EP1542955B1 - Alkoxylates exhibiting low residual alcohol content - Google Patents

Alkoxylates exhibiting low residual alcohol content Download PDF

Info

Publication number
EP1542955B1
EP1542955B1 EP03725099A EP03725099A EP1542955B1 EP 1542955 B1 EP1542955 B1 EP 1542955B1 EP 03725099 A EP03725099 A EP 03725099A EP 03725099 A EP03725099 A EP 03725099A EP 1542955 B1 EP1542955 B1 EP 1542955B1
Authority
EP
European Patent Office
Prior art keywords
compositions
composition
ppm
less
content
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.)
Revoked
Application number
EP03725099A
Other languages
German (de)
French (fr)
Other versions
EP1542955A1 (en
Inventor
Christian Wulff
Kai-Uwe Baldenius
Martin Scholtissek
Michael Stösser
Norbert Wagner
Edward Bohres
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 SE
Original Assignee
BASF SE
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=31969218&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1542955(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by BASF SE filed Critical BASF SE
Publication of EP1542955A1 publication Critical patent/EP1542955A1/en
Application granted granted Critical
Publication of EP1542955B1 publication Critical patent/EP1542955B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to compositions containing at least one alkoxylate of the general formula RO (A) n (B) m H, to processes for preparing such compositions, in particular in the presence of double metal cyanide compounds as catalyst, and to their use as emulsifier, foam regulator or wetting agent for hard surfaces. Moreover, the present invention also relates to the use of such compositions in detergents and surfactant formulations.
  • Alkoxylates of aliphatic alcohols are widely used as surfactants, emulsifiers or foam suppressants.
  • the wetting and emulsifying properties depend strongly on the type of alcohol and the type and amount of alkoxide adducts.
  • WO 94/11331 relates to the use of alkoxylates of 2-propylheptanol in detergent compositions for degreasing hard surfaces.
  • the alkoxylates have 2 to 16 alkylene oxide groups.
  • the major part of the alkylene oxide groups is in the form of ethylene oxide.
  • ethoxylated alcohols are used. It is further described that the alcohols can be reacted first with ethylene oxide and then with propylene oxide.
  • such alkoxylates are not examples or properties specified. It is stated that the described alkoxylates show a good detergent and wetting action, combined with a low foaming. In addition, it is stated that the alkoxylates have a desired thickening effect in formulations.
  • WO 94/11330 relates to alkoxylates of 2-propylheptanol and their use.
  • the alkoxylates is 2-propylheptanol, first with 1 to 6 moles of propylene oxide and then reacted with 1 to 10 moles of ethylene oxide before.
  • a 2-propylheptanol reacted first with 4 mol of propylene oxide and then with 6 mol of ethylene oxide is used.
  • the alkylene oxide adducts show an improved foam behavior to detergent effect.
  • the alkoxylates show a good wetting behavior. They are used in detergent compositions for cleaning textile materials.
  • US 2,508,036 relates to the use of 2-n-propylheptanolethoxylates containing from 5 to 15 moles of ethylene oxide as wetting agents in aqueous solutions. It is described that the products can be used as surfactants in detergents.
  • the DE-A-102 18 754 as well as the DE-A-102 18 753 relate to the use of C 10 -alkanolalkoxylate mixtures, in particular alkanolethoxylate mixtures, such C 10 -alkanol alkoxylate mixtures and processes for their preparation.
  • the DE-A-102 18 752 also describes alkoxylate mixtures and detergents containing them, as well as processes for the preparation of the alkoxylate mixtures and the use of the detergent for washing or cleaning textiles.
  • WO 02/50006 relates to branched primary alcohol-containing compositions and derivatives thereof.
  • a product derived from a branched primary C 9-24 alcohol initially reacted with one mole of propylene oxide and then ethylene oxide is described.
  • the alcohol can not be a primary alcohol because the R 2 group is a hydrocarbyl group.
  • the avoidance of larger amounts of residual alcohol present in the product is particularly advantageous for odor reasons.
  • the alcohol mixtures used according to the invention generally have an inherent odor which can be largely suppressed by complete alkoxylation. Alkoxylates obtained by conventional methods often have an inherent odor which is responsible for many applications are annoying. Furthermore, improved hard surface wetting, improved emulsification behavior, and lower CMC (Critical Micell Concentration) are desirable.
  • n and m denote an average value which is the average over all molecules. Therefore, n and m can also differ from integer values.
  • Propyleneoxy is in the context of the present invention for -CH 2 -CH (CH 3 ) -O- or - CH (CH 3 ) -CH 2 -O-.
  • Ethylenoxy stands for -CH 2 -CH 2 -O-.
  • propylene oxide is attached in a ring-opening manner to the radical RO.
  • n indicates the number of propylene oxide groups and is a whole or fractional number with 0 ⁇ n ⁇ 1.
  • Ethylene oxide or a mixture of ethylene oxide and propylene oxide is bound to the propylene oxide group.
  • M stands for the number of ethylene oxide or ethylene oxide and propylene oxide groups and is a whole or fractional number with 0 ⁇ m ⁇ 20, preferably 1 ⁇ m ⁇ 18, in particular 2 ⁇ m ⁇ 14, for example 2.5 ⁇ m ⁇ 14 or 3 ⁇ m ⁇ 8.
  • the present invention relates to compositions wherein m is an integer or fractional number from 2 to 14.
  • compositions according to the invention have a low residual alcohol content. It is surprising that the residual alcohol content in the compositions according to the invention which have a defined amount of propylene oxide and subsequently ethylene oxide or ethylene oxide and propylene oxide is lower than would theoretically be expected. From residual alcohol contents of products which contain only propylene oxide or only ethylene oxide, an expected value can be determined which is higher than the residual alcohol content actually determined for the copolymers according to the invention.
  • the alkoxylates contained in the compositions of the invention require to lower the residual alcohol content only a directly bound to the alcohol propylene oxide (PO) block of very short length. This is particularly advantageous because the biodegradability of the product decreases as the PO block lengthens. Such alkoxylates thus allow maximum degrees of freedom in the choice of the length of the PO block, the length down through the rising Residual alcohol content and is limited upwards by the deterioration of biodegradability. This is particularly advantageous if only a short ethylene oxide block follows the PO block.
  • PO alcohol propylene oxide
  • alkoxylates contained in the compositions of the invention can then be initially present in the alcohol radical propyleneoxy units and then ethyleneoxy units. If n and m have a value of more than 1, the corresponding alkoxy radicals are preferably present in block form.
  • a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to some extent by using different alkoxylation catalysts.
  • Groups A and B the property spectrum of the compositions of the invention can be adjusted according to practical requirements. Particularly preferred is first reacted with propylene oxide and then with ethylene oxide.
  • the present invention relates to compositions in which B is ethyleneoxy.
  • the alkyl radical R is in the context of the present invention C 5 H 11 CH (C 3 H 7 ) CH 2 -, except isomer mixtures of an alkyl group of the general empirical formula C 5 H 11 CH (C 3 H 7 ) CH 2 - from 70 to 99% by weight a radical R1 in which C 5 H 11 has the meaning nC 5 H 11 and 1 to 30% by weight of a radical R2 in which C 5 H 11 has the meaning C 2 H 5 CH (CH 3 ) CH 2 and / or CH 3 CH (CH 3 ) CH 2 CH 2 .
  • the alcohols used as starter compound may also be mixtures of different isomers.
  • compositions according to the invention can be used as catalyst.
  • the compositions of the invention thus obtained can have a residual metal content of greater than 0 and less than 50 ppm zinc (ie mg metal per kg product), in particular greater than 0 and less than 25 ppm zinc or preferably greater than 0 and less than 15 ppm zinc and greater as 0 and less than 25 ppm cobalt, in particular greater than 0 and less than 15 ppm cobalt or preferably greater than 0 and less than 7 ppm cobalt.
  • the present invention relates to compositions whose content of zinc is greater than 0 and less than or equal to 15 ppm or whose content of cobalt is greater than 0 and less than or equal to 7 ppm or whose content of zinc is greater than 0 and smaller or equal to 15 ppm and their content of cobalt is greater than 0 and less than or equal to 7 ppm.
  • the present invention also relates to a process for preparing the compositions by reacting at least one alcohol C 5 H 11 CH (C 3 H 7 ) CH 2 -OH with propylene oxide and ethylene oxide under alkoxylation conditions.
  • the content of residual alcohol in the alkoxylates can be reduced since propylene oxide is added more uniformly to the alcohol component.
  • ethylene oxide preferably reacts with ethoxylates, such that upon initial use of ethylene oxide to react with the alkanols, both a broad homolog distribution and a high residual alcohol content result.
  • the avoidance of larger amounts of residual alcohol present in the product is particularly advantageous for odor reasons.
  • the addition reaction is carried out at temperatures of about 90 to 240 ° C, preferably from 110 to 190 ° C, in a closed vessel.
  • the alkylene oxide or the mixture of different alkylene oxides is fed to the mixture of alkanol mixture according to the invention and catalyst under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature or at a higher pressure.
  • the alkylene oxide may be diluted with an inert gas (for example noble gases, nitrogen, CO 2) up to 99.9%.
  • Suitable alkoxylation conditions are described above and in Nikolaus Schonfeldt, Grenz inhabitassitule ⁇ thylenoxid adducts,ticianliche Verlagsgesellschaft mbH Stuttgart 1984 described.
  • the alkoxylation is carried out in the presence of basic catalysts such as KOH in substance.
  • the alkoxylation can also be carried out with the concomitant use of a solvent.
  • the alcohols are first reacted with a suitable amount of propylene oxide and then with a suitable amount of ethylene oxide.
  • a polymerization of the alkylene oxide is set in motion, which inevitably leads to a statistical distribution of homologues whose mean value is given here with n and m.
  • the length of the polyether chains (n + m) varies randomly within the reaction product by an average, which essentially results from the addition amount and the stoichiometric values.
  • different molecular weight distributions are obtained. For example, products with a narrow molecular weight distribution often have good solubility.
  • the alkoxylation is catalyzed by strong bases, which are suitably added in the form of an alkali metal alcoholate, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide, usually in an amount of 0.01 to 1 wt .-% based on the amount of the alkanol R-OH , (comp. G. Gee et al., J. Chem. Soc. (1961), p. 1345 ; B. Wojtech, Makromol. Chem. 66, (1966), p. 180 ).
  • Acid catalysis of the addition reaction is also possible.
  • Lewis acids such as AlCl 3 or BF 3 dietherate, BF 3 , BF 3 x H 3 PO 4 , SbCl 4 x 2 H 2 O hydrotalcite (Cf. PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963 )).
  • DMC double metal cyanide
  • the present invention relates to a process carried out in the presence of a double metal cyanide compound as a catalyst. Therefore, in a preferred embodiment, the present invention relates to a method for Preparation of compositions wherein the alkoxylation is carried out in the presence of a double metal cyanide compound (DMC compound) as a catalyst.
  • DMC compound double metal cyanide compound
  • DMC compound As a DMC compound, it is possible in principle to use all suitable compounds known to the person skilled in the art.
  • the organic additives P are: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, Polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic and maleic anhydride copolymers, hydroxyethylcellulose, Polyacetates, ionic surfactants and surface-active compounds,
  • catalysts can be crystalline or amorphous. In the case where k is zero, crystalline double metal cyanide compounds are preferred. In the case where k is greater than zero, both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.
  • a preferred embodiment is catalysts of the formula (I) in which k is greater than zero.
  • the preferred catalyst then contains at least one double metal cyanide compound, at least one organic ligand and at least one organic additive P.
  • k is zero, optionally e is also zero and X is exclusively a carboxylate, preferably formate, acetate and propionate.
  • Such catalysts are in the WO 99/16775 described.
  • crystalline double metal cyanide catalysts are preferred.
  • double metal cyanide catalysts as in WO 00/74845 described which are crystalline and platelike.
  • the preparation of the modified catalysts is carried out by combining a metal salt solution with a cyanometalate solution, which may optionally contain both an organic ligand L and an organic additive P. Subsequently, the organic ligand and optionally the organic additive are added.
  • an inactive double metal cyanide phase is first prepared and then converted by recrystallization in an active Doppelmetallcyanidphase, as in PCT / EP01 / 01893 described.
  • f, e and k are not equal to zero.
  • the catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as in the US 5,158,922 described.
  • catalyst for the alkoxylation double metal cyanide compounds containing zinc, cobalt or iron or two of them is particularly suitable.
  • Berlin Blue is particularly suitable.
  • crystalline DMC compounds Preference is given to using crystalline DMC compounds.
  • a Zn-Co type crystalline DMC compound is used as the catalyst containing zinc acetate as the further metal salt component.
  • Such compounds crystallize in monoclinic structure and have a platelet-shaped habit.
  • Such compounds are used for example in the WO 00/74845 or the PCT / EP01 / 01893 described.
  • DMC compounds suitable as catalyst can be prepared in any manner known to those skilled in the art.
  • the DMC compounds can be prepared by direct precipitation, "incipient wetness” method, by preparing a precursor phase and subsequent recrystallization.
  • the DMC compounds can be used as a powder, paste or suspension or be shaped into a shaped body, introduced into moldings, foams or the like, or applied to shaped bodies, foams or the like.
  • the catalyst concentration used for the alkoxylation, based on the final amount skeleton is typically less than 2000 ppm (ie mg catalyst per kg product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, more preferably less than 25 ppm.
  • compositions according to the invention show good wetting on hard surfaces.
  • the advantageous wetting behavior of the mixtures according to the invention can be determined, for example, by measurements of the contact angle on glass, polyethylene oxide or steel.
  • the present invention therefore also relates to the use of a composition according to the invention or a composition prepared by a process according to the invention as emulsifier, foam regulator and hard surface wetting agent, in particular the use in detergents, hard surface detergent formulations, humectants, cosmetic, pharmaceutical and crop protection formulations, Lacquers, coating compositions, adhesives, leather degreasing agents, formulations for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations.
  • compositions according to the invention are followed by better performance, in particular fast cleaning processes. This is surprising insofar as the chain extension of the starting alcohol usually reduces the dynamic and wetting properties. With the compositions according to the invention, it is thus possible to increase the wetting speed of aqueous formulations.
  • the compositions according to the invention can thus also be used as solubilizers which, in particular, do not negatively but positively influence the wetting power of wetting aids, even in dilute systems. They can be used to increase the solubility of wetting agents in aqueous formulations containing nonionic surfactants. They serve in particular to increase the wetting speed in aqueous wetting agents.
  • compositions according to the invention serve to reduce the interfacial tension, for example in aqueous surfactant formulations.
  • the reduced interfacial tension can be determined, for example, by the pendant drop method. This also results in a better effect of the compositions of the invention as an emulsifier or co-emulsifier.
  • the compositions of this invention may also be used to reduce interfacial tension at short times, usually less than one second, or to accelerate the adjustment of interfacial tension in aqueous surfactant formulations.
  • Such formulations usually contain ingredients such as surfactants, builders, fragrances and dyes, chelating agents, polymers and other ingredients.
  • Typical formulations are, for example, in WO 01/32820 described.
  • Other ingredients suitable for different applications are in EP-A-0 620 270 .
  • compositions of the invention can be used in all areas in which the action of surfactants is necessary.
  • the present invention therefore also relates to washing, cleaning, wetting, coating, adhesive, leather degreasing, moisturizing or textile treatment compositions or to cosmetic, pharmaceutical or crop protection formulations comprising a composition according to the invention or a composition prepared by a method according to the invention.
  • the compositions preferably contain 0.1 to 20 wt .-% of the compositions.
  • compositions of the invention are characterized in particular by a low residual alcohol content, so that they are advantageously suitable for a variety of applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Polyethers (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Composition (A) contains at least one alkoxylated 6-18C alkanol (I). Composition (A) contains at least one alkoxylated 6-18C alkanol of formula RO-(A)n-(B)m-H (I). R = 6-18C linear or branched alkyl; A = propyleneoxy (PO); B = ethyleneoxy (EO) or a mixture of EO and PO; n = integer or fractional number of 0-5; and m = integer or fractional number of 0-20. When R is C5H11CH(C3H7)CH2-, n is less than 1, provided that R is a mixture where 70-99 %, by weight of C5H11 is linear and 1-30 %, by weight is EtCH(Me)CH2 and/or MeCH(Me)CH-2CH2. An Independent claim is also included for a method for preparing (I) by reacting ROH with propylene and ethylene oxides.

Description

Die vorliegende Erfindung betrifft Zusammensetzungen, mindestens enthaltend ein Alkoxylat der allgemeinen Formel RO(A)n(B)mH, Verfahren zur Herstellung derartiger Zusammensetzungen, insbesondere in Gegenwart von Doppelmetallcyanid-Verbindungen als Katalysator, sowie deren Verwendung als Emulgator, Schaumregulierer oder als Netzmittel für harte Oberflächen. Darüber hinaus betrifft die vorliegende Erfindung auch die Verwendung derartiger Zusammensetzungen in Waschmitteln und Tensidformulierungen.The present invention relates to compositions containing at least one alkoxylate of the general formula RO (A) n (B) m H, to processes for preparing such compositions, in particular in the presence of double metal cyanide compounds as catalyst, and to their use as emulsifier, foam regulator or wetting agent for hard surfaces. Moreover, the present invention also relates to the use of such compositions in detergents and surfactant formulations.

Verfahren zur Alkoxylierung von aliphatischen Alkoholen sowie die erhaltenen Alkoxylate sind prinzipiell aus dem Stand der Technik bekannt. In der WO 01/04183 wird beispielsweise ein Verfahren zur Ethoxylierung von hydroxyfunktionellen Starterverbindungen beschrieben, das in Gegenwart einer Doppelmetallcyanid-Verbindung als Katalysator durchgeführt wird.Processes for the alkoxylation of aliphatic alcohols and the alkoxylates obtained are known in principle from the prior art. In the WO 01/04183 For example, a process for the ethoxylation of hydroxy-functional starter compounds is described, which is carried out in the presence of a double metal cyanide compound as a catalyst.

Alkoxylate von aliphatischen Alkoholen werden in großem Umfang als Tenside, Emulgatoren oder Schaumdämpfer eingesetzt. Die Benetzungs- und Emulgatoreigenschaften hängen dabei stark von der Art des Alkohols und der Art und Menge der Alkoxid-Addukte ab.Alkoxylates of aliphatic alcohols are widely used as surfactants, emulsifiers or foam suppressants. The wetting and emulsifying properties depend strongly on the type of alcohol and the type and amount of alkoxide adducts.

WO 94/11331 betrifft die Verwendung von Alkoxylaten von 2-Propylheptanol in Detergenzzusammensetzungen zur Entfettung harter Oberflächen. Die Alkoxylate weisen 2 bis 16 Alkylenoxid-Gruppen auf. Vorzugsweise liegt der überwiegende Teil der Alkylenoxid-Gruppen in Form von Ethylenoxid vor. Gemäß der Beispiele werden ausschließlich ethoxylierte Alkohole eingesetzt. Es ist ferner beschrieben, dass die Alkohole zunächst mit Ethylenoxid und sodann mit Propylenoxid umgesetzt werden können. Für derartige Alkoxylate sind jedoch keine Beispiele oder Eigenschaften angegeben. Es wird ausgeführt, dass die beschriebenen Alkoxylate eine gute Detergenz- und Benetzungswirkung zeigen, verbunden mit einem geringen Schäumen. Zudem wird angegeben, dass die Alkoxylate einen erwünschten Verdickungseffekt in Formulierungen haben. WO 94/11331 relates to the use of alkoxylates of 2-propylheptanol in detergent compositions for degreasing hard surfaces. The alkoxylates have 2 to 16 alkylene oxide groups. Preferably, the major part of the alkylene oxide groups is in the form of ethylene oxide. According to the examples, only ethoxylated alcohols are used. It is further described that the alcohols can be reacted first with ethylene oxide and then with propylene oxide. However, such alkoxylates are not examples or properties specified. It is stated that the described alkoxylates show a good detergent and wetting action, combined with a low foaming. In addition, it is stated that the alkoxylates have a desired thickening effect in formulations.

WO 94/11330 betrifft Alkoxylate von 2-Propylheptanol und deren Verwendung. In den Alkoxylaten liegt 2-Propylheptanol, zunächst mit 1 bis 6 mol Propylenoxid und sodann mit 1 bis 10 mol Ethylenoxid umgesetzt, vor. Gemäß den Beispielen wird ein zunächst mit 4 mol Propylenoxid und sodann mit 6 mol Ethylenoxid umgesetztes 2-Propylheptanol eingesetzt. Es wird angegeben, dass die Alkylenoxidaddukte ein verbessertes Verhältnis von Schaumverhalten zu Detergenzwirkung zeigen. Ferner ist angegeben, dass die Alkoxylate ein gutes Benetzungsverhalten zeigen. Sie werden in Detergenzzusammensetzungen zur Reinigung von Textilmaterialien eingesetzt. WO 94/11330 relates to alkoxylates of 2-propylheptanol and their use. In the alkoxylates is 2-propylheptanol, first with 1 to 6 moles of propylene oxide and then reacted with 1 to 10 moles of ethylene oxide before. According to the examples, a 2-propylheptanol reacted first with 4 mol of propylene oxide and then with 6 mol of ethylene oxide is used. It is stated that the alkylene oxide adducts show an improved foam behavior to detergent effect. It is further stated that the alkoxylates show a good wetting behavior. They are used in detergent compositions for cleaning textile materials.

US 2,508,036 betrifft die Verwendung von 2-n-Propylheptanolethoxylaten, die 5 bis 15 mol Ethylenoxid enthalten, als Netzmittel in wässrigen Lösungen. Es ist beschrieben, dass die Produkte als Tenside in Waschmitteln eingesetzt werden können. US 2,508,036 relates to the use of 2-n-propylheptanolethoxylates containing from 5 to 15 moles of ethylene oxide as wetting agents in aqueous solutions. It is described that the products can be used as surfactants in detergents.

Die DE-A-102 18 754 sowie die DE-A-102 18 753 betreffen die Verwendung von C10-Alkanolalkoxylat-Gemischen, insbesondere Alkanolethoxylat-Gemische, derartige C10-Alkanolalkoxylat-Gemische und Verfahren zu ihrer Herstellung. Die DE-A-102 18 752 beschreibt ebenfalls Alkoxylat-Gemische und diese enthaltende Waschmittel wie auch Verfahren zur Herstellung der Alkoxylat-Gemische und die Verwendung des Waschmittels zum Waschen oder Reinigen von Textilien.The DE-A-102 18 754 as well as the DE-A-102 18 753 relate to the use of C 10 -alkanolalkoxylate mixtures, in particular alkanolethoxylate mixtures, such C 10 -alkanol alkoxylate mixtures and processes for their preparation. The DE-A-102 18 752 also describes alkoxylate mixtures and detergents containing them, as well as processes for the preparation of the alkoxylate mixtures and the use of the detergent for washing or cleaning textiles.

WO 02/50006 betrifft verzweigte primäre Alkohole enthaltende Zusammensetzungen und Derivate davon. Es wird ein Produkt beschrieben, das sich von einem verzweigten primären C9-24-Alkohol ableitet, der zunächst mit einem Mol Propylenoxid und sodann Ethylenoxid umgesetzt wird. Bei dem Alkohol kann es sich aber nicht um einen primären Alkohol handeln, da der Rest R2 ein Hydrocarbylrest ist. WO 02/50006 relates to branched primary alcohol-containing compositions and derivatives thereof. A product derived from a branched primary C 9-24 alcohol initially reacted with one mole of propylene oxide and then ethylene oxide is described. However, the alcohol can not be a primary alcohol because the R 2 group is a hydrocarbyl group.

Insbesondere bei der Ethoxylierung von Alkoholen tritt das Problem auf, dass die Alkohole nicht vollständig abreagieren. Dies führt zu einem hohen Gehalt an Restalkohol in den erhaltenen Alkoxylierungsprodukten. Die Vermeidung von größeren Mengen an im Produkt vorliegendem Restalkohol ist insbesondere aus Geruchsgründen vorteilhaft. Die erfindungsgemäß eingesetzten Alkohol-Gemische haben in der Regel einen Eigengeruch, der durch die vollständige Alkoxylierung weitestgehend unterdrückt werden kann. Nach üblichen Verfahren erhaltene Alkoxylate weisen oftmals einen Eigengeruch auf, der für viele Anwendungen störend ist. Weiterhin sind eine verbesserte Netzung auf harten Oberflächen, verbessertes Emulgierverhalten und eine niedrigere CMC (Critical Micell Concentration) wünschenswert.Especially in the ethoxylation of alcohols, the problem arises that the alcohols do not completely react. This leads to a high content of residual alcohol in the resulting alkoxylation. The avoidance of larger amounts of residual alcohol present in the product is particularly advantageous for odor reasons. The alcohol mixtures used according to the invention generally have an inherent odor which can be largely suppressed by complete alkoxylation. Alkoxylates obtained by conventional methods often have an inherent odor which is responsible for many applications are annoying. Furthermore, improved hard surface wetting, improved emulsification behavior, and lower CMC (Critical Micell Concentration) are desirable.

Ausgehend von diesem Stand der Technik bestand eine Aufgabe der vorliegenden Erfindung darin, Zusammensetzungen bereitzustellen, die wenig Restalkohol aufweisen.Starting from this prior art, it was an object of the present invention to provide compositions which have little residual alcohol.

Erfindungsgemäß wird diese Aufgabe gelöst durch Zusammensetzungen, mindestens enthaltend ein Alkoxylat der allgemeinen Formel I:

  • RO(A)n(B)mH (I) in der
    • R ein Alkylrest der allgemeinen Formel C5H11CH(C3H7)CH2- ist,
    • A Propylenoxy ist,
    • B Ethylenoxy oder ein Gemisch aus Ethylenoxy und Propylenoxy ist,
    • n eine ganze oder gebrochene Zahl mit 0 < n < 1 ist,
    • m eine ganze oder gebrochene Zahl mit 0 < m ≤ 20 ist,
mit der Maßgabe, dass für R Isomerengemische eines Alkylrests der allgemeinen Summenformel C5H11CH(C3H7)CH2- aus 70 bis 99 Gew.-% eines Rests R1, in dem C5H11 die Bedeutung n-C5H11 hat und 1 bis 30 Gew.-% eines Rests R2, in dem C5H11 die Bedeutung C2H5CH(CH3)CH2 und/oder CH3CH(CH3)CH2CH2 hat, ausgenommen sind.According to the invention, this object is achieved by compositions comprising at least one alkoxylate of the general formula I:
  • RO (A) n (B) m H (I) in the
    • R is an alkyl radical of the general formula C 5 H 11 CH (C 3 H 7 ) CH 2 -,
    • A is propyleneoxy,
    • B is ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy,
    • n is an integer or fractional number with 0 <n <1,
    • m is an integer or fractional number with 0 <m ≤ 20,
with the proviso that for R isomer mixtures of an alkyl group of the general empirical formula C 5 H 11 CH (C 3 H 7 ) CH 2 - from 70 to 99 wt .-% of a radical R1 in which C 5 H 11 nC 5 H has 11 to 1 to 30 wt .-% of a radical R2 in which C 5 H 11 has the meaning C 2 H 5 CH (CH 3) CH 2 and / or CH 3 CH (CH 3) CH 2 CH 2, except that are.

In der allgemeinen Formel I bezeichnen n und m einen mittleren Wert, der sich als Durchschnitt über alle Moleküle ergibt. Daher können n und m auch von ganzzahligen Werten abweichen.In the general formula I, n and m denote an average value which is the average over all molecules. Therefore, n and m can also differ from integer values.

Propylenoxy steht im Rahmen der vorliegenden Erfindung für -CH2-CH(CH3)-O- oder - CH(CH3)-CH2-O-. Ethylenoxy steht für -CH2-CH2-O-.Propyleneoxy is in the context of the present invention for -CH 2 -CH (CH 3 ) -O- or - CH (CH 3 ) -CH 2 -O-. Ethylenoxy stands for -CH 2 -CH 2 -O-.

In dem in den erfindungsgemäßen Zusammensetzungen mindestens enthaltenen Alkoxylat der allgemeinen Formel I ist an den Rest RO Propylenoxid ringöffnend gebunden. n gibt die Anzahl der Propylenoxidgruppen an und ist eine ganze oder gebrochene Zahl mit 0<n<1.In the alkoxylate of the general formula I which is at least contained in the compositions according to the invention, propylene oxide is attached in a ring-opening manner to the radical RO. n indicates the number of propylene oxide groups and is a whole or fractional number with 0 <n <1.

An die Propylenoxidgruppe ist Ethylenoxid oder ein Gemisch aus Ethylenoxid und Propylenoxid gebunden m steht für die Anzahl der Ethylenoxid oder Ethylenoxid und Propylenoxidgruppen und ist eine ganze oder gebrochene Zahl mit 0 < m ≤ 20, bevorzugt 1 ≤ m ≤ 18, insbesondere 2 ≤ m ≤ 14, beispielsweise 2,5 ≤ m ≤ 14 oder 3 ≤ m ≤ 8.Ethylene oxide or a mixture of ethylene oxide and propylene oxide is bound to the propylene oxide group. M stands for the number of ethylene oxide or ethylene oxide and propylene oxide groups and is a whole or fractional number with 0 <m ≦ 20, preferably 1 ≦ m ≦ 18, in particular 2 ≦ m ≦ 14, for example 2.5 ≦ m ≦ 14 or 3 ≦ m ≦ 8.

In einer bevorzugten Ausführungsform betrifft die vorliegende Erfindung daher Zusammensetzungen, wobei m eine ganze oder gebrochen Zahl von 2 bis 14 ist.Thus, in a preferred embodiment, the present invention relates to compositions wherein m is an integer or fractional number from 2 to 14.

Die erfindungsgemäßen Zusammensetzungen weisen einen niedrigen Gehalt an Restalkohol auf. Überraschend ist, dass der Restalkoholgehalt bei den erfindungsgemäßen Zusammensetzungen, die eine definierte Menge Propylenoxid und anschließend Ethylenoxid oder Ethylenoxid und Propylenoxid aufweisen, niedriger ist, als theoretisch zu erwarten wäre. Aus Restalkoholgehalten von Produkten, die nur Propylenoxid oder nur Ethylenoxid enthalten, kann ein Erwartungswert ermittelt werden, der höher ist als der tatsächlich für die erfindungsgemäßen Copolymerisate bestimmte Restalkoholgehalt.The compositions according to the invention have a low residual alcohol content. It is surprising that the residual alcohol content in the compositions according to the invention which have a defined amount of propylene oxide and subsequently ethylene oxide or ethylene oxide and propylene oxide is lower than would theoretically be expected. From residual alcohol contents of products which contain only propylene oxide or only ethylene oxide, an expected value can be determined which is higher than the residual alcohol content actually determined for the copolymers according to the invention.

Die in den erfindungsgemäßen Zusammensetzungen enthaltenen Alkoxylate erfordern zum Absenken des Restalkohol-Gehaltes nur einen direkt an den Alkohol gebundenen Propylenoxid(PO)-Block von sehr kurzer Länge. Dies ist insbesondere deshalb sehr vorteilhaft, weil die biologische Abbaubarkeit des Produktes bei Verlängerung des PO-Blocks sinkt. Derartige Alkoxylate ermöglichen somit maximale Freiheitsgrade bei der Wahl der Länge des PO-Blockes, wobei die Länge nach unten durch den steigenden Restalkoholgehalt und nach oben durch die Verschlechterung der biologischen Abbaubarkeit begrenzt ist. Dies ist besonders dann vorteilhaft, wenn auf den PO-Block nur ein kurzer Ethylenoxid-Block folgt.The alkoxylates contained in the compositions of the invention require to lower the residual alcohol content only a directly bound to the alcohol propylene oxide (PO) block of very short length. This is particularly advantageous because the biodegradability of the product decreases as the PO block lengthens. Such alkoxylates thus allow maximum degrees of freedom in the choice of the length of the PO block, the length down through the rising Residual alcohol content and is limited upwards by the deterioration of biodegradability. This is particularly advantageous if only a short ethylene oxide block follows the PO block.

In den in den erfindungsgemäßen Zusammensetzungen enthaltenen Alkoxylaten können an den Alkoholrest anschließend zunächst Propylenoxy-Einheiten und daran anschließend Ethylenoxy-Einheiten vorliegen. Haben n und m einen Wert von mehr als 1, so liegen die entsprechenden Alkoxyreste vorzugsweise in Blockform vor. Bei der Alkoxylierung von Alkanolen wird im Allgemeinen eine Verteilung des Alkoxylierungsgrades erhalten, die in gewissem Umfang durch Einsatz unterschiedlicher Alkoxylierungskatalysatoren eingestellt werden kann. Durch die Auswahl geeigneter Mengen der Gruppen A und B kann das Eigenschaftsspektrum der erfindungsgemäßen Zusammensetzungen je nach praktischen Erfordernissen angepasst werden. Besonders bevorzugt wird zunächst mit Propylenoxid und anschließend mit Ethylenoxid umgesetzt.In the alkoxylates contained in the compositions of the invention can then be initially present in the alcohol radical propyleneoxy units and then ethyleneoxy units. If n and m have a value of more than 1, the corresponding alkoxy radicals are preferably present in block form. In the alkoxylation of alkanols, a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to some extent by using different alkoxylation catalysts. By selecting appropriate amounts of Groups A and B, the property spectrum of the compositions of the invention can be adjusted according to practical requirements. Particularly preferred is first reacted with propylene oxide and then with ethylene oxide.

In einer vorteilhaften Ausführungsform betrifft die vorliegende Erfindung Zusammensetzungen, in denen B Ethylenoxy ist.In an advantageous embodiment, the present invention relates to compositions in which B is ethyleneoxy.

Der Alkylrest R ist im Rahmen der vorliegenden Erfindung C5H11CH(C3H7)CH2-, ausgenommen Isomerengemische eines Alkylrests der allgemeinen Summenformel C5H11CH(C3H7)CH2- aus 70 bis 99 Gew.-% eines Rests R1, in dem C5H11 die Bedeutung n-C5H11 hat und 1 bis 30 Gew.-% eines Rests R2, in dem C5H11 die Bedeutung C2H5CH(CH3)CH2 und/oder CH3CH(CH3)CH2CH2 hat. The alkyl radical R is in the context of the present invention C 5 H 11 CH (C 3 H 7 ) CH 2 -, except isomer mixtures of an alkyl group of the general empirical formula C 5 H 11 CH (C 3 H 7 ) CH 2 - from 70 to 99% by weight a radical R1 in which C 5 H 11 has the meaning nC 5 H 11 and 1 to 30% by weight of a radical R2 in which C 5 H 11 has the meaning C 2 H 5 CH (CH 3 ) CH 2 and / or CH 3 CH (CH 3 ) CH 2 CH 2 .

Bei den als Starterverbindung eingesetzten Alkoholen kann es sich erfindungsgemäß auch um Gemische verschiedener Isomere handeln.According to the invention, the alcohols used as starter compound may also be mixtures of different isomers.

Bei der Herstellung der erfindungsgemäßen Zusammensetzungen können beispielsweise Doppelmetallcyanid-Verbindungen als Katalysator eingesetzt werden. Die so erhaltenen erfindungsgemäßen Zusammensetzungen können einen Restmetallgehalt von größer als 0 und weniger als 50 ppm Zink (d.h. mg Metall pro kg Produkt), insbesondere größer als 0 und weniger als 25 ppm Zink oder bevorzugt größer als 0 und weniger als 15 ppm Zink und größer als 0 und weniger als 25 ppm Cobalt, insbesondere größer als 0 und weniger als 15 ppm Cobalt oder bevorzugt größer als 0 und weniger als 7 ppm Cobalt aufweisen.In the preparation of the compositions according to the invention, for example, double metal cyanide compounds can be used as catalyst. The compositions of the invention thus obtained can have a residual metal content of greater than 0 and less than 50 ppm zinc (ie mg metal per kg product), in particular greater than 0 and less than 25 ppm zinc or preferably greater than 0 and less than 15 ppm zinc and greater as 0 and less than 25 ppm cobalt, in particular greater than 0 and less than 15 ppm cobalt or preferably greater than 0 and less than 7 ppm cobalt.

Daher betrifft die vorliegende Erfindung in einer weiteren Ausführungsform Zusammensetzungen, deren Gehalt an Zink größer als 0 und kleiner oder gleich 15 ppm ist oder deren Gehalt an Cobalt größer als 0 und kleiner oder gleich 7 ppm ist oder deren Gehalt an Zink größer als 0 und kleiner oder gleich 15 ppm und deren Gehalt an Cobalt größer als 0 und kleiner oder gleich 7 ppm ist.Therefore, in a further embodiment, the present invention relates to compositions whose content of zinc is greater than 0 and less than or equal to 15 ppm or whose content of cobalt is greater than 0 and less than or equal to 7 ppm or whose content of zinc is greater than 0 and smaller or equal to 15 ppm and their content of cobalt is greater than 0 and less than or equal to 7 ppm.

Darüber hinaus betrifft die vorliegende Erfindung auch ein Verfahren zur Herstellung der Zusammensetzungen durch Umsetzung mindestens eines Alkohols C5H11CH(C3H7)CH2-OH mit Propylenoxid und Ethylenoxid unter Alkoxylierungsbedingungen.Moreover, the present invention also relates to a process for preparing the compositions by reacting at least one alcohol C 5 H 11 CH (C 3 H 7 ) CH 2 -OH with propylene oxide and ethylene oxide under alkoxylation conditions.

Durch die erfindungsgemäß bevorzugt zunächst durchgeführte Propoxylierung und erst nachfolgende Ethoxylierung kann der Gehalt an Restalkohol in den Alkoxylaten vermindert werden, da Propylenoxid gleichmäßiger an die Alkoholkomponente addiert wird. Im Unterschied dazu reagiert Ethylenoxid vorzugsweise mit Ethoxylaten, so dass bei einer anfänglichen Verwendung von Ethylenoxid zur Umsetzung mit den Alkanolen sowohl eine breite Homologenverteilung als auch ein hoher Gehalt an Restalkohol resultieren. Die Vermeidung von größeren Mengen an im Produkt vorliegendem Restalkohol ist insbesondere aus Geruchsgründen vorteilhaft.By virtue of the propoxylation which is preferably carried out initially according to the invention and only subsequent ethoxylation, the content of residual alcohol in the alkoxylates can be reduced since propylene oxide is added more uniformly to the alcohol component. In contrast, ethylene oxide preferably reacts with ethoxylates, such that upon initial use of ethylene oxide to react with the alkanols, both a broad homolog distribution and a high residual alcohol content result. The avoidance of larger amounts of residual alcohol present in the product is particularly advantageous for odor reasons.

Überraschenderweise wurde gefunden, dass dieser Effekt bereits bei der Verwendung von geringen Mengen an Propylenoxid auftritt, also erfindungsgemäß weniger als 1,5 Äquivalente, bezogen auf den eingesetzten Alkohol, insbesondere weniger als 1,2 Äquivalente, besonders bevorzugt weniger als 1 Äquivalent.Surprisingly, it has been found that this effect occurs even when using small amounts of propylene oxide, that is, according to the invention less than 1.5 equivalents, based on the alcohol used, in particular less than 1.2 equivalents, more preferably less than 1 equivalent.

Die Additionsreaktion wird bei Temperaturen von etwa 90 bis 240°C, vorzugsweise von 110 bis 190°C, im geschlossenen Gefäß ausgeführt. Das Alkylenoxid oder die Mischung verschiedener Alkylenoxide wird der Mischung aus erfindungsgemäßen Alkanolgemisch und Katalysator unter dem bei der gewählten Reaktionstemperatur herrschenden Dampfdruck des Alkylenoxidgemisches oder einem höheren Druck zugeführt. Gewünschtenfalls kann das Alkylenoxid mit einem Inertgas (beispielsweise Edelgase, Stickstoff, CO2) bis zu 99,9% verdünnt werden. Dadurch wird insbesondere im Fall des Ethylenoxids eine zusätzliche Sicherheit gegen den Gasphasenzerfall dieses Alkylenoxids gegeben, wobei bei dieser Ausführungsform auch ein weiteres Alkylenoxid, beispielösweise Propylenoxid, als Inertgas im Sinne der Erfindung verwendet werden kann.The addition reaction is carried out at temperatures of about 90 to 240 ° C, preferably from 110 to 190 ° C, in a closed vessel. The alkylene oxide or the mixture of different alkylene oxides is fed to the mixture of alkanol mixture according to the invention and catalyst under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature or at a higher pressure. If desired, the alkylene oxide may be diluted with an inert gas (for example noble gases, nitrogen, CO 2) up to 99.9%. As a result, in particular in the case of ethylene oxide, additional safety is provided against the gas phase decomposition of this alkylene oxide, it also being possible in this embodiment for a further alkylene oxide, for example propylene oxide, to be used as the inert gas in the sense of the invention.

Geeignete Alkoxylierungsbedingungen sind vorstehend und in Nikolaus Schönfeldt, Grenzflächenaktive Äthylenoxid-Addukte, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart 1984 beschrieben. In der Regel wird die Alkoxylierung in Gegenwart basischer Katalysatoren wie KOH in Substanz durchgeführt. Die Alkoxylierung kann jedoch auch unter Mitverwendung eines Lösungsmittels durchgeführt werden.Suitable alkoxylation conditions are described above and in Nikolaus Schonfeldt, Grenzflächenaktive Äthylenoxid adducts, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart 1984 described. In general, the alkoxylation is carried out in the presence of basic catalysts such as KOH in substance. However, the alkoxylation can also be carried out with the concomitant use of a solvent.

Erfindungsgemäß werden die Alkohole zunächst mit einer geeigneten Menge an Propylenoxid und sodann mit einer geeigneten Menge an Ethylenoxid umgesetzt. Dabei wird eine Polymerisation des Alkylenoxids in Gang gesetzt, bei der es zwangsläufig zu einer statistischen Verteilung von Homologen kommt, deren Mittelwert vorliegend mit n und m angegeben wird.According to the invention, the alcohols are first reacted with a suitable amount of propylene oxide and then with a suitable amount of ethylene oxide. In this case, a polymerization of the alkylene oxide is set in motion, which inevitably leads to a statistical distribution of homologues whose mean value is given here with n and m.

Die Länge der Polyetherketten (n + m) schwankt innerhalb des Reaktionsprodukts statistisch um einen Mittelwert, der sich im Wesentlichen aus der Zusatzmenge und den stöchiometrischen Werten ergibt. Je nach eingesetzem Katalysator erhält man unterschiedliche Molekulargewichtsverteilungen. Produkte mit einer engen Molekulargewichtsverteilung weisen beispielsweise häufig eine gute Löslichkeit auf.The length of the polyether chains (n + m) varies randomly within the reaction product by an average, which essentially results from the addition amount and the stoichiometric values. Depending on the catalyst used, different molecular weight distributions are obtained. For example, products with a narrow molecular weight distribution often have good solubility.

Beispielsweise wird die Alkoxylierung durch starke Basen katalysiert, die zweckmäßigerweise in Form eines Alkalialkoholats, Alkalihydroxids, Erdalkalioxids oder Erdalkalihydroxids, in der Regel in einer Menge von 0,01 bis 1 Gew.-% bezogen auf die Menge des Alkanols R-OH, zugesetzt werden, (vergl. G. Gee et al., J. Chem. Soc. (1961), S. 1345 ; B. Wojtech, Makromol. Chem. 66, (1966), S. 180 ).For example, the alkoxylation is catalyzed by strong bases, which are suitably added in the form of an alkali metal alcoholate, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide, usually in an amount of 0.01 to 1 wt .-% based on the amount of the alkanol R-OH , (comp. G. Gee et al., J. Chem. Soc. (1961), p. 1345 ; B. Wojtech, Makromol. Chem. 66, (1966), p. 180 ).

Auch eine saure Katalyse der Additionsreaktion ist möglich. Neben Bronstedsäuren eignen sich auch Lewissäuren wie zum Beispiel AlCl3 oder BF3 Dietherat, BF3, BF3 x H3PO4, SbCl4 x 2 H2O Hydrotalcit (Vgl. P.H. Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963 )). Geeignet als Katalysator sind auch Doppelmetallcyanid (DMC) Verbindungen.Acid catalysis of the addition reaction is also possible. In addition to Bronsted acids are also Lewis acids such as AlCl 3 or BF 3 dietherate, BF 3 , BF 3 x H 3 PO 4 , SbCl 4 x 2 H 2 O hydrotalcite (Cf. PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press, New York (1963 )). Also suitable as a catalyst are double metal cyanide (DMC) compounds.

In einer Ausführungsform betrifft die vorliegende Erfindung ein Verfahren in Gegenwart einer Doppelmetallcyanid-Verbindung als Katalysator durchgeführt. Daher betrifft die vorliegende Erfindung in einer bevorzugten Ausführungsform ein Verfahren zur Herstellung von Zusammensetzungen, wobei die Alkoxylierung in Gegenwart einer Doppelmetallcyanid-Verbindung (DMC-Verbindung) als Katalysator erfolgt.In one embodiment, the present invention relates to a process carried out in the presence of a double metal cyanide compound as a catalyst. Therefore, in a preferred embodiment, the present invention relates to a method for Preparation of compositions wherein the alkoxylation is carried out in the presence of a double metal cyanide compound (DMC compound) as a catalyst.

Als DMC-Verbindung können prinzipiell alle dem Fachmann bekannten geeigneten Verbindungen verwendet werden.As a DMC compound, it is possible in principle to use all suitable compounds known to the person skilled in the art.

Als Katalysator geeignete DMC-Verbindungen sind beispielsweise in der WO 99/16775 und der DE-A-101 17 273 beschrieben. Insbesondere sind für die Alkoxylierung Doppelmetallcyanid-Verbindung der allgemeinen Formel I als Katalysator geeignet:

        M1 a[M2(CN)b(A)c]d · fM1 gXn ·h(H2O)· eL· kP     (I),

in der

  • M1 mindestens ein Metallion, ausgewählt aus der Gruppe bestehend aus Zn2+, Fe2+, Fe3+, Co3+, Ni2+, Mn2+, Co2+, Sn2+, Pb2+, Mo4+, Mo6+, A13+, V4+, V5+, Sr2+, W4+, W6+, Cr2+, Cr3+, Cd2+, Hg2+, Pd2+, Pt2+ V2+, Mg2+ Ca2+, B2+, C2+, La3+, Ce3+, Ce4+, Eu3+, Ti3+, Ti4+, Ag+, Rh2+ Rh3+, Ru2+, Ru3+ ist,
  • M2 mindestens ein Metallion, ausgewählt aus der Gruppe bestehend aus Fe2+, Fe3+, Co2+, Co3+, Mn2+, Mn3+, V4+, V5+, Cr2+, Cr3+, Rh3+, Ru2+, Ir3+ist,
  • A und X unabhängig voneinander ein Anion, ausgewählt aus der Gruppe, bestehend aus Halogenid, Hydroxid, Sulfat, Carbonat, Cyanid, Thiocyanat, Isocyanat, Cyanat, Carboxylat, Oxalat, Nitrat, Nitrosyl, Hydrogensulfat, Phosphat, Dihydrogenphosphat, Hydrogenphosphat oder Hydrogencarbonat sind,
  • L ein mit Wasser mischbarer Ligand ist, ausgewählt aus der Gruppe, bestehend aus Alkoholen, Aldehyden, Ketonen, Ethern, Polyethern, Estern, Polyestern, Polycarbonat, Harnstoffen, Amiden, primären, sekundären und tertiären Aminen, Liganden mit Pyridin-Stickstoff, Nitrilen, Sulfiden, Phosphiden, Phosphiten, Phosphanen, Phosphonaten und Phosphaten,
  • k eine gebrochene oder ganze Zahl größer oder gleich Null ist, und
  • P ein organischer Zusatzstoff ist,
  • a, b, c, d, g und n so ausgewählt sind, dass die Elektroneutralität der Verbindung (I) gewährleistet ist, wobei c = 0 sein kann,
  • e die Anzahl der Ligandenmoleküle eine gebrochenen oder ganze Zahl größer 0 oder 0 ist,
  • f und h unabhängig voneinander eine gebrochene oder ganze Zahl größer 0 oder 0 sind.
DMC compounds suitable as catalyst are described, for example, in US Pat WO 99/16775 and the DE-A-101 17 273 described. In particular, double metal cyanide compounds of general formula I are suitable as catalyst for the alkoxylation:

M 1 a [M 2 (CN) b (A) c ] d · f M 1 g X n · h (H 2 O) · e L · k P (I)

in the
  • M 1 is at least one metal ion selected from the group consisting of Zn 2+ , Fe 2+ , Fe 3+ , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Pb 2+ , Mo 4 + , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Hg 2+ , Pd 2+ , Pt 2+ V 2+ , Mg 2+ Ca 2+ , B 2+ , C 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Ti 3+ , Ti 4+ , Ag + , Rh 2 + Rh 3+ , Ru 2+ , Ru 3+ ,
  • M 2 is at least one metal ion selected from the group consisting of Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr 2+ , Cr 3 + , Rh 3+ , Ru 2+ , Ir 3+ ,
  • A and X are independently an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, bisulfate, phosphate, dihydrogen phosphate, hydrogen phosphate or bicarbonate,
  • L is a water miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphines, phosphonates and phosphates,
  • k is a fractional or integer greater than or equal to zero, and
  • P is an organic additive,
  • a, b, c, d, g and n are selected so as to ensure the electroneutrality of the compound (I), where c = 0,
  • e the number of ligand molecules is a fractional or integer greater than 0 or 0,
  • f and h independently of one another are a fractional or integer greater than 0 or 0.

Als organische Zusatzstoffe P sind zu nennen: Polyether, Polyester, Polycarbonate, Polyalkylenglykolsorbitanester, Polyakylenglykolglycidylether, Polyacrylamid, Poly(acrylamid-co-acrylsäure), Polyacrylsäure, Poly(acrylamid-co-maleinsäure), Polyacrylnitril, Polyalkylacrylate, Polyalkylmethacrylate, Polyvinylmethylether, Polyvinylethylether, Polyvinylacetat, Polyvinylalkohol, Poly-N-vinylpyrrolidon, Poly(N-vinylpyrrolidon-co-acrylsäure), Polyvinylmethylketon, Poly(4-vinylphenol), Poly(acrylsäure-co-styrol), Oxazolinpolymere, Polyalkylenimine, Maleinsäure- und Maleinsäureanhydridcopolymere, Hydroxyethylcellulose, Polyacetate, ionische oberflächen- und grenzflächenaktive Verbindungen, Gallensäure oder deren Salze, Ester oder Amide, Carbonsäureester mehrwertiger Alkohole und Glycoside.The organic additives P are: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamide, poly (acrylamide-co-acrylic acid), polyacrylic acid, poly (acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ether, polyvinyl ethyl ether, Polyvinyl acetate, polyvinyl alcohol, poly-N-vinylpyrrolidone, poly (N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly (4-vinylphenol), poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic and maleic anhydride copolymers, hydroxyethylcellulose, Polyacetates, ionic surfactants and surface-active compounds, bile acids or their salts, esters or amides, carboxylic esters of polyhydric alcohols and glycosides.

Diese Katalysatoren können kristallin oder amorph sein. Für den Fall, dass k gleich null ist, sind kristalline Doppelmetallcyanid-Verbindungen bevorzugt. Im Fall, dass k größer null ist, sind sowohl kristalline, teilkristalline, als auch substantiell amorphe Katalysatoren bevorzugt.These catalysts can be crystalline or amorphous. In the case where k is zero, crystalline double metal cyanide compounds are preferred. In the case where k is greater than zero, both crystalline, partially crystalline, and substantially amorphous catalysts are preferred.

Von den modifizierten Katalysatoren gibt es verschiedene bevorzugte Ausführungsformen. Eine bevorzugte Ausführungsform sind Katalysatoren der Formel (I), bei denen k größer null ist. Der bevorzugte Katalysator enthält dann mindestens eine Doppelmetallcyanid-Verbindung, mindestens einen organischen Liganden und mindestens einen organischen Zusatzstoff P.Of the modified catalysts, there are various preferred embodiments. A preferred embodiment is catalysts of the formula (I) in which k is greater than zero. The preferred catalyst then contains at least one double metal cyanide compound, at least one organic ligand and at least one organic additive P.

Bei einer anderen bevorzugten Ausführungsform ist k gleich null, optional ist e auch gleich null und X ist ausschließlich ein Carboxylat, bevorzugt Formiat, Acetat und Propionat. Derartige Katalysatoren sind in der WO 99/16775 beschrieben. Bei dieser Ausführungsform sind kristalline Doppelmetallcyanid-Katalysatoren bevorzugt. Ferner bevorzugt sind Doppelmetallcyanid-Katalysatoren, wie in der WO 00/74845 beschrieben, die kristallin und plättchenförmig sind.In another preferred embodiment, k is zero, optionally e is also zero and X is exclusively a carboxylate, preferably formate, acetate and propionate. Such catalysts are in the WO 99/16775 described. In this embodiment, crystalline double metal cyanide catalysts are preferred. Further preferred are double metal cyanide catalysts as in WO 00/74845 described which are crystalline and platelike.

Die Herstellung der modifizierten Katalysatoren erfolgt durch Vereinigung einer Metallsalz-Lösung mit einer Cyanometallat-Lösung, die optional sowohl einen organischen Liganden L als auch einen organischen Zusatzstoff P enthalten können. Anschließend werden der organische Ligand und optional der organische Zusatzstoff zugegeben. Bei einer bevorzugten Ausführungsform der Katalysatorherstellung wird zunächst eine inaktive Doppelmetallcyanid-Phase hergestellt und diese anschließend durch Umkristallisation in eine aktive Doppelmetallcyanidphase überführt, wie in der PCT/EP01/01893 beschrieben.The preparation of the modified catalysts is carried out by combining a metal salt solution with a cyanometalate solution, which may optionally contain both an organic ligand L and an organic additive P. Subsequently, the organic ligand and optionally the organic additive are added. In a preferred embodiment of the catalyst preparation, an inactive double metal cyanide phase is first prepared and then converted by recrystallization in an active Doppelmetallcyanidphase, as in PCT / EP01 / 01893 described.

Bei einer anderen bevorzugten Ausführungsform der Katalysatoren sind f, e und k ungleich Null. Dabei handelt es sich um Doppelmetallcyanid-Katalysatoren, die einen mit Wasser mischbaren organischen Ligand (im allgemeinen in Mengen von 0,5 bis 30 Gew.%) und einen organischen Zusatzstoff (im allgemeinen in Mengen von 5 bis 80 Gew.%) enthalten wie in der WO 98/06312 beschrieben. Die Katalysatoren können entweder unter starkem Rühren (24000U/Min mit Turrax) oder unter Rühren hergestellt werden wie in der US 5,158,922 beschrieben.In another preferred embodiment of the catalysts, f, e and k are not equal to zero. These are double metal cyanide catalysts containing a water-miscible organic ligand (generally in amounts of from 0.5 to 30% by weight) and an organic additive (generally in amounts of from 5 to 80% by weight) in the WO 98/06312 described. The catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as in the US 5,158,922 described.

Insbesondere als Katalysator geeignet sind für die Alkoxylierung Doppelmetallcyanid-Verbindungen, die Zink, Kobalt oder Eisen oder zwei davon enthalten. Besonders geeignet ist beispielsweise Berliner Blau.Particularly suitable as catalyst for the alkoxylation double metal cyanide compounds containing zinc, cobalt or iron or two of them. For example, Berlin Blue is particularly suitable.

Bevorzugt werden kristalline DMC-Verbindungen eingesetzt. In einer bevorzugten Ausführungsform wird eine kristalline DMC-Verbindung vom Zn-Co-Typ als Katalysator verwendet, der als weitere Metallsalzkomponente Zinkacetat enthält. Derartige Verbindungen kristallisieren in monokliner Struktur und weisen einen plättchenförmigen Habitus auf. Derartige Verbindungen werden beispielsweise in der WO 00/74845 oder der PCT/EP01/01893 beschrieben.Preference is given to using crystalline DMC compounds. In a preferred embodiment, a Zn-Co type crystalline DMC compound is used as the catalyst containing zinc acetate as the further metal salt component. Such compounds crystallize in monoclinic structure and have a platelet-shaped habit. Such compounds are used for example in the WO 00/74845 or the PCT / EP01 / 01893 described.

Als Katalysator geeignete DMC-Verbindungen können prinzipiell auf alle dem Fachmann bekannten Arten hergestellt werden. Beispielsweise können die DMC-Verbindungen durch direkte Fällung, "incipient wetness"-Methode, durch Herstellung einer Precursor-Phase und anschließende Umkristallisation hergestellt werden.In principle, DMC compounds suitable as catalyst can be prepared in any manner known to those skilled in the art. For example, the DMC compounds can be prepared by direct precipitation, "incipient wetness" method, by preparing a precursor phase and subsequent recrystallization.

Die DMC-Verbindungen können als Pulver, Paste oder Suspension eingesetzt werden oder zu einem Formkörper verformt werden, in Formkörpern, Schäume oder ähnliches eingebracht werden oder auf Formkörper, Schäume oder ähnliches aufgebracht werden.The DMC compounds can be used as a powder, paste or suspension or be shaped into a shaped body, introduced into moldings, foams or the like, or applied to shaped bodies, foams or the like.

Die zur Alkoxylierung eingesetzte Katalysator-Konzentration bezogen auf das Endmengengerüst ist typischerweise kleiner als 2000 ppm (d.h. mg Katalysator pro kg Produkt), bevorzugt kleiner als 1000 ppm, insbesondere kleiner als 500 ppm, besonders bevorzugt kleiner als 100 ppm, beispielsweise kleiner als 50 ppm oder 35 ppm, insbesondere bevorzugt kleiner als 25 ppm.The catalyst concentration used for the alkoxylation, based on the final amount skeleton, is typically less than 2000 ppm (ie mg catalyst per kg product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, more preferably less than 25 ppm.

Die erfindungsgemäßen Zusammensetzungen zeigen eine gute Netzung auf harten Oberflächen. Das vorteilhafte Netzungsverhalten der erfindungsgemäßen Gemische kann beispielsweise durch Messungen des Kontaktwinkels auf Glas, Polyethylenoxid oder Stahl ermittelt werden.The compositions according to the invention show good wetting on hard surfaces. The advantageous wetting behavior of the mixtures according to the invention can be determined, for example, by measurements of the contact angle on glass, polyethylene oxide or steel.

Daher betrifft die vorliegende Erfindung auch die Verwendung einer erfindungsgemäßen Zusammensetzung oder einer nach einem erfindungsgemäßen Verfahren hergestellten Zusammensetzung als Emulgator, Schaumregulierer und als Netzmittel für harte Oberflächen, insbesondere die Verwendung in Waschmitteln, Tensidformulierungen zur Reinigung harter Oberflächen, Feuchthaltemitteln, kosmetischen, pharmazeutischen und Pflanzenschutzformulierungen, Lacken, Beschichtungsmitteln, Klebstoffen, Lederentfettungsmitteln, Formulierungen für die Textilindustrie, Faserverarbeitung, Metallverarbeitung, Lebensmittelindustrie, Wasserbehandlung, Papierindustrie, Fermentation oder Mineralverarbeitung und in Emulsionspolymerisationen.The present invention therefore also relates to the use of a composition according to the invention or a composition prepared by a process according to the invention as emulsifier, foam regulator and hard surface wetting agent, in particular the use in detergents, hard surface detergent formulations, humectants, cosmetic, pharmaceutical and crop protection formulations, Lacquers, coating compositions, adhesives, leather degreasing agents, formulations for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations.

Aus dem verbesserten Netzungsverhalten der erfindungsgemäßen Zusammensetzungen folgt eine bessere Performance bei insbesondere schnellen Reinigungsprozessen. Dies ist insofern überraschend, da durch die Kettenverlängerung des Ausgangsalkohols üblicherweise die dynamischen und netzenden Eigenschaften vermindert werden. Mit den erfindungsgemäßen Zusammensetzungen kann damit die Benetzungsgeschwindigkeit von wässrigen Formulierungen erhöht werden. Die erfindungsgemäßen Zusammensetzungen können damit auch als Solubilisatoren eingesetzt werden, die insbesondere das Netzvermögen von Netzhilfsmitteln auch in verdünnten Systemen nicht negativ, sondern positiv beeinflussen. Sie können zur Erhöhung der Löslichkeit von Netzhilfsmitteln in wässrigen Formulierungen eingesetzt werden, die nicht-ionische Tenside enthalten. Sie dienen insbesondere zur Erhöhung der Benetzungsgeschwindigkeit in wässrigen Netzmitteln.The improved wetting behavior of the compositions according to the invention is followed by better performance, in particular fast cleaning processes. This is surprising insofar as the chain extension of the starting alcohol usually reduces the dynamic and wetting properties. With the compositions according to the invention, it is thus possible to increase the wetting speed of aqueous formulations. The compositions according to the invention can thus also be used as solubilizers which, in particular, do not negatively but positively influence the wetting power of wetting aids, even in dilute systems. They can be used to increase the solubility of wetting agents in aqueous formulations containing nonionic surfactants. They serve in particular to increase the wetting speed in aqueous wetting agents.

Ferner dienen die erfindungsgemäßen Zusammensetzungen zur Verminderung der Grenzflächenspannung, beispielsweise in wässrigen Tensidformulierungen. Die verminderte Grenzflächenspannung kann beispielsweise durch die Pendant-Drop-Methode bestimmt werden. Hieraus ergibt sich auch eine bessere Wirkung der erfindungsgemäßen Zusammensetzungen als Emulgator oder Co-Emulgator. Die erfindungsgemäßen Zusammensetzungen können auch zur Verminderung der Grenzflächenspannung bei kurzen Zeiten von üblicherweise unter einer Sekunde bzw. zur Beschleunigung der Einstellung der Grenzflächenspannung in wässrigen Tensidformulierungen eingesetzt werden.Furthermore, the compositions according to the invention serve to reduce the interfacial tension, for example in aqueous surfactant formulations. The reduced interfacial tension can be determined, for example, by the pendant drop method. This also results in a better effect of the compositions of the invention as an emulsifier or co-emulsifier. The compositions of this invention may also be used to reduce interfacial tension at short times, usually less than one second, or to accelerate the adjustment of interfacial tension in aqueous surfactant formulations.

Nachstehend werden bevorzugte Einsatzgebiete der erfindungsgemäßen Zusammensetzungen näher beschrieben.In the following, preferred fields of use of the compositions according to the invention are described in more detail.

Die erfindungsgemäßen Zusammensetzungen werden vorzugsweise in den folgenden Bereichen eingesetzt:

  • Tensidformulierungen zur Reinigung harter Oberflächen: Geeignete Tensidformulierungen, die mit den erfindungsgemäßen Alkoxylaten additiviert werden können, sind beispielsweise in Formulating Detergents and Personal Care Products von Louis Ho Tan Tai, AOCS Press, 2000 beschrieben.
The compositions according to the invention are preferably used in the following ranges:
  • Surfactant formulations for hard surface cleaning: Suitable surfactant formulations that can be additized with the alkoxylates of the present invention are described, for example, in Formulating Detergents and Personal Care Products by Louis Ho Tan Tai, AOCS Press, 2000.

Sie enthalten beispielsweise als weitere Komponenten Seife, anionische Tenside wie LAS oder Paraffinsulfonate oder FAS oder FAES, Säure wie Phosphorsäure, Amidosulfonsäure, Zitronensäure, Milchsäure, Essigsäure, andere organische und anorganische Säuren, Lösungsmittel wie Ethylenglykol, Isopropanol, Komplexbildner wie EDTA, NTA, MGDA, Phosphonate, Polymere wie Polyacrylate, Copolymere Maleinsäure-Acrylsäure, Alkalispender wie Hydroxide, Silicate, Carbonate, Parfümöle, Oxidationsmittel wie Perborate, Persäuren oder Trichloroisocyanursäure, Na- oder K-Dichlorisocyanurate, Enzyme; siehe auch Milton J. Rosen, Manilal Dahanayake, Industrial Utilization of Surfactants, AOCS Press, 2000 und Nikolaus Schönfeldt, Grenzflächenaktive Ethylenoxidaddukte. Hier sind auch Formulierungen für die anderen genannten Anwendungen im Prinzip abgehandelt. Es kann sich um Haushaltsreiniger wie Allzweckreiniger, Geschirrspülmittel für manuelles wie automatisches Geschirrspülen, Metallentfettung, Industrielle Applikationen wie Reinigungsmittel für die Nahrungsmittelindustrie Flaschenwäsche, etc. handeln. Es kann sich auch um Druckwalzen- und Druckplattenreinigungsmittel in der Druckindustrie handeln. Geeignete weitere Inhaltsstoffe sind dem Fachmann bekannt.

  • Feuchthaltemittel, insbesondere für die Druckindustrie.
  • Kosmetische, pharmazeutische und Pflanzenschutzformulierungen. Geeignete Pflanzenschutzformulierungen sind beispielsweise in der EP-A-0 050 228 beschrieben. Es können für Pflanzenschutzmittel übliche weitere Inhaltsstoffe vorliegen.
  • Lacke, Beschichtungsmittel, Farben, Pigmentpräparationen sowie Klebstoffe in der Lack- und Folienindustrie.
  • Lederentfettungsmittel.
  • Formulierungen für die Textilindustrie wie Egalisiermittel oder Formulierungen zur Garnreinigung;
  • Faserverarbeitung und Hilfsmittel für die Papier- und Zellstoffindustrie.
  • Metallverarbeitung wie Metallveredelung und Galvanobereich.
  • Lebensmittelindustrie.
  • Wasserbehandlung und Trinkwassergewinnung.
  • Fermentation.
  • Mineralverarbeitung und Staubkontrolle.
  • Bauhilfsmittel.
  • Emulsionspolymerisation und Herstellung von Dispersionen.
  • Kühl- und Schmiermittel.
They contain, for example as further components soap, anionic surfactants such as LAS or paraffin sulfonates or FAS or FAES, acid such as phosphoric acid, sulfamic acid, citric acid, lactic acid, acetic acid, other organic and inorganic acids, solvents such as ethylene glycol, isopropanol, complexing agents such as EDTA, NTA, MGDA , Phosphonates, polymers such as polyacrylates, copolymers of maleic-acrylic acid, alkali donors such as hydroxides, silicates, carbonates, perfume oils, oxidizing agents such as perborates, peracids or trichloroisocyanuric acid, Na or K-dichloroisocyanurates, enzymes; See also Milton J. Rosen, Manilal Dahanayake, Industrial Utilization of Surfactants, AOCS Press, 2000, and Nikolaus Schonfeldt, Ethylene Oxide Adduct Surfactants. Here are also formulations for the other applications mentioned dealt with in principle. It can be household cleaners such as all-purpose cleaners, dishwashing detergents for both manual and automatic dishwashing, metal degreasing, industrial applications such as detergents for the food industry, bottle washing, etc. It may also be printing roll and printing plate cleaning agents in the printing industry. Suitable further ingredients are known to the person skilled in the art.
  • Humectants, especially for the printing industry.
  • Cosmetic, pharmaceutical and crop protection formulations. Suitable crop protection formulations are for example in EP-A-0 050 228 described. There may be other usual ingredients for crop protection products.
  • Paints, coatings, paints, pigment preparations and adhesives in the paint and film industry.
  • Leather degreasing.
  • Formulations for the textile industry, such as leveling agents or formulations for cleaning yarn;
  • Fiber processing and auxiliaries for the paper and pulp industry.
  • Metalworking such as metal finishing and electroplating.
  • Food industry.
  • Water treatment and drinking water production.
  • Fermentation.
  • Mineral processing and dust control.
  • Building aids.
  • Emulsion polymerization and preparation of dispersions.
  • Coolants and lubricants.

Solche Formulierungen enthalten üblicherweise Inhaltsstoffe wie Tenside, Gerüst-, Duft- und Farbstoffe, Komplexbildner, Polymere und andere Inhaltsstoffe. Typische Formulierungen sind beispielsweise in WO 01/32820 beschrieben. Weitere für unterschiedliche Anwendungen geeignete Inhaltsstoffe sind in EP-A-0 620 270 , WO 95/27034 , EP-A-0 681 865 , EP-A-0 616 026 , EP-A-0 616 028 , DE-A-42 37 178 und US 5,340,495 und in Schönfeldt, s.o., beispielhaft beschrieben.Such formulations usually contain ingredients such as surfactants, builders, fragrances and dyes, chelating agents, polymers and other ingredients. Typical formulations are, for example, in WO 01/32820 described. Other ingredients suitable for different applications are in EP-A-0 620 270 . WO 95/27034 . EP-A-0 681 865 . EP-A-0 616 026 . EP-A-0 616 028 . DE-A-42 37 178 and US 5,340,495 and in Schönfeldt, as described by way of example.

Allgemein können die erfindungsgemäßen Zusammensetzungen in allen Bereichen eingesetzt werden, in denen die Wirkung von grenzflächenaktiven Stoffen notwendig ist.In general, the compositions of the invention can be used in all areas in which the action of surfactants is necessary.

Die vorliegende Erfindung betrifft daher auch Wasch-, Reinigungs-, Netz-, Beschichtungs-, Klebe-, Lederentfettungs-, Feuchthalte- oder Textilbehandlungsmittel oder kosmetische, pharmazeutische oder Pflanzenschutzformulierung, enthaltend eine erfindungsgemäße Zusammensetzung oder eine Zusammensetzung hergestellt nach einem erfindungsgemäßen Verfahren. Die Mittel enthalten dabei vorzugsweise 0,1 bis 20 Gew.-% der Zusammensetzungen.The present invention therefore also relates to washing, cleaning, wetting, coating, adhesive, leather degreasing, moisturizing or textile treatment compositions or to cosmetic, pharmaceutical or crop protection formulations comprising a composition according to the invention or a composition prepared by a method according to the invention. The compositions preferably contain 0.1 to 20 wt .-% of the compositions.

Die erfindungsgemäßen Zusammensetzungen zeichnen sich insbesondere durch einen geringen Restalkoholgehalt aus, so dass sie für eine Vielzahl von Anwendungsgebieten vorteilhaft geeignet sind.The compositions of the invention are characterized in particular by a low residual alcohol content, so that they are advantageously suitable for a variety of applications.

Claims (8)

  1. A composition at least comprising one alkoxylate of the formula I:

            RO(A)n(B)mH     (I)

    in which
    - R is an alkyl radical of the formula C5H11CH(C3H7) CH2 - ,
    - A is propyleneoxy,
    - B is ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy,
    - n is an integer or fraction where 0 < n < 1,
    - m is an integer or fraction where 0 < m0 ≤ 20,
    with the proviso that for R, isomer mixtures of an alkyl radical of the empirical formula C5H11CH (C3H7) CH2- comprising 70 to 99 % by weight of a radical R1 in which C5H11 has the meaning n-C5H11 and 1 to 30% by weight of a radical R2 in which C5H11 has the meaning C2H5CH (CH3) CH2 and/or CH3CH (CH3) CH2CH2,
    are excluded.
  2. The composition according to claim 1, wherein B is ethyleneoxy.
  3. The composition according to any of claims 1 or, wherein m is an integer or fraction from 2 to 14.
  4. The composition according to any of claims 1 to 3, wherein the content of zinc in the composition is greater than 0 and less than or equal to 15 ppm, or the content of cobalt is greater than 0 and less than or equal to 7 ppm, or the content of zinc is greater than 0 and less than or equal to 15 ppm and the content of cobalt is greater than 0 and less than or equal to 7 ppm.
  5. A process for the preparation of compositions according to any of claims 1 to 4 by reacting at least one alcohol C5H11CH (C3H7) CH2-OH with propylene oxide and ethylene oxide under alkoxylation conditions, the alkoxylation being carried out in the presence of a double-metal cyanide compound as catalyst.
  6. The use of compositions according to any of claims 1 to 4 as emulsifier, foam regulator or as wetting agent for hard surfaces.
  7. The use according to claim 6 in detergents, surfactant formulations for cleaning hard surfaces, humectants, cosmetic, pharmaceutical and crop protection formulations, paints, coating compositions, adhesives, leather-degreasing compositions, formulations for the textile industry, fiber processing, metalworking, food industry, water treatment, paper industry, fermentation or mineral processing and in emulsion polymerizations.
  8. A detergent, cleaner, wetting agent, coating composition, adhesive, leather-degreasing composition, humectant or textile-treatment composition or cosmetic, pharmaceutical or crop protection formulation comprising compositions according to any of claims 1 to 4.
EP03725099A 2002-09-18 2003-04-25 Alkoxylates exhibiting low residual alcohol content Revoked EP1542955B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10243365 2002-09-18
DE10243365A DE10243365A1 (en) 2002-09-18 2002-09-18 Composition containing propoxylated and ethoxylated alkanol, useful as surfactant in e.g. cleaning compositions and pharmaceuticals, has low free alcohol content
PCT/EP2003/004330 WO2004033405A1 (en) 2002-09-18 2003-04-25 Alkoxylates exhibiting low residual alcohol content

Publications (2)

Publication Number Publication Date
EP1542955A1 EP1542955A1 (en) 2005-06-22
EP1542955B1 true EP1542955B1 (en) 2010-10-06

Family

ID=31969218

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03725099A Revoked EP1542955B1 (en) 2002-09-18 2003-04-25 Alkoxylates exhibiting low residual alcohol content

Country Status (12)

Country Link
US (1) US7332465B2 (en)
EP (1) EP1542955B1 (en)
JP (1) JP5134762B2 (en)
CN (1) CN1296337C (en)
AT (1) ATE483675T1 (en)
AU (1) AU2003227678A1 (en)
BR (1) BR0314399A (en)
CA (1) CA2499351A1 (en)
DE (2) DE10243365A1 (en)
ES (1) ES2353745T3 (en)
MX (1) MXPA05002906A (en)
WO (1) WO2004033405A1 (en)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004021434A1 (en) * 2004-04-30 2005-11-24 Basf Ag Fast foam-free neters for hydrophobic surfaces
ATE516376T1 (en) 2004-12-24 2011-07-15 Basf Se USE OF NON-IONIC SURFACTANTS IN METAL EXTRACTION
DE102004063500A1 (en) 2004-12-24 2006-07-06 Basf Ag Use of surfactants in metal extraction
JP5366821B2 (en) * 2006-12-14 2013-12-11 ビーエーエスエフ ソシエタス・ヨーロピア Nonionic emulsifiers for emulsion concentrates for spontaneous emulsification
US20080255378A1 (en) * 2007-04-16 2008-10-16 Bayer Materialscience Llc High productivity process for non-phenolic ethoxylates
US7473677B2 (en) 2007-04-16 2009-01-06 Bayer Materialscience Llc High productivity process for alkylphenol ethoxylates
AR069725A1 (en) * 2007-06-27 2010-02-17 Shell Int Research PROCESS TO PREPARE A COMPOSITION OF ALCOXYLATE AND A COMPOSITION OF ALCOXYLATE
US7741265B2 (en) 2007-08-14 2010-06-22 S.C. Johnson & Son, Inc. Hard surface cleaner with extended residual cleaning benefit
CA2728411A1 (en) * 2008-06-18 2009-12-23 Dow Global Technologies Inc. Cleaning compositions containing mid-range alkoxylates
DE102009002371A1 (en) * 2009-04-15 2010-10-21 Evonik Goldschmidt Gmbh Process for the preparation of odorless polyether alcohols by means of DMC catalysts and their use in cosmetic and / or dermatological preparations
EP2477600B1 (en) * 2009-09-15 2017-12-20 Union Carbide Chemicals & Plastics Technology LLC Silicone replacements for personal care compositions
EP2588437B1 (en) * 2010-06-29 2019-01-02 Dow Global Technologies LLC Branched secondary alcohol alkoxylate surfactants and process to make them
ES2525017T3 (en) 2010-08-03 2014-12-16 Basf Se Abrasive carrier fluids
JP5260621B2 (en) * 2010-12-15 2013-08-14 花王株式会社 Fiber treatment agent
MX360811B (en) * 2011-04-13 2018-11-16 Basf Se Amine and diamine compounds and their use for inverse froth flotation of silicate from iron ore.
JP2015505574A (en) 2012-02-01 2015-02-23 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Cooling and / or lubricating liquid for wafer manufacture
GB201621396D0 (en) * 2016-12-15 2017-02-01 Syngenta Participations Ag Adjuvants
AR118833A1 (en) * 2019-05-03 2021-11-03 Sasol Performance Chemicals Gmbh NON-AQUEOUS DEFOAMING COMPOSITIONS AND THEIR USE IN FOAM CONTROL OF NON-AQUEOUS FOAMS
CN115124709B (en) * 2022-06-29 2023-04-21 东营市金美化工有限公司 Polyether demulsifier using decyl tetradecyl alcohol as initiator and preparation method and application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2508036A (en) 1950-05-16 Compounds having high wetting
SE501132C2 (en) 1992-11-19 1994-11-21 Berol Nobel Ab Use of alkoxylate of 2-propylheptanol in cleaning compositions
DE4416303A1 (en) * 1994-05-09 1995-11-16 Bayer Ag Low-foaming wetting agent and its use
BR0013193A (en) 1999-07-09 2002-07-02 Dow Chemical Co Polymerization of ethylene oxide using metal cyanide catalysts
DE10017197A1 (en) * 2000-04-07 2001-10-11 Basf Ag Alcohol alkoxylates as low-foaming or foam-suppressing surfactants
US6706931B2 (en) 2000-12-21 2004-03-16 Shell Oil Company Branched primary alcohol compositions and derivatives thereof
DE10218753A1 (en) 2002-04-26 2003-11-13 Basf Ag Alkoxylate mixture used as emulsifier, foam regulator and wetting agent, e.g. in detergent, humectant, cosmetic, pharmaceutical, plant protection, coating or emulsion polymerization, contains alkoxylates of 2-propyl-heptan-1-ol isomers
DE10218752A1 (en) 2002-04-26 2003-11-13 Basf Ag Alkoxylate mixture used in laundry and cleaning detergents for washing and cleaning textiles contains alkoxylates of alkanols with different chain lengths with ethylene oxide and optionally other alkylene oxide(s)
DE10218754A1 (en) 2002-04-26 2003-11-13 Basf Ag New and known 2-propyl-heptan-1-ol alkoxylates, used e.g. in cleaning, coating, adhesive, textile treatment, cosmetic, pharmaceutical or plant protection formulations, contain ethylene oxide and other alkylene oxide groups

Also Published As

Publication number Publication date
WO2004033405A1 (en) 2004-04-22
ES2353745T3 (en) 2011-03-04
EP1542955A1 (en) 2005-06-22
DE50313163D1 (en) 2010-11-18
CN1296337C (en) 2007-01-24
CA2499351A1 (en) 2004-04-22
MXPA05002906A (en) 2005-05-27
JP5134762B2 (en) 2013-01-30
CN1688529A (en) 2005-10-26
BR0314399A (en) 2005-07-19
AU2003227678A1 (en) 2004-05-04
US20050272626A1 (en) 2005-12-08
JP2005539133A (en) 2005-12-22
DE10243365A1 (en) 2004-04-01
ATE483675T1 (en) 2010-10-15
US7332465B2 (en) 2008-02-19

Similar Documents

Publication Publication Date Title
EP1503976B1 (en) C sb 10 /sb -ALKANOLALKOXYLATE MIXTURES AND THE USE THEREOF
EP1542955B1 (en) Alkoxylates exhibiting low residual alcohol content
EP1501776B1 (en) C10-alkanolalkoxylates and the use thereof
EP1675811B1 (en) C10 alkanolalkoxylate mixtures and use thereof as novel low-foaming wetting agents
EP1542954A1 (en) Method for producing alkanol alkoxylates at optimal reaction temperatures
EP1542953B1 (en) Method for producing alkoxylated products at optimized reaction pressures
DE10243363A1 (en) Alkoxylate mixture used as emulsifier, foam regulator and wetting agent, e.g. in detergent, humectant, cosmetic, pharmaceutical, plant protection, coating or emulsion polymerization, contains alkoxylates of 2-propyl-heptan-1-ol isomers
EP1663930B1 (en) Alkoxylates that are stable in alkalis
US11634642B2 (en) Biodegradable surfactant
DE10243360A1 (en) New and known 2-propyl-heptan-1-ol alkoxylates, used e.g. in cleaning, coating, adhesive, textile treatment, cosmetic, pharmaceutical or plant protection formulations, contain ethylene oxide and other alkylene oxide groups
DE10218753A1 (en) Alkoxylate mixture used as emulsifier, foam regulator and wetting agent, e.g. in detergent, humectant, cosmetic, pharmaceutical, plant protection, coating or emulsion polymerization, contains alkoxylates of 2-propyl-heptan-1-ol isomers
WO2005026273A1 (en) Solid water-free composite material
Ruland et al. C 10-alkanolalkoxylate mixtures and the use thereof
Ruland et al. C 10-alkanol alkoxylates and the use thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20050418

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

17Q First examination report despatched

Effective date: 20090922

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50313163

Country of ref document: DE

Date of ref document: 20101118

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Effective date: 20110222

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110106

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110207

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110107

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

26 Opposition filed

Opponent name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V.

Effective date: 20110629

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 50313163

Country of ref document: DE

Effective date: 20110629

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110430

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 483675

Country of ref document: AT

Kind code of ref document: T

Effective date: 20110425

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20120530

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110425

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110425

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R103

Ref document number: 50313163

Country of ref document: DE

Ref country code: DE

Ref legal event code: R064

Ref document number: 50313163

Country of ref document: DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20130429

Year of fee payment: 11

Ref country code: GB

Payment date: 20130430

Year of fee payment: 11

Ref country code: SE

Payment date: 20130426

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20130530

Year of fee payment: 11

Ref country code: FR

Payment date: 20130529

Year of fee payment: 11

Ref country code: IT

Payment date: 20130420

Year of fee payment: 11

Ref country code: NL

Payment date: 20130424

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101006

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20130628

Year of fee payment: 11

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

27W Patent revoked

Effective date: 20130721

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20130721

REG Reference to a national code

Ref country code: DE

Ref legal event code: R107

Ref document number: 50313163

Country of ref document: DE

Effective date: 20140123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 20101006

Ref country code: CH

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 20101006

REG Reference to a national code

Ref country code: AT

Ref legal event code: MA03

Ref document number: 483675

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130721

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC

REG Reference to a national code

Ref country code: SE

Ref legal event code: ECNC