Method for preparing bis-(1-hydroxyethane-1,1-diphosphonate(1-)) zinc (ii)

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for preparing bis-(1-hydroxyethane-1,1-diphosphonate(1-)) zinc (II). Method involves interaction of zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in a solvent medium, crystallization of the end product from solution, separation of deposit from solution and drying the deposit. Method involves using water-soluble zinc (II) salt with anion of strong acid as a zinc-containing reagent and preparing the solution with the concentration of zinc (II) salt from 0.2 to 2.2 mole/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 0.4 to 5.0 mole/l. The end product prepared by proposed method can be used in preparing phosphonate electrolytes for galvanic zinc-plating, for preparing zinc-phosphate inhibitors of steel corrosion, as trace supplement to vitamin preparations and fodders for animals, as a zinc microfertilizer in agriculture and for preparing other compounds of zinc (II). Invention provides enhancing purity and uniformity of the end product, increasing its yield, improved technological effectiveness of process, utilizing toxic waste in galvanic manufacturing.

EFFECT: improved preparing method.

8 cl, 1 tbl, 6 ex

The invention relates to chemical technology of organic compounds, in particular to a method for producing bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II), which is a complex of zinc(II) with 1-hydroxyethane-1,1-diphosphonic acid CH₃S(HE)(RHO₃H₂)₂(C₂H₈O₇P₂) composition Zn(C₂H₇O₇P₂)₂·4H₂O. the Substance obtained in this way can be used for the preparation of electrolytes galvanized with high scattering ability to obtain zinc-phosphonate corrosion inhibitors of steel, as a trace element Supplement vitamin drugs and animal feed, as zinc micronutrients in agriculture, for other 1-hydroxyethane-1,1-diphosphonates of zinc(II).

A method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) copper(II), based on the interaction of water-soluble salts of copper(II) and 1-hydroxyethane-1,1-diphosphonic acid when their concentrations in aqueous solution from 0.5 to 2.0 mol/l and from 2.0 to 6.0 mol/l, respectively, with subsequent crystallization of the desired product from the solution (Patent RF 2224763, publ. 27.02.2004,). The method does not allow for obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II).

A method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) cobalt is(II), based on the interaction of water-soluble salt of cobalt(II) and 1-hydroxyethane-1,1-diphosphonic acid when their concentrations in aqueous solution from 0.7 to 1.5 mol/l and from 1.5 to 4.0 mol/l, respectively, with subsequent crystallization of the desired product from the solution (Patent RF 2230069, publ. 10.06.2004 year). The method does not allow for obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II).

Known methods for producing bis(1-hydroxyethane-1,1-diphosphonates(1-)) zinc(II), Zn(C₂H₇O₇P₂)₂·4H₂O or Zn(C₂H₇O₇P₂)₂·5H₂O interaction of aqueous solutions of 1-hydroxyethane-1,1-diphosphonate(2-) zinc(II) and 1-hydroxyethane-1,1-diphosphonic acid, taken in a molar ratio of 1.0: 1.0, followed by separation of the target product from the solution with pH≤1.0 at slow or fast evaporation of the solution (Keshikbaeva KAPYSHEV Synthesis, properties and structure of complexions of some transition metals (Cu, Ni, Co, Mn, Zn) with oksietilidendifosfonovaya and ethylenediphosphonic acids. Dis. ... candles. chem. Sciences. - M.: Moscow state University, 1988). The disadvantage of these methods is the need to use reagent 1-hydroxyethane-1,1-diphosphonate(2-) zinc(II), which is not produced by the chemical industry.

Closest to the claimed is a method of obtaining bis(1-guide-roxita-1,1-diphosphonate is(1-)) zinc(II), including interaction zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in the aquatic environment, the crystallization of the desired product from the solution, separating the precipitate from the solution and drying the precipitate (Keshikbaeva KAPYSHEV Synthesis, properties and structure of complexions of some transition metals (cu, Ni, Co, Mn, Zn) with oksietilidendifosfonovaya and ethylenediphosphonic acids. Dis. ... candles. chem. Sciences. - M.: Moscow state University, 1988). As the zinc-containing reagent in the method according to the prototype uses zinc oxide(II), and the molar ratio of zinc oxide(II): 1-hydroxyethane-1,1-diphosphonic acid is 1,0:3,0. The method is based on the following chemical reaction:

However, as experimentally determined (see example 1), the way the prototype is not possible to obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) without impurity complexes of zinc(II) with 1-hydroxyethane-1,1-diphosphonic acid composition different from the composition of the target product. Other disadvantages of the method on the prototype are low reaction rate and the necessity of heating the reaction solution.

In the claimed invention, the aim was to increase the purity and homogeneity of bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II), to increase the yield of the target product, to improve the manufacturability of the process of its receipt, to dispose of Tox is CNY waste production, electroplating.

The problem is solved in that a method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) includes the interaction of the zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in the environment of the solvent, crystallization of the desired product from the solution, separating the precipitate from the solution and drying the precipitate. New this method is that as the zinc-containing reagent used water-soluble salt of zinc(II) with the anion of a strong acid and prepare a solution with a salt concentration of zinc(II) from 0.2 to 2.2 mol/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 0.4 to 5.0 mol/L. as a solvent, it is desirable to use water or filtrate after removal of the precipitate of the desired product, or a homogeneous mixture of water and an organic solvent. As an organic solvent is used preferably miscible with water, an organic solvent selected from the group consisting of methanol, ethanol, propanol-1, propanol-2, ethanoic acid, propanoic acid, propanone, butanone, acetonitrile. As salts of zinc(II) it is desirable to use a salt selected from the group consisting of chloride, bromide, sulfate, nitrate, perchlorate, chlorate, sulpham zinc(II), or waste galvanic production - exhaust electrolyte galvanizing. Salt of zinc(II) and 1-hydroxyethane-1,1-WPPT is Stanovoy acid it is desirable to take in a molar ratio, equal 1,0:(1,9-4,5).

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) is the preparation of an aqueous solution containing zinc(II) and 1-hydroxyethane-1,1-diphosphonic acid, by dissolving in water zinc salts(II), for example chloride, nitrate, sulfate, and 1-hydroxyethane-1,1-diphosphonic acid, the addition (if necessary) an organic solvent, crystallization of bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) from the solution, separating the precipitate from the solution, washing (if necessary) the precipitate with a solvent and drying the precipitate.

The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) based on the reactions, for example:

To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) it is necessary to use a salt of zinc(II)having high solubility in water. These salts react in solution with 1-hydroxyethane-1,1-diphosphonic acid according to the scheme:

However, the solution can be also adverse reactions of education 1-hydroxyethane-1,1-diphosphonate(2-) zinc(II):

Given that 1-hydroxyethane-1,1-diphosphonate(2-) zinc(II) it is soluble in water, what about the well-soluble in the presence of strong acids, to obtain pure and homogeneous bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) it is necessary to use a salt of zinc(II) with the anions of strong acids, such as chloride ZnCl₂·6H₂O, bromide ZnBr₂·3H₂O, sulfate ZnSO₄·7H₂O, sulpham Zn(H₂NSO₃)₂·4H₂O, methanesulfonate Zn(CH₃SO₃)₂, bansilalpet Zn(C₆H₅SO₃)₂the chlorate Zn(ClO₃)₂·6N₂O, perchlorate Zn(ClO₄)₂·6H₂O, nitrate Zn(NO₃)₂·6N₂O, tetrafluoroborate Zn(BF₄)₂·6H₂O, hexafluorosilicate ZnSiF₆·6H₂O and some other salts. As can be seen from examples 1 and 5, to obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) reagent zinc oxide(II) or salts of zinc(II) with the anions of weak acids, such as formate Zn(NCOA)₂·2H₂Oh, acetate Zn(CH₃Soo)₂·2H₂O, gidroksicarbonata Zn(OH)₂·nZnCO₃undesirable , as this may lead to the formation instead of the target product other zinc compounds(II) with 1-hydroxyethane-1,1-diphosphonic acid - ZnC₂H₆O₇P₂·5H₂O.

To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) with high yield it is necessary to prepare a solution with a concentration of zinc(II) 02-2,2 mol/l and 1-hydroxyethane-1,1-diphosphonic acid, and 0.4 to 5.0 mol/L. From solutions in which the concentration of the reagents indicated below, the target product is highlighted with output less than 50%. The upper limit of the concentration of reagents is limited by the solubility of substances in water, as well as the need to obtain a solution which does not separate when adding organic solvent.

Bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) is a water soluble substance, so get it by crystallization from an aqueous solution with a yield higher than 85% is not possible. A significant increase in the yield of the target product can be achieved by using as the solvent of the filtrate after removal of the precipitate. The solubility of bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) in some organic solvents (monohydroxy alcohols, monocarboxylic acids, ketones, NITRILES, chlorinated hydrocarbons) are much lower than in water. Therefore, if we carry out the crystallization of bis(1-hydroxyethane-1,1-di-phosphonate(1-)) zinc(II) from a homogeneous mixture of water and an organic solvent selected from the group consisting of methanol, ethanol, propanol-1, propanol-2, ethanoic acid, propanoic acid, propanone, butanone, acetonitrile, it is possible to improve the yield of the target product to 97-99% while maintaining its purity and uniformity.

Spent electrolytes galvanizing steel and iron are the Xia toxic waste electroplating and subject reduction (Harmful chemical substances. Inorganic compounds of elements of I-IV groups (Ed. by Filova L.A.). - M.: Chemistry, 1988, P.146. Kudryavtsev N.T. Electrolytic coating of metals. - M.: Chemistry, 1979, S. USSR GOST 9.305-84. Coating of metallic and non-metallic inorganic. Operation of the technological processes of obtaining coatings. - M: in state standard, 1988, P.67. Smirnov, D.N., Genkin VE wastewater treatment in the processing of metals. - M.: metallurgy, 1989, P.9), which requires significant material costs. Many of them can be used as a zinc-containing reagents for the synthesis of various compounds of zinc(II). To obtain bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) you can use spent electrolytes galvanizing containing high concentrations of salts of zinc(II), preferably waste sulfuric acid electrolytes-dip galvanizing, having the composition:

Zinc sulfate 140-230 g/l

Sulfuric acid 80-100 g/l

From solutions in which 1.0 mol of zinc(II) less than 1.9 mol 1-hydroxyethane-1,1-diphosphonic acid, can drop a residue, containing in addition to the bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) is also undesirable impurity 1-hydroxyethane-1,1-diphosphonate(2-) zinc(II) ZnC₂H₆O₇P₂·5H₂O. From solutions in which 1.0 mol of zinc(II) account for more than 5.0 mol 1-hydroxyethane-1,1-diphosphonic acid, Clevo is an outstanding product in pure form and high yield of the zinc(II), but his exit 1-hydroxyethane-1,1-diphosphonic acid is reduced, which leads to unproductive expenditure of this reagent. Therefore, to obtain a homogeneous bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) with high yield by zinc(II) and 1-hydroxyethane-1,1-diphosphonic acid, it is desirable to take salt of zinc(II) and 1-hydroxyethane-1,1-diphosphonic acid in a molar ratio equal to 1,0:(1,9-4,5).

Example 1 (the prototype).

To a solution of 12.6 g (0,06 mole) 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" to 18.0 ml of water under stirring was added 1.63 g (0,02 mol) of zinc oxide GOST 10262-73 brand "analytical grade" and heat the suspension to 50-70°until complete dissolution of the zinc oxide. The resulting solution was left to crystallize for 4 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with ethanol (two 10 ml) and dried in air at room temperature to constant weight. The zinc(II) 63%.

Found, %: C - 6,5; N - 4,5; P - 17, 0mm; Zn - 17,7.

Calculated for Zn(C₂H₇O₇P₂)₂·4H₂O, %: C - 8,78; N - Of 4.05; P - 22,63; Zn - 11,94.

Calculated for ZnC₂H₆O₇P₂·5H₂O %: Of 6.68; N - 4,49; P - 17,23; Zn - 18,18.

Example 2.

Mix a solution of 5.9 g ZnCl₂GOST 4529-78 mark "h" in 5.0 ml water and a solution of 27.5 g of 1-hidroxide who -1,1-diphosphonic acid THAT 6-09-713-84 mark "h" and 30.0 ml of water and make a crystal seed Zn(C ₂H₇O₇P₂)₂·4H₂O. the Solution is left to crystallize for 3 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with ethanol (three portions 5 ml) and dried in air at room temperature to constant weight. The zinc(II) 72%.

Found, %: C - 8,8; N - 4,0; P - 22, 0mm; Zn - 11,4.

Calculated for Zn(C₂H₇O₇P₂)₂·4H₂O, %: C - 8,78; N - Of 4.05; P - 22,63; Zn - 11,94.

Example 3.

In 10.0 ml of water at room temperature is first dissolved 10.6 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h", then 4.8 g ZnSO₄·7H₂O GOST 4174-77 mark "h". The solution is kept for crystallization at 4 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed first with 70%aqueous solution of acetic acid (two servings 2 ml), then acetone (two servings 2 ml) and dried in air at room temperature to constant weight. The zinc(II) 69%.

Found, %: C - 8,3; N - 3,9; P - 22, 0mm; Zn - 11,2.

Calculated for Zn(C₂H₇O₇P₂)₂·4H₂O, %: C - 8,78; N - Of 4.05; P - 22,63; Zn - 11,94.

Example 4.

In 10.0 ml of spent electrolyte galvanic zinc concentrations of zinc sulfate to 1.23 mol/l, with the nuclear biological chemical (NBC acid of 0.93 mol/l when heated to a temperature of 60-80° With the dissolve of 7.8 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h". The solution is kept for crystallization to 10 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter with ethanol (two servings 4 ml) and dried in air at room temperature to constant weight. The zinc(II) 72%.

Found, %: C And 8.6; N - 4,1; P - 21,9; Zn - 11,7.

Calculated for Zn(C₂H₇O₇P₂)₂·4H₂O, %: C - 8,78; N - Of 4.05; P - 22,63; Zn - 11,94.

Example 5.

In 10.0 ml water dissolve first of 12.6 g of 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h", then when heated to a temperature of 70-80°dissolved under stirring 4,39 g Zn(CH₃Soo)₂·2H₂O GOST 5823-78 brand "analytical grade". The solution is left to crystallize for 3 days at room temperature. The precipitate is filtered off on a glass filter THEN 16 under reduced pressure, washed on the filter first with 70%aqueous solution of acetic acid (the two portions of 3 ml), then with ethanol (two servings 3 ml) and dried in air at room temperature to constant weight. The zinc(II) 79%.

Found, %: C - 6,5; N - 4,3; P - 17,1; Zn - 17,4.

Calculated for ZnC₂H₆O₇P₂·5H₂O, %: Of 6.68; N - 4,49; P - 17,23; Zn - 18,18.

Example 6.

Mix a solution of 15.5 is 1-hydroxyethane-1,1-diphosphonic acid THAT 6-09-713-84 mark "h" of 12.0 ml of water with a solution of 6.1 g of ZnSO ₄·7H₂O GOST 4174-77 mark "h" in 6.0 ml of water and with stirring, is added to 40.0 ml of acetic acid GOST 61-75 marks "h". The resulting solution was left to crystallize for 6 days at room temperature. The precipitate is filtered off on a glass filter THEN 40 under reduced pressure, washed on the filter first 80%solution of acetic acid (three portions of 2 ml), then acetone (three portions 2 ml) and dried in air at room temperature to constant weight. The zinc(II) 97%.

Found, %: C - 8,4; N - 3,9; P - 22,1; Zn - 11,8.

Calculated for Zn(C₂H₇O₇P₂)₂·4H₂O, %: C - 8,78; N - Of 4.05; P - 22,63; Zn - 11,94.

As can be seen from example 1, method according to the prototype does not allow to reliably produce bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II)from aqueous solution obtained by the interaction of zinc oxide(II) and 1-hydroxyethane-1,1-diphosphonic acid, taken in a molar ratio of 1.0:3,0, instead of the target product composition Zn(C₂H₇O₇P₂)₂·4H₂O may fall 1-hydroxyethane-1,1-diphosphonate(2-) zinc(II) composition ZnC₂H₆O₇P₂·5H₂O x-ray powder infrared spectrum which is different from x-ray powder infrared spectrum of the target product. From examples 2-4,6, it follows that the claimed method allows the floor is the part with a high yield of bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II), corresponding to the formula Zn(C₂H₇O₇P₂)₂·4H₂O.

Obtained in examples 2-4,6 bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II) - a colorless crystalline substance, soluble in water, aqueous solutions of alkalis, ammonia, mineral acids, formic acid, ethylene glycol, glycerol, dimethylformamide (decomposition), dimethyl sulfoxide, slightly soluble in ethanol, propanol, acetic acid, 1,4-dioxane, chloroform, carbon tetrachloride, hexane, benzene. The substance does not change its composition during storage in air at room temperature and normal humidity.

The data of elemental analysis, x-ray powder and infrared spectroscopy, matching for drugs Zn(C₂H₇O₇P₂)₂·4H₂O, obtained by the claimed method in different conditions (table), indicate the phase homogeneity of the target product.

The adaptability of the inventive method is increased, so as to obtain the target is on the product does not require a heated and prolonged stirring of the reaction solution. Additional technical result of lowering the cost of the target product and reducing the cost of environmental protection is achieved by using as the source of the salts of zinc(II) galvanic waste production waste electrolytes galvanizing.

1. The method of obtaining bis(1-hydroxyethane-1,1-diphosphonate(1-)) zinc(II), including interaction zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in the environment of the solvent, crystallization of the desired product from the solution, separating the precipitate from the solution and drying the precipitate, characterized in that as the zinc-containing reagent used water-soluble salt of zinc(II) with the anion of a strong acid and prepare a solution with a salt concentration of zinc(II) from 0.2 to 2.2 mol/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 0.4 to 5.0 mol/L.

2. The method according to claim 1, characterized in that the solvent used water.

3. The method according to claim 1, characterized in that the solvent used, the filtrate after removal of the precipitate of the desired product.

4. The method according to claim 1, characterized in that the solvent used homogeneous mixture of water and an organic solvent.

5. The method according to claim 4, characterized in that the organic solvent used miscible with water and organic process is Italy, selected from the group consisting of methanol, ethanol, propanol-1, propanol-2, ethanoic acid, propanoic acid, propanone, butanone, acetonitrile.

6. The method according to claim 1, characterized in that salts of zinc(II) using salt selected from the group consisting of chloride, bromide, sulfate, nitrate, perchlorate, chlorate, sulpham zinc(II).

7. The method according to claim 1, characterized in that as the source of the salts of zinc(II) use waste galvanic production - exhaust electrolyte galvanizing.

8. The method according to claim 1, characterized in that the water-soluble salt of zinc(II) and 1-hydroxyethane-1,1-diphosphonic acid taken in a molar ratio equal to 1,0:(1,9-4,5).