EP1542955A1 - Alkoxylates exhibiting low residual alcohol content - Google Patents

Alkoxylates exhibiting low residual alcohol content

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Publication number
EP1542955A1
EP1542955A1 EP03725099A EP03725099A EP1542955A1 EP 1542955 A1 EP1542955 A1 EP 1542955A1 EP 03725099 A EP03725099 A EP 03725099A EP 03725099 A EP03725099 A EP 03725099A EP 1542955 A1 EP1542955 A1 EP 1542955A1
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European Patent Office
Prior art keywords
ppm
less
radical
integer
formulations
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EP03725099A
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German (de)
French (fr)
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EP1542955B1 (en
Inventor
Christian Wulff
Kai-Uwe Baldenius
Martin Scholtissek
Michael Stösser
Norbert Wagner
Edward Bohres
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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) “(B) m H, ner processes for producing such compositions, in particular in the presence of double metal cyanide compounds as a catalyst, and their use as an emulsifier, foam regulator or as a wetting agent for hard surfaces.
  • 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 strongly depend 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. Most of the alkylene oxide groups are preferably in the form of ethylene oxide. According to the examples, only ethoxylated alcohols are used. It is also described that the alcohols can be reacted first with ethylene oxide and then with propylene oxide. However, there are no examples or properties of such alkoxylates specified. It is stated that the alkoxylates described have a good detergent and wetting action combined with low foaming. It is also 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 contain 2-propylheptanol, first reacted with 1 to 6 mol of propylene oxide and then with 1 to 10 mol of ethylene oxide.
  • 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 ratio of foaming behavior to detergent action.
  • the alkoxylates show good wetting behavior. They are used in detergent compositions for cleaning textile materials.
  • No. 2,508,036 relates to the use of 2-n-propylheptanol ethoxylates which contain 5 to 15 mol of ethylene oxide as wetting agents in aqueous solutions. It is described that the products can be used as surfactants in detergents.
  • DE-A-102 18 754 and DE-A-102 18 753 relate to the use of cio-alkanol alkoxylate mixtures, in particular alkanol ethoxylate mixtures, such cio-alkanol alkoxylate mixtures and processes for their preparation.
  • DE-A-102 18 752 also describes alkoxylate mixtures and detergents containing them, as well as processes for producing the alkoxylate mixtures and the use of the detergent for washing or cleaning textiles.
  • the alcohol mixtures used according to the invention generally have their own smell, which can be largely suppressed by the complete alkoxylation. Alkoxylates obtained by conventional processes often have their own odor, which is for many applications is disruptive. Furthermore, improved wetting on hard surfaces, improved emulsification behavior and a lower CMC (Critical Micell Concentration) are desirable.
  • R is a linear or branched alkyl radical having 6 to 19 or 18 carbon atoms
  • A is propyleneoxy
  • - B is ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy
  • n is an integer or fractional number with 0 ⁇ n ⁇ 5
  • m is an integer or fractional number with 0 ⁇ m ⁇ 20
  • R is an alkyl radical of the general formula C 5 H ⁇ CH (C 3 H 7 ) CH -, n is an integer or fraction with 0 ⁇ n ⁇ 1,
  • n and m denote an average value which is the average of all molecules. Therefore, n and m can also deviate from integer values.
  • propyleneoxy represents -CH 2 -CH (CH 3 ) -O- or - CH (CH 3 ) -CH 2 -O-.
  • Ethyleneoxy stands for -CH 2 -CH 2 -O-.
  • n indicates the number of propylene oxide groups and is a whole or fractional number with 0 ⁇ n
  • R is an alkyl radical of the general formula C 5 HnCH (C 3 H 7 ) CH 2 -, n is an integer 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 an integer 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 therefore relates to compositions where m is an integer or fraction 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 then ethylene oxide or ethylene oxide and propylene oxide, is lower than would be expected in theory. From the 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 according to the invention require only a very short length of propylene oxide (PO) block bound directly to the alcohol in order to lower the residual alcohol content. This is particularly advantageous because the biodegradability of the product decreases when the PO block is extended. Such alkoxylates thus allow maximum degrees of freedom in the choice of the length of the PO block, the length decreasing due to the increasing Residual alcohol content and is capped by the deterioration in biodegradability. This is particularly advantageous if the PO block is followed by only a short ethylene oxide block.
  • PO propylene oxide
  • propyleneoxy units can then be present next to the alcohol radical and then ethyleneoxy units. If n and m have a value of more than 1, the corresponding alkoxy radicals are preferably in block form.
  • a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to a certain extent by using different alkoxylation catalysts.
  • the present invention relates to compositions in which B is ethyleneoxy.
  • the alkyl radical R is a linear or single or multiple branched alkyl radical having 6 to 19 or 18 carbon atoms, with the exception of isomer mixtures of an alkyl radical of the general empirical formula C 5 HnCH (C 3 H 7 ) CH 2 -
  • Suitable alcohols which are branched have the hydroxyl group z. B. in 2-, 3-, 4- position, etc.
  • the alkyl radical can be linear or branched again and z.
  • B. wear methyl or ethyl substituents.
  • Examples of suitable alcohols are 2-decanol, 2-dodecanol, 2-tetradecanol, 2-hexadecanol, each accessible by adding water to ⁇ -olefins, (6-ethyl) -2-nonaol, obtainable by reacting 2-ethylhexanol with acetone and subsequent hydrogenation, (7-Ethyl) -3-decanol or (3-methyl-6-ethyl) -2-nonanol, obtainable by reacting 2-ethylhexanol with methyl ethyl ketone and subsequent hydrogenation, 2-hexadecanol or 2-octadecanol, obtainable by reaction of C ⁇ 3 / C 15 - aldehyde with acetone, 3-nonadecanol or (3-methyl) -2-octadecanol, (3-methyl) -2-hexadecanol, 3-heptadecanol, obtainable by reaction of
  • Examples of other suitable alcohols are linear Ci 2 - ⁇ 4 alkanes with a hydroxyl group in a non-terminal position along the chain or mixtures thereof (e.g. Softanol ® alcohols from Nippen Shokubai or Tergitol ® alcohols from Dow.
  • R is an alkyl radical having 8 to 15 carbon atoms, preferably 10 to 15 carbon atoms, such as, for example, propylheptyl.
  • Alkyl radicals R which are suitable according to the invention are derived, for example, from the alcohols octanol, 2-ethylhexanol, nonanol, decanol, undekanol, dodekanol, tridekanol,
  • a preferred embodiment relates to the present compositions, where R is an alkyl radical of the general formula C 5 H ⁇ CH (C 3 H 7 ) CH 2 -.
  • the alcohols used as starter compounds according to the invention can be Guerbet alcohols, in particular ethylhexanol, propylheptanol,
  • the present invention particularly relates to one preferred embodiment, a method in which the starter compound is a Guerbet alcohol.
  • the alcohols used as starter compound can also be mixtures of different isomers.
  • Secondary alcohols or mixtures are also suitable. These can be obtained, for example, by adding ketones to aldehydes with subsequent hydrogenation as described in DE-A-100 35 617. Methyl ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone are preferred. Paraffin oxidation products which are produced, for example, by Bashkirov oxidation are also suitable. Products from Cn to C 6 paraffin mixtures, particularly products from C12-14 paraffin mixtures, are preferred here. Suitable alcohols are also e.g. B. secondary alcohols obtained by adding water to olefins or by radical or other oxidation of olefins.
  • Double metal cyanide compounds for example, can be used as catalysts in the preparation of the compositions according to the invention.
  • the compositions according to 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 of 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 have less than 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 therefore relates to compositions whose zinc content is greater than 0 and less than or equal to 15 ppm or whose cobalt content is greater than 0 and less than or equal to 7 ppm or whose zinc content is greater than 0 and less or equal to 15 ppm and whose cobalt content is greater than 0 and less than or equal to 7 ppm.
  • the present invention also relates to a process for the preparation of the compositions by reacting at least one alcohol ROH with propylene oxide and ethylene oxide under alkoxylation conditions.
  • the propoxylation which is preferably carried out first according to the invention and only subsequent ethoxylation can reduce the content of residual alcohol in the alkoxylates, since propylene oxide is added more uniformly to the alcohol component.
  • ethylene oxide preferably reacts with ethoxylates, so that when ethylene oxide is initially used for reaction with the alkanols, both a broad homolog distribution and a high content of residual alcohol result. Avoiding large amounts of residual alcohol present in the product is particularly advantageous for reasons of smell.
  • 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 the alkanol mixture according to the invention and the catalyst under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature or a higher pressure.
  • the alkylene oxide can be diluted with an inert gas (for example noble gases, nitrogen, CO 2 ) up to 99.9%. This provides additional security against the gas phase decay of this alkylene oxide, in particular in the case of ethylene oxide, and in this embodiment a further alkylene oxide, for example propylene oxide, can also be used as inert gas in the sense of the invention.
  • Suitable alkoxylation conditions are above and in Nikolaus Schönfeldt, interfacial ethylene oxide adducts,ticianliche Verlagsgesellschaft mbH Stuttgart 1984 described.
  • the alkoxylation is carried out in the presence of basic catalysts such as KOH in bulk.
  • the alkoxylation can also be carried out using a solvent.
  • the alcohols are first reacted with a suitable amount of propylene oxide and then with a suitable amount of ethylene oxide. This initiates polymerization of the alkylene oxide, which inevitably leads to a statistical distribution of homologs, the mean value of which is given here as n and m.
  • the length of the polyether chains (n + m) varies statistically within the reaction product around an average value, which essentially results from the amount added 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 expediently added in the form of an alkali metal alcoholate, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide, generally in an amount of 0.01 to 1% by weight, based on the amount of the alkanol R 2 --OH (see 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 A1C1 3 or BF 3 dietherate, BF 3 , BF 3 x H 3 PO 4 , SbCl 4 x 2 H 2 O, hydrotalcite (see PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press) are also suitable , New York (1963)).
  • Double metal cyanide (DMC) compounds are also suitable as catalysts.
  • 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, the alkoxylation taking place in the presence of a double metal cyanide compound (DMC compound) as a catalyst.
  • DMC compound double metal cyanide compound
  • DMC compounds suitable as catalysts are described, for example, in WO 99/16775 and DE-A-101 17 273.
  • double metal cyanide compounds of the general formula I are suitable as catalysts for the alkoxylation:
  • 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 + is
  • a and X independently of one another are an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrogen sulfate,
  • 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 whole number greater than or equal to zero
  • e the number of ligand molecules is a fractional or an integer greater than 0 or 0,
  • f and h are independently a fractional or whole number greater than 0 or 0.
  • organic additives P are mentioned: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyakylene glycol glycidyl ethers, polyacrylamide,
  • catalysts can be crystalline or amorphous. In the event that k is zero, crystalline double metal cyanide compounds are preferred. In the event that k is greater than zero, both crystalline, partially crystalline and substantially amorphous catalysts are preferred. There are various preferred embodiments of the modified catalysts. A preferred embodiment are 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 described in WO 99/16775.
  • crystalline double metal cyanide catalysts are preferred.
  • Double metal cyanide catalysts, as described in WO 00/74845, which are crystalline and platelet-shaped, are furthermore preferred.
  • the modified catalysts are produced by combining a metal salt solution with a cyanometalate solution, which can optionally contain both an organic ligand L and an organic additive P.
  • the organic ligand and optionally the organic additive are then added.
  • an inactive double metal cyanide phase is first produced and this is subsequently converted into an active double metal cyanide phase by recrystallization, as described in PCT / EP01 / 01893.
  • f, e and k are not equal to zero.
  • double metal cyanide catalysts which contain a water-miscible organic ligand (generally in amounts of 0.5 to 30% by weight) and an organic additive (generally in amounts of 5 to 80% by weight) such as described in WO 98/06312.
  • the catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as described in US Pat. No. 5,158,922.
  • Double metal cyanide compounds which contain zinc, cobalt or iron or two thereof are particularly suitable as catalysts for the alkoxylation. Berlin blue, for example, is particularly suitable.
  • Crystalline DMC compounds are preferably used.
  • a crystalline DMC compound of the Zn-Co type is used as the catalyst, which contains zinc acetate as a further metal salt component.
  • Such compounds crystallize in a monoclinic structure and have a platelet-shaped habit.
  • Such connections are described for example in WO 00/74845 or PCT / EP01 / 01893.
  • DMC compounds suitable as catalysts can in principle be produced in all ways known to the person skilled in the art.
  • the DMC compounds can be produced by direct precipitation, the “incipient wetness” method, by preparation of a precursor phase and subsequent recrystallization.
  • the DMC compounds can be used as a powder, paste or suspension or deformed into a shaped body, introduced into shaped bodies, foams or the like, or applied to shaped bodies, foams or the like.
  • the catalyst concentration used for the alkoxylation, based on the final quantity structure is typically less than 2000 ppm (ie mg catalyst per kg of 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, particularly 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 measuring 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 an emulsifier, foam regulator and as a wetting agent for hard surfaces, in particular the use in detergents, surfactant formulations for cleaning hard surfaces, humectants, cosmetic, pharmaceutical and crop protection formulations, Paints, coating materials, 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 results in better performance, in particular in fast cleaning processes. This is surprising in that the chain and lengthening of the starting alcohol usually reduces the dynamic and wetting properties. With the compositions according to the invention, the wetting rate of aqueous formulations can thus be increased.
  • the compositions according to the invention can thus also be used as solubilizers, which in particular do not negatively, but rather positively influence the wetting ability of wetting aids, even in dilute systems. They can be used to increase the solubility of wetting aids in aqueous formulations that contain non-ionic surfactants. They are used in particular to increase the wetting rate in aqueous wetting agents.
  • compositions according to the invention also serve to reduce the interfacial tension, for example in aqueous surfactant formulations.
  • the reduced interfacial tension can be determined, for example, using the pendant drop method. This also results in a better effect of the compositions according to the invention as an emulsifier or co-emulsifier.
  • the compositions according to the invention can also be used to reduce the interfacial tension in short times of usually less than one second or to accelerate the setting of the interfacial tension in aqueous surfactant formulations. Preferred areas of use of the compositions according to the invention are described in more detail below.
  • compositions according to the invention are preferably used in the following areas:
  • Surfactant formulations for cleaning hard surfaces Suitable surfactant formulations which can be added with the alkoxylates according to the invention are, for example, in Formulating Detergents and Personal Care
  • soap such as LAS or paraffin sulfonates or FAS or FAES
  • acids such as phosphoric acid, amidosulfonic 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 maleic acid-acrylic acid, alkali donors such as hydroxides, silicates, carbonates, perfumes, oxidizing agents such as perborates, peracids or trichloroisocyanuric acid, Na- or K-dichloroisocyanurates, enzymes; see also
  • Metal degreasing industrial applications such as detergents for the food industry, bottle washing, etc. It can also be printing roller and 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 are described, for example, in EP-A-0 050 228. There may be other common ingredients for pesticides.
  • Paints, coatings, paints, pigment preparations and adhesives in the paint and film industry Paints, coatings, paints, pigment preparations and adhesives in the paint and film industry.
  • Formulations for the textile industry such as leveling agents or formulations for yarn cleaning.
  • Metal processing such as metal finishing and electroplating.
  • Emulsion polymerization and preparation of dispersions Emulsion polymerization and preparation of dispersions.
  • Such formulations usually contain ingredients such as surfactants, builders, fragrances and dyes, complexing agents, polymers and other ingredients. Typical formulations are described, for example, in WO 01/32820. Further 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.
  • compositions according to the invention can be used in all areas in which the action of surface-active substances is necessary.
  • the present invention therefore also relates to detergents, cleaning agents, wetting agents, coatings, adhesives, leather degreasing agents, moisturizers or textile treatment agents or cosmetic, pharmaceutical or crop protection formulations comprising a composition according to the invention or a composition produced by a method according to the invention.
  • the agents preferably contain 0.1 to 20% by weight of the compositions.
  • compositions according to the invention are characterized in particular by a low residual alcohol content, so that they are advantageously suitable for a large number of fields of application.

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  • 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)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Medicinal Preparation (AREA)
  • Cosmetics (AREA)

Abstract

The invention concerns compositions comprising at least one alkoxylate of general formula RO(A)n(B)mH, a method for producing same, in particular in the presence of double metal cyanide compounds which act as catalysts, as well as their use as emulsifiers, foam adjusting or wetting agents for hard surfaces. The invention also concerns the use of said compositions in detergents and surfactant formulations.

Description

Alkoxylate mit niedrigem Restalkohol-Gehalt Low residual alcohol alkoxylates
Die vorliegende Erfindung betrifft Zusammensetzungen, mindestens enthaltend ein Alkoxylat der allgemeinen Formel RO(A)„(B)mH, Nerfahren zur Herstellung derartiger Zusammensetzungen, insbesondere in Gegenwart von Doppelmetallcyanid- Verbindungen als Katalysator, sowie deren Nerwendung als Emulgator, Schaumregulierer oder als Νetzmittel 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) “(B) m H, ner processes for producing such compositions, in particular in the presence of double metal cyanide compounds as a catalyst, and their use as an emulsifier, foam regulator or as a wetting agent for hard surfaces. The present invention also relates to the use of such compositions in detergents and surfactant formulations.
Nerfahren 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 Nerfahren zur Ethoxylierung von hydroxyfunktionellen Starterverbindungen beschrieben, das in Gegenwart einer Doppelmetallcyanid-Nerbindung als Katalysator durchgeführt wird.Processes for the alkoxylation of aliphatic alcohols and the alkoxylates obtained are known in principle from the prior art. WO 01/04183, for example, describes a ner process for the ethoxylation of hydroxy-functional starter compounds which is carried out in the presence of a double metal cyanide bond 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 strongly depend on the type of alcohol and the type and amount of alkoxide adducts.
WO 94/11331 betrifft die Nerwendung 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. Most of the alkylene oxide groups are preferably in the form of ethylene oxide. According to the examples, only ethoxylated alcohols are used. It is also described that the alcohols can be reacted first with ethylene oxide and then with propylene oxide. However, there are no examples or properties of such alkoxylates specified. It is stated that the alkoxylates described have a good detergent and wetting action combined with low foaming. It is also 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. The alkoxylates contain 2-propylheptanol, first reacted with 1 to 6 mol of propylene oxide and then with 1 to 10 mol of ethylene oxide. 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 ratio of foaming behavior to detergent action. It is also stated that the alkoxylates show 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.No. 2,508,036 relates to the use of 2-n-propylheptanol ethoxylates which contain 5 to 15 mol 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 Cio- Alkanolalkoxylat-Gemischen, insbesondere Alkanolethoxylat-Gemische, derartige Cio- 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.DE-A-102 18 754 and DE-A-102 18 753 relate to the use of cio-alkanol alkoxylate mixtures, in particular alkanol ethoxylate mixtures, such cio-alkanol alkoxylate mixtures and processes for their preparation. DE-A-102 18 752 also describes alkoxylate mixtures and detergents containing them, as well as processes for producing the alkoxylate mixtures and the use of the detergent for washing or cleaning textiles.
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.In particular, when ethoxylating alcohols, the problem arises that the alcohols do not react completely. This leads to a high content of residual alcohol in the alkoxylation products obtained. Avoiding large amounts of residual alcohol present in the product is particularly advantageous for reasons of smell. The alcohol mixtures used according to the invention generally have their own smell, which can be largely suppressed by the complete alkoxylation. Alkoxylates obtained by conventional processes often have their own odor, which is for many applications is disruptive. Furthermore, improved wetting on hard surfaces, improved emulsification behavior and a 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:According to the invention, this object is achieved by compositions containing at least one alkoxylate of the general formula I:
RO(A)n(B)mH (I) in derRO (A) n (B) m H (I) in the
R ein linearer oder verzweigter Alkylrest mit 6 bis 19 oder 18 C-Atomen ist, A Propylenoxy ist, - B Ethylenoxy oder ein Gemisch aus Ethylenoxy und Propylenoxy ist, n eine ganze oder gebrochene Zahl mit 0 < n < 5 ist, m eine ganze oder gebrochene Zahl mit 0 < m < 20 ist,R is a linear or branched alkyl radical having 6 to 19 or 18 carbon atoms, A is propyleneoxy, - B is ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy, n is an integer or fractional number with 0 <n <5, m is an integer or fractional number with 0 <m <20,
wobei wenn R ein Alkylrest der allgemeinen Formel C5HπCH(C3H7)CH - ist, n eine ganze oder gebrochene Zahl mit 0 < n < 1 ist,where R is an alkyl radical of the general formula C 5 HπCH (C 3 H 7 ) CH -, n is an integer or fraction with 0 <n <1,
mit der Maßgabe, dass für R Isomerengemische eines Alkylrests der allgemeinen Summenformel C5HπCH(C3H7)CH2- auswith the proviso that for R isomer mixtures of an alkyl radical of the general empirical formula C 5 H π CH (C 3 H 7 ) CH 2 -
70 bis 99 Gew.-% eines Rests Rl, in dem C5H11 die Bedeutung n-C5Hn hat und 1 bis 30 Gew.-% eines Rests R2, in dem C5Hι 1 die Bedeutung70 to 99 wt .-% of a radical Rl, in which C 5 H 11 has the meaning nC 5 Hn and 1 to 30 wt .-% of a radical R2, in which C 5 Hι 1 has the meaning
C2H5CH(CH3)CH2 und oder CH3CH(CH3)CH2CH2 hat, ausgenommen sind.C 2 H 5 CH (CH 3 ) CH 2 and or CH 3 CH (CH 3 ) CH 2 CH 2 , are excluded.
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. Propylenoxy steht im Rahmen der vorliegenden Erfindung für -CH2-CH(CH3)-O- oder - CH(CH3)-CH2-O-. Ethylenoxy steht für -CH2-CH2-O-.In the general formula I, n and m denote an average value which is the average of all molecules. Therefore, n and m can also deviate from integer values. In the context of the present invention, propyleneoxy represents -CH 2 -CH (CH 3 ) -O- or - CH (CH 3 ) -CH 2 -O-. Ethyleneoxy 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 < nIn the alkoxylate of the general formula I at least contained in the compositions according to the invention, propylene oxide is bonded to the radical RO in a ring-opening manner, n indicates the number of propylene oxide groups and is a whole or fractional number with 0 <n
< 5, beispielsweise 0 < n < 2, bevorzugt 0 < n < 1,5, besonders bevorzugt 0 < n < 1,2, insbesondere 0 < n < 1. Wenn R ein Alkylrest der allgemeinen Formel C5HnCH(C3H7)CH2- ist, ist n eine ganze oder gebrochene Zahl mit 0 < n < 1.<5, for example 0 <n <2, preferably 0 <n <1.5, particularly preferably 0 <n <1.2, in particular 0 <n <1. If R is an alkyl radical of the general formula C 5 HnCH (C 3 H 7 ) CH 2 -, n is an integer 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 1Ethylene 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 an integer or fractional number with 0 <m <20, preferably 1
< m < 18, insbesondere 2 < m < 14, beispielsweise 2,5 < m < 14 oder 3 < m < 8.<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.In a preferred embodiment, the present invention therefore relates to compositions where m is an integer or fraction 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 then ethylene oxide or ethylene oxide and propylene oxide, is lower than would be expected in theory. From the 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 according to the invention require only a very short length of propylene oxide (PO) block bound directly to the alcohol in order to lower the residual alcohol content. This is particularly advantageous because the biodegradability of the product decreases when the PO block is extended. Such alkoxylates thus allow maximum degrees of freedom in the choice of the length of the PO block, the length decreasing due to the increasing Residual alcohol content and is capped by the deterioration in biodegradability. This is particularly advantageous if the PO block is followed by only a short ethylene oxide 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 according to the invention, propyleneoxy units can then be present next to the alcohol radical and then ethyleneoxy units. If n and m have a value of more than 1, the corresponding alkoxy radicals are preferably in block form. In the alkoxylation of alkanols, a distribution of the degree of alkoxylation is generally obtained, which can be adjusted to a certain extent by using different alkoxylation catalysts. By selecting suitable amounts of groups A and B, the property spectrum of the compositions according to the invention can be adapted according to practical requirements. It is particularly preferred to react first 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 ein linearer oder einfach oder mehrfach verzweigter Alkylrest mit 6 bis 19 oder 18 C- Atomen, ausgenommen Isomerengemische eines Alkylrests der allgemeinen Summenformel C5HnCH(C3H7)CH2- ausIn the context of the present invention, the alkyl radical R is a linear or single or multiple branched alkyl radical having 6 to 19 or 18 carbon atoms, with the exception of isomer mixtures of an alkyl radical of the general empirical formula C 5 HnCH (C 3 H 7 ) CH 2 -
70 bis 99 Gew.-% eines Rests Rl, in dem C5Hπ die Bedeutung n-C5Hn hat und 1 bis 30 Gew.-% eines Rests R2, in dem C5Hn die Bedeutung C2H5CH(CH3)CH2 und/oder CH3CH(CH3)CH2CH2 hat.70 to 99% by weight of a radical Rl in which C 5 Hπ has the meaning nC 5 Hn and 1 to 30% by weight of a radical R2 in which C 5 Hn has the meaning C 2 H 5 CH (CH 3 ) Has CH 2 and / or CH 3 CH (CH 3 ) CH 2 CH 2 .
Geeignete Alkohole, die verzweigt sind, weisen die Hydroxylgruppe z. B. in 2-, 3-, 4- Position usw. auf. Der Alkylrest kann linear oder nochmals verzweigt sein und z. B. Methyl- oder Ethylsubstituenten tragen.Suitable alcohols which are branched have the hydroxyl group z. B. in 2-, 3-, 4- position, etc. The alkyl radical can be linear or branched again and z. B. wear methyl or ethyl substituents.
Beispiele geeigneter Alkohole sind 2-Decanol, 2-Dodecanol, 2-Tetradecanol, 2-Hexadecanol, jeweils zugänglich durch Addition von Wasser an α-Olefine, (6-Ethyl)-2-nonaol, erhältlich durch Umsetzung von 2- Ethylhexanol mit Aceton und anschließende Hydrierung, (7-Ethyl)-3-decanol bzw. (3- Methyl-6-ethyl)-2-nonanol, erhältlich durch Umsetzung von 2-Ethylhexanol mit Methylethylketon und anschließende Hydrierung, 2-Hexadecanol bzw. 2-Octadecanol, erhältlich durch Umsetzung von Cι3/C 15- Aldehyd mit Aceton, 3-Nonadecanol bzw. (3- Methyi)-2-octadecanol, (3-Methyl)-2-hexadecanol, 3-Heptadecanol, erhältlich durch Umsetzung von Cι3/Cι5-Aldehyd mit Methylethylketon. Die Umsetzungsprodukte auf Basis von Cι3/Cι5-Aldehyd sind im technischen Gemisch zu etwa 40 - 50% in alpha- Position verzweigt.Examples of suitable alcohols are 2-decanol, 2-dodecanol, 2-tetradecanol, 2-hexadecanol, each accessible by adding water to α-olefins, (6-ethyl) -2-nonaol, obtainable by reacting 2-ethylhexanol with acetone and subsequent hydrogenation, (7-Ethyl) -3-decanol or (3-methyl-6-ethyl) -2-nonanol, obtainable by reacting 2-ethylhexanol with methyl ethyl ketone and subsequent hydrogenation, 2-hexadecanol or 2-octadecanol, obtainable by reaction of Cι 3 / C 15 - aldehyde with acetone, 3-nonadecanol or (3-methyl) -2-octadecanol, (3-methyl) -2-hexadecanol, 3-heptadecanol, obtainable by reaction of Cι 3 / Cι 5 - Aldehyde with methyl ethyl ketone. The reaction products based on C 3 / C 5 aldehyde are branched in the technical mixture to about 40-50% in the alpha position.
Beispiele weiterer geeigneter Alkohole sind lineare Ci2-ι4-Alkane mit einer Hydroxylgruppe in einer nicht endständigen Position entlang der Kette bzw. Gemische davon (z. B. Softanol®-Alkohole von Nippen Shokubai oder Tergitol®-Alkohole von Dow.Examples of other suitable alcohols are linear Ci 2 -ι 4 alkanes with a hydroxyl group in a non-terminal position along the chain or mixtures thereof (e.g. Softanol ® alcohols from Nippen Shokubai or Tergitol ® alcohols from Dow.
Insbesondere ist R ein Alkylrest mit 8 bis 15 C-Atomen, bevorzugt 10 bis 15 C-Atomen wie beispielsweise Propylheptyl.In particular, R is an alkyl radical having 8 to 15 carbon atoms, preferably 10 to 15 carbon atoms, such as, for example, propylheptyl.
Erfindungsgemäß geeignete Alkylreste R leiten sich beispielsweise von den Alkoholen Octanol, 2-Ethylhexanol, Nonanol, Dekanol, Undekanol, Dodekanol, Tridekanol,Alkyl radicals R which are suitable according to the invention are derived, for example, from the alcohols octanol, 2-ethylhexanol, nonanol, decanol, undekanol, dodekanol, tridekanol,
Tetradekanol, Pentadekanol, iso-Octanol, iso-Nonanol, iso-Dekanol, iso-Undekanol, iso-Tetradekanol, pentadekanol, iso-octanol, iso-nonanol, iso-decanol, iso-undekanol, iso-
Dodekanol, 2-Butyloctanol, iso-Tridekanol, iso-Tetradekanol, iso-Pentadekanol, bevorzugt iso-Dekanol, 2-Propylheptanol, Tridekanol, iso-Tridekanol oder von Gemischen aus C13- bis C15-Alkoholen ab.Dodekanol, 2-butyloctanol, iso-tridekanol, iso-tetradekanol, iso-pentadecanol, preferably iso-decanol, 2-propylheptanol, tridekanol, iso-tridekanol or of mixtures of C13 to C15 alcohols.
Eine bevorzugte Ausführungsform betrifft die vorliegenden Zusammensetzungen, wobei R ein Alkylrest der allgemeinen Formel C5HιιCH(C3H7)CH2- ist.A preferred embodiment relates to the present compositions, where R is an alkyl radical of the general formula C 5 HιιCH (C 3 H 7 ) CH 2 -.
Beispielsweise kann es sich bei den erfindungsgemäß als Starterverbindung eingesetzten Alkoholen um Guerbet-Alkohole handeln, insbesondere Ethylhexanol, Propylheptanol,For example, the alcohols used as starter compounds according to the invention can be Guerbet alcohols, in particular ethylhexanol, propylheptanol,
Butyloctanol. Daher betrifft die vorliegende Erfindung auch in einer besonders bevorzugten Ausfiihrungsform ein Verfahren, wobei die Starterverbindung ein Guerbet- Alkohol ist.Butyloctanol. Therefore, the present invention particularly relates to one preferred embodiment, a method in which the starter compound is a Guerbet alcohol.
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 can also be mixtures of different isomers.
Weiterhin sind auch sekundäre Alkohole oder Gemische geeignet. Diese können beispielsweise erhältlich sein durch die Addition von Ketonen an Aldehyde mit nachfolgender Hydrierung wie in der DE-A-100 35 617 beschrieben. Bevorzugt sind dabei Methylketone wie Aceton, Methylethylketon oder Methylisobutylketon. Geeignet sind auch Paraffin-Oxidationsprodukte, die zum Beispiel durch Bashkirov-Oxidation entstehen. Hier sind Produkte aus Cn- bis Cι6-Paraffin-Gemischen, besonders Produkte aus C12-14- Paraffin-Gemischen, bevorzugt. Geeignete Alkohole sind auch z. B. sekundäre Alkohole, die man durch Addition von Wasser an Olefine oder durch radikalische oder sonstige Oxidation von Olefinen erhält.Secondary alcohols or mixtures are also suitable. These can be obtained, for example, by adding ketones to aldehydes with subsequent hydrogenation as described in DE-A-100 35 617. Methyl ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone are preferred. Paraffin oxidation products which are produced, for example, by Bashkirov oxidation are also suitable. Products from Cn to C 6 paraffin mixtures, particularly products from C12-14 paraffin mixtures, are preferred here. Suitable alcohols are also e.g. B. secondary alcohols obtained by adding water to olefins or by radical or other oxidation of olefins.
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.Double metal cyanide compounds, for example, can be used as catalysts in the preparation of the compositions according to the invention. The compositions according to 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 of 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 have less than 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. Darüber hinaus betrifft die vorliegende Erfindung auch ein Verfahren zur Herstellung der Zusammensetzungen durch Umsetzung mindestens eines Alkohols ROH mit Propylenoxid und Ethylenoxid unter Alkoxylierungsbedingungen.In a further embodiment, the present invention therefore relates to compositions whose zinc content is greater than 0 and less than or equal to 15 ppm or whose cobalt content is greater than 0 and less than or equal to 7 ppm or whose zinc content is greater than 0 and less or equal to 15 ppm and whose cobalt content is greater than 0 and less than or equal to 7 ppm. In addition, the present invention also relates to a process for the preparation of the compositions by reacting at least one alcohol ROH 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.The propoxylation which is preferably carried out first according to the invention and only subsequent ethoxylation can reduce the content of residual alcohol in the alkoxylates, since propylene oxide is added more uniformly to the alcohol component. In contrast, ethylene oxide preferably reacts with ethoxylates, so that when ethylene oxide is initially used for reaction with the alkanols, both a broad homolog distribution and a high content of residual alcohol result. Avoiding large amounts of residual alcohol present in the product is particularly advantageous for reasons of smell.
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 was found that this effect already occurs when small amounts of propylene oxide are used, that is, according to the invention, less than 1.5 equivalents, based on the alcohol used, in particular less than 1.2 equivalents, particularly 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 the alkanol mixture according to the invention and the catalyst under the vapor pressure of the alkylene oxide mixture prevailing at the selected reaction temperature or a higher pressure. If desired, the alkylene oxide can be diluted with an inert gas (for example noble gases, nitrogen, CO 2 ) up to 99.9%. This provides additional security against the gas phase decay of this alkylene oxide, in particular in the case of ethylene oxide, and in this embodiment a further alkylene oxide, for example propylene oxide, can also be used as 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 above and in Nikolaus Schönfeldt, interfacial ethylene oxide adducts, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart 1984 described. As a rule, the alkoxylation is carried out in the presence of basic catalysts such as KOH in bulk. However, the alkoxylation can also be carried out using 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. This initiates polymerization of the alkylene oxide, which inevitably leads to a statistical distribution of homologs, the mean value of which is given here as 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 statistically within the reaction product around an average value, which essentially results from the amount added 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 R2-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 expediently added in the form of an alkali metal alcoholate, alkali metal hydroxide, alkaline earth metal oxide or alkaline earth metal hydroxide, generally in an amount of 0.01 to 1% by weight, based on the amount of the alkanol R 2 --OH (see 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 A1C13 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, Lewis acids such as A1C1 3 or BF 3 dietherate, BF 3 , BF 3 x H 3 PO 4 , SbCl 4 x 2 H 2 O, hydrotalcite (see PH Plesch, The Chemistry of Cationic Polymerization, Pergamon Press) are also suitable , New York (1963)). Double metal cyanide (DMC) compounds are also suitable as catalysts.
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, the alkoxylation taking place 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.In principle, all suitable compounds known to the person skilled in the art can be used as the DMC compound.
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:DMC compounds suitable as catalysts are described, for example, in WO 99/16775 and DE-A-101 17 273. In particular, double metal cyanide compounds of the general formula I are suitable as catalysts for the alkoxylation:
M1 a[M2(CN)b(A)c]d fM'gXn h(H2O) eL kP (I),M 1 a [M 2 (CN) b (A) c ] d fM'gX n h (H 2 O) eL kP (I),
in derin the
- M1 mindestens ein Metallion, ausgewählt aus der Gruppe bestehend aus- M 1 at least one metal ion selected from the group consisting of
Zn2+, Fe2+, Fe3+, Co3+, Ni2+, Mn2+, Co2+, Sn2+, Pb2+, Mo4+, Mo6+, Al3+, V4+, V5+, Sr2*, W4*, W°+, Cr2*, Cr3+, Cd2+, Hg2+, Pd2+, Pt2", V2+, Mg2+, Ca2+, Ba2+, Cu2+, La3+, Ce3+, Ce4+, Eu3+, Ti3+, Ti4+, Ag+, Rh2+, Rh3+, Ru2+, Ru3+ ist,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 ° + , Cr 2 *, Cr 3+ , Cd 2+ , Hg 2+ , Pd 2+ , Pt 2 ", V 2+ , Mg 2+ , Ca 2+ , Ba 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ , Eu 3+ , Ti 3+ , Ti 4+ , Ag + , Rh 2+ , Rh 3+ , Ru 2+ , Ru is 3+ ,
- M2 mindestens ein Metallion, ausgewählt aus der Gruppe bestehend aus- M 2 at least one metal ion selected from the group consisting of
Fe2+, Fe3+, Co2+, Co3+, Mn2+, Mn3+, V4+, V5+, Cr2*, Cr3+, Rh3+, Ru2+, Ir3+ist,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 + is
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,A and X independently of one another are an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrogen sulfate,
Phosphat, Dihydrogenphosphat, Hydrogenphosphat oder Hydrogencarbonat sind,Are phosphate, dihydrogen phosphate, hydrogen phosphate or hydrogen carbonate,
L ein mit Wasser mischbarer Ligand ist, ausgewählt aus der Gruppe, bestehend aus Alkoholen, Aldehyden, Ketonen, Ethern, Polyethern, Estern,L is a water-miscible ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters,
Polyestern, Polycarbonat, Harnstoffen, Amiden, primären, sekundären und tertiären Aminen, Liganden mit Pyridin-Stickstoff, Nitrilen, Sulfiden, Phosphiden, Phosphiten, Phosphanen, Phosphonaten und Phosphaten,Polyesters, polycarbonate, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphines, phosphonates and phosphates,
k eine gebrochene oder ganze Zahl größer oder gleich Null ist, undk is a fractional or whole number greater than or equal to zero, and
P ein organischer Zusatzstoff ist,P is an organic additive,
a, b, c, d, g und n so ausgewählt sind, dass die Elektroneutralität der Verbindung (I) gewährleistet ist, wobei c = 0 sein kann,a, b, c, d, g and n are selected so that the electroneutrality of the compound (I) is ensured, where c = 0,
e die Anzahl der Ligandenmoleküle eine gebrochenen oder ganze Zahl größer 0 oder 0 ist,e the number of ligand molecules is a fractional or an integer greater than 0 or 0,
f und h unabhängig voneinander eine gebrochene oder ganze Zahl größer 0 oder 0 sind.f and h are independently a fractional or whole number greater than 0 or 0.
Als organische Zusatzstoffe P sind zu nennen: Polyether, Polyester, Polycarbonate, Polyalkylenglykolsorbitanester, Polyakylenglykolglycidylether, Polyacrylamid,The following organic additives P are mentioned: polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyakylene glycol glycidyl ethers, polyacrylamide,
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 (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(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.Poly (acrylic acid-co-styrene), oxazoline polymers, polyalkyleneimines, maleic acid and maleic anhydride copolymers, hydroxyethyl cellulose, polyacetates, ionic surface and surface-active compounds, bile acid or its salts, esters or amides, carboxylic acid 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. Von den modifizierten Katalysatoren gibt es verschiedene bevorzugte Ausfuhrungsformen. 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.These catalysts can be crystalline or amorphous. In the event that k is zero, crystalline double metal cyanide compounds are preferred. In the event that k is greater than zero, both crystalline, partially crystalline and substantially amorphous catalysts are preferred. There are various preferred embodiments of the modified catalysts. A preferred embodiment are 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 Ausfuhrungsform sind kristalline Doppelmetallcyanid-Katalysatoren bevorzugt. Femer bevorzugt sind Doppelmetallcyanid-Katalysatoren, wie in der WO 00/74845 beschrieben, die kristallin und plättchenformig 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 described in WO 99/16775. In this embodiment, crystalline double metal cyanide catalysts are preferred. Double metal cyanide catalysts, as described in WO 00/74845, which are crystalline and platelet-shaped, are furthermore preferred.
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 Doppelmetallcyamdphase überfuhrt, wie in der PCT/EP01/01893 beschrieben.The modified catalysts are produced by combining a metal salt solution with a cyanometalate solution, which can optionally contain both an organic ligand L and an organic additive P. The organic ligand and optionally the organic additive are then added. In a preferred embodiment of the catalyst preparation, an inactive double metal cyanide phase is first produced and this is subsequently converted into an active double metal cyanide phase by recrystallization, as described in PCT / EP01 / 01893.
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. 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.In another preferred embodiment of the catalysts, f, e and k are not equal to zero. These are double metal cyanide catalysts which contain a water-miscible organic ligand (generally in amounts of 0.5 to 30% by weight) and an organic additive (generally in amounts of 5 to 80% by weight) such as described in WO 98/06312. The catalysts can be prepared either with vigorous stirring (24,000 rpm with Turrax) or with stirring as described in US Pat. No. 5,158,922. Double metal cyanide compounds which contain zinc, cobalt or iron or two thereof are particularly suitable as catalysts for the alkoxylation. Berlin blue, for example, is particularly suitable.
Bevorzugt werden kristalline DMC -Verbindungen eingesetzt. In einer bevorzugten Ausfuhrungsform 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.Crystalline DMC compounds are preferably used. In a preferred embodiment, a crystalline DMC compound of the Zn-Co type is used as the catalyst, which contains zinc acetate as a further metal salt component. Such compounds crystallize in a monoclinic structure and have a platelet-shaped habit. Such connections are described for example in WO 00/74845 or PCT / EP01 / 01893.
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.DMC compounds suitable as catalysts can in principle be produced in all ways known to the person skilled in the art. For example, the DMC compounds can be produced by direct precipitation, the “incipient wetness” method, by preparation of 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 deformed into a shaped body, introduced into shaped bodies, 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 quantity structure, is typically less than 2000 ppm (ie mg catalyst per kg of 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, particularly 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. 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,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 measuring 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 an emulsifier, foam regulator and as a wetting agent for hard surfaces, in particular the use in detergents, surfactant formulations for cleaning hard surfaces, humectants, cosmetic, pharmaceutical and crop protection formulations, Paints, coating materials, adhesives,
Lederentfettungsmitteln, Formulierungen für die Textilindustrie, Faserverarbeitung, Metallverarbeitung, Lebensmittelindustrie, Wasserbehandlung, Papierindustrie, Fermentation oder Mineralverarbeitung und in Emulsionspolymerisationen.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 results in better performance, in particular in fast cleaning processes. This is surprising in that the chain and lengthening of the starting alcohol usually reduces the dynamic and wetting properties. With the compositions according to the invention, the wetting rate of aqueous formulations can thus be increased. The compositions according to the invention can thus also be used as solubilizers, which in particular do not negatively, but rather positively influence the wetting ability of wetting aids, even in dilute systems. They can be used to increase the solubility of wetting aids in aqueous formulations that contain non-ionic surfactants. They are used in particular to increase the wetting rate in aqueous wetting agents.
Femer 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. Nachstehend werden bevorzugte Einsatzgebiete der erfindungsgemäßen Zusammensetzungen näher beschrieben.The compositions according to the invention also serve to reduce the interfacial tension, for example in aqueous surfactant formulations. The reduced interfacial tension can be determined, for example, using the pendant drop method. This also results in a better effect of the compositions according to the invention as an emulsifier or co-emulsifier. The compositions according to the invention can also be used to reduce the interfacial tension in short times of usually less than one second or to accelerate the setting of the interfacial tension in aqueous surfactant formulations. Preferred areas of use of the compositions according to the invention are described in more detail below.
Die erfindungsgemäßen Zusammensetzungen werden vorzugsweise in den folgenden Bereichen eingesetzt:The compositions according to the invention are preferably used in the following areas:
Tensidformulierungen zur Reinigung harter Oberflächen: Geeignete Tensidformulierungen, die mit den erfindungsgemäßen Alkoxylaten additiviert werden können, sind beispielsweise in Formulating Detergents and Personal CareSurfactant formulations for cleaning hard surfaces: Suitable surfactant formulations which can be added with the alkoxylates according to the invention are, for example, in Formulating Detergents and Personal Care
Products von Louis Ho Tan Tai, AOCS Press, 2000 beschrieben.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, Parf möle, Oxidationsmittel wie Perborate, Persäuren oder Trichloroisocyanursäure, Na- oder K-Dichlorisocyanurate, Enzyme; siehe auchThey contain, for example, soap, anionic surfactants such as LAS or paraffin sulfonates or FAS or FAES, acids such as phosphoric acid, amidosulfonic 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 maleic acid-acrylic acid, alkali donors such as hydroxides, silicates, carbonates, perfumes, oxidizing agents such as perborates, peracids or trichloroisocyanuric acid, Na- or K-dichloroisocyanurates, enzymes; see also
Milton J. Rosen, Manual 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,Milton J. Rosen, Manual Dahanayake, Industrial Utilization of Surfactants, AOCS Press, 2000 and Nikolaus Schönfeldt, interfacial ethylene oxide adducts. In principle, formulations for the other applications mentioned are also dealt with here. It can be household cleaners such as all-purpose cleaners, dishwashing detergents for manual and automatic dishwashing,
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.Metal degreasing, industrial applications such as detergents for the food industry, bottle washing, etc. It can also be printing roller and plate cleaning agents in the printing industry. Suitable further ingredients are known to the person skilled in the art.
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.Humectants, especially for the printing industry. Cosmetic, pharmaceutical and crop protection formulations. Suitable crop protection formulations are described, for example, in EP-A-0 050 228. There may be other common ingredients for pesticides.
Lacke, Beschichtungsmittel, Farben, Pigmentpräparationen sowie Klebstoffe in der Lack- und Folienindustrie.Paints, coatings, paints, pigment preparations and adhesives in the paint and film industry.
Lederentfettungsmittel.Leather degreasing.
Formulierungen für die Textilindustrie wie Egalisiermittel oder Formulierungen zur Garnreinigung.Formulations for the textile industry such as leveling agents or formulations for yarn cleaning.
Faserverarbeitung und Hilfsmittel für die Papier- und Zellstoffindustrie.Fiber processing and tools for the paper and pulp industry.
Metallverarbeitung wie Metallveredelung und Galvanobereich.Metal processing such as metal finishing and electroplating.
Lebensmittelindustrie.Food industry.
- Wasserbehandlung und Trinkwassergewinnung.- Water treatment and drinking water production.
Fermentation.Fermentation.
Mineralverarbeitung und Staubkontrolle.Mineral processing and dust control.
Bauhilfsmittel.Building aids.
Emulsionspolymerisation und Herstellung von Dispersionen.Emulsion polymerization and preparation of dispersions.
- Kühl- und Schmiermittel. 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.- coolants and lubricants. Such formulations usually contain ingredients such as surfactants, builders, fragrances and dyes, complexing agents, polymers and other ingredients. Typical formulations are described, for example, in WO 01/32820. Further 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 according to the invention can be used in all areas in which the action of surface-active substances is necessary.
Die vorliegende Erfindung betrifft daher auch Wasch-, Reinigungs-, Netz-, Beschich- tungs-, 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 detergents, cleaning agents, wetting agents, coatings, adhesives, leather degreasing agents, moisturizers or textile treatment agents or cosmetic, pharmaceutical or crop protection formulations comprising a composition according to the invention or a composition produced by a method according to the invention. The agents preferably contain 0.1 to 20% by weight 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 according to the invention are characterized in particular by a low residual alcohol content, so that they are advantageously suitable for a large number of fields of application.

Claims

Patentansprüche claims
1. Zusammensetzung, mindestens enthaltend ein Alkoxylat der allgemeinen Formel I:1. Composition containing at least one alkoxylate of the general formula I:
RO(A)n(B)mH (I) in derRO (A) n (B) m H (I) in the
R ein linearer oder verzweigter Alkylrest mit 6 bis 19 C-Atomen ist, - A Propylenoxy ist,R is a linear or branched alkyl radical with 6 to 19 carbon atoms, - A is propyleneoxy,
B Ethylenoxy oder ein Gemisch aus Ethylenoxy und Propylenoxy ist, n eine ganze oder gebrochene Zahl mit 0 < n < 5 ist, m eine ganze oder gebrochene Zahl mit 0 < m < 20 ist,B is ethyleneoxy or a mixture of ethyleneoxy and propyleneoxy, n is an integer or fractional number with 0 <n <5, m is an integer or fractional number with 0 <m <20,
wobei wenn R ein Alkylrest der allgemeinen Formel C5HnCH(C3H )CH2- ist, n eine ganze oder gebrochene Zahl mit 0 < n < 1 ist,where R is an alkyl radical of the general formula C 5 HnCH (C 3 H) CH 2 -, n is an integer or fraction with 0 <n <1,
mit der Maßgabe, dass für R Isomerengemische eines Alkylrests der allgemeinen Summenformel C5HnCH(C3H7)CH2- aus 70 bis 99 Gew.-% eines Rests Rl, in dem C5Hn die Bedeutung n-C5Hπ hat und l bis 30 Gew.-% eines Rests R2, in dem C5H11 die Bedeutung C2H5CH(CH3)CH2 und/oder CH3CH(CH3)CH2CH2 hat, ausgenommen sind.with the proviso that for R isomer mixtures of an alkyl radical of the general empirical formula C 5 HnCH (C 3 H 7 ) CH 2 - from 70 to 99% by weight of a radical Rl in which C 5 Hn is nC 5 Hπ and l up 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 , are excluded.
2. Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass sich der Rest R von einem Guerbet-Alkohol ableitet.2. Composition according to claim 1, characterized in that the radical R is derived from a Guerbet alcohol.
3. Zusammensetzung nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass R ein Alkylrest der allgemeinen Formel C5HnCH(C3H )CH2- ist. 3. Composition according to one of claims 1 or 2, characterized in that R is an alkyl radical of the general formula C 5 HnCH (C 3 H) CH 2 -.
4. Zusammensetzung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass B Ethylenoxy ist.4. Composition according to one of claims 1 to 3, characterized in that B is ethyleneoxy.
5. Zusammensetzung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass m eine ganze oder gebrochen Zahl von 2 bis 14 ist.5. Composition according to one of claims 1 to 4, characterized in that m is an integer or fractional number from 2 to 14.
6. Zusammensetzung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Gehalt der Zusammensetzung an Zink größer als 0 und kleiner oder gleich 15 ppm ist oder der Gehalt an Cobalt größer als 0 und kleiner oder gleich 7 ppm ist oder der Gehalt an Zink größer als 0 und kleiner oder gleich 15 ppm und der Gehalt an Cobalt größer als 0 und kleiner oder gleich 7 ppm ist.6. Composition according to one of claims 1 to 5, characterized in that the zinc content of the composition is greater than 0 and less than or equal to 15 ppm or the cobalt content 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 cobalt content is greater than 0 and less than or equal to 7 ppm.
7. Verfahren zur Herstellung von Zusammensetzungen nach einem der Ansprüche 1 bis 6 durch Umsetzung mindestens eines Alkohols ROH mit Propylenoxid und Ethylenoxid unter Alkoxylierungsbedingungen, wobei die Alkoxylierung in7. A process for the preparation of compositions according to any one of claims 1 to 6 by reacting at least one alcohol ROH with propylene oxide and ethylene oxide under alkoxylation conditions, the alkoxylation in
Gegenwart einer Doppelmetallcyanid-Verbindung als Katalysator erfolgt.In the presence of a double metal cyanide compound as a catalyst.
8. Verwendung von Zusammensetzungen gemäß einem der Ansprüche 1 bis 6 als Emulgator, Schaumregulierer und als Netzmittel für harte Oberflächen.8. Use of compositions according to one of claims 1 to 6 as an emulsifier, foam regulator and as a wetting agent for hard surfaces.
9. Verwendung nach Anspruch 8 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,9. Use according to claim 8 in detergents, surfactant formulations for cleaning hard surfaces, humectants, cosmetic, pharmaceutical and crop protection formulations, paints, coating agents, adhesives, leather degreasing agents, formulations for the textile industry, fiber processing, metal processing, food industry, water treatment, paper industry,
Fermentation oder Mineralverarbeitung und in Emulsionspolymerisationen.Fermentation or mineral processing and in emulsion polymerizations.
10. Wasch-, Reinigungs-, Netz-, Beschichtungs-, Klebe-, Lederentfettungs-, Feuchthalte- oder Textilbehandlungsmittel oder kosmetische, pharmazeutische oder Pflanzenschutzformulierung, enthaltend Zusammensetzungen gemäß einem der10. washing, cleaning, wetting, coating, adhesive, leather degreasing, moisturizing or textile treatment agent or cosmetic, pharmaceutical or crop protection formulation, comprising compositions according to one of the
Ansprüche 1 bis 6. Claims 1 to 6.
EP03725099A 2002-09-18 2003-04-25 Alkoxylates exhibiting low residual alcohol content Revoked EP1542955B1 (en)

Applications Claiming Priority (3)

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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
DE10243365 2002-09-18
PCT/EP2003/004330 WO2004033405A1 (en) 2002-09-18 2003-04-25 Alkoxylates exhibiting low residual alcohol content

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US20050272626A1 (en) 2005-12-08
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