WO2021052768A1 - Dérivés d'acide phosphonique et leur procédé de préparation - Google Patents

Dérivés d'acide phosphonique et leur procédé de préparation Download PDF

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WO2021052768A1
WO2021052768A1 PCT/EP2020/074580 EP2020074580W WO2021052768A1 WO 2021052768 A1 WO2021052768 A1 WO 2021052768A1 EP 2020074580 W EP2020074580 W EP 2020074580W WO 2021052768 A1 WO2021052768 A1 WO 2021052768A1
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acid
solution
amino
compound according
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PCT/EP2020/074580
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Carsten Rudolph
Thomas Kreher
Ulrich Stoeck
Stephan Liebsch
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Zschimmer & Schwarz Mohsdorf GmbH & Co. KG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/365—Organic compounds containing phosphorus containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl

Definitions

  • the invention relates to phosphonic acid compounds according to formula (I), a process for their preparation using 1,4-dicarboxylic acid derivatives and chloroalkylaminobis (alkylphosphonic acids) and their use as a functional additive.
  • water plays a crucial role as a medium. It takes on the function of the solvent for additives and as a reaction medium, acts as a transport medium or serves as a heat transfer medium. Examples in which these functions can be used include the use of detergents and cleaning agents, energy generation, the production of ceramic slips or the bleaching of natural fibers. Furthermore, the production of drinking water from service water by means of desalination processes such as reverse osmosis is of increasing importance.
  • water-soluble homo- and copolymers based on acrylic acid can be used to prevent the deposition of poorly soluble alkaline earth salts, with polymer properties being varied through the targeted selection of monomers and their stoichiometric ratios.
  • Organic phosphonic acids with at least two phosphonic acid groups are also very suitable and often even more effective for avoiding deposits (so-called scale), which temporarily prevent precipitation and deposition even in an extremely low concentration range through special interactions with the substrate.
  • Complex-forming compounds are used to mask heavy metal ions and avoid undesirable effects.
  • complex-forming compounds are polyaminopolycarboxylates or polyaminopolymethylene phosphonates, some of which have extremely high complex formation constants.
  • the disadvantage of the cited classes of compounds is that they are considered to be not readily degradable according to the customary methods for determining the ready biodegradability.
  • Dispersing aids which, due to their chemical structure and (partial) charges, are able to adsorb on the surfaces of mineral particles can be used as dispersing aids.
  • the transfer of negative charges to the mineral particles causes them to experience mutual repulsion and remain homogeneously distributed in a liquid phase without sedimenting.
  • Common dispersants are homo- and copolymers of acrylic acid and organic phosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotris (methylenephosphonic acid) (ATMP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • DE 2 214 144 A discloses a process for the production of ethylenediamine-mono- ⁇ -propionic acid tri- (methylenephosphonic acid).
  • US 3,077,487 A discloses compounds of the formula wherein the radicals Zi and Z2 are 1,4-conjugated polycarboxyl group-containing lower alkenyl groups with at least two carboxyl groups.
  • EP 0 772 084 A2 describes metal complexes of various polyamino monosuccinic acids for use as bleaching agents in photographic developer solutions.
  • Iminodisuccinic acid for example disclosed in WO 201 ⁇ 179692 A1, EP 3 127 896 A1 and WO 9845251 A1, the aminosuccinic acid derivative 3-hydroxy-2,2'-iminodisuccinic acid (HIDS) described in DE 4024552 A1 and others in JPH 09157232 A disclosed aminopolycarboxylic acids as alternative complexing agents and corresponding processes for their preparation.
  • An advantageous property of these substances is their easy biodegradability.
  • their lower complex formation constants with heavy metals and the lack of a further functional property such as the ability to disperse particles are disadvantageous.
  • WO 9634126 A1 describes biodegradable chelating agents as complexing agents, in particular according to formula [1] or formula [2]
  • Organic aminomethylene phosphonic acids and their salts are usually prepared by the method of Moedritzer and Irani (Moedritzer and Irani, 1966).
  • the aminomethylene phosphonates that can be prepared on the basis of primary and secondary amines are generally not considered to be readily biodegradable.
  • EP 2 125 844 B1 and EP 2 716646 B1 disclose phosphonate derivatives by linking a reactive phosphonate with amino carboxylic acids or amino alcohols.
  • the pH of the reaction mixture is between pH 8 and pH 14, the reaction temperature between 0 ° C and 200 ° C or 50 ° C and 140 ° C.
  • the object of the present invention is therefore to provide biodegradable compounds with at least one functional property selected from complex formation, hardness stabilization (threshold activity), dispersibility, and corrosion inhibition.
  • a further object of the invention is to provide a method for their production. According to the invention, the object is achieved by a compound of the formula (I) in which
  • the compounds according to the invention are advantageously biodegradable according to the standard test methods published in the Technical Guidelines of the OECD, in particular inherently degradable according to OECD 302 and thus environmentally friendly.
  • the compounds according to the invention particularly advantageously have degradation rates which allow classification as readily biodegradable.
  • these compounds advantageously have the property that the biological degradation processes also take place in situations where there is a lack of phosphorus and the phosphorus contained in the molecule can be released and metabolized in the process.
  • the compounds according to the invention also advantageously have a high molar complexing capacity compared to conventional biodegradable complexing agents such as methylglycine diacetic acid (MGDA), N, N-bis (carboxylatomethyl) -L-glutamate (GLDA), iminodisuccinate (IDS) or hydroxyiminodisuccinic acid (HIDS).
  • MGDA methylglycine diacetic acid
  • GLDA N, N-bis (carboxylatomethyl) -L-glutamate
  • IDS iminodisuccinate
  • HIDS hydroxyiminodisuccinic acid
  • the compounds according to the invention are also advantageously not hazardous to health and have adequate stability.
  • the compounds according to the invention are advantageously capable of interacting with sparingly soluble alkaline earth salts through the terminal phosphonic acid groups and are thus an encrustation inhibitor that is less than stoichiometrically effective.
  • the compounds according to the invention show particularly good dispers
  • alkenyl radical is understood to mean an alkyl radical with at least one carbon-carbon double bond.
  • C1 to C25 alkyl and alkenyl radicals is understood to mean alkyl and alkenyl radicals with 1 to 25 carbon (C) atoms.
  • R 1 is selected from the group comprising —H, unsubstituted and substituted, unbranched and branched C1 to C7 alkyl and alkenyl radicals.
  • R 1 is selected from substituted alkyl radicals, the alkyl radicals having at least one substituent selected from aryl, heteroaryl, amide, carboxyl, guanidino and / or hydroxyl group. In an embodiment with at least two substituents, the substituents can be the same or different.
  • heteroaryl group is understood to mean aromatics whose ring structure contains at least one heteroatom.
  • heteroatoms is understood to mean atoms that are not carbon or hydrogen. Heteroatoms are preferably selected from the group comprising oxygen, nitrogen and sulfur. Is preferred an amino acid residue, particularly preferably an ⁇ -amino acid residue.
  • amino acid residue is understood to mean an organic compound comprising at least one amino group and at least one carboxyl group, the amino group being substituted.
  • proteinogenic amino acid residue is understood to mean amino acids, which are building blocks of peptides or proteins and are encoded by codons in the DNA. Proteinogenic amino acids are selected from alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine and valine.
  • R 1 is selected from the group comprising -H, -CH 3 and -phenyl.
  • m 0 to 2
  • ie m 0, 1 or 2.
  • n 2 or 3.
  • a short-chain alkyl group in particular an ethylene group or a propylene group, advantageously occupies several coordination sites between the nitrogen atoms in the compounds according to the invention Metal atom or ion achieved by a molecule and thus an increase in the ability to complex.
  • n 2.
  • salts is understood to mean the compounds according to the invention having at least one deprotonated carboxyl and / or phosphonic acid group and at least one positively charged counterion.
  • the compounds according to the invention are alkali or ammonium salts, preferably sodium or potassium salts, that is to say a salt comprising alkali or ammonium cations, preferably sodium or potassium cations as counterions.
  • the compounds according to the invention have 0 to 8 deprotonated carboxyl and / or phosphonic acid groups and alkali or ammonium cations as counterions, preferably 2 to 7 deprotonated carboxyl and / or phosphonic acid groups and alkali or ammonium cations as counterions.
  • the invention also relates to a process for the preparation of a compound according to the invention comprising a) providing a 1,4-dicarboxylic acid derivative and adding alkali metal hydroxide, b) reaction of the 1,4-dicarboxylic acid derivative with ammonia or a primary amine to form an aspartic acid derivative, c) reaction of the Aspartic acid derivative with a chloroalkylaminobis (alkylphosphonic acid).
  • the method takes place in the order of steps a), b) and c).
  • 1,4-dicarboxylic acid derivative is understood to mean an organic compound with two terminal carboxyl groups and a reactive structural unit in the 2,3-position, the reactive structural unit being selected from a double bond and an epoxy group.
  • the 1,4-dicarboxylic acid derivative is selected from maleic acid, maleic anhydride, citraconic acid and a 1,2-cis-epoxysuccinic acid.
  • amino acid derivative is understood to mean an organic compound with a secondary amino group and two terminal carboxyl groups in the 1,3-position, wherein the secondary amino group is derivatized by a group comprising -H, unsubstituted and substituted, unbranched and branched C1 to C25 alkyl and alkenyl radicals and a group comprising carboxyl and carboxyalkyl radicals.
  • the primary amine preferably has at least one carboxyl group.
  • the primary amine is an amino acid, preferably an ⁇ -amino acid.
  • the amino acid is an L-amino acid, a D-amino acid or a mixture of L- and D-amino acids, preferably an L-amino acid.
  • step a) taking place at a temperature in the range from 0 ° C. to 80 ° C., preferably in the range from 10 ° C. to 70 ° C., particularly preferably in the range from 40 ° C. to 60 ° C.
  • step b) at a temperature in the range from 80 ° C. to 150 ° C., preferably in the range from 90 ° C. to 150 ° C., particularly preferably in the range from 100 ° C. to 150 ° C.
  • step c) at a temperature in the range from 0 ° C. to 40.degree. C., preferably in the range from 20.degree. C. to 30.degree. C., particularly preferably at room temperature.
  • the alkali hydroxide is sodium hydroxide and / or potassium hydroxide.
  • the chloroalkylaminobis is selected from 2-chloroethylaminobis (methylene phosphonic acid) and 3-chloropropylaminobis (methylene phosphonic acid).
  • the reaction with a chloroalkylaminobis (alkylenephosphonic acid) takes place in step c) with the addition of alkali metal hydroxide, preferably sodium hydroxide and / or potassium hydroxide.
  • alkali metal hydroxide preferably sodium hydroxide and / or potassium hydroxide.
  • alkali hydroxide advantageously increases the solubility of the chloroalkylaminobis (alkylphosphonic acid).
  • step c) the chloroalkylaminobis (alkylphosphonic acid) is initially introduced into a solvent and the aspartic acid derivative is added, preferably continuously added dropwise as an aqueous solution.
  • step c) the aspartic acid derivative is initially charged and the chloroalkylaminobis (alkylphosphonic acid) is added, preferably continuously added dropwise as an aqueous solution.
  • alkali metal hydroxide is also added simultaneously and in parallel with the addition of the chloroalkylaminobis (alkylenephosphonic acid).
  • Another aspect of the invention relates to the use of at least one compound according to the invention as a functional additive, preferably a dispersant, complexing agent, corrosion inhibitor, hardness stabilizer.
  • the term “functional additive” is understood to mean an additive for modifying, in particular improving, the properties of a product, preferably for chemical products for use in water treatment, oil field chemistry, the detergent and cleaning agent industry or the pulp, paper and textile industry.
  • dispenser is understood to mean a substance which enables or stabilizes the optimal mixing of at least two non-homogeneously miscible substances, in particular suspensions.
  • complexing agent is understood to mean a substance which coordinates metal ions or metal atoms as Lewis acids, in particular for masking chemical properties of the metal ions or metal atoms. Complexing agents are advantageously used in washing or cleaning agents to mask the hardness of the water.
  • corrosion inhibitor is understood to mean a substance which temporarily or permanently protects materials against electrochemical attack. Corrosion inhibitors in a corrosive medium, in particular water, protect surfaces which are permanently in contact with the medium.
  • hardness stabilizer is understood to mean a substance which, in sub-stoichiometric amounts, prevents or delays the further formation and precipitation of the poorly soluble alkaline earth compounds through interactions with crystallites of poorly soluble alkaline earth compounds.
  • the compounds according to the invention are used as readily biodegradable complexing agents.
  • the compounds according to the invention are used as a functional additive, in particular as a hardness stabilizer, in cooling water systems, desalination plants, preferably thermal desalination plants, and / or in oil production.
  • the compounds according to the invention are used as a functional additive, in particular as a hardness stabilizer, in oil or gas production, in washing and cleaning processes, in textile, pulp or paper manufacture and treatment, in galvanic processes and in agrochemical applications such as fertilizing with trace elements or avoiding intolerances caused by water hardness.
  • the compounds according to the invention are used as complexing agents for the paper and pulp industry, as bleach stabilizers for hydrogen peroxide bleaching (so-called P stage) and as complexing agents for removing troublesome metal ions in what is known as complexing agent washing (so-called Q stage).
  • the compounds according to the invention are used as a dispersing additive for fillers and for adjusting the viscosity of paper coating slips in paper manufacture.
  • Another aspect of the invention relates to the use of the compounds according to the invention for the production of detergents or cleaning agents, for the production of formulations, preferably for textile, pulp and paper production and treatment for the ceramics industry, for the oil and natural gas industry or for Water treatment.
  • formulations preferably for textile, pulp and paper production and treatment for the ceramics industry, for the oil and natural gas industry or for Water treatment.
  • the use of the compounds according to the invention for the production of formulations for the electroplating industry and / or industrial agriculture is also included.
  • the compounds according to the invention are used in liquid or solid household detergents, in particular in household detergents in powder form or in granulated form.
  • the compounds according to the invention are used in industrial and institutional cleaner formulations, for example in cleaners for hard surfaces (HSC), in bottle cleaners or workshop and tarpaulin cleaners.
  • the compounds according to the invention are used as a dispersant additive in ceramic formulations and applications.
  • a further aspect of the invention relates to the use of the compounds according to the invention for the production of agrochemical formulations, for example for stabilizing agrochemicals that are sensitive to water hardness in aqueous preparation or for providing dissolved transition metal ions as trace elements or nutrients, preferably in chelated form, so as to enable them to be absorbed into the plant organisms to facilitate.
  • the compound according to the invention is used in formulations for electroplating processes, in particular by complexing dissolved metal ions in baths for electroplating.
  • FIG. 1 shows a diagram of the reaction A) an olefinic 1,4-dicarboxylic acid derivative with a primary amine to form an aspartic acid derivative and B) reaction of the aspartic acid derivative with a chloroalkylaminobis (alkylphosphonic acid).
  • FIG. 2 shows a diagram of the reaction of an aspartic acid derivative, which is obtained by reacting a 1,4-dicarboxylic acid derivative with ammonia, with a chloroalkylaminobis (alkylphosphonic acid).
  • FIG. 3 shows a diagram of the reaction of a 2,3-epoxy-1,4-dicarboxylic acid derivative with a primary amine to form an aspartic acid derivative.
  • FIG. 4 shows a graphic representation of the prevention of deposits in the dynamic tube blocking test with the inhibitors IDS, DTPMP and IDS-EABMP.
  • a round-bottom flask equipped with a heater, stirrer, internal thermometer, reflux condenser and solids metering unit is charged with 43.8 g of water and mixed with 77.8 g of 50% strength Sodium hydroxide solution added. After homogenization has taken place, 19.8 g of maleic anhydride are added slowly and with good cooling so that the internal reactor temperature remains below 60.degree. 28.1 g of L-aspartic acid are then dissolved in the resulting solution and then heated to 100-110 ° C. for 44 h. To dissolve the solids that have formed, 10 g of water are added and then cooled. The main component of the solution is the tetrasodium salt of iminodisuccinic acid (90.2%) and the sodium salts of maleic acid (0.9%), fumaric acid (5.5%) and aspartic acid (3.4%).
  • the main component of the solution is the tetrasodium salt of N- (1,2-dicarboxyethyl) -L-glutamic acid with a content of 92.6% determined by 1 H-NMR spectroscopy.
  • Sodium maleate (0.4%), sodium fumarate (0.8%) and sodium malate (6.2%) are identified and quantified analogously as by-products.
  • IDS-EABMP 24.2% calculated via complexometric titration with the molecular weight of the protonated form
  • the reaction mixture has a copper binding capacity of 71.8 mg Cu / g, corresponding to 1. 131 mmol Cu / g.
  • HIDS-EABMP 28.0% (calculated using complexometric titration with the molecular weight of the protonated form)
  • a dilute aqueous NaOH solution is prepared from 4.72 (59 mmol) of 50% strength NaOH solution and 7.3 g of water.
  • the solution from receiving vessel A at 0.5 ml / min and the solution from receiving vessel B at 0.1 ml / min are simultaneously dosed via separate feeds the reaction mixture was stirred for 80 minutes.
  • 50 ml (58.5 g) of an aqueous solution are prepared from 15.78 g (59 mmol) of 2-chloroethylaminobis (methylenephosphonic acid), 4.43 g (55.3 mmol) of 50% NaOH solution and 38.34 g of water placed in a reaction vessel and stirred at room temperature.
  • IDS-EABMP 21.9% (calculated using complexometric titration with the molecular weight of the protonated form)
  • GIS-EABMP 23.6% (calculated using complexometric titration with the molecular weight of the protonated form)
  • a reaction vessel with a Teflon lining 50 ml of deionized (VE) water are placed and 65.3 g (0.667 mol) of maleic anhydride are dissolved with stirring over the course of 30 minutes. 0.686 mol (61.1 g) of crystalline L-alanine are then added to this solution and the mixture is homogenized by stirring. A quantity of 1.212 mol of 50% strength NaOH solution (97.0 g) is then continuously added to the resulting slurry without additional cooling, the internal temperature rising to 90.degree. Finally, 0.808 mol of solid sodium hydroxide in prilled form is added and the mixture is heated to reflux, which begins at 105 ° C., with constant stirring. The reaction mixture is kept at this temperature for 27 hours and then cooled. 291.4 g of the reaction mixture are isolated, which are adjusted to a solids concentration of 49.6% by adding 86.6 g of deionized water.
  • VE deionized
  • the solution contains 139.3 g of the trisodium salt of (I-carboxyethyl) aspartic acid, corresponding to a yield of 91.8%.
  • Carboxyethyl) aspartic acid (corresponding to 0.1 mol) and an identical amount of substance NaOH solution (50%) are metered into the solution of the chloroethylaminobis (methylenephosphonic acid). The reaction takes place for a further hour and then it is cooled.
  • the reaction mixture has a copper binding capacity of 69.5 mg Cu / g or 1.094 mmol Cu / g.
  • the theoretically possible amount of N- (2- (bis (phosphonomethyl) amino) ethyl) -N- (1-carboxyethyl) aspartic acid is 0.581 mmol / g. This value corresponds to a molar ratio n Cu: n -Ala-IS-EABMP of 1.88: 1.
  • Copper binding capacity 69.5 mg Cu / g product ß-Ala-IS-EABMP: 23.9% (calculated using complexometric titration with the molecular weight of the protonated form)
  • the viscous and opaque liquid is adjusted to a solids content of 40% by adding deionized water.
  • the resulting aqueous solution is colorless and clear and contains 84.5% of the target compound as well as 10.2% malic acid, 3.6% fumaric acid and 0.4% maleic acid in the form of the completely neutralized sodium salts, regardless of the solvent.
  • a 250 ml round bottom flask equipped with a stirrer, internal thermometer, dropping funnel and reflux condenser is charged with 27.0 g of 2-chloroethylaminobis (methylenephosphonic acid) (purity 99%, 0.1 mol) and 81.1 g of deionized water and heated to 20 ° C . 0.0875 mol of NaOH in the form of a 50% solution (7.0 g) are added to the slurry and the mixture is stirred until a clear solution is obtained. This mixture is heated to 60 ° C.
  • the reaction mixture has a copper binding capacity of 33.2 mg Cu / g, corresponding to 0.529 mmol Cu / g.
  • the trisodium salt of (5-carboxypentyl) aspartic acid has no copper binding capacity.
  • 6-AHS-IS-EABMP 25.0% (calculated using complexometric titration with the molecular weight of the protonated form)
  • the viscous and cloudy liquid is adjusted to a solids content of approx. 45% by adding deionized water.
  • the resulting aqueous solution contains 87.7 mol% of the target compound and 8.6 mol% of malic acid, 3.3 mol% of fumaric acid and 0.4 mol% of maleic acid in the form , according to evaluation by 1 H-NMR spectroscopy of the completely neutralized sodium salts without taking the solvent into account.
  • a 250 ml round bottom flask equipped with a stirrer, internal thermometer, dropping funnel and reflux condenser is charged with 27.0 g of 2-chloroethylaminobis (methylenephosphonic acid) (purity 99%, 0.1 mol) and 81.1 g of deionized water and heated to 20 ° C . 0.0875 mol of NaOH in the form of a 50% solution (7.0 g) are then added to the slurry and the mixture is stirred until a clear solution is obtained. This mixture is heated to 60 ° C.
  • the reaction mixture has a copper binding capacity of 32.4 mg Cu / g, corresponding to 0.51 mmol Cu / g.
  • the trisodium salt of (5-carboxypentyl) aspartic acid has no measurable copper binding capacity.
  • GABA-IS-EABMP 22.8% (calculated using complexometric titration with the molecular weight of the protonated form)
  • the determination of the calcium binding capacity is based on the titration of a solution of a substance capable of complex formation or hardness stabilization with a calcium salt solution in the presence of carbonate ions at a defined pH value, which is kept constant during the titration by adding sodium hydroxide. The visible formation of calcium carbonate is prevented until the binding capacity is exhausted. The end point of the titration is therefore the first permanent appearance of turbidity in the titration solution.
  • Substances that only have a complexing (chelating) effect show a ratio of 1: 1 for the stoichiometric ratio of n (calcium): n (complexing agent).
  • Substances that also have a hardness-stabilizing or dispersing combination of effects have a ratio of at least or greater than 2: 1 for the above-mentioned ratio.
  • Table 1 shows the measured values of the calcium binding capacity of the compounds according to the invention with solutions adjusted to 25% dry matter in each case with 1 g weight of the solution for the titration at pH 11.
  • the stabilization of alkaline hydrogen peroxide bleach liquors is determined using synthetic water with 20 ° dH and pH 10 at a temperature of 75 ° C for 30 minutes with a concentration of manganese of 10 ppm and an amount of stabilizer of 0.5 g (in each case as Solution with 25% dry matter) (Tab. 2).
  • 1 liter of a 0.15% by weight solution of the product to be tested is prepared. It is produced by mixing the calculated amount of the product with 500 g of water, adjusting the pH of the resulting solution with NaOH solution (50%) to a pH of 11.5 and making up to 1000 g with water.
  • the substances according to the invention show a comparable dispersibility.
  • Phase A sediment phase at the bottom of the measuring cylinder
  • Phase B stable dispersion as the middle phase
  • Phase C clear phase (without visible particles) at the upper end of the measuring cylinder
  • Solution A (cation solution) NaCl 17.64 g / l
  • Solution B (anion solution) Na 2 SC> 4 * 10 H 2 0 73.66 g / l
  • Solution C (inhibitor solution) 10% solution adjusted to pH 6 (calculated on the active substance)
  • the turbidity in turn correlates with the amount of finely divided solid in the liquid phase.
  • the turbidity measurement also provides information about the calcium tolerance of the inhibitor.
  • calcium tolerance is understood to mean the solubility of the resulting calcium salts of the compounds used as inhibitors under the system conditions. If crystallization occurs at the bottom of the vessel, this indicates an insufficient ability of the test substance to influence the crystallization process.
  • the substances according to the invention prevent crystallization and show a reduced turbidity than the reference compounds. They therefore have an improved calcium tolerance compared to reference phosphonates.
  • the measuring principle is based on the injection of a) a cation solution, b) an anion solution and c) an anion solution containing the inhibitor of the same composition as under b), which are mixed homogeneously shortly before entering a heated capillary and thus exceed the maximum solubility at least one ion pair leads.
  • the increase in pressure in the capillary resulting from this cross-sectional reduction is recorded and when a defined limit differential pressure is reached, the test is automatically terminated and the capillary is prepared again for a new test according to a defined cleaning regime.
  • This method is used to determine the minimum inhibitor concentration (MIC) that is necessary to prevent the deposition of sparingly soluble salts within a defined time interval and with a defined salt load.
  • MIC minimum inhibitor concentration
  • DSL 625 Dynamic Scale Loop
  • PSL Dynamic Scale Loop
  • IDS iminodisuccinic acid
  • DTPMP diethylenetriaminepenta (methylenephosphonic acid)
  • IDS-EABMP 2,2 '- ((2- (bis (phosphonomethyl) amino) ethyl) azanediyl) disuccinic acid
  • MIC minimum inhibitor concentration
  • the determination of the ready biodegradability is carried out according to the standards OECD TG 301 A as well as 301 F.
  • the information about the breakdown of dissolved organic carbon (DOC) (OECD 301 A) or the oxygen consumption (OECD 301 F) allow the following assessments (Tab. 9).
  • Example 2 The specified individual components are mixed one after the other with stirring at room temperature. A clear formulation which is stable for several months is obtained in each case.
  • the specified individual components are mixed one after the other with stirring at room temperature. A clear formulation which is stable for several months is obtained in each case.
  • aqueous micronutrient concentrate containing 0.5% dissolved manganese in chelate form
  • 50 ml of water are mixed with 12.8 g of 25% IDS-EABMP, sodium salt.
  • 1.1 g of manganese (II) sulfate monohydrate are sprinkled into the stirred solution, then adjusted to a pH of 7.7 with 2.8 g of 45% strength potassium hydroxide solution and by further addition of 4.8 g of water to the desired metal concentration set.
  • the solution obtained is clear and colorless and can be combined with conventional NPK nutrient solutions.

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Abstract

L'invention concerne des dérivés d'acide phosphonique selon la formule (I), un procédé pour leur préparation à l'aide de dérivés d'acide 1,4-dicarboxylique et d'(acides) chloroalkylaminobis(-alkylphosphoniques) et leur utilisation en tant qu'additif fonctionnel.
PCT/EP2020/074580 2019-09-17 2020-09-03 Dérivés d'acide phosphonique et leur procédé de préparation WO2021052768A1 (fr)

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DE102019124958.9A DE102019124958B4 (de) 2019-09-17 2019-09-17 Phosphonsäurederivate und Verfahren zu deren Herstellung
DE102019124958.9 2019-09-17

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RU2796821C1 (ru) * 2022-10-14 2023-05-29 федеральное государственное автономное образовательное учреждение высшего образования "Казанский (Приволжский) федеральный университет" (ФГАОУ ВО КФУ) Применение биоразлагаемого хелатообразующего агента для удобрения микроэлементами

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