentrations by using temperatures up to 80 ° C.
  • R1, R2, R5 and / or R6 is an alkenyl radical, this can have 1 to 3 double bonds in the C chain.
  • the concentrates according to the invention contain 15 to 60% by weight of water, based on the entire mixture (concentrate).
  • the advantageous effect according to the invention occurs within such water contents.
  • Mix with less than 15% by weight of water is more difficult and costly to produce and sometimes does not have the desired low viscosity.
  • Mixtures with more than 60% by weight of water result in unnecessarily high transport and packaging costs and show no more favorable properties than conventional, mostly quaternary ammonium compounds of a comparable type.
  • the concentrates according to the invention can be prepared by mixing the individual components or advantageously by in-situ preparation of the ammonium compound (s), if appropriate in the presence of water and subsequent concentration by evaporation of solvents and, if necessary, by dilution with water,
  • the ammonium compound (s) are expediently produced, for example, from amines by addition of alkyl or alkylene esters, preferably strong acids, by processes known per se.
  • Suitable esters are, for example, those of phosphoric acid, sulfuric acid, phenylsulfonic acid, methylphenylsulfonic acid, hydrochloric acid or hydrobromic acid.
  • the alkyl and alkylene esters of carbonic acid are also very suitable.
  • the reaction of the amine with the ester can be carried out without a solvent, but it is often advantageous to use a solvent, in particular one which has a high dipole moment, such as water, acetonitrile, alkanols, such as isopropanol, alkylene glycols, such as ethylene glycol or propylene glycol, dialkylene glycols .
  • a solvent in particular one which has a high dipole moment, such as water, acetonitrile, alkanols, such as isopropanol, alkylene glycols, such as ethylene glycol or propylene glycol, dialkylene glycols .
  • solvents for example water and an alkanol having 1 to 4 carbon atoms or water and acrylonitrile
  • solvents for example water and an alkanol having 1 to 4 carbon atoms or water and acrylonitrile
  • unreacted starting materials such as amines and / or esters.
  • esters instead of the esters, a mixture of the corresponding alkanol or alkenol together with an acid, an acid anhydride, acid chloride or acid bromide can be used for the reaction with the amine, for example an alkanol and methylphenylsulfochloride, or an alkanol and hydrogen chloride.
  • the temperature for the reaction of the amine or the amines with the ester or the esters or their precursors acid and alcohol can vary within wide limits. Temperatures of 20 to 150 ° C are generally sufficient.
  • the reaction mixture can be operated at normal atmospheric pressure or at the autogenous pressure. In general, pressures up to 1 MPa are sufficient.
  • the concentrates according to the invention have a low viscosity, which makes them easy to pump, transport and dose. They can also be diluted with water without any appreciable increase in viscosity, which makes their use easier.
  • the concentrates contain practically no flammable solvents, which can make the concentrates flammable and increase the chemical oxygen demand of the wastewater that arises when the concentrates are used, making their disposal more difficult.
  • the contents of the flask are then placed in a rotary evaporator and the volatile constituents, essentially acetonitrile, are added for 4 hours at 320 revolutions per minute in a water bath at a temperature rising from 50 to 80 ° C. and a pressure falling from 9.6 to 1.8 kPa. distilled off.
  • N-tetradecyl-N-hexyl-N, N-dimethylammonium bromide (1) thus obtained is then dried at room temperature under a pressure of 40 Pa generated by an oil vacuum pump and used for the viscosity determinations described below.
  • the product is analyzed, the following values being determined: - N-tetradecyl-N-hexyl-N, N-dimethylammonium bromide (1) 98.4% by weight - N-tetradecyl-N, N-dimethylamine 0.23% by weight - N-tetradecyl-N, N-dimethylammonium bromide 1.34% by weight 2.
  • Preproduct for Examples 2 and 5 An apparatus as described in Example 1 is used.
  • N-hexadecyl-N-hexyl-N, N-dimethylammonium bromide (2) thus obtained is used for the viscosity measurements described below.
  • the following levels become analytical determined: - N-hexadecyl-N-hexyl-N, N-dimethylammonium bromide (2) 98.0% by weight - N-hexadecyl-N, N-dimethylamine 0.5% by weight - N-hexadecyl-N, N-dimethylammonium bromide 1.5% by weight 3.
  • N-tetradecyl-N-allyl-N, N-dimethylammonium bromide (3) thus obtained is used for the viscosity determinations described below.
  • the following contents are determined analytically: - N-tetradecyl-N-allyl-N, N-dimethylammonium bromide (3) 98.4% by weight - N-tetradecyl-N, N-dimethylamine 0.05% by weight - N-tetradecyl-N, N-dimethylammonium bromide 1.5% by weight 4.
  • N-tetradecyl-N-octyl-N, N-dimethylammonium bromide (4) thus obtained is used for the viscosity determinations described below.
  • the following contents are determined analytically: - N-tetradecyl-N-octyl-N, N-dimethylammonium bromide (4) 98.0% by weight - N-tetradecyl-N, N-dimethylamine 0.5% by weight - N-tetradecyl-N, N-dimethylammonium bromide 1.1% by weight
  • mixtures of water according to the invention (referred to as “example” with number) and non-inventive (referred to as “comparative test” with a capital letter) are mixed with water in the quantitative ratios listed in Table 1 below from the ammonium compounds whose preparation was described in the preceding sections prepared with stirring at 80 ° C, cooled to the measuring temperature and the viscosity (V) of the mixtures containing up to 70% by weight of ammonium compounds and a minimum of 30% by weight of water (W) at the specified temperature (T) and shear rate (D) measured with the Rheolab MC 10 rotary viscometer from "Physica", W-7000 Stuttgart 80, Germany, with the Z 1 (DIN) measuring body.
  • Table 1 Example / comparison test Concentrate composition compound / amount [g] W [% by weight] Viscosity measurement T [° C] D [1 / s] V [mPa ⁇ s] 1 a (1) / 10 --- H2O / 10 50 35 100 35 b (1) / 14 --- H2O / 6 30th 35 100 77 2 a (2) / 10 --- H2O / 10 50 35 100 59 b (2) / 13 --- H2O / 7 35 35 100 95 A a (3) / 10 --- H2O / 10 50 35 100 > 5000 B a (4) / 8 --- H2O / 12 60 35 100 35 b (4) / 12 --- H2O / 8 40 35 100 49 3 a (3) / 5 (4) / 5 H2O / 10 50 35 100 100 b (3) / 4 (4) / 4 H2O / 12 60 35 100 168
  • example 3 a mixture according to the invention of the two compounds (3) and (4) with water is used.
  • the mixtures of the individual compounds (3) or (4) with water are not according to the invention and are therefore referred to as a comparison test.
  • Example / comparison test Concentrate composition compound / amount [g] W [% by weight] T [° C] Viscosity assessment 4 a (1) / 37.5 --- H2O / 12.5 25th 30th thin b (1) / 40 --- H2O / 10 20th 50 thin 5 a (2) / 37.5 --- H2O / 12.5 25th 60 thin b (2) / 40 --- H2O / 10 20th 65 thin C.

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
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  • Textile Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Description

Die Erfindung betrifft ein wasserhaltiges Konzentrat von einer oder von mehreren alkyl- oder alkenylsubstituierten Ammoniumverbindungen, die ein N-Atom mit bis zu zwei H-Atomen oder bis zu zwei kurzkettigen Alkylsubstituenten, ferner einen mittelkettigen und einen langkettigen Alkyl- oder Alkenylsubstituenten enthalten.The invention relates to a water-containing concentrate of one or more alkyl- or alkenyl-substituted ammonium compounds which contain an N atom with up to two H atoms or up to two short-chain alkyl substituents, furthermore a medium-chain and a long-chain alkyl or alkenyl substituent.

Wasserlösliche Ammoniumverbindungen, die ein oder zwei mittel- bis längerkettige Alkyl- oder Alkenylsubstituenten am Stickstoffatom aufweisen, finden vielfach Anwendung, beispielsweise in der Waschmittel- und Textilhilfsmittelindustrie, wo sie in der Regel als verdünnte wäßrige Lösungen eingesetzt werden. Um einesteils Transport- und Verpackungskosten zu sparen und sie anderenteils leicht transportierbar und dosierbar zu machen, ist man bestrebt, die wasserlöslichen Ammoniumverbindungen flüssig, als möglichst konzentrierte Lösungen in Wasser oder wassermischbaren Lösungsmitteln anzuwenden. Nachteilig dabei ist, daß die Lösungsmittel in der Regel die konzentrierten Lösungen leicht brennbar und feuergefährlich machen sowie die Entsorgung der beim Verwender daraus erzeugten verdünnten wäßrigen Lösungen durch Erhöhung von deren chemischem Sauerstoffbedarf (CSB-Wert) erschweren. Konzentrierte Lösungen nur in Wasser zeigen in der Regel entweder als solche ungünstig hohe Viskositäten und/oder werden bei der Verdünnung mit Wasser hochviskos, was ihre gleichmäßige Verteilung und problemlose Verwendung behindert. Es besteht daher ein Bedarf an wasserhaltigen Konzentraten von alkyl- oder alkenylsubstituierten Ammoniumverbindungen mit längerkettigen Substituenten, die niedrigviskos und problemlos mit Wasser verdünnbar sind.Water-soluble ammonium compounds which have one or two medium to long-chain alkyl or alkenyl substituents on the nitrogen atom are widely used, for example in the detergent and textile auxiliaries industry, where they are generally used as dilute aqueous solutions. In order to save transport and packaging costs, on the one hand, and make them easy to transport and dose on the other, efforts are being made to use the water-soluble ammonium compounds in liquid form, as concentrated solutions as possible in water or water-miscible solvents. The disadvantages here are that the solvents generally make the concentrated solutions highly flammable and flammable, and make it more difficult to dispose of the dilute aqueous solutions produced by the user by increasing their chemical oxygen demand (COD value). Concentrated solutions only in water usually either have unfavorably high viscosities as such and / or are diluted with water highly viscous, which hinders their even distribution and problem-free use. There is therefore a need for water-containing concentrates of alkyl- or alkenyl-substituted ammonium compounds with longer-chain substituents that are low-viscosity and can be diluted with water without any problems.

Aus GB-A-1 165 007 ist ein Gemisch aus zwei Ammoniumverbindungen bekannt, von denen die eine zwei langkettige und zwei kurzkettige, die andere einen langkettigen und drei kurzkettige oder einen langkettigen, einen Arylalkylsubstituenten und Zwei kurzkettige Alkylsubstituenten am Stickstoffatom aufweist. Die beiden Ammoniumverbindungen sollen im Mischungsverhältnis 10 : 1 bis 1 : 1 angewendet werden. Neben anderen Verbesserungen sollen diese Mischungen keine schleimigen und Faden ziehenden Lösungen, die 3 bis 6 Gew.-% aktive Substanz enthalten, ergeben. Über das Verdünnungsverhältnis wäßriger Konzentrate, die Mischungen nach GB-A-1 165 007 enthalten, im üblichen viskositätskritischen Bereich von etwa 15 bis 50 Gew.-% aktive Substanz, ist nichts ausgesagt.GB-A-1 165 007 discloses a mixture of two ammonium compounds, one of which has two long-chain and two short-chain, the other one long-chain and three short-chain or one long-chain, one arylalkyl substituent and two short-chain alkyl substituents on the nitrogen atom. The two ammonium compounds should be used in a mixing ratio of 10: 1 to 1: 1. Among other improvements, these mixtures are said not to result in slimy and thread-pulling solutions containing 3 to 6% by weight of active substance. Nothing is said about the dilution ratio of aqueous concentrates containing mixtures according to GB-A-1 165 007 in the usual viscosity-critical range of about 15 to 50% by weight of active substance.

Ein flüssiges, mit Wasser leicht verdünnbares niedrigviskoses Konzentrat, das neben einem Anteil Wasser aus zwei mit organischen Resten substituierten Ammoniumsalzen besteht, ist aus der CA-A-1 186 619 bekannt. Eines dieser beiden Ammoniumsalze enthält einen langkettigen und zwei kurzkettige Alkylsubstituenten, das andere, als Lösungsvermittler dienende Ammoniumsalz, enthält zwei langkettige und einen kurzkettigen Alkylsubstituenten, beide Ammoniumverbindungen enthalten je einen Benzylsubstituent, der am aromatischen Kern seinerseits substituiert sein kann.A liquid, low-viscosity concentrate which can be easily diluted with water and which, in addition to a portion of water, consists of two ammonium salts substituted with organic radicals is known from CA-A-1 186 619. One of these two ammonium salts contains a long-chain and two short-chain alkyl substituents, the other ammonium salt, which serves as a solubilizer, contains two long-chain and one short-chain alkyl substituent, both ammonium compounds each contain a benzyl substituent, the most aromatic Core can in turn be substituted.

US-A-4 654 152 beschreibt pumpfähige Konzentratmischungen, die zwei in situ hergestellte, mit organischen Resten substituierte Stickstoffverbindungen, gelöst in einem Alkohol, der 1 bis 3 C-Atome aufweist, enthalten. Eine dieser N-Verbindungen ist ein Imidazoliniumsalz, die andere ein Ammoniumsalz, das am N-Atom zwei langkettige und zwei kurzkettige Alkylsubstituenten trägt. Die Lösung in Alkohol verteuert die Gemische und erhöht deren Feuergefährlichkeit erheblich. Der Alkoholgehalt von wäßrigen Verdünnungen dieser Gemische erhöht ferner deren chemischen Sauerstoffbedarf (CSB-Wert) und erschwert dadurch die Entsorgung solcher Verdünnungen nach deren Gebrauch.US Pat. No. 4,654,152 describes pumpable concentrate mixtures which contain two nitrogen compounds which have been prepared in situ and are substituted with organic radicals, dissolved in an alcohol which has 1 to 3 C atoms. One of these N compounds is an imidazolinium salt, the other an ammonium salt which carries two long-chain and two short-chain alkyl substituents on the N atom. The solution in alcohol makes the mixtures more expensive and increases their flammability considerably. The alcohol content of aqueous dilutions of these mixtures further increases their chemical oxygen demand (COD value) and thereby makes it difficult to dispose of such dilutions after use.

In FR-A-2 391 991 werden Ammoniumverbindungen insbesondere als Hilfsmittel beim Färben von Fasermaterialien mit kationischen Farbstoffen beschrieben, wobei zwei Substituenten am N-Atom -CH₃ sind, ein weiterer Substituent unter anderem ein C₈ bis C₃₀-Alkylrest ist, der über ein sekundäres Kohlenstoffatom an das Stickstoffatom gebunden ist, und der vierte Substituent unter anderem ein C₁ bis C₂₀-Alkylrest oder ein C₂ bis C₂₀-Alkenylrest ist. Über eine Anwendung der beschriebenen Ammoniumverbindungen in Form von wäßrigen Konzentraten wird nichts gesagt.In FR-A-2 391 991 ammonium compounds are described in particular as auxiliaries in the dyeing of fiber materials with cationic dyes, two substituents on the N atom being -CH₃, a further substituent including a C₈ to C₃₀ alkyl radical, which is via a secondary Carbon atom is attached to the nitrogen atom, and the fourth substituent is, inter alia, a C₁ to C₂₀ alkyl radical or a C₂ to C₂₀ alkenyl radical. Nothing is said about the use of the ammonium compounds described in the form of aqueous concentrates.

Aus WO-A-90/05129 sind schließlich Ammoniumverbindungen zur antistatischen Ausrüstung von Polymeren bekannt, wobei von den Substituenten R, R¹, R² und R³ am N-Atom R unter anderem ein C₂ bis C₂₂-Alkyl, R¹ ein C₁ bis C₃-Alkyl oder C₈ bis C₁₈-Alkyl, R² ein C₁ bis C₃-Alkyl und R³ ein Alkylenoxyrest ist. Auch hier werden keine konkreten wasserhaltigen Zusammensetzungen aus den beschriebenen Ammoniumverbindungen erwähnt.Finally, from WO-A-90/05129 ammonium compounds for the antistatic finishing of polymers are known, among the substituents R, R¹, R² and R³ on the N atom R, inter alia, a C₂ to C₂₂-alkyl, R¹ a C₁ to C₃-alkyl or C₈ to C₁₈ alkyl, R² is a C₁ to C₃ alkyl and R³ is an alkyleneoxy radical. Again, no specific water-containing compositions from the ammonium compounds described are mentioned.

Aufgabe der Erfindung ist es, ein wasserhaltiges Konzentrat von einer oder von mehreren alkyl- oder alkenylsubstituierten Ammoniumverbindungen zur Verfügung zu stellen, das in dem für eine leichte Handhabung wichtigen Temperaturbereich von 15 bis 40 °C über einen weiten Konzentrationsbereich niedrige Viskosität aufweist und mit Wasser ohne wesentliche Viskositätssteigerung beliebig verdünnt werden kann, das ferner bei sehr hohen Konzentrationen durch Anwendung von Temperaturen bis 80 °C dünnflüssig und leicht verdünnbar gemacht werden kann.The object of the invention is to provide a water-containing concentrate of one or more alkyl- or alkenyl-substituted ammonium compounds which has low viscosity over a wide concentration range in the temperature range of 15 to 40 ° C. which is important for easy handling and with water without substantial viscosity increase can be diluted as desired, which can also be made thin and easily dilutable at very high concentrations by using temperatures up to 80 ° C.

Die Aufgabe wird gelöst durch ein wasserhaltiges Konzentrat von mindestens einer alkyl- oder alkenylsubstituierten Ammoniumverbindung, bestehend im wesentlichen aus

  • a) 40 bis 85 Gew.-% von einer Ammoniumverbindung der Formel
    Figure imgb0001
     worin bedeuten
    R¹
    einen geradkettigen Alkylrest oder einen geradkettigen Alkenylrest mit 12, 14, 16 oder 18 C-Atomen,
    R²
    einen geradkettigen Alkylrest oder einen geradkettigen Alkenylrest (1) mit 4, 5 oder 6 C-Atomen, wenn R¹ 12 C-Atome hat, (2) mit 5 oder 6 C-Atomen, wenn R¹ 14 C-Atome hat, (3) mit 6 oder 7 C-Atomen, wenn R¹ 16 C-Atome hat, oder (4) mit 7 oder 8 C-Atomen, wenn R¹ 18 C-Atome hat,
    R³ und R⁴,
    gleich oder verschieden, das Wasserstoffatom oder den Methylrest und
    X
    ein Chlorid-, Bromid-, Methylsulfat-, Phenylsulfonat- oder Methylphenylsulfonat-Anion,
    oder von einer Mischung solcher Ammoniumverbindungen, und
  • b) 15 bis 60 Gew.-% Wasser, Gewichtsprozente bezogen auf das gesamte Gemisch.
The object is achieved by a water-containing concentrate of at least one alkyl- or alkenyl-substituted ammonium compound, consisting essentially of
  • a) 40 to 85 wt .-% of an ammonium compound of the formula
    Figure imgb0001
     in what mean
    R¹
    a straight-chain alkyl radical or a straight-chain alkenyl radical having 12, 14, 16 or 18 carbon atoms,
    R²
    a straight-chain alkyl radical or a straight-chain alkenyl radical (1) with 4, 5 or 6 C atoms if R¹ has 12 C atoms, (2) with 5 or 6 C atoms if R¹ has 14 C atoms, (3) with 6 or 7 C atoms if R¹ has 16 C atoms, or (4) with 7 or 8 C atoms if R¹ has 18 C atoms,
    R³ and R⁴,
    the same or different, the hydrogen atom or the methyl radical and
    X
    a chloride, bromide, methyl sulfate, phenyl sulfonate or methylphenyl sulfonate anion,
    or a mixture of such ammonium compounds, and
  • b) 15 to 60 wt .-% water, percentages by weight based on the entire mixture.

Die genannte Aufgabe wird erfindungsgemäß auch gelöst durch ein wasserhaltiges Konzentrat von mehreren alkyl- oder alkenylsubstituierten Ammoniumverbindungen, bestehend im wesentlichen aus

  • a) 40 bis 85 Gew.-% von einem Gemisch von einer ersten Ammoniumverbindung der Formel
    Figure imgb0002
     worin bedeuten
    R¹
    einen geradkettigen Alkylrest oder einen geradkettigen Alkenylrest mit 12, 14, 16 oder 18 C-Atomen,
    R⁵
    einen geradkettigen Alkylrest oder einen geradkettigen Alkenylrest (1) mit 3 C-Atomen, wenn R¹ 12 C-Atome hat, (2) mit 3 oder 4 C-Atomen, wenn R¹ 14 C-Atome hat, (3) mit 4 C-Atomen, wenn R¹ 16 C-Atome hat, oder (4) mit 5 oder 6 C-Atomen, wenn R¹ 18 C-Atome hat,
    R³ und R⁴,
    gleich oder verschieden, das Wasserstoffatom oder den Methylrest und
    X
    ein Chlorid-, Bromid-, Methylsulfat-, Phenylsulfonat- oder Methylphenylsulfonat-Anion,
    und einer zweiten Ammoniumverbindung der Formel
    Figure imgb0003
     worin bedeuten
    R¹
    einen geradkettigen Alkylrest oder einen geradkettigen Alkenylrest mit 12, 14, 16 oder 18 C-Atomen,
    R⁶
    einen geradkettigen Alkylrest oder einen geradkettigen Alkenylrest (1) mit 7 oder 8 C-Atomen, wenn R¹ 12 C-Atome hat, (2) mit 8, 9 oder 10 C-Atomen, wenn R¹ 14 C-Atome hat, oder (3) mit 9, 10, oder 11 C-Atomen, wenn R¹ 16 C-Atome oder 18 C-Atome hat,
    R³ und R⁴,
    gleich oder verschieden, das Wasserstoffatom oder den Methylrest und
    X
    ein Chlorid-, Bromid-, Methylsulfat-, Phenylsulfonat- oder Methylphenylsulfonat-Anion,
    wobei die beiden Ammoniumverbindungen (II) und (III) in einem solchen Verhältnis gemischt worden sind, daß der Mittelwert der Anzahl der C-Atome von R⁵ und R⁶ im Gemisch einen Wert von n/2 - p hat, wobei n die Anzahl der C-Atome in R¹ ist und p 1 bis 2 ist, und
  • b) 15 bis 60 Gew.-% Wasser, Gewichtsprozente bezogen auf das gesamte Gemisch.
According to the invention, this object is also achieved by a water-containing concentrate of several alkyl- or alkenyl-substituted ammonium compounds, consisting essentially of
  • a) 40 to 85 wt .-% of a mixture of a first ammonium compound of the formula
    Figure imgb0002
     in what mean
    R¹
    a straight-chain alkyl radical or a straight-chain alkenyl radical having 12, 14, 16 or 18 carbon atoms,
    R⁵
    a straight-chain alkyl radical or a straight-chain alkenyl radical (1) with 3 C atoms if R¹ has 12 C atoms, (2) with 3 or 4 C atoms if R¹ has 14 C atoms, (3) with 4 C- Atoms if R¹ has 16 C atoms, or (4) with 5 or 6 C atoms if R¹ has 18 C atoms,
    R³ and R⁴,
    the same or different, the hydrogen atom or the methyl radical and
    X
    a chloride, bromide, methyl sulfate, phenyl sulfonate or methylphenyl sulfonate anion,
    and a second ammonium compound of the formula
    Figure imgb0003
     in what mean
    R¹
    a straight-chain alkyl radical or a straight-chain alkenyl radical having 12, 14, 16 or 18 carbon atoms,
    R⁶
    a straight-chain alkyl radical or a straight-chain alkenyl radical (1) with 7 or 8 C atoms if R¹ has 12 C atoms, (2) with 8, 9 or 10 C atoms if R¹ has 14 C atoms, or (3 ) with 9, 10, or 11 carbon atoms if R¹ has 16 carbon atoms or 18 carbon atoms,
    R³ and R⁴,
    the same or different, the hydrogen atom or the methyl radical and
    X
    a chloride, bromide, methyl sulfate, phenyl sulfonate or methylphenyl sulfonate anion,
    wherein the two ammonium compounds (II) and (III) have been mixed in such a ratio that the mean of the number of carbon atoms of R⁵ and R⁶ in the mixture has a value of n / 2 - p, where n is the number of C -Atoms in R¹ and p is 1 to 2, and
  • b) 15 to 60 wt .-% water, percentages by weight based on the entire mixture.

Sofern R¹, R², R⁵ und/oder R⁶ ein Alkenylrest ist, kann dieser 1 bis 3 Doppelbindungen in der C-Kette aufweisen.If R¹, R², R⁵ and / or R⁶ is an alkenyl radical, this can have 1 to 3 double bonds in the C chain.

Die erfindungsgemäßen Konzentrate enthalten 15 bis 60 Gew.-% Wasser, bezogen auf das gesamte Gemisch (Konzentrat). Innerhalb solcher Wassergehalte tritt die vorteilhafte erfindungsgemäße Wirkung auf. Gemische mit weniger als 15 Gew.-% Wasser sind schwieriger und kostenaufwendiger herstellbar und haben bisweilen auch nicht die gewünschte niedrige Viskosität. Gemische mit über 60 Gew.-% Wasser ergeben unnötig hohe Transport- und Verpackungskosten und Zeigen gegenüber üblichen, meist quartären Ammoniumverbindungen eines vergleichbaren Typs keine günstigeren Eigenschaften.The concentrates according to the invention contain 15 to 60% by weight of water, based on the entire mixture (concentrate). The advantageous effect according to the invention occurs within such water contents. Mix with less than 15% by weight of water is more difficult and costly to produce and sometimes does not have the desired low viscosity. Mixtures with more than 60% by weight of water result in unnecessarily high transport and packaging costs and show no more favorable properties than conventional, mostly quaternary ammonium compounds of a comparable type.

Die erfindungsgemäßen Konzentrate können durch Mischung der einzelnen Komponenten hergestellt werden oder vorteilhaft durch in-situ-Herstellung der Anmoniumverbindung(en), gegebenenfalls in Gegenwart von Wasser und anschließende Aufkonzentrierung durch Abdampfen von Lösungsmitteln und, sofern erforderlich, durch Verdünnung mit Wasser,The concentrates according to the invention can be prepared by mixing the individual components or advantageously by in-situ preparation of the ammonium compound (s), if appropriate in the presence of water and subsequent concentration by evaporation of solvents and, if necessary, by dilution with water,

Die Ammoniumverbindung(en) werden beispielsweise zweckmäßig nach an sich bekannten Verfahren aus Aminen durch Anlagerung von Alkyl- oder Alkylenestern vorzugsweise starker Säuren erzeugt. Geeignete Ester sind beispielsweise die der Phosphorsäure, Schwefelsäure, Phenylsulfonsäure, Methylphenylsulfonsäure, Chlor- oder Bromwasserstoffsäure. Gut geeignet sind auch die Alkyl- und Alkylenester der Kohlensäure. Es kann vorteilhaft sein, nach Herstellung des entsprechenden, am N ganz oder teilweise substituierten Ammoniumsalzes mit einem gut reagierenden Säureester, beispielsweise einem Alkylbromid oder einem Dialkylcarbonat, das Anion des Ammoniumsalzes gegen ein anderes Anion, beispielsweise Chlorid, auszutauschen, wenn dessen Ester, beispielsweise Alkylchlorid, nicht so reaktionsfähig ist als der für die Reaktion mit dem Amin verwendete Ester.The ammonium compound (s) are expediently produced, for example, from amines by addition of alkyl or alkylene esters, preferably strong acids, by processes known per se. Suitable esters are, for example, those of phosphoric acid, sulfuric acid, phenylsulfonic acid, methylphenylsulfonic acid, hydrochloric acid or hydrobromic acid. The alkyl and alkylene esters of carbonic acid are also very suitable. It can be advantageous, after preparation of the corresponding ammonium salt which is wholly or partially substituted on the N with a well-reacting acid ester, for example an alkyl bromide or a dialkyl carbonate, to replace the anion of the ammonium salt with another anion, for example chloride, if the ester thereof, for example alkyl chloride , is not as reactive as the ester used for the reaction with the amine.

Die Reaktion des Amins mit dem Ester kann ohne lösungsmittel durchgeführt werden, es ist jedoch häufig vorteilhaft ein Lösungsmittel einzusetzen, insbesondere ein solches, das ein hohes Dipolmoment aufweist, wie Wasser, Acetonitril, Alkanole, wie Isopropanol, Alkylenglykole, wie Ethylenglykol oder Propylenglykol, Dialkylenglykole.The reaction of the amine with the ester can be carried out without a solvent, but it is often advantageous to use a solvent, in particular one which has a high dipole moment, such as water, acetonitrile, alkanols, such as isopropanol, alkylene glycols, such as ethylene glycol or propylene glycol, dialkylene glycols .

Auch Lösungsmittelgemische, beispielsweise Wasser und ein Alkanol mit 1 bis 4 C-Atomen oder Wasser und Acrylnitril, können mit Vorteil angewendet werden. Ein Teil des oder der verwendeten Lösungsmittel oder, wenn das Lösungsmittel nicht Wasser ist, auch die ganze Lösungsmittelmenge kann beispielsweise durch Abdampfen entfernt und wiedergewonnen werden. Das gleiche gilt auch für nicht umgesetzte Ausgangsstoffe, wie Amine und/oder Ester. Die verbleibende Ammoniumverbindung beziehungsweise, wenn ein Gemisch von Aminen oder ein Gemisch von Estern oder ein Gemisch von Aminen und von Estern eingesetzt wurde, die verbleibenden Ammoniumverbindungen werden dann mit Wasser in einer Menge versetzt, daß das Konzentrat 15 bis 60 Gew.-% Wasser, bezogen auf das Konzentrat, enthält.Mixtures of solvents, for example water and an alkanol having 1 to 4 carbon atoms or water and acrylonitrile, can also be used with advantage. Part of the or the used solvent or, if the solvent is not water, the entire amount of solvent can be removed and recovered, for example by evaporation. The same also applies to unreacted starting materials, such as amines and / or esters. The remaining ammonium compound or, if a mixture of amines or a mixture of esters or a mixture of amines and esters has been used, the remaining ammonium compounds are then mixed with water in an amount such that the concentrate contains 15 to 60% by weight of water, based on the concentrate.

Anstelle der Ester kann für die Umsetzung mit dem Amin auch eine Mischung des entsprechenden Alkanols beziehungsweise Alkenols zusammen mit einer Säure, einem Säureanhydrid, Säurechlorid oder Säurebromid verwendet werden, beispielsweise ein Alkanol und Methylphenylsulfochlorid, oder ein Alkanol und Chlorwasserstoff.Instead of the esters, a mixture of the corresponding alkanol or alkenol together with an acid, an acid anhydride, acid chloride or acid bromide can be used for the reaction with the amine, for example an alkanol and methylphenylsulfochloride, or an alkanol and hydrogen chloride.

Die Temperatur für die Umsetzung des Amins oder der Amine mit dem Ester oder den Estern beziehungsweise deren Vorprodukten Säure und Alkohol kann in weiten Grenzen schwanken. Temperaturen von 20 bis 150 °C sind im allgemeinen ausreichend. Es kann bei normalem Atmosphärendruck oder dem autogenen Druck der Reaktionsmischung gearbeitet werden. Im allgemeinen sind Drucke bis zu 1 MPa ausreichend.The temperature for the reaction of the amine or the amines with the ester or the esters or their precursors acid and alcohol can vary within wide limits. Temperatures of 20 to 150 ° C are generally sufficient. The reaction mixture can be operated at normal atmospheric pressure or at the autogenous pressure. In general, pressures up to 1 MPa are sufficient.

Die erfindungsgemäßen Konzentrate haben eine geringe Viskosität, die sie gut pumpbar, transportfähig und dosierbar macht. Sie sind ferner mit Wasser ohne nennenswerte Viskositätserhöhung verdünnbar, was ihre Anwendung erleichtert. Die Konzentrate enthalten praktisch keine brennbaren Lösungsmittel, die die Konzentrate feuergefährlich machen können und den chemischen Sauerstoffbedarf der Abwässer, die bei der Anwendung der Konzentrate entstehen, erhöhen, wodurch deren Entsorgung erschwert wird.The concentrates according to the invention have a low viscosity, which makes them easy to pump, transport and dose. They can also be diluted with water without any appreciable increase in viscosity, which makes their use easier. The concentrates contain practically no flammable solvents, which can make the concentrates flammable and increase the chemical oxygen demand of the wastewater that arises when the concentrates are used, making their disposal more difficult.

Nachfolgende Beispiele sollen die Erfindung erläutern.
1. Vorprodukt für Beispiele 1 und 4
In einen Kolben von 1 dm³ Inhalt, der mit einem Rührer, einem Rückflußkühler und einem Kontakt-Thermometer ausgerüstet ist und in seinem Unterteil von einer elektrisch heizbaren Hülle umgeben ist, die von dem Kontakt-Thermometer gesteuert wird, werden bei Raumtemperatur nacheinander unter Rühren gegeben: 145,3 g (0,6 mol) N-Tetradecyl-N,N-dimethylamin, 249,3 g (6,07 mol) Acetonitril und 104,0 g (0,63 mol) 1-Bromhexan. Unter Fortsetzung des Rührens wird das Gemisch auf eine Temperatur von 85 °C erwärmt und während 4 Stunden auf dieser Temperatur gehalten, dann auf Raumtemperatur abgekühlt, eine Probe entnommen und in dieser der Rest-Amin-Gehalt bestimmt. Aufgrund dieser Bestimmung liegt der Amin-Umsatz bei 99 %. Nun wird der Kolbeninhalt in einen Rotationsverdampfer gegeben und während 4 Stunden bei 320 Umdrehungen pro Minute im Wasserbad bei einer von 50 auf 80 °C steigenden Temperatur und einem von 9,6 auf 1,8 kPa fallenden Druck die flüchtigen Bestandteile, im wesentlichen Acetonitril, abdestilliert. Das so erhaltene N-Tetradecyl-N-hexyl-N,N-dimethylammoniumbromid (1) wird anschließend bei Raumtemperatur unter einem von einer Öl-Vakuum-Pumpe erzeugten Druck von 40 Pa getrocknet und für die nachfolgend beschriebenen Viskositätsbestimmungen verwendet. Das Produkt wird analysiert, wobei folgende Werte ermittelt werden: - N-Tetradecyl-N-hexyl-N,N-dimethylammoniumbromid (1) 98,4 Gew.-% - N-Tetradecyl-N,N-dimethylamin 0,23 Gew.-% - N-Tetradecyl-N,N-dimethylammoniumbromid 1,34 Gew.-%
2. Vorprodukt für Beispiele 2 und 5
Es wird eine Apparatur, wie in Beispiel 1 beschrieben, verwendet. In den Kolben werden nacheinander unter Rühren gegeben: 164,8 g (0,6 mol) N-Hexadecyl-N,N-dimethylamin, 268,8 g (6,55 mol) Acetonitril und 104,0 g (0,63 mol) 1-Bromhexan. Das Gemisch wird unter Rühren während 4 Stunden auf 85 °C erwärmt, dann auf Raumtemperatur abgekühlt und in einer Probe der Rest-Amin-Gehalt bestimmt und daraus ein Amin-Umsatz von 99,1 % ermittelt. Die Aufarbeitung vermittels Rotationsverdampfer und anschließende Behandlung im Ölpumpen-Vakuum erfolgt, wie in Beispiel 1 beschrieben. Das so erhaltene N-Hexadecyl-N-hexyl-N,N-dimethylammoniumbromid (2) wird für die nachfolgend beschriebenen Viskositätsmessungen verwendet. Folgende Gehalte werden analytisch ermittelt: - N-Hexadecyl-N-hexyl-N,N-dimethylammoniumbromid (2) 98,0 Gew.-% - N-Hexadecyl-N,N-dimethylamin 0,5 Gew.-% - N-Hexadecyl-N,N-dimethylammoniumbromid 1,5 Gew.-%
3. Vorprodukt für Vergleichsversuche A und C sowie Beispiele 3 und 6
Es wird verfahren, wie in Beispiel 1 beschrieben, jedoch werden in den Kolben nacheinander unter Rühren gegeben: 157,4 g (0,65 mol) N-Tetradecyl-N,N-dimethylamin, 240,0 g (5,85 mol) Acetonitril und 82,6 g (0,683 mol) Allylbromid. Der Kolbeninhalt erwärmt sich ohne Heizung von außen innerhalb von 20 Minuten auf 61 °C. Nun wird vermittels der Außenheizung weiter auf 70 °C erwärmt und während 1 Stunde unter Rühren auf dieser Temperatur gehalten, dann auf Raumtemperatur abgekühlt und in einer Probe des Kolbeninhaltes anhand einer Rest-Amin-Bestimmung ein Amin-Umsatz von 99,7 % ermittelt. Die Aufarbeitung erfolgt, wie in Beispiel 1 beschrieben. Das so erhaltene N-Tetradecyl-N-allyl-N,N-dimethylammoniumbromid (3) wird für die nachfolgend beschriebenen Viskositätsbestimmungen verwendet. Folgende Gehalte werden analytisch ermittelt: - N-Tetradecyl-N-allyl-N,N-dimethylammoniumbromid (3) 98,4 Gew.-% - N-Tetradecyl-N,N-dimethylamin 0,05 Gew.-% - N-Tetradecyl-N,N-dimethylammoniumbromid 1,5 Gew.-%
4. Vorprodukt für Vergleichsversuche B und D sowie Beispiele 3 und 6
Es wird verfahren, wie in Beispiel 1 beschrieben, jedoch werden in den Kolben nacheinander unter Rühren gegeben: 145,3 g (0,60 mol) N-Tetradecyl-N,N-dimethylamin, 267,0 g (6,5 mol) Acetonitril und 121,7 g (0,63 mol) 1-Bromoctan. Das Gemisch wird unter Rühren auf 80 °C erwärmt und 4 Stunden bei dieser Temperatur gehalten, dann auf Raumtemperatur abgekühlt und in einer Probe des Kolbeninhaltes anhand einer Rest-Amin-Bestimmung ein Amin-Umsatz von 98 % ermittelt. Die Aufarbeitung erfolgt, wie in Beispiel 1 beschrieben. Das so erhaltene N-Tetradecyl-N-octyl-N,N-dimethylammoniumbromid (4) wird für die nachfolgend beschriebenen Viskositätsbestimmungen verwendet. Folgende Gehalte werden analytisch ermittelt: - N-Tetradecyl-N-octyl-N,N-dimethylammoniumbromid (4) 98,0 Gew.-% - N-Tetradecyl-N,N-dimethylamin 0,5 Gew.-% - N-Tetradecyl-N,N-dimethylammoniumbromid 1,1 Gew.-% The following examples are intended to explain the invention.
1. Preproduct for Examples 1 and 4
In a flask of 1 dm³, which is equipped with a stirrer, a reflux condenser and a contact thermometer and is surrounded in its lower part by an electrically heatable sleeve, which is controlled by the contact thermometer, are added in succession at room temperature with stirring : 145.3 g (0.6 mol) of N-tetradecyl-N, N-dimethylamine, 249.3 g (6.07 mol) of acetonitrile and 104.0 g (0.63 mol) of 1-bromohexane. While continuing to stir, the mixture is heated to a temperature of 85 ° C. and held at this temperature for 4 hours, then cooled to room temperature, a sample is taken and in this the residual amine content is determined. Based on this determination, the amine conversion is 99%. The contents of the flask are then placed in a rotary evaporator and the volatile constituents, essentially acetonitrile, are added for 4 hours at 320 revolutions per minute in a water bath at a temperature rising from 50 to 80 ° C. and a pressure falling from 9.6 to 1.8 kPa. distilled off. The N-tetradecyl-N-hexyl-N, N-dimethylammonium bromide (1) thus obtained is then dried at room temperature under a pressure of 40 Pa generated by an oil vacuum pump and used for the viscosity determinations described below. The product is analyzed, the following values being determined: - N-tetradecyl-N-hexyl-N, N-dimethylammonium bromide (1) 98.4% by weight - N-tetradecyl-N, N-dimethylamine 0.23% by weight - N-tetradecyl-N, N-dimethylammonium bromide 1.34% by weight
2. Preproduct for Examples 2 and 5
An apparatus as described in Example 1 is used. The following are successively added to the flask with stirring: 164.8 g (0.6 mol) of N-hexadecyl-N, N-dimethylamine, 268.8 g (6.55 mol) of acetonitrile and 104.0 g (0.63 mol ) 1-bromohexane. The mixture is heated to 85 ° C. for 4 hours with stirring, then cooled to room temperature and the residual amine content is determined in a sample and an amine conversion of 99.1% is determined therefrom. Working up by means of a rotary evaporator and subsequent treatment in an oil pump vacuum is carried out as described in Example 1. The N-hexadecyl-N-hexyl-N, N-dimethylammonium bromide (2) thus obtained is used for the viscosity measurements described below. The following levels become analytical determined: - N-hexadecyl-N-hexyl-N, N-dimethylammonium bromide (2) 98.0% by weight - N-hexadecyl-N, N-dimethylamine 0.5% by weight - N-hexadecyl-N, N-dimethylammonium bromide 1.5% by weight
3. Preproduct for comparative tests A and C and examples 3 and 6
The procedure is as described in Example 1, but the following are successively added to the flask with stirring: 157.4 g (0.65 mol) of N-tetradecyl-N, N-dimethylamine, 240.0 g (5.85 mol) Acetonitrile and 82.6 g (0.683 mol) allyl bromide. The contents of the flask heat up to 61 ° C within 20 minutes without heating. Now the external heating is used to further heat to 70 ° C. and to keep it at this temperature for 1 hour while stirring, then it is cooled to room temperature and an amine conversion of 99.7% is determined in a sample of the flask contents using a residual amine determination. Working up is carried out as described in Example 1. The N-tetradecyl-N-allyl-N, N-dimethylammonium bromide (3) thus obtained is used for the viscosity determinations described below. The following contents are determined analytically: - N-tetradecyl-N-allyl-N, N-dimethylammonium bromide (3) 98.4% by weight - N-tetradecyl-N, N-dimethylamine 0.05% by weight - N-tetradecyl-N, N-dimethylammonium bromide 1.5% by weight
4. Preproduct for comparative tests B and D and examples 3 and 6
The procedure is as described in Example 1, but the following are added to the flask in succession with stirring: 145.3 g (0.60 mol) of N-tetradecyl-N, N-dimethylamine, 267.0 g (6.5 mol) of acetonitrile and 121.7 g (0.63 mol) of 1-bromooctane. The mixture is heated to 80 ° C. with stirring and kept at this temperature for 4 hours, then cooled to room temperature and an amine conversion of 98% is determined in a sample of the contents of the flask using a residual amine determination. Working up is carried out as described in Example 1. The N-tetradecyl-N-octyl-N, N-dimethylammonium bromide (4) thus obtained is used for the viscosity determinations described below. The following contents are determined analytically: - N-tetradecyl-N-octyl-N, N-dimethylammonium bromide (4) 98.0% by weight - N-tetradecyl-N, N-dimethylamine 0.5% by weight - N-tetradecyl-N, N-dimethylammonium bromide 1.1% by weight

Zur Viskositätsmessung werden aus den Ammoniumverbindungen, deren Herstellung in den vorangegangenen Abschnitten beschrieben wurde, erfindungsgemäße (bezeichnet als "Beispiel" mit Nummer) und nicht erfindungsgemäße (bezeichnet als "Vergleichsversuch" mit großem Buchstaben) Mischungen mit Wasser in den in nachfolgender Tabelle 1 aufgeführten Mengenverhältnissen unter Rühren bei 80 °C hergestellt, auf Meßtemperatur abgekühlt und an den Mischungen, die bis zu 70 Gew.-% Ammoniumverbindungen und minimal 30 Gew.-% Wasser (W) enthalten, die Viskosität (V) bei der angegebenen Temperatur (T) und Scherrate (D) mit dem Rotationsviskosimeter Rheolab MC 10 der Firma "Physica", W-7000 Stuttgart 80, Deutschland, mit dem Meßkörper Z 1 (DIN) gemessen. Die erhaltenen Ergebnisse sind in nachfolgender Tabelle 1 aufgeführt: Tabelle 1 Beispiel/Vergleichsversuch Konzentratzusammensetzung Verbindung/Menge [g] W [Gew.-%] Viskositätsmessung T [°C] D [1/s] V [mPa · s] 1 a (1)/10 --- H₂O/10 50 35 100 35 b (1)/14 --- H₂O/6 30 35 100 77 2 a (2)/10 --- H₂O/10 50 35 100 59 b (2)/13 --- H₂O/7 35 35 100 95 A a (3)/10 --- H₂O/10 50 35 100 >5000 B a (4)/8 --- H₂O/12 60 35 100 35 b (4)/12 --- H₂O/8 40 35 100 49 3 a (3)/5 (4)/5 H₂O/10 50 35 100 100 b (3)/4 (4)/4 H₂O/12 60 35 100 168 For viscosity measurement, mixtures of water according to the invention (referred to as "example" with number) and non-inventive (referred to as "comparative test" with a capital letter) are mixed with water in the quantitative ratios listed in Table 1 below from the ammonium compounds whose preparation was described in the preceding sections prepared with stirring at 80 ° C, cooled to the measuring temperature and the viscosity (V) of the mixtures containing up to 70% by weight of ammonium compounds and a minimum of 30% by weight of water (W) at the specified temperature (T) and shear rate (D) measured with the Rheolab MC 10 rotary viscometer from "Physica", W-7000 Stuttgart 80, Germany, with the Z 1 (DIN) measuring body. The results obtained are shown in Table 1 below: Table 1 Example / comparison test Concentrate composition compound / amount [g] W [% by weight] Viscosity measurement T [° C] D [1 / s] V [mPa · s] 1 a (1) / 10 --- H₂O / 10 50 35 100 35 b (1) / 14 --- H₂O / 6 30th 35 100 77 2 a (2) / 10 --- H₂O / 10 50 35 100 59 b (2) / 13 --- H₂O / 7 35 35 100 95 A a (3) / 10 --- H₂O / 10 50 35 100 > 5000 B a (4) / 8 --- H₂O / 12 60 35 100 35 b (4) / 12 --- H₂O / 8 40 35 100 49 3 a (3) / 5 (4) / 5 H₂O / 10 50 35 100 100 b (3) / 4 (4) / 4 H₂O / 12 60 35 100 168

Die Herstellung der Verbindungen (1) bis (4) sind vorstehend beschrieben, ebenso die Bedeutung von T, D, V und W (= Gew.-% Wasser im Konzentrat).The preparation of the compounds (1) to (4) are described above, as are the meaning of T, D, V and W (=% by weight of water in the concentrate).

Im Beispiel 3 wird eine erfindungsgemäße Mischung der beiden Verbindungen (3) und (4) mit Wasser eingesetzt. Die Mischungen der einzelnen Verbindungen (3) oder (4) mit Wasser sind nicht erfindungsgemäß und folglich als Vergleichsversuch bezeichnet.In example 3, a mixture according to the invention of the two compounds (3) and (4) with water is used. The mixtures of the individual compounds (3) or (4) with water are not according to the invention and are therefore referred to as a comparison test.

Ab etwa 70 Gew.-% und mehr Ammoniumverbindungen entsprechend 30 Gew.-% und weniger Wasser ist die Viskositätsmessung, insbesondere bei erhöhten Temperaturen, schwierig, da die Mischungen in offenen Systemen zu mehr oder weniger starker Hautbildung an der Oberfläche neigen, wodurch keine reproduzierbaren Viskositätsmeßwerte erhalten werden können. Hier wurde zum Vergleich folgendes Verfahren angewendet: Mit den zu untersuchenden Mischungen werden zylindrische Glasbehälter, deren Durchmesser der Grundfläche 5 cm und deren Höhe 10 cm betragen zu 1/4 ihres Inhaltes gefüllt, dicht verschlossen und während 1 Stunde auf die Untersuchungstemperatur gebracht. Dann werden die Behälter geschüttelt und das viskose Verhalten ihres Inhaltes visuell beurteilt. Die Versuchsbedingungen und Ergebnisse sind in nachfolgender Tabelle 2 aufgeführt: Tabelle 2 Beispiel/Vergleichsversuch Konzentratzusammensetzung Verbindung/Menge [g] W [Gew.-%] T [°C] Viskositätsbeurteilung 4 a (1)/37,5 --- H₂O/12,5 25 30 dünnflüssig b (1)/40 --- H₂O/10 20 50 dünnflüssig 5 a (2)/37,5 --- H₂O/12,5 25 60 dünnflüssig b (2)/40 --- H₂O/10 20 65 dünnflüssig C (3)/35 --- H₂O/15 30 70 Mischung von dünnflüssigen und festen, gelartigen Bestandteilen, nicht homogenisierbar D (4)/35 --- H₂O/15 30 70 gelartig, nicht gießbar 6 a (3)/17,5 (4)/17,5 H₂O/15 30 70 dünnflüssig b (3)/20 (4)/20 H₂O/10 20 70 zähflüssig, jedoch gießbar From about 70 wt .-% and more ammonium compounds corresponding to 30 wt .-% and less water, the viscosity measurement, especially at elevated temperatures, is difficult because the mixtures in open systems tend to more or less severe skin formation on the surface, so that no reproducible Viscosity measurements can be obtained. The following procedure was used here for comparison: With the mixtures to be examined, cylindrical glass containers with a diameter of 5 cm and a height of 10 cm are filled to 1/4 of their contents, sealed and brought to the examination temperature for 1 hour. The containers are then shaken and the viscous behavior of their contents is assessed visually. The test conditions and results are listed in Table 2 below: Table 2 Example / comparison test Concentrate composition compound / amount [g] W [% by weight] T [° C] Viscosity assessment 4 a (1) / 37.5 --- H₂O / 12.5 25th 30th thin b (1) / 40 --- H₂O / 10 20th 50 thin 5 a (2) / 37.5 --- H₂O / 12.5 25th 60 thin b (2) / 40 --- H₂O / 10 20th 65 thin C. (3) / 35 --- H₂O / 15 30th 70 Mixture of thin and solid, gel-like components, cannot be homogenized D (4) / 35 --- H₂O / 15 30th 70 gel-like, not pourable 6 a (3) / 17.5 (4) / 17.5 H₂O / 15 30th 70 thin b (3) / 20 (4) / 20 H₂O / 10 20th 70 viscous, but pourable

Claims (2)

  1. A water-containing concentrate of at least one alkyl- or alkenyl-substituted ammonium compound, consisting essentially of
    a) 40 to 85% by weight of an ammonium compound of the formula
    Figure imgb0007
     in which
    R¹   is a straight-chain alkyl radical or a straight-chain alkenyl radical having 12, 14, 16, or 18 carbon atoms,
    R²   is a straight-chain alkyl radical or a straight-chain alkenyl radical (1) having 4, 5, or 6 carbon atoms in case that R¹ has 12 carbon atoms, (2) having 5 or 6 carbon atoms in case that R¹ has 14 carbon atoms, (3) having 6 or 7 carbon atoms in case that R¹ has 16 carbon atoms, or (4) having 7 or 8 carbon atoms in case that R¹ has 18 carbon atoms,
    R³ and R⁴,   which are identical or different, are a hydrogen atom or a methyl radical, and
    X   is a chloride, bromide, methylsulfate, phenylsulfonate, or methylphenylsulfonate anion,
    or of a mixture of such ammonium compounds, and
    b) 15 to 60% by weight of water, percentages by weight being relative to the total mixture.
  2. A water-containing concentrate of more alkyl- or alkenyl-substituted ammonium compounds, consisting essentially of
    a) 40 to 85% by weight of a mixture consisting of a first ammonium compound of the formula
    Figure imgb0008
     in which
    R¹   is a straight-chain alkyl radical or a straight-chain alkenyl radical having 12, 14, 16, or 18 carbon atoms,
    R⁵   is a straight-chain alkyl radical or a straight-chain alkenyl radical (1) having 3 carbon atoms in case that R¹ has 12 carbon atoms, (2) having 3 or 4 carbon atoms in case that R¹ has 14 carbon atoms, (3) having 4 carbon atoms in case that R¹ has 16 carbon atoms, or (4) having 5 or 6 carbon atoms in case that R¹ has 18 carbon atoms,
    R³ and R⁴,   which are identical or different, are a hydrogen atom or a methyl radical, and
    X   is a chloride, bromide, methylsulfate, phenylsulfonate, or methylphenylsulfonate anion,
    and of a second ammonium compound of the formula
    Figure imgb0009
     in which
    R¹   is a straight-chain alkyl radical or a straight-chain alkenyl radical having 12, 14, 16, or 18 carbon atoms,
    R⁶   is a straight-chain alkyl radical or a straight-chain alkenyl radical (1) having 7 or 8 carbon atoms in case that R¹ has 12 carbon atoms, (2) having 8, 9, or 10 carbon atoms in case that R¹ has 14 carbon atoms, or (3) having 9, 10, or 11 carbon atoms in case that R¹ has 16 carbon atoms or 18 carbon atoms,
    R³ and R⁴,   which are identical or different, are a hydrogen atom or a methyl radical, and
    x   is a chloride, bromide, methylsulfate, phenylsulfonate, or methylphenylsulfonate anion,
    the two ammonium compounds (II) and (III) having been mixed in such a ratio that the average of the numbers of the carbon atoms of R⁵ and R⁶ in the mixture has a value of n/2 - p, wherein n is the number of the carbon atoms of R¹ and p is 1 to 2, and
    b) 15 to 60% by weight of water, the percentages by weight being relative to the total mixture.
EP92102533A 1991-02-15 1992-02-14 Aqueous concentrate of at least one alkyl- or alkenyl substituted ammonium compound Expired - Lifetime EP0499282B1 (en)

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DE4104618A DE4104618A1 (en) 1991-02-15 1991-02-15 A WATER-CONSISTENT CONCENTRATE OF AT LEAST ONE ALKYL OR ALKENYL SUBSTITUTED AMMONIUM COMPOUND
DE4104618 1991-02-15

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US6013615A (en) 1995-07-26 2000-01-11 The Clorox Company Antimicrobial hard surface cleaner
JPH11509781A (en) * 1996-04-26 1999-08-31 セルビシオ インダストリアル ド マルカジェ イコディフィカシオン，エス．エイ． Apparatus and method for marking or perforation
DE50106924D1 (en) * 2001-05-07 2005-09-01 Epcos Ag CERAMIC CONSTRUCTION ELEMENT WITH AIR CONDITIONER CONTACT
JP4673935B2 (en) * 2008-12-26 2011-04-20 神戸天然物化学株式会社 Method for producing concentrated liquid for photoresist stripping solution with low water content

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WO1985000617A1 (en) * 1983-07-21 1985-02-14 Akzona Incorporated Quaternary ammonium salts useful as fabric softeners
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DE3135013A1 (en) * 1981-09-04 1983-03-24 Hoechst Ag, 6000 Frankfurt "SOFT SOFT DETERGENT"
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WO1985000617A1 (en) * 1983-07-21 1985-02-14 Akzona Incorporated Quaternary ammonium salts useful as fabric softeners
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