Method for at least partially removing aldehydes from composition comprising 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, comprising the steps of: a) contacting the composition with at least one cation exchanger and / or an acid at a temperature of from 20.0 DEG C to 250.0 DEG C; b) at least partially separating aldehydes from the composition, and optionally treating the separated aldehydes, said treatment being selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation and pyrolysis; thereby obtaining a composition having a reduced aldehyde content; wherein the composition to be treated in step a) comprises at least one compound having at least one alkylene oxide unit in its chemical structure and having a molecular weight of 200 g / mol or more, and 3.5 wt% or less, based on the total weight of the composition, of an alcohol having 1 to 6 carbon atoms. The invention also relates to a composition comprising at least one composition having at least one alkylene oxide unit in its chemical structure and having a molecular weight of 200 g / mol or more, the total aldehyde content being 1000 ppm or less.

Description

Technical Field

[0001] This invention relates to a method for at least partially removing aldehydes from a composition to obtain a chemical product with a low aldehyde content. The chemical product is contacted with at least one cation exchanger and / or acid, and then the aldehydes are removed from the product by a separation method. Thus, a product with an aldehyde content reduced by approximately 10% from its initial value can be prepared. Background Technology

[0002] Aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde, are undesirable byproducts generated during the reaction of alkenyl oxides (such as ethylene oxide, propylene oxide, and butyric acid) to form alkylene oxide adducts (such as polyalkylene glycols and nonionic surfactants). They can only be reduced to some extent by adjusting process parameters (such as temperature). Due to regulatory requirements or the use of these products in critical applications (such as hygiene products), reduced aldehyde content is essential.

[0003] Existing technology EP0638538A1 describes a method for removing formaldehyde from an aqueous solution of acetic acid by adding methanesulfonic acid (and, if necessary, a polyol). According to US5,440,058, formaldehyde is converted to a sodium salt of hydroxymethanesulfonic acid by adding NaHSO3. EP0309915A1 describes the removal of formaldehyde from an aqueous solution of butynediol by adding an acidic surfactant (such as methanesulfonic acid or a cation exchanger) and methanol to generate dimethylformaldehyde and then removing it by distillation.

[0004] According to US6,187,973, an aqueous solution of ethylene glycol containing aldehydes (such as formaldehyde, acetaldehyde, etc.) is contacted with a solid high-alkalinity anion exchange resin treated with bisulfite to separate a solution with reduced aldehyde content.

[0005] CA1330350 discloses a method for purifying ethylene glycol using a basic ion exchange resin containing bisulfite or hydroxyl groups. The anion exchange resin adsorbs aldehyde impurities from ethylene glycol.

[0006] DE1668052 describes a method for purifying diols to remove chromogenic substances using a cation exchanger, wherein diols that are substantially free of formaldehyde are used in this purification method.

[0007] The removal of aldehydes in the aforementioned patent documents is limited to low molecular weight compounds.

[0008] WO2019 / 097407 discloses polymer resins functionalized with primary amines for the removal of aldehydes. These resins are capable of removing aliphatic and aromatic aldehydes from a variety of feed streams. These resins form covalent imine bonds with aldehyde impurities. However, as required in WO2019 / 0974707, the use of basic ion exchangers alone does not significantly reduce the aldehyde content in alkoxylates.

[0009] EP3228649A1 describes a method for treating base-catalyzed alkoxylation products using a sulfonic acid ion exchanger, comprising: providing a mixture containing the base-catalyzed alkoxylation product to be treated, an alcohol having 1 to 4 carbon atoms, and water; treating the mixture with a sulfonic acid cation exchanger at >40°C; and separating the alkoxylation product from the mixture treated in this manner.

[0010] Technical Purpose Therefore, the technical objective of this invention is to provide a method by which aldehydes in alkoxylates (especially alkoxylates with higher molecular weights) can be significantly reduced. Furthermore, a preferred objective is to remove other undesirable impurities from alkoxylates besides aldehyde removal. In particular, an objective of this invention is to reduce or avoid the use of solvents (such as alcohols) in methods for purifying alkoxylates or removing aldehydes from alkoxylates. Summary of the Invention

[0011] This invention provides a method for at least partially removing aldehydes from a composition, the method comprising the following steps: a) Contact the composition with at least one cation exchanger and / or acid at a temperature of 20.0°C to 250.0°C; b) At least partially separating the aldehyde from the composition, and optionally treating the separated aldehyde, said treatment being selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation and pyrolysis; This results in a composition with reduced aldehyde content; Wherein, the composition to be treated in step a) comprises at least one compound having at least one epoxide unit in its chemical structure and having a molecular weight of 200 g / mol or higher, and Based on the total weight of the composition, 3.5 wt% or less of an alcohol having 1 to 6 carbon atoms.

[0012] In a preferred method, based on the total weight of the composition, the composition to be treated in step a) (which comprises at least one compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher) 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%, very particularly preferably 0.5 wt% or less, and most preferably 0.1 wt% or less of an alcohol having 1 to 6 carbon atoms. Particularly preferred is that the composition to be treated in step a) does not contain any (i.e., 0.0 wt%) an alcohol having 1 to 6 carbon atoms.

[0013] In another preferred method, based on the total weight of the composition, the composition to be treated in step a) (which comprises at least one compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher) contains 3.5 wt% or less, preferably 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% or less of a solvent having 1 to 6 carbon atoms. Here, alcohol having 1 to 6 carbon atoms represents solvent having 1 to 6 carbon atoms.

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

[0015] In a preferred method, the aldehyde is selected from the group consisting of aldehydes with 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 applies to aldehydes to be removed prior to the method, aldehydes separated by the method, and aldehydes with reduced content (if present).

[0016] Therefore, the present invention provides a method for removing aldehydes not only from chemical products and compositions separately, but also from those containing diols and (poly)epoxide compounds with larger molecular weights. Furthermore, within the scope of the invention, the inventors have found that other impurities, such as dioxanes and metal ions, can also be removed from such compositions. Moreover, the inventors have found that, unlike prior art methods, the desired purification effect can be achieved without adding a solvent (such as an alcohol, particularly an alcohol having 1 to 6 carbon atoms) to the composition to be treated. The method according to the invention is preferred because it eliminates the need to provide the corresponding alcohol, nor to separate and recover it. Therefore, the workload and cost of the method are reduced. Preferably, the above also applies to the aforementioned solvents.

[0017] The terms "composition to be purified" or "purified composition with reduced aldehyde content" are understood to refer to a liquid composition or liquid, preferably a solution or emulsion, wherein the composition to be purified or the purified composition comprises at least one compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher. In this document, the liquid aggregate state of the composition is present at least under the conditions of the method according to the invention, particularly at the temperature applied during the process.

[0018] Surprisingly, it was found that treating the composition or chemical product 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), followed by a subsequent separation process to remove aldehydes (step b), yielded a product with an aldehyde content reduced by at least 10% from the initial value. In a particularly preferred method, 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 particularly preferably 85°C to 120°C.

[0019] The method according to the invention can be operated continuously or intermittently.

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

[0021] The matrix of the ion exchange resin can be obtained, for example, by condensation (phenolic matrix) or polymerization (polystyrene matrix; styrene-divinylbenzene copolymer matrix; polyacrylic acid matrix; acrylate, methacrylate, or acrylonitrile-divinylbenzene copolymer matrix). The ion exchanger used according to the invention can exist in various forms, such as solid fine particles and granules (spherical, bead-like), as well as membranes, films, fibers, and fabrics. Preferably, solid fine particles and granules (spherical, bead-like) are used as the form of the ion exchange resin.

[0022] In continuous operation, the ion exchanger may be present, for example, in a column or container. The column or container may have nozzle plates or discharge systems for the entry and / or exit of the chemical product to be treated. During operation, the ion exchanger may be continuously operated in various ways, such as countercurrent, cocurrent, layered bed, multi-chamber, dual-flow, sandwich, or mixed-bed ion exchangers.

[0023] In batch operations, ion exchangers may exist, for example, in their free form in the composition (i.e., the chemical product) or in a porous container in contact with the composition.

[0024] In another preferred method, the acid used in step a) is selected from the group consisting of sulfuric acid, phosphoric acid, phosphonic acid, phosphonoglyceric acid, hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, and alkylbenzenesulfonic acid, with methanesulfonic acid being preferred. 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 method of using an acid in step a), it is particularly preferred that the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is a compound having a carbon skeleton.

[0025] As described above, according to the present invention, in step b), the aldehyde is partially separated from the composition, preferably followed by treatment of the separated aldehyde. The treatment is selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and pyrolysis. The preferred step for treating the separated aldehyde after step b) is selected from the group consisting of condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation, and pyrolysis, and may be referred to as step c).

[0026] In another preferred embodiment, step b) is performed using a thermal separation method selected from the group consisting of distillation, rectification, stripping, and flash evaporation. The above-mentioned thermal separation methods can also be used in combination. Furthermore, to improve separation efficiency, a solvent (such as water) or an entrainer can be added to the composition to be purified.

[0027] In step b), a thermal separation method selected from the group consisting of distillation, rectification, stripping, and flash evaporation, aldehydes are removed from the composition (i.e., the product stream) via the gas phase. In a particularly preferred embodiment, distillation, rectification, or stripping is carried out under vacuum. In stripping, the stripping gas can be, for example, steam, nitrogen, carbon dioxide, air, or argon. Substances contained in the gas stream (e.g., aldehydes) can be at least partially removed from the gas phase by commonly used waste gas purification or waste air purification methods. It should be understood that biological waste gas purification is also included. Substances contained in the gas phase (e.g., aldehydes) can be condensed and collected, or absorbed, for example, by an absorption medium (e.g., a washing liquid). If the absorption capacity of the absorption medium (e.g., water) is insufficient, chemical aids can be used to supplement absorption through a chemical reaction (chemical absorption). Furthermore, substances contained in the gas stream can be adsorbed by an adsorption medium (e.g., activated carbon), or chemically bonded, for example, by an ion exchanger, or chemically transformed. Typically, chemical transformation includes catalytic and non-catalytic processes. In non-catalytic chemical processes, chemical aids (such as bisulfites) can be used to form aldehyde adducts to at least partially remove aldehydes. Furthermore, substances in the gas phase can be decomposed through oxidation or pyrolysis (including re-combustion processes). It should be understood that the above methods (condensation, absorption, adsorption, chemical bonding, chemical transformation, oxidation, and pyrolysis) can be used in combination.

[0028] Exemplary thermal separation equipment that can operate under vacuum includes distillation columns, rectification columns, evaporators (e.g., forced circulation and natural circulation evaporators, horizontal evaporators, rotary evaporators, falling film evaporators, thin-film evaporators, short-path evaporators, or degassers), or spray dryers, preferably with a waste gas purification unit or waste air purification unit installed downstream of the evaporation unit. As absorbers, Venturi scrubbers, spray scrubbers, jet scrubbers, or cyclone scrubbers can be used. As adsorbers, fixed-bed adsorbers, rotating-bed adsorbers, fluidized-bed adsorbers, or moving-bed adsorbers can be used. To separate gaseous substances (such as aldehydes) into liquids, a cooling unit for condensation can be installed downstream of the thermal separation equipment. Additionally, an afterburner can be installed downstream of the thermal separation equipment. In the case of biological waste gas purification, biological scrubbers, biological filters, biotrickling bed reactors, etc., can be used.

[0029] In an alternative preferred embodiment of the method, step b) is performed by contacting an ion exchanger having amino or bisulfite functional groups, wherein step b) is preferably performed at a temperature of 20°C to 250°C. Here, the aldehyde binds to the ion exchanger and is removed from the composition (i.e., the product (stream)).

[0030] Amino-functionalized ion exchangers can exist, for example, in a matrix based on branched polystyrene with functionalized amino groups. The amino-functionalized ion exchanger is contacted with a chemical product (stream) to bind the aldehydes contained therein to the amino groups, thereby removing them from the product (stream). The primary amino groups of the resin can, for example, covalently bind to the aldehydes by forming imine compounds.

[0031] For example, bisulfite-functionalized ion exchangers can be prepared by treating highly basic ion exchange resins with hydroxyl groups with a bisulfite solution. Through this treatment, the basic ion exchanger is converted into one with (resin-HSO3) hydroxyl groups. - The bisulfite form of the ) group. The following example illustrates the preparation of the bisulfite form by treating a highly basic ion exchange resin with sodium bisulfite solution: resin-OH - +Na + HSO3 - (solution) → resin - HSO3 - +Na + OH - (solution) When in contact with chemical products (resin-HSO3) - The ) group can combine with the aldehyde contained therein, thereby removing it from the product (stream). Taking the removal of formaldehyde as an example, the following reaction mechanism is expected: Resin-HSO3 - +HCOH→resin-HOCH2SO3 - In another preferred method, based on the total weight of the composition, 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 higher in the composition used 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%. These contents are also preferably applicable to compositions with reduced aldehyde content obtained after step b).

[0032] The method according to the invention can remove aldehydes not only from aqueous solutions but also from concentrated compositions or chemical products, respectively. Therefore, based on the total weight of the composition, 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, more preferably 40 wt% or less, more preferably 30 wt% or less, 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. These water contents are also preferably applicable to compositions with reduced aldehyde content obtained after step b).

[0033] In another preferred embodiment of the invention, the aldehyde to be removed from the composition has at least one aldehyde group in its structure. The aldehyde may have other functional groups and may also contain heteroatoms in its structure. In a preferred method, the aldehyde is selected from the group consisting of aldehydes with a molecular weight of 200 g / mol or lower. More preferably, the aldehyde is selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.

[0034] Significant purification is achieved, particularly with respect to aldehydes, by using the method according to the invention. In a preferred method, after step b), a composition is obtained having 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%, even more preferably at least 99% compared to the initial value. In a preferred method, the total aldehyde content is defined as the total content of aldehydes with a molecular weight of 200 g / mol or less. In another preferred method, the total aldehyde content is defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.

[0035] In a particularly preferred method, after step b), a composition is obtained having 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 referred to herein means, based on the total weight of the composition, a composition having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher, containing at least 10 wt%, particularly preferably at least 50 wt%. In a preferred method, total aldehyde content is defined as the total content of aldehydes with a molecular weight of 200 g / mol or less. In another preferred method, total aldehyde content is defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. “ppm” indicates the total aldehyde content in mg / kg of the composition.

[0036] In another preferred method, after step b), a composition is obtained in which, based on the total weight of the composition, the content of a compound having at least one epoxide in its chemical structure and a molecular weight of 200 g / mol or higher is at least 10 wt%, particularly preferably at least 50 wt%, and the total aldehyde content is 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, most preferably 10 ppm or less, wherein the total aldehyde content is defined as the total content of aldehydes with a molecular weight of 200 g / mol or lower, and wherein 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. "ppm" indicates the total aldehyde content in mg / kg of the composition.

[0037] In addition to the separation of aldehydes, it has been surprisingly found that dioxanes can also be removed using the method according to the invention. Regarding dioxanes, the following description primarily refers to 1,4-dioxane. However, other dioxane isomers are also considered. Therefore, dioxanes include one or more substances selected from the group consisting of 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane, preferably 1,4-dioxane. Thus, in another preferred method, step b) is carried out by a thermal separation method selected from the group consisting of distillation, rectification, stripping, and flash evaporation, wherein after step b) a composition is obtained 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, even more preferably 50 ppm or less, and most preferably 10 ppm or less. In particularly preferred embodiments, the residual dioxane content mentioned herein refers to a composition having at least 10 wt%, particularly preferably at least 50 wt%, of a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher, based on the total weight of the composition. “ppm” indicates the amount of dioxane in mg / kg of the composition.

[0038] In addition to separating aldehydes, the method of the present invention can also remove alkoxylation catalysts (such as NaOH or KOH) or metal-cyanide complex catalysts as shown in US5,158,922 or US2003 / 0119663 by using a cation exchanger in step a). Therefore, in another preferred method, the composition is contacted with at least one cation exchanger in step a), thereby obtaining a composition after step b) with a metal ion 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 particularly preferred embodiments, the residual metal ion content referred to herein means a composition having at least 10 wt%, particularly preferably at least 50 wt%, of a compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher, based on the total weight of the composition. In preferred embodiments, the metal ions are 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). “ppm” indicates the amount of metal ions in mg / kg of the composition.

[0039] Compounds having at least one alkylene oxide unit in their chemical structure and a molecular weight of 200 g / mol or higher In another particularly preferred method, the composition or a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is obtained by epoxide polymerization or by an alkoxylation method. In this application, the description of the molecular weight of "a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher" always refers to the 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.

[0040] Number-average molecular weight can be calculated, for example, from the amount used in the synthesis. For instance, if a fatty alcohol having five ethylene oxide (EO) units is to be synthesized, then for the synthesis of this alkoxylated compound, a weighted average mass ratio of fatty alcohol to ethylene oxide (EO) would be such that one 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-octadecyl alcohol: 270.5 g / mol) to the molecular weight of the five ethylene oxide units (5 × 44.05 g / mol).

[0041] Number-average molecular weight can be determined by freezing point depression, boiling point elevation, vapor pressure permeation (for molar masses up to approximately 50,000 g / mol), permeation (for molar masses up to approximately 10,000 g / mol), or NMR spectroscopy. Furthermore, based on molar mass distribution, number-average molecular weight can be determined by gel permeation chromatography (GPC) and mass spectrometry (MALDL-TOF).

[0042] In addition, the average molecular weight can be determined according to test 118 (Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography) in the OECD Guidelines for the Testing of Chemicals, Part 1.

[0043] As an epoxide, a compound having the following formula (I) can be used:

[0044] Among them, R 2 and R 3 Each residue independently represents a hydrogen or hydrocarbon residue; wherein the hydrocarbon residue may be an alicyclic hydrocarbon residue, preferably a straight-chain or branched hydrocarbon residue, particularly having 1 to 20, preferably 1 to 6, carbon atoms, and particularly preferably methyl, ethyl, or phenyl residues. Residue R 2 and R 3 It can also be a part of a cyclic group, R 2 and R 3 Forming binary residues. Hydrocarbon residue R 2 and R 3Furthermore, it can contain functional groups such as halogens, hydroxyl groups, and glycidyl propoxy groups. Such epoxides include epichlorohydrin, 2,3-epoxy-1-propanol, and polyfunctional epoxides such as 1,2-ethyl glycidyl ether, 1,4-butyl glycidyl ether, and 1,6-hexyl glycidyl ether. Preferably, the two residues R... 2 Or R 3 At least one of them is hydrogen. Particularly preferred is that the epoxide used is selected from the group consisting of ethylene oxide, propylene oxide, 1,2- or 2,3-epoxybutane, isobutane oxide, 1,2-epoxydodecane, cyclohexane oxide, ethylene cyclohexene oxide, and phenylene oxide.

[0045] As epoxides, glycidyl compounds, such as glycidyl ethers or glycidyl esters, can also be used, wherein at least one glycidylpropoxy group is linked via an ether or ester functional group to a straight-chain or branched alkyl residue, aromatic or alicyclic residue having 1 to 24 carbon atoms. Examples of such compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, cyclohexyl glycidyl ether, benzyl glycidyl ether, and C... 12 / C 14 Fatty alcohol glycidyl ethers, phenyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, and o-cresol glycidyl ethers. Preferred glycidyl esters include, for example, glycidyl methacrylate, glycidyl acrylate, and glycidyl neodecanoate.

[0046] In another particularly preferred method, the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher has at least one (multi)alkylene oxide group, preferably at least 1, preferably at least 2, preferably at least 3, more preferably at least 4, even more preferably at least 5, even more preferably at least 6, even more preferably at least 8, even more preferably at least 10, 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. There is no particular upper limit on the number of alkylene oxide units. In a preferred embodiment, the number of alkylene oxide units is 500 or less, more preferably 200 or less, even more preferably 150 or less. The alkylene oxide units are preferably selected from the group consisting of ethylene oxide, propylene oxide, and butane oxide, with ethylene oxide and / or propylene oxide being particularly preferred.

[0047] In another particularly preferred method, the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher has at least one of the formula -(C2H4-O). l -(C3H6-O) m -(C4H8-O) n -or-(C2H4-O) l-(C3H6-O) m -(C4H8-O) n -H (poly)epoxyalkyl groups, wherein l, m, and n are independently 0 or greater, and wherein 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. There is no particular upper limit on the number of epoxyalkyl units. In other embodiments, a sum of l, m, and n of 1 to 500 is preferred, a sum of l, m, and n of 1 to 200 is more preferred, and a sum of l, m, and n of 1 to 150 is even more preferred. In another particularly preferred embodiment, the sum of l, m, and n is a number from 2 to 500, preferably a number from 2 to 200, and particularly preferably a number from 2 to 150.

[0048] In another particularly preferred embodiment, the compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher has at least one of the formula -(C x H 2x -O) y -or-(C x H 2x -O) y -H polyepoxide alkyl groups, wherein x is 2, 3, or 4, and y is 1 or greater, preferably y is 2 or greater, 3 or greater, 4 or greater, 5 or greater, 6 or greater, 8 or greater, 10 or greater, 12 or greater, 15 or greater, 50 or greater, or 100 or greater. There is no particular upper limit on the number of epoxide units. In other embodiments, it is preferred that y is a number between 1 and 500, more preferably y is a number between 1 and 200, and even more preferably y is a number between 1 and 150. In another particularly preferred embodiment, y is a number between 2 and 500, preferably y is a number between 2 and 200, and particularly preferably y is a number between 2 and 150.

[0049] In preferred embodiments, the molecular weight of the compound having at least one epoxide unit in its chemical structure is 250 g / mol or higher, preferably 300 g / mol or higher, more preferably 400 g / mol or higher, even more preferably 500 g / mol, particularly preferably 1000 g / mol or higher, and especially preferably 2000 g / mol. There is no particular upper limit to the molecular weight of the compound having at least one epoxide unit in its chemical structure. In preferred embodiments, the molecular weight of the compound having at least one epoxide unit in its chemical structure is 100,000 g / mol or lower, preferably 50,000 g / mol or lower, more preferably 25,000 g / mol or lower, even more preferably 20,000 g / mol or lower, especially preferably 15,000 g / mol or lower, and particularly preferably 12,000 g / mol or lower.

[0050] In another particularly preferred method, the epoxide unit of a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is selected from the group consisting of ethylene oxide, propylene oxide and epoxide.

[0051] In another preferred embodiment of the method, a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher represents a (poly)epoxide adduct having at least one other residue selected from the group consisting of carboxylic acid residues, carboxylic ester residues, carboxamide residues, phenol residues, and alcohol residues. The epoxide unit is preferably selected from the group consisting of ethylene oxide, propylene oxide, and butane oxide, with ethylene oxide and / or propylene oxide being particularly preferred.

[0052] In the sense of this specification, (poly)epoxide adducts are reaction products of alkoxylated starting materials, such as carboxylic acids (e.g., ethylhexanoic acid, benzoic acid), or fatty acids (e.g., caprylic acid, capric acid, lauric acid, coconut oil, palmitic acid, stearic acid, oleic acid, ricinoleic acid), or those having multiple carboxyl groups (e.g., citric acid, agaric acid, and propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, trimesic acid, pyromellitic acid, and benzohexaic acid), and mixtures thereof; carboxylic acid esters, such as triglycerides (e.g., castor oil, rapeseed oil, soybean oil, sunflower oil, coconut oil), or diglycerides (e.g., dioleate), or monoglycerides (e.g., monooleate), or dehydrated sorbitol. Alcohol esters (such as sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, sorbitan sesquiisostearate), or polyglycerol fatty acid esters (such as polyglycerol cocoate, polyglycerol ricinoleate, polyglycerol oleate), or fatty acid esters (such as methyl oleate); carboxamides, such as fatty acid amides (such as cocoamide, cocoyl monoethanolamide, cocoyl diethanolamide, oleamide); phenols (such as alkylphenols, tristyrylphenols); monohydric alcohols (such as methanol, ethanol, propanol, butanol, ethylhexanol, methoxyethanol, methyl diethylene glycol); or fatty alcohols (such as lauryl alcohol, stearyl alcohol, oleyl alcohol); or carbonyl alcohols (such as isotretinoin, straight-chain or branched carbonyl alcohols -C 12 -C 15 The (poly)epoxide adduct has at least one epoxide unit, i.e., it has 1-500, preferably 1-200, more preferably 1-150 epoxide units. The epoxide units are preferably selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide, particularly preferably ethylene oxide and / or propylene oxide. The (poly)epoxide adduct can be composed of the same or different epoxides, for example, block or statistically arranged ethylene oxide and propylene oxide; therefore, this application also includes such "mixed" epoxide adducts.

[0053] In another preferred embodiment of the method, the compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is selected from the group consisting of polyethylene glycol, polyalkylene glycol, block copolymers, carboxylic acid alkoxylates, polyethylene glycol carboxylic acid esters, alkoxylated carboxylic acid 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 butane oxide, with ethylene oxide and / or propylene oxide being particularly preferred.

[0054] Compounds having at least one alkylene oxide unit in their chemical structure and a molecular weight of 200 g / mol or higher are preferably derived from C2-C4 alkylene oxides, more preferably C2-C3 alkylene oxides. Particularly preferred are alkylene oxides or propylene oxides, or mixtures thereof. In specific embodiments, compounds having at least one alkylene oxide unit in their chemical structure and a molecular weight of 200 g / mol or higher are those having the formula H-[O-C2H4]. p -[O-C3H6] q -[O-C4H8] r Polyethylene glycol with -OH groups, wherein p, q, and r are independently 0 or greater, and the sum of p, q, and r is 5 or greater, preferably 6 or greater, more 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. There is no particular upper limit on the number of epoxide units. In other embodiments, it is preferred that the sum of p, q, and r is from 5 to 500, more preferably from 5 to 200, and even more preferably from 5 to 150. In another particularly preferred embodiment, the sum of p, q, and r is from 10 to 500, preferably from 10 to 200, and especially preferably from 10 to 150.

[0055] In specific embodiments, compounds having at least one epoxide unit in their chemical structure and a molecular weight of 200 mg / mol or higher are nonionic surfactants. Exemplary nonionic surfactants are selected from the group consisting of carboxylic acid alkoxylates, ethylene glycol carboxylic acid esters, alkoxylated carboxylic acid esters, alkoxylated carboxamides, alkoxylated phenols, poly(epoxide)-based block copolymers, and alcohol alkoxylates. It should be understood that the above-described types of nonionic surfactants may have other functional groups or heteroatoms in their structure.

[0056] Exemplary carboxylic acid alkoxylates and carboxylic acid polyethylene glycol esters are based on 2-ethylhexanoic acid, benzoic acid, or fatty acid alkoxylates and fatty acid polyethylene glycol esters, respectively. The fatty acid alkoxylates and fatty acid polyethylene glycol esters are based on octanoic acid, capric acid, lauric acid, coconut oil acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid, and mixtures thereof, respectively. Carboxylic acid alkoxylates and carboxylic acid polyethylene glycol esters, which may have multiple ester groups in their structure, are, for example, alkoxylates or polyethylene glycol esters based on citric acid, agaric acid, propane-1,2,3-tricarboxylic acid, trimellitic acid, pyromellitic acid, pyromellitic tetroxide, and benzohexaic acid, and mixtures thereof.

[0057] Exemplary alkoxylated carboxylic esters are alkoxylated products based on triglycerides (e.g., castor oil, rapeseed oil, soybean oil, sunflower oil, coconut oil), or diglycerides (e.g., dioleate), monoglycerides (e.g., monooleate), sorbitan esters (e.g., sorbitan monolaurate, sorbitan monooleate, sorbitan trioleate, sorbitan monostearate, sorbitan sesquiisostearate), or polyglycerol fatty acid esters (e.g., polyglycerol cocoate, polyglycerol castor oil, polyglycerol oleate), or fatty acid esters (e.g., methyl oleate) and mixtures thereof. Typically, the carboxylic ester used as a starting material has at least one hydroxyl and / or carboxylic ester group, or is partially saponified prior to alkoxylation. Furthermore, carboxylic esters can be converted into corresponding alkoxylated products via insertion alkoxylation reactions.

[0058] Exemplary alkoxylated carboxamides are alkoxylated derivatives based on fatty acid amides (e.g., cocoamide, cocoyl monoethanolamide, cocoyl diethanolamide, oleamide, and mixtures thereof).

[0059] Exemplary alkoxylated phenols are alkoxylated derivatives based on alkylphenol derivatives (e.g., n-propylphenol, isopropylphenol, butylphenol, pentylphenol, hexylphenol, heptaylphenol, octylphenol, nonylphenol, dodecylphenol, methylphenol (cresol), dimethylphenol (xylenol), and ethylphenol or tristyrylphenol and mixtures thereof).

[0060] An exemplary block copolymer based on poly(epoxide) is an ethylene oxide / propylene oxide block polymer.

[0061] Exemplary alcohol alkoxylates are monohydric alcohols alkoxylated from methanol, ethanol, propanol, butanol, ethylhexanol, methoxyethanol, or methyl diethylene glycol; or fatty alcohol alkoxylates based on lauryl alcohol, stearyl alcohol, or oleyl alcohol; or based on isotretinoin, straight-chain or branched carbonyl alcohols -C 12 -C 15 Carbonyl alcohol alkoxylates, or alkoxylated cyclic alcohols (such as cyclohexanol), or Gelbert alcohol alkoxylates based on butyloctanol, hexyldecanol and octyldecanol, or alkoxylated polyols based on ethylene glycol, propylene glycol, butanediol, diethylene glycol, glycerol, polyglycerol, alkyl glycosides, sorbitol, mannitol, dehydrated sorbitol, isosorbide, trimethylolpropane, pentaerythritol, dipentaerythritol and mixtures thereof.

[0062] The present invention also provides a composition comprising at least one compound having at least one epoxide unit in its chemical structure and having a molecular weight of 200 g / mol or higher, wherein 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 with a molecular weight of 200 g / mol or lower. 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. "ppm" indicates the total aldehyde content in mg / kg of the composition.

[0063] As described above, it has been surprisingly found that, according to the present invention, processing a composition comprising a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher yields a product, i.e., the corresponding composition, with an aldehyde content reduced by at least 10% compared to the initial value.

[0064] Compositions comprising compounds having at least one epoxide unit in their chemical structure and a molecular weight of 200 g / mol or higher, as well as preferred embodiments and preferred features of the compounds themselves, as have been described above with respect to the method according to the invention.

[0065] In a preferred embodiment of the composition, based on the total weight of the composition, the content of a compound having at least one epoxide unit in its chemical structure and having a molecular weight of 200 g / mol or higher 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%.

[0066] In another preferred embodiment of the composition, based on the total weight 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, more preferably 40 wt% or less, more preferably 30 wt% or less, 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.

[0067] 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 referred to herein means, based on the total weight of the composition, a composition having at least one epoxide unit in its chemical structure and a molecular weight of 200 mg / mol or higher, containing at least 10 wt%, particularly preferably at least 50 wt%. As described above, in a preferred embodiment, the total aldehyde content is defined as the total content of aldehydes with 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.

[0068] In another particularly preferred embodiment of the composition, based on the total weight of the composition, the content of a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is at least 10 wt%, particularly preferably at least 50 wt%, wherein 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, 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, most preferably 10 ppm or less, wherein the total aldehyde content is defined as the total content of aldehydes with a molecular weight of 200 g / mol or lower, and wherein the total aldehyde content is also preferably defined as the total content of aldehydes selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde. "ppm" indicates the total aldehyde content in mg / kg of the composition.

[0069] As described above, dioxane can be removed in addition to aldehydes. Therefore, in another preferred embodiment of the composition, the dioxane content is 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. The dioxane is preferably selected from the group consisting of 1,2-dioxane, 1,3-dioxane, and 1,4-dioxane, with 1,4-dioxane being particularly preferred. In a particularly preferred embodiment, the residual dioxane content mentioned herein refers to a composition having at least 10 wt%, particularly preferably at least 50 wt%, of a compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher, based on the total weight of the composition. "ppm" indicates the amount of dioxane in mg / kg of the composition.

[0070] In addition to removing aldehydes, the alkoxylation catalyst, such as NaOH or KOH, can also be removed after step a) of the method by using a cation exchanger. 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 particularly preferred embodiments, the residual metal ion content referred to herein means a composition, based on the total weight of the composition, containing at least 10 wt% of a compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 mg / mol or higher, and particularly preferably at least 50 wt%. In a preferred embodiment, the metal ions are 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). "ppm" indicates the amount of metal ions in mg / kg of the composition.

[0071] Table A below lists other preferred embodiments of compositions according to the invention, wherein the compositions comprise at least one compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher, and are defined in terms of the combination of realized or achievable aldehyde and dioxane content or with respect to the combination of realized or achievable aldehyde, dioxane, and metal ion content. Values ​​are expressed in ppm and indicate the value or less in ppm. Preferably, based on the total weight of the composition, the content of the compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is at least 10 wt%, particularly preferably at least 50 wt%. Therefore, Table A below also lists preferred embodiments of the method, with respect to compositions obtained after step b) with undesirable reductions in the content of impurities (aldehyde and dioxane; aldehyde, dioxane, and metal ions), as listed in the table.

[0072] Table A: Preferred embodiments of the methods and compositions with respect to aldehydes, dioxanes, and metal ion impurities.

[0073]

[0074] 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 higher has at least one (multi)alkylene oxide group, preferably at least 1, preferably at least 2, preferably at least 3, more preferably at least 4, even more preferably at least 5, even more preferably at least 6, even more preferably at least 8, even more preferably at least 10, 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. There is no particular upper limit on the number of alkylene oxide units. 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 butane oxide, particularly preferably ethylene oxide and / or propylene oxide.

[0075] In another preferred embodiment of the composition, the compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher has at least one of the formula –(C2H4-O). l -(C3H6-O) m -(C4H8-O) n -or –(C2H4-O) l -(C3H6-O) m -(C4H8-O) n-H (poly)epoxyalkyl groups, wherein l, m, and n are independently 0 or greater, and wherein 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, preferably 50 or greater, most preferably 100 or more. There is no particular upper limit to the number of alkyl oxide units. In other embodiments, it is preferred that the sum of l, m, and n is from 1 to 500, more preferably from 1 to 200, and even more preferably from 1 to 150. In another particularly preferred embodiment, the sum of l, m, and n is a number from 2 to 500, preferably a number from 2 to 200, and particularly preferably a number from 2 to 150.

[0076] In another preferred embodiment of the composition, the compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher has at least one formula -(C x H 2x -O) y -or–(C x H 2x -O) y -H (poly)epoxyalkyl groups, wherein x is 2, 3, or 4, and y is 1 or greater, preferably y is 2 or greater, 3 or greater, 4 or greater, 5 or greater, 6 or greater, 8 or greater, 10 or greater, 12 or greater, 15 or greater, 50 or greater, or 100 or greater. There is no particular upper limit on the number of epoxyalkyl units. In other embodiments, it is preferred that y is a number from 1 to 500, more preferably y is a number from 1 to 200, and even more preferably y is a number from 1 to 150. In another particularly preferred embodiment, y is a number from 2 to 500, preferably y is a number from 2 to 200, and particularly preferably y is a number from 2 to 150.

[0077] In another preferred embodiment of the composition, the molecular weight of the compound having at least one epoxide unit in its chemical structure is 250 g / mol or higher, preferably 300 g / mol or higher, more preferably 400 g / mol or higher, even more preferably 500 g / mol or higher, particularly preferably 1000 g / mol or higher, especially preferably 2000 g / mol or higher. There is no particular upper limit to the molecular weight of the compound having at least one epoxide unit in its chemical structure. In a preferred embodiment, the molecular weight of the compound having at least one epoxide unit in its chemical structure is 100000 g / mol or lower, preferably 50000 g / mol or lower, more preferably 25000 g / mol or lower, even more preferably 20000 g / mol or lower, especially preferably 15000 g / mol or lower, particularly preferably 12000 g / mol or lower.

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

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

[0080] 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 higher is selected from the group consisting of polyethylene glycol, polyalkylene glycol, block copolymers, carboxylic acid alkoxylates, polyethylene glycol carboxylic acid esters, alkoxylated carboxylic acid 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 butane oxide, with ethylene oxide and / or propylene oxide being particularly preferred.

[0081] In another preferred embodiment of the composition, the compound having at least one epoxide unit in its chemical structure and a molecular weight of 200 g / mol or higher is of the formula H–[O-C2H4]. p -[O-C3H6] q -[O-C4H8] rPolyethylene glycol with -OH groups, wherein p, q, and r are independently 0 or greater, and the sum of p, q, and r is 5 or greater, preferably 6 or greater, more 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. There is no particular upper limit on the number of epoxide units. In other embodiments, it is preferred that the sum of p, q, and r is from 5 to 500, more preferably from 5 to 200, and even more preferably from 5 to 150. In another particularly preferred embodiment, the sum of p, q, and r is from 10 to 500, preferably from 10 to 200, and particularly preferably from 10 to 150. Attached Figure Description

[0082] Figure 1 A schematic arrangement is shown for a continuous method of reducing aldehydes using two heatable double-jacketed towers.

[0083] Figure 2 A schematic arrangement is shown for a continuous method of reducing aldehydes using a heatable double-jacketed tower and an evaporation unit. Detailed Implementation

[0084] Figure 1 A schematic arrangement is shown for a continuous method of removing aldehydes using two heatable, double-jacketed stainless steel towers. The product stream (A) to be purified is passed through two towers (1, 2) connected in series. The first tower (1) contains an acidic SO3H ion exchanger, and the downstream tower (2) contains a basic NH2 ion exchanger. Both towers (1, 2) can be operated, for example, at a temperature of 100°C. The resulting purified product stream (B) has a reduced aldehyde content.

[0085] Figure 2 A schematic arrangement for a continuous process is shown, wherein the product stream (A) to be purified passes through a heatable double-jacketed column (1) containing an acidic SO3H ion exchanger. An evaporation unit is installed at the outlet of column (1), which allows the release of aldehydes to be removed from the departing product stream by means of a vacuum (C) through the gas phase. Column (1) can, for example, be operated at a temperature of 100°C. The resulting purified product stream (B) has a reduced aldehyde content.

[0086] The following examples illustrate the features and advantages of the present invention through different implementation methods.

[0087] Example Within the scope of this invention, methods for reducing the aldehyde content in polyethylene glycol compounds and various alkoxylated compounds prepared for experimental purposes at high alkoxylation temperatures were investigated. In the experiments, Lanxess's sulfonic acid-functionalized ion exchanger "Lewatit SP 112 H", referred to in this example as "SO3H ion exchanger", was used as the cation exchanger. Lanxess's product "Lewatit VP OC 1065", referred to hereinafter as the "NH2 ion exchanger", was used as the basic ion exchanger. The aldehydes contained in the chemical compositions were derivatized with a 2,4-dinitrophenylhydrazine solution, separated from other substances by HPLC, and determined and quantified by UV detection (according to B. Reindl, HJ. Stan, Agric. Food Chem., 30 (1982) 849–854 and JR Dahlgran, MN Jameson, J. Assoc. Off. Anal. Chem., 71 / 3 (1988) 560–563). In the following examples, "ppm" represents the amount of the measured substance or the measured ion, expressed in mg / kg of the composition.

[0088] Example 1: Treatment of alkoxylated rapeseed oil (18 EO / 6 PO) with SO3H and NH2 ion exchangers To investigate the effect of ion exchangers on aldehyde reduction, 100 g of alkoxylated rapeseed oil with 18 EO units (corresponding to 18 ethylene oxide units) and 6 PO units (corresponding to 6 propylene oxide units) was stirred in a 150 mL beaker at 100 °C for 30 minutes. Experiments were conducted with and without 10 wt% acidic SO3H and basic NH2 ion exchangers. If ion exchangers were present, they were removed after treatment, and the residual acetaldehyde and propionaldehyde content in the remaining product was determined. The results are summarized in Table 1. Before treatment, the acetaldehyde content of the alkoxylated rapeseed oil with 18 EO units and 6 PO units was 6840 ppm, and the propionaldehyde content was 805 ppm. This experiment shows that acidic SO3H ion exchangers can significantly reduce aldehydes. Basic NH2 ion exchangers alone cannot substantially reduce aldehydes.

[0089] 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) = 1440.6 g / mol. According to DIN EN ISO 3681, DGF C-V3, the molecular weight of rapeseed oil was derived from the saponification value of 187.5 mg KOH / g.

[0090] Table 1: Effect of ion exchangers on aldehyde content in alkoxylated rapeseed oil with 18 EO and 6 PO (initial value of acetaldehyde was 6840 ppm, and the initial value of propionaldehyde was 805 ppm).

[0091]

[0092] Example 2a: Treatment of alkoxylated rapeseed oil (18 EO / 6 PO) with SO3H and NH2 ion exchangers To investigate the effect of the combination of acidic ion exchanger and subsequently used basic ion exchanger on aldehyde reduction, 100 g of alkoxylated rapeseed oil with 18 EO and 6 PO atoms was stirred in a 150 mL beaker at 60 °C, 80 °C, and 100 °C for 15 min and 30 min, respectively, with 5 wt% and 10 wt% acidic SO3H ion exchanger, respectively (Method A). After treatment, the ion exchanger was separated from the product, and samples were taken to determine the aldehyde content. In the second Method B, 5 wt% and 10 wt% basic NH2 ion exchanger were added to the product, and the mixture was stirred at different temperatures for 15 min and 30 min, respectively. Subsequently, the ion exchanger was removed, and the aldehyde content was determined. Before treatment, the alkoxylated rapeseed oil with 18 EO and 6 PO atoms had an acetaldehyde content of 7050 ppm and a propionaldehyde content of 990 ppm. The results are summarized in Table 2a. This series of experiments shows that a combination of treatment using an acidic ion exchanger followed by an alkaline NH2 ion exchanger can significantly reduce aldehydes. A higher percentage of ion exchanger and a higher temperature of 100°C are beneficial for this reduction.

[0093] The number-average molecular weight (M) of the alkoxylated rapeseed oil used n The calculation is as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1440.6 g / mol. According to DIN EN ISO 3681, DGF C-V3, the molecular weight of rapeseed oil is derived from the saponification value of 187.5 mg KOH / g.

[0094] Table 2a: Effect of ion exchanger combination on aldehyde content in alkoxylated rapeseed oil with 18 EO and 6 PO atoms.

[0095]

[0096] Example 2b: Treatment of alkoxylated dehydrated sorbitan monolaurate (20 EOs) with SO3H and NH2 ion exchangers The experimental procedure corresponds to Example 2a), where, instead of alkoxylated rapeseed oil with 18 EOs and 6 POs, dehydrated sorbitan monolaurate with 20 EOs was tested. Before treatment, the acetaldehyde content of dehydrated sorbitan monolaurate with 20 EOs was 1070 ppm. The results are summarized in Table 2b. This series of experiments demonstrates that a combination of acidic and subsequent basic ion exchanger treatment can significantly reduce acetaldehyde content.

[0097] The number-average molecular weight (M) of the alkoxylated sorbitan monolaurate used was... n The calculation is as follows: 541.5 g / mol (sorbitan monolaurate) + 20 × 44.05 g / mol (ethylene oxide) = 1422.5 g / mol.

[0098] Table 2b: Effect of ion exchanger combination on aldehyde content in ethoxylated sorbitan monolaurate + 20 EOs.

[0099]

[0100] Example 2c: Treatment of alkoxylated isotretinoin (7 EOs) with SO3H and NH2 ion exchangers The experimental procedure corresponds to Example 2a), where isotrimethylenetetramine with 7 PO was tested instead of alkoxylated rapeseed oil with 18 EO and 6 PO. Before treatment, the acetaldehyde content of isotrimethylenetetramine with 7 EO was 17 ppm. The results are summarized in Table 2c. This series of experiments demonstrates that a combination of acidic and subsequent basic ion exchanger treatment can significantly reduce aldehydes.

[0101] The number-average molecular weight (M) of the ethoxylated isotridecyl alcohol used n The calculation is as follows: 196.9 g / mol (isotridecyl alcohol) + 7 × 44.05 g / mol (ethylene oxide) = 505.2 g / mol. According to the European Pharmacopoeia 2.5.3, the molecular weight of isotrexol is derived from the hydroxyl value of 285 mg KOH / g.

[0102] Table 2c: Effect of ion exchanger combination on aldehyde content in ethoxylated isotridecyl alcohol + 7 EOs.

[0103]

[0104] Compare with Example 3a: Treatment of ethoxylated coconut oil acid (9 EOs) by steam distillation. 350 g of ethoxylated coconut oil acid with 9 EO atoms was weighed into a steam distillation apparatus consisting of a 500 mL flask, distillation accessories, a steam inlet pipe, and a stirring unit. The product was heated to 105 °C with stirring. At 105 °C, saturated steam was introduced for 240 min, and the distillate was collected via a receiver. Samples were taken at 105 °C (corresponding to a residence time of 0 min), and also after steam treatment at 105 °C for 60 min and 240 min, respectively. The aldehyde and 1,4-dioxane contents of the samples were analyzed. The results are summarized in Table 3a. Before treatment, the formaldehyde content of the coconut oil acid ethoxylate was 58 ppm, the acetaldehyde content was 2740 ppm, and the 1,4-dioxane content was 3200 ppm.

[0105] The number-average molecular weight (M) of the coconut oil ethoxylates used n The calculation is as follows: 209.0 g / mol (cocoacid) + 9 × 44.05 g / mol (ethylene oxide) = 605.4 g / mol. According to DIN EN ISO 3682, the molecular weight of cocoacid is derived from its acid value of 268.5 mg KOH / g.

[0106] Table 3a (Control Example): Aldehyde and 1,4-dioxane content of ethoxylated coconut oil acid with 9 EOs after treatment by steam distillation at 105°C for 240 min.

[0107]

[0108] Example 3b: Treatment of ethoxylated coconut oil acid (9 EOs) with SO3H ion exchanger and steam distillation The experimental procedure corresponds to Example 3a, where 2 wt% acidic SO3H ion exchanger was first added to ethoxylated coconut oil acid with 9 EO atoms. The results are summarized in Table 3b. A comparison of Table 3b with Table 3a shows that the presence of the acidic SO3H ion exchanger has a significant effect on reducing aldehyde content. The content of 1,4-dioxane can also be reduced.

[0109] Table 3b: Aldehyde and 1,4-dioxane content of ethoxylated coconut oil acid with 9 EO atoms after steam distillation at 105 °C for 240 min in the presence of SO3H ion exchanger.

[0110]

[0111] Example 3c: Treatment of ethoxylated coconut oil acid (9 EOs) with methanesulfonic acid and steam distillation The experimental procedure corresponds to Example 3a, where 0.5 wt% methanesulfonic acid was first added to coconut oil acid containing 9 EOs. The results are summarized in Table 3c. A comparison of Table 3c with Table 3a shows that the presence of methanesulfonic acid has a significant effect on reducing aldehyde content. The 1,4-dioxane content also decreased.

[0112] Table 3c: Aldehyde and 1,4-dioxane content of ethoxylated coconut oil acid with 9 EOs after steam distillation at 105°C for 240 min in the presence of methanesulfonic acid.

[0113]

[0114] Compare with Example 4a: Treatment of ethoxylated coconut oil acid (9 EOs) by distillation. In a distillation apparatus consisting of a 500 mL flask, distillation attachments, and a stirring unit, 350 g of ethoxylated coconut oil acid with 9 EO atoms was weighed and 35 g of water was added. The coconut oil acid with 9 EO atoms was prepared by ethoxylation with ethylene oxide using potassium hydroxide as a catalyst. The mixture of coconut oil acid with 9 EO atoms and water was heated to 80 °C with stirring, and a sample was taken at 80 °C (corresponding to a residence time of 0 min). Then, a vacuum was applied (final pressure: 200 mbar), and water (including byproducts) was distilled off. Samples were taken after 60 min and 240 min, at which point the vacuum was released. The aldehyde, 1,4-dioxane, and potassium contents of the samples were analyzed. The results are summarized in Table 4a. Before treatment, the formaldehyde content of the coconut oil acid ethoxylate was 58 ppm, the acetaldehyde content was 2740 ppm, the 1,4-dioxane content was 3200 ppm, and the potassium content was 1100 ppm.

[0115] The number-average molecular weight (M) of the ethoxylated coconut oil acid used n The calculation is as follows: 209.0 g / mol (cocoacid) + 9 × 44.05 g / mol (ethylene oxide) = 605.4 g / mol. According to DIN EN ISO 3682, the molecular weight of cocoacid is derived from its acid value of 268.5 mg KOH / g.

[0116] Table 4a: (Comparative Example): Aldehyde, 1,4-dioxane and potassium content of ethoxylated coconut oil acid with 9 EOs treated with 10wt% water by distillation for 240 min at 80°C under vacuum.

[0117]

[0118] Example 4b: Treatment of ethoxylated coconut oil acid (9 EOs) with SO3H ion exchanger and distillation The experimental procedure corresponds to Example 4a, wherein 2 wt% acidic SO3H ion exchanger and water are first added to ethoxylated coconut oil acid having 9 EO atoms. The results are summarized in Table 4b. A comparison of Table 4b with Table 4a shows that the presence of the acidic SO3H ion exchanger has a significant effect on reducing the aldehyde content. The 1,4-dioxane content can also be reduced. Furthermore, by using a cation exchanger, the potassium content can be significantly reduced, with the potassium ions derived from potassium hydroxide used as a catalyst in the ethoxylation reaction. Therefore, by applying the method according to the invention, a product with reduced aldehyde, 1,4-dioxane, and cation contents relative to the initial values ​​can be prepared.

[0119] Table 4b: Aldehyde, 1,4-dioxane and potassium content of ethoxylated coconut oil with 9 EOs after distillation at 80 °C for 240 min under vacuum in the presence of SO3H ion exchanger and 10 wt% water.

[0120]

[0121] Example 5: Purification of alkoxylated rapeseed oil (18 EO / 6 PO) by passing it through towers containing SO3H ion exchanger and NH2 ion exchanger, respectively.

[0122] In the experiment, a continuous method was used to reduce aldehydes, employing two heatable, series-connected, double-jacketed stainless steel towers (e.g., each approximately 250 cm³ in volume). Figure 1 (As shown) and a feed pump with a flow rate of approximately 2 g / min. The first column was filled with approximately 150 g of acidic SO3H ion exchanger, and the downstream column was filled with approximately 150 g of basic NH2 ion exchanger. Both columns were operated at a temperature of 100 °C. The liquid product stream consisted of alkoxylated rapeseed oil with 18 EO and 6 PO atoms, with an initial acetaldehyde concentration of 6840 ppm and an initial propionaldehyde concentration of 805 ppm. After a 2-hour pre-run, approximately 20 g of sample was taken from the outflowing product stream every hour to determine its aldehyde content. The results are summarized in Table 5. The results in Table 5 indicate that under the above conditions, the aldehyde content can be reduced by more than 90%.

[0123] The number-average molecular weight (M) of the alkoxylated rapeseed oil used n The calculation is as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1440.6 g / mol. According to DIN EN ISO 3681, DGFC-V3, the molecular weight of rapeseed oil is derived from the saponification value of 187.5 mg KOH / g.

[0124] Table 5: According to Figure 1The change of aldehyde content over time in alkoxylated rapeseed oil with 18 EO and 6 PO atoms treated by a continuous method.

[0125]

[0126] Example 6: Purification of polyethylene glycol 400 by passing it through columns containing SO3H ion exchanger and NH2 ion exchanger respectively. The experimental procedure was similar to that in Example 5, with the product stream consisting of polyethylene glycol 400 and an initial formaldehyde content of 68 ppm. The results are summarized in Table 6. The results in Table 6 indicate that, under the above conditions, the formaldehyde content can be reduced by more than 90%.

[0127] According to the European Pharmacopoeia 2.5.3, the number-average molecular weight (Mn) of the polyethylene glycol 400 used is... n The value is derived from the hydroxyl value of 281 mg KOH / g, which is 399.4 g / mol.

[0128] Table 6: According to Figure 1 The change of formaldehyde content in polyethylene glycol 400 over time using a continuous method.

[0129]

[0130] Example 7: Purification of alkoxylated rapeseed oil (18 EO / 6 PO) through a column containing SO3H ion exchanger and a downstream connected evaporation unit.

[0131] In the experiment, a continuous method was used to reduce aldehydes, employing a heatable, double-jacketed stainless steel tower with a volume of approximately 250 cm³ (e.g., Figure 2 (As shown) and a feed pump with a flow rate of approximately 2 g / min. An evaporation unit was installed at the outlet of the column, which allowed the release of aldehydes to be removed through the gas phase by means of a 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 with 18 EO and 6 PO, with an initial acetaldehyde concentration of 6440 ppm and an initial propionaldehyde concentration of 818 ppm. After a 2-hour pre-run, approximately 20 g of sample was taken from the outflowing product stream every hour to determine its aldehyde content. The results are summarized in Table 7.

[0132] The results in Table 7 show that, under the above conditions, the aldehyde content can be reduced by more than 60%.

[0133] The number-average molecular weight (M) of the alkoxylated rapeseed oil used nThe calculation is as follows: 299.3 g / mol (rapeseed oil) + 18 × 44.05 g / mol (ethylene oxide) + 6 × 58.08 g / mol (propylene oxide) = 1440.6 g / mol. According to DIN EN ISO 3681, DGFC-V3, the molecular weight of rapeseed oil is derived from the saponification value of 187.5 mg KOH / g.

[0134] Table 7: According to Figure 2 The change of aldehyde content over time in alkoxylated rapeseed oil with 18 EO and 6 PO atoms treated by a continuous method.

[0135]

Claims

1. A process for at least partially removing aldehydes from a composition, the process comprising the steps of: a) contacting the composition with at least one cation exchanger and / or an acid at a temperature of from 20.0 °C to 250.0 °C; b) at least partially separating the aldehydes from the composition, and optionally treating the separated aldehydes by condensation, absorption, adsorption, chemical bonding, chemical reaction, oxidation and pyrolysis; thereby obtaining a composition with a reduced aldehyde content; wherein the composition to be treated in step a) comprises at least one compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more, and 3.5 wt% or less of alcohols having 1 to 6 carbon atoms, based on the total weight of the composition.

2. The method of claim 1, wherein, Step a) is carried out at a temperature of from 40 °C to 140 °C.

3. The method according to claim 1 or 2, characterized in that, The cation exchanger used in step a) is an acidic cation exchanger comprising an acid group selected from the group consisting of -SO3H, -COOH and -OP(OH)3.

4. The method 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, preferably methanesulfonic acid.

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

6. The method according to any one of claims 1 to 4, characterized in that, Step b) is carried out by contacting an ion exchanger having an amino or sulfite function, wherein step b) is preferably carried out at a temperature of from 20 °C to 250 °C.

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

8. The method according to any one of claims 1 to 7, characterized in that, After step b) a composition is obtained having a total aldehyde content which is at least 10% lower than the initial value.

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

10. The method according to any one of claims 1 to 9, characterized in that, Step b) is carried out by a thermal separation method selected from the group consisting of distillation, rectification, stripping and flashing, wherein after step b) a composition is obtained having a dioxane content of 1000 ppm or less.

11. The method according to any one of claims 1 to 10, characterized in that, The compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more has at least one (poly)alkylene oxide group having at least 1, preferably at least 2, preferably at least 3, more preferably at least 4, even more preferably at least 5 alkylene oxide units.

12. The method according to any one of claims 1 to 11, characterized in that, The compound having at least one alkylene oxide unit in its chemical structure and a molecular weight of 200 g / mol or more 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 method according to any one of claims 1 to 11, characterized in that, 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 polyethylene glycol, polyalkylene glycol, block copolymer, carboxylic acid alkoxylate, carboxylic acid polyethylene glycol ester, alkoxylated carboxylic acid ester, alkoxylated carboxamide, alkoxylated phenol and alcohol alkoxylate.

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

15. The composition of claim 14, wherein, 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. The metal ion content is 1000 ppm or less.

Images