MXPA00005386A

MXPA00005386A - Method for producing oxalkylated amines or alcohols

Info

Publication number: MXPA00005386A
Application number: MXPA/A/2000/005386A
Authority: MX
Inventors: Mohr Jurgen; Dockner Toni
Original assignee: Basf Ag 67063 Ludwigshafen De
Priority date: 1997-12-23
Filing date: 2000-06-01
Publication date: 2001-07-03

Abstract

The invention relates to a method for producing oxalkylated amines or alcohols, whereby a reaction mixture containing an amine or an alcohol or a mixture of two or more amines and/or alcohols and an alkylene oxide or a mixture of two or more different alkylene oxides are made to react in one or several successive reaction steps. At least one of the steps of the reaction occurs in the presence of a basic catalyst and the reaction mixture in at least one of the reaction steps contains formic acid or a formic acid salt or a mixture of the two or more or the reaction mixture is mixed with formic acid or a formic acid salt or a mixture of the two or more when oxalkylation is finished. The alkoxylates obtained using the inventive method have little natural colour or odour.

Description

PREPARATION OF ALCOXYLATED AMINES The present invention relates to a process for preparing alkoxylated amines or alcohols or mixtures thereof, in which an amine or a mixture of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines and one or more alcohols, is reacted with an alkylene oxide, or a mixture of two or more different alkylene oxides, in one or more successive reaction steps.

The products of the reaction of amines or alcohols with alkylene oxide are known as active surface compounds and interface actives and are used in a wide variety of industrial fields. Specific examples are detergents and cleaners for laundry, personal care products or industrial applications, for example, for use as emulsifiers, dispersants, emulsion breakers or dispersion breakers, or as intermediates, thickeners or lubricants. The processes known in the prior art for alkylation of amines are generally carried out in one or two stages, while the single-step processes are generally preferred for alkoxylation of alcohols. Thus, for example, DE-A 195 44 739 describes a process for preparing alkoxylated polyethylene imines by alkoxylation of polyethyleneimines in one or two process steps to obtain the reaction products containing from 1 to 200 mol of alkylene oxide groups by amino group in polyethyleneimine. In the single-stage process, the anhydrous polyethyleneimines and from 1 to 20 mol%, based on. the polyethylenimine, from at least one anhydrous base are initially placed in the reaction vessel or the aqueous solutions of these materials are dried and after removal of all the water at > 135 at 150 ° C react with at least one alkylene oxide. In the two-stage process, the polyethyleneimine is reacted in the first step of the process from 80 to 100 ° C with from 0.7 to 0.9 mole, based on one mole of the amino groups in the polymer, of at least one oxide of alkylene in the solution in the aqueous solution, and in the second step of the process the reaction product obtained in the first reaction is reacted from 120 to 150 ° C with at least one alkylene oxide in the absence of water and in the presence of to 20 mol%, based on the polyethylenimine, of an alkaline catalyst to obtain the alkoxylated polyethylenimines containing from 1 to 200 moles of alkylene oxide groups per amino group in the polyethylenimine. According to this publication, products with a light color or almost colorless are only obtained when a high concentration of catalyst is used. This publication does not give information on the olfactory properties of the resulting product. Suggestions for suitable reaction conditions in the preparation of the interface active alkoxylation products can be found, for example, in N. Schdnfeldt, Grenzfláchenaktive Athylenoxid-Addukte, -Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart, 1976, p. 15 ff. And p. 83 ff. However, under the commonly selected alkoxylation conditions, in addition to the products of the actual alkoxylation, by-products are formed whose type, number and amount may differ depending on the variable of the selected process. For example, carbonyl or acetaldehyde compounds (as a general rule, when ethylene oxide is used) or higher aldehydes also their downstream products are frequently formed, and these may include in a color and odor of the alkoxylation product. The amines and alkoxylated alcohols, in particular the aforementioned polyethylene imines, which can be obtained by the methods described in the prior art can therefore, depending on the degree of alkoxylation, be strongly discolored and have an extremely unpleasant odor, or it is necessary to work under non-economic process conditions, for example, using large amounts of catalyst, to reduce coloration. Attempts to at least substantially eliminate the compounds that cause discoloration and subsequent odor, for example, by oxidative or reductive bleaching or by distillation, for example, nitrogen or steam, also generally do not give rise to the desired success. It is an object of the present invention to provide a process for the alkoxylation of amines or alcohols or mixtures thereof to products having very little discoloration and having only a very small proportion of compounds that cause unpleasant odors. We have found that this objective is achieved by performing the alkoxylation in the presence of formic acid or a formic acid salt or a mixture of two or more thereof. The present invention therefore provides a process for preparing an alkoxylated amine or a mixture of two or alkoxylated amines, or an alkoxylated alcohol or a mixture of two or more alkoxylated alcohols, or a mixture of 7 or more alkoxylated amine and one or more alcohols alkoxylates, in which a reaction mixture containing an amine or a mixture of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines and one or more alcohols, and an oxide of alkylene, or a mixture of two or more alkylene oxides is reacted in one or more successive reaction steps, wherein at least one of the reaction steps is carried out in the presence of a basic catalyst and wherein formic acid or a The salt of formic acid, or a mixture of two or more thereof, is present in the reaction mixture in at least one of the reaction steps, to provide an alkoxylated reaction product. For the purposes of the present invention, the term "reaction step" means a total reaction after which a product that can be isolated or intermediate is present that is no longer subjected to other reactions (with the possible exception of side reactions) that come at a low speed). The process of the present invention, therefore, is carried out for example in a single "reaction step" regardless of how many individual reaction events actually occur in the reaction mixture provided that the desired final product is present after the term of the reaction. However, the process of the present invention is also performed in a plurality of steps, that is, individual steps that give rise to the desired final product, can be performed in sequence so that the term of the first step is followed by a second step that it may, at a later time, be carried out in the same reaction vessel or in a different reaction vessel. If appropriate, this can be followed by other steps until the desired final product has been obtained. In the process of the present invention, it is possible, for example, to subject any of the compounds that carry at least one amino group (amines) to an alkoxylation, wherein the amines can be compounds that can have one or more primary or secondary amino groups and , if desired, in addition one or more tertiary amino groups. Mixtures of two or more of these compounds can also be subjected to the processes of the present invention. Accordingly, the process of the present invention is not limited to the reaction of the compounds having only one amino group, but it is also possible, for example, to use diamines or polyamines. Examples of suitable amines are ammonia, methylamine, ethylamine, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, 1-pentylamine, 2-pentylane, 3-pentylamine, hexylamines, heptylamines, octylamines, nonyl amines. , corresponding isomeric decylamines and also linear or branched higher alkylamines which can be obtained, for example, amination of fatty alcohols having up to 24 carbon atoms, In the same way, the corresponding secondary amines of the aforementioned compounds are suitable as they can be obtained, for example, by onoalkylation of the mentioned compounds. Examples are dimethylamine, N-methylethylamine, N-diethylamine, N-methylpropylane, N-methylbutylamine, N-methylpentylamine, N-methylhexylamine and the like. Other suitable compounds are oligoamines having at least two amino groups per molecule. These include, for example, ethylenediamine, propylene diamine, butylene diamine, pentamethylene diamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine and the like.; this list is proposed to comprise any of the positional isomers of the mentioned compounds. The process of the present invention can likewise be carried out using amines having primary and secondary amino groups and, if desired, also one or more tertiary amino groups in a molecule. These include, for example, N-methylethylenediamine, N-ethyleylenediamine, N-methylpropylenediamine, N-ethylpropylenediamine, N-methylbutylenediamine, N-ethylbutylenediamine, N-ethylpentamethylenediamine, N-methylhexamethylenediamine and the like, and also their higher homologs, eg ^, N-monoalkylated diamines having up to 2-6 carbon atoms, which may be linear or branched. In the same way, amines having a different number of primary, secondary and, if desired, tertiary amino groups in a molecule are suitable. These include, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N- (3-aminopropyl) ethylenediamine, N- (4-aminobutyl) ethylenediamine, N- (4-aminobutyl) propylenediamine, and the like. Other suitable amines are compounds selected from the group of polyethyleneimines having a weight average molecular weight (Mw) of, for example, from 250 to 2,000,000, preferably from about 4580 to about 10,000. These polyethyleneimines are generally prepared by polymerizing ethyleneimine in aqueous medium, in the presence of acid catalysts. Examples of suitable acid catalysts are mineral acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid and hydroiodic acid and also organic acids such as formic acid, acetic acid and propionic acid, amidosulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid. , sodium acid sulfate, potassium acid sulfate, sulfuric acid addition products in ethylenediamine and the addition products of carbon dioxide in ethylenedimine. Also suitable are alkylating agents such as methyl chloride, ethyl chloride, propyl chloride, lauryl chloride, and benzyl chloride, and also Lewis acids such as boron trifluoride. The amount of catalysts, based on ethyleneimine, is, for example, less than 1% by weight and, preferably, is in the range from 0.01 to 1% by weight. In a preferred embodiment of the present invention, the polyethyleneimine having a molecular weight Mw from 600 to 6000 is subjected to an alkoxylation according to the present invention. It is particularly advantageous that formic acid has been used in the preparation of polyethyleneimine. In a preferred embodiment of the invention, the polyethyleneimine having a molecular weight Mw from 600 to 6000 which has been prepared using formic acid, is therefore subjected to an alkoxylation according to the present invention. In the process of the present invention, it is also possible to subject the compounds carrying at least one OH group (alcohols) to an alkoxylation, wherein the alcohols can each be composed having one or more primary or secondary or tertiary OH groups, or at the same time two or more of the different OH groups mentioned. Mixtures of two or more of these compounds can also be subjected to the process of the present invention. The process of the present invention, therefore, is not limited to the reaction of compounds having only one OH group. (monoalcohols), but it is also possible to use, for example, dialcoholes or polyalcohols. For example, C?-Linear, reaminated or cyclic aliphatic alcohols having from 1 to about 10 OH groups are suitable for use in the process of the present invention. In the same way, the C6- < Or monocyclic or polycyclic, aromatic or heteroaromatic having from 1 to about 10 OH groups, where the aromatic or heteroaromatic alcohols can, for example, have aliphatic or cycloaliphatic substituents or parts of the ring structure can be cycloaliphatic. In the same way they are ~ adequate, for example, polymers having OH groups, as may be obtained, for example, by polymerization, polyaddition or polycondensation. Examples of suitable monoalcohols are methanol, ethanol, propanol, isopropanol, 1-butanol, 2-butanol, tert-butanol, pentanols, hexanols, heptanols, isomeric octane, for example, 2-ethylhexanoic, C9-fatty alcohols. 24 linear and branched, which can be obtained, for example, by the oxo process, cycloaliphatic alcohols, cyclohexanol, cycloheptanol, cyclooctanol, hydroxymethylcyclohexane, hydroxymethylcycloheptane, hydroxymethylcycloheptane, hydroxymethylcyclooctane, monohydroxyaromatics and substituted monohydroxyaromatics, for example, phenol, methylphenol, ethylphenol, propylphenol, butylphenol and its alguyl counterparts, for example, octylphenol or nonylphenol, and the like, examples of suitable diols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, the pentylene glycols and isomeric hexylene glycols, for example, 1,6-hexanediol and its higher homologs, o-, m- and p-dihydroxybenzene, or-, m- and p-bis (hydroxymethyl) benzene, 4, 4'-dihydroxybenzyl, bisphenol A- and also the products of the partial or complete hydrogenation of the aromatic double bonds of the mentioned compounds. Equally suitable are higher alcohols having up to about 10 OH groups, in particular from about 3 to about 6 OH groups, for example, glycerol, trimethylolpropane, triethylolpropane, pentaerythritol or carbohydrates such as sorbitol. Also suitable are condensation products (monoethers and polyethers) of the aforementioned compounds with themselves or two or more. more of the aforementioned compounds, having up to about 20 or 30 OH groups. OH-containing polymers, as may be used for the purposes of the present invention, include, for example, polyvinyl alcohol or hydroxyl-containing polyacrylates which can be obtained, for example, by the oropolymerization or -copolymerization of acrylic esters containing OH. For the purposes of the present invention, the term "alkoxylation" refers to the reaction of one of the amines mentioned above, or a mixture of two or more of the amines mentioned above, or one of the aforementioned alcohols or a mixture of two or more of the mentioned alcohols or a mixture of one or more of the amines mentioned above and one or more of the aforementioned alcohols in an alkylene oxide, or a mixture of two or more different alkylene oxides. The alkylene oxides which can be used for the alkoxylation in the process of the present invention are preferably alkylene oxides of the formula I. where R1, R2, R3 and R4 are identical or different and are each, independently of each other, hydrogen, C1-C10 alkyl, C2-C? alkynyl / C2-C10 alkynyl, C3-C? cycloalkyl or , C3-C10 cycloalkenyl, C6-C12 aryl or heteroaryl, where the alkyl, alkenyl or alkynyl radicals can be linear or branched and can in turn carry other functional groups, and the cycloalkyl, aryl and heteroaryl radicals can in turn carrying other functional groups such as may be substituted by the C3-C10 alkyl / alkenyl, alkynyl or aryl radicals. The alkylene oxides of the formula I which are preferably used are, for example, ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, pentyl oxide or styrene oxide or mixtures of two or more thereof, giving preference to ethylene oxide, propylene oxide or 1,2-butylene oxide or mixtures of two or more thereof.

The ethylene oxide or mixture of two or more of the different alkylene oxides which can be used in the present process can originate from any source or from any of the different sources, that is, they can have been prepared by any desired process. For example, ethylene oxide can be obtained by catalytic oxidation of ethylene, where ethylene and an oxygen-molecular containing gas, for example air, air enriched with oxygen or pure oxygen, react in a gas phase on a silver-containing catalyst. The alkylene oxide or mixture of two or more or more of the different ethylene oxides which can be used for the purposes of the present invention is preferably used in pure form. This means that the ethylene oxides used are practically free of impurities and thus consist of almost 100% alkylene oxide or the mixture of two or more of the different alkylene oxides. However, in the same way it is possible to use a technical grade of the alkylene oxides which still contain impurities which are usually present before the purification of the alkylene oxide after its production. The alkoxylation can be carried out using only one type of alkylene oxide, but also - it can be - a mixed alkoxylation. If, for example, a mixture of two or more different alkylene oxides is introduced into the reaction mixture, this generally gives rise, if the reactants of the alkylene oxides are practically comparable to random polyether chains in which the constituents of the Mix are not present in any specific order. However, if different aliphylene oxides are fed to the reaction mixture in succession, ie, only another alkylene oxide proposed for the reaction is fed, when the previously fed has reacted completely, it is possible to obtain polyether segments consisting of blocks and in which the order and length of the individual alkylene oxide segments in the polyether chain is dependent on the order of addition of the respective alkylene oxide and its amount. In a preferred embodiment of the invention, the ratio of alkylene oxide groups to the acid hydrogen atoms attached to nitrogen in the amine or in the mixture of two or more amines, or in alcohol or in the mixture of two or more alcohols or in the mixture of two or more amines or one or more alcohols, it is from about 1: 1 to about 300: 1. The basic catalyst used in the process of the present invention is generally an alkaline compound commonly used for base catalyzed reactions, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide or cesium hydroxide, alkoxides of alkali metal such as potassium sodium methoxide, potassium ethoxide, isopropoxide. potassium otassium or tert-butyxide or mixtures of two or more of them. Instead of the mentioned potassium alkoxides, it is also possible to use the corresponding sodium alkoxides. Other suitable base catalysts are sodium hydride from heterogeneous catalysts, for example, hydrotalcite which can be modified or unmodified, or mixtures thereof. The amount of basic catalyst in the reaction mixture can be from about 0.1 to 20 mol%, based on the acid hydrogen atoms attached to the nitrogen in the amine or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the mixture of one or more amines and one or more alcohols. It is preferred from about 1 to about 10% mol and particularly preferably from about 2 to about % mo1. The process of the present invention can be carried out in one or more successive reaction steps, with formic acid or a formic acid salt, or a mixture of two or more of the same, being present in the reaction mixture in at least one of the reaction steps. In a particularly preferred embodiment, the formic acid or the formic acid salt, or a mixture of two or more thereof, is present in the reaction mixture at the start of the alkoxylation. As salts of formic acid, it is possible in principle to use all the salts, but the alkali metal forms, for example, the lithium, sodium or potassium formats, or the conformable ammonium formats can be obtained, for example, from of formic acid and ammonia or organic amines are particularly suitable as salts of formic acid. Particular preference is given to sodium format and potassium format. Formic acid or formic acid salt, or a mixture of two or more thereof, is generally used in the process of the present invention in an amount from about 0.1 to about 10 mol%, based on the atoms of hydrogen acids attached to the nitrogen in the amine or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the mixture of one or more amines and one or more alcohols. In the preferred embodiments of the present invention, use is made, for example, of amounts from about 0.5 to about 8 mol%, for example, from about 1 to about 6 mol% or from about 2 to about 5% mol. In the same way quantities of, for example, from about 3 to about 4 mol% are convenient. The process of the present invention can, for example, be carried out in one step. In this case, a reaction mixture containing an amine or a mixture of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines and one or more alcohols, a basic catalyst, formic acid or a formic acid salt or a mixture of two or more thereof, together with an alkylene oxide, or a mixture of two or more different alkylene oxides In a preferred embodiment, the reaction is carried out from about 80 ° C to about 170 ° C. A one-step reaction procedure is preferred when the reaction mixture is practically without water, ie the water content of the reaction mixture is less than 1000 ppm, preference to less than 500 ppm To obtain such a water content, it is possible, for example, to use the individual constituents of the reaction mixture in Jeorma with practically no water, but in the same way it is possible to liberate the water mixture from the water. reaction before the reaction If, for example, one or more of the components present in the reaction mixture has too high a water content. This can be achieved, for example, by distilling all the water from the reaction mixture. For this purpose, the reaction mixture is generally subjected to a reduced pressure or elevated temperature, or preferably both at the same time, in order to distill the water present in the reaction mixture. It is necessary to be careful that none of the other components that are present in the reaction mixture and that are proposed for the reaction distill together with the water. If, for example, the components whose boiling point is lower than that of water, or that form an azeotrope together with the water are present in the reaction mixture, it is advisable to use the compounds in practically no water form and remove any water present in the water. the reaction mixture in the manner described, before these are added. The elimination of water, likewise, can be carried out, for example, by means of an azeotropic distillation by adding a tracer such as benzene, toluene or xylene or by removing the water in azeotropic form. The additional entrainer may then be distilled at reduced pressure or may remain in the reaction mixture during the alkoxylation. When the process of the present invention is carried out in a single step, the reaction temperature is preferably from about 100 to 160 ° C, for example, from about 120 to about 135 ° C or from about 135 to about 150 ° C. The reaction time is generally from about 4 to about 20 hours, for example, from about 8 to about 12 hours. The single-step process, in a preferred embodiment of the invention, is used especially in the alkoxylation of alcohols. In another preferred embodiment of the invention, the reaction is carried out in two steps, where: a) in a first step, a reaction mixture containing an amine or a mixture of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines and one or more alcohols, formic acid or a formic acid salt, or a mixture of two or more thereof, together with an alkylene oxide, or a mixture of two or more different alkylene oxides, is reacted to form a reaction product del-. First step; and b) in a second step, a reaction mixture is reacted containing the reaction product of the first step, a basic catalyst and an alkylene oxide, or a mixture of two or more different alkylene oxides.

The reaction temperature is, for example, from about 80 ° C to about 130 ° C in the first step and, for example, from more than about 130 ° C to about 170 ° C in the second step. The two-step process for the process of the present invention is used, in particular, when the reaction mixture contains an amine or a mixture of two or more amines.

When in the process of the present invention an amine or a mixture of two or more amines will react, the reaction mixture - the first step contains, in a preferred embodiment of the invention, the amine or the mixture of two or more amines as an aqueous solution. In this case, it is preferred that the amine or the mixture of two or more ines be present in the aqueous solution in a concentration of from about 20% by weight to about 80% by weight, in particular from about 40% by weight. weight to about 60% by weight. The other components present in the reaction mixture - from the first step in the same way can be used in the form of their aqueous solutions, for example, the basic catalyst can be used as a solution having a concentration from about 20 to about 80% by weight, preferably from about 40 to about 60% by weight. Of course, the same applies also to formic acid or formic acid salt, or the mixture of two or more thereof. In a preferred embodiment of the invention, the water is almost completely removed from the reaction product of the first step before performing the second step. The use of at least one of the components present in Aa as an aqueous solution is advantageous when all the components of the reaction mixture are soluble in water. If one or more of the components present in the reaction mixture does not have sufficient water solubility, it is generally preferred that the process of the present invention is not carried out using aqueous solutions. A component is sufficiently soluble in water if the component dissolves at least in part, preferably mainly in water at the temperature of the reaction. If desired, the process of the present invention can also be carried out in organic solvents or without solvents. Suitable organic solvents are, in particular, all polar, aprotic solvents, for example, dimethylformamide (DMF) or dimethylacetamide (DMAc), but preference is given to not using solvents. The non-use of solvents is a possibility when, in particular, the compound to be alkoxylated or the mixture of the compounds to be alkoxylated are in the liquid state at the temperature of the reaction. The temperature of the reaction in the first step is from about 80 to about 13 ° C, preferably from about 80 to about 100 ° C. The reaction time in the first step is, for example, from about 2 to about 12 hours, preferably from about 4 to about 8 hours. The molar ratio of the alkylene oxide groups to the acid hydrogen atoms attached to nitrogen in the amine or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the The mixture of one or more amines or one or more alcohols can be, for example, approximately 1: 1 in the first step. However, it has been found that the color of the formed product is furthermore affected in an advantageous manner if a ratio of less than 1 is selected, for example, from about 0.4: 1 to about 0.99: 1, particularly preferably from about 0.6: 1 to about 0.9: 1. The first step can be carried out at atmospheric pressure, but the reaction can also be carried out in an autoclave at pressures of up to about 2Q Joar. In the second step, a reaction mixture containing the reaction product of the first step, a basic catalyst and an alkylene oxide, or a mixture of two or more different alkylene oxides, is reacted from > 130 ° C to about 170 ° C. To prepare for the second step, the procedure can be, for example, first evaporate the product of the reaction obtained in the first step of the process to dryness, if a solvent has been used and the JIO reaction product itself is liquid, and then add the basic catalyst. If the first step of the process has been carried out in aqueous solution, it is particularly preferred to add the basic catalyst to the obtained aqueous reaction product, in the first reaction step and subsequently to remove the water, for example, by distillation under reduced pressure or by means of of an azeotropic distillation by adding, for example, a tracer such as benzene, toluene or xylene and removing the water from the azeotrope. The alkoxylation in the second step of the process is carried out from more than about 130 ° C to about 170 ° C, preferably in the range from more than about 130 ° C to about 145 ° C. The reaction can be carried out under atmospheric pressure or preferably under superatmospheric pressure. It is preferable to perform it in an autoclave provided with an agitator at pressures from about 1 to about 20 bar, preferably from about 2 to about 10 bar. The amount of alkylene oxide, or a mixture of two or more different alkylene oxides, in the second step is established so that the product formed is an alkoxylated amine or a mixture of two or more alkoxylated amines, or an alkoxylated alcohol or a mixture of two or more alkoxylated alcohols, or a mixture of one or more alkoxylated amines and one or more alkoxylated alcohols, having from about 1 to about 200 moles of alkylene oxide groups-by hydrogen-acid atoms attached to the nitrogen in the amine or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the mixture of one or more amines and "one or more alcohols." The alkoxylated products formed in the second step of the process, preferably they contain from about 1 to about 20 moles of the alkylene oxide which they react, or a mixture of two or more different alkylene oxides which reacted, by acid hydrogen atoms attached to the nitrogen in the ami or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols or in the mixture of one or more amines and one or more alcohols. The reaction time in the second step of the process is from about 2 to about 15 hours and, preferably it is in the range from about 5 to about 12 hours. In a preferred embodiment of the invention, the alkoxylated reaction product is maintained from 40 ° C to 140 ° C and a pressure from 0.1 to 100 mbar for a period from 5 minutes to 5 hours after the conclusion of the reaction, by means of of which, for example, the volatile compounds can be eliminated. The process of the present invention generally provides the alkoxylated products having a lighter color and a better odor compared to the known products of the prior art, it being possible to significantly reduce the amount of catalyst needed below the amount needed in the known processes of the prior art by the use according to the present invention of formic acid or formic acid sulfate. The invention is illustrated by the following examples, but without the examples implying any limitation in the scope of the invention.

Examples Example 1: First step: 1470 g of a 50% strength aqueous solution of polyethylene imine (corresponding to 17.1 mol of acid hydrogen atoms attached to nitrogen) were placed in a stainless steel autoclave having a capacity of approximately 20 1 Subsequently 8 g of formic acid were added, the reactor was closed and flooded with nitrogen and then heated with stirring at 100 ° C, and 748 g (17 mol) of ethylene oxide were added at this temperature at a maximum pressure of 5. bar for a period of 2 to 3 hours. After the addition was complete and a constant pressure was reached, the reaction mixture was maintained at 100 ° C for another 2 hours, after which it was cooled to 50 ° C and depressurized. 2nd step: The reaction product obtained from the first step was mixed in the same reactor with 74 g of a 50% aqueous KOH solution. The reactor was closed, evacuated at a pressure of 20 mbar and slowly heated to 100 ° C. To remove most of the water from the reaction mixture, the reactor was kept under these conditions for 6 hours, then nitrogen was admitted. In the reactor, and during the course of about 10 hours, 14,300 g (325 mol) of ethylene oxide were metered in at 140 ° C and a maximum pressure of 5 bar, after which the addition was complete and a constant pressure was reached. , the mixture was stirred for another 2 hours at 140 ° C. Subsequently the reactor was slowly depressurized at atmospheric pressure and cooled to approximately 80 ° C. Then the reactor was evacuated from about 20 to 50 mbar and left to these conditions for 1 hour to remove the volatile constituents, this was subsequently cooled to room temperature, depressurized and drained, the yield was 15,800 g of ethoxylate having an average degree of ethoxylation. n of about 20. The product obtained is a yellow oil that slowly solidifies at room temperature and has a weak odor. The color number in an aqueous solution ~ 10% concentration is 2 (color number of iodine). If the experiment is carried out without the addition of formic acid according to the present invention, the final product obtained is an amber oil that slowly solidifies and has a color number of iodine (10% concentration in water) of 8. This has a pungent odor, very unpleasant. The difference in the smell of the two products can be demonstrated even more clearly by perceiving the odor of an aqueous solution at 0.5 or 1% concentration. Although the product of the present invention only has a weak odor, the comparative product has a pungent and pungent odor.

Example 2: a) Comparative Example using a traditional procedure: 2300 g of isononylphenol were placed together with 2.5 g of potassium hydroxide in a suitable reactor for alkoxylation. The reactor was closed and the mixture was heated to 140 ° C, applying a vacuum at the same time.The mixture was dried in this way for 2 hours at 30 mbar and then nitrogen was admitted. = At 140 ° C and a pressure of At about 5 bar, 2580 g of ethylene oxide were then metered in over the course of 3 to 4 hours After the dosing was complete, the mixture was stirred for about 2 hours to complete the reaction. at about 20 to 50 mbar and Tlesde about "100 to 140 ° C to remove any of the volatile constituents present. After cooling and draining the reactor, approximately 3800 g of ethoxylate were obtained having a color number of 67 (APHA) and a distinct aldehyde odor. b) Process of the present invention The experiment was repeated using the process parameters identical to those indicated in a) except that 3.5 g of potassium format was added to the isononylphenol / potassium hydroxide mixture at the start. The alkoxylate obtained in this way was distinctly light in color than that obtained in a), as could be observed by direct comparison. He had a color number of 35 (APHA) and a smell very scarcely noticeable.

Claims

CLAIMS A process for preparing an alkoxylated amine or a mixture of two or more alkoxylated amines, or an alkoxylated alcohol a mixture of one or more alkoxylated amines, or one or more alkoxylated alcohols, in which a reaction mixture containing an amine Cr Tina emixtures of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines - and one or more alcohols, and an alkylene oxide or a mixture of two or more alkylene oxides are made reacting in one or more successive reaction steps, wherein - at least one of the reaction steps is carried out in the presence of a basic catalyst, and wherein formic acid or a formic acid salt or a mixture of two or more of the The same is present in the reaction mixture in at least one of the reaction steps, to obtain an alkoxylated reaction product. The process as recited in claim 1, wherein the formic acid or the formic acid salt, or a mixture of two or more thereof, is present in the reaction mixture at the start of the alkoxylation. The process as recited in claim 1 or 2, wherein the formic acid or the formic acid salt, or a mixture of two or more thereof, is used in an amount of 0.1 to 10 mol%, based on in the total amount of acid hydrogen atoms attached to nitrogen in the amine or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the mixture of one or more amines and one or more alcohols. The process as mentioned in any of claims 1 to 3, wherein the molar ratio of the alkylene oxide groups to acid hydrogen atoms attached to nitrogen in the amine or in the mixture fingers or more amines or in the alcohol or in the the mixture of two or more alcohols or in the mixture of one or more amines and one or more alcohols is from 1: 1 to 300: 1. The process as recited in any one of claims 1 to 4, wherein the reaction is carried out in one step by reacting a reaction mixture-containing a amine or a mixture of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines, and one or more alcohols, a basic catalyst, formic acid or a formic acid salt or a mixture of two or more thereof, together with an alkylene oxide or a mixture of two or more different alkylene oxides. The process, as mentioned in any of claims 1 to 4, wherein the reaction is carried out in two steps, wherein - - - - - a) in a first step, a reaction mixture - containing an amine or a mixture of two or more amines, or an alcohol or a mixture of two or more alcohols, or a mixture of one or more amines and one or more. more alcohols, formic acid a. - a formic acid salt, or - a mixture of two or more thereof, together with an alkylen oxide, or a mixture of two or more different alkylene oxides, is reacted to form a reaction product of the first He passed; and b) in a second step, a reaction mixture containing the reaction product of the first step, a basic catalyst - and an alkylene oxide, or a mixture of two or more different alkylene oxides is reacted. The process, as mentioned in claim 6, wherein the reaction mixture in the first step contains an amine or a mixture of two or more amines, wherein the amine or the mixture of two or more amines is present as a solution water and the water is almost completely eliminated from the reaction product of the first step before the second step is carried out. The process, as mentioned in claim 6 6 7, wherein the molar ratio of the "alkylene oxide groups to the acid hydrogen atoms attached to nitrogen in the amine or in the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the mixture of one or more amines and one or more alcohols, in the first step is from 0.6.1 to 0.9: 1. The process, as mentioned in claim 1 to 8, wherein the alkoxylated reaction product is maintained from 40 ° C to 140 ° C and a pressure from 0.1 to 100 mbar for a period from 5 minutes to 5 hours after finishing the reaction. The process, as mentioned in claim 1 to 9, wherein the amount of basic catalyst in the reaction mixture is from 0.1 to 20 mol%, based on the acid hydrogen atoms attached to nitrogen in the amine or the mixture of two or more amines, or in the alcohol or in the mixture of two or more alcohols, or in the mixture of one or more amines and one or more alcohols.