Fatty acid esters of polyglycerol polyalkylene glycols as thickeners

Abstract

The invention relates to fatty acid esters of polyglycerol polyalkylene glycols of formula (I) R - ([OEt]x - [OAIk]y - [OEt]z - A)n formula (I) where R = a polyglycerol group, [OEt] = an oxyethylene group, of formula -(CH2CH2O)-, [OAIk] = an oxyalkylene group, of formula -(CH2CHR2O)-, where R2 = CH3, C2H5, C6H5 or C10H21, preferably CH3, C2H5, particularly preferably CH3, n = 2 to 12, preferably 3 to 10, particularly preferably 4 to 8, n*x = 50 to 600, preferably 100 to 450, particularly preferably 200 to 350, n*y = 10 to 150, preferably 20 to 120, particularly preferably 30 to 100, n*z = 5 to 150, preferably 15 to 100, particularly preferably 30 to 70, with the proviso that the repeating units -[OEt]x - [OAIk]y- denoted by the indices x and y are contained mixed in the polyether chain in a random sequence or in alternating blocks, and n*x + n*z is at least 150, preferably 200 to 500, particularly preferably 250 to 400, A = in each case independently of one another H or a grouping of formula -C(=O)R1, where R1 = C4 to C24 alkyl, preferably C10 to C20 alkyl, particularly preferably C12 to C18 alkyl, C4 to C24 hydroxyalkyl or C4 to C24 alkenyl, with the proviso that at least one group A of the groups A provided n times corresponds to a grouping of formula - C(=O)R1.

Description

[0001] Fatty acid esters of polyglycerol polyalkylene glycols as thickening agents

[0002] The invention relates to fatty acid esters of polyglycerol polyalkylene glycols, their production and use as thickening agents.

[0003] Coatings are applied to surfaces for decorative and / or protective purposes. Many coating applications utilize formulations containing particles such as pigments and / or fillers.

[0004] Pigments are coloring substances that are dispersed insoluble form in the application medium. Application media include, for example, paints, varnishes, pigment preparations, printing inks, as well as organic solvents and other preparations into which the pigment is incorporated. Typically, the crude pigments produced during synthesis are milled or crushed before use; for example, so-called dry and wet milling processes are employed. However, small-diameter particles are particularly prone to agglomeration and therefore require stabilization.

[0005] Pigment stabilization is of great importance in the coatings industry, as pigments, being a key formulation component, determine the optical appearance and physicochemical properties of a coating. To ensure they function optimally within the coating, they must not only be stabilized against flocculation, but their rheology must also be adjusted to prevent settling and the resulting sediment.

[0006] Commercially available paint formulations are only mono-pigmented in some applications; more often, they are mixtures of two or more different pigments. The white pigment, usually titanium dioxide, is typically ground into the base color. The colored pigments very often come from pigment concentrates, which have a higher concentration of pigment particles and are specifically used for coloring paints and varnishes.

[0007] The rheological adjustment of pigment concentrates presents an additional challenge due to the higher pigment concentration. On the one hand, the pigment concentration should be very high for economic reasons, which necessitates the use of high-performance wetting and dispersing additives. On the other hand, the pigment concentration must not be too high, as this would make precise color adjustment impossible. Especially in automated dosing systems, a lower pigment load is generally more beneficial to the quality of the color adjustment.

[0008] Lower pigment concentrations result in lower viscosity, which in turn increases the risk of settling and impairs dosing. Furthermore, the increased water content of these pigment concentrates causes an undesirable water-drop effect when added to the base coat. The lower pigment content and the associated higher concentration of the pigment concentrate also promote this water-drop effect and make efficient coating application more difficult.

[0009] Several methods are currently used to increase the viscosity and adjust the rheology of pigment concentrates. These methods are also used to adjust the viscosity and rheology of paints and varnishes and are well-known and described in that context.

[0010] Depending on the application area of ​​the coating, the following rheology additives are used in pigment concentrates:

[0011] Cellulose thickeners represent the simplest option. They thicken the water phase of pigment concentrates and can induce Newtonian as well as pseudoplastic flow behavior. Some disadvantages of cellulose thickeners are their powdered form, which requires dissolving or activation, and their very poor water resistance.

[0012] Acrylate thickeners can also thicken the aqueous phase. These are acrylate polymers that absorb water in alkaline media, thereby increasing viscosity. Many pigments, especially iron oxides, tend to lower the pH. This can cause the acrylate thickener to lose its effectiveness.

[0013] Polyurethane-based thickeners, on the other hand, act associatively; that is, they do not thicken the aqueous phase but form a network of polymer molecules that exhibits pseudoplastic rheology. They are pH-independent and relatively water-resistant. However, polyurethane thickeners preferentially use binder droplets as the centers for their network. Since pigment concentrates are binder-free systems, the effectiveness of polyurethane thickeners is severely limited. Furthermore, polyurethane thickeners are, in most cases, incompatible with solvent-based alkyd systems and therefore unsuitable for use in universal pastes.

[0014] Another method for thickening pigment concentrates, which can also be considered state of the art, is the use of various fillers, mostly layered silicates. These particles increase the solids content of the pigment concentrate and thus its viscosity. They can also form networks, similar to polyurethane thickeners, thereby adjusting the rheology. However, achieving the desired viscosity is difficult because the particles themselves must first be dispersed into the liquid phase, and adding more particles later is almost impossible. Furthermore, fillers usually have a negative impact on the compatibility of universal pigment pastes in solvent-based alkyd paints.

[0015] Furthermore, fatty acid esters of polyglycerols are known from EP 1 518900A2, which are waxes at room temperature. EP 1 518 900A2 describes the solution in a solvent-water mixture and the uses of these preparations in cosmetic, dermatological, or pharmaceutical applications.

[0016] US Patent 4,895,681 describes fatty acid esters of polyglycerol polyglycol ethers, in which polyglycerols are first reacted with ethylene oxide and then with propylene oxide, and subsequently esterified with fatty acids. These fatty acid esters are used as defoamers. Defoamers made from alkylene oxide block polymers are also known (US Patent 4,745,231).

[0017] It is therefore desirable to provide compounds that can be used as thickening agents, preferably in pigment concentrates, whose processability is improved and, for example, do not exhibit dilatancy in pigment concentrates, and which overcome at least one disadvantage of the prior art.

[0018] Surprisingly, it was found that fatty acid esters of polyglycerol polyalkylene glycols according to formula (I)

[0019] R - ([OEtJx - [OAIk] y - [OEt] z - A) n Formula (I) with R = polyglycerol residue

[0020] [OEt] = oxyethylene residue, according to the formula -(CH2CH2O)-, [OAlk] = oxyalkylene residue, according to the formula -(CH2CHR2O)-, with R2 = CH3, C2H5, CeHs, C10H21, preferably CH3, C2H5, particularly preferably CH3, n = 2 to 12, preferably 3 to 10, particularly preferably 4 to 8, n*x = 50 to 600, preferably 100 to 450, particularly preferably 200 to 350, n*y = 10 to 150, preferably 20 to 120, particularly preferably 30 to 100, n*z = 5 to 150, preferably 15 to 100, particularly preferably 30 to 70, with the proviso that the repeating units designated with the indices x and y -[OEt] x - [OAIk] y - are mixed in statistical sequence or in alternating blocks in the polyether chain, and n*x + n*z is at least 150, preferably 200 to 500, particularly preferably 250 to 400,

[0021] A = each independently of one another H or a group of the formula -C(=O)Ri, with Ri = C4- to C24-alkyl, preferably C10- to C20-alkyl, particularly preferably C12- to C18-alkyl, C4- to C24-hydroxyalkyl or C4- to C24-alkenyl, with the proviso that of the n-fold present residues A at least one residue A corresponds to a group of the formula -C(=O)Ri, are excellently suited as thickeners and are universally applicable.

[0022] As described at the beginning, thickening agents, especially for pigment concentrates, are subject to special requirements, such as:

[0023] Good processability, i.e., the product is flowable at room temperature, thickening effect in pigment concentrates and paint formulations, ensuring the desired rheological properties, e.g., avoiding dilatancy.

[0024] Reduction of viscosity drop after tinting and suitability for use in universal pastes.

[0025] It would also be desirable to reduce the volatile organic content (VOC) in paints and, ultimately, in pigment preparations. The German Chemicals Regulation on the Limitation of Emissions of Volatile Organic Compounds (VOCs) by Restricting the Marketing of Solvent-Based Paints and Varnishes (ChemVOOFarbV) regulates the use of VOCs in architectural paints and vehicle coatings. This regulation has triggered a general trend in the paint and coatings industry, so that industrial paint manufacturers are now also striving to reduce VOCs. For example, the Commission decision of 28 May 2014 establishing the environmental criteria for the award of the EU Ecolabel for interior and exterior paints and coatings sets upper limits of 10 g / L VOC and 30 g / L SVOC for matte white interior wall paints.

[0026] Thickening agents, rheology additives, universal thickeners and thickeners are understood as synonyms.

[0027] Pigment preparation, pigment concentrate, pigment pastes and universal pastes are understood as synonyms.

[0028] Completely unexpectedly, it was found that the compounds according to the invention, as defined in formula (I), meet at least two of these requirements.

[0029] In addition to their thickening properties in pigment concentrates and their ability to control the rheology of the pigment concentrates and prevent dilatancy, the compounds according to formula (I) of the invention preferably have the property of being flowable. "Flowable" here means that the compound according to the invention can be used directly in the manufacturing process without requiring pretreatment, such as dissolving in water, a solvent, or a solvent / water mixture.

[0030] Universal pastes are easily dosable pigment preparations or pigment concentrates used for coloring both aqueous and solvent-based coating materials. In contrast, purely aqueous pigment preparations are used only for coloring aqueous coating materials.

[0031] The compounds according to the invention can be used as thickeners, preferably for universal pigment pastes.

[0032] Preferably, the compounds according to the invention are obtained according to formula (I) by the reaction of at least one polyether polyol of the general formula (II)

[0033] R - ([OEtJx - [OAIk] y - [OEt] z - OH) n Formula (II), with R = polyglycerol residue,

[0034] [OEt] = oxyethylene residue, according to the formula -(CH2CH2O)-, [OAlk] = oxyalkylene residue, according to the formula -(CH2CHR2O)-, with R2 = CH3, C2H5, CeHs, C10H21, preferably CH3, C2H5, particularly preferably CH3, n = 2 to 12, preferably 3 to 10, particularly preferably 4 to 8, n*x = 50 to 600, preferably 100 to 450, particularly preferably 200 to 350, n*y = 10 to 150, preferably 20 to 120, particularly preferably 30 to 100, n*z = 5 to 150, preferably 15 to 100, particularly preferably 30 to 70, with the proviso that the repeating units designated with the indices x and y -[OEt] x - [OAIk] y- are mixed in a statistical sequence or in alternating blocks in the polyether chain, and n*x + n*z is at least 150, preferably 200 to 500, particularly preferably 250 to 400, comprising at least one straight-chain and / or branched saturated and / or unsaturated fatty acid with 4 - 24 carbon atoms, preferably with 10 - 20 carbon atoms, particularly preferably with 12 - 18 carbon atoms, or with at least one fatty acid alkyl ester with 4 - 24 carbon atoms, preferably with 10 - 20 carbon atoms, particularly preferably with 12 - 18 carbon atoms.

[0035] When number ranges are specified in the form "X to Y", where X and Y represent the limits of the range, this is equivalent to stating "from at least X to and including Y", unless otherwise specified. Range specifications therefore include the range limits X and Y, unless otherwise stated.

[0036] Wherever molecules or molecular fragments have one or more stereocenters, or can be differentiated into isomers due to symmetries, or can be differentiated into isomers due to other effects, such as restricted rotation, all possible isomers are preferably included in the present invention.

[0037] Formulas (I) and (II) describe compounds or residues composed of repeating units, such as repeating fragments, blocks, or monomer units, which may exhibit a molecular weight distribution. The frequency of the repeating units is indicated by indices. Unless explicitly stated otherwise, these indices are to be considered statistical means (number means). The index numbers used, as well as the ranges of values ​​given for the indices, are understood as means of the possible statistical distribution of the actual existing structures and / or their mixtures. The various fragments or repeating units of the compounds described in Formulas (I) and (II) may be statistically distributed.The distributions are structured block-wise with any number of blocks and any sequence, or they are subject to a randomized distribution. They can also be structured alternately, or form a gradient over the chain, if one exists. In particular, they can also form all mixed forms, in which groups of different distributions may follow one another. Formula (I) and Formula (II) include all permutations of repeating units.

[0038] Therefore, if compounds described within the scope of the present invention can contain multiple instances of different units, these units can occur in these compounds in a disordered manner, e.g., statistically distributed, or in an ordered manner. The information regarding the number or relative frequency of units in such compounds is to be understood as an average value (numerical mean) averaged over all corresponding compounds.

[0039] Preferably, the repeating units designated with the index z exhibit -[OEt] z - a block-like arrangement.

[0040] Preferably, the [OEt], [OAIk] residues, also called alkylene oxide units, of general formula (I) or formula (II) can be arranged in any order. This includes, in particular, a statistical order or an arrangement in the form of [OEt], [OAIk] blocks or an arrangement in the form of a gradient, for example an enrichment or depletion of [OEt] or the other alkoxy units along the polyalkylene oxide chain.

[0041] The [OAIk] groups are preferably formed from epoxides such as propylene oxide, butylene oxide, styrene oxide, 1,2-dodecene oxide, epichlorohydrin, or glycidyl ethers such as allyl, butyl, 2-ethylhexyl, propargyl, cyclohexyl, benzyl, C12 / C14 fatty alcohol, phenyl, p-tert-butylphenyl, furfuryl, neodecanoic acid, or o-cresyl glycidyl ethers, or any mixtures of the aforementioned epoxides. [OEt] groups are formed from ethylene oxide.

[0042] For the purposes of the invention, all carboxy-functional organic compounds can be used, preferably monocarboxy-functional compounds, especially fatty acids.

[0043] Preferably, the fatty acids are selected from the group consisting of nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, neodecanoic acid, isononanic acid, isotridecanoic acid, isostearic acid, 2-ethylhexanoic acid, and / or preferably their esters. Further examples include: caproic acid, caprylic acid, palmitoleic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtainable from the pyrolysis of ricinoleic acid), petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, eicosapentaenoic acid, docosahexaenoic acid, and arachidonic acid.

[0044] Preferably, the total molar ratio of the repeating units designated by the indices x and z is -[OEt] x - and -[OEt] z - greater than the molar ratio of the repeating units designated with the indices y -[ OAIk] y -,

[0045] Preferably, the compounds according to the invention exhibit a thickening property in aqueous or solvent-containing compositions, preferably in coating compositions, paints and varnish systems.

[0046] Another object of the invention is the method for producing the compounds according to the invention, which comprises the following steps:

[0047] 1) Alkoxylation of polyglycerols for the preparation of polyether polyols according to formula (II), wherein for the formation of the polyether chain (i) a mixture of ethylene oxide and another epoxide, which is not ethylene oxide, is first added to the reaction mixture and (ii) a further addition of ethylene oxide is then carried out, followed by

[0048] 2) Esterification or transesterification of the polyether polyols from step 1) with at least one straight-chain and / or branched saturated or unsaturated fatty acid with 4–24 carbon atoms, preferably with 10–20 carbon atoms, particularly preferably with 12–18 carbon atoms, or with at least one fatty acid alkyl ester, preferably fatty acid methyl ester and / or fatty acid ethyl ester, with 4–24 carbon atoms, preferably with 10–20 carbon atoms, particularly preferably with 12–18 carbon atoms, optionally

[0049] 3) Removal of any by-products by suitable processing techniques such as stripping with nitrogen, distillation on a thin-film evaporator, steam distillation, azeotropic distillation, or post-treatment of the product with adsorbents such as magnesium and aluminosilicates, bentonite, perlite, zeolites, or magnesium and aluminum oxides. The process according to the invention can also be varied such that the alkoxylation can take place after the esterification or transesterification, i.e., steps 1) and 2) can be reversed.

[0050] Another variation of the formation of the polyether chain (i) in the alkoxylation step could also be designed such that first ethylene oxide, then a mixture of ethylene oxide and another epoxide that is not ethylene oxide, is added to the reaction mixture and (ii) a further addition of ethylene oxide is carried out afterwards.

[0051] As starting materials for the preparation of the polyether polyols according to formula (II) of the invention, glycerin oligomers such as diglycerol, triglycerol, and linear or branched tetraglycerol can be used. It is conceivable to use technical-grade polyglycerols, which are mixtures of a series of glycerin oligomers. Such technical-grade polyglycerols can be obtained by known processes through the condensation of glycerol at elevated temperature and reduced pressure in the presence of alkaline catalysts under exclusion of air, followed by removal of the catalyst, e.g., by means of ion exchangers. The average degree of polymerization can be controlled by the reaction conditions, in particular by the duration of heating.The products manufactured in this way contain, in addition to a certain proportion of non-condensed glycerol, practically all oligomers up to the maximum degree of polymerization achieved, which can reach values ​​up to 30. Preferably, the fatty acid esters according to the invention are produced from technical-grade polyglycerols containing the glycerol oligomers from diglycerol to heptaglycerol and, in addition, up to 20% by weight of monomeric glycerol. Such technical-grade polyglycerols also occur as distillation residues during the industrial production of glycerol. Preferably, technical-grade polyglycerols with hydroxyl values ​​in the range of 900 to 1100 are used.

[0052] Preferably, the alkoxylation for the preparation of the polyether polyols according to formula (II) is carried out at a temperature of 80 °C to 200 °C, preferably 100 °C to 170 °C, particularly preferably 110 °C to 150 °C.

[0053] The alkoxylation reaction is preferably carried out in the presence of catalysts. The catalyst can preferably be selected from the group consisting of potassium hydroxide, potassium hydroxide, sodium alkoxides, potassium alkoxides, and / or zinc / cobalt double metal cyanide catalysts. The alkoxylation can preferably be carried out without solvents.

[0054] It is conceivable that the alkoxylation is carried out in a hydrocarbon as a solvent and that the solvent is preferably removed by distillation before the esterification reaction.

[0055] For the process according to the invention, the amount of total ethylene oxide used is preferably greater than the amount of alkylene oxide used.

[0056] Preferably, > 0 - 50 wt.%, particularly preferably 10 - 35 wt.% alkylene oxide is used, based on the total amount of ethylene oxide and alkylene oxide used.

[0057] The esterification is preferably carried out at 100 °C to 250 °C, preferably at 120 °C to 200 °C.

[0058] The condensation product formed during esterification is preferably removed by distillation.

[0059] Preferably, an acidic catalyst selected from the group of mineral acids, sulfonic acids, carboxylic acids, preferably sulfuric acid and sulfonic acids, particularly preferably p-toluenesulfonic acid and methanesulfonic acid, can be used in the esterification.

[0060] The method of preparation of the compound according to the invention can also be varied by first esterifying the poly- / oligoglycerols with fatty acid in the corresponding molar ratio and then alkoxylating them.

[0061] A preferably two-stage process for producing the compounds according to the invention according to formula (I) is explained in more detail below:

[0062] Step 1) Production of the polyether polyols

[0063] The polyether polyols of formula (II) are produced by an alkoxylation reaction.

[0064] The alkoxylation can be carried out according to methods known in the prior art.

[0065] Preferably, the polyether polyols of formula (II) are prepared according to the following process: In the first step, at least one polyol is catalytically reacted as a starting compound with epoxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, 1,2-dodecene oxide, epichlorohydrin, or glycidyl ethers such as allyl, butyl, 2-ethylhexyl, propargyl, cyclohexyl, benzyl, C12 / C14 fatty alcohol, phenyl, p-tert-butylphenyl, furfuryl, neodecanoic acid, or o-cresyl glycidyl ethers, preferably with ethylene oxide and propylene oxide, or any mixtures of the aforementioned epoxides, preferably with an alkylene oxide content of > 0-50 wt% based on the total polyether, preferably with mixtures of ethylene oxide and propylene oxide with a propylene oxide content of > 0 - 50 wt.%, particularly preferably 10 - 35 wt.%, converted.

[0066] In the context of the present invention, "starting compounds" are understood to be substances that form the initial (starting) stage of the polyether polyol to be produced, which is obtained by the addition of alkylene oxides. Alcohols, particularly polyols with 2 to 12 OH groups, especially preferably with 3 to 10 OH groups, and most preferably with 4 to 8 OH groups, are preferably used for the preparation of the polyether polyols of formula (II). The condensation products of glycerol, also called polyglycerols, are particularly preferred. The starting compounds can be used alone or in any mixtures.

[0067] Alkaline catalysts known to those skilled in the art, such as potassium hydroxide, potassium hydroxide, sodium alkoxides, or potassium alkoxides, as well as zinc / cobalt double metal cyanide catalysts, are used as catalysts for the alkoxylation reaction. The starting compound and catalyst are introduced into the reactor at the beginning of the process, prior to the addition of the alkylene oxide. The amount of catalyst is adjusted to ensure sufficient catalytic activity for the process. The catalyst can be added as a solid, a solution, or a catalyst suspension. It can be added to the reactor either in a single portion or in several successive portions during the alkoxylation reaction. The reactor should preferably be clean and dry.

[0068] It is preferred that the catalyst concentration, except when using double-metal cyanide catalysts, is 0.05 wt% to 1.0 wt%, more preferably 0.06 wt% to 0.5 wt%, and most preferably 0.08 wt% to 0.3 wt% based on the total mass of the products obtained during alkoxylation. If the polyether synthesis is carried out in several stages, the total amount of catalyst can be divided between the different stages as required. When using double-metal cyanide catalysts, concentrations of 10–1000 ppm, and particularly preferably 30–500 ppm, based on the total mass of the products obtained, are used.

[0069] The epoxide monomers can be used in pure form or mixed to obtain homopolymers or statistical copolymers. Following the addition of a first monomer or monomer mixture, further monomers can be added to obtain block structures. Alternatively, the addition of further epoxides to an epoxide already present in the reaction mixture can be carried out continuously over time, creating an increasing concentration gradient of the continuously added epoxide. The relationship between dosage and product structure is well known to those skilled in the art.

[0070] The sequence of the epoxy monomer units can be varied within wide limits by adjusting the order of addition. According to the inventive process, the molar masses of the resulting polyethers can be varied within wide limits and controlled precisely and reproducibly via the molar ratio of the added epoxy monomers relative to the OH group of the at least one OH-functional starter.

[0071] In principle, any suitable reactor type that can control the reaction and its heat of reaction can be used as reactors for the alkoxylation in the first process step. The first process step can be carried out continuously, semi-continuously, or batchwise in a manner known in process engineering.

[0072] Preferably, the alkoxylation is carried out at a temperature of 80 °C to 200 °C, preferably 100 °C to 170 °C, particularly preferably 110 °C to 150 °C.

[0073] The internal pressure of the reactor is preferably from 0.5 bar (absolute) to 20 bar (absolute), more preferably from 1.0 bar (absolute) to 12 bar (absolute), and most preferably from 1.5 bar (absolute) to 8 bar (absolute).

[0074] Preferably, before the first addition of the epoxide, the reactor, which is partially filled with the starter and the alkaline catalyst, is inertized, for example, with nitrogen. This is achieved, for example, by repeatedly and alternately evacuating and adding nitrogen. It is advantageous to evacuate the reactor to below 200 mbar after the final addition of nitrogen. The addition of the first quantity of epoxide monomer thus preferably takes place in the evacuated reactor. The monomers are preferably added while stirring and, if necessary, cooling to dissipate the heat of reaction released and to maintain the preselected reaction temperature. The starter is at least one polyglycerol or a polyether polyol already prepared according to the process described in step 1).

[0075] The reaction can be carried out, for example, in a suitable solvent to reduce viscosity.

[0076] After completion of the epoxide addition, a post-reaction preferably follows to complete the conversion. This post-reaction can be carried out, for example, by continuing the reaction under controlled conditions (i.e., maintaining the temperature and pressure) without adding any reactants. Preferably, the post-reaction is performed while mixing the reaction mixture, particularly by stirring.

[0077] Unreacted epoxides and possibly other volatile components can then be removed, for example, by vacuum distillation, steam or gas stripping, or other deodorization methods.

[0078] It is not always possible to achieve the desired molar mass of the alkoxylation product in a single alkoxylation step. This is particularly true when long polyether chains are targeted, as large amounts of epoxide monomers must be added. The reactor geometry sometimes does not permit this. The polyether polyols produced are themselves suitable as initiators for the synthesis of higher molecular weight products of formula (II). Therefore, in accordance with the invention, they also represent potential precursors and starting compounds for the synthesis of polyether polyols with higher molar mass. The alkoxylation reaction can thus be carried out in several steps. The corresponding intermediates can be used directly for further alkoxylation or optionally subjected to further treatment steps, such as neutralization, filtration, and / or distillation, and subsequently used as starting compounds.

[0079] Surprisingly, a final addition of ethylene oxide monomers has proven to be particularly advantageous.

[0080] If an alkaline catalyst is used, it is preferred to neutralize the alkaline reaction product with an acid such as lactic acid, acetic acid, propionic acid, or phosphoric acid and, if necessary, to remove the resulting salts by filtration. It is also possible to omit the neutralization and use the alkaline polyether polyol in step 2) of the esterification.

[0081] The number-average molar mass M n , weight-average molar mass M w and polydispersity (M w / M nThe molecular weight of the polyether polyol produced in step 1) is arbitrary. The polyether polyols according to formula (II) preferably have a number-average molar mass of 2,000 to 60,000 g / mol, more preferably of 5,000 to 35,000 g / mol, and particularly preferably of 10,000 to 25,000 g / mol. They are preferably colorless to yellow products, which may be clear or opaque. Depending on the structure of the polyoxyalkylene chain, the products are preferably liquid to pasty at room temperature. They are not waxy.

[0082] The polydispersity (M w / M n ) of the polyether polyols according to formula (II) is variable in wide ranges and is preferably from 1.01 to 5, more preferably from 1.05 to 3 and particularly preferably from 1.05 to 2.

[0083] For the polyether polyols used here, the number-average molar masses determined by measuring the hydroxyl number are usually used as a basis.

[0084] Unless otherwise stated, where average values ​​are given below, they are numerical averages. Where measured values, parameters, or material properties are given below that are determined by measurement, they are measured values, parameters, or material properties measured at 25 °C and preferably at a pressure of 101,325 Pa (standard pressure), unless otherwise stated.

[0085] Step 2) Esterification

[0086] Esterifications of alcohols and acids are generally well-known chemical reactions in the literature. Esters can be prepared directly from the acid by distillation to remove the water produced at elevated temperature, or using a catalyst, or from reactive derivatives of the acid. For example, an acid-catalyzed reaction of acid and alcohol to form the corresponding ester, or a base-catalyzed transesterification, e.g., from the methyl ester of an acid to the desired alcohol, is possible.

[0087] The esterification of the polyether polyols from step 1) can be carried out via various synthesis routes, preferably by reacting the at least one fatty acid with the polyether polyol using a catalyst, preferably acids or metal alkoxides, particularly preferably under acid catalysis with e.g. sulfonic acids as a catalyst.

[0088] Saturated or unsaturated fatty acids with 4 to 24 carbon atoms, preferably with 10 to 20 carbon atoms, and particularly preferably with 12 to 18 carbon atoms, can be used as fatty acids for the production of the structures according to the invention. The fatty acids can optionally be used individually in pure form or in any mixture of different fatty acids. Examples of preferred fatty acids include nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, neodecanoic acid, isononanic acid, isotridecanoic acid, isostearic acid, and 2-ethylhexanoic acid.

[0089] Other examples include: caproic acid, caprylic acid, palmitoleic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtainable from the pyrolysis of ricinoleic acid), petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0090] The esterification reaction preferably takes place at the OH groups of the alkoxylation products from step 1) at 100 °C to 250 °C, preferably at 120 °C to 200 °C. Any water produced is preferably removed by distillation.

[0091] Preferably, the reaction vessel is inerted with nitrogen before the reaction. The reaction and distillation-based removal of the water or alkyl alcohol can optionally take place at atmospheric pressure or under vacuum.

[0092] It is preferred that the reaction takes place in the presence of at least one acidic catalyst, which is optionally subsequently neutralized with at least one base.

[0093] Preferably, the at least one acidic catalyst is selected from the group consisting of mineral acids, sulfonic acids, and carboxylic acids. Phosphoric acid, sulfuric acid, and the group of sulfonic acids are preferred. Sulfuric acid, p-toluenesulfonic acid, and methanesulfonic acid are particularly preferred.

[0094] Preferably, the concentration of the acidic catalyst, based on the total number of hydroxyl groups in the polyether, is 3 to 35 mol%, particularly preferably 5 to 20 mol%. Preferably, the at least one fatty acid is used in a maximum equimolar amount, but more preferably in a molar deficit, based on the total number of hydroxyl groups in the polyether polyol. Preferably, the molar ratio of the total number of COOH groups of the at least one fatty acid or the COOR groups of the at least one fatty acid ester to the total number of OH groups in the polyether polyol is 0.10:1 to 1.00:1, more preferably 0.30:1 to 1.00:1, and more preferably 0.50:1 to 0.90:1.

[0095] The progress of the esterification reaction can be monitored analytically, e.g., by measuring the acid number. The conversion of the esterification varies depending on the selected reaction conditions, whereby for the compounds according to the invention a conversion of > 60%, preferably > 80%, and particularly preferably > 90% is achieved based on the total number of COOH groups of the at least one fatty acid. The reaction mixture is stirred at the respective reaction temperature until the desired conversion of the esterification reaction is achieved.

[0096] At the end of the esterification reaction, the acidic catalyst can optionally be neutralized with any base. According to the invention, neutralization with sodium hydroxide is preferred. The resulting salts can remain in the reaction product or be filtered off. Preferably, the salts are removed by filtration to obtain a clear, non-turbid final product.

[0097] Instead of fatty acids, the corresponding fatty acid alkyl esters, preferably fatty acid methyl esters and fatty acid ethyl esters, can also be used in step 2) in an analogous manner. A transesterification reaction takes place, and the alkanol released, such as methanol or ethanol, is preferably removed from the reaction mixture by distillation. It is preferred that the transesterification is carried out in the presence of at least one catalyst, which is optionally subsequently removed and, if necessary, neutralized.

[0098] Metal alkoxides such as titanium(IV) tetraisopropoxide, titanium(IV) butoxide and basic transesterification catalysts selected from the group of alkali hydroxides and alkali alkoxides are preferred, sodium hydroxide, potassium hydroxide, sodium methoxide and potassium methoxide are particularly preferred.

[0099] It is optional to use stabilizers or antioxidants to stabilize the products from step 2). Suitable examples include sterically hindered phenols, known to those skilled in the art, commercially available as Anox® 20, Irganox® 1010 (BASF), Irganox® 1076 (BASF) and Irganox® 1135 (BASF).

[0100] Another aspect of the invention is the use of the compounds according to formula (I) or fatty acid esters produced according to the inventive method as thickening agents in coating compositions and pigment concentrates.

[0101] Pigment concentrates thickened with the compound according to the invention show little influence on the rheology of the base color and are compatible with solvent-based alkyd varnishes.

[0102] The thickening agent according to formula (I) or fatty acid ester produced according to the inventive process is preferably flowable at room temperature.

[0103] Thickening agents according to formula (I) or fatty acid esters prepared according to the inventive process preferably do not contain any solvent.

[0104] Thickening agents according to formula (I) or fatty acid esters produced according to the inventive method preferably exhibit a thickening effect in pigment concentrates.

[0105] Thickening agents according to formula (I) or fatty acid esters prepared according to the inventive process preferably do not produce dilatancy in pigment concentrates.

[0106] Dilatancy refers to a dilatant flow behavior in which viscosity increases with increasing shear (shear-thickening). Examples include highly filled suspensions or high-molecular-weight liquid polymers.

[0107] Surprisingly, the compounds according to the invention are easy to process; that is, they do not need to be activated or pre-dissolved and can be dosed using commonly available devices. Furthermore, they can be added to adjust the viscosity of the finished pigment concentrate and do not require a specific pH value to be effective.

[0108] The following examples describe the present invention by way of example, without limiting the invention, the scope of which is evident from the entire description and the claims, to the embodiments mentioned in the examples.

[0109] methods

[0110] NMR spectroscopy:

[0111] The structures according to the invention were developed via 1 Dog 13The samples were characterized by 13C NMR analyses. A Bruker Avance 400 NMR spectrometer equipped with a 10 mm probe head (BBO 10 mm BB / H) was used. Samples were typically dissolved in deuterated chloroform (as an approximately 10% solution). Chromium(III) acetylacetonate dissolved in deuterated chloroform was used as a relaxation accelerator.

[0112] 1 H-NMR measurements were performed at a frequency of 400 MHz and a temperature of 295 K and 13 C-NMR measurements were performed at a frequency of 100 MHz and a temperature of 295 K. All measurements were carried out using standard parameters.

[0113] Gel permeation chromatography (GPC):

[0114] GPC measurements for determining polydispersity (M w / M n ), the weight-average molar mass (M w ) and the number-average molar mass (M n) were carried out under the following measurement conditions: Column combination SDV 1000 / 10000 Ä (length 65 cm), temperature 30 °C, THF as mobile phase, flow rate 1 ml / min, sample concentration 10 g / l, Rl detector, evaluation against polypropylene glycol standard.

[0115] OH numbers:

[0116] OH numbers were determined using the phthalic anhydride (PSA) method in accordance with ASTM D 4274 C. Samples were reacted with phthalic anhydride in the presence of pyridine, and the consumption of phthalic anhydride was determined by potentiometric titration (Eco Titrator from Metrohm) with 0.5 N sodium hydroxide solution.

[0117] Determination of acid number:

[0118] The acid number determination was carried out using a titration method in accordance with DIN EN ISO 2114.

[0119] Viscosity measurements:

[0120] The dynamic viscosities were measured using a Haake Höppler falling ball viscometer at 25 °C and 60 °C in accordance with DIN 53015. Methods for the

[0121] Rub-Out Test

[0122] For the "rub-out test," the tinted basecoats were applied to a Leneta test substrate using a 150 µm squeegee. After a 10-minute drying time, the "rub-out test" was performed. This test involves mixing the applied coating with a friction tool, such as a gloved finger, using medium pressure in circular motions. The goal is to avoid both the coating being completely pushed away from the substrate and the coating film tearing.

[0123] After the coating has dried, the color values ​​are determined on the area of ​​the "rub-out" test as well as on an adjacent area not subjected to the "rub-out" test. The AE (Delta E) is calculated from both values. This difference in color coordinates is a measure of the quality of the pigment stabilization.

[0124] Determination of color values

[0125] The color values ​​and the Delta E value were determined using an X-Rite SP 62 spectrometer. The L*a*b* color space is known to describe all perceptible colors. It utilizes a three-dimensional color space where the lightness value L* is perpendicular to the color plane (a*, b*). This color model is described in EN ISO 11664-4 "Colorimetry - Part 4: CIE 1976 L*a*b* Colour space". Typically, the measuring instrument measures the values ​​L*, a*, and b*. These values ​​then define a color locus in a coordinate system, where L* represents the lightness (0 = black; 100 = white), a* the green / red value (- green / + red), and b* the blue / yellow value (- blue / + yellow).

[0126] Color intensity

[0127] The standard color values ​​X, Y, and Z were also determined using an X-Rite SP 62 spectrometer and used to determine the color intensity. The standard color value Y is the reflectance at the wavelength of maximum absorption and is determined using the spectrometer.

[0128] The color intensity F was determined using the following formula:

[0129] (100 - Y) 2

[0130] F = -

[0131] 2 Y

[0132] A high color intensity (F) is desired.

[0133] Viscosity profile

[0134] The Haake RheoStress 1 rheometer was used for the rheological viscosity profiles. Measurement parameters: cone / plate C35 / 2°, 23 °C, multiple measurement points in the range of 1–1000 1 / s. The viscosity at 100 1 / s was used to determine the thickening effect. The viscosity in the range of 500 1 / s to 1000 1 / s was used to determine the dilatancy.

[0135] Determination of viscosity drop after tinting - “water drop”

[0136] To determine the viscosity drop, the viscosity of the basecoat and the tinted basecoat were measured at a shear rate of 100*1 / s using a Haake RheoStress 1 rheometer with the following parameters: cone / plate C35 / 2°, 23 °C. The difference in viscosity is the value for the "water drop". The lower the water drop, the better the processability.

[0137] Storage stability

[0138] The pigment pastes were stored in an oven at 50 °C. After one, two, and four weeks of storage, the pigment pastes were cooled to room temperature and assessed for sedimentation and homogeneity. The storage stability of the pigment pastes was evaluated using the rheological viscosity profile. 1. Production of fatty acid esters based on polyglycerol polyalkylene glycols

[0139] 1.1 Production of fatty acid esters FSE1 - FSE3 according to the invention

[0140] For the fatty acid esters FSE1 - FSE3 according to the invention, a manufacturing procedure for example FSE1 has been described. It is known to those skilled in the art that the process conditions must be varied and optimized accordingly when the quantities are changed.

[0141] Step 1) Alkoxylation

[0142] In a 5-liter autoclave, 127 g of polyglycerol-4 (starter), preheated to 60 °C and with an OH number of 1071 mg KOH / g, and 7 g of potassium methoxide powder were placed under a nitrogen atmosphere. The mixture was then heated to 115 °C with stirring, and the reactor was evacuated to an internal pressure of approximately 20 mbar to remove any volatile components by distillation. 65 g of an initial mixture of ethylene oxide (EO) and propylene oxide (PO), as specified in Table 1, were added while stirring and cooling at 115 °C. After a significant pressure drop, the remainder of the mixture was added over approximately 3.5 hours while stirring and cooling at 115 °C and a maximum reactor internal pressure of 2.5 bar (gauge). A 1.5-hour post-reaction at 115 °C was followed by degassing. Volatile components were distilled off under vacuum at 95 °C. The product was cooled to 50 °C and drained under nitrogen.

[0143] The alkaline intermediate obtained in the first step is then used as a starter for a further alkoxylation under analogous conditions.

[0144] 787 g of the intermediate were placed in a 5-liter autoclave at room temperature under a nitrogen atmosphere, and 3.3 g of potassium methoxide were added. The mixture was heated to 115 °C with stirring, and the reactor was evacuated to an internal pressure of approximately 20 mbar to remove any volatile components by distillation. A second mixture of ethylene oxide (EO) and propylene oxide (PO), according to the specifications in Table 1, was added over approximately 1.5 hours with stirring and cooling at 115 °C and a maximum reactor internal pressure of 2.5 bar (gauge). After the addition, the mixture was stirred for a further 2 hours at 115 °C. Subsequently, ethylene oxide (EO), according to the specifications in Table 1, was added over approximately 15 minutes at 115 °C and a maximum reactor internal pressure of 2.5 bar (gauge). The 1.5-hour post-reaction at 115 °C was followed by degassing. Volatile components were distilled off under vacuum at 95 °C.For neutralization, 132.0 g of water, 25.8 g of 30% phosphoric acid, and 13.2 g of saturated sodium dihydrogen phosphate solution were added and stirred for 30 minutes. The water was then distilled off at 95–120 °C and < 20 mbar. The product was drawn off at approximately 80 °C, and salts were removed by filtration. A clear, slightly yellowish, viscous liquid was obtained.

[0145] The product was developed using 1 Dog 13 C NMR spectroscopy, gel permeation chromatography, determination of hydroxyl and acid number as well as viscosity are characterized.

[0146] The product had the following key figures:

[0147] M w = 12123 g / mol ; M n = 9817 g / mol ; M w / M n = 1.23.

[0148] OH number = 20.7 mg KOH / g Acid number = 0.1 mg KOH / g

[0149] Viscosity = 4700 mPas (25 °C)

[0150] Step 2) Esterification

[0151] In a 1 L four-necked round-bottom flask equipped with a KPG stirrer, thermometer, and distillation bridge, 3050 g of the product from step 1, 16 g of p-toluenesulfonic acid, 129.5 g of lauric acid, and 55.5 g of stearic acid were placed under a nitrogen atmosphere. The mixture was heated stepwise to 140 °C with stirring and evacuated to approximately 50 mbar. Stirring continued at 140 °C, and any water produced was removed from the reaction solution by distillation. The reaction progress was monitored by determining the acid number. After reaching a conversion of > 90%, the reaction was stopped, and the reaction mixture was cooled to 70 °C. It was neutralized by adding sodium hydroxide solution, water was distilled off again, and any salts present were removed by filtration. The compound according to the invention was obtained as a clear, amber-colored liquid.

[0152] The product was developed using 1 Dog 13C NMR spectroscopy, gel permeation chromatography, determination of hydroxyl and acid number as well as viscosity are characterized.

[0153] The FSE1 exhibited the following key figures:

[0154] M w = 12437 g / mol ; M n = 8003 g / mol ; M w / M n = 1.55.

[0155] OH number = 7.4 mg KOH / g Acid number = 1.0 mg KOH / g

[0156] Viscosity = 3500 mPas (25 °C)

[0157] The comparative examples FSE-VG1 and FSE-VG2 were produced based on the teachings of EP 1 518 900. The comparative example FSE-VG3 was produced based on the process according to the invention. In contrast to the fatty acid esters FSE1, FSE2 and FSE3 according to the invention, ethylene oxide (EO) and then propylene oxide (PO) were added first in the second alkoxylation step; a final addition of ethylene oxide (EO) was not carried out, as shown in Table 1.

[0158] Table 1

[0159] 2. Application-related tests

[0160] For the application-related tests, pigment pastes were first prepared using a carbon black and an organic pigment, and optionally mixed with the fatty acid ester according to the invention. These pigment pastes were used for tinting a water-based and a solvent-based basecoat. Both the pigment pastes and the basecoats tinted with these pastes were used for application-related tests.

[0161] Pigment pastes and pigment concentrates are used synonymously.

[0162] The comparative example VG-PO (viscosity determination) consisted only of the raw materials according to Table 2, without the addition of the fatty acid ester.

[0163] The comparison example VG-BO (determination of the water drop) consisted only of the respective base coat without pigment paste.

[0164] 2.1 Production of pigment pastes

[0165] The pigment pastes were produced according to the information in Table 2.

[0166] The following pigments were used: Printex G (OrionCarbons) and Hostaperm Rosa E (Clariant). The raw materials from Table 2 were dispersed with 200g of glass beads (d = 2.5–2.8 mm) using a Scandex shaker from Lau for a period of 2 hours. The pigment pastes were then separated from the glass beads.

[0167] It was found that the fatty acid esters according to the invention could be used directly due to their flowability. In contrast, FSE-VG1, FSE-VG2, and FSE-VG3 had to be made flowable by heat. Table 2 2.2 Production of tinted basecoats

[0168] To produce the tinted basecoats, the pigment pastes from Table 2 and a water-based interior wall paint from Chemische Werke Kluthe GmbH (OMalerWeiß) or a solvent-based alkyd paint from Brillux (Olmpredur 840) with the addition of TEGO ColorAid 7060 were used as basecoats.

[0169] 20.0 g of the respective basecoat and 2.2 g of the respective pigment paste from Example 2.1 were weighed into a 60 mL PP screw-top container. The mixture was then homogenized using the Speed ​​Mixer DAC 150.1 FVZ (Hauschild) for 1 minute at 2,000 rpm. The tinted basecoats were used for the application tests. 3. Testing of the pigment pastes

[0170] 3.1 Thickening property

[0171] For the sake of simplicity, the designations from Table 1 have been used. These were the tinted basecoats from Section 2.2, where required by the method.

[0172] Table 3.1.1 Printex G

[0173] The pigment pastes according to the invention with the fatty acid esters according to the invention exhibited a better increase in viscosity level as well as an advantageously reduced percentage change in viscosity during storage compared to the comparative examples.

[0174] Table 3.1.2 Hostaperm Rosa E

[0175] The pigment paste according to the invention also showed better thickening properties with the red pigment than the comparison example. 3.2 Dilatancy test

[0176] A technically undesirable rheological profile is dilatancy. An increase in viscosity at higher shear rates can lead to blockage or bursting of hoses during the manufacturing process of the pigment paste or during its further processing. Dilatancy can occur particularly when fillers are used. Fillers such as China Clay Supreme, which are used to thicken pigment concentrates, exhibit this undesirable effect. Therefore, the comparison example FSE-VG4 with China Clay Supreme, as shown in Table 3.2.1, was used. Table 3.2.2 shows the measured values.

[0177] Table 3.2.1

[0178] Table 3.2.2 The pigment paste according to the invention showed no dilatancy. In contrast, the comparative example exhibited an increase in viscosity from a shear rate D of 500 1 / s.

[0179] 4 Testing of tinted basecoats 4.1 Water-drop test

[0180] The drop in viscosity after tinting (water drop) is evident in aqueous basecoats.

[0181] Therefore, only aqueous basecoats were considered to verify the effect.

[0182] Table 4.1.1 Water-based, black Printex G

[0183] The decrease in viscosity after tinting (water drop) could be reduced in the pigment paste using the fatty acid ester according to the invention.

[0184] Table 4.1.2 water-based, Hostaperm Rosa E

[0185] The viscosity decrease after tinting (water drop) of the organic pigment could also be reduced using the fatty acid ester according to the invention in the pigment paste. 4.2 Testing the color values ​​of the tinted basecoats

[0186] Table 4.2.1 Water-based, black Printex G

[0187] The tinted basecoats according to the invention showed no negative impact on color strength and exhibited an advantageously lower rub-out (AE*), which was not the case with the comparative examples. Table 4.2.2 water-based, Hostaperm Rosa E

[0188] The fatty acid ester according to the invention showed no negative influence on color strength in the aqueous tinted basecoat and an advantageously lower rub-out (AE*).

[0189] 5. Suitability of the fatty acid esters according to the invention in universal pastes

[0190] Section 4 demonstrated the suitability of the fatty acid esters according to the invention for use in aqueous basecoats.

[0191] Universal pastes are water-based pastes that, in addition to being suitable for tinting water-based basecoats, can also be used for tinting solvent-based alkyd paints. The necessary compatibility is demonstrated by rub-out values ​​(AE) and color strength (F).

[0192] Table 5.1 Solvent-based, black Printex G

[0193] The fatty acid ester according to the invention showed no negative influence on the color strength in the non-polar, solvent-based tinted basecoat and exhibited an advantageously lower rub-out (AE*). The comparison example showed significantly worse results.

[0194] Table 5.2 Solvent-based, Hostaperm Rosa E

[0195] The fatty acid ester according to the invention shows no negative influence on color strength in the non-polar solvent-containing tinted basecoat and an advantageously lower rub-out (AE*) than the values ​​of the comparative example.

Claims

Patent claims 1. Fatty acid esters of polyglycerol polyalkylene glycols according to formula (I) R - ([OEtJx - [OAIk] y - [OEt] z - A) n Formula (I) with R = polyglycerol residue, [OEt] = oxyethylene residue, according to the formula -(CH2CH2O)-, [OAIk] = oxyalkylene residue, according to the formula -(CH2CHR2O)-, with R2 = CH3, C2H5, CeHs, C10H21, preferably CH3, C2H5, particularly preferably CH3, n = 2 to 12, preferably 3 to 10, particularly preferably 4 to 8, n*x = 50 to 600, preferably 100 to 450, particularly preferably 200 to 350, n*y = 10 to 150, preferably 20 to 120, particularly preferably 30 to 100, n*z = 5 to 150, preferably 15 to 100, particularly preferably 30 to 70, with the proviso that the repeating units designated by the indices x and y -[OEt] x - [OAIk] y- are mixed in a statistical sequence or in alternating blocks in the polyether chain, and n*x + n*z at least 150, preferably 200 to 500, particularly preferably 250 to 400, A = each independently of one another H or a group of the formula -C(=O)Ri, with Ri = C4- to C24-alkyl, preferably C10- to C20-alkyl, particularly preferably C12- to C18-alkyl, C4- to C24-hydroxyalkyl or C4- to C24-alkenyl, with the proviso that of the n-fold present residues A at least one residue A corresponds to a group of the formula -C(=O)Ri.

2. Compounds according to formula (I) obtainable by the reaction of at least one polyether polyol of general formula (II) R - ([OEtJx - [OAIkJy - [OEt] z - OH) n Formula (II), with R = polyglycerol residue, [OEt] = oxyethylene residue, according to the formula -(CH2CH2O)-, [OAIk] = Oxyalkylene residue, according to the formula -(CH2CHR2O)-, with R2 = CH3, C2H5, CeHs, C10H21, preferably CH3, C2H5, particularly preferably CH3, n = 2 to 12, preferably 3 to 10, particularly preferably 4 to 8 n*x = 50 to 600, preferably 100 to 450, particularly preferably 200 to 350, n*y = 10 to 150, preferably 20 to 120, particularly preferably 30 to 100, n*z = 5 to 150, preferably 15 to 100, particularly preferably 30 to 70, provided that the repeating units designated by the indices x and y -[OEt] x - [OAIk] y- are mixed in a statistical sequence or in alternating blocks in the polyether chain, and n*x + n*z is at least 150, preferably 200 to 500, particularly preferably 250 to 400, comprising at least one straight-chain and / or branched saturated and / or unsaturated fatty acid with 4 to 24 carbon atoms, preferably with 10 to 20 carbon atoms, particularly preferably with 12 to 18 carbon atoms, or with at least one fatty acid alkyl ester, preferably fatty acid methyl ester and / or fatty acid ethyl ester, comprising 4 to 24 carbon atoms, preferably with 10 to 20 carbon atoms, particularly preferably with 12 to 18 carbon atoms.

3. Compounds according to claim 1 or 2, characterized in that the repeating units designated with the index z -[OEt] z - exhibit a block-like arrangement.

4. Compounds according to any of the preceding claims, characterized in that the fatty acid is selected from the group consisting of nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, neodecanoic acid, isononanic acid, isotridecanoic acid, isostearic acid, 2-ethylhexanoic acid and / or their alkyl esters.

5. Compounds according to one of the preceding claims, characterized in that the total molar ratio of the repeating units designated by the indices x and z -[OEt] x - and -[OEt] z - is greater than the molar ratio of the repeating units designated with the indices y -[OAIk] y -, 6. Compounds according to one of the preceding claims, characterized in that they exhibit a thickening property in aqueous pigment concentrates.

7. A method for producing a compound according to claim 1 or claim 2, comprising the following steps: 1) Alkoxylation of polyglycerols to produce polyether polyols according to formula (II), wherein for the formation of the polyether chain (i) a mixture (i) ethylene oxide and another epoxide, which is not ethylene oxide, are added to the reaction mixture and (ii) a further addition of ethylene oxide is then carried out, followed by 2) Esterification or transesterification of the polyether polyols from step 1) with at least one straight-chain and / or branched saturated or unsaturated fatty acid having 4–24 carbon atoms, preferably with 10–20 carbon atoms, particularly preferably with 12–18 carbon atoms, or with at least one fatty acid alkyl ester, preferably fatty acid methyl ester and / or fatty acid ethyl ester, having 4–24 carbon atoms, preferably with 10–20 carbon atoms, particularly preferably with 12–18 carbon atoms, optionally 3) Removal of any by-products by means of suitable processing techniques such as stripping with nitrogen, distillation on a thin-film evaporator, steam distillation, azeotropic distillation, post-treatment of the product with adsorbents such as magnesium and aluminosilicates, bentonite, perlite, zeolites, magnesium and aluminum oxides.

8. Method according to claim 7, characterized in that the alkoxylation and esterification or transesterification can be carried out in reverse order.

9. Method according to claims 7 - 8, characterized in that the alkoxylation for the production of the polyether polyols according to formula (II) is carried out at a temperature of 80 °C to 200 °C, preferably 100 °C to 170 °C, particularly preferably 110 °C to 150 °C.

10. Method according to one of claims 7 - 9, characterized in that the alkoxylation reaction is carried out in the presence of at least one catalyst.

11. Method according to claim 10, characterized in that the catalyst is selected from the group consisting of potassium hydroxide, potassium hydroxide, sodium alkoxides, potassium alkoxides and / or zinc / cobalt double metal cyanide catalysts.

12. Method according to one of claims 7 - 11, characterized in that the alkoxylation is carried out without solvent or in a hydrocarbon as solvent, wherein the solvent is then preferably removed by distillation before the esterification reaction.

13. Method according to one of claims 7 - 12, characterized in that the amount of total ethylene oxide used is greater than the amount of alkylene oxide used.

14. Method according to one of claims 7 - 13, characterized in that preferably > 0 - 50 wt.%, particularly preferably 10 - 35 wt.% alkylene oxide is used, based on the total amount of ethylene oxide and alkylene oxide used.

15. Method according to one of claims 7 - 14, characterized in that the esterification is carried out at 100 °C to 250 °C, preferably at 120 °C to 200 °C.

16. Method according to one of claims 7 - 15, characterized in that the condensation product formed during esterification is preferably removed by distillation.

17. A process according to one of claims 7 - 16, characterized in that an acidic catalyst is used in the esterification, selected from the group consisting of mineral acids, sulfonic acids, carboxylic acids, preferably sulfuric acid and sulfonic acids, particularly preferably p-toluenesulfonic acid and methanesulfonic acid.

18. Method according to one of claims 7-17, characterized in that the molar ratio of the totality of the COOH groups of the at least one fatty acid or of the COOR groups of the at least one fatty acid ester to the totality of the OH groups of the polyether polyol is 0.10:1 to 1.00:1, preferably 0.30:1 to 1.00:1, particularly preferably 0.50 to 0.90:

1.

19. Use of the compounds according to any one of claims 1-6 as thickening agents in coating compositions, pigment concentrates.

20. Thickening agent according to claim 19, characterized in that it is flowable at room temperature.

21. Thickening agent according to claim 19 and / or 20, characterized in that it does not contain a solvent.

22. Thickening agent according to claim 19, characterized in that it has a thickening effect in pigment concentrates.

23. Thickening agent according to claim 19 or 22, characterized in that it has no dilatancy in pigment concentrates.

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