EP0174610B1 - Use of ether sulfonates as low-foaming wetting agents in aqueous, acid and alcaline technical treating compositions - Google Patents
Use of ether sulfonates as low-foaming wetting agents in aqueous, acid and alcaline technical treating compositions Download PDFInfo
- Publication number
- EP0174610B1 EP0174610B1 EP85111229A EP85111229A EP0174610B1 EP 0174610 B1 EP0174610 B1 EP 0174610B1 EP 85111229 A EP85111229 A EP 85111229A EP 85111229 A EP85111229 A EP 85111229A EP 0174610 B1 EP0174610 B1 EP 0174610B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- wetting agents
- alkaline
- aqueous
- low
- ether sulfonates
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000000080 wetting agent Substances 0.000 title claims abstract description 28
- -1 ether sulfonates Chemical class 0.000 title claims abstract description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000005187 foaming Methods 0.000 title description 12
- 239000000203 mixture Substances 0.000 title description 6
- 239000002253 acid Substances 0.000 title description 2
- 239000006260 foam Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 125000004450 alkenylene group Chemical group 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000004061 bleaching Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- RZXLPPRPEOUENN-UHFFFAOYSA-N Chlorfenson Chemical compound C1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=C(Cl)C=C1 RZXLPPRPEOUENN-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000003513 alkali Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims 1
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 150000005215 alkyl ethers Chemical class 0.000 abstract description 5
- 150000008053 sultones Chemical class 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 2
- 238000006277 sulfonation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 7
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 6
- 229940055577 oleyl alcohol Drugs 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 229960000541 cetyl alcohol Drugs 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005237 degreasing agent Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- JXNPEDYJTDQORS-HZJYTTRNSA-N (9Z,12Z)-octadecadien-1-ol Chemical compound CCCCC\C=C/C\C=C/CCCCCCCCO JXNPEDYJTDQORS-HZJYTTRNSA-N 0.000 description 2
- MHGOKSLTIUHUBF-UHFFFAOYSA-N 2-ethylhexyl sulfate Chemical compound CCCCC(CC)COS(O)(=O)=O MHGOKSLTIUHUBF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001348 alkyl chlorides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- JXNPEDYJTDQORS-UHFFFAOYSA-N linoleyl alcohol Natural products CCCCCC=CCC=CCCCCCCCCO JXNPEDYJTDQORS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
-
- 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
Definitions
- aqueous treatment agents for the treatment of solid surfaces e.g. B. fibers, textiles, metals, ceramics or glass are strongly acidic or alkaline.
- Technical treatment agents of this type e.g. B. bleach, mercerizing, decoction.
- Cleaning and degreasing agents, descaling, etching, pickling and rust removal agents require the addition of wetting agents. to achieve a quicker and more intimate contact between the treatment agent and the solid surface.
- wetting agents that are suitable for such acidic and alkaline, technical treatment agents must have good water solubility, even in acidic and alkaline medium, and must be largely stable against hydrolysis in these media. Since the technical treatment methods mentioned are often associated with strong mechanical movement, undesirable foaming easily occurs. Suitable wetting agents must therefore be very low-foaming. If this is not the case, the use of anti-foaming agents is necessary. The use of anti-foaming agents is not only associated with costs, but often has undesirable side effects, e.g. B. an uneven treatment of the surface or the formation of hydrophobic residues on the treated surface.
- technical wetting agents should be environmentally friendly, that is, in particular, readily biodegradable and non-toxic to aquatic organisms.
- wetting agents are characterized by very good water solubility, even in the presence of high concentrations of dissolved electrolytes, especially in the presence of acids and alkalis.
- the invention therefore relates to the use of these ether sulfonates as wetting agents, especially in strongly acidic and strongly alkaline technical treatment solutions, especially in solutions which have a pH below 3 or above 10.
- the ether sulfonates to be used according to the invention are therefore preferably mixtures of compounds of the formula 1 in which R 2 is alkenylene, hydroxyalkylene and hydroxyalkenylene groups.
- the starting products of formula 11 are accessible by methods known from the literature. They are manufactured from unsaturated alcohols of the formula R 3 -OH. If X is a number from 1-30, these are, according to the process known from the literature, using X mol of an alkylene oxide of the formula C n H 2n O, for. B. with ethylene oxide or propylene oxide or mixtures of these alkylene oxides. Mixtures of homologous oxalkylates are obtained, the average degree of oxalkylation corresponding to the amount of alkylene oxide added.
- the etherification of the terminal hydroxyl group of the unsaturated alcohols and / or their oxalkylates is carried out by methods which are also known from the literature. You can e.g. B.
- the alcohol or the oxalkylate is converted into the alcoholate with an alkali metal and this with an alkyl halide, for. B. is reacted with an alkyl chloride of the formula R 1 -Cl.
- Another method is to react the alcohol or the oxalkylate with an alkyl halide in the presence of a finely powdered alkali metal hydroxide at an elevated temperature.
- the alkoxylate can 1 is -Cl or R l Br DE-PS-2 800 710 are reacted in the presence of an aqueous solution of NaOH or KOH in accordance with an alkyl chloride or alkyl bromide of the formula R.
- the unsaturated alcohol R 3 OH is preferably an unsaturated fatty alcohol with 16-22 C atoms, ie an alcohol from the group palmitole alcohol, oleyl alcohol, linoleyl alcohol, erucalcohol or a mixture such alcohols, e.g. B. a technical, consisting mainly of such alcohols fatty alcohol cut used.
- Low levels of saturated alcohols, e.g. B. on cetyl and stearyl alcohol are portable, especially if the products of general formula 11 produced therefrom by oxyalkylation and etherification are themselves water-soluble.
- Technical cetyl-oleyl and oleyl-linoleyl alcohol cuts with an iodine number in the range of 70-130 are preferably used.
- Preferred wetting agents of the general formula 1 are preferably obtained by adding 3 to 10 mol of ethylene oxide to these alcohols, etherification with alkyl halide, for. B. R 1 Cl, and sulfonation with S0 3 obtained.
- the wetting agents used according to the invention are distinguished by a particularly low foaming power. This is of particular advantage in strongly alkaline treatment agents, e.g. B. in alkaline cold bleaching liquors, hot bleaching liquors, mercerizing liquors, alkaline boiling and degreasing agents, since such alkaline treatment agents tend particularly to form foam.
- the cause of the foam formation can either be the use of a foaming wetting agent or the formation of highly foaming hydrolysis products under the conditions of the surface treatment, e.g. B. the formation of soaps from hydrolyzed fats or foaming protein breakdown products from protein compounds.
- alkaline treatment agents are e.g. B. mercerizing liquors, alkaline decoction solutions, alkaline degreasing agents and alkaline bleaching baths.
- ether sulfonates as low-foaming wetting agents in aqueous alkaline bleaching liquors is particularly interesting. These contain hydrogen peroxide or compounds which form hydrogen peroxide in aqueous solution as a bleaching agent.
- the pH value of the bleach baths is with strong bases, e.g. B. with NaOH, KOH, Na 2 C0 3 , K 2 C0 3 and / or water glass to 10-14.
- strong bases e.g. B. with NaOH, KOH, Na 2 C0 3 , K 2 C0 3 and / or water glass to 10-14.
- the well-known anionic and nonionic wetting agents which are stable and effective in this medium, tend to produce a lot of foam in the high-speed apparatus. For this reason, the use of foam damping agents, for. B. of the type of silicone oils, common.
- a preferred object of the invention is therefore the use of the ether sulfonates of the general formula I in aqueous cold bleaching solutions containing 0.3-3% by weight of hydrogen peroxide, 0.05-1 mol / l of a strong base from the group sodium hydroxide, potassium hydroxide , Sodium carbonate, potassium carbonate, sodium silicate and / or potassium silicate as low-foaming wetting agent, preferably in an amount of 0.05-1% by weight of the bleaching solution.
- Such bleaching solutions are used at temperatures of 10 - 142 ° C, but preferably at a temperature of approx. 20 ° C (cold bleaching).
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
Zahlreiche wäßrige Behandlungsmittel für die Behandlung fester Oberflächen, z. B. von Fasern, Textilien, Metallen, Keramik oder Glas sind stark sauer oder alkalisch eingestellt. Technische Behandlungsmittel dieser Art, z. B. Bleichmittel, Mercerisierlaugen, Abkoch-. Reinigungs- und Entfettungsmittel, Entzunderungs-, Ätz-, Beiz- und Entrostungsmittel erfordern den Zusatz von Netzmitteln. um einen rascheren und innigeren Kontakt zwischen dem Behandlungsmittel und der festen Oberfläche zu erreichen.Numerous aqueous treatment agents for the treatment of solid surfaces, e.g. B. fibers, textiles, metals, ceramics or glass are strongly acidic or alkaline. Technical treatment agents of this type, e.g. B. bleach, mercerizing, decoction. Cleaning and degreasing agents, descaling, etching, pickling and rust removal agents require the addition of wetting agents. to achieve a quicker and more intimate contact between the treatment agent and the solid surface.
Netzmittel, die für solche sauren und alkalischen, technischen Behandlungsmittel geeignet sind, müssen eine gute Wasserlöslichkeit, auch in saurem und alkalischem Medium besitzen und gegen Hydrolyse in diesen Medien weitgehend stabil sein. Da die genannten technischen Behandlungsverfahren oft mit starker mechanischer Bewegung verbunden sind, kommt es leicht zu einer unerwünschten Schaumbildung. Geeignete Netzmittel müssen daher sehr schaumarm sein. Wenn dies nicht der Fall ist, wird der Einsatz von Antischaummitteln erforderlich. Der Einsatz von Antischaummitteln ist jedoch nicht nur mit Unkosten verbunden, sondern hat oft unerwünschte Nebenwirkungen zur Folge, z. B. eine ungleichmäßige Behandlung der Oberfläche oder die Bildung hydrophober Rückstände auf der behandelten Oberfläche.Wetting agents that are suitable for such acidic and alkaline, technical treatment agents must have good water solubility, even in acidic and alkaline medium, and must be largely stable against hydrolysis in these media. Since the technical treatment methods mentioned are often associated with strong mechanical movement, undesirable foaming easily occurs. Suitable wetting agents must therefore be very low-foaming. If this is not the case, the use of anti-foaming agents is necessary. The use of anti-foaming agents is not only associated with costs, but often has undesirable side effects, e.g. B. an uneven treatment of the surface or the formation of hydrophobic residues on the treated surface.
Darüber hinaus sollen technische Netzmittel umweltfreundlich, also insbesondere gut biologisch abbaufähig und nicht toxisch gegen Wasserorganismen sein.In addition, technical wetting agents should be environmentally friendly, that is, in particular, readily biodegradable and non-toxic to aquatic organisms.
Es wurde gefunden, daß die gestellten Anforderungen weitgehend erfüllt werden, wenn man als Netzmittel für wäßrige, saure und alkalische technische Behandlungsmittel Ethersulfonate der allgemeinen Formel 1
- R' eine Alkylgruppe mit 1 - 6 C-Atomen,
- n eine ganze Zahl von 2 - 4,
- x - 0 oder eine Zahl bis 30,
- R2 eine lineare Alkenylen, Hydroxyalkylen- oder Hydroxyalkenylengruppe mit 6 - 22 C-Atomen und
- M Wasserstoff, ein Alkaliatom, insbesondere Natrium oder Kalium, darstellt.
- R 'is an alkyl group with 1-6 C atoms,
- n is an integer from 2 to 4,
- x - 0 or a number up to 30,
- R 2 is a linear alkenylene, hydroxyalkylene or hydroxyalkenylene group with 6-22 C atoms and
- M represents hydrogen, an alkali atom, in particular sodium or potassium.
Diese Netzmittel zeichnen sich durch eine sehr gute Wasserlöslichkeit, auch in Gegenwart hoher Konzentrationen gelöster Elektrolyte, insbesondere in Gegenwart von Säuren und Laugen aus. Gegenstand der Erfindung ist daher die Verwendung dieser Ethersulfonate als Netzmittel, vor allem in stark sauren und stark alkalischen, technischen Behandlungslösungen, namentlich in Lösungen, die einen pH-Wert unterhalb 3 oder oberhalb 10 aufweisen.These wetting agents are characterized by very good water solubility, even in the presence of high concentrations of dissolved electrolytes, especially in the presence of acids and alkalis. The invention therefore relates to the use of these ether sulfonates as wetting agents, especially in strongly acidic and strongly alkaline technical treatment solutions, especially in solutions which have a pH below 3 or above 10.
Die erfindungsgemäß zu verwendenden Ethersulfonate lassen sich dadurch herstellen, daß man einen olefinisch ungesättigten Fettalkyl-niedrigalkylether oder einen olefinisch ungesättigten Fettalkyl-(polyoxyalkyl)-niedrigalkylether der allgemeinen Formel
- R1, n und x die vorgenannte Bedeutung haben und
- R3 eine einfach oder zweifach ungesättigte lineare Alkenylgruppe mit 6 - 22 C-Atomen darstellt, mit Schwefeltrioxid umsetzt, das Umsetzungsprodukt in die wäßrige Lösung von 1 - 1,2 Mol eines Alkalihydroxids pro Mol angelagertes S03 einträgt und die Lösung bis zur Hydrolyse gebildeter Sultone erwärmt.
- R 1 , n and x have the abovementioned meaning and
- R 3 represents a mono- or di-unsaturated linear alkenyl group with 6 - 22 C atoms, reacted with sulfur trioxide, the reaction product in the aqueous solution of 1 - 1.2 mol of an alkali metal hydroxide per mole of S0 3 added and the solution formed until hydrolysis Sultons warmed up.
Bei der Umsetzung der ungesättigten Fettalkyl-(polyoxyalkyl)-niedrigalkylether der allgemeinen Formel mit Schwefeltrioxid entstehen neben ungesättigten Ethersulfonsäuren auch Sultone. Durch Hydrolyse dieser Sultone entstehen daraus die entsprechenden Hydroxysulfonsäuren und z.T. auch (unter Wasseraustritt) ungesättigte Sulfonsäuren bzw. deren Alkalisalze. Die erfindungsgmäß einzusetzenden Ethersulfonate sind daher bevorzugt Gemische aus Verbindungen der Formel 1, in welchen R2 Alkenylen, Hydroxyalkylen und Hydroxyalkenylengruppen sind.When the unsaturated fatty alkyl (polyoxyalkyl) lower alkyl ethers of the general formula are reacted with sulfur trioxide, sultones are formed in addition to unsaturated ether sulfonic acids. By hydrolysis of these sultones, the corresponding hydroxysulfonic acids and partly also unsaturated sulfonic acids or their alkali salts are formed (with water escaping). The ether sulfonates to be used according to the invention are therefore preferably mixtures of compounds of the formula 1 in which R 2 is alkenylene, hydroxyalkylene and hydroxyalkenylene groups.
Die Ausgangsprodukte der Formel 11 sind nach literaturbekannten Verfahren zugänglich. Ihre Herstellung geht aus von ungesättigten Alkoholen der Formel R3-OH. Diese werden, wenn X eine Zahl von 1 - 30 ist, nach literaturbekanntem Verfahren mit X Mol eines Alkylenoxids der Formel CnH2nO, z. B. mit Ethylenoxid oder Propylenoxid oder Gemischen dieser Alkylenoxide umgesetzt. Dabei werden Gemische homologer Oxalkylate erhalten, deren mittlerer Oxalkylierungsgrad der Menge des angelagerten Alkylenoxids entspricht. Die Veretherung der endständigen Hydroxylgruppe der ungesättigten Alkohole und/oder deren Oxalkylate erfolgt nach ebenfalls literaturbekannten Methoden. Sie kann z. B. in der Weise durchgeführt werden, daß der Alkohol oder das Oxalkylat mit einem Alkalimetall in das Alkoholat überführt wird und dieses mit einem Alkylhalogenid, z. B. mit einem Alkylchlorid der Formel R1-Cl, zur Umsetzung gebracht wird. Ein anderes Verfahren besteht darin, daß der Alkohol oder das Oxalkylat mit einem Alkylhalogenid in Gegenwart eines feinpulverisierten Alkalimetallhydroxids bei erhöhter Temperatur umgesetzt wird. Schließlich kann das Oxalkylat mit einem Alkylchlorid oder Alkylbromid der allgemeinen Formel R1-Cl oder Rl-Br in Gegenwart einer wäßrigen Lösung von NaOH oder KOH gemäß DE-PS-2 800 710 zur Umsetzung gebracht werden.The starting products of formula 11 are accessible by methods known from the literature. They are manufactured from unsaturated alcohols of the formula R 3 -OH. If X is a number from 1-30, these are, according to the process known from the literature, using X mol of an alkylene oxide of the formula C n H 2n O, for. B. with ethylene oxide or propylene oxide or mixtures of these alkylene oxides. Mixtures of homologous oxalkylates are obtained, the average degree of oxalkylation corresponding to the amount of alkylene oxide added. The etherification of the terminal hydroxyl group of the unsaturated alcohols and / or their oxalkylates is carried out by methods which are also known from the literature. You can e.g. B. be carried out in such a way that the alcohol or the oxalkylate is converted into the alcoholate with an alkali metal and this with an alkyl halide, for. B. is reacted with an alkyl chloride of the formula R 1 -Cl. Another method is to react the alcohol or the oxalkylate with an alkyl halide in the presence of a finely powdered alkali metal hydroxide at an elevated temperature. Finally, the alkoxylate can 1 is -Cl or R l Br DE-PS-2 800 710 are reacted in the presence of an aqueous solution of NaOH or KOH in accordance with an alkyl chloride or alkyl bromide of the formula R.
Als ungesättigter Alkohol R3-OH wird bevorzugt ein ungesättigter Fettalkohol mit 16 - 22 C-Atomen, d. h. ein Alkohol aus der Gruppe Palmitoleyalkohol, Oleylalkohol, Linoleylalkohol, Erucaalkohol oder ein Gemisch solcher Alkohole, z. B. ein technischer, überwiegend aus solchen Alkoholen bestehender Fettalkoholschnitt eingesetzt. Geringe Anteile an gesättigten Alkoholen, z. B. an Cetyl und Stearylalkohol sind tragbar, vor allem, wenn die daraus durch Oxalkylierung und Veretherung hergestellten Produkte der allgemeinen Formel 11 selbst wasserlöslich sind. Bevorzugt werden technische Cetyl-Oleyl- und Oleyl-Linoleyl-Alkoholschnitte mit einer Jodzahl im Bereich von 70 -130 eingesetzt.The unsaturated alcohol R 3 OH is preferably an unsaturated fatty alcohol with 16-22 C atoms, ie an alcohol from the group palmitole alcohol, oleyl alcohol, linoleyl alcohol, erucalcohol or a mixture such alcohols, e.g. B. a technical, consisting mainly of such alcohols fatty alcohol cut used. Low levels of saturated alcohols, e.g. B. on cetyl and stearyl alcohol are portable, especially if the products of general formula 11 produced therefrom by oxyalkylation and etherification are themselves water-soluble. Technical cetyl-oleyl and oleyl-linoleyl alcohol cuts with an iodine number in the range of 70-130 are preferably used.
Bevorzugt geeignete Netzmittel der allgemeinen Formel 1 werden durch Anlagerung von 3 - 10 Mol Ethylenoxid an diese Alkohole, Veretherung mit Alkylhalogenid, z. B. R1Cl, und Sulfonierung mit S03 erhalten. In der allgemeinen Formel ist daher bevorzugt n = 2, x = 3 - 10 und R2 eine Alkenylen, Hydroxyalkylen oder Hydroxyalkenylengruppe mit 16 - 22 C-Atomen.Preferred wetting agents of the general formula 1 are preferably obtained by adding 3 to 10 mol of ethylene oxide to these alcohols, etherification with alkyl halide, for. B. R 1 Cl, and sulfonation with S0 3 obtained. In the general formula, therefore, n = 2, x = 3 - 10 and R 2 is preferably an alkenylene, hydroxyalkylene or hydroxyalkenylene group with 16 - 22 C atoms.
Die erfindungsgemäß verwendeten Netzmittel zeichnen sich durch ein besonders geringes Schaumvermögen aus. Dies ist von besonderem Vorteil in stark alkalischen Behandlungsmitteln, z. B. in alkalischen Kaltbleichflotten, Heissbleichflotten, Mercerisierlaugen, alkalischen Abkoch- und Entfettungsmitteln, da solche alkalische Behandlungsmittel besonders zur Bildung von Schaum neigen. Ursache für die Schaumbildung kann entweder die Verwendung eines schäumenden Netzmittels sein oder die Bildung stark schäumender Hydrolyseprodukte unter den Bedingungen der Oberflächenbehandlung, z. B. die Bildung von Seifen aus hydrolysierten Fetten oder von schäumenden Proteinabbauprodukten aus Eiweißverbindungen. In solchen alkalischen Behandlungslösungen ist der Einsatz der schaumarmen Ethersulfonate von besonderem Wert, da diese Netzmittel einerseits selbst keinen Schaum entwickeln, andererseits der Bildung von Schaum aus schäumenden Hydrolyseprodukten erfolgreich entgegenwirken.The wetting agents used according to the invention are distinguished by a particularly low foaming power. This is of particular advantage in strongly alkaline treatment agents, e.g. B. in alkaline cold bleaching liquors, hot bleaching liquors, mercerizing liquors, alkaline boiling and degreasing agents, since such alkaline treatment agents tend particularly to form foam. The cause of the foam formation can either be the use of a foaming wetting agent or the formation of highly foaming hydrolysis products under the conditions of the surface treatment, e.g. B. the formation of soaps from hydrolyzed fats or foaming protein breakdown products from protein compounds. In such alkaline treatment solutions, the use of low-foam ether sulfonates is of particular value, since on the one hand these wetting agents do not develop any foam themselves, and on the other hand they successfully counteract the formation of foam from foaming hydrolysis products.
Beispiele für alkalische Behandlungsmittel sind z. B. Mercerisierlaugen, alkalische Abkochlösungen, alkalische Entfettungsmittel und alkalische Bleichbäder.Examples of alkaline treatment agents are e.g. B. mercerizing liquors, alkaline decoction solutions, alkaline degreasing agents and alkaline bleaching baths.
Besonders interessant ist die Verwendung der Ethersulfonate als schaumarme Netzmittel in wäßrigen alkalischen Bleichflotten. Diese enthalten als bleichendes Agens Wasserstoffperoxid oder Verbindungen, die in wäßriger Lösung Wasserstoffperoxid bilden. Der pH-Wert der Bleichbäder wird mit starken Basen, z. B. mit NaOH, KOH, Na2C03, K2C03 und/oder Wasserglas auf 10 - 14 eingestellt. Die bekannten anionischen und nichtionogenen Netzmittel, die in diesem Medium beständig und wirksam sind, neigen in den schnellaufenden Apparaturen zu starker Schaumentwicklung. Aus diesem Grunde ist der Einsatz von Schaumdämpfungsmitteln, z. B. vom Typ der Siliconöle, üblich. Die erfindungsgemäß zu verwendenden Ethersulfonate entwickeln in solchen Bädern hingegen praktisch keinen Schaum, so daß ein Zusatz von Antischaummitteln entfällt. Ein bevorzugter Gegenstand der Erfindung ist daher die Verwendung der Ethersulfonate der allgemeinen Formel I in wäßrigen Kaltbleichlösungen mit einem Gehalt an 0,3 - 3 Gew.-% Wasserstoffperoxid, 0,05 - 1 Mol/1 einer starken Base aus der Gruppe Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat, Kaliumcarbonat, Natriumsilicat und/oder Kaliumsilicat als schaumarmes Netzmittel, bevorzugt in einer Menge von 0,05 - 1 Gew.- % der Bleichlösung.The use of ether sulfonates as low-foaming wetting agents in aqueous alkaline bleaching liquors is particularly interesting. These contain hydrogen peroxide or compounds which form hydrogen peroxide in aqueous solution as a bleaching agent. The pH value of the bleach baths is with strong bases, e.g. B. with NaOH, KOH, Na 2 C0 3 , K 2 C0 3 and / or water glass to 10-14. The well-known anionic and nonionic wetting agents, which are stable and effective in this medium, tend to produce a lot of foam in the high-speed apparatus. For this reason, the use of foam damping agents, for. B. of the type of silicone oils, common. In contrast, the ether sulfonates to be used according to the invention develop practically no foam in such baths, so that the addition of anti-foaming agents is not necessary. A preferred object of the invention is therefore the use of the ether sulfonates of the general formula I in aqueous cold bleaching solutions containing 0.3-3% by weight of hydrogen peroxide, 0.05-1 mol / l of a strong base from the group sodium hydroxide, potassium hydroxide , Sodium carbonate, potassium carbonate, sodium silicate and / or potassium silicate as low-foaming wetting agent, preferably in an amount of 0.05-1% by weight of the bleaching solution.
Die Anwendung solcher Bleichlösungen erfolgt bei Temperaturen von 10 - 142°C, bevörzugt jedoch bei einer Temperatur von ca. 20° C (Kaltbleiche).Such bleaching solutions are used at temperatures of 10 - 142 ° C, but preferably at a temperature of approx. 20 ° C (cold bleaching).
Die folgenden Beispiele sollen den Gegenstand der Erfindung näher erläutern ohne ihn hierauf zu beschränken:The following examples are intended to explain the subject matter of the invention in more detail without restricting it thereto:
1. Herstellung von Oleylalkohol-5E0-butylethersulfonat, Na-Salz.
- 886 g (ca. 1.6 Mol) des n-Butylethers eines Anlagerungsproduktes von 5 Mol Ethylenoxid an einen technischen Oleylalkohol der Jodzahl 94 (HD-Ocenol® 92/96) wurden mit 187,8 g (ca. 2.35 Mol) gasförmigem (aus Oleum ausgetriebenem) S03 bei 60°C in einem Fallfilmreaktor kontinuierlich umgesetzt. Das Reaktionsprodukt wurde nach dem Austritt aus dem Reaktor in eine Lösung von 98 g (2,45 Mol) NaOH in 1600 g Wasser eingetragen. Die dabei erhaltene Lösung wurde 6 h unter Rückfluß zum Sieden erhitzt. Dabei wurde eine Lösung des Ethersulfonats mit folgenden Kenndaten erhalten:
- 886 g (approx. 1.6 mol) of the n-butyl ether of an adduct of 5 mol of ethylene oxide with a technical oleyl alcohol of iodine number 94 (HD-Ocenol® 92/96) were gaseous (from oleum. 187.8 g (approx. 2.35 mol)) driven) S0 3 continuously implemented at 60 ° C in a falling film reactor. After leaving the reactor, the reaction product was introduced into a solution of 98 g (2.45 mol) of NaOH in 1600 g of water. The solution thus obtained was heated to boiling under reflux for 6 h. A solution of the ether sulfonate was obtained with the following characteristics:
2. Cetyl/Oleylalkohol + 5 EO-butylether-sulfonat, Na-Salz.
- Analog Beispiel 1 wurde ein Ethersulfonat ausgehend von dem n-Butylether eines Anlagerungsproduktes von von 5 Mol Ethylenoxid an einem Cetyl/Oleylalkohol der Jodzahl 52 (HD-Ocenole 50/55) hergestellt.
- Analogously to Example 1, an ether sulfonate was prepared starting from the n-butyl ether of an adduct of 5 moles of ethylene oxide with a cetyl / oleyl alcohol of iodine number 52 (HD-Ocenol e 50/55).
3. Cetyl/Oleylalkohol + 5 EO-butylether-sulfonat, Na-Salz.
- Analog Beispiel 1 wurde ein Ethersulfonat ausgehend von dem n-Butylether eines Anlagerungsproduktes von 5 Mol Ethylenoxid an einen Oleyl/Linoleylalkoholschnitt der Jodzahl 120 (HD-Ocenol® 110/130) hergestellt.
- Analogously to Example 1, an ether sulfonate was prepared starting from the n-butyl ether of an adduct of 5 moles of ethylene oxide with an oleyl / linoleyl alcohol cut of iodine number 120 (HD-Ocenol® 110/130).
4. Prüfung der Netzwirkung einer alkalischen Kaltbleichlösung.4. Testing the wetting effect of an alkaline cold bleach solution.
Die Netzwirkung dieser Flotten wurde bei 20°C analog DIN 53901 (Bestimmung des Tauchnetzvermögens von Tensidlösungen) bestimmt.The wetting effect of these liquors was determined at 20 ° C. in accordance with DIN 53901 (determination of the immersion wetting power of surfactant solutions).
Für die Kaltbleichlösungen mit den Netzmitteln gemäß Beispiel 1 - 3 wurden folgende Netzzeiten erhalten:
- Netzmittel Beispiel 1 : 8 (s)
- Netzmittel Beispiel 2 : 8 (s)
- Netzmittel Beispiel 3 : 8 (s).
- Wetting agent example 1: 8 (s)
- Wetting agent example 2: 8 (s)
- Wetting agent Example 3: 8 (s).
5. Prüfung des Schaumverhaltens der alkalischen Kaltbleichlösungen gemäß Beispiel 4.5. Testing the foaming behavior of the alkaline cold bleaching solutions according to Example 4.
Das Schaumverhalten der Kaltbleichlösungen gemäß Beispiel 4, in welchen als Netzmittel die Produkte gemäß Beispiel 1, 2 und 3 sowie zum Vergleich 2-Ethylhexylsulfat-Na-Salz, ein bekanntes, alkalistabiles Netzmittel enthalten waren, wurden bei 20° C in einer Apparatur überprüft, in welcher die Lösungen aus einem Vorratsbehälter über eine Rohrleitung und eine freie Fallstrecke von 30 cm in diesen zurückgepumpt wurden. Durch das Umpumpen bildete sich auf der Oberfläche der Lösungen Schaum, dessen Volumen nach einer Umpumpzeit von 5 Minuten gemessen wurde.The foaming behavior of the cold bleaching solutions according to Example 4, in which the products according to Examples 1, 2 and 3 and, for comparison, 2-ethylhexyl sulfate Na salt, a known, alkali-stable wetting agent, were present as wetting agents, were checked in an apparatus at 20 ° C. in which the solutions were pumped back out of a storage container via a pipeline and a free fall distance of 30 cm. By pumping around, foam formed on the surface of the solutions, the volume of which was measured after a pumping time of 5 minutes.
Für die Kaltbleichlösungen mit den Netzmitteln gemäß Beispiel 1 - 3 wurden folgende Schaumwerte (in % der Schaummenge der Vergleichslösung, die als Netzmittel 2-Ethylhexylsulfat-Na-Salz enthielt) erhalten:
- Netzmittel Beispiel 1 : 40 %
- Netzmittel Beispiel 2 : 0 % (schaumfrei)
- Netzmittel Beispiel 3 : 45 %.
- Wetting agent example 1: 40%
- Wetting agent example 2: 0% (foam-free)
- Wetting agent Example 3: 45%.
6. Weitere Anwendungsbeispiele:6. Further application examples:
6.1 Alkalische Abkochung
6.3 Carbonisier-Lösung (zur Strang- und Breit-Carbonisierung von Wolle)
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT85111229T ATE42331T1 (en) | 1984-09-13 | 1985-09-05 | USE OF ETHERSULFONATES AS LOW-FOAMING WETTING AGENT IN AQUEOUS, ACIDIC AND ALKALINE TECHNICAL TREATMENT AGENTS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843433593 DE3433593A1 (en) | 1984-09-13 | 1984-09-13 | USE OF ETHERSULPHONATES AS LOW-FOAM WETSING AGENTS IN AQUEOUS, ACID AND ALKALINE TECHNICAL TREATMENT AGENTS |
| DE3433593 | 1984-09-13 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0174610A2 EP0174610A2 (en) | 1986-03-19 |
| EP0174610A3 EP0174610A3 (en) | 1987-05-27 |
| EP0174610B1 true EP0174610B1 (en) | 1989-04-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP85111229A Expired EP0174610B1 (en) | 1984-09-13 | 1985-09-05 | Use of ether sulfonates as low-foaming wetting agents in aqueous, acid and alcaline technical treating compositions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4612142A (en) |
| EP (1) | EP0174610B1 (en) |
| AT (1) | ATE42331T1 (en) |
| DE (2) | DE3433593A1 (en) |
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| US4720492A (en) * | 1981-01-19 | 1988-01-19 | Petrolite Corporation | Quaternary ammonium derivatives of 1,4-thiazine sulfonic acids |
| DE3435841A1 (en) * | 1984-09-29 | 1986-04-17 | Henkel KGaA, 4000 Düsseldorf | USE OF ETHERSULPHONATES AS ANTISTATICS |
| DE3633421C1 (en) * | 1986-10-01 | 1987-07-23 | Goldschmidt Ag Th | Polyoxyalkylene ethers containing hydroxyl and sulfonate groups and their use in the production of dispersible polyurethanes |
| FI75918C (en) * | 1986-10-08 | 1988-08-08 | Safematic Ltd Oy | Mechanical seals |
| DE3725030A1 (en) * | 1987-07-29 | 1989-02-09 | Henkel Kgaa | SURFACE ACTIVE HYDROXYSULFONATE |
| JP2672385B2 (en) * | 1988-06-20 | 1997-11-05 | ピーピージー・インダストリーズ・インコーポレイテッド | Polymerizable surfactant |
| US5296627A (en) * | 1988-06-20 | 1994-03-22 | Ppg Industries, Inc. | Ethylenically unsaturated poly(alkyleneoxy) surfactants |
| US5075042A (en) * | 1989-05-01 | 1991-12-24 | Ppg Industries, Inc. | Surfactant blend containing an alkyl poly(ethyleneoxy)sulfonate to reduce dermal irritation |
| US5269850A (en) * | 1989-12-20 | 1993-12-14 | Hughes Aircraft Company | Method of removing organic flux using peroxide composition |
| EP0458948B1 (en) * | 1989-12-20 | 1994-08-31 | Hughes Aircraft Company | Peroxide composition for removing flux residue and method of using same |
| US5196134A (en) * | 1989-12-20 | 1993-03-23 | Hughes Aircraft Company | Peroxide composition for removing organic contaminants and method of using same |
| DE4004883A1 (en) * | 1990-02-16 | 1991-08-22 | Basf Ag | New vinyl-polyether alcohol derivs. - useful as surfactants and intermediates for polyether sulphonate(s), prepd. by reacting polyether alcohol with vinyl oxirane |
| US5206286A (en) * | 1990-04-02 | 1993-04-27 | Ppg Industries, Inc. | Aqueous emulsion polymers prepared with crosslinkable non-ionic surfactants |
| US5244960A (en) * | 1990-04-02 | 1993-09-14 | Ppg Industries, Inc. | Thermosetting waterborne coating compositions prepared from aqueous emulsion polymers |
| US5138095A (en) * | 1990-10-09 | 1992-08-11 | Texaco Chemical Company | Bisulfite addition products of ketone-terminated polyoxyalkylene compounds |
| US5110696A (en) * | 1990-11-09 | 1992-05-05 | Bell Communications Research | Rechargeable lithiated thin film intercalation electrode battery |
| ES2182880T3 (en) * | 1994-08-11 | 2003-03-16 | Ciba Sc Holding Ag | COMPOSITIONS OF MULTIFUNCTIONAL TEXTILE AGENTS. |
| FR2736936B1 (en) * | 1995-07-19 | 1997-08-14 | Air Liquide | DEGREASING PROCESS BASED ON HYDROGEN PEROXIDE AND APPLICATIONS TO METAL ARTICLES |
| DE19631150B4 (en) * | 1996-08-01 | 2007-04-19 | Süd-Chemie AG | Process for the removal of printing inks (deinking) of cellulosic print substrates |
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| US2062958A (en) * | 1931-05-16 | 1936-12-01 | Ether compounds | |
| US3197333A (en) * | 1960-08-30 | 1965-07-27 | Berol Aktiebolag | Processes of treating textile fibres before forming the same into a yarn |
| BE731492A (en) * | 1968-05-25 | 1969-09-15 | ||
| US3592796A (en) * | 1969-03-10 | 1971-07-13 | Celanese Corp | Linear polyester polymers containing alkali metal salts of sulfonated aliphatic compounds |
| US3639291A (en) * | 1969-08-25 | 1972-02-01 | Monsanto Co | Surfactant composition and liquid detergent formulations containing same |
| BE792145A (en) * | 1971-12-02 | 1973-05-30 | Bayer Ag | ACRYLONITRILE POLYMERS HAVING REDUCED SURFACE RESISTANCE AND THEIR PREPARATION PROCESS |
| CA1075453A (en) * | 1976-06-01 | 1980-04-15 | Melvin E. Tuvell | Oil recovery method and alkyl alkoxy propio sulfonate surfactants |
| GB1566770A (en) * | 1977-12-28 | 1980-05-08 | Kuraray Co | Etherification of polyocyalkylene compounds |
| JPS5950200B2 (en) * | 1978-02-17 | 1984-12-06 | ライオン株式会社 | Improved liquid cleaning composition |
| US4468335A (en) * | 1981-04-30 | 1984-08-28 | Mobil Oil Corporation | Branched alkylpolyethoxypropane sulfonates and their use in enhanced oil recovery |
-
1984
- 1984-09-13 DE DE19843433593 patent/DE3433593A1/en not_active Withdrawn
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1985
- 1985-09-05 US US06/772,827 patent/US4612142A/en not_active Expired - Fee Related
- 1985-09-05 DE DE8585111229T patent/DE3569569D1/en not_active Expired
- 1985-09-05 EP EP85111229A patent/EP0174610B1/en not_active Expired
- 1985-09-05 AT AT85111229T patent/ATE42331T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
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| EP0174610A2 (en) | 1986-03-19 |
| US4612142A (en) | 1986-09-16 |
| ATE42331T1 (en) | 1989-05-15 |
| DE3569569D1 (en) | 1989-05-24 |
| EP0174610A3 (en) | 1987-05-27 |
| DE3433593A1 (en) | 1986-03-20 |
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