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WO1991008034A1 - Utilisation de derives de thiodiglycol comme inhibiteurs de mousse - Google Patents

Utilisation de derives de thiodiglycol comme inhibiteurs de mousse Download PDF

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Publication number
WO1991008034A1
WO1991008034A1 PCT/EP1990/002030 EP9002030W WO9108034A1 WO 1991008034 A1 WO1991008034 A1 WO 1991008034A1 EP 9002030 W EP9002030 W EP 9002030W WO 9108034 A1 WO9108034 A1 WO 9108034A1
Authority
WO
WIPO (PCT)
Prior art keywords
mono
weight
general formula
foam
active chlorine
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.)
Ceased
Application number
PCT/EP1990/002030
Other languages
German (de)
English (en)
Inventor
Gerhard Stoll
Adolf Asbeck
Thomas Schuster
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
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
Publication of WO1991008034A1 publication Critical patent/WO1991008034A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances
    • B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
    • B01D19/0422—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing S-atoms

Definitions

  • the invention describes the foam-inhibiting effect of the mono- and / or bis-ethers and mono- and / or bis-esters of thiodiglycol sulfoxides and / or sulfones of the general formula I
  • X 1 and / or X 2 mean ⁇ -hydroxyl-substituted alkyl radicals with 8 to 30 C atoms and / or acyl radicals of alkyl monocarboxylic acids with 8 to 30 C atoms, in which X 1 and X 2 are identical or different, in which case the monoether or monoester X 1 or X 2 is hydrogen and in which the number z stands for 1 or 2, in detergents containing active chlorine, in sugar production and in emulsion paints.
  • dishwashing detergents for machine use, but the invention is not restricted to these.
  • Shaped, granulated or liquid alkaline cleaning agents are used which essentially consist of builders, alkali metal silicates, alkali metal carbonates and / or alkali metal hydroxides and additionally contain active chlorine compounds.
  • a foam inhibitor is usually added to prevent excessive foaming.
  • Polychlorinated cyanuric acids and their salts, in particular trichloroisocyanuric acid have proven successful as active chlorine compounds in powdery, granulated, liquid or liquid-pasty dishwashing detergents.
  • German patent DE 28 51 832 already contains sulfoxides or sulfones of the general formula II
  • R 1 is an alkyl radical with 1 to 22 C atoms
  • R 2 is hydrogen or an alkyl radical with 1 to 22 C atoms
  • R 3 is an alkyl radical with 1 to 22 C atoms or the radical CHR 2 -CHOH-R 1 and n the numbers 0, 1 or 2, with the proviso that at least one of the radicals R 1 -CHOH-CH-R 2 contains 10 to 24 carbon atoms, are known as foam inhibitors both in detergents and cleaning agents and in synthetic resin dispersions.
  • the compounds of the general formula II are obtainable according to DE-OS-1768266 and DE-OS-1948385 by the applicant by reacting epoxides with hydrogen sulfide or alkyl mercaptans or by reacting mixtures of epoxides and olefins with hydrogen sulfide.
  • a major disadvantage of this synthetic route consists in the production of the sulfide building blocks, which is complex and expensive for industrial purposes, since the handling of the unpleasant smelling raw materials, hydrogen sulfide or alkyl mercaptans, is undesirable.
  • thiodiglycol derivatives in cleaning agents of the type concerned here are effective foam inhibitors which are neither destroyed by active chlorine compounds nor in turn reduce the active chlorine content of the corresponding cleaning agents or damage the compounds containing active chlorine.
  • the present invention accordingly relates to the use of the mono- and / or bis-ethers and mono- and / or bis-esters of thiodiglycolsulfoxides or sulfones of the general formula I
  • X 1 and / or X 2 mean ⁇ -hydroxyl-substituted alkyl radicals with 8 to 30 C atoms and / or acyl radicals of alkyl monocarboxylic acids with 8 to 30 C atoms, in which X 1 and X 2 are identical or different, in which case the mono-ether or mono-ester X 1 or X 2 is hydrogen and in which the number z stands for 1 or 2, as foam inhibitors in the household and commercial sector.
  • the not yet published patent application by the applicant (D 7892) relates to the new thiodiglycol derivatives according to the invention, processes for their preparation and their use as plasticizers for textiles. They can be produced by reacting thiodiglycol with ⁇ -olefin epoxide compounds having 8 to 30 carbon atoms in the molecule or by reacting the thiodiglycol with alkyl monocarboxylic acids of comparable chain length.
  • ring opening results in the formation of the corresponding mono- and / or bis-ether of thiodiglycol of general formula I in X 1 and / or X 2 ß -Hydroxylalkyl groupings.
  • the thiodiglycol is reacted in the desired molar ratio (1: 1 to 1: 2) with the C 8 to C 30 - ⁇ -olefin epoxide in such a way that a conventional basic catalyst, such as an alkali metal hydroxide and / or an alkali metal methoxylate, in an amount of at least 0.05 to about 5% by weight, preferably from about 0.1 to 1% by weight, based in each case on the total weight.
  • a conventional basic catalyst such as an alkali metal hydroxide and / or an alkali metal methoxylate
  • the reaction of thiodiglycol with ⁇ -olefin epoxides of the chain lengths mentioned can in principle also be catalyzed by acids.
  • the actual reaction takes place at temperatures of at least 140 to about 200 °, preferably from 160 to 170 ° within about 3 to 6 hours to an epoxy content of below 0.5, preferably below 0.2.
  • the epoxy content is used for constant reaction control and ultimately also for determining the quantitative course of the reaction.
  • selected narrow subclasses are particularly distinguished by their particular suitability for the aim as foam inhibitor aimed at according to the invention.
  • radicals X 1 and X 2 are derived from ⁇ -hydroxyl-substituted alkyl radicals or from acyl radicals having 12 to 24 carbon atoms and in particular having about 12 to 18 carbon atoms.
  • the preferred residues of this type for X 1 and X 2 are corresponding straight-chain residues.
  • the thiodiglycol derivatives and their mixtures according to the invention are usually solid at room temperature and have melting points in the range from 60 to 200 °.
  • the finely divided, flowable dispersions of the foam inhibitors in the liquid carrier phase are particularly easy to get into the Incorporate alkaline dishwashing detergent containing active chlorine.
  • suitable liquid carriers are, above all, organic compounds which have a sufficiently low pour point or melting point, preferably less than 5 ° C.
  • liquid carrier phase can in turn have a defoaming effect or can only serve as a carrier for the defoamer in the sense of the invention.
  • Particularly suitable organic carrier liquids with an additional defoaming effect are mineral oils with a boiling point above 140 ° C. and branched-chain alcohols with 8 to 32 carbon atoms, for example 2-hexyldecanol-1 or 2-octyldodecanol-2.
  • Liquid esters of branched or unsaturated fatty acids with 8 to 18 carbon atoms with mono- or polyhydric alcohols for example glycol diesters or glycerol triesters of oleic acid, isostearic acid, and also esters based on branched-chain or unsaturated, liquid fatty acids with branched-chain or unsaturated fatty alcohols with 8 can also be used to 18 carbon atoms, for example isotridecyl alcohol or oleyl alcohol. Mixtures of the carrier substances mentioned can also be used according to the invention.
  • the dispersions to be processed advantageously contain about 5 to 15% by weight of thiodiglycol derivatives of the general formula I.
  • the dispersions of the thiodiglycol derivatives in the liquid carrier can be stabilized by suitable additives.
  • Additives of approximately 0.3 to 3% by weight of magnesium stearate, calcium stearate or aluminum stearate are suitable, for example.
  • the defoamers and defoamer mixtures of the general formula I added to the alkaline active chlorine-containing cleaning agents show a sufficient defoaming action even in small amounts of 0.01 to 2% by weight.
  • Their content is preferably not more than about 1% by weight, based on dry cleaning agent.
  • Dishwashing detergents which contain the foam inhibitors according to the invention can therefore have the following composition
  • the preparation of the defoamer-containing cleaning agents or the incorporation of the defoamer or the defoamer dispersion can be done by mixing the dry individual components together with admixing the defoamer dispersion, by mixing under granulating conditions, that is to say simultaneous application of water or a water glass solution to the dry premix or also by subsequent addition Mix or spray the defoamer dispersion onto pre-formed granules.
  • the type of preparation or the sequence in which the individual ingredients are added has no significant influence on the action or the interaction between defoamer and active chlorine compound.
  • the foam inhibitors of the general formula I according to the invention can be used within sugar production.
  • sugar plays a role manufacturing the biodegradability and the food safety.
  • the defoamer composition further contains about 80 to 95% by weight of a commercially available mineral oil, 1 to 5% by weight of polypropylene glycol distearate (with an EO degree of 33 to 34%) and about 0.1 to 0.5% by weight of a metal stearate, preferably aluminum stearate.
  • bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfone or a 1: 1 mixture of bis- [2- (2-hydroxydodecyloxy) ethyl] sulfone and bis- [2- (2-hydroxytetradecyloxy) ethyl] sulfone used.
  • foam inhibitors of the general formula I according to the invention can also be used successfully in aqueous synthetic resin dispersions.
  • Aqueous synthetic resin dispersions include, for example, polyvinyl acetates and copolymers of vinyl acetate with styrene, vinyl chloride, vinylidene chloride, vinyl alcohol, vinyl ethers, maleic acid, acrylic acid or its esters, crotonic acid, acrylamide and acrylonitrile.
  • the defoamer composition according to the invention also contains about 80 to 95% by weight of a commercially available mineral oil, 1 to 5% by weight of polypropylene glycol distearate (with an EO degree of 33 to 34%) and about 0.1 to 0.5% by weight of a metal stearate, preferably aluminum stearate.
  • defoamer particles that cannot be solubilized, saponified or hydrolyzed are particularly suitable.
  • the thiodiglycol derivatives of the mono- or bis-ether sulfone type for example bis- [2- (2-hydroxyhexadecyloxy) ethyl] sulfone, are particularly preferably used.
  • the foam-inhibiting effect of the investigated dishwashing detergent - measured by the respective volume of foam and liquid phase - was determined immediately after the dishwashing detergent had been produced and after storage at 40 ° C. after a period of 3 months.
  • Dishwashing detergent composition selected:
  • the components were mixed and granulated for 10 minutes at room temperature in a rotating drum while spraying the water glass solution.
  • the active chlorine content (Table 1) was determined as follows:
  • Examples 1 to 4 showed a better and longer-lasting foam-inhibiting effect compared to the defoamer active ingredients known from the prior art (Examples 5 to 12), wherein the active chlorine content remained much more stable, especially in long-term trials.
  • the defoamers according to the invention are surprisingly distinguished by an extremely rapid decrease in the foam volume.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention décrit l'utilisation de mono- et/ou bis-ethers ainsi que de mono- et/ou bis-esters d'oxydes sulfoniques et/ou de sulfones de thiodiglycol de la formule générale (I), où X1 et/ou X2 représentent des résidus alkyle substitués par β-hydroxyle comportant de 8 à 30 atomes C et/ou des résidus acyle d'acides monocarboxyliques d'alkyle comportant de 8 à 30 atomes C, et dans laquelle le nombre z est 1 ou 2, comme inhibiteurs de mousse dans les domaines ménagers et industriels.
PCT/EP1990/002030 1989-12-06 1990-11-27 Utilisation de derives de thiodiglycol comme inhibiteurs de mousse Ceased WO1991008034A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19893940338 DE3940338A1 (de) 1989-12-06 1989-12-06 Verwendung von thiodiglykolderivaten als schauminhibitoren
DEP3940338.6 1989-12-06

Publications (1)

Publication Number Publication Date
WO1991008034A1 true WO1991008034A1 (fr) 1991-06-13

Family

ID=6394922

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1990/002030 Ceased WO1991008034A1 (fr) 1989-12-06 1990-11-27 Utilisation de derives de thiodiglycol comme inhibiteurs de mousse

Country Status (2)

Country Link
DE (1) DE3940338A1 (fr)
WO (1) WO1991008034A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000044470A1 (fr) * 1999-01-29 2000-08-03 Basf Aktiengesellschaft Antimousses et/ou desaerateurs a base de dispersions huile dans eau

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2851832A1 (de) * 1978-11-30 1980-06-19 Henkel Kgaa Schauminhibitoren
US4830636A (en) * 1987-04-07 1989-05-16 Mobil Oil Corporation Hydrocarbon fuels containing sulfonyl dialkanol esters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2851832A1 (de) * 1978-11-30 1980-06-19 Henkel Kgaa Schauminhibitoren
US4830636A (en) * 1987-04-07 1989-05-16 Mobil Oil Corporation Hydrocarbon fuels containing sulfonyl dialkanol esters

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000044470A1 (fr) * 1999-01-29 2000-08-03 Basf Aktiengesellschaft Antimousses et/ou desaerateurs a base de dispersions huile dans eau
US6864292B1 (en) 1999-01-29 2005-03-08 Basf Aktiengesellschaft Defoamer and/or deareator on the basis of oil-in-water dispersions

Also Published As

Publication number Publication date
DE3940338A1 (de) 1991-06-13

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