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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/03—Organic sulfoxy compound containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/03—Organic sulfoxy compound containing
  • Y10S516/05—Organic amine, amide, or n-base containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
  • Y10S526/911—Emulsifying agents

Definitions

• Alkyl ether sulfates are in particular sulfates of alkoxylated non-aromatic alcohols having 8 to 24 carbon atoms, in particular 8 to 18 carbon atoms.
• Alcohols of this type can be obtained from raw materials of natural origin, for example coconut or palm kernel oil, or are available as synthetic materials, e.g. in the form of the known Ziegler or oxo alcohols.
• non-aromatic alcohols with saturated or unsaturated, optionally also branched alkyl radicals of the type mentioned are first alkoxylated to produce detergents with lower alkylene oxides, in particular with ethylene oxide and / or with propylene oxide, then sulfated and then converted into the corresponding water-soluble salts
• Detergents of this type are used for many purposes, for example in liquid cleaning agents, foam baths and shampoos.
• Aqueous solutions with a. comparatively low content of alkyl ether sulfate - for example with a content of about 10 wt .-% detergent (WAS) - show the special property of this class of detergents can be thickened by adding neutral salts such as NaCl or Na 2 SO 4 .
• WAS wt .-% detergent
• Anionic surfactants also play a dominant role as emulsifiers for the technical production of polymer dispersions.
• alkyl sulfates, alkyl ether sulfates and alkyl benzene sulfonates, alkylaryl polyglycol ether sulfates and sulfosuccinates of natural and synthetic alcohol polyglycol ethers or alkylphenol ethoxylates are mainly used today.
• Emulsifiers of the type concerned are usually commercially available in the form of dilute aqueous solutions. Highly concentrated mixtures can only be produced by adding up to 20% lower alcohols such as ethanol or isopropanol.
• lower alcohols such as ethanol or isopropanol.
• organic solvents for example the alcohols mentioned, is not always desirable in polymer dispersions for technical reasons, and they are also because of their easy flammability associated with a considerable safety risk both in the manufacture of the emulsifiers and during transport, storage and use. It is also known that even slight shifts in the ratio water / alcohol can result in such concentrates g undesirable Sedimentationserscheinun- s.
• the object of the invention is to provide aqueous surfactant concentrates of the type described, which can be pumped even in high concentrations and, when diluted with water, show no undesirable increase in the viscosity or thickening of the gel state.
• the invention aims to provide alcohol-free aqueous surfactant concentrates of alkyl ether sulfates, alkyl aryl ether sulfates, alkyl aryl sulfonates and of sulfosuccinates of alkyl and alkyl aryl polyglycol ether alcohols, as well as fatty alcohols, which can be pumped even in high concentrations, and when diluted with water shows no undesirable increase in the viscosity or thickening of the gel state and without the addition of metal salts, e.g.
• colloidal gel phases are suitable as detergent surfactants, for shampoo production, for emulsifying natural fats or as polymerization emulsifiers.
• the formation of colloidal gel phases is to be counteracted in particular. Nevertheless, it should be possible to effectively thicken alkyl ether sulfates in the diluted state at low concentrations of WAS by adding neutral salts such as sodium chloride or sodium sulfate.
• the technical solution to this problem is based on the finding that water-soluble salts of mono- and / or disulfates of lower polyalkylene ether glycols - in particular of polyethylene glycol and / or of polypropylene glycol (here in particular 1,2-polypropylene glycol) - effective viscosity regulators for aqueous surfactant concentrates here are affected.
• water-soluble salts of mono- and / or disulfates of lower polyalkylene ether glycols - in particular of polyethylene glycol and / or of polypropylene glycol (here in particular 1,2-polypropylene glycol) - effective viscosity regulators for aqueous surfactant concentrates here are affected.
• it was found that the effect of these viscosity regulators increases with the increase in the molecular weight of the underlying polyether glycol.
• the invention relates in a first embodiment to aqueous surfactant concentrates containing at least about 20% by weight of water-soluble salts of one or more of the following surfactants together with small amounts of viscosity regulators: alkyl polyglycol ether sulfates, alkyl aryl polyglycol ether sulfates, alkyl sulfates, alkyl aryl sulfonates, alkyl polyglycol ether sulfosulfinate sulfosate sulfinate sulfosate.
• surfactant concentrates are characterized in that they contain, as viscosity regulators, water-soluble salts of mono- and / or disulfates of a lower polyalkylene ether glycol with a molecular weight of the polyalkylene ether glycol of at least about 600. If desired, nonionic lower polyalkylene glycols with a molecular weight of at least 1500 can also be used together with the water-soluble salts of the mono- and / or disulfates mentioned for the lower polyalkylene ether glycols.
• the surfactants are preferably present in amounts of at least about 25% by weight, in particular at least about 30% by weight, e.g. in amounts of 50 to 80% by weight, based on the aqueous surfactant concentrate.
• Lower polyalkylene ether glycols of the type concerned here are derived from straight-chain or branched glycols having a maximum of up to 5 carbon atoms. Of particular importance have the appropriate polyethylene ether glycols and / or P olypropylenetherglykole - where in the last Fall.der compounds mentioned again, particular from 1,2-propylene glycol derived polyether meaning possess. This information is also valid for the water-soluble salts of the mono- and / or disulfates of the lower polyalkylene ether glycols used as viscosity regulators according to the invention.
• the invention relates to a process for improving the flow behavior of difficult to move aqueous surfactant concentrates of the type mentioned above in connection with the first embodiment of the invention, this process being characterized in that water-soluble salts of mono- and / or disulfates are used as viscosity regulators uses lower polyalkylene ether glycols with a molecular weight of at least 600, preferably of at least 1000. If desired, the non-sulfated, free, lower polyalkylene ether glycols with a molecular weight of at least 1500 can also be used in the viscosity regulator.
• the sulfates and here in particular the disulfates of lower polyalkylene ether glycols, in particular of polyethylene oxide and / or of 1,2-polypropylene oxide, have proven to be particularly effective viscosity regulators for highly concentrated aqueous surfactant concentrates of the type concerned by the present invention.
• the viscosity-reducing effect or the thickening state of the gel of these regulators increases with increasing molecular weight or increasing degree of polycondensation of the alkylene glycol.
• the molecular weight of the base material for the viscosity regulator is preferably at least about 1000. Molecular weights of up to 6000 or even more can be considered.
• Disulphates of polyalkylene glycols of the stated type with molecular weights in the range from 1500 to 4000 are particularly preferred.
• the disulfates used according to the invention as viscosity regulators thus generally originate from polyether glycols which differ from the polyalkylene glycols, as they can be caused by the slight traces of water in the alkoxylation of alcoholic components.
• the teaching of the invention allows also use the viscosity regulators in a determinable manner according to type and quantity, so that predictable targeted effects with regard to the reduction of the gel state are possible.
• the viscosity regulators used according to the invention are themselves effective washing-active substances (WAS). An undesirable load with inactive components is avoided.
• WAS washing-active substances
• the surfactant mixtures according to the invention can not only be pumped as such in a highly concentrated form, when diluted with water there is no increase in the gel state, but the desired dilution effect.
• any water-soluble salts of the viscosity regulators used according to the invention can be used.
• Alkaline salts, soluble alkaline earth metal salts, for example corresponding magnesium salts, the ammonium salts and / or salts with organic amines are particularly suitable for practical use.
• Suitable amine salts are, for example, alkylolamine salts.
• the sodium salts are of particular importance.
• the most important salt for practical use is the sodium salt of the disulfate of polyethylene ether glycols and / or 1,2 polypropylene ether glycols with the minimum molecular weights indicated in each case.
• the statements made here regarding the salt-forming cations of the viscosity regulators can have corresponding validity for the salt-forming cations present in the surfactants.
• the viscosity regulators can be present in the aqueous surfactant concentrates in amounts of up to 20% by weight, preferably in amounts of 0.1 to 10% by weight. Amounts of at least 1% by weight, in particular from 2 to 5% by weight, can be particularly preferred. These figures relate to the aqueous surfactant concentrate. In particular, the amount of the viscosity regulator is determined by the desired lowering of the gel point and / or by the thickening effect of the respective surfactant. In terms of the last point of view, the special structure of the surfactant can be significant. If surfactants of the type mentioned are present which contain polyalkoxy radicals, the extent of the polyalkoxylation of the alcohol on which they are based can be significant.
• low alkoxylated alcohols can usually be effectively influenced even in high concentrations with 2 to 5% by weight of the viscosity regulator, while somewhat larger amounts of the viscosity regulator may be required together with highly polyalkoxylated alcohols (degree of polymerization of the polyalkoxy radical above 10 to 100, for example).
• free polyethylene glycol and / or free polypropylene glycol can be used together with the sulfates of the polyethylene glycol and / or the polypropylene glycol as a viscosity-regulating component.
• these non-sulfated polyalkylene ether glycols that effect its appearance more pronounced the higher the molecular weight of the P olyalkylenetherglykols.
• These free polyalkylene ether glycols which may also be used, should have at least a molecular weight of 1500, preferably their molecular weight is at least 2000 and is, for example, in the range from 2000 to 6000, in particular in the range from 3000 to 5000.
• the mixing ratio of the sulfates of the lower polyalkylene ether glycols - especially the disulfates - to the free polyalkylene ether glycols is desirably in the range from 1: 0 to 1: 3.
• the mixing range from 1: 0 to 1: 1 is generally preferred.
• the viscosity regulator can be added to the aqueous surfactant concentrate as a preformed compound or as a preformed compound mixture.
• the viscosity regulator is expediently used as a concentrated aqueous solution (content of WAS for example 50 to 90% by weight) and mixed with the aqueous solution of the respective surfactant.
• the viscosity regulator by sulfating the lower polyalkylene ether glycols in situ in the presence of the surfactant-forming basic components.
• the sulfation can thus take place, for example, in the presence of an alkyl polyglycol ether alcohol or an alkyl aryl polyglycol ether alcohol.
• the sulfation of both the alcoholic surfactant-forming component and the preformed lower polyalkylene ether glycols are expediently combined.
• the desired mixing ratios of the surfactant-forming alcoholic component (s) and the polyalkylene ether glycols forming the viscosity regulator are simply set here and then this mixture of substances is subjected to the sulfation known per se. Finally, the sulfates formed are converted into the desired water-soluble salt. The same cation is set in the surfactant and in the viscosity regulator.
• alkyl ether sulfates are sulfates of alkoxylated C 8 -C 24 alcohols, preferably such derivatives with a carbon chain of 8 to 18 carbon atoms.
• Non-aromatic alcohols with carbon chains of 10 to 16 links can be particularly preferred.
• the carbon chain can be straight-chain and / or branched and saturated and / or unsaturated.
• alcohols of the type mentioned are accessible both from natural products and by synthesis.
• the alcohols are alkoxylated with lower alkylene oxides.
• the low alkoxylated derivatives up to 10 or 12, preferably 1 to 4, in particular 2 to 3, alkoxy groups are added to the alcohol radical.
• the highly alkoxylated derivatives polyalkoxy radicals with a number of members over 10 or 12, for example up to 100, in particular 20 to 80, are provided.
• the most important alkoxylating agents are ethylene oxide and / or 1,2-propylene oxide.
• Suitable as a group of suitable water-soluble salts of the sulfated polyalkoxylated compounds is the one mentioned above in connection with the viscosity regulator Group of cations.
• Suitable salts are therefore in particular the alkali metal salts, soluble alkaline earth metal salts, ammonium salts and salts with organic amines.
• the most important salt in practice is the sodium salt of alkyl ether sulfate.
• the preferred surfactants of this class can be represented by the general formula
• R alkyl radical which can be straight-chain or branched and can be saturated or unsaturated. Alkyl radicals having 4 to 16 carbon atoms, in particular having 6 to 14 carbon atoms, are preferred here. Alkyl radicals with 8 to 12 carbon atoms can be of particular importance.
• n 1 or 2, 1 being preferred as a rule.
• A lower alkylene radical, which can be straight-chain and / or branched.
• the preferred lower alkylene radicals are ethylene and / or propylene (1,2).
• n 1 to 100.
• low alkoxylated derivatives up to 12 ins special 2 to 10 alkoxy groups added to the alcohol residue.
• polyalkoxy radicals with a number of members greater than 12, for example up to 100, in particular 20 to 50, are provided.
• M cation of a soluble salt, in particular alkali, water-soluble alkaline earth, ammonium or organic amines. The most preferred cation is sodium.
• the compounds preferably correspond to the general formula
• R-O- residue of a non-aromatic alcohol which can be straight-chain or branched and can be saturated or unsaturated and generally has 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms.
• Ar phenylene or naphthylene, the phenylene radical is preferred
• the S0 3M group can also be interchanged within the succinic acid residue.
• this alkyl radical preferably contains at least 8 carbon atoms, radicals with 10 to 18 carbon atoms can be particularly preferred.
• A lower alkylene radical, which can be straight-chain and / or branched.
• the Favor q th Alkvlenreste are
• n is preferably 1 to 12, in particular 2 to 10.
• n has a value> 12 to in particular 100, preferably 20 to 50.
• the sulfonic acid residue in succinic acid may also be interchanged in surfactants of this type.
• the diester of sulfosuccinic acid is again present.
• Z -OM or -OR (diester of sulfosuccinic acid)
• aqueous surfactant concentrates according to the invention can also contain other surface-active agents.
• nonionic WAS for example alkylphenol polyglycol ethers, are suitable.
• inorganic salts such as sodium chloride and / or sodium sulfate are usually present in the aqueous concentrates of the invention from the preparation of the alkyl and alkylaryl ether sulfates and the sulfosuccinates described and / or the viscosity regulators used according to the invention, see also the statements relating to the prior art.
• Na-C12 / 14-fatty alcohol-2-EO sulfate is used as the surfactant in the starting solution.
• Surfactant used Na-C12 / 14-fatty alcohol-2-EO-sulfate
• Na-C12 / 14-2 sulfate is liquefied with 3% by weight or 6% by weight of the viscosity regulator and after dilution with water to a content of 10% by weight WAS is examined for its thickenability with sodium chloride.
• WAS a content of 10% by weight
• Tables a) and b) show that even small amounts of the viscosity regulators according to the invention have a liquefying effect on highly concentrated fatty alcohol ether sulfates. At the transition to lower concentrations i.e. when diluted, the viscosity is not increased abruptly, but a decrease occurs.
• An adduct of 50 moles of ethylene oxide with one mole of C12 / 14 fatty alcohol is sulfated with chlorosulfonic acid alone and in the blends with polyethylene glycol given in Table 6 under customary conditions. 1.05 moles of chlorosulfonic acid are used per mole of hydroxyl groups (calculated according to the OH number). After neutralizing with sodium hydroxide solution and setting an active substance concentration of 25% by weight, the gel points listed in Table 6 are found.
• This example explains the use of polyglycols or polyglycol disulfates to lower the gel point of a highly ethoxylated alkylphenol ether sulfate.
• the aqueous solution of a dodecylphenol + 40 EO sulfate, Na salt, with an active substance content of 30% by weight has a gel point of +12.5 o C. To lower the gel point, are used.
• the Höppler viscosity at 25 ° C of a 30% C 12 / C 15 oxo alcohol sulfate Na salt (abbreviated here with OAS) is approx. 8500 mPa ⁇ s.
• OAS oxo alcohol sulfate Na salt
• the viscosity-breaking influence of PEG disulfates on such aqueous alkyl sulfate concentrates is determined.
• the following blends are made by OAS and the Höppler viscosity is measured.
• ABS 50% n-dodecylbenzenesulfonate
• Viscosity-breaking influence of polyethylene glycols and PEG disulfates on such aqueous ABS concentrates determined.
• the following mixes of ABS are produced and the Höppler viscosity is measured.
• the di-Na-sulfosuccinic acid half-ester of octylphenol + 11 EO forms a non-pourable, immobile gel at 30% AS in aqueous solution, which only becomes fluid at 33 ° C (gel point).
• the Höppler viscosity of the gel at 25 ° C is naturally not measurably high.
• the gel point can be reduced to -2 ° C, the Höppler viscosity at 25 ° C is measurable and is only 80 - 100 mPa s.
• 10% PEG 4000 disulphate, Na salt, as a 33% aqueous solution the gel point can be reduced even further and is then ⁇ -10 ° C.

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• 1980
  • 1980-08-23 EP EP80105017A patent/EP0024711B2/fr not_active Expired
  • 1980-08-23 DE DE8080105017T patent/DE3066054D1/de not_active Expired
  • 1980-08-26 US US06/181,639 patent/US4384978A/en not_active Expired - Lifetime
  • 1980-08-28 CA CA000359228A patent/CA1152850A/fr not_active Expired
• 1983
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