WO1994024255A1 - Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivates - Google Patents

Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivates Download PDF

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Publication number
WO1994024255A1
WO1994024255A1 PCT/EP1994/001198 EP9401198W WO9424255A1 WO 1994024255 A1 WO1994024255 A1 WO 1994024255A1 EP 9401198 W EP9401198 W EP 9401198W WO 9424255 A1 WO9424255 A1 WO 9424255A1
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WIPO (PCT)
Prior art keywords
water
weight
acid
oil
soluble
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PCT/EP1994/001198
Other languages
German (de)
French (fr)
Inventor
Kurt Dahmen
Erich KÜSTER
Reinmar PEPPMÖLLER
Original Assignee
Chemische Fabrik Stockhausen Gmbh
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Priority to EP94914400A priority Critical patent/EP0701598A1/en
Publication of WO1994024255A1 publication Critical patent/WO1994024255A1/en

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Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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
    • D06M13/35—Heterocyclic compounds
    • D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides

Definitions

  • the invention relates to aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives which are stabilized by water-in-oil dispersions of cationic, crosslinked, water-swellable polymers.
  • Quaternary ammonium or cyclic amidine compounds from oleochemical raw materials which are used, for example, as active ingredient components in fabric and fabric softener formulations, often have only a limited solubility in water and therefore tend to separate when introduced into water and the solubility limit is exceeded. This leads not only to difficulties in warehousing, but also to inaccurate or incorrect dosing during use. There has been no shortage of attempts to find means with which storage-stable, pourable or pasty dispersions can be produced.
  • WO 91/12364 describes aqueous preparations which can be stored well and contain an active ingredient combination based on condensation products of carboxylic acids or carboxylic acid derivatives with hydroxyalkyl polyamines and quaternary ammonium compounds.
  • the object of the invention is therefore to further improve the effect of the known stabilizing additives.
  • This object is achieved according to the invention with weakly crosslinked, water-swellable copolymers based on cationic monoethylenically unsaturated carboxylic acid derivatives.
  • Polymers which bring about an increase in viscosity due to the presence of water-swellable particles in water or aqueous solutions, are used in many fields of technology, cosmetics and pharmacy.
  • Naturally occurring substances such as alginates, guar flour and starch, unchanged or chemically modified, are increasingly being replaced by synthetic polymers, with polymers of acrylic compounds among others being used.
  • water-in-oil emulsion polymers of these acrylic compounds produced by inverse emulsion polymerization, offer advantages because of their ease of incorporation into water or aqueous media.
  • the preparation of water-soluble polymers of this class of substances by emulsion polymerization is described in US Pat. No. 3,284,393 and in DE-OS 22 26 143. Since these products are water-in-oil dispersions which contain the polymer in the emulsified "water droplets", a reversible emulsifier for dispersing the outer oil phase in accordance with DE-OS 22 26 143 must be added to dissolve in water. The emulsion type is reversed after oil-in-water.
  • the wetting agent can already be contained in the dispersion, which makes it self-inverting.
  • Crosslinked, water-insoluble or water-swellable polymers of nonionic or anionic monomers from the acrylic series are described, for example, in the patents GB 20 07 238 and US 4,554,018.
  • Water-soluble, non-crosslinked, inverse emulsion polymers from the acrylic series with cationic monomers are described in DE-OS 27 56 697, the manufacture and use of which, however, are tailored to their specific use as flocculants.
  • EP 0196 162 mentions weakly crosslinked, inverse emulsion polymers with cationic (meth) acrylic esters as thickeners for non-aqueous solutions.
  • Corresponding water-in-oil dispersions of water-swellable, weakly crosslinked, cationic polymers are proposed in DE 37 30 781 C2 for the production of printing pastes for textile printing.
  • N- Substituted (meth) acrylic acid aminoalkylamides are regarded as particularly suitable because of the greater hydrophilicity of the amide group compared to the ester function and thus because of the better water swellability. At the same time, these amides have better hydrolysis stability, which is important for long-term use in aqueous solution.
  • EP 0 186 361 reports that the thickening effect of partially ionic, preferably anionic, weakly crosslinked polymers in electrolyte-containing media is caused by addition of ionic surfactants when these are in the oil phase of the water-in-oil Dispersions are soluble to a greater extent than in the water phase, can be improved. While there anionic polymers and anionic surfactants are treated in detail and in detail, cationic products are only taken into account when the possible uses are mentioned, without reference to experimental results.
  • the invention therefore relates to the use of water-in-oil dispersions of water-swellable, predominantly cationic, crosslinked polymers for stabilizing aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives, such as those e.g. can be used as so-called textile and fabric softeners.
  • aqueous dispersions contain, as customary active ingredients, for example NN-distearyl-N, N-dimethylammonium chloride (DSDMAC), imidazoline derivatives (see, for example, US Pat. No. 4,762,645, EP-A 0199 383), quaternized fatty acid esters of triethanolamine (so-called ester quats) , see US Pat. No. 4,830,771) or 2,3-dihydroxypropyl-1-trimethyl-ammonium salt derivatives (DE-OS 27 28 841).
  • DSDMAC N-dimethylammonium chloride
  • imidazoline derivatives see, for example,
  • R] an alkyl group with 1 to 4 carbon atoms, especially methyl
  • R2 an alkyl or alkenyl group with 1 to 22 carbon atoms, or a hydroxyalkyl group with 2 to 4 carbon atoms,
  • R3 an alkyl or alkenyl group with 1 to 22 carbon atoms, an acyloxyalkyl group, the acyl radical of which is derived from saturated or unsaturated, linear or branched fatty acids with 10 to 22 carbon atoms and the oxyalkyl group which is oxyethyl or oxypropyl or oxyisopropyl group,
  • X " mean an anion.
  • the creaming or / or sediment formation that generally occurs in the case of unstable suspensions during storage is slowed down by increasing the viscosity but is not eliminated.
  • the stabilizers according to the invention are used, the state of dispersion is improved in such a way that the homogeneity in storage and handling is ensured.
  • the water-in-oil dispersions used for stabilization consist of:
  • the homo- or copolymers are prepared by polymerizing a monomer mixture of
  • R j hydrogen or methyl
  • R-2 > - -3 hydrogen or identical or different alkyl radicals with 1 to 4
  • A anion of an organic or inorganic acid, preferably hydrochloric acid or methylsulfuric acid, b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate, c) 0 to 40% by weight of one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and / or their salts, d) 0.001 - 5.0% by weight % of a polyfunctional monomer
  • Quaternized dimethylaminoethyl (meth) acrylate, quaternized dimethylaminopropyl (meth) acrylamide, quaternized dimethylamino-2,2-dimethylpropyl (meth) acrylamide, diallyldimethylammonium chloride, diallyldiethylammonium chloride and mixtures thereof with one another are used as cationic monomers.
  • the quaternization is preferably carried out using methyl chloride, sodium chloroacetate, dimethyl sulfate and dimethyl carbonate.
  • hydrophobic, organic liquids aromatic and aliphatic linear, branched and cyclic hydrocarbons, the boiling points of which are at a pressure of 1013 hPa in the range from 110 to 380 ° C.
  • aromatic and aliphatic linear, branched and cyclic hydrocarbons the boiling points of which are at a pressure of 1013 hPa in the range from 110 to 380 ° C.
  • These include n- and iso-paraffins, distillates from paraffinic, naphthenic and aromatic petroleum as well as toluene, xylene and mesitylene.
  • linear and branched liquid esters of natural and synthetic origin can also be used as the oil phase.
  • oil-soluble emulsifiers with a low HLB value such as partial esters of glycerol, di- and polyglycerol, sorbitol, sorbitan and addition products of alkylene oxides, such as ethylene oxide and propylene oxide, are used to prepare the polymerization and preparation of the monomer-containing water-in-oil emulsion higher linear and branched alcohols, fatty acids or nonylphenol.
  • polymeric emulsifiers can also be used alone or in a mixture, as is described, inter alia, in US Pat. No. 4,786,681.
  • Polyunsaturated vinyl, acrylic or allyl compounds and compounds with several epoxy groups are used as crosslinking monomers. Suitable compounds are, for example, methylenebisacrylamide and quaternized triallylamine, in particular tetraallyl or triallyl methylammonium chloride.
  • the crosslinking can take place during the polymerization or afterwards.
  • Water-soluble epoxy compounds which are derived from polyhydric alcohols are particularly suitable for postcrosslinking.
  • the technique of polymerization with emulsion formation, homogenization of the mixture and initiation of the polymerization is known. It is preferably carried out adiabatically, but can also be carried out isothermally at a preselected temperature. After the polymerization has ended, the water-in-oil dispersion can be introduced directly into the aqueous, cationic dispersion of the quaternary ammonium or cyclic amidine compounds.
  • the water-in-oil dispersions can be used to stabilize aqueous dispersions of limited water-soluble quaternary ammonium salts such as dimethyl distearylammonium chloride, dimethyldilaurylammonium chloride and and quaternary esters, e.g.
  • the limited water-soluble quaternary ammonium salts or imidazoline derivatives are usually in the form of aqueous slurries / dispersions, e.g. B. with solids contents of 5 wt .-%.
  • the solids content is otherwise not critical.
  • the application concentrations range between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight, in particular between 0.2 and 2% by weight, depending on the desired stabilization of the dispersion.
  • further viscosity-increasing nonionic or cationic substances can be used.
  • DMAEA dimethylaminoethyl acrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • TEMAPA NN2.2-tetramethylaminopropylacrylamide
  • AMPS 2-acrylamido-2-methyl-propanesulfonic acid
  • TAMAC triallylmethylammonium chloride
  • ABAH azo-bis- (2-amidinopropane hydrochloride)
  • EDTA ethylenediaminetetraacetic acid
  • TBHP tert-butyl hydroperoxide
  • KWST isoparaffic hydrocarbon with a boiling range of 210 -
  • DMAEA-CH3CI and 40 g of acrylamide are dissolved in 165 g of water.
  • the pH is then adjusted to 4.5 with phosphoric acid and 0.4 g of EDTA is added.
  • the solution is poured with stirring into a mixture of 120 g KWST, 10 g sorbitan monoisostearate and 0.62 g TAMAC and homogenized with a household mixing stick (viscosity of the emulsion: 4200 mPa * s, Brookfield RVT , MK 11/20 at 20 ° C).
  • the dissolved oxygen is expelled by blowing nitrogen with simultaneous heating of the emulsion to 60 ° C.
  • Nitrogen is passed in for about 30 minutes and then the polymerization is started by adding 0.11 g of AIBN, dissolved in 4 g of KWST. The temperature rises to approx. 102 ° C due to the adiabatic exothermic reaction. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
  • Example 2 a) Preparation of a dispersion of a polymer from 80% DIMAPA-CH3CI and 20% acrylamide with 40% wS.
  • Example 4 a) Preparation of a dispersion of 92% DMAEMA-CH3CI and 8% acrylamide with 50% wS.
  • Example 1 230 g of DMAEMA-CH3CI and 20 g of acrylamide are dissolved in 110 g of water and 0.5 g of EDTA and 0.6 g of AB AH are added. The pH value is with conc. Hydrochloric acid set to 0.6.
  • the emulsion is formed as in Example 1 with 120 g KWST and 10 g sorbitan monoisostearate (viscosity: 1400 mPa * s at 20 ° C). It is catalyzed with 6 mg TBHP and 12 mg sulfur dioxide at 20 ° C, with a peak temperature of 72 ° C being reached within 150 minutes. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
  • 160 g DMAEA-CH3CI, 36 g acrylamide, 19 g AMPS are dissolved in 114 g water and after adjusting the pH to 4.5 with hydrochloric acid with stirring in 100 g KWST, 10 g diglycerol sesquioleate, 0.8 g TAMAC and 0 Poured 2 g EDTA. It is homogenized, flushed with nitrogen and the polymerization is started with 1 g ACBN.
  • Percentage composition of the polymers (% by weight):

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Aqueous dispersions of barely water-soluble quaternary ammonium compounds and/or imidazoline derivates are stabilized by adding water-in-oil dispersions of water-swelling cationic cross-linked polymers. The stabilizing water-in-oil dispersions consist of 30 to 70 % by weight of a cationic homo- or copolymer, 20 to 50 % by weight of a hydrophobic organic liquid, 0.5 to 10 % by weight of a water-in-oil emulsifyer and 0 to 10 % by weight of a cross-linking agent, the remaining percentage being constituted by water. These stabilizing cationic cross-linked polymers are preferably prepared by inverse emulsion polymerisation. Also disclosed is the use of such stabilizing aqueous dispersions as textile and laundry softeners.

Description

Stabile wäßrige Dispersionen von quartären Ammoniumverbinduneen und Stable aqueous dispersions of quaternary ammonium compounds and
Imidazolin-DerivatenImidazoline derivatives
Die Erfindung betrifft wäßrige Dispersionen von quartären Ammoniumverbindungen und Imidazolin-Derivaten, die durch Wasser-in-Öl-Dispersionen kationischer, vernetzter, was-serquellbarer Polymerisate stabilisiert werden.The invention relates to aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives which are stabilized by water-in-oil dispersions of cationic, crosslinked, water-swellable polymers.
Quartäre Ammonium- bzw. cyclische Amidinverbindungen aus fettchemischen Rohstof¬ fen, die beispielsweise als Wirkstofϊkomponenten in Textil- und Wäscheweichspüler-For- mulierungen eingesetzt werden, besitzen oftmals nur eine begrenzte Wasserlöslichkeit und neigen daher bei Einbringung in Wasser und Überschreitung der Löslichkeitsgrenze zu Abscheidungen. Dies fuhrt nicht nur zu Schwierigkeiten bei der Lagerhaltung, sondern auch zu ungenauen bzw. fehlerhaften Dosierungen bei der Anwendung. Es hat daher nicht an Versuchen gefehlt, Mittel zu finden, mit denen lagerstabile, gießfähige bzw. pastöse Dispersionen herstellbar sind. So beschreibt die WO 91/12364 wässrige Zube-reitungen, die gut lagerfähig sind und eine Wirkstoffkombination auf der Basis von Kon-densationsprodukten aus Carbonsäuren oder Carbonsäure-Derivaten mit Hydroxyalkyl-polyaminen und quartären Ammoniumverbindungen enthalten. Es gehört ebenfalls zum Stand der Technik, den bei Raumtemperatur festen, kationischen Ammonium- bzw. cyclischen Amidinverbindungen niedrigviskose, wasserlösliche Alkohole, wie Methanol, Ethanol oder Isopropanol zuzusetzen. Auch Ethylenglykol, Propandiol-1,2 und die homo-logen, höhermolekularen Polyalkylenglykolether finden wegen ihres höheren Flamm-punktes Verwendung. Als nachteilig kann bewertet werden, daß diese Lösemittel nicht nur in hohem Maße brennbar sind und gegenüber Kunststoffverpackungsmaterialien migrationsfähig sein können, sondern auch bei weiterer Verdünnung mit Wasser desta-bilisierend auf die Dispersion wirken. Wünschenswert ist daher ein Stabilisator für wäßrige, kationische Dispersionen, dessen Flammpunkt über 100 °C liegt und dessen Eigenschaften jede Kunststoffverpackung zulassen.Quaternary ammonium or cyclic amidine compounds from oleochemical raw materials, which are used, for example, as active ingredient components in fabric and fabric softener formulations, often have only a limited solubility in water and therefore tend to separate when introduced into water and the solubility limit is exceeded. This leads not only to difficulties in warehousing, but also to inaccurate or incorrect dosing during use. There has been no shortage of attempts to find means with which storage-stable, pourable or pasty dispersions can be produced. For example, WO 91/12364 describes aqueous preparations which can be stored well and contain an active ingredient combination based on condensation products of carboxylic acids or carboxylic acid derivatives with hydroxyalkyl polyamines and quaternary ammonium compounds. It is also part of the prior art to add low-viscosity, water-soluble alcohols, such as methanol, ethanol or isopropanol, to the cationic ammonium or cyclic amidine compounds which are solid at room temperature. Ethylene glycol, 1,2-propanediol and the homologous, higher molecular weight polyalkylene glycol ethers are also used because of their higher flash point. A disadvantage is that these solvents are not only highly flammable and can migrate to plastic packaging materials, but also have a de-bilizing effect on the dispersion when further diluted with water. It is therefore desirable to have a stabilizer for aqueous, cationic dispersions, the flash point of which is above 100 ° C. and the properties of which permit any plastic packaging.
Aufgabe der Erfindung ist es daher, die bekannten Stabilisierungszusätze in ihrer Wirkung weiter zu verbessern. Diese Aufgabe wird erfindungsgemäß gelöst mit schwach vernetzten, wasserquellbaren Copolymerisaten auf Basis von kationischen monoethylenisch ungesättigten Carbonsäure-derivaten.The object of the invention is therefore to further improve the effect of the known stabilizing additives. This object is achieved according to the invention with weakly crosslinked, water-swellable copolymers based on cationic monoethylenically unsaturated carboxylic acid derivatives.
Polymere, die durch das Vorhandensein von wasserquellbaren Partikeln in Wasser oder wäßrigen Lösungen eine Viskositätserhöhung bewirken, werden in vielen Bereichen der Technik, Kosmetik und Pharmazie verwendet. Natürlich vorkommende Stoffe wie Algi- nate, Guarmehl und Stärke in unveränderter oder chemisch modifizierter Art werden in zunehmendem Maße durch synthetische Polymere ersetzt, wobei unter anderem Poly¬ mere von Acrylverbindungen zum Einsatz kommen.Polymers, which bring about an increase in viscosity due to the presence of water-swellable particles in water or aqueous solutions, are used in many fields of technology, cosmetics and pharmacy. Naturally occurring substances such as alginates, guar flour and starch, unchanged or chemically modified, are increasingly being replaced by synthetic polymers, with polymers of acrylic compounds among others being used.
Hierbei werden durch Verwendung mehrfiinktioneller Verbindungen in geringer Menge dreidimensionale Netzwerke geschaffen, so daß die Produkte große Mengen Wasser aufnehmen können, ohne vollständig in den Lösungszustand überzugehen. Sie sind nur noch wasserquellbar, obwohl sie im allgemeinen noch wasserlösliche Anteile enthalten.Here, by using multifunctional compounds in small quantities, three-dimensional networks are created so that the products can absorb large quantities of water without completely changing to the solution state. They are only water-swellable, although they generally still contain water-soluble components.
Insbesondere Wasser-in-Öl-Emulsionspolymerisate dieser Acrylverbindungen, hergestellt durch inverse Emulsionspolymerisation, bieten wegen ihrer leichten Einbringbarkeit in Wasser oder wässrige Medien Vorteile. Die Herstellung von wasserlöslichen Polymeren dieser Substanzklasse durch Emulsionspolymerisation wird in der US-PS 32 84 393 und in der DE-OS 22 26 143 beschrieben. Da diese Produkte Wasser-in-Öl-Dispersionen darstellen, die das Polymer in den emulgierten "Wassertröpfchen" enthalten, muß zur Auflösung in Wasser ein Umkehremulgator zur Dispergierung der äußeren Ölphase ge¬ mäß DE-OS 22 26 143 zugesetzt werden. Der Emulsionstyp kehrt sich nach Öl-in-Was- ser um. Nach DE-OS 24 31 794 kann das Netzmittel bereits in der Dispersion enthalten sein, wodurch diese selbstinvertierend wird. Vernetzte, wasserunlösliche bzw. wasser- quellbare Polymere von nichtionogenen bzw. anionischen Monomeren aus der Acrylreihe werden z.B in den Patentschriften GB 20 07 238 und US 4 554 018 beschrieben.In particular, water-in-oil emulsion polymers of these acrylic compounds, produced by inverse emulsion polymerization, offer advantages because of their ease of incorporation into water or aqueous media. The preparation of water-soluble polymers of this class of substances by emulsion polymerization is described in US Pat. No. 3,284,393 and in DE-OS 22 26 143. Since these products are water-in-oil dispersions which contain the polymer in the emulsified "water droplets", a reversible emulsifier for dispersing the outer oil phase in accordance with DE-OS 22 26 143 must be added to dissolve in water. The emulsion type is reversed after oil-in-water. According to DE-OS 24 31 794, the wetting agent can already be contained in the dispersion, which makes it self-inverting. Crosslinked, water-insoluble or water-swellable polymers of nonionic or anionic monomers from the acrylic series are described, for example, in the patents GB 20 07 238 and US 4,554,018.
Wasserlösliche, nicht vernetzte, inverse Emulsionspolymerisate aus der Acrylreihe mit kationischen Monomeren werden in der DE-OS 27 56 697 beschrieben, deren Her¬ stellung und Anwendungsweise jedoch auf ihren speziellen Einsatzzweck als Flockungs¬ mittel zugeschnitten sind. Als Verdicker für nicht wäßrige Lösungen werden in der EP- Anmeldung 0196 162 schwach vernetzte, inverse Emulsionspolymeriate mit kationischen (Meth)acrylsäureestern erwähnt. Entsprechende Wasser-in-Öl-Dispersionen von was¬ serquellbaren, schwach vernetzten, kationischen Polymeren werden in DE 37 30 781 C2 zur Herstellung von Druckpasten für den Textildruck vorgeschlagen. Weiter werden N- substituierte (Meth)acrylsäureaminoalkylamide wegen der stärkeren Hydrophilie der Amidgruppe gegenüber der Esterfünktion und somit wegen der besseren Wasserquell- barkeit als besonders geeignet angesehen. Gleichzeitig besitzen diese Amide eine bessere Hydrolysestabilität, was für Langzeitanwendungen in wäßriger Lösung wichtig ist.Water-soluble, non-crosslinked, inverse emulsion polymers from the acrylic series with cationic monomers are described in DE-OS 27 56 697, the manufacture and use of which, however, are tailored to their specific use as flocculants. EP 0196 162 mentions weakly crosslinked, inverse emulsion polymers with cationic (meth) acrylic esters as thickeners for non-aqueous solutions. Corresponding water-in-oil dispersions of water-swellable, weakly crosslinked, cationic polymers are proposed in DE 37 30 781 C2 for the production of printing pastes for textile printing. Further N- Substituted (meth) acrylic acid aminoalkylamides are regarded as particularly suitable because of the greater hydrophilicity of the amide group compared to the ester function and thus because of the better water swellability. At the same time, these amides have better hydrolysis stability, which is important for long-term use in aqueous solution.
Da die Viskosität ionischer Polymerisate durch Elektrolytzusatz erheblich abfällt wird in EP 0 186 361 berichtet, daß die Verdickungswirkung von teilweise ionischen, bevorzugt anionischen schwach vernetzten Polymeren in elektrolythaltigen Medien durch Zusätze von ionischen Tensiden, wenn diese in der Ölphase der Wasser-in-Öl-Dispersionen in einem größeren Ausmaß löslich sind als in der Wasserphase, verbessert werden kann. Während dort anionische Polymere und anionische Tenside ausführlich und detailliert behandelt werden, finden kationische Produkte lediglich Berücksichtigung bei Nennung der Anwendungsmöglichkeiten, ohne Bezug auf experimentelle Befunde.Since the viscosity of ionic polymers drops considerably as a result of the addition of electrolytes, EP 0 186 361 reports that the thickening effect of partially ionic, preferably anionic, weakly crosslinked polymers in electrolyte-containing media is caused by addition of ionic surfactants when these are in the oil phase of the water-in-oil Dispersions are soluble to a greater extent than in the water phase, can be improved. While there anionic polymers and anionic surfactants are treated in detail and in detail, cationic products are only taken into account when the possible uses are mentioned, without reference to experimental results.
Gegenstand der Erfindung ist daher die Anwendung von Wasser-in-Öl-Dispersionen was-serquellbarer, überwiegend kationischer, vernetzter Polymerer zur Stabilisierung von wäßrigen Dispersionen von quartären Ammoniumverbindungen und Imidazolin-Deriva¬ ten, wie sie z.B. als sogenannte Textil- und Wäscheweichspüler Verwendung finden. Sol¬ che wäßrigen Dispersionen enthalten als gebräuchliche Wirkstoffe beispielsweise N.N- Distearyl-N,N-dimethylammoniumchlorid (DSDMAC), Imidazolin-Derivate (s. u.a. US- PS 4 762 645, EP-A 0199 383), quaternierte Fettsäureester des Triethanolamins (sog. Esterquats, s. u.a. US-PS 4 830 771) oder 2,3-Dihydroxypropyl-l-trimethyl-ammonium- salz-Derivate (DE-OS 27 28 841).The invention therefore relates to the use of water-in-oil dispersions of water-swellable, predominantly cationic, crosslinked polymers for stabilizing aqueous dispersions of quaternary ammonium compounds and imidazoline derivatives, such as those e.g. can be used as so-called textile and fabric softeners. Such aqueous dispersions contain, as customary active ingredients, for example NN-distearyl-N, N-dimethylammonium chloride (DSDMAC), imidazoline derivatives (see, for example, US Pat. No. 4,762,645, EP-A 0199 383), quaternized fatty acid esters of triethanolamine (so-called ester quats) , see US Pat. No. 4,830,771) or 2,3-dihydroxypropyl-1-trimethyl-ammonium salt derivatives (DE-OS 27 28 841).
Allgemein werden Ammoniumverbindungen der Formel [RιR2R3R4N]~r X" verwendet, wobei:Ammonium compounds of the formula [RιR2R3R4N] ~ r X "are generally used, where:
R] = eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen, insbesondere Methyl,R] = an alkyl group with 1 to 4 carbon atoms, especially methyl,
R2 = eine Alkyl- oder Alkenylgruppe mit 1 bis 22 Kohlenstoffatomen ist, oder eine Hydroxyalkylgruppe mit 2 bis 4 Kohlenstoffatomen,R2 = an alkyl or alkenyl group with 1 to 22 carbon atoms, or a hydroxyalkyl group with 2 to 4 carbon atoms,
R3 = eine Alkyl- oder Alkenylgruppe mit 1 bis 22 Kohlenstoffatomen, eine Acyloxyal- kylgruppe, deren Acylrest sich von gesättigten oder ungesättigten, linearen oder verzweigten Fettsäuren mit 10 bis 22 Kohlenstoffatomen ableitet und deren Oxyalkylgruppe, die Oxyethyl- oder Oxypropyl- oder Oxyisopropylgruppe ist,R3 = an alkyl or alkenyl group with 1 to 22 carbon atoms, an acyloxyalkyl group, the acyl radical of which is derived from saturated or unsaturated, linear or branched fatty acids with 10 to 22 carbon atoms and the oxyalkyl group which is oxyethyl or oxypropyl or oxyisopropyl group,
R4 - R3 oder R2 undR4 - R3 or R2 and
X" = ein Anion bedeuten. Die im allgemeinen bei instabilen Suspensionen während der Lagerung eintretenden Auf¬ rahmungen bzw./oder Bodensatzbildungen, werden durch Viskositätserhöhung zwar ver¬ langsamt aber nicht beseitigt. Bei Einsatz der erfindungsgemäßen Stabilisatoren wird der Dispersionszustand so verbessert, daß die Homogenität bei der Lagerung und Handha¬ bung gewährleistet ist.X "= mean an anion. The creaming or / or sediment formation that generally occurs in the case of unstable suspensions during storage is slowed down by increasing the viscosity but is not eliminated. When the stabilizers according to the invention are used, the state of dispersion is improved in such a way that the homogeneity in storage and handling is ensured.
Die zur Stabilisierung verwendeten Wasser-in-Öl-Dispersionen bestehen aus:The water-in-oil dispersions used for stabilization consist of:
A) 30 bis 70 Gew.-% kationisch wirksamen Homo- oder Copolymer,A) 30 to 70% by weight of cationically active homopolymer or copolymer,
B) 20 bis 50 Gew.-% hydrophober, organischer Flüssigkeit,B) 20 to 50% by weight of hydrophobic organic liquid,
C) 0 bis 10 Gew.-% Wasser-in-Öl-EmulgatorC) 0 to 10 wt .-% water-in-oil emulsifier
D) ggf. 0,5 bis 10 Gew.-% eines Netzmittels undD) optionally 0.5 to 10% by weight of a wetting agent and
E) einer Restmenge Wasser.E) a residual amount of water.
Die Summe der Komponenten A) - E) ergibt 100 Gew.-%.The sum of components A) - E) is 100% by weight.
Die Herstellung der Homo- oder Copolymeren erfolgt durch Polymerisation einer Monomeren-Mischung vonThe homo- or copolymers are prepared by polymerizing a monomer mixture of
a) mind. 50 Gew.-% eines oder mehrerer kationischer Monomeren der allgemeinen Formel:a) at least 50% by weight of one or more cationic monomers of the general formula:
[CH2=C(R1)-CO-X-(CH2)n-C(R2R3)-CH2-N(R4R5R6)]+ A",[CH2 = C (R 1 ) -CO-X- (CH 2 ) n -C (R2R3) -CH2-N (R 4 R5R 6 )] + A ",
in derin the
Rj = Wasserstoff oder Methyl-,R j = hydrogen or methyl,
•R-2> - -3 = Wasserstoff oder gleiche bzw. verschiedene Alkylreste mit 1 bis 4• R-2 > - -3 = hydrogen or identical or different alkyl radicals with 1 to 4
C-Atomen, R4, R5, R = gleiche oder verschiedene Alkylreste mit 1 bis 4 C-Atomen, n = 0 oder 1C atoms, R4, R5, R = identical or different alkyl radicals with 1 to 4 C atoms, n = 0 or 1
X = -O- oder -NH-undX = -O- or -NH-and
A = Anion einer organischen oder anorganischen Säure, vorzugsweise Salzsäure oder Methylschwefelsäure bedeuten, b) 0 bis 40 Gew.% eines oder mehrerer nichtionischer, wasserlöslicher Monomerer, wie Acrylamid und Methacrylamid, Allylalkohol, Allylpolyethylenglykolether und Hydroxyethylmethacrylat, c) 0 bis 40 Gew.-% eines oder mehrerer anionischer, wasserlöslicher Monomerer, wie Acrylsäure, Methacrylsäure, (Meth)acrylamidomethylbutansäure und/ oder Acrylamido-2-methylpropansulfonsäure und/oder deren Salze, d) 0,001 - 5,0 Gew.-% eines polyfunktionellen MonomerenA = anion of an organic or inorganic acid, preferably hydrochloric acid or methylsulfuric acid, b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate, c) 0 to 40% by weight of one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and / or their salts, d) 0.001 - 5.0% by weight % of a polyfunctional monomer
Als kationische Monomere werden quaterniertes Dimethylaminoethyl(meth)acrylat, quaterniertes Dimethylaminopropyl(meth)acrylamid, quaterniertes Dimethylamino-2,2- dimethylpropyl(meth)acrylamid, Diallyldimethylammoniumchlorid, Diallyldi-ethylammo- niumchlorid und deren Mischungen untereinander verwendet. Die Quaternierung wird bevorzugt mit Methylchlorid, Natriumchloracetat, Dimethylsulfat und Dimethylcarbonat durchgeführt.Quaternized dimethylaminoethyl (meth) acrylate, quaternized dimethylaminopropyl (meth) acrylamide, quaternized dimethylamino-2,2-dimethylpropyl (meth) acrylamide, diallyldimethylammonium chloride, diallyldiethylammonium chloride and mixtures thereof with one another are used as cationic monomers. The quaternization is preferably carried out using methyl chloride, sodium chloroacetate, dimethyl sulfate and dimethyl carbonate.
Als hydrophobe, organische Flüssigkeiten sind einsetzbar: aromatische und aliphatische lineare, verzweigte und cyclische Kohlenwasserstoffe, deren Siedepunkte bei einem Druck von 1013 hPa im Bereich von 110 bis 380 °C liegen. Hierzu zählen n- und iso¬ Paraffine, Destillate aus paraffinischen, naphthenbasischen und aromatischen Erdölen sowie Toluol, Xylol und Mesitylen. Weiterhin können auch lineare und verzweigte flüs¬ sige Ester natürlichen und synthetischen Ursprungs als Ölphase verwendet werden.The following can be used as hydrophobic, organic liquids: aromatic and aliphatic linear, branched and cyclic hydrocarbons, the boiling points of which are at a pressure of 1013 hPa in the range from 110 to 380 ° C. These include n- and iso-paraffins, distillates from paraffinic, naphthenic and aromatic petroleum as well as toluene, xylene and mesitylene. Furthermore, linear and branched liquid esters of natural and synthetic origin can also be used as the oil phase.
Zur Zubereitung der Polymerisation und Herstellung der monomerenhaltigen Wasser-in- Öl-Emulsion werden bekannte öllösliche Emulgatoren mit niedrigem HLB-Wert benutzt, wie Teilester von Glycerin, Di- und Polyglycerin, Sorbit, Sorbitan und Additionspro¬ dukte von Alkylenoxiden, wie Ethylenoxid und Propylenoxid an höhere lineare und ver¬ zweigte Alkohole, Fettsäuren bzw. Nonylphenol. Es können auch die sogenannten poly- meren Emulgatoren allein oder im Gemisch verwendet werden, wie es unter anderem in US-PS 4 786 681 beschrieben wird.Known oil-soluble emulsifiers with a low HLB value, such as partial esters of glycerol, di- and polyglycerol, sorbitol, sorbitan and addition products of alkylene oxides, such as ethylene oxide and propylene oxide, are used to prepare the polymerization and preparation of the monomer-containing water-in-oil emulsion higher linear and branched alcohols, fatty acids or nonylphenol. The so-called polymeric emulsifiers can also be used alone or in a mixture, as is described, inter alia, in US Pat. No. 4,786,681.
Als vernetzende Monomere werden mehrfach ungesättigte Vinyl-, Acryl- oder Allylver- bindungen sowie Verbindungen mit mehreren Epoxygruppen verwendet. Geeignete Ver¬ bindungen sind beispielsweise Methylenbis-acrylamid sowie quaterniertes Triallylamin, insbesondere Tetraallyl- bzw. Triallylmethylammoniumchlorid. Die Vernetzung kann während der Polymerisation oder auch danach erfolgen. Für eine Nachvernetzung sind wasserlösliche Epoxiverbindungen, die sich von mehrwertigen Alkoholen ableiten, beson-ders geeignet. Die Technik der Polymerisation mit Emulsionsbildung, Homogenisierung der Mischung und Initiierung der Polymerisation ist bekannt. Sie erfolgt vorzugsweise ädiabatisch, kann aber auch isotherm bei vorgewählter Temperatur erfolgen. Nach Beendigung der Polyme-risation kann die Wasser-in-Öl-Dispersion direkt in die wäßrige, kationische Dispersion der quartären Ammonium- bzw. cyclischen Amidinverbindungen eingebracht werden.Polyunsaturated vinyl, acrylic or allyl compounds and compounds with several epoxy groups are used as crosslinking monomers. Suitable compounds are, for example, methylenebisacrylamide and quaternized triallylamine, in particular tetraallyl or triallyl methylammonium chloride. The crosslinking can take place during the polymerization or afterwards. Water-soluble epoxy compounds which are derived from polyhydric alcohols are particularly suitable for postcrosslinking. The technique of polymerization with emulsion formation, homogenization of the mixture and initiation of the polymerization is known. It is preferably carried out adiabatically, but can also be carried out isothermally at a preselected temperature. After the polymerization has ended, the water-in-oil dispersion can be introduced directly into the aqueous, cationic dispersion of the quaternary ammonium or cyclic amidine compounds.
Die Wasser-in-Öl-Dispersionen sind verwendbar zur Stabilisierung von wäßrigen Dispersionen begrenzt wasserlöslicher, quartärer Ammoniumsalze, wie Dimethyl- distearylammoniumchlorid, Dimethyldilaurylammoniumchlorid und und quartäre Ester, z.B. N-Methyl-N,N-bis[2-(acyloxy)ethyl]-N-2-hydroxy-ethyl)-ammonium-methosulfat oder N,N,N-Trimethyl-N-[l,2-di(acyl-oxy)propyl]-ammoniumchlorid, bzw. Imidazolin- Derivate auf der Basis von Fettsäure, z.B. l-[(Fettacyloxy)ethyl]-2-alkylimidazolin.The water-in-oil dispersions can be used to stabilize aqueous dispersions of limited water-soluble quaternary ammonium salts such as dimethyl distearylammonium chloride, dimethyldilaurylammonium chloride and and quaternary esters, e.g. N-methyl-N, N-bis [2- (acyloxy) ethyl] -N-2-hydroxy-ethyl) ammonium methosulfate or N, N, N-trimethyl-N- [l, 2-di (acyl- oxy) propyl] ammonium chloride, or imidazoline derivatives based on fatty acid, for example l - [(fatty acyloxy) ethyl] -2-alkylimidazoline.
Die begrenzt wasserlöslichen , quartären Ammoniumsalze bzw. Imidazolin-Derivate liegen üblicherweise als wäßrige Aufschlämmungen/Dispersionen vor, z. B. mit Fest¬ stoffgehalten von 5 Gew.-%. Der Feststoffgehalt ist im übrigen nicht kritisch.The limited water-soluble quaternary ammonium salts or imidazoline derivatives are usually in the form of aqueous slurries / dispersions, e.g. B. with solids contents of 5 wt .-%. The solids content is otherwise not critical.
Die Anwendungskonzentrationen bewegen sich zwischen 0,01 und 10 Gew.-%, vor¬ zugsweise zwischen 0,1 und 5 Gew.-%, insbesondere zwischen 0,2 und 2 Gew.-%, je nach gewünschter Stabilisierung der Dispersion. Zusätzlich können weitere viskosi- tätserhöhende nichtionische bzw. kationische Substanzen benutzt werden.The application concentrations range between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight, in particular between 0.2 and 2% by weight, depending on the desired stabilization of the dispersion. In addition, further viscosity-increasing nonionic or cationic substances can be used.
Überraschenderweise hat sich gezeigt, daß die Stabilität von wäßrigen, kationischen Dispersionen, insbesondere von begrenzt wasserlöslichen quartären Ammoniumsalzen, mit Hilfe von Wasser-in-Öl-Dispersionen kationischer vernetzter wasserquellbarer Poly¬ mere deutlich erhöht wird.Surprisingly, it has been shown that the stability of aqueous, cationic dispersions, in particular quaternary ammonium salts with limited water solubility, is significantly increased with the aid of water-in-oil dispersions of cationically crosslinked water-swellable polymers.
Die Erfindung wird durch die folgenden Beispiele näher erläutert:The invention is illustrated by the following examples:
In der Beschreibung der nachfolgenden Beispiele werden die Abkürzungen mit folgender Bedeutung benutzt:Abbreviations with the following meanings are used in the description of the following examples:
DMAEA = DimethylaminoethylacrylatDMAEA = dimethylaminoethyl acrylate
DMAEMA = DimethylaminoethylmethacrylatDMAEMA = dimethylaminoethyl methacrylate
DIMAPA = DimethylaminopropylacrvlamidDIMAPA = dimethylaminopropylacrvlamid
TEMAPA = N.N.2.2-Tetramethylaminopropylacrylamid AMPS = 2-Acrylamido-2-methyl-propansulfonsäureTEMAPA = NN2.2-tetramethylaminopropylacrylamide AMPS = 2-acrylamido-2-methyl-propanesulfonic acid
TAMAC = TriallylmethylammoniumchloridTAMAC = triallylmethylammonium chloride
ABAH = Azo-bis-(2-amidinopropan-hydrochlorid)ABAH = azo-bis- (2-amidinopropane hydrochloride)
AJBN = AzoisobuttersäuredinitrilAJBN = azoisobutyronitrile
EDTA = EthylendiamintetraessigsäureEDTA = ethylenediaminetetraacetic acid
TBHP = tert.-ButylhydroperoxidTBHP = tert-butyl hydroperoxide
EO = EthylenoxidEO = ethylene oxide
KWST = isoparaffmischer Kohlenwasserstoff mit einem Siedebereich von 210 -KWST = isoparaffic hydrocarbon with a boiling range of 210 -
250 °C und einer Dichte von 0,79 g/cm3 Alle %-Angaben bedeuten Gew.-%.250 ° C and a density of 0.79 g / cm 3 All percentages mean% by weight.
Beispiel 1 :Example 1 :
a) Herstellung der Dispersion eines Polymeren aus 80 % DMAEA-CH3CI und 20 % Acrylamid mit 40 % wirksamer Substanz (wS).a) Preparation of the dispersion of a polymer from 80% DMAEA-CH3CI and 20% acrylamide with 40% active substance (wS).
Man löst 160 g DMAEA-CH3CI und 40 g Acrylamid in 165 g Wasser. Sodann wird der pH- Wert mit Phosphorsäure auf 4,5 eingestellt und 0,4 g EDTA zugesetzt. Nach voll¬ ständiger Auflösung des Komplexbildners gießt man die Lösung unter Rühren in eine Mischung von 120 g KWST, 10 g Sorbitanmonoisostearat und 0,62 g TAMAC und ho¬ mogenisiert mit einem haushaltsüblichen Mixstab (Viskosität der Emulsion: 4200 mPa*s, Brookfield RVT, MK 11/20 bei 20 °C). Der gelöste Sauerstoff wird bei gleichzeitigem Erhitzen der Emulsion auf 60 °C durch Emblasen von Stickstoff ausgetrieben . Man leitet ca. 30 Minuten lang weiter Stickstoff ein und startet anschließend die Polymerisation durch Zusatz von 0, 11 g AIBN, gelöst in 4 g KWST. Durch die adiabatisch geführte, exotherme Reaktion steigt die Temperatur auf ca. 102 °C. Man läßt ca. 1 h nachrühren und versetzt mit 10 g 9-EO-Nonylphenol.160 g of DMAEA-CH3CI and 40 g of acrylamide are dissolved in 165 g of water. The pH is then adjusted to 4.5 with phosphoric acid and 0.4 g of EDTA is added. After the complexing agent has completely dissolved, the solution is poured with stirring into a mixture of 120 g KWST, 10 g sorbitan monoisostearate and 0.62 g TAMAC and homogenized with a household mixing stick (viscosity of the emulsion: 4200 mPa * s, Brookfield RVT , MK 11/20 at 20 ° C). The dissolved oxygen is expelled by blowing nitrogen with simultaneous heating of the emulsion to 60 ° C. Nitrogen is passed in for about 30 minutes and then the polymerization is started by adding 0.11 g of AIBN, dissolved in 4 g of KWST. The temperature rises to approx. 102 ° C due to the adiabatic exothermic reaction. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
b) λlit Hilfe eines schnellaufenden Rührers werden 5 g dieser Dispersion in 1 1 einer 5 %- igen Aufschlämmung von methylquaterniertem Ditalgfettsäuretriethanolaminester ein¬ gebracht, wobei eine lagerstabile Dispersion, die über einen Zeitraum von 6 Wochen keine Veränderung zeigt, entsteht.b) With the aid of a high-speed stirrer, 5 g of this dispersion are introduced into 1 l of a 5% strength slurry of methylquaternized ditallow fatty acid triethanolamine ester, resulting in a storage-stable dispersion which shows no change over a period of 6 weeks.
Beispiel 2: a) Herstellung einer Dispersion eines Polymeren aus 80 % DIMAPA-CH3CI und 20 % Acrylamid mit 40 % wS.Example 2: a) Preparation of a dispersion of a polymer from 80% DIMAPA-CH3CI and 20% acrylamide with 40% wS.
Man löst 160 g DIMAPA-CH3CI und 40 g Acrylamid in 170 g Wasser. Sodann wird mit konz. Salzsäure der pH- Wert auf 4,5 eingestellt und 0,4 g EDTA zugesetzt. Nach voll¬ ständiger Auflösung des Komplexbildners gießt man die Lösung unter Rühren in eine Mischung von 115 g KWST, 10 g Glycerinmonooleat und 0,62 g TAMAC und ho¬ mogenisiert (Viskosität der Emulsion: 4500 mPa*s, Brookfield RVT, MK 11/20 bei 20 °C). Nach Beseitigung des gelösten Sauerstoffs mit Stickstoff wird die Polymerisation bei 60 °C durch Zusatz von 0, 11 g ATBN, gelöst in 4 g KWST, gestartet. Es erfolgt ein Temperaturanstieg auf ca. 102 °C. Man läßt ca. 1 h nachrühren und versetzt mit 10 g 9- EO-Nonylphenol.160 g of DIMAPA-CH3CI and 40 g of acrylamide are dissolved in 170 g of water. Then with conc. Hydrochloric acid adjusted the pH to 4.5 and added 0.4 g EDTA. After the complexing agent has completely dissolved, the solution is poured with stirring into a mixture of 115 g KWST, 10 g glycerol monooleate and 0.62 g TAMAC and homogenized (viscosity of the emulsion: 4500 mPa * s, Brookfield RVT, MK 11 / 20 at 20 ° C). After removal of the dissolved oxygen with nitrogen, the polymerization is started at 60 ° C. by adding 0.11 g of ATBN, dissolved in 4 g of KWST. The temperature rises to approx. 102 ° C. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
b) Durch Einrühren von 5 g dieser Dispersion in 1 1 einer 5 %-igen Aufschlämmung von Distearyldimethylammoniumchlorid in Wasser entsteht eine lagerstabile Dispersion deren Zustand sich über einen Zeitraum von 6 Wochen nicht ändert.b) Stirring 5 g of this dispersion in 1 l of a 5% slurry of distearyldimethylammonium chloride in water results in a storage-stable dispersion whose state does not change over a period of 6 weeks.
Beispiel 3 :Example 3:
a) Herstellung einer Dispersion eines Polymeren aus 75 % DEMAPA-CH3CI, 12,5 % Acryl-amid und 12,5 % Acrylsäure mit 40 % wS.a) Preparation of a dispersion of a polymer from 75% DEMAPA-CH3CI, 12.5% acrylic amide and 12.5% acrylic acid with 40% wS.
150 g DIMAPA-CH3CI, 25 g Acrylamid und 0,4 g EDTA werden in 170 g Wasser ge¬ löst und 25 g Acrylsäure zugesetzt. Danach stellt man die Lösung mit Natronlauge auf einen pH- Wert von ca. 4,5 ein und gießt sie unter Rühren in eine Mischung von 115 g KWST, 10 g Sorbitanmonoisostearat und 0,62 g TAMAC. Es wird mit einem Mixstab homogenisiert, mit Stickstoff gespült und anschließend die Polymerisation mit 0,0275 g ABN, gelöst in 4 g KWST, gestartet.150 g of DIMAPA-CH3CI, 25 g of acrylamide and 0.4 g of EDTA are dissolved in 170 g of water and 25 g of acrylic acid are added. The solution is then adjusted to a pH of about 4.5 with sodium hydroxide solution and poured into a mixture of 115 g of KWST, 10 g of sorbitan monoisostearate and 0.62 g of TAMAC while stirring. It is homogenized with a mixing stick, flushed with nitrogen and then the polymerization is started with 0.0275 g ABN, dissolved in 4 g KWST.
b) Nach Abschluß der Polymerisation werden 5 g dieser Dispersion in 1 1 einer 5 %-igen Aufschlämmung von methylquaterniertem Di-talgfettsäuretriethanolaminester einge¬ bracht, wobei eine lagerstabile Dispersion entsteht, deren Zustand über 6 Wochen stabil bleibt.b) After the end of the polymerization, 5 g of this dispersion are introduced into 1 liter of a 5% slurry of methyl-quaternized di-tallow fatty acid triethanolamine ester, resulting in a storage-stable dispersion whose state remains stable over 6 weeks.
Beispiel 4: a) Herstellung einer Dispersion von 92 % DMAEMA-CH3CI und 8 % Acrylamid mit 50 % wS.Example 4: a) Preparation of a dispersion of 92% DMAEMA-CH3CI and 8% acrylamide with 50% wS.
Man löst 230 g DMAEMA-CH3CI und 20 g Acrylamid in 110 g Wasser und fügt 0,5 g EDTA und 0,6 g AB AH hinzu. Der pH- Wert wird mit konz. Salzsäure auf 0,6 einge¬ stellt. Die Bildung der Emulsion erfolgt wie in Beispiel 1 mit 120 g KWST und 10 g Sorbitanmonoisostearat (Viskosität: 1400 mPa*s bei 20 °C). Es wird mit 6 mg TBHP und 12 mg Schwefeldioxid bei 20 °C katalysiert, wobei innerhalb von 150 Minuten eine Spitzentemperatur von 72 °C erreicht wird. Man läßt ca. 1 h nachrühren und versetzt mit 10 g 9-EO-Nonylphenol.230 g of DMAEMA-CH3CI and 20 g of acrylamide are dissolved in 110 g of water and 0.5 g of EDTA and 0.6 g of AB AH are added. The pH value is with conc. Hydrochloric acid set to 0.6. The emulsion is formed as in Example 1 with 120 g KWST and 10 g sorbitan monoisostearate (viscosity: 1400 mPa * s at 20 ° C). It is catalyzed with 6 mg TBHP and 12 mg sulfur dioxide at 20 ° C, with a peak temperature of 72 ° C being reached within 150 minutes. The mixture is stirred for about 1 h and mixed with 10 g of 9-EO nonylphenol.
b) 5 g der Dispersion ergeben in 1 1 einer 5 %-igen Aufschlämmung von Distearyldime- thylammoniumchlorid bei 20 °C eine lagerstabile Suspension, ohne Neigung zur Boden¬ satzbildung bzw. Aufrahmung.b) 5 g of the dispersion in 1 l of a 5% slurry of distearyldimethylammonium chloride at 20 ° C. gives a suspension which is stable in storage and has no tendency to form sediment or cream.
Beispiel 5:Example 5:
a) Herstellung einer Dispersion von 60 % DMAEA-CH3CI, 37 % Acrylamid und 3 % AMPS mit 46 % wS.a) Preparation of a dispersion of 60% DMAEA-CH3CI, 37% acrylamide and 3% AMPS with 46% wS.
160 g DMAEA-CH3CI, 36 g Acrylamid, 19 g AMPS werden in 114 g Wasser gelöst und nach Einstellen des pH-Wertes mit Salzsäure auf 4,5 unter Rühren in 100 g KWST, 10 g Diglycerinsesquioleat, 0,8 g TAMAC und 0,2 g EDTA gegossen. Es wird homo¬ genisiert, mit Stickstoff gespült und die Polymerisation mit 1 g ACBN gestartet.160 g DMAEA-CH3CI, 36 g acrylamide, 19 g AMPS are dissolved in 114 g water and after adjusting the pH to 4.5 with hydrochloric acid with stirring in 100 g KWST, 10 g diglycerol sesquioleate, 0.8 g TAMAC and 0 Poured 2 g EDTA. It is homogenized, flushed with nitrogen and the polymerization is started with 1 g ACBN.
b) 5 g dieser Dispersion ergeben in 1 1 einer 5 %-igen Aufschlämmung von Distearyl- dimethylammoniumchlorid eine lagerstabile Suspension ohne Tendenz zur Inhomoge¬ nität. Weitere Beispiele mit unterschiedlichen Zusammensetzungen der Polvmerprodukte:b) 5 g of this dispersion in 1 1 of a 5% slurry of distearyldimethylammonium chloride give a storage-stable suspension with no tendency to inhomogeneity. Further examples with different compositions of the polymer products:
a) Die Herstellung der Dispersionen entspricht der Verfahrensweise der vorstehenden Beschreibungen. Die Polymerisationen wurden bei Raumtemperatur gestartet.a) The preparation of the dispersions corresponds to the procedure of the above descriptions. The polymerizations were started at room temperature.
Mengenverhältnisse der eingesetzten Rohstoffe (g):Quantities of the raw materials used (g):
Figure imgf000012_0001
Figure imgf000012_0001
Prozentuale Zusammensetzung der Polymeren (Gew.-%):Percentage composition of the polymers (% by weight):
Beispiel 6 7 8 9 10 11Example 6 7 8 9 10 11
Acrvlsäure 6 19 40 7 27Acrylic acid 6 19 40 7 27
Acrvlamid 17 10Acrvlamid 17 10
DIMAPA-Quat 81 60 81 68DIMAPA-Quat 81 60 81 68
TEMAPA-Quat 83 84 5TEMAPA-Quat 83 84 5
Alle in der Tabelle aufgeführten Dispersionen ergeben mit einem Zusatz von 5 g zu 5 %- igen Aufschlämmungen von N-Methyl-N,N-bis[2-(C16/18-acyloxy)-ethyl]-N-(2- hydroxyethyl)-ammoniummethosulfat lagerstabile Suspensionen ohne Neigung zu Bodensatzbildung oder Aufrahmungen. All the dispersions listed in the table with the addition of 5 g to 5% slurries of N-methyl-N, N-bis [2- (C16 / 18-acyloxy) ethyl] -N- (2-hydroxyethyl) -ammonium methosulfate storage stable suspensions without tendency to sedimentation or creaming.

Claims

PatentansprücheClaims
1) Wäßrige Dispersionen begrenzt wasserlöslicher, quartärer Ammoniumverbindungen und/oder Imidazolin-Derivate, dadurch gekennzeichnet, daß sie durch einen Zusatz von Wasser-in-Öl-Dispersionen wasserquellbarer, kationisch wirksamer, vernetzter Polymerer im Dispersionszustand stabilisiert sind.1) Aqueous dispersions of limited water-soluble, quaternary ammonium compounds and / or imidazoline derivatives, characterized in that they are stabilized in the dispersion state by the addition of water-in-oil dispersions of water-swellable, cationically active, crosslinked polymers.
2) Wäßrige Dispersionen begrenzt wasserlöslicher, quartärer Ammoniumverbindungen und/oder Imidazolin-Derivate nach Anspruch 1 , dadurch gekennzeichnet, daß die Wasser-in-Öl-Dispersion wasserquellbarer, kationisch wirksamer, vernetzter Polymerer aus den Komponenten2) Aqueous dispersions limited water-soluble, quaternary ammonium compounds and / or imidazoline derivatives according to claim 1, characterized in that the water-in-oil dispersion of water-swellable, cationically active, crosslinked polymer from the components
A) 30 bis 70 Gew.-% eines kationisch wirksamen Homo- oder Copolymeren,A) 30 to 70% by weight of a cationically active homopolymer or copolymer,
B) 20 bis 50 Gew.-% einer hydrophoben, organischen Flüssigkeit,B) 20 to 50% by weight of a hydrophobic, organic liquid,
C) 0,5 bis 10 Gew.-% eines Wasser-in-Öl-EmulgatorsC) 0.5 to 10% by weight of a water-in-oil emulsifier
D) 0 bis 10 Gew.-% eines Netzmittels undD) 0 to 10% by weight of a wetting agent and
E) einer Restmenge Wasser erhalten werden, wobei die Summe der Komponenten A) bis E) 100 Gew.-% ergibt.E) a residual amount of water is obtained, the sum of components A) to E) giving 100% by weight.
3) Wäßrige Dispersionen begrenzt wasserlöslicher, quartärer Ammoniumverbindungen und/oder Imidazolin-Derivaten nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die wasserquellbaren, kationisch wirksamen vernetzten Polymeren als Homo- oder Copolymere durch inverse Emulsionspolymerisation aus3) Aqueous dispersions limited water-soluble, quaternary ammonium compounds and / or imidazoline derivatives according to claims 1 and 2, characterized in that the water-swellable, cationically active crosslinked polymers as homopolymers or copolymers by inverse emulsion polymerization
a) 50 bis 100 Gew.-% eines Monomeren der allgemeinen Formela) 50 to 100 wt .-% of a monomer of the general formula
[CH2=C(R1)-CO-X-(CH2)n-C(R2R3)-CH2-N(R4R5R6)]+ A",[CH 2 = C (R 1 ) -CO-X- (CH 2 ) n -C (R2R3) -CH2-N (R4R 5 R 6 )] + A ",
in derin the
Rj = Wasserstoff oder Methyl-,R j = hydrogen or methyl,
R2, R3 = Wasserstoff* oder gleiche bzw. verschiedene Alkylreste mit 1 bis 4R2, R3 = hydrogen * or identical or different alkyl radicals with 1 to 4
C-Atomen, R4, R5, R£= gleiche oder verschiedene Alkylreste mit 1 bis 4 C-Atomen, n = 0 oder 1 X = -O- oder -NH-undC atoms, R4, R5, R £ = identical or different alkyl radicals with 1 to 4 C atoms, n = 0 or 1 X = -O- or -NH-and
A = Anion einer organischen oder anorganischen Säure, vorzugsweise Salzsäure oder Methylschwefelsäure bedeuten, b) 0 bis 40 Gew.% eines oder mehrerer nichtionischer, wasserlöslicher Monomerer, wie Acrylamid und Methacrylamid, Allylalkohol, Allylpolyethylenglykolether und Hydroxyehylmethacrylat, c) 0 bis 40 Gew.% eines oder mehrerer anionischer, wasserlöslicher Monomerer, wie Acrylsäure, Methacrylsäure, (Meth)acrylamidomethylbutansäure und/ oder Acrylamido-2-methylpropansulfonsäure und/oder deren Salze, d) 0,001 - 5,0 Gew.% eines polyfünktionellen vernetztenden Monomeren erhalten werden, wobei die Summe der Komponenten a) bis d) 100 Gew.-% ergibt.A = anion of an organic or inorganic acid, preferably hydrochloric acid or methyl sulfuric acid, b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate, c) 0 to 40% by weight one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and / or their salts, d) 0.001-5.0% by weight of a polyfunctional crosslinking monomer, wherein the Sum of components a) to d) gives 100% by weight.
4) Wäßrige Dispersionen nach einem der Ansprüche 1 - 3, gekennzeichnet durch einen Zusatz von Wasser-in-Öl-Dispersion wasserquellbarer, kationisch wirksamer vernetzter Polymere von 0,01 - 10 Gew.-%, bezogen auf die zu stabilisierende Dispersion.4) Aqueous dispersions according to one of claims 1-3, characterized by an addition of water-in-oil dispersion of water-swellable, cationically active crosslinked polymers of 0.01-10% by weight, based on the dispersion to be stabilized.
5) Verwendung von Wasser-in-Öl-Dispersionen, deren Wasserphase wasserquellbare kationische, vernetzte Polymere enthält, zur Stabilisierung von wäßrigen Dispersionen begrenzt wasserlöslicher, quartärer Ammonium- bzw. cyclischer Amidinverbindungen.5) Use of water-in-oil dispersions, the water phase of which contains water-swellable cationic, crosslinked polymers, for the stabilization of aqueous dispersions of water-soluble, quaternary ammonium or cyclic amidine compounds.
6) Verwendung von Wasser-in-Öl-Dispersionen nach Anspruch 4, dadurch gekennzeichnet, daß diese aus den Komponenten6) Use of water-in-oil dispersions according to claim 4, characterized in that they consist of the components
A) 30 bis 70 Gew.-% eines kationisch wirksamen Homo- oder Copolymeren,A) 30 to 70% by weight of a cationically active homopolymer or copolymer,
B) 20 bis 50 Gew.-% einer hydrophoben, organischen Flüssigkeit,B) 20 to 50% by weight of a hydrophobic, organic liquid,
C) 0,5 bis 10 Gew.-% eines Wasser-in-Öl-EmulgatorsC) 0.5 to 10% by weight of a water-in-oil emulsifier
D) 0 bis 10 Gew.-% eines Netzmittels undD) 0 to 10% by weight of a wetting agent and
E) einer Restmenge Wasser erhalten werden, wobei die Summe der Komponenten A) bis E) 100 Gew.-% ergibt.E) a residual amount of water is obtained, the sum of components A) to E) giving 100% by weight.
7) Verwendung von Wasser-in-Öl-Dispersionen nach den Ansprüchen 4 und 5, dadurch gekennzeichnet, daß das kationisch wirksame Homo- bzw. Copolymer durch inverse Emulsionspolymerisation aus a) 50 bis 100 Gew.-% eines Monomeren der allgemeinen Formel7) Use of water-in-oil dispersions according to claims 4 and 5, characterized in that the cationically active homo- or copolymer by inverse emulsion polymerization a) 50 to 100 wt .-% of a monomer of the general formula
[CH2=C(R1)-CO-X-(CH2)n-C(R2R3)-CH2-N(R4R5R6)]+ A",[CH 2 = C (R 1 ) -CO-X- (CH2) n -C (R 2 R3) -CH2-N (R4R 5 R 6 )] + A ",
in derin the
R = Wasserstoff oder Methyl-,R = hydrogen or methyl,
R2, R3 = Wasserstoff oder gleiche bzw. verschiedene Alkylreste mit 1 bis 4R2, R3 = hydrogen or the same or different alkyl radicals with 1 to 4
C-Atomen, R4, R5, R£= gleiche oder verschiedene Alkylreste mit 1 bis 4 C-Atomen, n = 0 oder 1C atoms, R4, R5, R £ = identical or different alkyl radicals with 1 to 4 C atoms, n = 0 or 1
X = -O- oder -NH-undX = -O- or -NH-and
A = Anion einer organischen oder anorganischen Säure, vorzugsweise Salzsäure oder Methylschwefelsäure bedeuten, b) 0 bis 40 Gew.% eines oder mehrerer nichtionischer, wasserlöslicher Monomerer, wie Acrylamid und Methacrylamid, Allylalkohol, Allylpolyethylenglykolether und Hydroxyehylmethacrylat, c) 0 bis 40 Gew.% eines oder mehrerer anionischer, wasserlöslicher Monomerer, wie Acrylsäure, Methacrylsäure, (Meth)acrylamidomethylbutansäure und/ oder Acrylamido-2-methylpropansulfonsäure und oder deren Salze, d) 0,001 - 5,0 Gew.%o eines polyfünktionellen vernetztenden Monomeren erhalten wird, wobei die Summe der Komponenten a) bis d) 100 Gew.-% ergibt.A = anion of an organic or inorganic acid, preferably hydrochloric acid or methyl sulfuric acid, b) 0 to 40% by weight of one or more nonionic, water-soluble monomers, such as acrylamide and methacrylamide, allyl alcohol, allyl polyethylene glycol ether and hydroxyethyl methacrylate, c) 0 to 40% by weight one or more anionic, water-soluble monomers, such as acrylic acid, methacrylic acid, (meth) acrylamidomethylbutanoic acid and / or acrylamido-2-methylpropanesulfonic acid and or their salts, d) 0.001-5.0% by weight of a polyfunctional crosslinking monomer, the Sum of components a) to d) gives 100% by weight.
8) Verwendung von wäßrigen Dispersionen begrenzt wasserlöslicher, quartärer8) Use of aqueous dispersions limited water-soluble, quaternary
Ammoniumverbindungen und/oder Imidazolin-Derivaten, stabilisiert mit Wasser- in-Öl-Dispersionen gemäß den Ansprüchen 1 bis 3 als Textil- und Wäscheweichmacher. Ammonium compounds and / or imidazoline derivatives, stabilized with water-in-oil dispersions according to claims 1 to 3 as textile and laundry softeners.
PCT/EP1994/001198 1993-04-21 1994-04-18 Stable aqueous dispersions of quaternary ammonium compounds and imidazoline derivates WO1994024255A1 (en)

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