EP0489769B1 - Utilisation de melanges de polyglycol-ethers comme agents antimousse - Google Patents

Utilisation de melanges de polyglycol-ethers comme agents antimousse Download PDF

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Publication number
EP0489769B1
EP0489769B1 EP90912440A EP90912440A EP0489769B1 EP 0489769 B1 EP0489769 B1 EP 0489769B1 EP 90912440 A EP90912440 A EP 90912440A EP 90912440 A EP90912440 A EP 90912440A EP 0489769 B1 EP0489769 B1 EP 0489769B1
Authority
EP
European Patent Office
Prior art keywords
mol
mixtures
polyethylene glycol
general formula
decanol
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
EP90912440A
Other languages
German (de)
English (en)
Other versions
EP0489769A1 (fr
Inventor
Karl-Heinz Dr. Schmid
Gilbert Dr. Schenker
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.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT9090912440T priority Critical patent/ATE105333T1/de
Publication of EP0489769A1 publication Critical patent/EP0489769A1/fr
Application granted granted Critical
Publication of EP0489769B1 publication Critical patent/EP0489769B1/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
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic

Definitions

  • the invention relates to the use of selected mixtures of end group-capped 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 invention is also based on the object to enable optimization of the performance profile of the auxiliaries used in practical use, on the one hand, but on the other hand to provide selected polyethylene glycol ethers of the type mentioned, which ensures improved formulation of these auxiliaries in commercially available concentrate form. This last-mentioned aspect has considerable practical significance and can be understood from the following:
  • foam-suppressing aids is mostly due to the fact that the contaminants detached from the substrates and accumulating in the cleaning baths act as foaming agents.
  • the cleaning agents themselves can also contain constituents which give rise to undesirable foaming under the given working conditions.
  • anionic surfactants are widely used anionic surfactants.
  • aqueous acid concentrates and in particular corresponding concentrates of aqueous phosphoric acid play a considerable role as a mixture component of the overall system in industrial cleaning.
  • foam-suppressing additives in admixture with these concentrates.
  • the foam-suppressing components can be mixed homogeneously into these aqueous acid concentrates within the temperature range of, for example, 0 to 50 ° C., which is important in practice. Separation processes lead to unacceptable phase separations in the active substance concentrate and thus make the dosing of the active substance mixture difficult or even impossible, especially in large-scale use.
  • the invention is based, inter alia, on the task of providing systems which, particularly with regard to the aspect discussed last, make improved technical action possible.
  • DE-OS 38 00 493 (D 8113) describes the use of polyethylene glycol ethers of the general formula (I) given above, but now in this formula R 1 is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 carbon atoms, R2 is an alkyl radical with 4 to 8 carbon atoms and n is a number from 6 to 20.
  • R 1 is a straight-chain or branched alkyl or alkenyl radical having 20 to 28 carbon atoms
  • R2 is an alkyl radical with 4 to 8 carbon atoms
  • n is a number from 6 to 20.
  • the crucial modification here is the use of longer chain residues R 1.
  • These end group-capped polyglycol ethers are also characterized by 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 teaching of the present invention is based on the finding that the task of optimizing the performance profile on the one hand and the ability to formulate the polyethylene glycol ethers of the general formula (I) mentioned at the outset in commercially available concentrate form is possible if selected mixtures of polyethylene glycol ethers of the general formula (I) can be used.
  • n in each case denotes a number from 5 to 9.
  • the use of mixtures of substances in which the radicals R 1 - are derived from alcohol mixtures of the following composition can be preferred according to the invention in the context of the end group-capped polyethylene glycol ether mixtures according to definition (a): at least 45 mol% of the isomer mixture of 2-hexyldodecanol-1 and 2-octyldecanol-1, 0 to 55 mol% of 2-hexyldecanol-1 and not more than 30 mol% of 2-octyldodecanol.
  • the invention predominantly or preferably exclusively uses straight-chain fatty alcohols for the preparation of the 2-branched Guerbet alcohols and ultimately for the synthesis of the compounds of the general formula (I). It is known that fatty alcohols of natural origin have at least largely predominantly even chain lengths, so that their 2-branched Guerbet alcohol with 18 C atoms cannot be obtained as a uniform condensation product of only one selected fatty alcohol via their dimerization.
  • the necessary dimerization of a mixture of the two fatty alcohols with 8 and 10 C atoms leads to the isomer mixture of the 18 C Guerbet alcohol from 2-hexyldodecanol-1 and 2-octyldecanol-1.
  • the condensation products of the two alcohols used arise with themselves, ie the 2-hexyldecanol-1 from the octanol used and the 2-octyldodecanol-1 from the decanol used.
  • the end group-capped fatty alcohol polyglycol ethers of the formula (I) are prepared 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: 5 to 1: 9 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 using straight-chain or branched C4 to C8 alkyl halides.
  • n-butyl radical for the radical R2 from the general formula (I) is of particular importance in the course of the inventive action.
  • examples of such a final etherification are accordingly n-butyl halides such as n-butyl chloride.
  • the invention is not limited to this. Further examples are amyl halides, hexyl halides and the higher alkyl halides in the range mentioned.
  • alkyl halide and alkali in a stoichiometric excess, for example from 10 to 50%, over the hydroxyl groups to be etherified.
  • the cleaning agents in which the end-capped polyglycol ether mixtures of the invention are used can contain the constituents customary in such agents, such as wetting agents, builders and complexing agents, alkalis or acids, Corrosion inhibitors and optionally also contain organic solvents.
  • the surfactants used are non-ionic surface-active compounds of the polyglycol ether type, 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 alkylolamine salts of fatty acids, alkylsulfuric acids, alkylsulfonic acids and alkylbenzenesulfonic acids Consideration.
  • the builders can contain 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 acids and ethylenediaminetetra (methylenephosphonic acid), phosphonoalkane polycarboxylic acids, e.g. B. 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. If special cleaning effects are desired, the cleaning agents can contain organic solvents, for example alcohols, gasoline fractions and chlorinated hydrocarbons as well as free alkylolamines.
  • aqueous phosphoric acid concentrates which contain approximately equal amounts of phosphoric acid and water can be mixed with the mixtures of the formula (I) according to the invention to give concentrates which are single-phase in the temperature range from 0 to 50 ° C. and are therefore particularly suitable for simple practical use .
  • end group-sealed polyglycol ether mixtures 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 defoaming action is tested under the following conditions: 300 ml of a 1% strength by weight aqueous sodium hydroxide solution are heated to 20 ° C. or 65 ° C. in a double-walled 2 liter measuring cylinder. 0.1 ml of the defoaming surfactant to be determined is added to this solution. With the help of a peristaltic pump, the liquid is circulated at a rate of 4 l / min. pumped around. The test liquor is approx.
  • a 1% by weight aqueous solution of the triethanolamine salt of tetrapropylene benzene sulfonate is used as the test foam. This is metered in at intervals of one minute in amounts of 1 ml each of the liquor in circulation. The resulting total volume of foam and liquid is determined.
  • the foam-inhibiting effect of the surfactant material used in each case is all the better the longer the period of time required to reach the 2000 ml mark in the measuring cylinder due to the total volume of the liquid and foam phases.
  • the respective are corresponding Numerical values for this time are given in minutes or in ml of test foamers.
  • R2OH 2-hexyldecanol-1

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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)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne l'utilisation de polyéthylèneglycol-éthers de formule générale (I): R1O-(CH2CH2O)n-R2, dans laquelle R1 désigne un résidu alkyle et/ou alkényle ramifié à chaîne longue, R2 un résidu alkyle avec 4 à 8 atomes de C et n un nombre au moins égal à 4, comme additifs antimousse pour des produits de lavage peu moussants, caractérisée en ce que, pour optimiser d'une part l'efficacité et d'autre part les possibilités de formulation des polyéthylèneglycols-éthers sous forme de concentrés courants, on emploie des mélanges de polyéthylèneglycol-éthers de formule générale (I), dans lesquels le résidu R1O- résulte des mélanges alcooliques (a) ou (b) suivants: a) 10 à 100 moles % d'un mélange isomérique équimolaire de 2-hexyldodécanol-1 et de 2-octyldécanol-1, 0 à 90 moles % de 2-hexyldécanol-1, 0 à 50 moles % de 2-octyldodécanol-1 ou b) 40 à 70 moles % de 2-hexyldécanol-1, 60 à 30 moles % de 2-octyldodécanol-1 et n désigne un nombre de 5 à 9.

Claims (3)

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



            R₁O-(CH₂CH₂O)n-R₂   (I)



    dans laquelle
    R₁ représente un radical alkyle et/ou alcényle ramifié à chaîne longue
    R₂ correspond à un radical alkyle comportant 4 à 8 atomes de C et
    n est un nombre d'au moins 4
    comme additifs antimousse pour les agents de nettoyage à mousse freinée, caractérisée en ce que pour l'optimisation, d'une part, du profil de rendement et, d'autre part, de la formulabilité des polyéthylèneglycoléthers dans la forme de concentré usuelle, on met en oeuvre des mélanges de polyéthylèneglycoléthers de la formule générale (I), dans lesquels le radical R₁O- est dérivé des mélanges d'alcools (a) ou (b) ci-après:
    a)
       10 à 100 moles % d'un mélange isomérique équimolaire de 2-hexyldodécanol-1 et de 2-octyldécanol-1
       0 à 90 moles % de 2-hexyldécanol-1
       0 à 50 moles % de 2-octyldodécanol-1
    ou
    b)
       40 à 70 moles % de 2-hexyldécanol-1
       60 à 30 moles % de 2-octyldodécanol-1
    et n représente un nombre de 5 à 9.
  2. Forme de réalisation selon la revendication 1, caractérisée en ce que l'on met en oeuvre des mélanges de polyéthylèneglycoléthers de la formule générale (I), dont les radicaux R₁O- sont dérivés de mélanges d'alcools présentant la composition suivante: au moins 45 moles % du mélange isomérique de 2-hexyldodécanol-1 et de 2-octyldécanol-1
    0 à 55 moles % de 2-hexyldécanol-1
    pas plus de 30 moles % de 2-octyldodécanol.
  3. Forme de réalisation selon les revendications 1 et 2, caractérisée en ce que les mélanges de polyéthylèneglycoléthers sont mis en oeuvre dans des concentrés acides aqueux stables en température, formulables en phase unique, en particulier conjointement avec de l'acide phosphorique aqueux.
EP90912440A 1989-08-30 1990-08-21 Utilisation de melanges de polyglycol-ethers comme agents antimousse Expired - Lifetime EP0489769B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT9090912440T ATE105333T1 (de) 1989-08-30 1990-08-21 Verwendung von polyglykolethergemischen als antischaummittel.

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3928604A DE3928604A1 (de) 1989-08-30 1989-08-30 Verwendung ausgewaehlter gemische von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3928604 1989-08-30
PCT/EP1990/001380 WO1991003537A1 (fr) 1989-08-30 1990-08-21 Utilisation de melanges de polyglycol-ethers comme agents antimousse

Publications (2)

Publication Number Publication Date
EP0489769A1 EP0489769A1 (fr) 1992-06-17
EP0489769B1 true EP0489769B1 (fr) 1994-05-04

Family

ID=6388140

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912440A Expired - Lifetime EP0489769B1 (fr) 1989-08-30 1990-08-21 Utilisation de melanges de polyglycol-ethers comme agents antimousse

Country Status (7)

Country Link
US (1) US5921910A (fr)
EP (1) EP0489769B1 (fr)
JP (1) JPH05500073A (fr)
CA (1) CA2065349A1 (fr)
DE (2) DE3928604A1 (fr)
ES (1) ES2052266T3 (fr)
WO (1) WO1991003537A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4102709C1 (en) * 1991-01-30 1992-07-30 Joachim F. Dipl.-Chem. Dr. 4330 Muelheim De Marx Degreasing metal surfaces using aq. prepn. - contg. biologically degradable adducts of lower alkylene oxide(s), fatty alcohol(s) and cationic surfactants
US5612305A (en) * 1995-01-12 1997-03-18 Huntsman Petrochemical Corporation Mixed surfactant systems for low foam applications
US6686330B2 (en) 1999-12-08 2004-02-03 The Procter & Gamble Company Compositions including ether-capped poly (oxyalkylated) alcohol wetting agents
WO2001041911A2 (fr) 1999-12-08 2001-06-14 The Procter & Gamble Company Procede de preparation d'agents tensioactifs a base d'alcool poly(oxyalkyle) a blocage ether
US6844309B1 (en) 1999-12-08 2005-01-18 The Procter & Gamble Company Ether-capped poly(oxyalkylated) alcohol surfactants
US6593287B1 (en) * 1999-12-08 2003-07-15 The Procter & Gamble Company Compositions including ether-capped poly(oxyalkylated) alcohol surfactants

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1223822B (de) * 1965-01-27 1966-09-01 Deutsche Erdoel Ag Verfahren zur Herstellung von beta-verzweigten, gesaettigten und ungesaettigten Aldehyden
US3862994A (en) * 1973-06-06 1975-01-28 Continental Oil Co Process for condensation of alcohols
US4011273A (en) * 1975-08-04 1977-03-08 Henkel Inc. Method for the production of guerbet alcohols utilizing insoluble lead catalysts
DE3115644A1 (de) * 1981-04-18 1982-11-04 Henkel KGaA, 4000 Düsseldorf "pulverfoermiger entschaeumer fuer waessrige systeme, verfahren zu seiner herstellung und seine verwendung"
DE3305430A1 (de) * 1983-02-17 1984-08-23 Henkel KGaA, 4000 Düsseldorf Verwendung von alkoholen und deren derivaten als viskositaetsregler fuer hochviskose technische tensid-konzentrate
DE3315951A1 (de) * 1983-05-02 1984-11-08 Henkel KGaA, 4000 Düsseldorf Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3400008A1 (de) * 1984-01-02 1985-07-11 Henkel KGaA, 4000 Düsseldorf Zur verwendung in tensidhaltigen mitteln geeignetes schaumregulierungsmittel
DE3727378A1 (de) * 1987-08-17 1989-03-02 Henkel Kgaa Schaumdrueckende zusaetze in schaumarmen reinigungsmitteln
DE3800493A1 (de) * 1988-01-11 1989-07-20 Henkel Kgaa Verwendung von polyglykolethern als schaumdrueckende zusaetze in schaumarmen reinigungsmitteln, die insbesondere auch fuer die kaltreinigung geeignet sind
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

Also Published As

Publication number Publication date
DE3928604A1 (de) 1991-03-07
EP0489769A1 (fr) 1992-06-17
DE59005647D1 (de) 1994-06-09
CA2065349A1 (fr) 1991-03-01
WO1991003537A1 (fr) 1991-03-21
US5921910A (en) 1999-07-13
ES2052266T3 (es) 1994-07-01
JPH05500073A (ja) 1993-01-14

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