EP0326795B1 - Utilisation d'éthers polyglycoliques comme agents antimoussants pour détergents - Google Patents

Utilisation d'éthers polyglycoliques comme agents antimoussants pour détergents Download PDF

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Publication number
EP0326795B1
EP0326795B1 EP89100009A EP89100009A EP0326795B1 EP 0326795 B1 EP0326795 B1 EP 0326795B1 EP 89100009 A EP89100009 A EP 89100009A EP 89100009 A EP89100009 A EP 89100009A EP 0326795 B1 EP0326795 B1 EP 0326795B1
Authority
EP
European Patent Office
Prior art keywords
foam
polyethylene glycol
radical
polyglycol ethers
glycol ethers
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 - Lifetime
Application number
EP89100009A
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German (de)
English (en)
Other versions
EP0326795A3 (en
EP0326795A2 (fr
Inventor
Karl Heinz Dr. Schmid
Alfred Dr. Meffert
Gilbert Dr. Schenker
Adolf Asbeck
Rolf Scharf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0326795A2 publication Critical patent/EP0326795A2/fr
Publication of EP0326795A3 publication Critical patent/EP0326795A3/de
Application granted granted Critical
Publication of EP0326795B1 publication Critical patent/EP0326795B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the invention relates to the use of selected end group-sealed polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents.
  • the invention aims to provide tools of the type mentioned which combine high effectiveness with physiological harmlessness and biodegradability.
  • the new auxiliaries of the invention should in particular also be suitable for effectively suppressing undesirable foam formation in the case of strongly foam-generating cleaning processes, for example spray cleaning, in the range of low temperatures, in particular in the range of room temperature or only slightly elevated temperatures.
  • Aqueous cleaning agents intended for use in trade and industry in particular those for cleaning metal, glass and ceramic surfaces, generally contain substances which are able to counteract undesirable foam development.
  • foam-suppressing additives is due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents.
  • anti-foaming agents may also be necessary due to the fact that the cleaning agents themselves Contain components that give rise to undesirable foaming under the specified working conditions.
  • anionic surfactants widely used in cleaning agents.
  • Addition products of alkylene oxides with organic compounds with reactive hydrogen atoms in the molecule have long been used as foam-suppressing additives.
  • addition products of propylene oxide onto aliphatic polyalcohols - see, for example, DE-PS 1 280 455 and DE-PS 1 621 592 - and onto aliphatic polyamines - compare, for example, DE-PS 1 289 597 and DE-PS 1 621 593 - and addition products of ethylene oxide and propylene oxide to aliphatic polyamines, especially ethylenediamine - compare DE-PS 1 944 569 - proven in practice.
  • these alkylene oxide addition products also have the alkali stability which is usually required for use in commercial and industrial cleaning agents.
  • the compounds in this class are not sufficiently biodegradable to meet the applicable legal requirements.
  • the European patent application EP-A-0 322 781 relates to a process for the preparation of a large number of mixed ethers which have a linear or branched C1-C20alkyl radical (R1), hydrogen or a linear or branched, aliphatic, araliphatic or aromatic hydrocarbon radical with 0 to Have 19 carbon atoms (R2) and 2 to 50 ethylene glycol and 0 to 10 propylene glycol units.
  • R1-C20alkyl radical R1
  • R2 linear or branched, aliphatic, araliphatic or aromatic hydrocarbon radical with 0 to Have 19 carbon atoms (R2) and 2 to 50 ethylene glycol and 0 to 10 propylene glycol units.
  • R1-C20alkyl radical R1
  • R2 linear or branched, aliphatic, araliphatic or aromatic hydrocarbon radical with 0 to Have 19 carbon atoms (R2) and 2 to 50 ethylene glycol and 0 to 10 propylene glycol units.
  • German patent application DE-A 25 56 544 relates to machine dishwashing detergents containing mixed ethers in which R1 for linear or branched alkyl or alkenyl radicals having 6 to 22 carbon atoms, R2 for a tert-butyl radical and n for 5 to 50 ethylene glycol or Propylene glycol units.
  • mixed ethers are considered to be particularly advantageous in which R 1 is a linear alkyl radical having 8 to 14 carbon atoms.
  • US Pat. No. 3,684,723 relates to detergents containing anionic surfactants, builder salts, soaps and foam-regulating nonionic surfactants of the mixed ether type, which have a very low HLB value in the range from 1 to 4.
  • the teaching of the present invention is based on the surprising finding that even more effective auxiliaries of the type concerned here can be obtained by slightly varying the structure of the last-mentioned end group-sealed fatty alcohol polyethylene glycol ethers.
  • foam-suppressing additives are often to be carried out at low temperatures, for example in order to carry out an energy-saving pre-cleaning.
  • Conventional, foam-suppressing additives are often characterized by the fact that they are very effective in combating foam in the temperature range of approximately 50 ° C. and above, but their use at temperatures of approximately 20 ° C. leads to comparatively weaker foam damping.
  • the additives according to the invention described below develop particular effectiveness precisely at lower temperatures and also exhibit this property when they are blended with structurally similar, known components.
  • the carbon number of this radical is increased compared to the radicals described above, and is at least 20 carbon atoms.
  • Fatty alcohols of natural origin of this type can be obtained in a manner known per se by hydrogenating the upper sections of natural fatty acid mixtures or the methyl esters obtained therefrom.
  • the class of Guerbet alcohols is affected by the invention.
  • alcohols of this type are formed by the condensation of fatty alcohols with a lower carbon number in the presence of alkali, for example potassium hydroxide or potassium alcoholate.
  • the reaction takes place, for example, at temperatures of 200 to 300 ° C and leads to branched Guerbet alcohols, which branch in the 2-position to the hydroxyl group.
  • Selected fatty alcohols or also mixtures of different fatty alcohols can be used for the synthesis; the resulting alcohol mixture with a higher carbon number is of correspondingly complex composition.
  • 2-octyldodecanol-1 and 2-decyl-tetradecanol-1 and their mixtures can be used as the starting material for the preparation of the polyglycol ethers of the formula (I).
  • the end group-capped fatty alcohol polyglycol ethers of the formula (I) are produced in accordance with the specifications of DE-OS 33 15 951.
  • the fatty alcohols of higher carbon number described above are advantageously reacted with ethylene oxide in a molar ratio of 1: 6 to 1:20 and then etherified the hydroxyl groups present in the reaction product obtained.
  • the reaction with ethylene oxide takes place under the known alkoxylation conditions, preferably in the presence of suitable alkaline catalysts.
  • the etherification of the free hydroxyl groups is preferably carried out under the known conditions of Williamson's ether synthesis with n-butyl halides. Accordingly, an example of such a final etherification is n-butyl iodide.
  • the invention is not limited to this.
  • alkyl halide and alkali for example from 10 to 50%, use the hydroxyl groups to be etherified.
  • the end group-capped polyglycol ethers of the formula (I) to be used according to the invention are used in an important embodiment in a mixture with structurally identical polyethylene glycol ethers, but in which the radical R 1 is a straight-chain or branched alkyl or alkenyl radical with 8 to 18 C atoms and n is one Number is from 7 to 12, and preferably from 8 to 10.
  • the invention thus provides to blend the newly described here, longer R1 long-chain polyglycol ethers with the foam-suppressing additives from DE-OS 33 15 951.
  • Mixing ratios of the two types in the range from 10 to 90 to 90 to 10% by weight, in particular in weight ratios from 60 to 40 to 40 to 60% by weight, are suitable for this embodiment.
  • end group-capped polyglycol ethers of the formula (I) which are now to be used according to the invention are also notable for high alkali and acid stability. Their foam-preventing effect in alkaline and neutral cleaning liquors is strengthened in the specified sense, moreover they also meet the legal requirements for biodegradability.
  • the cleaning agents in which the end-group-capped polyglycol ethers of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, and corrosion inhibitors and optionally also contain organic solvents.
  • Suitable wetting agents are nonionic surface-active compounds such as polyglycol ethers, which are obtained by adding ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic wetting agents such as alkali metal, amine and alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids.
  • the cleaning agents can, above all, alkali metal orthophosphates, polymer phosphates, silicates, borates, carbonates, polyacrylates and gluconates, as well as citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane-1,1-diphosphonic acid and ethylenediphosphonic acid, Contain phosphonoalkane polycarboxylic acids such as phosphonobutane tricarboxylic acid and alkali metal salts of these acids.
  • Highly alkaline cleaning agents especially those for bottle cleaning, contain considerable amounts of caustic alkali in the form of sodium and / or potassium hydroxide.
  • the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons as well as free alkylolamines.
  • cleaning agents are once understood to mean the aqueous solutions intended for direct application to the substrates to be cleaned, but the term cleaning agents also includes the concentrates and solid mixtures intended for the preparation of the application solutions.
  • the ready-to-use solutions can be acidic to strongly alkaline; they are generally used at temperatures of around 20 to 90 ° C.
  • the end group-sealed polyglycol ethers to be used according to the invention give effective effects even in low concentrations. They are preferably added to the cleaning agents in amounts such that their concentration in the ready-to-use solutions is approximately in the range from 50 to 500 ppm.
  • the foam attenuation of the additives selected according to the invention - and, in comparison, structurally similar additives but not within the scope of the invention - is determined using a test method which is described as follows: 300 ml of a 1% aqueous sodium hydroxide solution are heated to 20 or 65 ° C. in a double-walled 2 l measuring cylinder. The selected foam-suppressing additive is then added in the amounts specified below. With the help of a laboratory hose pump, the liquid is pumped around at a circulation rate of 4 l per minute. The test solution is sucked in approx.
  • test foamer a 1% aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate
  • test foamer 1 ml of a 1% aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate
  • a foam-suppressing additive A selected according to the invention is used in each case at 20 ° C. and 65 ° C. and its foam-suppressing effect is compared with an additive of the prior art (product B).
  • the foam-suppressing additives A and B are used in the test method specified in amounts of 0.1 ml of the pure substance.
  • the products A and B used are the following:
  • Table 1 ml test foamer Product A Product B 20 ° C 65 ° C 20 ° C 65 ° C 0 300 300 400 300 1 300 300 460 320 2nd 300 300 580 340 3rd 300 300 680 360 4th 340 300 800 400 5 380 300 1000 420 6 400 320 1400 440 7 420 400 1600 460 8th 420 460 1820 540 9 460 520 2000 780 10th 480 620 940 11 500 760 1240 12th 540 860 1760 13 580 1000 1880 14 600 1100 1940 15 660 1220 2000 16 720 1480 17th 800 1620 18th 1000 1760 19th 1300 1860 20th 1680 2000 21 2000
  • the test method specified 2 bottle cleaner formulations with the composition given in Table 2 below are examined.
  • the first of the two formulations contains only the previously mentioned product B of the prior art as a foam-suppressing additive.
  • the second recipe uses a mixture of the foam-suppressing additive A in admixture with the product B according to the prior art in the sense of the inventive action.
  • the bottle cleaner formulation according to the invention is also stable in storage as a liquid phase at temperatures below 0 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (3)

  1. Utilisation de polyéthylèneglycoléthers de la formule générale (I)



            R¹O-(CH₂CH₂O)n-R²   (I)



    dans laquelle R¹ représente un radical alkyle ramifié, comportant 20 à 24 atomes de carbone, R² correspond à un radical n-butyle et n est égal à des nombres de 6 à 12,
    comme additifs antimoussants pour les agents nettoyants à mousse freinée.
  2. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise les polyglycoléthers de la formule générale (I) en mélange avec des polyéthylèneglycoléthers de structure identique, dans lesquels R¹ représente toutefois un radical alkyle ou alcényle à chaîne droite ou ramifiée comportant 8 à 18 atomes de carbone, tandis que n est égal à des nombres de 7 à 12.
  3. Utilisation selon la revendication 1, caractérisée en ce que l'on utilise les polyéthylèneglycoléthers de la formule générale (I) en quantités telles que leur concentration représente environ 50 à 500 ppm dans les solutions prêtes à l'emploi.
EP89100009A 1988-01-11 1989-01-02 Utilisation d'éthers polyglycoliques comme agents antimoussants pour détergents Expired - Lifetime EP0326795B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3800493 1988-01-11
DE3800493A DE3800493A1 (de) 1988-01-11 1988-01-11 Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln, die insbesondere auch fuer die kaltreinigung geeignet sind

Publications (3)

Publication Number Publication Date
EP0326795A2 EP0326795A2 (fr) 1989-08-09
EP0326795A3 EP0326795A3 (en) 1990-08-22
EP0326795B1 true EP0326795B1 (fr) 1994-08-17

Family

ID=6345046

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89100009A Expired - Lifetime EP0326795B1 (fr) 1988-01-11 1989-01-02 Utilisation d'éthers polyglycoliques comme agents antimoussants pour détergents

Country Status (11)

Country Link
US (1) US4954283A (fr)
EP (1) EP0326795B1 (fr)
JP (1) JPH01215894A (fr)
AT (1) ATE110105T1 (fr)
BR (1) BR8900095A (fr)
CA (1) CA1327932C (fr)
DE (2) DE3800493A1 (fr)
DK (1) DK1589A (fr)
ES (1) ES2056957T3 (fr)
TR (1) TR24792A (fr)
ZA (1) ZA89197B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3928604A1 (de) * 1989-08-30 1991-03-07 Henkel Kgaa Verwendung ausgewaehlter gemische von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3928603A1 (de) * 1989-08-30 1991-03-07 Henkel Kgaa Antischaumittel fuer die gewerbliche reinigung, insbesondere fuer die flaschen- und cip-reinigung
DE3928600A1 (de) * 1989-08-30 1991-03-07 Henkel Kgaa Schaumdaempfende mehrstoffgemische mit tensidcharakter fuer die maschinelle geschirr- und flaschenreinigung
DE3928602A1 (de) * 1989-08-30 1991-03-07 Henkel Kgaa Alkalistabile und stark alkalisch formulierbare antischaummittel fuer die gewerbliche reinigung, insbesondere fuer die flaschen- und cip-reinigung
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
DE19959311A1 (de) 1999-12-09 2001-08-23 Henkel Ecolab Gmbh & Co Ohg Entschäumerzubereitung und deren Verwendung
WO2001094513A1 (fr) 2000-06-05 2001-12-13 S. C. Johnson & Son, Inc. Composition de nettoyage biocide
JP2011021266A (ja) * 2009-07-21 2011-02-03 Hakko Sangyo Kk Ｇｌ熱交換器用洗浄液とそれを用いたｇｌ熱交換器の洗浄方法
FR3000086B1 (fr) * 2012-12-20 2014-12-26 Coatex Sas Agent pour obtenir une composition aqueuse stable comprenant des particules en suspension
EP2968092B1 (fr) * 2013-03-15 2020-05-27 Croda, Inc. Ethers alkyliques d'alcools gras alcoxylés et produits les contenant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0322781A2 (fr) * 1987-12-30 1989-07-05 Henkel Kommanditgesellschaft auf Aktien Utilisation de polyglycoléthers à groupes terminaux bloqués

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK126125A (fr) * 1964-04-21
DE2556544A1 (de) * 1975-12-16 1977-06-30 Hoechst Ag Maschinengeschirrspuelmittel
DE3315951A1 (de) * 1983-05-02 1984-11-08 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3315952A1 (de) * 1983-05-02 1984-11-08 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3345349A1 (de) * 1983-12-15 1985-06-27 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
EP0197434B1 (fr) * 1985-04-03 1989-07-19 Henkel Kommanditgesellschaft auf Aktien Produits de rinçage pour le lavage mécanique de la vaisselle
DE3531212A1 (de) * 1985-08-31 1987-03-05 Henkel Kgaa Als entschaeumer verwendbare alkylenoxid-blockpolymere
US4836951A (en) * 1986-02-19 1989-06-06 Union Carbide Corporation Random polyether foam control agents
ATE68519T1 (de) * 1986-07-24 1991-11-15 Henkel Kgaa Schaumarme und/oder schaumdaempfende tensidgemische und ihre verwendung.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0322781A2 (fr) * 1987-12-30 1989-07-05 Henkel Kommanditgesellschaft auf Aktien Utilisation de polyglycoléthers à groupes terminaux bloqués

Also Published As

Publication number Publication date
US4954283A (en) 1990-09-04
DK1589A (da) 1989-07-12
CA1327932C (fr) 1994-03-22
EP0326795A3 (en) 1990-08-22
ZA89197B (en) 1990-08-29
DE58908196D1 (de) 1994-09-22
JPH01215894A (ja) 1989-08-29
BR8900095A (pt) 1989-09-05
ES2056957T3 (es) 1994-10-16
TR24792A (tr) 1992-03-10
DK1589D0 (da) 1989-01-03
ATE110105T1 (de) 1994-09-15
DE3800493A1 (de) 1989-07-20
EP0326795A2 (fr) 1989-08-09

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