EP0040713B1 - Use of mixed formals of alkylpolyglycol ethers as foam suppressing agents - Google Patents
Use of mixed formals of alkylpolyglycol ethers as foam suppressing agents Download PDFInfo
- Publication number
- EP0040713B1 EP0040713B1 EP81103326A EP81103326A EP0040713B1 EP 0040713 B1 EP0040713 B1 EP 0040713B1 EP 81103326 A EP81103326 A EP 81103326A EP 81103326 A EP81103326 A EP 81103326A EP 0040713 B1 EP0040713 B1 EP 0040713B1
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- EP
- European Patent Office
- Prior art keywords
- mixed formals
- agents
- alkali
- cleaning
- cleaning agents
- 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.)
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- 239000006260 foam Substances 0.000 title description 6
- 150000002170 ethers Chemical class 0.000 title 1
- 239000012459 cleaning agent Substances 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 239000000047 product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- -1 aliphatic alcohols Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 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 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 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
- 239000000126 substance Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 238000007869 Guerbet synthesis reaction Methods 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- 239000004435 Oxo alcohol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 150000002171 ethylene diamines Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 125000001421 myristyl 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])[H] 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 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 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000010457 zeolite Substances 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked 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
- 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
Definitions
- the invention relates to the use of certain alkyl polyglycol ether mixed formals as anti-foaming agents in strongly alkaline cleaning agents.
- Industrial cleaning agents in particular those used in automatic systems for cleaning rigid surfaces such as metal, ceramic or glass, and in particular for bottle cleaning, should have a low level of foaming with a strong cleaning power.
- the industrial cleaning agents of the type mentioned are mostly products which contain strongly alkaline substances, such as, in particular, alkali metal hydroxides or also alkali metal silicates or alkali metal orthophosphates, individually or in a mixture. In the case of such products, high demands are placed on the defoamers not only with regard to the anti-foam effect but also with regard to the storage stability in the corresponding solid products.
- the storage stability is not always sufficient in the case of packaging, for example in solid cleaning agents which contain a very high alkali content, in particular more than 50% and more caustic alkali. It is also desirable that the anti-foaming agents have good biodegradability, are alkali-stable, so that they do not lose their effectiveness during the cleaning process under constant exposure to temperature.
- alkyl polyglycol ether mixed formals of the formula are used as anti-foaming agents in alkaline cleaning agents in which R is a straight-chain or branched alkyl or alkylene radical having 8 to 22 carbon atoms, R 2 is a straight-chain or branched alkyl radical having 1 to 5 carbon atoms, m is a number from 2 to 30 and n is a number from 1 to 3.
- R 1 is an alkyl radical having 12 to 18 carbon atoms
- R 2 is an alkyl radical having 2 to 4 carbon atoms
- m is an integer from 7 to 15
- n is 1.
- the alkyl polyglycol ether mixed formals of the formula given above which are used can be prepared, for example by reaction of fatty alcohol ethoxylate of the formula with a di-alkyl glycol formal of the formula in the presence of a strong acid, such as sulfuric acid, by heating to temperatures of about 150 ° C. for several hours.
- R 1 and R 2 have the same meaning as given in formula I.
- Suitable starting products for the fatty alcohol ethoxylates are straight-chain or branched aliphatic alcohols, such as hexadecyl, tetradecyl and octadecyl alcohols, and the corresponding branched iso alcohols.
- Branched aliphatic alcohols which can be prepared by the so-called Guerbet reaction (dimerization of primary alcohols) can also be used.
- synthetic fatty alcohols or mixtures thereof, such as those obtained in oxo synthesis can also be used.
- the strongly alkaline cleaning agents (pH above 10) contain sodium or potassium hydroxide in particular.
- other strongly alkaline substances such as alkali carbonate and alkali orthophosphates, are used alone or in a mixture with alkali hydroxides.
- the alkaline cleaning agents can also contain the usual constituents, such as alkali silicates, alkali borates, polymeric alkali phosphates and / or complexing agents, such as phosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid or 2-phosphonobutane-1, 2,4-tricarboxylic acid.
- the molar ratio of Na 2 0 or K 2 0: P 2 0 5 can be 1: 1 to 2: 1.
- sodium tripolyphosphate is used.
- Finely divided synthetically produced, water-insoluble, bound water-containing aluminosilicates of the general formula can also be used as substitutes for the polyphosphates in the cat a cation of valence n, preferably sodium, exchangeable for calcium, x a number from 0.7 to 1.5, preferably 0.9 to 1.3, and y a number from 0.8 to 6, preferably of 1 , 3 to 4, which have a calcium binding capacity of 50 to 200, preferably 100 to 200 mg CaO / g of the anhydrous aluminosilicate can be used.
- aluminosilicates can be crystalline or X-ray amorphous.
- the crystalline sodium aluminosilicates are preferred, in particular the zeolites A and X.
- alkali stable anionic surfactants such as alkyl and / or aryl sulfonates, are also suitable as constituents.
- the amount of antifoam added is about 0.1 to 1 g / l, based on the solution used. The amount added depends on the desired antifoam effect and the impurities or bath concentration of the cleaning agent.
- the cleaning agents are generally used with a bath concentration of 0.2 to 10% depending on the intended use.
- the application temperature is generally between 40 and 90 ° C.
- the cleaning agents prepared in this way were each stored in closed polypropylene containers at 45 ° C. and the defoamer tests were carried out at intervals of 2 weeks each.
- the free fall cycle method consists in heating 500 ml of cleaning solution to 60 ° C in a jacketed 2-1 measuring cylinder.
- this solution is brought into constant circulation at a throughput capacity of 4 l / minute so that the solution is sucked from the bottom of the measuring cylinder with a glass tube and in the second via a second glass tube with the 2000 ml mark of the measuring cylinder free fall is returned.
- a constant initial foam volume (for example 2,000 ml) is established.
- composition of the cleaning agents specified under a was used. Comparable results were obtained with the cleaning agents of composition b.
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
Gegenstand der Erfindung ist die Verwendung bestimmter Alkylpolyglykolethermischformale als Antischaummittel in stark alkalischen Reinigungsmitteln. Industrielle Reinigungsmittel, insbesondere solche, die in automatischen Anlagen zur Reinigung von starren Oberflächen wie Metall, Keramik oder Glas sowie insbesondere zur Flaschenreinigung eingesetzt werden, sollen bei starker Reinigungskraft eine geringe Schaumentwicklung aufweisen. Bei den industriellen Reinigungsmitteln der genannten Art handelt es sich meist um Produkte, die stark alkalische Stoffe wie insbesondere Alkalihydroxide oder auch Alkalisilikate oder Alkaliorthophosphate einzeln oder im Gemisch enthalten. Bei derartigen Produkten werden an die Entschäumer nicht nur hinsichtlich der Antischaumwirkung sondern auch hinsichtlich der Lagerstabilität in den entsprechenden festen Produkten hohe Anforderungen gestellt.The invention relates to the use of certain alkyl polyglycol ether mixed formals as anti-foaming agents in strongly alkaline cleaning agents. Industrial cleaning agents, in particular those used in automatic systems for cleaning rigid surfaces such as metal, ceramic or glass, and in particular for bottle cleaning, should have a low level of foaming with a strong cleaning power. The industrial cleaning agents of the type mentioned are mostly products which contain strongly alkaline substances, such as, in particular, alkali metal hydroxides or also alkali metal silicates or alkali metal orthophosphates, individually or in a mixture. In the case of such products, high demands are placed on the defoamers not only with regard to the anti-foam effect but also with regard to the storage stability in the corresponding solid products.
Es ist bekannt, sowohl in festen als auch in flüssigen Produkten für die industrielle Reinigung, Anlagerungsprodukte von Ethylenoxid und Propylenoxid an Verbindungen wie Fettalkohole, Fettsäuren, Polyglycerin und Ethylendiamine als Entschäumer einzusetzen.It is known to use both in solid and in liquid products for industrial cleaning, adducts of ethylene oxide and propylene oxide with compounds such as fatty alcohols, fatty acids, polyglycerol and ethylenediamines as defoamers.
Es hat sich jedoch gezeigt, daß bei der Konfektionierung beispielsweise in festen Reinigungsmitteln, die einen sehr hohen Alkaligehalt, insbesondere an über 50 % und mehr Ätzalkali enthalten die Lagerstabilität nicht immer hinreichend ist. Auch ist es erwünscht, daß die Antischaummittel eine gute biologische Abbaubarkeit besitzen, laugenstabil sind, indem sie während des Reinigungsprozesses unter andauernder Temperaturbelastung ihre Wirksamkeit nicht verlieren.However, it has been shown that the storage stability is not always sufficient in the case of packaging, for example in solid cleaning agents which contain a very high alkali content, in particular more than 50% and more caustic alkali. It is also desirable that the anti-foaming agents have good biodegradability, are alkali-stable, so that they do not lose their effectiveness during the cleaning process under constant exposure to temperature.
Aus der DE-A-2 523 588 ist es weiterhin bekannt, bestimmte Polyglykolethermischformale der dort angegebenen Formel herzustellen und in alkalischen Reinigungsmitteln als Antischaummittel zu verwenden. Diese sind jedoch mit den erfindungsgemäß verwendeten Produkten nicht identisch. Die dort beschriebenen nicht mit den erfindungsgemäß verwendeten Produkten identischen Polyglykolethermischformale sind zwar zum Teil biologisch abbaubar, aber sie genügen bezüglich der Alkalistabilität bei hohen Ansprüchen nicht. Es hat sich gezeigt, daß sie bei Reinigungsprozessen unter andauernder Temperaturbelastung oder bei längerer Lagerzeit ihre Wirkungverlieren.From DE-A-2 523 588 it is also known to produce certain polyglycol ether mixed formals of the formula given there and to use them as anti-foaming agents in alkaline cleaning agents. However, these are not identical to the products used according to the invention. The polyglycol ether mixed formals not described there which are identical to the products used according to the invention are partly biodegradable, but they are not sufficient in terms of alkali stability with high demands. It has been shown that they lose their effectiveness in cleaning processes under constant temperature stress or with a long storage period.
Es wurde nun gefunden, daß in besonderem Maße die Anforderungen an die Alkalistabilität und die Dispergierbarkeit und biologische Abbaubarkeit erfüllt werden, wenn man als Antischaummittel in alkalischen Reinigungsmitteln Alkylpolyglykolethermischformale der Formel
Insbesondere hat sich die Verwendung der Verbindungen der Formel I als geeignet erwiesen, in der R1 einen Alkylrest mit 12 bis 18 Kohlenstoffatomen, R2 einen Alkylrest mit 2 bis 4 Kohlenstoffatomen, m eine ganze Zahl von 7 bis 15 und n gleich 1 ist. Die zur Anwendung gelangenden Alkylpolyglykolethermischformale der oben angegebenen Formel können hergestellt werden, beispielsweise durch Umsetzung von Fettalkoholethoxilat der Formel
Als Ausgangsprodukte für die Fettalkoholethoxilate kommen gradkettige oder auch verzweigte aliphatische Alkohole, wie Hexadecyl-, Tetradecyl- und Octadecylalkohole sowie die entsprechenden verzweigten Isoalkohole in Betracht. Auch können als verzweigte aliphatische Alkohole solche verwendet werden, die durch die sogenannte Guerbet-Reaktion (Dimerisierung von primären Alkoholen) herstellbar sind. Es können jedoch auch synthetische Fettalkohole oder Gemische davon, wie sie bei der Oxosynthese anfallen, Anwendung finden.Suitable starting products for the fatty alcohol ethoxylates are straight-chain or branched aliphatic alcohols, such as hexadecyl, tetradecyl and octadecyl alcohols, and the corresponding branched iso alcohols. Branched aliphatic alcohols which can be prepared by the so-called Guerbet reaction (dimerization of primary alcohols) can also be used. However, synthetic fatty alcohols or mixtures thereof, such as those obtained in oxo synthesis, can also be used.
Die stark alkalischen Reinigungsmittel (pH-Wert über 10) enthalten insbesondere Natrium- oder Kaliumhydroxid. Es werden jedoch auch andere stark alkalisch reagierende Stoffe, wie Alkalicarbonat und Alkaliorthophosphate, allein oder im Gemisch mit Alkalihydroxiden, verwendet. Die alkalischen Reinigungsmittel können jedoch darüber hinaus auch die üblichen Bestandteile, wie Alkalisilikate, Alkaliborate, polymere Alkaliphosphate und/oder Komplexbildner, wie Phosphonsäuren, insbesondere 1-Hydroxy-ethan-1,1-diphosphonsäure, Aminotrimethylenphosphonsäure oder 2-Phosphono-butan-1,2,4-tricarbonsäure, enthalten.The strongly alkaline cleaning agents (pH above 10) contain sodium or potassium hydroxide in particular. However, other strongly alkaline substances, such as alkali carbonate and alkali orthophosphates, are used alone or in a mixture with alkali hydroxides. However, the alkaline cleaning agents can also contain the usual constituents, such as alkali silicates, alkali borates, polymeric alkali phosphates and / or complexing agents, such as phosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid or 2-phosphonobutane-1, 2,4-tricarboxylic acid.
Bei den polymeren Phosphaten kann das Molverhältnis von Na20 oder K20 : P205 1 : 1 bis 2 : 1 betragen. Insbesondere wird Natriumtripolyphosphat verwendet.In the polymeric phosphates, the molar ratio of Na 2 0 or K 2 0: P 2 0 5 can be 1: 1 to 2: 1. In particular, sodium tripolyphosphate is used.
Als Substitute für die Polyphosphate können auch feinteilige synthetisch hergestellte, wasserunlösliche, gebundenes Wasser enthaltende Aluminosilikate der allgemeinen Formel
Ferner kommen in besonderen Fällen Alkali stabile anionische Tenside, wie Alkyl- und/oder Arylsulfonate, als Bestandteile in Betracht.In special cases, alkali stable anionic surfactants, such as alkyl and / or aryl sulfonates, are also suitable as constituents.
Die zugesetzte Menge an Antischaummitel beträgt etwa 0,1 bis 1 g/I, bezogen auf die zur Anwendung gelangende Lösung. Die Zusatzmenge richtet sich nach der gewünschten Antischaumwirkung und nach den Verunreinigungen beziehungsweise der Badkonzentration des Reinigungsmittels. Die Reinigungsmittel werden im allgemeinen mit einer Badkonzentration von 0,2 bis 10 % je nach dem Verwendungszweck eingesetzt. Die Anwendungstemperatur liegt im allgemeinen zwischen 40 und 90 °C.The amount of antifoam added is about 0.1 to 1 g / l, based on the solution used. The amount added depends on the desired antifoam effect and the impurities or bath concentration of the cleaning agent. The cleaning agents are generally used with a bath concentration of 0.2 to 10% depending on the intended use. The application temperature is generally between 40 and 90 ° C.
Durch intensives Vermischen der Bestandteile wurden verschiedene Reinigungsmittel, wie sie insbesondere für die Flaschenreinigung üblich sind, hergestellt. Diese hatten die folgende Zusammensetzung :
- a) 75 % technisches Natriumhydroxid in Schuppenform
- 6 % Natriumtripolyphosphat
- 15,5% Natriummetasilikat . 5 Hydrat
sowie jeweils- 3,5 % des zu prüfenden Entschäumers
- b) 15 % Natriumhydroxid
- 25 % Natriumtripolyphosphat
- 25 % Natriummetasilikat
- 32% Natriumcarbonat
- 3 % des zu prüfenden Entschäumers
- a) 75% technical sodium hydroxide in the form of flakes
- 6% sodium tripolyphosphate
- 15.5% sodium metasilicate. 5 hydrate
as well as each- 3.5% of the defoamer to be tested
- b) 15% sodium hydroxide
- 25% sodium tripolyphosphate
- 25% sodium metasilicate
- 32% sodium carbonate
- 3% of the defoamer to be tested
Die so hergestellten Reinigungsmittel wurden jeweils bei 45 °C in verschlossenen Behältern aus Polypropylen gelagert und die Entschäumerteste in Zeitabständen von je 2 Wochen durchgeführt.The cleaning agents prepared in this way were each stored in closed polypropylene containers at 45 ° C. and the defoamer tests were carried out at intervals of 2 weeks each.
Zur Prüfung wurden je 1,5% der Reinigermischung in jeweils eine 0,025 %ige Schmierseifenbeziehungsweise 0,025 %ige Alkylbenzolsulfonat-Lösung eingeführt. Je 500 ml dieser Lösungen wurden anschließend nach der Freifallkreislaufmethode geprüft und die Schaumwerte bestimmt.For testing, 1.5% of the detergent mixture was introduced into a 0.025% grease soap or 0.025% alkylbenzenesulfonate solution. Each 500 ml of these solutions were then tested using the free-fall cycle method and the foam values were determined.
Die Freifallkreislaufmethode besteht darin, daß 500 ml Reinigerlösung in einem ummantelten 2-1-Meßzylinder auf 60 °C erhitzt werden.The free fall cycle method consists in heating 500 ml of cleaning solution to 60 ° C in a jacketed 2-1 measuring cylinder.
Mit Hilfe einer Pumpe wird diese Lösung bei einer Durchlaufkapazität von 4 I/Minute so in einen ständigen Umlauf gebracht, daß die Lösung mit einem Glasrohr vom Boden des Meßzylinders angesaugt und über ein zweites, mit der 2000-ml-Marke des Meßzylinders abschließendes Glasrohr im freien Fall zurückgeführt wird. Nach kurzer Laufzeit stellt sich hierbei ein konstantes Ausgangsschaumvolumen (zum Beispiel 2 000 ml) ein.With the help of a pump, this solution is brought into constant circulation at a throughput capacity of 4 l / minute so that the solution is sucked from the bottom of the measuring cylinder with a glass tube and in the second via a second glass tube with the 2000 ml mark of the measuring cylinder free fall is returned. After a short running time, a constant initial foam volume (for example 2,000 ml) is established.
Die sich ergebenden Gesamtvolumina, Schaum und Lösung, wurden in Abständen von 1, 3, 5, 10, 20 und 30 Minuten abgelesen.The resulting total volumes, foam and solution, were read at 1, 3, 5, 10, 20 and 30 minute intervals.
Bei den Produkten, die nicht oder nur beschränkt nach einer mehrwöchigen Lagerzeit stabil sind, tritt entweder keine schaumdrückende Wirkung auf oder die Schaumdepression nimmt nach kurzer Zeit, zum Beispiel innerhalb 10 bis 30 Minuten, erheblich ab. Bei stabilen Produkten bleibt die Antischaumwirkung von Anfang an bis zum Ende der. Prüfzeit (30 Minuten) praktisch konstant. Bei instabilen Produkten erreicht der Schaum nach wenigen Minuten seine maximale Höhe, zum Beispiel 2 000 ml.For products that are not stable or only stable to a limited extent after a storage period of several weeks, either there is no foam-suppressing effect or the foam depression decreases considerably after a short time, for example within 10 to 30 minutes. In the case of stable products, the anti-foam effect remains from the beginning to the end of the. Test time (30 minutes) practically constant. In the case of unstable products, the foam reaches its maximum height after a few minutes, for example 2,000 ml.
Die nachstehende Tabelle gibt einen Überblick über die Stabilität und Entschäumerwirkung der erfindungsgemäßen Produkte im Vergleich mit ähnlichen Handelsprodukten.The table below gives an overview of the stability and defoaming action of the products according to the invention in comparison with similar commercial products.
Dabei wurde die unter a angegebene Zusammensetzung der Reinigungsmittel verwendet. Mit-den Reinigungsmitteln der Zusammensetzung b wurden vergleichbare Ergebnisse erhalten.The composition of the cleaning agents specified under a was used. Comparable results were obtained with the cleaning agents of composition b.
Ein Mittel zur Dampfstrahlreinigung von metallischen Oberflächen hatte folgende Zusammensetzung :
- 51 % Wasser
- 5% gesättigte Fettsäure (C8/C10)
- 8 % Mischformal von Fettalkohol C12/C18 + 9 EO mit Butylglycol
- 26% Kalilauge (38 %ig)
- 10% Kaliumpyrophosphat
- 51% water
- 5% saturated fatty acid (C 8 / C 10 )
- 8% mixed formal of fatty alcohol C 12 / C 18 + 9 EO with butyl glycol
- 26% potassium hydroxide solution (38%)
- 10% potassium pyrophosphate
Man erhält ein klares Mischprodukt mit extrem schwachem Schaumverhalten, welches als 1 %ige Lösung eingesetzt wird.A clear mixed product with extremely weak foaming behavior is obtained, which is used as a 1% solution.
Ein alkalisches Reinigungsgranulat zur Entfettung von Metalloberflächen bestehend aus folgender Zusammensetzung :
- 75% NaOH granuliert
- 19% Trinatriumphosphat
- 3 % Natrium-tripolyphosphat
- 2% Natrium-dodecylbenzolsulfonat
- 1 % Mischformal von Oxoalkohol C14/C15 + 11 EO mit Butylglycol
- 75% NaOH granulated
- 19% trisodium phosphate
- 3% sodium tripolyphosphate
- 2% sodium dodecylbenzenesulfonate
- 1% mixed formal of oxo alcohol C 14 / C 15 + 11 EO with butyl glycol
Eine 5 %ige Lösung dieses Reinigers zeigt bei 60 bis 90 °C ein extrem schwaches Schaumverhalten und sehr gute Entfettungswirkung.A 5% solution of this cleaner shows an extremely weak foaming behavior and very good degreasing effect at 60 to 90 ° C.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT81103326T ATE5328T1 (en) | 1980-05-12 | 1981-05-02 | USE OF ALKYLPOLYGLYCOLE THERMAL FORMALS FOR ANTIFOAM. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803018149 DE3018149A1 (en) | 1980-05-12 | 1980-05-12 | USE OF ALKYLPOLYGLYKOLETHERMAL FORMAL FOR FOAM PREVENTION |
DE3018149 | 1980-05-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0040713A1 EP0040713A1 (en) | 1981-12-02 |
EP0040713B1 true EP0040713B1 (en) | 1983-11-16 |
Family
ID=6102215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP81103326A Expired EP0040713B1 (en) | 1980-05-12 | 1981-05-02 | Use of mixed formals of alkylpolyglycol ethers as foam suppressing agents |
Country Status (15)
Country | Link |
---|---|
US (1) | US4364777A (en) |
EP (1) | EP0040713B1 (en) |
JP (1) | JPS5715806A (en) |
AR (1) | AR223116A1 (en) |
AT (1) | ATE5328T1 (en) |
BR (1) | BR8102900A (en) |
CA (1) | CA1157736A (en) |
DE (2) | DE3018149A1 (en) |
DK (1) | DK166781A (en) |
ES (1) | ES502104A0 (en) |
FI (1) | FI66900C (en) |
MX (1) | MX7094E (en) |
NO (1) | NO151244C (en) |
TR (1) | TR21341A (en) |
ZA (1) | ZA813128B (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3048641A1 (en) * | 1980-12-23 | 1982-07-15 | Hoechst Ag, 6000 Frankfurt | "TENSIDE-CONTAINING MIXTURE FOR CLEANING HARD SURFACES" |
US4394273A (en) * | 1981-12-10 | 1983-07-19 | Nl Industries, Inc. | Defoamers for aqueous liquids containing soluble zinc salts |
DE3315951A1 (en) * | 1983-05-02 | 1984-11-08 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
DE3338923C1 (en) * | 1983-10-27 | 1985-02-21 | Th. Goldschmidt Ag, 4300 Essen | Use of copolymers of polyoxyalkylene ethers of allyl and / or methallyl alcohol and vinyl esters as demulsifiers for crude oil containing water |
DE3345349A1 (en) * | 1983-12-15 | 1985-06-27 | Henkel KGaA, 4000 Düsseldorf | USE OF POLYGLYCOLETHERS AS FOAM-PRESSING ADDITIVES IN LOW-FOAM CLEANERS |
DE3418523A1 (en) * | 1984-05-18 | 1985-11-21 | Basf Ag, 6700 Ludwigshafen | END-GROUP LOCKED FATTY ALCOHOL ALCOXYLATES FOR INDUSTRIAL CLEANING PROCESSES, ESPECIALLY FOR BOTTLE WASHING AND FOR METAL CLEANING |
DE3641447A1 (en) * | 1986-12-04 | 1988-06-09 | Henkel Kgaa | TENSIDE MIXTURES AS COLLECTORS FOR THE FLOTATION OF NON-SULFIDIC ORES |
SE462599B (en) * | 1987-04-06 | 1990-07-23 | Berol Kemi Ab | PRE-PACKING THAT PREVENTS FOAM PREPARATION, PREPARING SUCH PRE-PACKAGING AND ANTI-DUMPING AGENTS |
KR960002629B1 (en) * | 1987-06-25 | 1996-02-24 | 가오 가부시끼가이샤 | Additive for alkaline detergent and the composition containing the same |
GB8906820D0 (en) * | 1989-03-23 | 1989-05-10 | Ici Plc | Novel chemical compounds and their use as low foam surfactants and antifoamingagents |
US5068444A (en) * | 1989-10-31 | 1991-11-26 | Texaco Chemical Company | Tetramines by amination of dialdehyde glycol adducts |
CH684933A5 (en) * | 1992-04-01 | 1995-02-15 | Ciba Geigy Ag | Low foaming surfactants. |
US5399239A (en) * | 1992-12-18 | 1995-03-21 | Ceridian Corporation | Method of fabricating conductive structures on substrates |
US11051510B2 (en) | 2014-01-30 | 2021-07-06 | Basf Se | Asymmetric formales and acetales as adjuvants for crop protection |
CN109607648A (en) * | 2018-12-19 | 2019-04-12 | 宁波瑞凌新能源科技有限公司 | A kind of radiation refrigeration formula desalination plant |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2905719A (en) * | 1959-09-22 | Cxhzo | ||
CA656004A (en) * | 1963-01-15 | A. Bixler Dean | Detergent composition | |
US2905718A (en) * | 1957-09-24 | 1959-09-22 | Rohm & Haas | Surface-active acetals and formals |
US2905720A (en) * | 1957-09-24 | 1959-09-22 | Rohm & Haas | Surface-active acetals and formals |
US3048548A (en) * | 1959-05-26 | 1962-08-07 | Economics Lab | Defoaming detergent composition |
NL128174C (en) * | 1962-02-28 | |||
DE1225800B (en) * | 1964-01-11 | 1966-09-29 | Henkel & Cie Gmbh | Low-foaming detergents and cleaning agents |
DE2523588C2 (en) | 1975-05-28 | 1983-11-10 | Hoechst Ag, 6230 Frankfurt | Polyglycol ether mixed formals and their use as caustic alkali-resistant wetting agents, detergents and cleaning agents |
US4070298A (en) * | 1976-07-26 | 1978-01-24 | Olin Corporation | Defoaming detergent additive |
DE2812443C2 (en) | 1978-03-22 | 1982-12-02 | Hoechst Ag, 6000 Frankfurt | Polyglycol ether thermal formals and their use as fiber finishes |
-
1980
- 1980-05-12 DE DE19803018149 patent/DE3018149A1/en not_active Withdrawn
-
1981
- 1981-04-13 DK DK166781A patent/DK166781A/en not_active IP Right Cessation
- 1981-04-13 FI FI811131A patent/FI66900C/en not_active IP Right Cessation
- 1981-04-13 NO NO811284A patent/NO151244C/en unknown
- 1981-04-27 US US06/257,855 patent/US4364777A/en not_active Expired - Fee Related
- 1981-04-30 CA CA000376613A patent/CA1157736A/en not_active Expired
- 1981-05-02 EP EP81103326A patent/EP0040713B1/en not_active Expired
- 1981-05-02 AT AT81103326T patent/ATE5328T1/en not_active IP Right Cessation
- 1981-05-02 DE DE8181103326T patent/DE3161415D1/en not_active Expired
- 1981-05-08 MX MX819442U patent/MX7094E/en unknown
- 1981-05-11 BR BR8102900A patent/BR8102900A/en unknown
- 1981-05-11 ZA ZA00813128A patent/ZA813128B/en unknown
- 1981-05-11 ES ES502104A patent/ES502104A0/en active Granted
- 1981-05-12 AR AR285290A patent/AR223116A1/en active
- 1981-05-12 JP JP7287381A patent/JPS5715806A/en active Pending
- 1981-05-12 TR TR21341A patent/TR21341A/en unknown
Also Published As
Publication number | Publication date |
---|---|
MX7094E (en) | 1987-06-08 |
ES8300018A1 (en) | 1982-10-01 |
FI66900C (en) | 1984-12-10 |
DK166781A (en) | 1981-11-13 |
NO811284L (en) | 1981-11-13 |
JPS5715806A (en) | 1982-01-27 |
US4364777A (en) | 1982-12-21 |
ES502104A0 (en) | 1982-10-01 |
DE3161415D1 (en) | 1983-12-22 |
ZA813128B (en) | 1982-05-26 |
EP0040713A1 (en) | 1981-12-02 |
FI811131L (en) | 1981-11-13 |
DE3018149A1 (en) | 1981-11-19 |
NO151244C (en) | 1985-03-06 |
AR223116A1 (en) | 1981-07-15 |
BR8102900A (en) | 1982-02-02 |
ATE5328T1 (en) | 1983-12-15 |
TR21341A (en) | 1984-04-16 |
FI66900B (en) | 1984-08-31 |
CA1157736A (en) | 1983-11-29 |
NO151244B (en) | 1984-11-26 |
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