A process for at least partially removing an aldehyde from a composition containing at least one compound having at least one alkylene oxide unit.

Abstract

The present invention relates to a process for at least partially removing aldehydes from a composition, the process comprising the following steps: a) A step of bringing the composition into contact with at least one cation exchanger and / or acid at a temperature of 20.0°C to 250.0°C, b) Separating the aldehyde at least partially from the composition, and optionally performing a treatment on the separated aldehyde selected from condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and thermal decomposition, Includes, This results in a composition having a reduced aldehyde content. In that case, the composition to be treated in step a) contains at least one alkylene oxide unit and at least one compound having a molecular weight of 200 g / mol or more in its chemical structure, and The composition contains 3.5 wt% or less of an alcohol having 1 to 6 carbon atoms, based on the total weight of the composition. The present invention also relates to a composition containing at least one alkylene oxide unit and at least one compound having a molecular weight of 200 g / mol or more in its chemical structure, wherein the total aldehyde content is 1000 ppm or less.

Description

[Technical Field]

[0001] The present invention relates to a process for at least partially removing aldehydes from a composition resulting in a chemical having a low aldehyde content. The chemical is contacted with at least one cation exchanger and / or acid, and then the aldehyde is removed from the product using a separation process. As a result, it is possible to prepare a product having an aldehyde content reduced by 10% from its initial value. [Background technology]

[0002] Aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde are undesirable byproducts when reacting alkenyl oxides (such as ethylene oxide, propylene oxide, and butylene oxide) to alkylene oxide adducts such as polyalkylene glycols and non-ionogenic surfactants, and these can only be reduced to a certain range by process parameters such as temperature. Reducing aldehydes may be necessary due to regulatory requirements or uses of the aforementioned products in critical applications (e.g., sanitary products).

[0003] European Patent Application Publication No. 0638538A1 describes the removal of formaldehyde from an aqueous acetic acid solution by adding methanesulfonic acid (and optionally a polyol). According to U.S. Patent No. 5,440,058, formaldehyde is converted to the sodium salt of hydroxymethanesulfonic acid by adding NaHSO3. European Patent Application Publication No. 0309915A1 describes the removal of formaldehyde from an aqueous butynediol solution by adding an "acidifying agent" such as methanesulfonic acid or a cation exchanger and methanol to produce dimethylformal, which is then distilled off.

[0004] According to U.S. Patent No. 6,187,973, an aqueous ethylene glycol solution containing aldehydes such as formaldehyde and acetaldehyde is contacted with a solid bisulfite-treated highly basic anion exchange resin to separate a solution having a reduced aldehyde content.

[0005] Canadian Patent No. 1330350 discloses a process for the purification of ethylene glycol using a basic ion exchange resin containing bisulfite or a hydroxy group. The anion exchange resin adsorbs aldehyde impurities from ethylene glycol.

[0006] German Patent No. 1668052 describes a method for purifying glycol so that discoloration-causing substances are removed through a cation exchanger, and in this purification method, basically aldehyde-free glycol is used.

[0007] The removal of aldehydes in the above-mentioned patent documents is limited to low-molecular chemical compounds.

[0008] International Publication No. 2019 / 097407 discloses a polymeric resin functionalized with a primary amine for removing aldehydes. The resin is capable of removing aliphatic and aromatic aldehydes from a plurality of feed streams. The resin forms a covalent imine bond with aldehyde impurities. However, when exclusively using a basic ion exchanger as claimed in International Publication No. 2019 / 0974707, in the case of alkoxylate, a significant reduction in aldehydes is not achieved.

[0009] EP 3228649 A1 describes a method for treating an alkali-catalyzed alkoxylation product using a sulfonic acid ion exchanger, which includes providing a mixture containing the alkali-catalyzed alkoxylation product to be treated, an alcohol having 1 to 4 carbon atoms, and water, treating this mixture with a sulfonic acid cation exchanger at a temperature > 40 °C, and further separating the alkoxylation product from the thus-treated mixture.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] For this reason, the technical object of the present invention was to provide a process capable of achieving a significant reduction in aldehydes in alkoxylates, particularly for alkoxylates having a higher molecular weight. Moreover, a preferred object was to remove further unwanted impurities other than aldehydes from the alkoxylates. In particular, the object of the present invention was to reduce or avoid the use of solvents such as alcohols in each of the processes for purifying alkoxylates or removing aldehydes from alkoxylates.

MEANS FOR SOLVING THE PROBLEMS

[0011] The present invention provides a process for at least partially removing aldehydes from a composition, the process comprising the following steps: a) contacting the composition with at least one cation exchanger and / or an acid at a temperature of 20.0 °C to 250.0 °C; b) at least partially separating aldehydes from the composition and, optionally, performing a treatment selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and thermal decomposition of the separated aldehydes; and thereby obtaining a composition having a reduced aldehyde content. In that case, the composition to be treated in step a) is a compound having at least one alkylene oxide unit in its chemical structure and at least one compound having a molecular weight of 200 g / mol or more, Based on the total weight of the composition, an alcohol having 1 to 6 carbon atoms is present in an amount of 3.5 wt% or less, It contains.

[0012] In a preferred process, the composition to be treated in step a) (which contains at least one alkylene oxide unit in its chemical structure and at least one compound having a molecular weight of 200 g / mol or more) contains 3.0 wt% or less, more preferably 2.5 wt% or less, even more preferably 2.0 wt% or less, particularly preferably 1.5 wt% or less, especially preferably 1.0 wt%, most preferably 0.5 wt% or less, and most preferably 0.1 wt% or less of an alcohol having 1 to 6 carbon atoms, based on the total weight of the composition. It is particularly preferable that the composition to be treated in step a) contains no alcohol having 1 to 6 carbon atoms at all (i.e., 0.0 wt%).

[0013] In another preferred process, the composition to be treated in step a) (which contains at least one alkylene oxide unit in its chemical structure and at least one compound having a molecular weight of 200 g / mol or more) contains a solvent having 1 to 6 carbon atoms in an amount of 3.5 wt%, preferably 3.0 wt%, more preferably 2.5 wt%, even more preferably 2.0 wt%, particularly preferably 1.5 wt%, and especially preferably 1.0 wt%, based on the total weight of the composition. In this case, an alcohol having 1 to 6 carbon atoms corresponds to a solvent having 1 to 6 carbon atoms.

[0014] In the alternative process, the composition to be treated in step a) (which contains at least one alkylene oxide unit in its chemical structure and at least one compound having a molecular weight of 200 g / mol or more) contains a solvent selected from the group consisting of aliphatic ethers, cyclic ethers, hydrocarbons, ketones, and alcohols having 1 to 6 carbon atoms in an amount of 3.5 wt% or less, preferably 3.0 wt% or less, more preferably 2.5 wt% or less, even more preferably 2.5 wt% or less, even more preferably 2.0 wt% or less, even more preferably 2.0 wt% or less, even more preferably 1.5 wt% or less, particularly preferably 1.5 wt% or less, and especially preferably 1.0 wt% or less, based on the total weight of the composition.

[0015] In a preferred process, the aldehyde is selected from the group of aldehydes having a molecular weight of 200 g / mol or less. More preferably, the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. This also applies to the aldehyde to be removed before the process, the aldehyde separated by the process, and any aldehyde present at a reduced concentration.

[0016] Accordingly, the present invention provides a process for removing aldehydes not only from each chemical and composition but also from those containing higher molecular weight glycols and (poly)alkylene oxide compounds. Furthermore, within the scope of the present invention, the inventors have found that it is possible to remove other impurities such as dioxanes and metal ions from such compositions. Moreover, the inventors of the present invention have found that, in contrast to prior art methods, it is not necessary to add a solvent such as an alcohol, specifically an alcohol having 1 to 6 carbon atoms, to the composition to be treated in order to achieve the desired purification. The process according to the present invention is advantageous because it does not require the provision or separation and recycling of each alcohol. This reduces the labor and cost of the process. The same is equally preferable for the solvents mentioned above.

[0017] In each of the terms "composition to be purified" and "purified composition having a reduced aldehyde content," each of the composition to be purified and the purified composition shall contain at least one alkylene oxide unit and at least one compound having a molecular weight of 200 g / mol or more in its chemical structure, and shall be understood as a liquid composition or liquid, preferably a solution or emulsion. In this case, under the conditions of the process according to the present invention, and specifically at the temperature applied during the process, at least a liquid aggregate state of the composition exists.

[0018] Surprisingly, it has been found that by treating the composition or chemical with at least one cation exchanger and / or acid at a temperature of 20°C to 250°C, preferably 40°C to 140°C (step a), and a subsequent separation process to remove the aldehyde (step b), a product having an aldehyde content reduced by at least 10% from the initial value can be obtained. In a particularly preferred process, step a) is carried out at a temperature of 40°C to 140°C, more preferably 60°C to 120°C, even more preferably 80°C to 120°C, and especially preferably 85°C to 120°C.

[0019] The process according to the present invention can be operated continuously or discontinuously.

[0020] In another preferred process, the cation exchanger used in step a) is an acidic cation exchanger containing an acidic group selected from the group consisting of -SO3H, -COOH, and -OP(OH)3. Therefore, the cation exchanger preferably has a sulfonic acid group (-SO3H), a carboxyl group (-COOH), or an orthophosphate group (-OP(OH)3) as an unloaded functional group.

[0021] The matrix of the ion exchange resin can be obtained, for example, by condensation (phenol-formaldehyde matrix) or by polymerization (polystyrene matrix, matrix of styrene-divinylbenzene copolymer, polyacrylic matrix, acrylate, methacrylate, or matrix of acrylonitrile-divinylbenzene copolymer). The ion exchange resin used according to the present invention may exist in various forms such as solid granules and particles (pellets, beads), and further as membranes, films, fibers, and structures. Preferably, solid granules and particles (pellets, beads) are used as the form of the ion exchange resin.

[0022] During continuous operation, the ion exchanger may be located, for example, in a column or vessel. The column or vessel may have a nozzle floor or discharge system for the entry and / or exit of the treatment chemical. During operation, the ion exchanger may be continuously operated in various realizations, such as counterflow, parallel flow, layered bed, multi-chamber, double flow, sandwich, or mixed-bed ion exchangers.

[0023] During discontinuous operations, the ion exchanger may be present, for example, in its free form within the composition, i.e., within the chemical, or in a perforated container in contact with the composition.

[0024] In another preferred process, the acid used in step a) is selected from the group consisting of sulfuric acid, phosphoric acid, phosphonic acid, phosphinic acid, hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, and alkylbenzenesulfonic acid, and is preferably methanesulfonic acid. The concentration of the acid used is preferably 10 wt% or less, more preferably 5.0 wt% or less, particularly preferably 2.0 wt% or less, and most preferably 1.0 wt% or less. In the process using the acid in step a), the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is particularly preferably a compound having a carbon skeleton.

[0025] As specified above, according to the present invention, step b) is a partial separation of aldehydes from the composition, which is preferably followed by treatment of the separated aldehydes selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and thermal decomposition. A preferred step for treating the separated aldehydes after step b) may be selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and thermal decomposition, and may be called step c).

[0026] In another preferred embodiment, step b) is carried out via a thermal separation process selected from the group consisting of distillation, rectification, stripping, and flash evaporation processes. The thermal separation processes described above may also be used in combination. Furthermore, to enhance separation efficiency, a solvent such as water or an entrainer may be added to the composition to be purified.

[0027] In process step b), namely a thermal separation process selected from the group consisting of distillation, rectification, stripping, and flash evaporation processes, the aldehyde is removed from the composition (i.e., from the product (stream)) via the gas phase. In a particularly preferred embodiment, the distillation, rectification, or stripping process is carried out under vacuum. In the stripping process, for example, steam, nitrogen, carbon dioxide, air, or argon may be used as the stripping gas. Substances contained in the gas stream, such as aldehydes, can be removed at least partially from the gas phase by conventional methods of waste gas purification or waste air purification. Biological waste gas purification is also understood to be included. Substances such as aldehydes contained in the gas phase can be condensed and collected, for example, or absorbed by an absorbent medium such as a washing solution. If the absorbent capacity of an absorbent medium such as water is insufficient, absorption can be supplemented by a chemical reaction (chemioadsorption) using a chemical adjuvant. Furthermore, substances contained in the gas stream can be adsorbed by an adsorption medium such as activated carbon, or chemically bonded or chemically transformed by, for example, an ion exchanger. Generally, chemical transformations include catalytic or non-catalytic processes. In non-catalytic chemical processes, it is possible to form aldehyde adducts using chemical adjuvants such as bisulfites to remove aldehydes at least partially. Furthermore, it is possible to decompose substances in the gas phase by oxidation or thermal decomposition, including the process of re-firing. The methods described above—condensation, absorption, adsorption, chemical bonding, chemical transformation, oxidation, and thermal decomposition—are understood to be usable in combination.

[0028] Exemplary thermal separation devices that can be operated under vacuum include distillation columns, rectification columns, evaporators such as forced-circulation and natural-circulation evaporators, horizontal evaporators, rotary evaporators, falling-film evaporators, thin-film evaporators, short-path evaporators, or degassers or spray dryers, in which case, preferably, a waste gas purification unit or waste air purification unit is installed downstream of the evaporation unit. Absorbers that can be used include, in particular, venturi scrubbers, spray washers, jet scrubbers, or swirl washers. Adsorbers that can be used include, in particular, fixed-bed, rotating-bed, fluidized-bed, or moving-bed adsorbers. To separate gaseous substances such as aldehydes as liquids, a cooling unit for condensation may be installed downstream of the thermal separation device. Furthermore, an afterburner may be installed downstream of the thermal separation device. In the case of biological waste gas purification, bioscrubbers, biofilters, and biotrickling filter bed reactors may be used.

[0029] In a preferred alternative embodiment of the process, step b) is carried out by contacting an ion exchanger having an amino or bisulfite functional group, in which case step b) is preferably carried out at a temperature of 20°C to 250°C. In this case, the aldehyde is bound to the ion exchanger and removed from the composition (i.e., from the product (stream)).

[0030] Amino-functional ion exchangers exist, for example, as a matrix based on branched polystyrene having functional amino groups. The amino-functional ion exchanger, upon contact with a chemical (stream), binds the aldehyde contained therein to the amino groups, thus removing it from the product (stream). The primary amino groups of the resin can covalently bond to the aldehyde, for example, by forming an imine compound.

[0031] A bisulfite-functionalized ion exchanger can be prepared, for example, by treating a highly basic ion exchange resin having a hydroxyl group with a bisulfite solution. This treatment results in a basic ion exchanger (resin-HSO3 -) It is converted into a bisulfite form having a base. The preparation of the bisulfite form is exemplified as follows by an exemplary method that utilizes treating a highly basic ion-exchange resin with a sodium bisulfite solution: Resin - OH - + Na + HSO3 - (Solution) → Resin - HSO3 - + Na + OH - (Solution)

[0032] When contacted with a chemical, the (Resin - HSO3 - ) group binds to the aldehyde contained therein, and thus it can be removed from the product (stream). In that case, for example, the following reaction mechanism using the desorption of formaldehyde should be expected: Resin - HSO3 - + HCOH → Resin - HOCH2SO3 -

[0033] In another preferred process, the content rate of a compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in the composition utilized is at least 10 wt%, preferably at least 20 wt%, preferably at least 50 wt%, more preferably at least 80%, even more preferably at least 90.0 wt%, even more preferably at least 95.0%, even more preferably at least 98.0 wt%, even more preferably at least 99.0 wt%, and most preferably at least 99.5 wt% based on the total weight of the composition. These content rates preferably also apply to the composition obtained after step b) having a reduced aldehyde content rate.

[0034] The process according to the present invention removes aldehydes not only from aqueous compositions or chemicals but also from concentrated compositions or chemicals. For this reason, the water content of the composition used is preferably 90 wt% or less, more preferably 70 wt% or less, even more preferably 50 wt% or less, even more preferably 40 wt% or less, even more preferably 30 wt% or less, even more preferably 20 wt% or less, even more preferably 10.0 wt% or less, even more preferably 5.0 wt% or less, even more preferably 2.0 wt% or less, even more preferably 1.0 wt% or less, and most preferably 0.5 wt% or less, based on the total weight of the composition. These water content percentages preferably also apply to compositions obtained after step b) having a reduced aldehyde content.

[0035] In another preferred embodiment of the present invention, the aldehyde to be removed from the composition has at least one aldehyde group in its structure. The aldehyde may have further functional groups in its structure and may also contain heteroatoms. In a preferred process, the aldehyde is selected from the group consisting of aldehydes having a molecular weight of 200 g / mol or less. More preferably, the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.

[0036] By using the process according to the present invention, excellent purification is achieved, particularly with respect to aldehydes. In a preferred process, after step b), a composition is obtained with a total aldehyde content reduced by at least 10%, more preferably at least 30%, preferably at least 50%, more preferably at least 80%, even more preferably at least 90%, even more preferably at least 95%, even more preferably at least 98%, and even more preferably at least 99% of the initial value. In a preferred process, the total aldehyde content is defined as the total content of aldehydes having a molecular weight of 200 g / mol or less. In another preferred process, the total aldehyde content is defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.

[0037] In a particularly preferred process, after step b), a composition is obtained with a total aldehyde content reduced to 1000 ppm or less, more preferably 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, and most preferably 10 ppm or less. In a particularly preferred embodiment, the residual aldehyde content described herein refers to a composition in which the content of at least one alkylene oxide unit and a compound having a molecular weight of 200 g / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. In a preferred process, the total aldehyde content is defined as the total content of aldehydes having a molecular weight of 200 g / mol or less. In another preferred process, the total aldehyde content is defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. The notation "ppm" means the total aldehyde content in mg per kg of composition.

[0038] In another most preferred process, after step b), the content of at least one alkylene oxide and a compound having a molecular weight of 200 g / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50%, based on the total weight of the composition, and the total aldehyde content is 1000 ppm or less, more preferably 900 ppm or less, preferably 800 ppm or less, even more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, and even more preferably 200 ppm or less. A composition can be obtained in which the aldehyde content is reduced to pm or less, more preferably to 150 ppm or less, more preferably to 100 ppm or less, more preferably to 50 ppm or less, and most preferably to 10 ppm or less, in which case the total aldehyde content is defined as the total content of aldehydes having a molecular weight of 200 g / mol or less, and in which case the total aldehyde content is defined more preferably as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. The notation "ppm" means the total aldehyde content in mg per 1 kg of composition.

[0039] In addition to the separation of aldehydes, it has been surprisingly found that dioxane can also be removed using the process according to the present invention. With respect to dioxane, the following description mainly concerns 1,4-dioxane. However, other dioxane isomers also exist that are similarly subject to consideration. Therefore, dioxane comprises one or more substances selected from the group consisting of 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane, preferably 1,4-dioxane. Therefore, in another preferred process, step b) is carried out by a thermal separation process selected from the group consisting of a distillation process, a rectification process, a stripping process, and a flash evaporation process, in which case, after step b), a composition with a dioxane content reduced to 1000 ppm or less, more preferably 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, and even more preferably 50 ppm or less, is obtained, most preferably reduced to 10 ppm or less. In a particularly preferred embodiment, the residual dioxane content described herein refers to a composition in which the content of a compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. The "ppm" notation indicates the amount of dioxane in milligrams per kilogram of the composition.

[0040] In addition to the separation of aldehydes, alkoxylation catalysts, such as NaOH or KOH, or metal cyanide complex catalysts as described in U.S. Patent No. 5,158,922 or U.S. Patent Application Publication No. 2003 / 0119663, can also be removed by the process of the present invention if a cation exchanger is used in step a). Thus, in another preferred process, contacting the composition with at least one cation exchanger in step a) yields a composition with a metal ion content reduced after step b) to 1000 ppm or less, more preferably 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, and most preferably 50 ppm or less, with a metal ion content reduced to 10 ppm or less. In a particularly preferred embodiment, the residual metal ion content described herein refers to a composition in which the content of at least one alkylene oxide unit and a compound having a molecular weight of 200 g / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. In a preferred embodiment, the metal ion is selected from the group consisting of Na(I), K(I), Zn(II), Fe(II), Fe(III), Co(II), Co(III), Ni(II), Mn(II), Mn(III), Ir(III), Rh(III), Ru(II), V(IV), V(V), Co(II), Sn(II), Pb(II), Mo(IV), Mo(VI), Al(III), V(IV), V(V), Sr(II), W(IV), W(VI), Cu(II)Cr(II), and Cr(III). The "ppm" notation indicates the amount of metal ions in milligrams per kilogram of compound.

[0041] Compounds having at least one alkylene oxide unit in their chemical structure and a molecular weight of 200 g / mol or more. In another particularly preferred process, compositions or compounds having at least one alkylene oxide unit in their chemical structure and a molecular weight of 200 g / mol or more are obtained from polymerization of alkylene oxides or from an alkoxylation process. In this application, the definition of molecular weight in “compounds having at least one alkylene oxide unit in their chemical structure and a molecular weight of 200 g / mol or more” always means number-average molecular weight. The terms “number-average molecular weight” and “average molecular weight” are used synonymously herein. Furthermore, the terms “molecular weight” and “molar mass” are used synonymously.

[0042] The number-average molecular weight can be calculated, for example, from the amount used in synthesis. For instance, when attempting to synthesize a fatty alcohol containing 5 ethylene oxide (EO) units, an appropriate mass ratio of fatty alcohol to ethylene oxide (EO) is considered for the synthesis of this alkoxylate, assuming that 1 EO unit is equivalent to 44.05 g / mol. The number-average molecular weight of the ethoxylated fatty alcohol is calculated by adding the molecular weight of the fatty alcohol (e.g., 1-octadecanol: 270.5 g / mol) and the 5 ethylene oxide units (5 × 44.05 g / mol).

[0043] The number-average molecular weight can be determined by freezing point depression, boiling point elevation, vapor pressure / osmotic pressure measurement (for molar masses up to approximately 50,000 g / mol), osmotic pressure measurement (for molar masses up to approximately 10,000 g / mol), or NMR spectroscopy. Furthermore, the number-average molecular weight can be determined from the molar mass distribution via gel permeation chromatography (GPC) and mass spectrometry (MALDI-TOF).

[0044] Furthermore, the average molecular weight can be determined in accordance with the OECD guidelines (Guidelines for Testing Chemicals, Section 1) by test number 118 (Determination of number-average molecular weight and molecular weight distribution of polymers using gel permeation chromatography).

[0045] As alkylene oxide, the following formula (I): [ka] (In the formula, R 2 and R 3 Each of these independently represents a hydrogen or hydrocarbon residue, in which case the hydrocarbon residue may be a cyclic aliphatic hydrocarbon residue, preferably a linear or branched hydrocarbon residue, particularly a hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, and especially preferably a methyl, ethyl, or phenyl residue. Compounds containing the residue R can be used. 2 and R 3 It can also be part of a cyclic group, and in that case, R 2 and R 3 This forms a divalent residue. Hydrocarbon residue R 2 and R 3 This can subsequently support functional groups such as halogens, hydroxyl groups, and glycidyloxypropyl groups. Such alkylene oxides include epichlorohydrin, 2,3-epoxy-1-propanol, and polyfunctional epoxy compounds such as 1,2-ethyl, 1,4-butyl, and 1,6-hexylglycidyl ethers. Preferably, two residues R 2 or R 3 At least one of them is hydrogen. The alkylene oxide used is particularly preferably selected from the group consisting of ethylene oxide, propylene oxide, 1,2- or 2,3-butylene oxide, isobutylene oxide, 1,2-dodecene oxide, cyclohexene oxide, vinylcyclohexene oxide, and styrene oxide.

[0046] As alkylene oxides, glycidyl compounds such as glycidyl ethers and glycidyl esters may also be used, and at least one glycidyloxypropyl group thereof may be bonded via an ether or ester functional group to a linear or branched alkyl residue, aromatic residue, or cyclic aliphatic residue having 1 to 24 carbon atoms. Compounds in this class include, for example, allyl, butyl, 2-ethylhexyl, cyclohexyl, benzyl, C12 / C14 fatty alcohols, phenyl, p-tert-butylphenyl, and o-cresylglycidyl ethers. Preferably used glycidyl esters include, for example, glycidyl methacrylate, glycidyl acrylate, and glycidyl neodecanoate esters.

[0047] In another particularly preferred process, a compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure has at least one (poly)alkylene oxide group, along with at least one (poly)alkylene oxide group, along with at least one (poly)alkylene oxide unit, along with at least one (poly)alkylene oxide unit, along with at least six (poly)alkylene oxide units, along with at least eight (poly)alkylene oxide units, along with at least ten (poly)alkylene oxide units, along with at least twelve (poly)alkylene oxide units, along with at least fifteen (poly)alkylene oxide units, along with at least fifteen (poly)alkylene oxide units, along with at least fifteen (poly)alkylene oxide units, along with at least fifteen (poly)alkylene oxide units, along with at least fifteen (poly)alkylene oxide units, along with at least one (poly)alkylene oxide group, along with at least one (poly)alkylene oxide group, along with at least six (poly)alkylene oxide units, along with at least eight (poly)alkylene oxide units, along with at least ten (poly)alkylene oxide units, along with at least twelve (poly)alkylene oxide units, along with at least fifteen

[0048] In another particularly preferred process, a compound having at least one alkylene oxide in its chemical structure and a molecular weight of 200 g / mol or more is given the formula -(C2H4-O) l-(C3H6-O) m -(C4H8-O) n -or-(C2H4-O) l -(C3H6-O) m -(C4H8-O) n -H has at least one (poly)alkylene oxide group, in which case l, m, and n are independently 0 or greater, and in which case the sum of l, m, and n is 1 or greater, preferably the sum of l, m, and n is 2 or greater, preferably the sum of l, m, and n is 3 or greater, more preferably 4 or greater, even more preferably 5 or greater, even more preferably 6 or greater, even more preferably 8 or greater, even more preferably 10 or greater, even more preferably 12 or greater, particularly preferably 15 or greater, especially preferably 50 or greater, and most preferably 100 or greater. The upper limit of alkylene oxide units is not particularly limited. In further embodiments, the sum of l, m, and n is preferably a number from 1 to 500, more preferably a number from 1 to 200, and even more preferably a number from 1 to 150. In another particularly preferred embodiment, the sum of l, m, and n is a number between 2 and 500, preferably a number between 2 and 200, and especially preferably a number between 2 and 150.

[0049] In another particularly preferred embodiment, a compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is defined by formula -(C X H 2X -O) x -or-(C x H 2x -O) yIt has at least one polyoxyalkylene group of -H. In this case, x is 2, 3, or 4, and y is 1 or more, preferably y is 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, 12 or more, 15 or more, 50 or more, or 100 or more. There is no particular upper limit to the alkylene oxide units. In further embodiments, y is preferably a number from 1 to 500, more preferably a number from 1 to 200, and even more preferably a number from 1 to 150. In another particularly preferred embodiment, y is a number from 2 to 500, preferably a number from 2 to 200, and particularly preferably a number from 2 to 150.

[0050] In preferred embodiments, the molecular weight of a compound having at least one alkylene oxide in its chemical structure is 250 g / mol or more, preferably 300 g / mol or more, more preferably 400 g / mol or more, even more preferably 500 g / mol, particularly preferably 1,000 g / mol or more, and especially preferably 2,000 g / mol. There is no particular upper limit to the molecular weight of a compound having at least one alkylene oxide unit in its chemical structure. In preferred embodiments, the molecular weight of a compound having at least one alkylene oxide unit in its chemical structure is 100,000 g / mol or less, preferably 50,000 g / mol or less, more preferably 25,000 g / mol or less, even more preferably 20,000 g / mol or less, particularly preferably 15,000 g / mol or less, and especially preferably 12,000 g / mol or less.

[0051] In another particularly preferred process, the alkylene oxide unit of a compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.

[0052] In another preferred embodiment of the process, a compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure represents a (poly)alkylene oxide adduct having at least one further residue selected from the group consisting of carboxylate residues, carboxylic acid ester residues, carboxamide residues, phenol residues, and alcohol residues. The alkylene oxide unit is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and particularly preferably ethylene oxide and / or propylene oxide.

[0053] (Poly)alkylene oxide adducts as used herein refer to starting materials that can be alkoxylated, such as carboxylic acids like ethylhexanoic acid and benzoic acid, or fatty acids like caprylic acid, capric acid, lauric acid, cocoyl acid, palmitic acid, stearic acid, oleic acid, and ricinoleic acid, or those having multiple carboxylic acid groups such as citric acid, agaric acid, and propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, pyromelitic acid, and mellitic acid, as well as mixtures thereof, carboxylic acid esters, such as castor oil and rapeseed oil. , triglycerides such as soybean oil, sunflower oil, and coconut oil, or diglycerides such as glyceryl dioleate, or monoglycerides such as glyceryl monooleate, or sorbitan esters such as sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, and sorbitan sesquiisostearate, or polyglycerol fatty acid esters such as polyglycerol cocoate, polyglycerol ricinolate, and polyglycerol oleate, or fatty acid esters such as methyl oleate The reaction product is a carboxamide, such as fatty acid amides like cocoyl acid amide, cocoyl acid monoethanolamide, cocoyl acid diethanolamide, and oleic acid amide; phenols like alkylphenols and tristyrylphenol; monohydric alcohols like methanol, ethanol, propanol, butanol, ethylhexanol, methoxyethanol, and methyldiglycol; or fatty alcohols like lauryl alcohol, stearyl alcohol, and oleyl alcohol; or oxo alcohols like isotridecyl alcohol, linear or branched oxo alcohols - C12 to C15; or cyclic alcohols, such as cyclohexanol, or Guerbet alcohols like butyloctanol, hexyldecanol, and octyldecanol; or polyhydric alcohols like ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerol, polyglycerol, alkyl glycosides, sorbitol, mannitol, sorbitan, isosorbit, trimethylolpropane, pentaerythritol, and dipentaerythritol; and mixtures thereof.The (poly)alkylene oxide adduct has at least one alkylene oxide unit, i.e., 1 to 500, preferably 1 to 200, and more preferably 1 to 150 alkylene oxide units. The alkylene oxide units are preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and are particularly preferably ethylene oxide and / or propylene oxide. Since the (poly)alkylene oxide adduct described may be constructed from the same or different alkylene oxides, for example, from block-like or statistically arranged ethylene oxide and propylene oxide, the present application also includes such “mixed” alkylene oxide adducts.

[0054] In a preferred alternative embodiment of the process, the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure is selected from the group consisting of polyglycols, polyalkylene glycols, block copolymers, carboxylate alkoxylates, carboxylate polyglycol esters, alkoxylated carboxylate esters, alkoxylated carboxamides, alkoxylated phenols, and alcohol alkoxylates. The alkylene oxide unit is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and particularly preferably ethylene oxide and / or propylene oxide.

[0055] Preferably, the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure is derived from the group of C2-C4 alkylene oxides, preferably C2-C3 alkylene oxides. Particularly preferably, the alkylene oxide unit is derived from ethylene oxide or propylene oxide or a mixture thereof. In a particular embodiment, the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure is of the formula H-[O-C2H4] p -[O-C3H6] q -[O-C4H8] rThe polyglycol has -OH (wherein p, q, and r are each independently of each other and are numbers of 0 or more, and the sum of p, q, and r is a number of 5 or more, preferably a number of 6 or more, preferably a number of 8 or more, more preferably a number of 10 or more, even more preferably a number of 12 or more, particularly preferably a number of 15 or more, especially preferably a number of 50 or more, and most preferably a number of 100 or more). The upper limit of alkylene oxide units is not particularly limited. In further embodiments, the sum of p, q, and r is preferably a number of 5 to 500, more preferably a number of 5 to 200, and even more preferably a number of 5 to 150. In another particularly preferred embodiment, the sum of p, q, and r is a number of 10 to 500, preferably a number of 10 to 200, and especially preferably a number of 10 to 150.

[0056] In certain embodiments, compounds having at least one alkylene oxide unit and a molecular weight of 200 mg / mol or more in their chemical structure are non-ionogenic surfactants. Exemplary non-ionogenic surfactants are selected from the group consisting of carboxylate alkoxylates, carboxylate glycol esters, alkoxylated carboxylate esters, alkoxylated carboxamides, alkoxylated phenols, poly(alkylene oxide)-based block copolymers, and alcohol alkoxylates. It should be understood that the above-mentioned class of non-ionogenic surfactants may have additional functional groups or heteroatoms in their structure.

[0057] Exemplary carboxylate alkoxylates and carboxylate polyglycol esters are based on 2-ethylhexanoic acid, benzoic acid, or fatty acid alkoxylates and fatty acid polyglycol esters are based on caprylic acid, capric acid, lauric acid, cocoyl acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, and mixtures thereof, respectively. Carboxylate alkoxylates and carboxylate polyglycol esters that may have multiple ester groups in their structure are, for example, citric acid, agaric acid, and alkoxylates or polyglycol esters based on propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, pyromelitic acid, and mellitic acid, and mixtures thereof.

[0058] Exemplary alkoxylated carboxylic acid esters are alkoxylates based on triglycerides such as castor oil, rapeseed oil, soybean oil, sunflower oil, and coconut oil; diglycerides such as glycerol dioleate; monoglycerides such as glycerol monooleate; sorbitan esters such as sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, and sorbitan sesquiisostearate; polyglycerol fatty acid esters such as polyglycerol cocoate, polyglycerol ricinolate, and polyglycerol oleate; or fatty acid esters such as methyl oleate, and mixtures thereof. Typically, the carboxylic acid esters used as starting materials have at least one hydroxyl and / or carboxylate group or are partially saponified before alkoxylation. Furthermore, it is possible to react carboxylic acid esters so that each alkoxylate is obtained via an insertion alkoxylation process.

[0059] Exemplary alkoxylated carboxamides are alkoxylates based on fatty acid amides such as cocoyl acid amide, cocoyl acid monoethanolamide, cocoyl acid diethanolamide, oleamide, and mixtures thereof.

[0060] Exemplary alkoxylated phenols are alkoxylates based on alkylphenol derivatives such as n-propylphenol, isopropylphenol, butylphenol, amylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, dodecylphenol, methylphenol (cresol), dimethylphenol (xylenol), ethylphenol, or tristyrylphenol, and mixtures thereof.

[0061] An exemplary block copolymer based on poly(alkylene oxide) is the ethylene oxide / propylene oxide block polymer.

[0062] Exemplary alcohol alkoxylates include alkoxylated monohydric alcohols based on methanol, ethanol, propanol, butanol, ethylhexanol, methoxyethanol, methyl diglycol, or fatty alcohol alkoxylates based on lauryl alcohol, stearyl alcohol, oleyl alcohol, or isotridecyl alcohol, linear or branched oxoalcohol-C 12 ~C 15 These include oxo alcohol alkoxylates or alkoxylated cyclic alcohols based on cyclohexanol, or gerbet alcohol alkoxylates based on butyloctanol, hexyldecanol, and octyldecanol, or alkoxylated polyhydric alcohols, polyols, and mixtures thereof based on ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerol, polyglycerol, alkyl glycoside, sorbitol, mannitol, sorbitan, isosorbit, trimethylolpropane, pentaerythritol, and dipentaerythritol.

[0063] The present invention further provides a composition containing at least one alkylene oxide unit and at least one compound having a molecular weight of 200 g / mol or more in its chemical structure, in which case the total aldehyde content is 1000 ppm or less. In a preferred embodiment, the total aldehyde content is defined as the total content of aldehydes having a molecular weight of 200 g / mol or less. In another preferred embodiment, the total aldehyde content is defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. The notation "ppm" means the total aldehyde content in mg per kg of composition.

[0064] As stated above, compositions treated according to the present invention containing at least one alkylene oxide unit and a compound having a molecular weight of 200 g / mol or more in their chemical structure were found to surprisingly yield products having an aldehyde content reduced by at least 10% from the initial value, i.e., each respective composition.

[0065] Preferred embodiments and characteristics of compositions containing at least one alkylene oxide unit and a compound having a molecular weight of 200 g / mol or more in their chemical structure, as well as of the compounds themselves, have already been described above with respect to the process according to the present invention.

[0066] In preferred embodiments of the composition, the content of compounds having at least one alkylene oxide unit in the chemical structure and a molecular weight of 200 g / mol or more is at least 10 wt%, preferably at least 20 wt%, preferably at least 50 wt%, more preferably at least 80 wt%, even more preferably at least 90.0 wt%, even more preferably at least 95.0 wt%, even more preferably at least 98.0 wt%, even more preferably at least 99.0 wt%, and most preferably at least 99.5 wt%, based on the total weight of the composition.

[0067] In another preferred embodiment of the composition, the water content of the composition is preferably 90 wt% or less, more preferably 70 wt% or less, even more preferably 50 wt% or less, even more preferably 40 wt% or less, even more preferably 30 wt% or less, even more preferably 20 wt% or less, even more preferably 10.0 wt% or less, even more preferably 5.0 wt% or less, even more preferably 2.0 wt% or less, even more preferably 1.0 wt% or less, and most preferably 0.5 wt% or less, based on the total weight of the composition.

[0068] In another preferred embodiment of the composition, the total aldehyde content is 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, and most preferably 10 ppm or less. In a particularly preferred embodiment, the residual aldehyde content described herein refers to a composition in which the content of at least one aldehyde oxide unit and a compound having a molecular weight of 200 mg / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. As already stated above, in a preferred embodiment, the total aldehyde content is defined as the total content of aldehydes having a molecular weight of 200 g / mol or less. In another preferred embodiment, the total aldehyde content is defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.

[0069] In other particularly preferred embodiments of the composition, the content of compounds having at least one alkylene oxide unit in the chemical structure and a molecular weight of 200 g / mol or more is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition, in which case the total aldehyde content is 1000 ppm or less, preferably 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, and even more preferably 500 ppm or less. The total aldehyde content is preferably 200 ppm or less, more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, and most preferably 10 ppm or less. In this case, the total aldehyde content is defined as the total content of aldehydes having a molecular weight of 200 g / mol or less. In this case, the total aldehyde content is more preferably defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. The notation "ppm" means the total aldehyde content in mg per 1 kg of composition.

[0070] As described above, it is possible to remove dioxane in addition to aldehydes. For this reason, in another preferred embodiment of the composition, the dioxane content is 1000 ppm or less, more preferably 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, and most preferably reduced to 10 ppm or less. The dioxane is preferably selected from the group consisting of 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane, and particularly preferably 1,4-dioxane. In particularly preferred embodiments, the residual dioxane content described herein refers to compositions in which the content of at least one alkylene oxide unit and a compound having a molecular weight of 200 g / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. The notation "ppm" means the amount of dioxane in mg per kg of composition.

[0071] In addition to the removal of aldehydes, alkoxylation catalysts such as NaOH and KOH can also be removed after step a) of the process by using cation exchangers. Therefore, in another preferred embodiment of the composition, the metal ion content is 1000 ppm or less, more preferably 900 ppm or less, preferably 800 ppm or less, more preferably 500 ppm or less, even more preferably 400 ppm or less, even more preferably 300 ppm or less, even more preferably 200 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 50 ppm or less, and most preferably 10 ppm or less. In a particularly preferred embodiment, the residual metal ion content described herein refers to a composition in which the content of at least one alkylene oxide unit and a compound having a molecular weight of 200 mg / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. In a preferred embodiment, the metal ion is selected from the group consisting of Na(I), K(I), Zn(II), Fe(II), Fe(III), Co(II), Co(III), Ni(II), Mn(II), Mn(III), Ir(III), Rh(III), Ru(II), V(IV), V(V), Co(II), Sn(II), Pb(II), Mo(IV), Mo(VI), Al(III), V(IV), V(V), Sr(II), W(IV), W(VI), Cu(II)Cr(II), and Cr(III). The notation "ppm" refers to the amount of metal ions in mg per 1 kg of the composition.

[0072] Table A below lists further preferred embodiments of the compositions according to the present invention, in which the compositions comprising at least one alkylene oxide unit and at least one compound having a molecular weight of 200 g / mol or more in their chemical structure are defined with respect to the achieved or achievable content of each aldehyde and dioxane, or the combination of the content of each aldehyde, dioxane, and metal ions. The values ​​are expressed in ppm units and represent values ​​less than or equal to the values ​​specified in ppm units. Preferably, the content of at least one alkylene oxide unit and the compound having a molecular weight of 200 g / mol or more in its chemical structure is at least 10 wt%, particularly preferably at least 50 wt%, based on the total weight of the composition. Therefore, Table A below also lists preferred embodiments of the process with respect to compositions obtained after step b) having reduced content of undesirable impurities (aldehydes and dioxanes, aldehydes, dioxanes, and metal ions), as specified in the table.

[0073] [Table 1]

[0074] In another preferred embodiment of the composition, a compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure has at least one (poly)alkylene oxide group, along with at least one, preferably at least two, preferably at least three, more preferably at least four, and even more preferably at least five alkylene oxide units, and even more preferably at least six, even more preferably at least eight, even more preferably at least ten, even more preferably at least 12, even more preferably at least 15, even more preferably at least 50, and most preferably at least 100 alkylene oxide units. The upper limit of the alkylene oxide units is not particularly limited. In a preferred embodiment, the number of alkylene oxide units is 500 or less, more preferably 200 or less, and even more preferably 150 or less. The alkylene oxide units are preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and are particularly preferably ethylene oxide and / or propylene oxide.

[0075] In another preferred embodiment of the composition, the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is defined by the formula -(C2H4-O) l -(C3H6-O) m -(C4H8-O) n -or-(C2H4-O) l -(C3H6-O) m -(C4H8-O) n-H has at least one (poly)alkylene oxide group, in which case l, m, and n are each independently 0 or greater, and in which case the sum of l, m, and n is 1 or greater, preferably 2 or greater, preferably 3 or greater, more preferably 4 or greater, even more preferably 5 or greater, even more preferably 6 or greater, even more preferably 8 or greater, even more preferably 10 or greater, even more preferably 12 or greater, particularly preferably 15 or greater, especially preferably 50 or greater, and most preferably 100 or greater. The upper limit of alkylene oxide units is not particularly limited. In further embodiments, the sum of l, m, and n is preferably a number from 1 to 500, more preferably a number from 1 to 200, and even more preferably a number from 1 to 150. In another particularly preferred embodiment, the sum of l, m, and n is a number between 2 and 500, preferably a number between 2 and 200, and particularly preferably a number between 2 and 150.

[0076] In another preferred embodiment of the composition, the compound having at least one aldehyde oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is defined as formula -(C x H 2x -O) y -or-(C x H 2x -O) y It has at least one (poly)alkylene oxide group of -H. In this case, x is 2, 3, or 4, and y is 1 or more, preferably y is 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 8 or more, 10 or more, 12 or more, 15 or more, 50 or more, or 100 or more. The upper limit of alkylene oxide units is not particularly limited. In further embodiments, y is preferably a number from 1 to 500, more preferably a number from 1 to 200, and even more preferably a number from 1 to 150. In another particularly preferred embodiment, y is a number from 2 to 500, preferably a number from 2 to 200, and particularly preferred a number from 2 to 150.

[0077] In another preferred embodiment of the composition, the molecular weight of the compound having at least one alkylene oxide unit in its chemical structure is 250 g / mol or more, preferably 300 g / mol or more, more preferably 400 g / mol or more, even more preferably 500 g / mol, particularly preferably 1,000 g / mol or more, and especially preferably 2,000 g / mol. There is no particular upper limit to the molecular weight of the compound having at least one alkylene oxide unit in its chemical structure. In a preferred embodiment, the molecular weight of the compound having at least one alkylene oxide unit in its chemical structure is 100,000 g / mol or less, preferably 50,000 g / mol or less, more preferably 25,000 or less, even more preferably 20,000 g / mol or less, particularly preferably 15,000 or less, and especially preferably 12,000 g / mol or less.

[0078] In another preferred embodiment of the composition, the alkylene oxide unit of the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide.

[0079] In another preferred embodiment of the composition, the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure represents a (poly)alkylene oxide adduct having at least one further residue selected from the group consisting of carboxylic acid residues, carboxylic acid ester residues, carboxamide residues, phenol residues, and alcohol residues. The alkylene oxide unit is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and is particularly preferably ethylene oxide and / or propylene oxide.

[0080] In another preferred embodiment of the composition, the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure is selected from the group consisting of polyglycols, polyalkylene glycols, block copolymers, carboxylate alkoxylates, carboxylate polyglycol esters, alkoxylated carboxylate esters, alkoxylated carboxamides, alkoxylated phenols, and alcohol alkoxylates. The alkylene oxide unit is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, and particularly preferably ethylene oxide and / or propylene oxide.

[0081] In another preferred embodiment of the composition, the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more is defined by the formula H-[O-C2H4] p -[O-C3H6] q -[O-C4H8] r The polyglycol of -OH (wherein p, q, and r are each independently 0 or greater, and the sum of p, q, and r is 5 or greater, preferably 6 or greater, preferably 8 or greater, more preferably 10 or greater, even more preferably 12 or greater, particularly preferably 15 or greater, especially preferably 50 or greater, and most preferably 100 or greater). The upper limit of alkylene oxide units is not particularly limited. In further embodiments, the sum of p, q, and r is preferably a number from 5 to 500, more preferably a number from 5 to 200, and even more preferably a number from 5 to 150. In another particularly preferred embodiment, the sum of p, q, and r is a number from 10 to 500, preferably a number from 10 to 200, and particularly preferably a number from 10 to 150. [Brief explanation of the drawing]

[0082] [Figure 1] A schematic configuration for a continuous process for aldehyde reduction using two heatable double-jacketed towers is shown. [Figure 2] A schematic configuration for a continuous process for aldehyde reduction using a heatable double-jacketed tower and evaporation unit is shown. [Modes for carrying out the invention]

[0083] Figure 1 shows a schematic configuration for a continuous process for aldehyde reduction using two heat-recoverable double-jacketed stainless steel columns. The product stream to be purified (A) is transported through two sequentially connected columns (1, 2), namely, a first column (1) containing an acidic SO3H ion exchanger and a downstream column (2) containing a basic NH2 ion exchanger. The two columns (1, 2) are operated at a temperature of, for example, 100°C. The resulting purified product stream (B) contains a reduced aldehyde content.

[0084] Figure 2 shows a schematic configuration for a continuous process in which a product stream (A) to be purified is transported through a heatable double-jacketed column (1) containing an acidic SO3H ion exchanger. An evaporation unit is installed at the outlet of column (1) to remove released aldehydes from the delivery product stream via the gas phase by vacuum (C). Column (1) is operated at a temperature of, for example, 100°C. The resulting purified product stream (B) contains a reduced aldehyde content.

[0085] The following examples illustrate the features and advantages of the present invention through different embodiments. [Examples]

[0086] Within the scope of this invention, we investigated how the aldehyde content is reduced in polyglycol compounds and in various alkoxylates prepared for experimental purposes at high alkoxylation temperatures. For the experiment, we used Lanxess's sulfonic acid-functionalized ion exchanger "Lewatit SP112H" as the cation exchanger. This will be referred to as "SO3H ion exchanger" in the examples. As the basic ion exchanger, we used Lanxess's product "Lewatit VP OC1065". Hereafter, this will be referred to as "NH2 ion exchanger". After derivatization with a 2,4-dinitrophenylhydrazine solution, the aldehyde contained in the chemical composition was separated from other substances by HPLC, and then measured and quantified by UV detection (according to B. Reindl, H.-J. Stan, Agric. Food Chem., 30(1982)849-854, and JR Dahlgran, M.N. Jameson, J. Assoc. Off. Anal. Chem., 71 / 3(1988)560-563). In the following examples, "ppm" indicates the amount of the measured substance or ion in mg per 1 kg of composition.

[0087] Example 1: Treatment of alkoxylated rapeseed oil (18EO / 6PO) with SO3H and NH2 ion exchangers To investigate the effect of ion exchangers on aldehyde reduction, 100 g of alkoxylated rapeseed oil containing 18EO (corresponding to 18 ethylene oxide units) and 6PO (corresponding to 6 propylene oxide units) was stirred in a 150 ml beaker at 100°C for 30 min. The experiment was conducted with and without 10 wt% acidic SO3H and basic NH2 ion exchangers. When ion exchangers were present, they were removed after treatment, and the residual acetaldehyde and propionaldehyde content in the residual product was determined. The results are summarized in Table 1. Before treatment, the alkoxylated rapeseed oil containing 18EO and 6PO had an acetaldehyde content of 6840 ppm and a propionaldehyde content of 805 ppm. From this experiment, it is clear that a significant aldehyde reduction was made possible by the acidic SO3H ion exchanger. No substantial aldehyde reduction was obtained with basic NH2 ion exchanger alone.

[0088] The number-average molecular weight (Mn) of the alkoxylated rapeseed oil used was calculated as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1,440.6 g / mol. The molecular weight of the rapeseed oil was derived from the saponification value of 187.5 mg KOH / g in accordance with DIN EN ISO3681, DGF C-V3.

[0089] [Table 2]

[0090] Example 2a: Treatment of alkoxylated rapeseed oil (18EO / 6PO) with SO3H and NH2 ion exchanger To investigate the effect of acidic and subsequent basic ion exchanger combinations on aldehyde reduction, 100 g of alkoxylated rapeseed oil containing 18EO and 6PO was stirred in a 150 ml beaker with 5 and 10 wt% of each acidic SO3H ion exchanger for 15 and 30 mins, respectively, at 60°C, 80°C, and 100°C, respectively (Process Step A). ​​After treatment, the ion exchangers were separated from the product, and the aldehyde content was determined from the sample. In the second Process Step B, 5 and 10 wt% of each basic NH2 ion exchanger were added to the product and stirred for 15 and 30 mins, respectively, at different temperatures. Subsequently, the ion exchangers were removed, and the aldehyde content was determined. Before treatment, the alkoxylated rapeseed oil containing 18EO and 6PO had an acetaldehyde content of 7050 ppm and a propionaldehyde content of 990 ppm. The results are summarized in Table 2a. From this series of experiments, it is clear that a combination treatment using an acidic ion exchanger first, followed by an NH2 ion exchanger, promotes reduction at a higher percentage of ion exchanger and a higher temperature of 100°C, and a significant reduction of aldehydes is possible.

[0091] The number-average molecular weight (M) of the alkoxylated rapeseed oil used. N The saturation ratio was calculated as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1,440.6 g / mol. The molecular weight of rapeseed oil was derived from the saponification value of 187.5 mg KOH / g in accordance with DIN EN ISO3681, DGF C-V3.

[0092] [Table 3]

[0093] Example 2b: Treatment of alkoxylated sorbitan monolaurate (20EO) with SO3H and NH2 ion exchangers The experimental procedure corresponds to Example 2a). However, sorbitan monolaurate containing 20EO was tested instead of alkoxylated rapeseed oil containing 18EO and 6PO. Before treatment, sorbitan monolaurate containing 20EO had an acetaldehyde content of 1070 ppm. The results are summarized in Table 2a. From this series of experiments, it is clear that a significant reduction in aldehyde content is possible through a combination treatment of an acidic ion exchanger and a subsequent basic ion exchanger.

[0094] The number average molecular weight (M) of the alkoxylated sorbitan monolaurate used N The concentration was calculated as follows: 541.5 g / mol (sorbitan monolaurate) + 20 × 44.05 g / mol (ethylene oxide) = 1,422.5 g / mol.

[0095] [Table 4]

[0096] Example 2c: Treatment of alkoxylated isotridecyl alcohol (7EO) with SO3H and NH2 ion exchanger The experimental procedure corresponds to Example 2a). However, isotridecyl alcohol containing 7PO was tested instead of alkoxylated rapeseed oil containing 18EO and 6PO. Before treatment, isotridecyl alcohol containing 7EO had an acetaldehyde content of 17 ppm. The results are summarized in Table 2c. From this series of experiments, it is clear that a significant reduction in aldehydes is possible by a combination treatment of an acidic ion exchanger and a subsequent basic ion exchanger.

[0097] The number average molecular weight (M) of the ethoxylated isotridecyl alcohol used. N The molecular weight was calculated as follows: 196.9 g / mol (isotridecyl alcohol) + 7 × 44.05 g / mol (ethylene oxide) = 505.2 g / mol. The molecular weight of isotridecyl alcohol was derived from the hydroxyl value of 285 mg KOH / g in accordance with Ph.Eur.2.5.3.

[0098] [Table 5]

[0099] Reference example 3a: Treatment of ethoxylated cocoyl acid (9EO) by steam distillation 350 g of ethoxylated cocoyl acid containing 9EO was weighed into a steam distillation apparatus consisting of a 500 ml flask equipped with a distillation attachment, a steam inlet pipe, and a stirring unit. Under stirring, the product was heated to 105°C, and when it reached 105°C, saturated steam was introduced for 240 mins, and the distillate was collected in a receiver. Samples were also taken when the temperature reached 105°C (corresponding to a residence time of 0 mins) and after steam treatments of 60 and 240 mins at 105°C, respectively. The samples were analyzed for aldehyde and 1,4-dioxane content. The results are summarized in Table 3a. Before treatment, the cocoyl acid ethoxylate had a formaldehyde content of 58 ppm, an acetaldehyde content of 2740 ppm, and a 1,4-dioxane content of 3200 ppm.

[0100] The number average molecular weight (M) of the cocoyl ethoxylate used N The ) was calculated as follows: 209.0 g / mol (cocoyl acid) + 9 × 44.05 g / mol (ethylene oxide) = 605.4 g / mol. The molecular weight of cocoyl acid was derived from the acid value of 268.5 mg KOH / g in accordance with DIN EN ISO3682.

[0101] [Table 6]

[0102] Example 3b: Treatment of ethoxylated cocoyl acid (9EO) using SO3H ion exchanger and steam distillation. The experimental procedure corresponds to that of Example 3a. However, 2 wt% of an acidic SO3H ion exchanger was initially added to ethoxylated cocoyl acid containing 9EO. The results are summarized in Table 3b. A comparison of Table 3b and Table 3a shows that the presence of the acidic SO3H ion exchanger had a significant effect on reducing the aldehyde content. The 1,4-dioxane content could also be reduced.

[0103] [Table 7]

[0104] Example 3c: Treatment of ethoxylated cocoyl acid (9EO) using methanesulfonic acid and steam distillation The experimental procedure corresponds to Example 3a, except that 0.5 wt% methanesulfonic acid was initially added to cocoyl acid containing 9EO. The results are summarized in Table 3c. A comparison of Table 3c and Table 3a shows that the presence of methanesulfonic acid had a significant effect on reducing the aldehyde content. The 1,4-dioxane content could also be reduced.

[0105] [Table 8]

[0106] Reference example 4a: Treatment of ethoxylated cocoyl acid (9EO) by distillation 350 g of ethoxylated cocoyl acid containing 9EO and 35 g of water were weighed into a distillation apparatus consisting of a 500 ml flask equipped with a distillation attachment and a stirring unit. The cocoyl acid containing 9EO used was prepared by ethoxylation of cocoyl acid with ethylene oxide with the help of potassium hydroxide as a catalyst. The mixture of cocoyl acid containing 9EO and water was heated to 80°C under stirring, and the sample was removed when the temperature reached 80°C (corresponding to a residence time of 0 min). Then, a vacuum (final pressure: 200 mbar) was applied and the water, including by-products, was removed by distillation. The vacuum was broken and the sample was removed after 60 and 240 mins, respectively. The samples were analyzed for the content of aldehydes, 1,4-dioxane, and potassium. The results are summarized in Table 4a. Before treatment, the cocoyl ethoxylate contained 58 ppm of formaldehyde, 2740 ppm of acetaldehyde, 3200 ppm of 1,4-dioxane, and 1100 ppm of potassium.

[0107] The number average molecular weight (M) of the ethoxylated cocoyl acid used N The ) was calculated as follows: 209.0 g / mol (cocoyl acid) + 9 × 44.05 g / mol (ethylene oxide) = 605.4 g / mol. The molecular weight of cocoyl acid was derived from the acid value of 268.5 mg KOH / g in accordance with DIN EN ISO3682.

[0108] [Table 9]

[0109] Example 4b: Treatment of ethoxylated cocoyl acid (9EO) using SO3H ion exchanger and distillation The experimental procedure corresponds to Example 4a. However, initially, 2 wt% of an acidic SO3H ion exchanger was added to ethoxylated cocoyl acid containing 9EO along with water. The results are summarized in Table 4b. A comparison of Table 4b and Table 4a shows that the presence of the acidic SO3H ion exchanger had a significant effect on reducing the aldehyde content. The 1,4-dioxane content could also be reduced. Furthermore, by using a cation ion exchanger, the potassium content could be significantly reduced. The potassium ions originate from the use of potassium hydroxide as a catalyst in the ethoxylation reaction. Therefore, by applying the process according to the present invention, it is possible to prepare products having reduced content of aldehyde, 1,4-dioxane, and cations compared to the initial values.

[0110] [Table 10]

[0111] Example 5: Purification of alkoxylated rapeseed oil (18EO / 6PO) via columns equipped with SO3H ion exchanger and NH2 ion exchanger, respectively. For the experiment, a continuous process was used to reduce aldehydes, in which case two approximately 250 cm³ 3 A heatable, sequentially connected, double-jacketed stainless steel column (shown in Figure 1) with a volume of , along with a feed pump with a flow rate of approximately 2 g / min, was used. The first column was packed with approximately 150 g of acidic SO3H ion exchanger, and the downstream column was packed with approximately 150 g of basic NH2 ion exchanger. The two columns were operated at a temperature of 100°C. The liquid product stream consisted of alkoxylated rapeseed oil containing 18EO and 6PO, with initial values ​​of 6840 ppm acetaldehyde and 805 ppm propionaldehyde. After a lead time of 2 hours, approximately 20 g of sample was taken from the discharged product stream every hour and tested for its aldehyde content. The results are summarized in Table 5. The results in Table 5 show that it is possible to reduce the aldehyde content by more than 90% under the conditions described above.

[0112] The number-average molecular weight (M) of the alkoxylated rapeseed oil used. N The saturation ratio was calculated as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1,440.6 g / mol. The molecular weight of rapeseed oil was derived from the saponification value of 187.5 mg KOH / g in accordance with DIN EN ISO3681, DGF C-V3.

[0113] [Table 11]

[0114] Example 6: Purification of polyethylene glycol 400 via a column equipped with SO3H ion exchanger and NH2 ion exchanger. The experimental procedure was carried out by analogy with Example 5, and the product stream consisted of polyethylene glycol 400 with an initial formaldehyde content of 68 ppm. The results are summarized in Table 6. The results in Table 6 show that it is possible to reduce the formaldehyde content by more than 90% under the conditions described above.

[0115] The number-average molecular weight (MN) of polyethylene glycol 400 used at 399.4 g / mol was derived from the hydroxy value of 281 mg KOH / g in accordance with Ph.Eur.2.5.3.

[0116] [Table 12]

[0117] Example 7: Purification of alkoxylated rapeseed oil (18EO / 6PO) via a column equipped with an SO3H ion exchanger and an evaporation unit mounted downstream. For the experiment, approximately 250 cm 3A continuous process for reducing aldehydes was applied using a heatable double-jacketed stainless steel column (shown in Figure 2) with a volume of , and a feed pump with a flow rate of approximately 2 g / min. An evaporation unit was installed at the outlet of the column to remove released aldehydes via the gas phase by vacuum (approximately 200 mbar). The column was packed with approximately 150 g of acidic SO3H ion exchanger. The column was operated at a temperature of 100 °C. The liquid product stream consisted of alkoxylated rapeseed oil containing 18EO and 6PO, with an initial acetaldehyde level of 6440 ppm and an initial propionaldehyde level of 818 ppm. After a lead time of 2 hours, approximately 20 g of sample was taken from the discharged product stream every hour and tested for its aldehyde content. The results are summarized in Table 7.

[0118] The results in Table 7 show that it is possible to reduce the aldehyde content by more than 60% under the conditions described above.

[0119] The number-average molecular weight (M) of the alkoxylated rapeseed oil used. N The saturation ratio was calculated as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1,440.6 g / mol. The molecular weight of rapeseed oil was derived from the saponification value of 187.5 mg KOH / g in accordance with DIN EN ISO3681, DGF C-V3.

[0120] [Table 13]

Claims

1. A process for at least partially removing an aldehyde from a composition, the process comprising the following steps: a) The step of bringing the composition into contact with at least one cation exchanger and / or acid at a temperature of 20.0°C to 250.0°C, b) Separating the aldehyde at least partially from the composition, and optionally performing a treatment on the separated aldehyde selected from condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and thermal decomposition, Includes, This results in a composition having a reduced aldehyde content. In that case, the composition to be treated in step a) comprises at least one alkylene oxide unit in its chemical structure and at least one compound having a molecular weight of 200 g / mol or more, Based on the total weight of the aforementioned composition, an alcohol having 1 to 6 carbon atoms is present in an amount of 3.5 wt% or less, A process that includes [the following].

2. The process according to claim 1, characterized in that step a) is performed at a temperature of 40°C to 140°C.

3. The cation exchanger used in step a) is -SO ３ H, -COOH, and -OP(OH) ３ The process according to claim 1 or 2, characterized in that it is an acidic cation exchanger containing an acid group selected from the above.

4. The process according to claim 1 or 2, characterized in that the acid used in step a) is selected from the group consisting of sulfuric acid, phosphoric acid, phosphonic acid, phosphinic acid, hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, and alkylbenzenesulfonic acid, and is preferably methanesulfonic acid.

5. The process according to any one of claims 1 to 4, characterized in that step b) is carried out by a thermal separation process selected from the group consisting of a distillation process, a rectification process, a stripping process, and a flash evaporation process.

6. The process according to any one of claims 1 to 4, wherein step b) is carried out by contacting an ion exchanger having an amino or bisulfite functional group, and in that case, step b) is preferably carried out at a temperature of 20°C to 250°C.

7. The process according to any one of claims 1 to 6, characterized in that the content of a compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure is at least 10 wt% of the composition used based on the total weight of the composition.

8. The process according to any one of claims 1 to 7, characterized in that, after step b), a composition is obtained having a total aldehyde content reduced by at least 10% from the initial value.

9. The process according to any one of claims 1 to 8, characterized in that, after step b), a composition with a total aldehyde content reduced to 1000 ppm or less is obtained.

10. The process according to any one of claims 1 to 9, wherein step b) is carried out by a thermal separation process selected from the group consisting of a distillation process, a rectification process, a stripping process, and a flash evaporation process, and in that case, after step b), a composition with a dioxane content reduced to 1000 ppm or less is obtained.

11. The process according to any one of claims 1 to 10, characterized in that the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure has at least one (poly)alkylene oxide group together with at least one, preferably at least two, preferably at least three, more preferably at least four, and even more preferably at least five alkylene oxide units.

12. The process according to any one of claims 1 to 11, characterized in that the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure represents a (poly)alkylene oxide adduct having at least one further residue selected from the group consisting of carboxylic acid residues, carboxylic acid ester residues, carboxamide residues, phenol residues, and alcohol residues.

13. The process according to any one of claims 1 to 11, characterized in that the compound having at least one alkylene oxide unit and a molecular weight of 200 g / mol or more in its chemical structure is selected from the group consisting of polyglycols, polyalkylene glycols, block copolymers, carboxylate alkoxylates, carboxylate polyglycol esters, alkoxylated carboxylate esters, alkoxylated carboxamides, alkoxylated phenols, and alcohol alkoxylates.

14. A composition characterized by having a total aldehyde content of 1000 ppm or less, containing at least one alkylene oxide unit and at least one compound having a molecular weight of 200 g / mol or more in its chemical structure.

15. The composition according to claim 14, characterized in that the dioxane content is 1000 ppm or less.

16. The composition according to claim 14 or 15, characterized in that the metal ion content is 1000 ppm or less.

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