Dispersant based on polyetheramide aminophosphonic acids

Abstract

The invention relates: 1) to a method for preparing polyetheramide aminophosphonic acids or polyetheramide aminophosphonate salts or aqueous solutions thereof, the method comprising the following steps: a) reacting at least one salicylic acid ester as a starting compound of an alkoxylation reaction in the presence of at least one double metal cyanide (DMC) catalyst with at least one epoxide to form at least one polyether; b) reacting the at least one polyether from step a) with at least one polyamine which bears at least two amino groups, selected from the group consisting of primary and secondary amino groups, to form at least one polyetheramide amine; c) reacting the at least one polyetheramide amine from step b) with at least one aldehyde and phosphonic acid to form at least one polyetheramide aminophosphonic acid; and optionally d) dissolving the at least one polyetheramide aminophosphonic acid from step c) in water; and optionally e) fully or partially neutralising the at least one polyetheramide aminophosphonic acid from step c) or the aqueous solution thereof from step d) using at least one base to form at least one polyetheramide aminophosphonate salt or the aqueous solution thereof; characterised in that (i) the at least one salicylic acid ester is selected from compounds of formula (1), where R is a hydrocarbon group having at least three carbon atoms; and (ii) at least propylene oxide is used as the epoxide, and, prior to optional reaction with further epoxides, the at least one salicylic acid ester is firstly reacted with propylene oxide; 2) to products which can be prepared according to this method; 3) to the use of these products as dispersant; 4) and to a hydraulically curing composition which these products contain.

Description

[0001] Dispersants based on polyetheramidaminephosphonic acids

[0002] The invention lies in the field of polyetheramidaminephosphonic acids, polyetheramidaminephosphonate salts and their aqueous solutions, their preparation, their use as dispersants, in particular in hydraulically setting compositions.

[0003] Dispersants have been known for a long time. Their basic property is that they possess ionic or non-ionic structural units, which enable them to interact with the surfaces of other materials. Those skilled in the art are familiar with polymers such as polyethers, for example, which are primarily produced in an alkoxylation reaction of propylene oxide and ethylene oxide. These polymers, through the introduction of comonomers or subsequent chemical modification with polar or ionic adhesive groups, represent effective dispersants. Depending on the application and the type of particles to be dispersed, these substances can have very different structures.

[0004] The type of particles to be dispersed can be organic or inorganic and ranges from completely non-polar substances such as carbon black or graphite to oxidic color pigments such as titanium dioxide and strongly basic substances such as iron hydroxide and cement particles to complex organic molecules that are used, for example, as dyes, pharmaceutical or agrochemical active ingredients.

[0005] Dispersants often function as additives in a wide variety of mixture compositions. Their task is, for example, to disperse water-insoluble solid particles in a water-based formulation so finely and permanently that sedimentation or agglomeration of the solids does not occur, even over an extended period of time. Especially in aqueous systems, dispersants must be chemically structured in such a way that they not only possess the functional groups capable of interacting with the particle surfaces, but are also water-soluble and hydrolysis-stable.

[0006] The state of the art knows numerous polyether alcohols that are prepared in an alkoxylation reaction and, in a subsequent reaction, functionalized with an ionic group at the terminal hydroxyl group. This ionic group acts as an adhesive group for the solid particles to be dispersed and also improves water solubility. Widely used examples include polyether phosphates, which are obtained, for example, by reacting polyether alcohols with polyphosphoric acid. Polyethers with terminal carboxyl groups, such as those obtained from polyether alcohols and cyclic anhydrides such as succinic anhydride or maleic anhydride by ring opening, have also been known for a long time. A special class are sulfosuccinates of polyethers, which contain a carboxyl group as well as a sulfonic acid group.In order to demonstrate sufficient effectiveness as a dispersant, the structure of the polyethers and the type of ionic or non-ionic adhesion group must be ideally tailored to the chemical composition of the final formulation in the application.

[0007] Relatively little is known in the prior art about dispersants based on polymeric amines and equipped with phosphonic acid groups. This applies particularly to polyamines, which are linked to a polyether residue on the one hand and functionalized with at least one phosphonic acid residue via one or more nitrogen atoms on the other. Such compounds are characterized by their ability to interact with the surfaces of particles, for example, via polar and ionic interactions. The substances are usually present as inner salts. The acidic phosphonic acid groups are at least partially deprotonated and exist as anionic phosphonate groups, while the nitrogen atoms are partially protonated and are contained as cationic units in the same molecule.

[0008] US 3,288,846 discloses a process for producing aminophosphonic acids by reacting a primary or secondary amine such as ethylamine or di-n-propylamine with formaldehyde and phosphonic acid. The reaction products do not contain any polyether residues. Applications include fabric softeners and water softeners.

[0009] US 5,338,477 describes linear polyether polyaminomethylene phosphonates produced by phosphonation of polyether diamines. These products, which contain four phosphonic acid units at both chain ends of the polyether via the amine nitrogen, are used for water softening due to their good interaction with calcium compounds, for example.

[0010] In "Phosphonated Polyethyleneimines (PEIP) as Multi-Use Polymers," Phosphorus, Sulfur, and Silicon, the Related Elements, 190:879-890, 2015, Didier Villemin et al. describe phosphonated hyperbranched polyethyleneimines obtained by reacting polyethyleneimines with formaldehyde and phosphonic acid under microwave irradiation. The fully phosphonated polyethyleneimines are resins suitable as corrosion inhibitors. Partially phosphonated polyethyleneimines stabilize iron oxide and silver nanoparticles.

[0011] US 4,080,375 discloses a process for the preparation of methylenephosphonates from amine-terminated alkoxylation products, such as polyethers containing two or more amino groups, in which the amine-terminated alkoxylation products are phosphonated by a reaction with phosphonic acid and formaldehyde. They serve as chelating agents for metal cations, as detergents, soaps, and as auxiliaries in textile and paper processing, as well as in petroleum production. In contrast to US 4,080,375, US 5,879,445 is limited to polyether monoamines, which are functionalized with one or a maximum of two phosphonic acid groups in a similar way by reaction with formaldehyde and phosphonic acid. The resulting products are thinners for aqueous suspensions of mineral particles, particularly cement particles, and reduce the viscosity of hydraulic binders.

[0012] US 2012 / 0129981 A1 discloses that the phosphonated polyetheramines mentioned in US 5,879,445 are used as additives in hydraulic binders which also contain another additive component such as polycarboxylate ethers.

[0013] Due to the monofunctionality of the polyetheramines used, the phosphonic acid functionality of the products claimed in US 5,879,445 and US 2012 / 0129981 A1 is limited to a maximum of two units per molecule.

[0014] CN 113121815 A describes polyetherphosphonates produced in a three-step process. In the first step, a hydroxycarboxylic acid methyl ester or an hydroxycarboxylic acid ethyl ester is alkoxylated at the hydroxyl group in the presence of a double metal cyanide (DMC) catalyst and benzoic acid as a cocatalyst. In the second step, an amidation reaction with a polyamine such as ethylenediamine or diethylenetriamine takes place at the ester group, whereby the methanol or ethanol previously bound as an ester is split off and removed by distillation. In the third step, the resulting amidamine is phosphonated by a reaction with phosphonic acid and an aldehyde such as formaldehyde in the presence of a strong acid.Compared to the processes described in US 5,879,445 and US 2012 / 0129981 A1, the process has the advantage of greater structural diversity, as it enables access to polyetheramidoamine phosphonates as flow improvers in mineral binders, whose functionality at phosphonic acid groups can be adjusted within wide limits depending on the polyamine used.

[0015] Nevertheless, the process described in CN 113121815 A has several disadvantages. Only methyl and ethyl esters of hydroxycarboxylic acids are suitable as starting compounds, since the analogous esters of longer alcohols are difficult to cleave in the subsequent amidation reaction due to their steric hindrance. However, quantitative aminolysis is a prerequisite for further conversion to the phosphonates and the desired high phosphonic acid functionality in the final product. The inventors have now discovered that the methyl and ethyl esters of hydroxycarboxylic acids are not very suitable starting compounds for the alkoxylation reaction. When using the DMC catalyst, the addition of benzoic acid as a cocatalyst is therefore essential for the reaction to start. Furthermore, the polyether amidamine phosphonates described in CN 113121815 A cause a delayed setting of the hydraulic binders, which is undesirable in many cases.The current state of the art makes it clear that there are few applications for the amine phosphonate product class beyond water softening and construction chemistry. Furthermore, the polyether phosphonates known to date and used as additives in mineral binders have the disadvantage of delaying setting. For example, Luigi Coppola et al. in "Performance and Compatibility of Phosphonate-Based Superplasticizers for Concrete," Buildings 2017, 7, 62, explain the diluting dispersing effect in hydraulic binders such as concrete by the formation of complexes with the inorganic species. This complexation inevitably influences the hydration reactions of the binder and leads to delayed setting of the concrete. Slow setting can be advantageous in some cases, such as high ambient temperatures or long transport distances.In many cases, however, this is a disadvantage, as the slow hardening of the hydraulic binder slows down construction progress.

[0016] The object of the present invention was therefore to overcome at least one disadvantage of the prior art. In particular, the object was to provide an improved, industrially applicable process for the production of dispersants based on polyetheramidoaminephosphonic acid. In particular, the process should be able to operate without the mandatory use of cocatalysts. Furthermore, the dispersants produced in this way should, if possible, not lead to delayed setting in hydraulic setting compositions.

[0017] Surprisingly, it has now been found that a special method as described in the claims solves the above-mentioned problem.

[0018] This special process differs at least in that from the process described in CN 113121815 A, in that in a first step, at least one salicylic acid ester as starting compound of an alkoxylation reaction is reacted in the presence of at least one double metal cyanide (DMC) catalyst with at least one epoxide to form at least one polyether, wherein

[0019] (i) the at least one salicylic acid ester is selected from compounds of formula (1)

[0020] Formula (1 ) where R is a hydrocarbon radical having at least three carbon atoms; and

[0021] (ii) at least propylene oxide is used as the epoxide, and the at least one salicylic acid ester is first reacted with propylene oxide before optionally reacting with other epoxides. This process has the advantage over the process described in CN 113121815 A that cocatalysts such as benzoic acid can be dispensed with in the reaction, since no methyl and ethyl esters of hydroxycarboxylic acids need to be used.

[0022] The products obtained by the process according to the invention also differ from those described in CN 113121815 A, at least in that at least one oxypropylene unit is bonded to the oxygen atom originally derived from the hydroxy group of the salicylic acid ester used. This is because, in the course of the alkoxylation described above, the first monomer unit bonded to the starting compound is an oxypropylene radical or propyleneoxy radical resulting from the ring opening of propylene oxide. The dispersants thus obtained have the advantage over the dispersants disclosed in CN 113121815 A that they do not lead to delayed setting behavior in hydraulically setting compositions.

[0023] The object of the present invention is therefore achieved by the subject matter of the independent claims.

[0024] Advantageous embodiments of the inventive subject matter can be found in the claims, the examples, and the description. Furthermore, it is expressly pointed out that the disclosure of the inventive subject matter includes all combinations of individual features of the description of the invention and the patent claims. In particular, embodiments of one inventive subject matter also apply mutatis mutandis to the embodiments of the other inventive subject matter.

[0025] The subject matter of the invention is described below by way of example, without intending to limit the invention to these exemplary embodiments. Where ranges, general formulas, or classes of compounds are specified below, these are intended to encompass not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by removing individual values ​​(ranges) or compounds. If documents are cited within the scope of this description, their entire content is intended to be part of the disclosure of the present invention.

[0026] Unless otherwise stated, mean values ​​given below are numerical averages. Unless otherwise stated, measured values, parameters, or material properties given below that are determined by measurement are measured at 25 °C and preferably at a pressure of 101325 Pa (standard pressure).

[0027] The number average molar mass M n , the weight-average molecular mass M w and the polydispersity (M w / M n ) are preferably determined in the context of the present invention by means of gel permeation chromatography (GPC), as described in the examples, unless explicitly stated otherwise.

[0028] If numerical ranges are specified below in the form "X to Y," where X and Y represent the limits of the numerical range, this is equivalent to the statement "from at least X up to and including Y," unless otherwise stated. Therefore, range specifications include the range limits X and Y, unless otherwise stated.

[0029] 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.

[0030] The formulas (2) and (3) below describe compounds or residues that are composed of repeating units, such as repeating fragments, blocks, or monomer units, and can have a molecular weight distribution. The frequency of the repeating units is indicated by indices. The indices used in the formulas are to be regarded as statistical averages (number averages), unless explicitly stated otherwise. The index numbers used as well as the value ranges of the specified indices are understood as averages of the possible statistical distribution of the actual structures present and / or their mixtures. The various fragments or repeating units of the compounds described in the following formulas (2) and (3) can be statistically distributed.Statistical distributions are structured in blocks with any number of blocks and any sequence, or are subject to a random distribution. They can also be structured in alternating sequences, or they can form a gradient across the chain, if one exists. In particular, they can also form all mixed forms, in which groups of different distributions may follow one another. The following formulas include all permutations of repeating units.

[0031] Therefore, if compounds are described within the scope of the present invention that can contain various units multiple times, these units can occur in these compounds either in an unordered manner, e.g., randomly distributed, or in an ordered manner. The information on the number or relative frequency of units in such compounds is to be understood as the mean (numerical average) averaged over all corresponding compounds. Specific embodiments may result in the statistical distributions being restricted by the embodiment. For all areas not affected by the restriction, the statistical distribution remains unchanged.

[0032] A first aspect of the invention is a process for the preparation of polyetheramidaminephosphonic acids or polyetheramidaminephosphonate salts or their aqueous solutions, which comprises the following steps: a) reacting at least one salicylic acid ester as starting compound of an alkoxylation reaction in the presence of at least one double metal cyanide (DMC) catalyst with at least one epoxide to form at least one polyether; b) reacting the at least one polyether from step a) with at least one polyamine which carries at least two amino groups selected from the group consisting of primary and secondary amino groups to form at least one polyetheramidamine; c) reacting the at least one polyetheramidamine from step b) with at least one aldehyde and phosphonic acid to form at least one polyetheramidaminephosphonic acid; and optionally d) dissolving the at least one polyetheramidaminephosphonic acid from step c) in water;and optionally e) complete or partial neutralization of the at least one polyetheramidaminephosphonic acid from step c) or its aqueous solution from step d) with at least one base to form at least one polyetheramidaminephosphonate salt or its aqueous solution; characterized in that;

[0033] (i) the at least one salicylic acid ester is selected from compounds of formula (1)

[0034] Formula (1 ) where R is a hydrocarbon radical having at least three carbon atoms; and

[0035] (ii) at least propylene oxide is used as epoxide, and the at least one salicylic acid ester is first reacted with propylene oxide before an optional reaction with further epoxides.

[0036] Steps a), b), c) are carried out in the specified order, i.e. first a), then b) and then c). The process can optionally comprise steps d) and / or e). Steps d) and e) are therefore optional. If step d) is carried out, it follows step c). If step e) is carried out, it follows step c) or d). The above-mentioned process steps a), b), c), d) and e) can follow one another directly or indirectly. The process can comprise further upstream steps, intermediate steps, or downstream steps, such as, for example, purification of the reactants, the intermediates and / or the end products. The above-mentioned process steps are described in detail below. Whether the process comprises steps d) and / or e) depends on whether polyetheramidaminephosphonic acids, polyetheramidaminephosphonate salts or their aqueous solutions are to be obtained as the process product.

[0037] Step a)

[0038] Salicylic acid esters of the formula (1 ) are used as starting compounds (hereinafter also referred to as starters) for the alkoxylation reaction.

[0039] Formula (1 ) can be used, where R is a hydrocarbon radical having at least three carbon atoms.

[0040] Preferably, R in formula (1) is a saturated or unsaturated, linear or branched hydrocarbon radical having 3 to 8, preferably 4 to 6, more preferably 4 carbon atoms, and particularly preferably an isobutyl radical. Isobutyl salicylate is therefore particularly preferably used as the starting compound.

[0041] The compounds of formula (1) can be used alone or in any mixtures.

[0042] The reaction takes place in the presence of at least one double metal cyanide catalyst (DMC catalyst). Zinc / cobalt DMC catalysts are preferably used, especially those containing zinc hexacyanocobaltate(III). The DMC catalysts described in US 5,158,922, US 20030119663, and WO 01 / 80994 are preferably used. The DMC catalysts can be amorphous or crystalline.

[0043] It is preferred that the catalyst concentration is from >0 wppm to 1000 wppm, more preferably from >0 wppm to 700 wppm, most preferably from >10 wppm to 500 wppm, based on the total mass of the resulting products. The abbreviation "wppm" stands for parts per million by weight.

[0044] Preferably, the catalyst is added only once to the reactor. The reactor should preferably be clean, dry, and free of basic impurities that could inhibit the DMC catalyst. The catalyst quantity should preferably be adjusted to ensure sufficient catalytic activity for the process. The catalyst can be added as a solid or in the form of a catalyst suspension. If a suspension is used, the initiator is particularly suitable as a suspending agent.

[0045] To start the DMC-catalyzed reaction, it is advantageous to first activate the catalyst with a portion of propylene oxide.

[0046] The polyethers prepared according to the invention are thus characterized by having an oxypropylene unit or propyleneoxy unit formed by ring opening of propylene oxide as the first monomer unit on the starting compound. According to the invention, the continuous addition of any epoxide monomers begins only after the alkoxylation reaction has begun.

[0047] The reaction temperature is preferably from 50 °C to 180 °C, more preferably from 60 °C to 150 °C and most preferably from 80 °C to 140 °C.

[0048] The inventive use of a salicylic acid ester and in particular of isobutyl salicylate, in combination with the use of propylene oxide as the first monomer, allows the DMC-catalyzed alkoxylation reaction to be started in a simple manner, so that the addition of a cocatalyst required according to CN 113121815 A can be dispensed with.

[0049] It is therefore preferred that no benzoic acid is used as a cocatalyst in step a).

[0050] The internal pressure of the reactor is preferably from 0.02 bar to 20 bar, more preferably from 0.05 bar to 10 bar, most preferably from 0.1 bar to 5 bar (absolute). A DMC-catalyzed reaction is most preferably carried out at a temperature of 80 °C to 140 °C and a pressure of 0.1 bar to 5 bar.

[0051] The reaction is an alkoxylation reaction, i.e., a polyaddition of epoxides to at least one salicylic acid ester as the starting compound. According to the invention, at least propylene oxide is used as the epoxide, and the at least one salicylic acid ester is first reacted with propylene oxide before optionally reacting with other epoxides.

[0052] Preferably, in addition to propylene oxide, further epoxides selected from the group consisting of ethylene oxide and alkylene oxides having 4 to 8 carbon atoms, preferably selected from the group consisting of ethylene oxide, 1-butylene oxide and styrene oxide, are reacted.

[0053] The epoxides can be added individually in pure form, alternately in any dosing sequence, or simultaneously mixed. However, at least a portion of the propylene oxide used is first reacted with the at least one salicylic acid ester as the starting compound before other epoxides and, if appropriate, the remaining amount of the propylene oxide used are reacted in the alkoxylation reaction. The sequence of monomer units in the resulting polyether chain is thus subject to a blockwise distribution, a random distribution, or a gradual distribution in the final product.

[0054] The sequence of the epoxy monomer units can be varied within wide limits by changing the order of addition. The molar masses of the resulting polyethers can be varied within wide limits by the process according to the invention and can be controlled specifically and reproducibly by adjusting the molar ratio of the added epoxy monomers to the OH group of the at least one salicylic acid ester.

[0055] Preferably, the molar ratio of the total of the epoxides to the total of the salicylic acid esters is from 5 to 250, preferably from 10 to 200, particularly preferably from 15 to 100.

[0056] The number average molar mass M n , weight-average molecular weight M w and polydispersity (M w / M n ) of the polyether prepared in step a) of the process are arbitrary.

[0057] It is preferred that the number average molecular weight M nof the polyether prepared in step a) of the process is from 400 g / mol to 20,000 g / mol, more preferably from 500 g / mol to 10,000 g / mol, most preferably from 600 g / mol to 4,000 g / mol.

[0058] The polydispersity (M w / M n ) the polyether (F) is variable within wide ranges and is preferably from 1.01 to 3, more preferably from 1.02 to 2, particularly preferably from 1.03 to 1.5.

[0059] The polyethers prepared in step a) of the process are preferably compounds of formula (2), where

[0060] R is a saturated or unsaturated, linear or branched hydrocarbon radical having 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms, particularly preferably 4 carbon atoms and in particular an isobutyl radical;

[0061] R 1each independently of one another is a monovalent radical having 2 to 6 carbon atoms, preferably an ethyl radical or a phenyl radical; with m = 1 to 300, preferably 3 to 200, most preferably 5 to 100; n = 0 to 300, preferably 0 to 200, most preferably 0 to 100; o = 0 to 300, preferably 0 to 200, most preferably 0 to 100; with the proviso that i) the sum of m, n and o is from 5 to 250, preferably from 10 to 200, most preferably from 15 to 100; and ii) the first monomer unit bonded to the starting compound is an oxypropylene radical

[0062] CH3

[0063] - U | - - 1, which is derived from the ring opening of propylene oxide.

[0064] The general spelling Formula (2) and in the following formula

[0065] CH3- — -

[0066] (3) represents both a unit of the formula as well as for a unit of the formula , but preferably for a unit of the formula

[0067] The general spelling Formula (2) and in the following formula

[0068] (3) represents both a unit of the formula as well as for a unit of the formula , but preferably for a unit of the formula

[0069] Preferably, before the first epoxy feed, the reactor partially filled with the starter and the DMC catalyst is inerted, e.g., with nitrogen. This is achieved, e.g., by repeatedly alternately evacuating and supplying nitrogen. It is advantageous to evacuate the reactor to below 200 mbar after the last introduction of nitrogen. The addition of the first amount of epoxy monomer thus preferably takes place in the evacuated reactor. The monomers are preferably added with stirring and, if appropriate, cooling in order to dissipate the released reaction heat and to maintain the preselected reaction temperature. At least one salicylic acid ester serves as the starter, or a polyether already prepared according to the process according to the invention can also be used as the starter.

[0070] The reaction can be carried out in a suitable solvent, for example, to reduce the viscosity. After the epoxide addition is complete, a post-reaction preferably follows to complete the conversion. The post-reaction can be carried out, for example, by continuing the reaction under reaction conditions (i.e., maintaining the temperature, for example) without adding reactants. The DMC catalyst usually remains in the reaction mixture.

[0071] Unreacted epoxides and any other volatile components can be removed after the reaction by vacuum distillation, steam or gas stripping, or other deodorization methods. The finished product is preferably filtered at <100 °C to remove any turbidity.

[0072] It is optional to use stabilizers or antioxidants to stabilize the products. Suitable stabilizers include, for example, the 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).

[0073] It is not always possible to achieve the desired molecular weight of the final product in a single alkoxylation step. Especially when long polyether chains are desired, large amounts of epoxy monomers must be added. The reactor geometry sometimes does not allow this. The polyethers produced carry terminal OH groups and are therefore suitable as initiators for the synthesis of higher molecular weight derivatives. Within the meaning of the invention, they therefore also represent potential precursors and starting compounds for the synthesis of polyethers with higher molecular weight. The alkoxylation reaction in step a) can therefore be carried out in several substeps.

[0074] reactors

[0075] For the process according to the invention, in particular for carrying out step a), any suitable reactor types can be used that allow the reaction and any heat of reaction to be controlled. The reaction can be conducted continuously, semi-continuously, or batchwise in a manner known in process engineering and can be flexibly adapted to the available production facilities. In addition to conventional stirred tank reactors, jet loop reactors with a gas phase and internal heat exchanger tubes, as described in WO 01 / 062826, can also be used. Gas-phase-free loop reactors can also be used.

[0076] Step b)

[0077] The at least one polyether from step a) is reacted in step b) with at least one polyamine bearing at least two amino groups selected from the group consisting of primary and secondary amino groups in an amidation reaction to form at least one polyether amide amine. In the amidation reaction, the ester groups are converted into amide groups with elimination of alcohol of the formula R-OH, where R is as defined above. The eliminated alcohol R-OH is removed from the reaction vessel by distillation. The amidation takes place in the temperature range from 80 °C to 250 °C, preferably from 100 °C to 200 °C, particularly preferably from 120 °C to 180 °C. The reaction vessel is preferably inertized with nitrogen before the reaction. The reaction and distillative removal of the alcohol R-OH can take place either at atmospheric pressure or under vacuum.Preferably, the reaction is started at normal pressure and the internal pressure is gradually reduced to <100 mbar during the reaction using a vacuum pump.

[0078] It is preferred that the reaction takes place in the presence of at least one basic catalyst, which is optionally subsequently neutralized with at least one acid. It is further preferred that the pKß value of the at least one basic catalyst is below the pKß values ​​of the reacted polyamine and is preferably less than 1.0, particularly preferably less than 0.5. Preferably, the at least one basic catalyst is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxide, alkali metal alkoxide, strong amine bases and guanidine compounds. Particularly preferably, the at least one basic catalyst is selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium ethanolate, potassium ethanolate, sodium methoxide and potassium methoxide. The alkali metal hydroxides can be used either in solid form or as aqueous solutions.The alkali metal methanolates and alkali metal ethanolates can be used in solid form or as methanolic or ethanolic solutions. The concentration of the basic catalyst is preferably 0.1% by weight to 2.0% by weight, more preferably 0.2% by weight to 1.5% by weight, most preferably 0.3% by weight to 1.0% by weight, based on the amount of polyether used. The percentages relate in each case to the amount of solid, i.e. undissolved, catalyst. The use of a basic catalyst allows the rapid and quantitative conversion of the ester group into an amide group with elimination of R-OH. The problem mentioned in CN 113121815 A of steric hindrance when using hydroxycarboxylic acid esters based on longer-chain alcohols such as isobutanol is solved in this way.

[0079] In principle, any compound containing at least two amino groups selected from the group consisting of primary and secondary amino groups can be used as a polyamine. Preferably, the at least one polyamine is selected from the group consisting of ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and polyethyleneimine. Any mixtures of these amines can also be used.

[0080] The molar ratio of the at least one polyether to the at least one polyamine is always chosen such that after the amidation reaction at least one NH group not belonging to the amide group is available for the subsequent phosphonation reaction (step c)). In step b), the molar ratio of the at least one polyether to the at least one polyamine is therefore always chosen such that in addition to the at least one amidic NH group formed during the reaction in step b), at least one aminic NH group is available for the subsequent reaction in step c). The at least one polyether is preferably used at least equimolarly, but more preferably in a molar excess based on the at least one polyamine in order to reduce the content of unreacted polyamine.Preferably, therefore, the molar ratio of the total of the polyethers to the total of the polyamines is from 1.00:1 to 1.80:1, preferably from 1.05:1 to 1.60:1, particularly preferably from 1.10:1 to 1.40:1.

[0081] The amidation reaction can, in principle, take place at any primary or secondary amino group of the polyamine. Thus, the resulting polyetheramidoamine represents a mixture of singly and multiply amidated polyamines. According to the invention, the reaction conditions are chosen so that virtually all ester groups of the polyether are converted into the respective amide group with the elimination of R-OH. Low concentrations of unreacted polyamine do not interfere.

[0082] At the end of step b), the basic catalyst can optionally be neutralized with any acid. According to the invention, neutralization with a carboxylic acid, especially lactic acid, is preferred. The resulting salts can remain in the reaction product.

[0083] The polyether amide amines prepared according to the invention are preferably compounds of formula (3), where R 1 , m, n and o have the meanings defined above and X represents a nitrogen-containing radical derived from the polyamine used.

[0084] Depending on the polyamine used, by using the molar excess of the polyether used in step b) relative to the polyamine, one or more polyether residues can be chemically bonded to the polyamine via an amide group. Thus, the residue X can contain amide-linked polyether residues in addition to primary and secondary amino groups.

[0085] Step c)

[0086] According to the invention, the at least one polyetheramidamine from step b) is reacted with at least one aldehyde and phosphonic acid to form at least one polyetheramidaminephosphonic acid. The reaction is preferably carried out in the presence of at least one acid with a pKa value below that of phosphonic acid, preferably with a pKa value of less than 1.5, particularly preferably less than 1.0. Although it is not necessary to use another acid in addition to phosphonic acid, it has been shown that this significantly increases the conversion.

[0087] The at least one acid is preferably selected from the group consisting of hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and phosphoric acid. These acids are preferably added in the form of their aqueous solutions. The use of concentrated hydrochloric acid is particularly preferred.

[0088] Preferably, the at least one polyetheramidamine from step b) is admixed with the at least one acid while stirring. The amount used depends on the number of amino groups of the polyetheramidamine to be phosphonated, the molar ratio of acidic protons of the acid to the aminic NH groups of the entirety of the polyetheramidamines being 0.3:1 to 1.5:1, preferably 0.7:1 to 1.3:1, particularly preferably 0.9:1 to 1.1:1. A secondary amino group has precisely one such aminic NH group, whereas a primary amino group has precisely two such aminic NH groups. The NH groups which are part of the amide functions of the polyetheramidamine used are not included. The acid can be added at any desired temperature, preferably between 20°C and 90°C.

[0089] Phosphonic acid, also called phosphorous acid, is then added to the reaction mixture with stirring. The amount used is preferably based on the number of amino groups of the at least one polyetheramidamine to be phosphonated. The molar ratio of phosphonic acid to the aminic NH groups of the entirety of the polyetheramidamines is preferably 0.3:1 to 1.5:1, more preferably 0.7:1 to 1.3:1, particularly preferably 0.9:1 to 1.1:1. The NH groups which are part of the amide functions of the polyetheramidamine used are not included. Particular preference is given to using the optionally additionally used acid in an equimolar amount based on the amount of phosphonic acid used. The phosphonic acid can be added in pure form as a solid or as an aqueous solution and optionally in one portion or in portions and over a period of time at any desired temperature between 20°C and 90°C.Preferably, the addition is carried out as solid phosphonic acid in portions within 10 min to 30 min at 30 °C to 70 °C.

[0090] The reaction mixture is then heated to preferably 90°C to 100°C and reacted with at least one aldehyde. The amount of aldehyde used depends on the number of amino groups of the polyetheramidamine to be phosphonated. The molar ratio of the total of the aldehydes to the aminic NH groups of the total of the polyetheramidamines is preferably 0.3:1 to 1.5:1, more preferably 0.7:1 to 1.3:1, particularly preferably 0.9:1 to 1.1:1. The NH groups which are part of the amide functions of the polyetheramidamine used are not included. Particular preference is given to using aldehyde in an equimolar amount based on the amount of phosphonic acid. The aldehyde is preferably added continuously or in portions over a period of 30 minutes. The reaction mixture is preferably stirred for several hours at 90°C to 100°C until conversion is complete. It is preferred that the aldehyde is formaldehyde.Different formaldehyde sources can be used here. Suitable formaldehyde sources include, for example, an aqueous solution of formaldehyde (formalin solution), solid paraformaldehyde, or 1,3,5-trioxane. Formaldehyde can be added either as an aqueous solution (formalin solution) or in the form of solid paraformaldehyde. The use of solid paraformaldehyde and aqueous formaldehyde solutions in the concentration range of 30 wt.% to 45 wt.% formaldehyde is particularly preferred.

[0091] In a final distillation step, water and any residues of formaldehyde and acid are preferably removed. Distillation preferably takes place at 80 °C to 120 °C under vacuum to <20 mbar internal pressure until no distillate is detectable. The anhydrous polyetheramidaminephosphonic acid thus produced is a mostly brownish product and can either be bottled or optionally further processed according to step d) and / or step e).

[0092] In the phosphonation reaction according to the invention, the primary and / or secondary amino groups present in the radical X of formula (3) are converted to the corresponding phosphonic acid groups. This conversion can occur a maximum of once for secondary amino groups and a maximum of twice for primary amino groups. The reaction yields structural units of formula (4):

[0093] Formula (4)

[0094] The nitrogen atom shown in formula (4) originates from the reacted primary or secondary amino group. The radical R shown 2 comes from the converted aldehyde R 2 -CHO, where CHO represents an aldehyde group and R 2 each independently of one another represents an organic radical or hydrogen, preferably an alkyl radical having 1 to 4 carbon atoms or hydrogen, particularly preferably hydrogen.

[0095] In a particularly preferred embodiment, the polyetheramidoaminephosphonic acids prepared according to the invention are characterized in that the radical X from formula (3) contains at least one, preferably at least two of the following structural units selected from formula (4a), (4b) and (4c):

[0096] Formula (4a) Formula (4b) Formula (4c)

[0097] Optional step d)

[0098] In optional step d) of the process, the at least one polyetheramidoaminephosphonic acid from step c) is dissolved in water. The polyetheramidoaminephosphonic acid from step c) can therefore be dissolved in water as desired, depending on the application. Solutions with a polyetheramidoaminephosphonic acid content of 10 wt.% to 80 wt.% are preferred, more preferably 20 wt.% to 70 wt.%, and most preferably 25 wt.% to 60 wt.%.

[0099] Optional step e)

[0100] In the optional step e) of the process, a complete or partial neutralization of the at least one polyetheramidaminephosphonic acid from step c) or its aqueous solution from step d) with at least one base takes place to form at least one polyetheramidaminephosphonate salt or its aqueous solution;

[0101] The base is preferably selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, and basic nitrogen compounds. The base is particularly preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, ethanolamine, isopropanolamine, diethanolamine, and diisopropanolamine. The bases can be used either individually or in any desired mixture. This gives aqueous salt solutions of polyetheramidaminephosphonic acid, the pH of which can be adjusted as desired depending on the intended use via the amount of base added. The amount of base is preferably selected such that the salt solutions of polyetheramidaminephosphonic acid (Q) have a pH of 2 to 9, preferably of 3 to 7, particularly preferably of 4 to 6. Preference is given to solutions having a polyetheramidaminephosphonic acid content (regardless of whether this is present as an acid or as a dissolved salt) of 10% to 80% by weight, particularly preferably of 20% to 70% by weight.-% and most preferably from 25 wt.% to 60 wt.%.

[0102] Process products

[0103] The invention further relates to the products producible by the process according to the invention. The present invention thus also relates to the previously described polyetheramidoaminephosphonic acids, polyetheramidoaminephosphonate salts, and their aqueous solutions, which are produced by the process according to the invention.

[0104] The products are preferably aqueous solutions of polyetheramidaminephosphonic acids and / or polyetheramidaminephosphonate salts with a total content of these compounds of 10% to 80% by weight, particularly preferably of 20% to 70% by weight, and very particularly preferably of 25% to 60% by weight, as already explained above. The mass fraction of the total polyetheramidaminephosphonic acids and / or polyetheramidaminephosphonate salts in the aqueous solution is therefore from 10% to 80%, particularly preferably from 20% to 70%, and very particularly preferably from 25% to 60%, based on the total mass of the aqueous solution.

[0105] The products are preferably aqueous solutions of polyetheramidaminephosphonic acids and / or polyetheramidaminephosphonate salts having a pH of 2 to 9, preferably of 3 to 7, particularly preferably of 4 to 6.

[0106] Dispersants and hydraulically setting compositions

[0107] The process products are suitable as dispersants, especially as dispersants in hydraulically setting compositions. They are particularly distinguished by the fact that they do not lead to delayed setting of hydraulically setting compositions.

[0108] A further object of the invention is therefore the use of the products according to the invention as dispersants, in particular the use as dispersants in hydraulically setting compositions.

[0109] Dispersants are additives that enable or stabilize dispersion, i.e., the optimal mixing of at least two immiscible phases. This includes the formation of emulsions and, in particular, suspensions, both of which are classified as dispersions. While emulsions are a fine mixture of two liquids, such as oil and water, a suspension is a sufficiently stable suspension of very small solids in a liquid. In coating materials, these can be pigments or fillers incorporated into a liquid (dispersion medium, also known as millbase).

[0110] A hydraulically setting composition is understood to be a composition that hardens in the presence or upon addition of (additional) water (additional water, mixing water). The total amount of water in the composition results from the sum of the amount of added water and the amount of water contained in the composition according to the invention, in particular the emulsion. Hardening is achieved by reacting the water with the hydraulic binder. This usually involves the formation of a crystal structure with the water being incorporated as crystal water. Examples of hydraulic binders are cement or burnt gypsum. The preferred hydraulic binder is cement. The hydraulically setting composition is therefore preferably a hydraulically setting cement mixture, in particular mortar, screed, or concrete.In addition to the binding agent cement, these cement mixtures also contain aggregates such as sand, gravel, limestone, or chalk, with varying maximum particle sizes and particle size distributions. Hydraulically setting cement mixtures are generally referred to as mortar if the maximum particle size of the aggregates is less than 4 mm, up to 8 mm for screeds, and larger than 8 mm for concrete. Regardless of this, hydraulically setting cement mixtures contain water for their application and may also contain other additives, admixtures, and / or other hydraulically acting mineral additives, such as—but not limited to—pozzolans or fly ash, for special applications.

[0111] The invention therefore also further relates to hydraulically setting compositions comprising the components: a) at least one hydraulic binder, preferably cement; b) at least one product producible by the process according to the invention; c) preferably at least one aggregate selected from the group consisting of sand, gravel, chippings, crushed sand, limestone and chalk; d) preferably additional water; and e) preferably at least one flow agent, in particular based on polycarboxylate ether.

[0112] It is preferred that the hydraulically setting composition

[0113] - 100 parts by weight of component a);

[0114] - 0.1 to 10, preferably 0.5 to 5 parts by weight of component b);

[0115] - 100 to 600, preferably 200 to 400 parts by weight of component c);

[0116] - 20 to 100, preferably 30 to 70 parts by weight of component d); and

[0117] - 0.1 to 10, preferably 0.5 to 5 parts by weight of component e).

[0118] The products according to the invention are particularly preferably used in hydraulically setting cement mixtures by adding the product according to the invention together with the mixing water and optionally together with the superplasticizer during the production of an applicable mortar, screed, or concrete in a mixer. Alternatively, the product according to the invention can be added to the mixture all at once or in portions and incorporated largely evenly by mixing. Superplasticizers are additives with a particularly plasticizing effect. Superplasticizers reduce water demand and / or improve workability. The superplasticizers are preferably selected from the group consisting of naphthalenesulfonate, melaminesulfonate, ligninsulfonate, and polycarboxylate ethers. Polycarboxylate ethers are particularly preferred superplasticizers. These superplasticizers are known to those skilled in the art.

[0119] The use of the product according to the invention as an additive in hydraulically setting cement mixtures is particularly advantageous, in particular in concrete (including aerated concrete, underwater concrete, reinforced concrete, textile concrete, or textile fiber concrete), screed, and mortar (including two-component mortars and concrete repair mortars), to name just a few examples. In the case of a two-component mortar, the second component is added in liquid form to the first component (usually a dry mortar mix) directly before application. These can be, for example, polymer latex emulsions known to those skilled in the art for increasing the elasticity of the hydraulically setting cement mixture.

[0120] In summary, it can be stated that the hydraulically setting composition is particularly preferably a mortar, a screed or a concrete.

[0121] In the examples listed below, the present invention is described by way of example, without the invention, the scope of which emerges from the entire description and the claims, being intended to be limited to the embodiments mentioned in the examples.

[0122] Examples:

[0123] General methods:

[0124] Gel Permeation Chromatography (GPC):

[0125] GPC measurements to determine polydispersity (Mw / Mn), weight-average molecular weight (Mw) and number-average molecular weight (M n ) of the polyethers (E) 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, RI detector, evaluation against polypropylene glycol standard.

[0126] Determination of the acid number:

[0127] The acid number determination was carried out using a titration method based on DIN EN ISO 2114.

[0128] Determination of the hydroxyl number (OH number): Hydroxyl numbers were determined according to the DGF CV 17 a (53) method of the German Society for Fat Science. Samples were acetylated with acetic anhydride in the presence of pyridine, and the consumption of acetic anhydride was determined by titration with 0.5 N potassium hydroxide solution in ethanol against phenolphthalein.

[0129] Step a): Preparation of polyethers by alkoxylation reaction

[0130] Example a1 (according to the invention) - Alkoxylation of isobutyl salicylate - started with propylene oxide: 284.2 g of isobutyl salicylate and 0.60 g of Zn / Co-DMC catalyst were placed in a 5-liter autoclave under nitrogen. The reactor was heated to 90 °C with stirring, and then evacuated to an internal pressure of 30 mbar to remove any volatile components by distillation. To activate the catalyst, detectable by a noticeable pressure drop in the reactor, and for the propylene oxide starting block, the internal temperature was increased to 135 °C, and 170 g of propylene oxide were added with stirring. After a 15-minute intermediate reaction, a further 679 g of propylene oxide and 1867 g of ethylene oxide were continuously added over 2.5 hours while stirring and cooling at 135 °C and a maximum reactor pressure of 1.4 bar (absolute). After a post-reaction of 15 minutes at 135 °C, the reaction mixture was degassed.Volatile components such as residual ethylene oxide and propylene oxide were removed by distillation under vacuum. The product was cooled to 120 °C, mixed with 1.5 g of Irganox® 1076, and cooled to <70 °C. This yielded 3 kg of the colorless polyether, which was liquid at room temperature. The polyether has an OH number of 28.2 mg KOH / g and an acid number of 0.1 mg KOH / g. According to GPC analysis, it has a Mw of 2007 g / mol, an M. n of 1906 g / mol and a polydispersity M w / M n of 1 .05.

[0131] Example a2 (according to the invention) - Alkoxylation of isobutyl salicylate - started with propylene oxide: 583.5 g of isobutyl salicylate and 0.90 g of Zn / Co-DMC catalyst were placed in a 5-liter autoclave under nitrogen. The reactor was heated to 90 °C with stirring, and then evacuated to an internal pressure of 30 mbar to remove any volatile components by distillation. To activate the catalyst, detectable by a noticeable pressure drop in the reactor, and for the propylene oxide starting block, the internal temperature was raised to 135 °C, and 349 g of propylene oxide were added with stirring. After a 15-minute intermediate reaction, a further 349 g of propylene oxide and 1719 g of ethylene oxide were continuously added over 1.25 hours while stirring and cooling at 135 °C and a maximum reactor pressure of 1.3 bar (absolute). After a post-reaction of 25 minutes at 135 °C, the reaction mixture was degassed.Volatile components such as residual ethylene oxide and propylene oxide were removed by distillation under vacuum. The product was cooled to 120 °C, mixed with 1.5 g of Irganox® 1076, and cooled to <70 °C. This yielded 3 kg of the colorless polyether, which was liquid at room temperature. The polyether has an OH number of 55.9 mg KOH / g and an acid number of 0.1 mg KOH / g. According to GPC analysis, it has a Mw of 917 g / mol, an M. n of 870 g / mol and a polydispersity M w / M nof 1.05. Example a3 (not according to the invention) - Alkoxylation of methyl salicylate with propylene oxide started: 328 g of methyl salicylate and 0.60 g of Zn / Co-DMC catalyst were initially charged under nitrogen in a 5-liter autoclave. The reactor was heated to 90 °C with stirring and evacuated to an internal pressure of 30 mbar in order to remove any volatile components by distillation. The internal temperature was increased to 135 °C and, to activate the catalyst, a total of 88 g of propylene oxide were gradually added in portions over a period of 3.5 hours. The pressure rose gradually to 1.2 bar (absolute) without a drop in pressure or the onset of exotherm indicating that the reaction had started. The reactor temperature was then increased to 140 °C, but activation of the DMC catalyst was still not possible. The experiment was unsuccessfully terminated after 1 h at 140 °C.

[0132] Example a4 (not according to the invention) - Alkoxylation of ethyl salicylate - initiated with propylene oxide: 354.9 g of ethyl salicylate and 0.60 g of Zn / Co-DMC catalyst were initially charged under nitrogen in a 5-liter autoclave. The reactor was heated to 90°C with stirring, and then evacuated to an internal pressure of 30 mbar to remove any volatile components by distillation. The internal temperature was increased to 135°C, and a total of 93 g of propylene oxide were gradually added in portions over a period of 6 hours to activate the catalyst. The pressure rose gradually to 1.2 bar (absolute) without any pressure drop or onset of exotherm indicating the onset of the reaction. Activation of the DMC catalyst was not possible, and the experiment was discontinued without success.

[0133] Example a5 (not according to the invention) - Alkoxylation of isobutyl salicylate - started with ethylene oxide: 300.0 g of isobutyl salicylate and 0.39 g of Zn / Co-DMC catalyst were initially charged under nitrogen in a 5-liter autoclave. The mixture was heated to 90 °C with stirring and evacuated by distillation to an internal pressure of 20 mbar in order to remove any volatile components present. To activate the catalyst, the reactor contents were heated to 135 °C. 54 g of ethylene oxide were added over the course of 15 minutes. The pressure rose to 2.8 bar (absolute). The mixture was stirred for 30 minutes without any discernible pressure drop or exotherm. The internal temperature was increased to 140 °C and the mixture was stirred for a further 1.5 hours. Activation of the DMC catalyst was still not possible and the experiment was aborted without success.

[0134] Step b): Preparation of polyetheramidamines by amidation reaction

[0135] Example b1 (according to the invention) - Amidation with triethylenetetramine:

[0136] A 2-liter reaction vessel was charged with 500 g of the polyether from Example a1 and 9.0 g of sodium methoxide solution (30% in methanol). After inerting with nitrogen, the mixture was heated to 90 °C and methanol was distilled off under full vacuum at <20 mbar within 30 minutes. Subsequently, 27.4 g of triethylenetetramine (TETA) were added at 90 °C and the mixture was heated to the reaction temperature of 140 °C. The resulting isobutanol was continuously distilled off during a 5-hour post-reaction at 140 °C and full vacuum. After 5 hours, the distillation was complete. The mixture was cooled to 90 °C and neutralized by adding 4.5 g of lactic acid (90% in water). After stirring for 10 minutes, the finished polyetheramide amine was cooled to <70 °C and drained off. According to 13 C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide.

[0137] Example b2 (according to the invention) - Amidation with diethylenetriamine:

[0138] In a 2-liter reaction vessel, 500.3 g of the polyether from experiment a1 and 8.9 g of sodium methoxide solution (30% in methanol) were placed. After inerting with nitrogen, the mixture was heated to 90 °C and methanol was distilled off under full vacuum at <20 mbar within 30 minutes. Subsequently, 21.0 g of diethylenetriamine (DETA) were added at 90 °C and the mixture was heated to the reaction temperature of 140 °C. During a 5-hour post-reaction at 140 °C and full vacuum, the resulting isobutanol was continuously distilled off. The mixture was cooled to 90 °C and neutralized by adding 14.4 g of lactic acid (90% in water). After stirring for 10 minutes, the finished polyetheramideamine was cooled to <70 °C and drained off. According to 13 C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide.

[0139] Example b3 (according to the invention) - Amidation with ethylenediamine:

[0140] In a 2-liter reaction vessel, 500 g of the polyether from experiment a1 and 8.7 g of sodium methoxide solution (30% in methanol) were placed. After inerting with nitrogen, the mixture was heated to 90 °C and distilled off under full vacuum at <20 mbar within 30 minutes. Subsequently, 14.7 g of ethylenediamine were added at 90 °C and the mixture was heated to the reaction temperature of 160 °C. The resulting isobutanol was continuously distilled off during a 4-hour reaction at 160 °C and full vacuum. The mixture was cooled to 90 °C and neutralized by adding 4.4 g of lactic acid (90% in water). After stirring for 10 minutes, the finished polyetheramideamine was cooled to <70 °C and drained off. According to 13 C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide.

[0141] Example b4 (according to the invention) - Amidation with hexamethylenediamine:

[0142] In a 2-liter reaction vessel, 500 g of the polyether from experiment a1 and 9.0 g of sodium methoxide solution (30% in methanol) were placed. After inerting with nitrogen, the mixture was heated to 90 °C and distilled off under full vacuum at <20 mbar within 30 minutes. Subsequently, 27.0 g of hexamethylenediamine were added at 90 °C and the mixture was heated to the reaction temperature of 140 °C. The resulting isobutanol was continuously distilled off during a 7-hour post-reaction at 140 °C and full vacuum. The mixture was cooled to 90 °C and neutralized by adding 5.0 g of lactic acid (90% in water). After stirring for 10 minutes, the finished polyetheramideamine was cooled to <70 °C and drained off. According to 13C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide. Example b5 (according to the invention) - Amidation with ethylenediamine:

[0143] In a 2-liter reaction vessel, 500 g of the polyether from experiment a2 and 9.0 g of sodium methoxide solution (30% in methanol) were placed. After inerting with nitrogen, the mixture was heated to 90 °C and distilled off under full vacuum at <20 mbar within 30 minutes. Subsequently, 29.9 g of ethylenediamine were added at 90 °C and the mixture was heated to the reaction temperature of 160 °C. The resulting isobutanol was continuously distilled off during a 3.30-hour post-reaction at 160 °C and full vacuum. The mixture was cooled to 90 °C and neutralized by adding 4.5 g of lactic acid (90% in water). After stirring for 10 minutes, the finished polyetheramideamine was cooled to <70 °C and drained off. According to 13C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide.

[0144] Example b6 (according to the invention) - Amidation with triethylenetetramine - sodium ethanolate in EtOH as catalyst:

[0145] In a 2-liter reaction vessel, 500 g of the polyether from experiment a1, 12.7 g of sodium ethanolate solution (21% in ethanol), and 27.4 g of triethylenetetramine (TETA) were placed. After inerting with nitrogen, the mixture was heated to the reaction temperature of 140 °C. In a 2-h post-reaction at 140 °C and full vacuum, ethanol and the resulting isobutanol were continuously distilled off. After 2 h, the distillation was complete. The mixture was cooled to 90 °C and neutralized by adding 3.5 g of lactic acid (90% in water). After 10 min of stirring, the finished polyetheramidamine was cooled to <70 °C and drained off. According to 13C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide.

[0146] Example b7 (according to the invention) - Amidation with polyethyleneimine:

[0147] A 2-liter reaction vessel was charged with 501.4 g of the polyether from experiment a1 and 8.5 g of sodium methoxide solution (30% in methanol). After inerting with nitrogen, the mixture was heated to 90 °C and methanol was distilled off under full vacuum at <20 mbar within 30 minutes. Subsequently, 47.0 g of polyethyleneimine (Lupasol PR 8515 from BASF, average molecular weight approx. 2000 g / mol) were added at 90 °C and the mixture was heated to the reaction temperature of 140 °C. During a 7-hour post-reaction at 140 °C under full vacuum, the resulting isobutanol was continuously distilled off. The mixture was cooled to <80 °C and drained. According to 13C-NMR spectrum, isobutanol was quantitatively removed and the isobutyl ester was completely converted to the desired amide.

[0148] Step c) and optionally step d) and optionally step e): Preparation of the polyetheramidamine phosphonic acids, polyetheramidamine phosphonate salts or their aqueous solutions

[0149] Example c1 (according to the invention):

[0150] The reaction vessel used was a 5-neck glass flask equipped with a stirrer, vacuum pump, heating and cooling unit, and optionally a reflux condenser or distillation device including a distillate receiver. 500 g of the product from experiment b1 were initially charged at 40 °C and inertized with nitrogen. 79.0 g of HCl (37% in water) were added over 5 minutes and stirred for 15 minutes. 65.7 g of phosphonic acid (solid at RT) were added portionwise at 55-60 °C over 10-15 minutes with stirring. The reaction mixture was then heated to 100 °C. 24.1 g of paraformaldehyde were added over 5-10 minutes with stirring at a reaction temperature of 100 °C. The mixture was then stirred at 100 °C for 4 hours. The solid paraformaldehyde dissolved and reacted. The reaction mixture turned brownish. Water, HCl, and any formaldehyde residues were distilled off at 100 °C over a period of 1 h. The pressure was gradually reduced to <20 mbar using a vacuum pump.Vacuum distillation was continued for 30 minutes at 100 °C and <20 mbar until no more distillate was obtained. The reaction mixture was cooled to 70 °C and diluted with 575 g of water as described in step d). A homogeneous aqueous solution with a pH of 0.7 (pH electrode) was obtained. For neutralization as described in step e), 70.4 g of sodium hydroxide solution (45%) were added with stirring at 40-70 °C until a pH of 4.0 to 4.5 was reached. Heat of neutralization was released. The mixture was diluted with water to a solids content of 30 wt.% and drained off. This yielded 1.95 kg of the final, homogeneously dissolved, brownish polyetheramidaminephosphonate with a pH of 4.4.

[0151] Example c2 (according to the invention):

[0152] Analogous to example c1, 490 g of the product from experiment b2 were initially charged at 40 °C and inertized with nitrogen. 60.5 g of HCl (37% in water) were added over 5 min and stirred for 15 min. 50.2 g of phosphonic acid (solid at RT) were added portionwise at 45-50 °C over 10-15 min with stirring. The reaction mixture was then heated to 100 °C. 18.4 g of paraformaldehyde were added over 5-10 min with stirring at a reaction temperature of 100 °C. The mixture was then stirred at 100 °C for 4 h. The solid paraformaldehyde dissolved and the reaction mixture turned brownish. Water, HCl and any residues of formaldehyde were distilled off at 100 °C over 1 h. The pressure was gradually reduced to <20 mbar using a vacuum pump. The vacuum distillation was continued for 30 minutes at 100 °C and <20 mbar until no more distillate was produced. The reaction mixture was cooled to 70 °C and bottled.450 g of the resulting product were weighed into a reaction vessel and diluted with 500 g of water as described in step d). A homogeneous aqueous solution with a pH of 0.75 (pH electrode) was obtained. For neutralization as described in step e), 52.6 g of sodium hydroxide solution (45%) were added while stirring at 40-70 °C until a pH of 4.0 to 4.5 was reached. Heat of neutralization was released. The mixture was diluted with water to a solids content of 30 wt.% and drained off. 1.52 kg of the finished, homogeneously dissolved, brownish polyetheramidaminephosphonate with a pH of 4.7 was obtained.

[0153] Example c3 (according to the invention):

[0154] Analogous to example c1, 430 g of the product from experiment b3 were initially charged at 30 °C and made inert with nitrogen. 41.7 g of HCl (37% in water) were added over 5 min and stirred for 15 min. 34.6 g of phosphonic acid (solid at RT) were added portionwise at 30-35 °C over 5-10 min with stirring. The reaction mixture was then heated to 100 °C. 12.7 g of paraformaldehyde were added at 100 °C over 5-10 min with stirring. The mixture was then stirred at 100 °C for 5 h. The solid paraformaldehyde dissolved and the reaction mixture turned brownish. Water, HCl and any residues of formaldehyde were distilled off at 100 °C over 1 h. The pressure was gradually reduced to <20 mbar using a vacuum pump. The vacuum distillation was continued for 30 minutes at 100 °C and <20 mbar until no more distillate was produced. The reaction mixture was cooled to 70 °C and bottled.437 g of the resulting product were weighed into a reaction vessel and diluted with 500 g of water as described in step d). A homogeneous aqueous solution with a pH of 0.7 (pH electrode) was obtained. For neutralization as described in step e), 31.4 g of sodium hydroxide solution (45%) were added with stirring at 50-60 °C until a pH of 4.0 to 4.5 was reached. Heat of neutralization was released. The mixture was diluted with water to a solids content of 30 wt.% and drained off. 1.47 kg of the finished, homogeneously dissolved, brownish polyetheramidaminephosphonate with a pH of 4.4 was obtained.

[0155] Example c4 (according to the invention):

[0156] Analogous to example c1, 470 g of the product from experiment b4 were initially charged at 40 °C and made inert with nitrogen. 41.8 g of HCl (37% in water) were added over 5 min and stirred for 15 min. 34.8 g of phosphonic acid (solid at room temperature) were added portionwise at 30-35 °C over 5-10 min with stirring. The reaction mixture was then heated to 100 °C. 12.7 g of paraformaldehyde were added over 5 min with stirring at a reaction temperature of 100 °C. The mixture was then stirred at 100 °C for 5 h. The solid paraformaldehyde dissolved and the reaction mixture turned brownish. Water, HCl and any residues of formaldehyde were distilled off at 100 °C over 1 h. The pressure was gradually reduced to <20 mbar using a vacuum pump. The vacuum distillation was continued for 30 minutes at 100 °C and <20 mbar until no more distillate was produced. The reaction mixture was cooled to 70 °C and bottled.395 g of the resulting product were weighed into a reaction vessel and diluted with 700 g of water as described in step d). A homogeneous aqueous solution with a pH of 0.86 (pH electrode) was obtained. For neutralization as described in step e), 23.9 g of sodium hydroxide solution (45%) were added while stirring at 50-60 °C until a pH of 4.4 was reached. Heat of neutralization was released. The mixture was diluted with water to a solids content of 30 wt.% and drained off. 1.32 kg of the finished, homogeneously dissolved, brownish polyetheramidaminephosphonate with a pH of 4.5 was obtained.

[0157] Example c5 (according to the invention) - Excess of formaldehyde, hydrochloric acid, phosphonic acid with respect to NH groups:

[0158] Analogous to example c1, 460 g of the product from experiment b5 were initially charged at 22 °C and inertized with nitrogen. 119.2 g of HCl (37% in water) were added over 15 min and stirred for 15 min. 99.1 g of phosphonic acid (solid at RT) were added portionwise at 55-60 °C over 5-10 min with stirring. The reaction mixture was then heated to 100 °C. 36.3 g of paraformaldehyde were added at 100 °C over 15 min with stirring. The mixture was then stirred at 100 °C for 5 h. The solid paraformaldehyde dissolved and the reaction mixture turned brownish. Water, HCl and any residues of formaldehyde were distilled off at 100 °C over 1 h. The pressure was gradually reduced to <20 mbar using a vacuum pump. The vacuum distillation was continued for 30 minutes at 100 °C and <20 mbar until no more distillate was produced. The reaction mixture was cooled to 70 °C and bottled.500 g of the resulting product were weighed into a reaction vessel and diluted with 900 g of water as described in step d). A homogeneous aqueous solution with a pH of 0.57 (pH electrode) was obtained. For neutralization as described in step e), 88.1 g of sodium hydroxide solution (45%) were added with stirring at 50-60 °C until a pH of 4.0 to 4.5 was reached. Heat of neutralization was released. The mixture was diluted with water to a solids content of 30 wt.% and drained off. 1.7 kg of the finished, homogeneously dissolved, brownish polyetheramidaminephosphonate with a pH of 4.5 was obtained.

[0159] Example c6 (according to the invention) - without strong acid / hydrochloric acid:

[0160] Analogous to example c1, 275 g of the product from experiment b6 and 22.5 g of water were initially charged at 40 °C and made inert with nitrogen. 36.1 g of phosphonic acid (solid at RT) were added portionwise at 55-60 °C over 10-15 minutes with stirring. The reaction mixture was then heated to 90 °C. 18.4 g of paraformaldehyde were added at 90 °C over 5 minutes with stirring. The mixture was then stirred for 3.5 hours at 100 °C. The solid paraformaldehyde dissolved and the reaction mixture turned brownish. Water and any residues of formaldehyde were distilled off at 100 °C over 1 hour. The pressure was gradually reduced to <20 mbar using a vacuum pump. The vacuum distillation was continued for 30 minutes at 100 °C and <20 mbar until no more distillate was obtained. The reaction mixture was cooled to 70 °C and bottled. According to 31According to the P NMR spectrum, the phosphonation reaction did not proceed to the desired extent. Unidentified byproducts were formed, and the target product content was estimated to be <20 mol%. Neutralization and dilution with water were therefore omitted.

[0161] Example c7 (according to the invention):

[0162] Analogous to Example c1, 533.5 g of the product from Experiment b7 were initially charged at 40 °C and inertized with nitrogen. 62.8 g of HCl (37% in water) were added over 15 minutes at 40-60 °C and stirred for 15 minutes. The viscosity increased, and 300 g of water were added for dilution. 52.3 g of phosphonic acid (solid at room temperature) were added to the solution in portions at 60-90 °C over 5-10 minutes with stirring. 19.2 g of paraformaldehyde were added over 10 minutes with stirring at a reaction temperature of 90 °C. The mixture was then stirred for 3.5 hours at 100 °C. The solid paraformaldehyde dissolved, and the reaction mixture turned brownish. Water, HCl, and any residual formaldehyde were distilled off over 1 hour at 100 °C. The pressure was gradually reduced to approximately 200 mbar using a vacuum pump. The viscosity increased rapidly, and the distillation was terminated at a water content of 15 wt.%. The reaction mixture was cooled to 70 °C and bottled.A homogeneous aqueous acidic solution with a solids content of 85% and a pH value of approximately 1 (pH electrode) was obtained. Application testing:

[0163] From the examples c1-c7 listed according to the invention, the measured values ​​generated with products c1, c3, and c7 are explained as examples. The products were investigated for their use as dispersants and their influence on typical industrial application parameters in a mortar. The focus was on measured values ​​characterizing the application-related rheological properties. A mortar without a dispersing additive served as a reference. The comparison product is a commercially available, conventionally used anionic polymer-based dispersing additive.

[0164] 1. Composition of the mortar mixture and its preparation

[0165] The composition of the mortar mixture is shown in Table 1.

[0166] Table 1: Composition of the mortar mixture

[0167] * based on cement content

[0168] The mortar preparation for determining the fresh and hardened mortar properties is carried out according to the following procedure:

[0169] The dry components (cement, limestone flour, sand) are placed in the mixing bowl of a Hobart mixer and mixed for 30 seconds at speed 1

[0170] The liquid components (PCE, dispersing additive) are first added to the water and the additive-water mixture is added to the dry components over a period of 30 seconds while stirring at speed 1. Stir for 1 minute at speed 1.

[0171] Mixing pause for 30 seconds, the bottom and walls of the pot are freed from adhering mortar components

[0172] Finally, stir for 1 minute at speed 2

[0173] The mortar is available for further investigations

[0174] 2. Determination of the slump

[0175] The determination is carried out using an in-house laboratory method. The mortar mixture is poured flush into the ring (diameter d 67 mm, height h 35 mm). After 5 minutes of standing time, the mortar mixture is lifted. After 5 minutes, the diameter of the mortar cake is determined in mm using a caliper. The slump serves as a practical measure for describing the yield point. The greater the mortar cake spreads, the lower the yield point.

[0176] 3. Determination of the funnel flow time

[0177] The determination is carried out in a V-shaped funnel for mortar testing with the dimensions 275 (upper circle diameter) x 30 x 320 mm 3 and a spout of 30 x 30 mm 2The hopper flow time (tir) is the time in seconds within which the mortar flows from a hopper of specified dimensions. It serves as a measure for describing the viscosity of the mortar. The faster the mortar flows from the hopper, the lower its viscosity.

[0178] 4. Determination of setting behavior

[0179] The 'Thermokurve-2022' measuring device from Physikalische Messsysteme was used to determine the setting behavior of the mortar mixtures. Using a temperature sensor, the temperature of the mortar sample, which is placed in an insulated container, is measured over time. For cement-containing samples, characteristic curves are obtained that describe the processes involved in the reaction of the cement with water. This method can be used to reliably determine the influence of admixtures on the setting behavior of the respective mixture, depending on the shift in the maximum temperature Tmax towards longer or shorter setting times, as well as the value of Tmax, compared to the respective reference mixture. The results are presented in Table 2.

[0180] Table 2: Results of the application tests in mortar

[0181] The results show that the inventive examples significantly improve the flowability of the mortar compared to the reference. The yield point and viscosity are reduced. Compared to the reference product, the lower impact on cement setting is noteworthy.

Claims

Patent claims 1. A process for the preparation of polyetheramidaminephosphonic acids or polyetheramidaminephosphonate salts or their aqueous solutions, which comprises the following steps: a) reacting at least one salicylic acid ester as starting compound of an alkoxylation reaction in the presence of at least one double metal cyanide (DMC) catalyst with at least one epoxide to form at least one polyether; b) reacting the at least one polyether from step a) with at least one polyamine which carries at least two amino groups selected from the group consisting of primary and secondary amino groups to form at least one polyetheramidamine; c) reacting the at least one polyetheramidamine from step b) with at least one aldehyde and phosphonic acid to form at least one polyetheramidaminephosphonic acid; and optionally d) dissolving the at least one polyetheramidaminephosphonic acid from step c) in water;and optionally e) complete or partial neutralization of the at least one polyetheramidaminephosphonic acid from step c) or its aqueous solution from step d) with at least one base to form at least one polyetheramidaminephosphonate salt or its aqueous solution; characterized in that; (i) the at least one salicylic acid ester is selected from compounds of formula (1) Formula (1 ) where R is a hydrocarbon radical having at least three carbon atoms; and (ii) at least propylene oxide is used as epoxide, and the at least one salicylic acid ester is first reacted with propylene oxide before an optional reaction with further epoxides.

2. Process according to claim 1, characterized in that R in formula (1) is a saturated or unsaturated, linear or branched hydrocarbon radical having 3 to 8, preferably 4 to 6, more preferably 4 carbon atoms and particularly preferably an isobutyl radical.

3. Process according to claim 1 or 2, characterized in that no benzoic acid is used as a cocatalyst in step a).

4. Process according to one of claims 1 to 3, characterized in that in step a) in addition to propylene oxide, further epoxides selected from the group consisting of ethylene oxide and alkylene oxides having 4 to 8 carbon atoms, preferably selected from the group consisting of ethylene oxide, 1-butylene oxide and styrene oxide, are reacted.

5. Process according to one of claims 1 to 4, characterized in that in step a) the molar ratio of the total of the epoxides to the total of the salicylic acid esters is from 5 to 250, preferably from 10 to 200, particularly preferably from 15 to 100.

6. Process according to one of claims 1 to 5, characterized in that in step b) the reaction takes place in the presence of at least one basic catalyst, which is optionally subsequently neutralized with at least one acid.

7. The process according to any one of claims 1 to 6, characterized in that in step b) the polyamine is selected from the group consisting of ethylenediamine, 1,3-propylenediamine, 1,6-hexamethylenediamine, isophoronediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) and polyethyleneimine.

8. Process according to one of claims 1 to 7, characterized in that in step b) the molar ratio of the total of the polyethers to the total of the polyamines is from 1.00:1 to 1.80:1, preferably from 1.05:1 to 1.60:1, particularly preferably from 1.10:1 to 1.40:

1.

9. The process according to any one of claims 1 to 8, characterized in that in step c) the reaction is carried out in the presence of at least one acid having a pKa value below the pKa value of phosphonic acid, preferably having a pKa value of less than 1.5, particularly preferably of less than 1.

0.

10. Method according to one of claims 1 to 9, characterized in that in step c) the molar ratio of phosphonic acid to the aminic NH groups of the totality of the polyetheramidamines is from 0.3:1 to 1.5:1, preferably from 0.7:1 to 1.3:1, particularly preferably from 0.9:1 to 1.1:1; and / or the molar ratio of the totality of the aldehydes to the aminic NH groups of the totality of the polyetheramidamines is from 0.3:1 to 1.5:1, preferably from 0.7:1 to 1.3:1, particularly preferably from 0.9:1 to 1.1:

1.

11. Process according to one of claims 1 to 10, characterized in that in step c) the aldehyde is formaldehyde.

12. Product producible by the process according to one of claims 1 to 11.

13. Use of the product according to claim 12 as a dispersant.

14. A hydraulically setting composition comprising the components: a) at least one hydraulic binder, preferably cement; b) at least one product according to claim 12; c) preferably at least one aggregate selected from the group consisting of sand, gravel, grit, crushed sand, limestone, and chalk; d) preferably additional water; and e) preferably at least one flow agent, in particular based on polycarboxylate ether.

15. Hydraulically setting composition according to claim 14, characterized in that it is a mortar, a screed or a concrete.

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