EP0497790B1 - Utilisation d'alkylpolyethyleneglycol-ethers comme additifs antimousse pour des produits de nettoyage - Google Patents

Utilisation d'alkylpolyethyleneglycol-ethers comme additifs antimousse pour des produits de nettoyage Download PDF

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Publication number
EP0497790B1
EP0497790B1 EP90914909A EP90914909A EP0497790B1 EP 0497790 B1 EP0497790 B1 EP 0497790B1 EP 90914909 A EP90914909 A EP 90914909A EP 90914909 A EP90914909 A EP 90914909A EP 0497790 B1 EP0497790 B1 EP 0497790B1
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Prior art keywords
foam
hydrotalcites
alkyl
use according
formula
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German (de)
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EP0497790A1 (fr
Inventor
Jürgen Geke
Gilbert Schenker
Hans-Christian Raths
Raina Hirthe
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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 end-capped alkyl polyethylene glycol ethers as foam-suppressing additives in low-foam cleaning agents.
  • Aqueous cleaning agents intended for use in trade and industry in particular those for cleaning metal, glass, ceramic and plastic 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 constituents which give rise to undesirable foaming under the given working conditions, for example anionic surfactants or nonionic surfactants foaming at working temperature.
  • these compounds show no anti-foaming effect below 15 ° C.
  • the foam blanket (foam height) when testing the anti-foam effect was ⁇ 1 cm at temperatures ⁇ 15 ° C.
  • the alkyl polyethylene glycols not yet end-capped have a broad homolog distribution with respect to n. This homolog distribution remains unchanged in the subsequent etherification reaction step.
  • a foaming effect at even lower temperatures is desirable.
  • these additives have the disadvantage of phase separation, which starts even with small fractions, in terms of the amounts that can be mixed into the formulations.
  • the object of the present invention was therefore to find foam-suppressing substances whose application properties are superior to those of the prior art at temperatures below 15 ° C. and at the same time have the required biodegradability.
  • the additions with regard to the ability to be assembled should exceed the additions of the prior art.
  • alkyl polyethylene glycol ethers which have a narrow homolog distribution with respect to the number of (CH2CH2O) units contained in the molecule, down to temperatures of 5 ° C have an even better foam inhibition and a much better packaging, which in larger possible ready-to-use quantities is expressed.
  • a narrow homolog distribution was achieved by using calcined hydrotalcites as catalysts in the ethoxylation of the fatty alcohols.
  • Hydrotalcite is a natural mineral with the ideal formula Mg6Al2 (OH) 16CO3. 4 H2O, whose structure is derived from that of brucite (Mg (OH) 2). Brucite crystallizes in a layer structure with the metal ions in octahedral gaps between two layers of densely packed hydroxyl ions, with only every second layer of the octahedral gaps being occupied. In the hydrotalcite, some magnesium ions are replaced by aluminum ions, which gives the layer package a positive charge. This is compensated for by the anions, which are located in the intermediate layers together with zeolitic crystal water. The layer structure is evident in the X-ray powder diagram (ASTM card No. 14-191), which can be used for characterization.
  • Synthetically produced hydrotalcites are also known, e.g. in DE-PS 15 92 126, DE-OS 33 46 943, DE-OS 33 06 822 and EP-A 0 207 811 are described.
  • the Mg2+: Al3+ ratio can vary between about 1 and 5.
  • the ratio of OH ⁇ : CO32 ⁇ can fluctuate.
  • Natural and synthetic hydrotalcites can be represented by the general formula (II) Mg x Al (OH) y (CO3) z .
  • Natural or synthetic hydrotalcites continuously release water when heated or calcined. The drainage is at 200 ° C completely, whereby it could be proven by X-ray diffraction that the structure of the hydrotalcite is still preserved. The further increase in temperature leads to the breakdown of the structure with the elimination of hydroxyl groups (as water) and carbon dioxide. Natural and artificially produced hydrotalcites according to various processes, for example according to the above publications, show generally similar behavior in the calcination.
  • catalysts for polyalkoxylation include Calcium and strontium hydroxides, alkoxides and phenoxides (EP-A 0 092 256), calcium alkoxides (EP-A 0 091 146), barium hydroxide (EP-B-0 115 083), basic magnesium compounds, e.g. Alkoxides (EP-A-0 082 569), magnesium and calcium fatty acid salts (EP-A-0 085 167) have been used.
  • the aforementioned catalysts have i.a. the disadvantage that they are difficult to incorporate into the reaction system and / or are difficult to manufacture.
  • Other common polyalkoxylation catalysts are potassium hydroxide and sodium methylate.
  • the fatty alcohols each react with several molecules of ethylene oxide.
  • the calcined hydrotalcites used according to the invention also have the advantage that they can be easily incorporated into the ethoxylation reaction mixture and, because of their insolubility in the reaction mixture, can be separated off again by simple measures. However, they can also remain in the reaction mixture if their presence does not interfere with the further use of the reaction products.
  • Suitable fatty alcohols R 1 OH are all alcohols with a straight-chain, branched or cyclic alkyl radical or alkenyl radical with 6 to 18 carbon atoms, in particular n-hexanol, cyclohexanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n- Dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, n-octadec-9-en-1-ol (oleyl alcohol) as well as their isomers branched on the alkyl radical and their isomers OH groups on internal carbon atoms and oxo alcohols of the carbon atom number mentioned, individually or in a mixture. In the mixtures
  • the calcined hydrotalcites are added to the reaction mixtures in an amount of 0.1 to 2% by weight, based on the end product of the ethoxylation.
  • the calcined hydrotalcites to be used can be obtained from the natural or synthetic hydrotalcites by heating for several hours can be obtained at temperatures above 100 ° C. Calcination temperatures of 400 to 600 ° C. are particularly preferred.
  • the catalyst obtained in this way is added to the reaction mixture consisting of one of the fatty alcohols and ethylene oxide described above.
  • the molar ratio of fatty alcohol to ethylene oxide is preferably 1: 3.5 to 1: 5, particularly preferably 1: 4.5.
  • biodegradability of the end group-capped alkyl polyethylene glycol ethers of the general formula (I) to be used according to the invention corresponds to the statutory methods of determination RVO for detergent law.
  • the end-capped alkyl polyethylene glycol ethers of the formula (I) to be used according to the invention are notable for their alkali and acid stability.
  • the foam-preventing action at temperatures down to 5 ° C. in alkaline to weakly acidic cleaning liquors is superior to the known foam inhibitors.
  • the foam height is relatively low and is between 0 and 0.5 cm.
  • the cleaning agents in which the end-capped alkyl polyethylene glycol ethers (I) are used according to the invention can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, corrosion inhibitors and, if appropriate, also antimicrobial active substances and / or organic solvents.
  • the surfactants used are nonionic surface-active substances, such as polyglycol ethers, which are obtained by the addition of ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides, and anionic surfactants, such as alkali metal, amine and alkanolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids into consideration.
  • nonionic surface-active substances such as polyglycol ethers, which are obtained by the addition of ethylene oxide to alcohols, in particular fatty alcohols, alkylphenols, fatty amines and carboxamides
  • anionic surfactants such as alkali metal, amine and alkanolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids into consideration.
  • the cleaning agents can especially alkali metal orthophosphates, polyphosphates, silicates, borates, carbonates, polyacrylates and gluconates as well as citric acid, nitriloacetic acid, ethylenediaminetetraacetic acid, 1-hydroxyalkane-1,1-diphosphonic acid, amine tri and ethylenediaminetetra- (methylenephosphonic acid), phosphonoalkane polycarboxylic acids, e.g. Phosphonobutane tricarboxylic acid, and alkali metal salts and / or amine salts of these acids.
  • citric acid nitriloacetic acid
  • ethylenediaminetetraacetic acid 1-hydroxyalkane-1,1-diphosphonic acid
  • phosphonoalkane polycarboxylic acids e.g. Phosphonobutane tricarboxylic acid
  • the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons, and free alkanolamines.
  • cleaning agents are once understood to mean the aqueous solutions intended for direct application to the substrates to be cleaned; in addition, the term “cleaning agent” also includes the liquid concentrates and solid mixtures intended for the preparation of the application solutions.
  • the ready-to-use solutions can be slightly acidic to strongly alkaline.
  • quaternary ammonium compounds (DE-OS 36 20 011, DE-PS 27 12 900), can be used and can be foam-inhibited by the now possible, but also necessary higher dose of mixed ethers, and on the other hand that it is possible to introduce foaming substances in with the introduction of the corresponding industrial cleaning baths to achieve a significantly more effective foam inhibition. This means a higher effectiveness per se with a temporarily longer inhibition phase. Longer bath lifetimes are the result; the waste water volume is minimized.
  • the surfactants are used in particular in industrial cleaners, either for assembling cold-sprayable industrial cleaners, or for industrial cleaners, which are generally also cold-sprayable, but which, for example, also include quaternary ammonium compounds or other additional nonionic surfactants with a higher cloud point are packaged, which would not be sprayable without disruptive foam if these mixed ethers were not used.
  • the end-capped alkyl polyethylene glycol ethers to be used according to the invention are preferably added to the cleaning agents in amounts such that their concentration in the ready-to-use application solutions is 10 to 2500 ppm, particularly preferably 50 to 500 ppm.
  • FIGS. 1 to 4 show the curves of the homolog distribution, determined by gas chromatography, of various polyethylene glycol ethers which were prepared using calcined hydrotalcites as a catalyst, in comparison with those which were prepared in the presence of sodium methoxide as a catalyst.
  • a commercially available synthetic hydrotalcite was calcined at 500 ° C. for 8 hours.
  • the lauryl alcohol was placed in a pressure reactor and mixed with 0.5% by weight, based on the expected end product, of the previously obtained calcined hydrotalcite.
  • the reactor was purged with nitrogen and evacuated at a temperature of 100 ° C for 30 minutes. The temperature was then raised to 180 ° C. and the desired amount of ethylene oxide was pressed in at a pressure of 4 to 5 bar. After the reaction had ended, the mixture was left to react for 30 minutes. After filtering off the suspended catalyst, the desired reaction mixture was obtained, the characteristics of which are shown in Table 1.
  • Example 1 Analogously to the manner described in Example 1, the fatty alcohols listed in Table 1 were reacted with ethylene oxide using calcined synthetic hydrotalcites.
  • the compounds used, the amounts of ethylene oxide converted, the calcination conditions for the hydrotalcites, the catalyst concentration, the reaction time of the ethoxylation and the OH numbers of some of the ethoxylation products obtained are summarized in Table 1 for some compounds.
  • Table 1 also shows for some compounds the figure in which the homologue compounds obtained are shown in comparison to sodium methylate.
  • Surfactants A and B are comparative compounds whose alkyl polyethylene glycol ether precursors were prepared by the conventional method with alkaline catalysts (DE-OS 37 27 378) and have a broad homolog distribution.
  • the alkyl polyethylene glycol ether precursors of surfactants C and D were prepared in the presence of calcined hydrotalcites as a catalyst.
  • n represents the maximum of the respective homolog of the homolog distribution.
  • the antifoam effect was tested in a practical 10 l continuous spraying system at a spray pressure of 3 to 10 bar (30 mm smooth jet nozzle). The circulation volume was about 10 to 19 l / min.
  • the cleaning solutions were designated as application-technically injectable with minimal foam exposure at the respective application temperatures, which had practically no foam blanket (0 to ⁇ 0.5 cm) in continuous operation with otherwise rapid foam disintegration.
  • Table 2 Surfactant Composition (I) E.g. sprayable R1 R2 n A C8 ⁇ 10H17 ⁇ 21 C4H9 4th See 1, 3, 4 ⁇ 15 ° C B C8 ⁇ 10H17 ⁇ 21 C4H9 3rd See 2 ⁇ 15 ° C C. C8H17 C4H9 4th 6 - 9 ⁇ 5 ° C D C8H17 C4H9 4.5 6 - 9 ⁇ 5 ° C
  • Basis 1 and 2 represent examples of cleaner formulations to which the surfactants C or D according to the invention have been added. The comparison is made with formulations containing the comparative surfactant A.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

  1. Utilisation d'éthers d'alkylpolyéthylèneglycol enfermés dans des groupes terminaux de formule :



            R¹-0-(CH₂CH₂0)n-R²   (I)



    dans laquelle :
    R¹ représente un alkyle ou alcényle à chaîne droite ou ramifiée ou cyclique avec de 6 à 18 atomes de C.
    R² est un alkyle avec de 4 à 8 atomes de C et
    n est un nombre compris entre 3 et 6,
    produits à partir d'oxyde d'éthylène et d'un alcool ou d'un mélange d'alcool contenant R¹ et éthérification consécutive avec un halogénure d'alkyle contenant R² par éthoxylation de l'alcool gras en présence d'hydrotalcites calcinées comme catalyseur,
    utilisés comme additifs anti-mousse pour des produits de nettoyage peu moussants.
  2. Utilisation selon la revendication 1, caractérisée en ce que les hydrotalcites ayant la calcination ont une composition de formule (II) ;



            MgxAl(OH)y(C₃)z . m H₂0   (II)



    dans laquelle sont valables les conditions 1 < x < 5, y > z, (y + 0,5z) = 2 x + 3
    Figure imgb0005
     et O < m < 10.
  3. Utilisation selon les revendications 1 et 2, caractérisée en ce que pour les hydrotalcites de formule générale (II) x est un nombre de 1,8 à 3 et y, z ainsi que m sont définis comme ci-dessus.
  4. Utilisation selon les revendications 1 à 3, caractérisée en ce que les hydrotalcites ont été calcinées à des températures comprises entre 400 et 600°C.
  5. Utilisation selon les revendications 1 à 4, caractérisée en ce qu'on met en oeuvre les hydrotalcites calcinés en une quantité de 0,1 % a 2 % en poids, par rapport au produit final de l'éthoxylation.
  6. Utilisation selon les revendications 1 à 5, caractérisée en ce que dans la formule I n est compris entre 3,5 et 5 et correspond de préférence à 4,5.
  7. Utilisation selon les revendications 1 à 6, caractérisée en ce que dans la formule (I) R² = n - butyle et R¹ = octyle, décyle ou dodécyle.
  8. Utilisation selon les revendications 1 à 7, caractérisé en ce que les éthers d'alkylpolyéthylène glycol enfermés dans des groupes terminaux sont mis en oeuvre dans des quantités telles, que leur concentration dans les solutions prêtes à l'usage va de 10 à 2500 ppm, de préférence de 50 à 500 ppm.
EP90914909A 1989-10-24 1990-10-15 Utilisation d'alkylpolyethyleneglycol-ethers comme additifs antimousse pour des produits de nettoyage Expired - Lifetime EP0497790B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3935374 1989-10-24
DE3935374A DE3935374A1 (de) 1989-10-24 1989-10-24 Alkylpolyethylenglykolether als schaumdrueckende zusaetze fuer reinigungsmittel
PCT/EP1990/001743 WO1991006620A1 (fr) 1989-10-24 1990-10-15 Utilisation d'alkylpolyethyleneglycol-ethers comme additifs antimousse pour des produits de nettoyage

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EP0497790A1 EP0497790A1 (fr) 1992-08-12
EP0497790B1 true EP0497790B1 (fr) 1994-08-03

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EP (1) EP0497790B1 (fr)
JP (1) JPH05501272A (fr)
AT (1) ATE109503T1 (fr)
BR (1) BR9007774A (fr)
CA (1) CA2070415A1 (fr)
DE (2) DE3935374A1 (fr)
DK (1) DK0497790T3 (fr)
ES (1) ES2057591T3 (fr)
TR (1) TR25066A (fr)
WO (1) WO1991006620A1 (fr)
ZA (1) ZA908485B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4324396A1 (de) * 1993-07-21 1995-01-26 Henkel Kgaa Reinigungsmittel mit hohem Benetzungsvermögen
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3727378A1 (de) * 1987-08-17 1989-03-02 Henkel Kgaa Schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3833076A1 (de) * 1987-09-29 1989-04-06 Lion Corp Alkoxylierungskatalysator

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CA2070415A1 (fr) 1991-04-25
BR9007774A (pt) 1992-08-11
TR25066A (tr) 1992-11-01
DE59006725D1 (de) 1994-09-08
ATE109503T1 (de) 1994-08-15
DE3935374A1 (de) 1991-04-25
ES2057591T3 (es) 1994-10-16
WO1991006620A1 (fr) 1991-05-16
ZA908485B (en) 1991-08-28
DK0497790T3 (da) 1995-01-02
JPH05501272A (ja) 1993-03-11
EP0497790A1 (fr) 1992-08-12

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