Method of zirconium carboxylate production

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of derivative transition metal and can be used in chemical industry while producing transition metal carboxylate and refers to improved method of zirconium carboxylate production through interreacting of zirconium chloride with carboxylate derivatives of general formula RCOOM, where R-linear and branched alkyl C_nH_2n+1 or non-saturated acid residue, where n=0-16, and M - proton or cation of alcali metal, in which alkali acid of aliphatic or non-saturated acids are used as RCOOM compounds, interacting of zirconium chloride with the compounds leads to solvent absence in solid with mechanical activation at mole ratio ZrCl₄: RCOOM within 1<m<4.5, where m is integral and broken number with the following extraction of derived zirconium carboxylate with an organic solvent.

EFFECT: duration decrease and efficiency increase of zirconium carboxylate production; elimination of chemically pollutant effluents formation.

5 cl, 1 tbl, 14 ex

The invention relates to the field of chemical derivatives of transition metals, specifically to methods for producing transition metal carboxylates. The transition metal carboxylates are used as the basis of catalysts in various chemical processes, when receiving a metal-containing polymers, upon receipt of ceramic materials and coatings, dyes, pigments, additives for industrial oils, and other lubricants.

The zirconium carboxylates are used, in particular, as the basis of the catalysts for the oligomerization of ethylene to higher linear alpha olefins (LAO) [1] A.S. USSR 1042701, C08F 10/02 from 19.07.1978; B. I. 1983. No. 35 [2] Application Italy 2449879.

This scope uses zirconium carboxylates highest degree of purity, since spurious impurities, including water, carboxylic acids and their salts, inhibit the oligomerization of ethylene in LAO and reduce its technical and economic indicators.

In the scientific literature [3] Blumenthal CB Chemistry of zirconium. M IL. 1963, [4] Mehrotra R.. et al. // Metal Carboxylates. L.Academ. Pres. 1983, describes many ways to get carboxylates using different compounds of zirconium, in particular the interaction of acids with alkoxides or hydrides of zirconium reaction tetramethylsilane with carbon dioxide, the effect of anhydrides of carboxylic acids with chloride replaced metaldoor adicheskii derivatives of zirconium:

Zr(OR)₄+4RCOOH→Zr(OCOR)₄+4ROH

(C₂H₅)₂ZrH₂+RCOOH→C₅H₅Zr(OCOR)₃

Zr(CH₂C₆H₅)₄+CO₂→and(C₆H₅CH₂)_x(ASON₂With₆H₅)_y

Such methods are characterized by complex technological design and in most cases does not allow to obtain high-purity zirconium carboxylates of a given structure, which is necessary for use as base catalysts for the oligomerization of ethylene to linear alpha-olefins.

All of these techniques are difficult and expensive zirconium compounds.

Closest to the proposed method on the technical solution and the results achieved is the method [5] U.S. Pat. USA 4730067, MKI 07F 7/00, [6] Justitie, Avicen, Eoeatu, Anemarrhena, Thegrowing, Lounasmaa. Synthesis of zirconium carboxylates. Syktyvkar. 1995. 28 C. (Scientific reports / Komi scientific center, Ural branch of the Russian Academy of Sciences; VIP), according to which the zirconium carboxylates obtained by reaction of salts of zirconium (in particular, OZr(SO₃OH)₂) with a carboxylic acid in an aqueous-alkaline solution at a certain pH value. The reaction is performed by mixing the two pre-prepared reagent solutions at temperatures 40-98°C. the Setpoint pH supports the Ute by adding to the reaction medium carbonates of ammonium or alkali metals. The resulting zirconium carboxylates from the reaction mixture allocate the extraction of aromatic and/or aliphatic hydrocarbon solvent, and then subjected desolvatation and vacuum drying. When implementing this method, it is very important observe all process parameters, since the deviation from the predetermined mode leads to the deposition of hydroxyoxide zirconium and reduce the yield of the target product. However, this method allows to obtain mainly derived Zirconia (Zr=O) and allows you to get tetracarboxylate zirconium (RCOO)₄Zr.

Closest to the proposed method according to the technical solution and the results achieved is the way in which the zirconium carboxylates produced by reactions of zirconium or its derivatives with carboxylic acids or their derivatives [3] Blumenthal CB Chemistry of zirconium. M IL. 1963, [4] Mehrotra R.. et al. // Metal Carboxylates. L.Academ. Pres. 1983. The most widely used method of producing zirconium carboxylates interaction of zirconium tetrachloride with a carboxylic acid in the medium of organic solvent boiling [7] J.Ludvig, D.Schwarz. Inorg. Chem. 1970. V.9. P.607-611 (prototype).

The interaction of these reagents takes place at elevated temperatures (100-150° (C) speed in accordance with the following scheme:

ZrCl₄+HOCOR⇔RCOOZrCl₃+HCl

RCOOZrCl₃+HOCOR⇔(RCO) ₂ZrCl₂+HCl

(RCOO)₂ZrCl₂+HOCOR⇔(RCOO)₃ZrCl+HCl

(RCOO)₃ZrCl+HOCOR⇔(RCOO)₄Zr+HCl

This way we consider as a prototype, as it is the same as in the developed method, are used as reagents salt of zirconium (including zirconium tetrachloride) and compounds containing carboxyl radical RCOO.

The selected prototype method also has a number of disadvantages: low speed and a longer duration of response (10 hours or more); the allocation of hydrogen chloride, which leads to corrosion of the equipment; the reversibility of the reaction, requiring the removal of hydrogen chloride and its subsequent chemical bonding; the complexity of the selection of target products from the reaction mixture, especially in the case of high-boiling acids, the complexity of the technological design process. To address some of the shortcomings of this method is the reaction of zirconium tetrachloride with carboxylic acids is carried out in the presence of pyridine or ammonia [3] Blumenthal CB Chemistry of zirconium. M IL. 1963, [4] Mehrotra R.. et al. // Metal Carboxylates. L.Academ. Pres. 1983.

However, the improved method has a significant disadvantage in that the resulting zirconium carboxylates polluted respectively pyridinecarboxamide or ammonium chloride.

The objective of the proposed izobreteny who is getting carboxylates, zirconium, the reduction in the duration, increasing the selectivity and the simplification of the technological design process, enabling the production of high-purity zirconium carboxylates desired composition and structure, eliminating the release of large quantities of corrosive hydrogen chloride.

The problem is solved in that the zirconium carboxylates produced by interaction of zirconium tetrachloride with derivatives of carboxylic acids in the solid phase during mechanical activation and subsequent extraction of the formed zirconium carboxylate organic solvent. The subsequent allocation of zirconium carboxylate from a solution in an organic solvent to produce well-known techniques. Upon receipt of tetracarboxylates zirconium reduction in the duration of the process can be achieved by thermal treatment of the reaction mixture after a short mechanical activation.

In the developed method as derivatives of carboxylic acids using alkali metal salts of aliphatic, cycloaliphatic, unsaturated or aromatic carboxylic acids RCOOM, where M=Li, Na, K.

The molar ratio between the alkali salts of carboxylic acids (RCOOM) and zirconium tetrachloride ((RCOOM/ZrCl₄)=m) vary in the range 1<m<4.5, where m is a whole or fractional number. When the integer values m=1, 2, 3 on uchitsya individual zirconium carboxylates, containing one, two, or three carboxylate groups, respectively. In the case of fractional values "m" obtained a mixture of zirconium carboxylates. At m≥4 out completely replaced individual zirconium carboxylates containing four carboxylate groups. An excess of alkali metal salts of carboxylic acids used to more quickly complete substitution reactions.

As alkaline salts of carboxylic acids using lithium, sodium or potassium salts of linear or branched aliphatic acids of the General formula RCOOH, where R is a C_nH_2n+1when n=0-16 cyclohexanecarbonyl, as well as acrylic, methacrylic, oleic, linoleic, linolenic, propargilovyh, benzoic, cinnamic and phenylacetic unsaturated or aromatic carboxylic acids, respectively.

Most preferred are the alkali metal salts of such carboxylic acids for use in the synthesis ensures zirconium carboxylates, soluble in the environment of aliphatic and aromatic solvents, such as heptane or toluene. To the preferred alkaline salts of carboxylic acids are, in particular, sodium salt 2-methylpropanol (somaclonal), 2,2-DIMETHYLPROPANE, 2-ethylhexanol, stearic, cyclohexanecarbonyl, methacrylic, oleic acid and benzoic acid. Obtained at the Snov, carboxylates, zirconium soluble in n-heptane and/or toluene, easily distinguished from the reaction products when you receive them and form the most active catalysts for the oligomerization of ethylene in LAO. On the other hand, the substitution of alkaline salts mentioned monocarboxylic acids in an alkaline or alkaline earth salts of mono-, bi - or poly- (including polymer) carboxylic or sulfonic acids, and salts haloesters carboxylic acid (trichloroacetic, triperoxonane, pentafluorobenzoyl and the like) allows to further extend the capabilities of the method.

Mechanical activation of a mixture of zirconium tetrachloride with anhydrous alkaline salt of carboxylic acid in the solid phase is carried out on a mechanical vibrator with a frequency of 5-50 Hz and amplitude of 5-20 mm in the reactor of stainless steel using as a trigger nozzle steel balls with a diameter of 5-15 mm, at temperatures of 10-40°for 15-180 minutes if the ratio of the mass of the trigger of the nozzle to the mass of the payload within (50-150):1.

Under mechanical activation of the mixture of reagents is implied supply energy to the particles of the reactants. As a result of mechanical impact in certain areas solids creates a stress field. Relaxation of the stress field can occur in several ways: by crushing the particles of the reactants with the formation of new highly active surface, mixing ("the fusion") solids, the formation of various types of defects in the microcrystals, the emission of electrons from the splitting of crystals, heat, excitement and break some ties, initiation and propagation of chemical reactions in the solid phase. In control experiments established that the mixture of powder of zirconium tetrachloride with anhydrous powders of alkaline salts of carboxylic acids in vibromaster without steel balls and even subsequent heat treatment of the thus obtained mixture at temperatures of 50-150°C for 60 minutes does not cause chemical reaction with the formation of zirconium carboxylates. In these conditions, thermal reaction is impossible due to the lack of mobility of atoms or molecules. This means that the mechanical activation of a mixture of these reactants is the limiting stage.

Experiments show that all the parameters of the stage of mechanical activation reagents are critical in the extreme. In particular, the mechanical activation of a mixture of the above-mentioned reagents with other constant parameters and process conditions effectively achieved only steel balls, the diameter of which exceeds 2 mm, on the other hand, the increase in the diameter of the Sha is offering more than 15 mm leads to a decrease in the selectivity of the process due to mechanochemically feedstock and the resulting zirconium carboxylates. A similar effect of varying frequency, amplitude and duration of functioning of the mills.

It is established that for the case of a cylindrical reactor made of stainless steel with a volume of 200 cm³optimum results are obtained when loading into the reactor from 2 to 5 g of the reactants and the ratio of useful load/trigger nozzle ˜ 1/50-1/150 (about 200-300 g of steel balls (diameter 12 mm) using eccentric vibrator with a frequency of 5-50 Hz and amplitude of 5-20 mm

The mechanical activation can be thought of as the process of passing the system through a series of sequential steps: mixing, dispersing, fusion, reorganization of the atomic structure, the excitation of the translational mobility of the atoms and move them relative to each other. All these stages contribute to the process of chemical transformation. When this chemical reaction happens not throughout the mass of solid matter, but only at specific points on the contacts particle reagents of different nature, where occurs, and then relaxes stress field.

The number of contacts between particles of the reacting substances increases in time due to dispersion.

The fact of reactions that culminates in the formation of the product with a quantitative yield, indicates the possibility of a deep (at the molecular or cluster level is) mixing component in the dynamic zones of contact of the particles of the reactants. Mechanical treatment of a mixture of powdered reagents, apparently, eliminates kinetic ban on mass transfer and he is on the contact surface, in the surface layer and even in volume. In particular, a mixture of solid ZrCl₄and alkaline salts of carboxylic acids as a result of mechanical activation acquires the ability to comprehensive chemical interaction in the solid phase, which leads to the formation of tetracarboxylate zirconium. Mechanical activation of a mixture of zirconium tetrachloride with anhydrous alkaline salt of carboxylic acid in the solid phase is carried out with the use of devices for dispersing solid materials energonapryazhennosti 0.5 to 100 kW/kg, which provide chipped, cut, shear, break or plastic displacement of the fragments of the solid particles relative to each other. To solve this problem suitable vibratory ball, bead, planetary, drums, abrasive (coffee) mills, cage mills, mixers and extruders.

It is established that long-term (within 2-10 hours) mechanical activation of a mixture of zirconium tetrachloride with an alkali salt of carboxylic acid usually causes reaction and the formation of zirconium carboxylates with high (not less than 50 wt.% from theoretically possible) output. The duration of mechanical activation, providing spontaneous (sa is proizvolnoi) the transformation of the initial reagents in the reaction products, significantly depends on the nature of the initial reagents. It is observed that the higher the perfection of the crystals of the initial reactants, the faster the completed stage of mechanical activation and the higher the output of the zirconium carboxylates.

In the case of imperfect crystals of at least one of the reagents (for example, ZrCl₄+ sodium oleate) duration of mechanical activation increases, and the selectivity of the process (determined by the ratio of real output to theoretically expected output of the zirconium carboxylate) is reduced. The latter is due to mechanical destruction as initial reagents and the resulting zirconium carboxylate.

To investigate the possibility of preventing these unwanted processes we have conducted a thermographic study of mixtures of zirconium tetrachloride with an alkali salts of carboxylic acids at different duration of mechanical activation. It is established that the curves of differential thermal analysis of the mixture of zirconium tetrachloride with pivalate sodium (sodium salt of 2,2-dimethylpropionic acid) (RCOONa/ZrCl₄=4), mechanically activated within 15-60 minutes, there is a new exothermic effect at 130°C. In control experiments established that the exothermic effects on the curves of differential thermal analysis of the initial reactants and the final products of the reaction no longer is so From this it follows that the reaction ZrCl₄with NaOCOR accompanied by a significant exothermic effect. Increasing the duration of mechanical activation of a mixture of ZrCl₄with NaOCOR the magnitude of the exothermic effect during subsequent heat treatment is reduced to almost 0. After the disappearance of the exothermic effect of the reaction mixture by the method of extraction with toluene or chloroform managed high yield select tetracarboxylate Zirconia.

As a result of studying the effect of the duration of mechanical activation of the mixture, the influence of initial temperature and duration of heat treatment of mechanically activated mixture in the solid-phase process of obtaining zirconium carboxylates found that heat treatment of mechanically activated mixture can be thermal pulse, which provides further autothermal self-propagating chemical reaction on the whole reaction mixture.

Depending on the duration of mechanical activation initiated by thermal impulse response between ZrCl₄and MOCOR can occur in three different modes. At the time of activation of the mixture less than five minutes autothermal self-propagating chemical reaction to initiate does not work: interaction ZrCl₄and MOCOR flows only near the area of coverage of th the first pulse. At the time of mechanical activation of a mixture of from 5 to 15 minutes autothermal mode of self-propagating chemical reaction is possible, but unstable and poorly reproducible. At the time of mechanical activation 15-60 minutes-initiated thermal pulse mode autothermal self-propagating chemical reaction stable and reproducible. In the case when the duration of mechanical activation of a mixture of large (90-180 minutes) and is sufficient for the chemical reaction was essentially completed as a result of mechanical impact, thermal pulse, as expected, does not initiate autothermal self-propagating chemical reaction.

The combination of the obtained results shows that after a short mechanical activation of the mixture of the solid-phase reaction ZrCl₄and alkali metal salts of carboxylic acids can be initiated by three methods: further mechanical impact, thermal processing of mechanically activated mixtures of any heated part of the mechanically activated mixture of local thermal pulse.

The resulting reaction mixture after completion mechanochemical solid-phase synthesis contains a zirconium carboxylate, alkali metal chloride (LiCl, NaCl, KCl) and excess unreacted source reagent and MOCOR.

The zirconium carboxylate from the reaction mixture, the separation of the Ute extraction boiling organic solvent (limit or aromatic hydrocarbons or their galoidoproizvodnykh or ethers).

The proposed solution has a number of significant differences from the prototype: different composition of the starting materials, as well as the fact that the original reactants introduced into the reaction in solution and in the form of individual substances and the reaction is conducted in solution and in the solid phase by mechanochemical activation of the mixture of reagents. The resulting zirconium carboxylates separated from the reaction mixture upon completion of the process by extraction with an organic solvent. All these differences indicate that the proposed solution meets the criterion of "novelty".

On the other hand, the proposed solution allows you to:

- significantly reduce the duration of the process;

- significantly increase the selectivity and to simplify the technological process;

to obtain high-purity zirconium carboxylates desired composition and structure,

- eliminate the formation of large amounts of corrosive hydrogen chloride.

These features developed technical solutions indicate that it meets the criterion of "positive effect".

Mechanical activation of a mixture of powders ZrCl₄and alkali metal salts of carboxylic acids was performed in a steel cylindrical reactor made of stainless steel CHNC volume of 200 cm³using vibrating arawai mills with replaceable Cam device. The latter allowed to change the operating frequency of the shaking of the reactor from 5 to 50 Hz and the amplitude of the shaking from 5 to 20 mm at ambient temperature (10-40° (C) within a specified time.

Usually in the reactor in an inert atmosphere downloaded activating the nozzle in the form of 150-300 g of steel balls with a diameter of 5-15 mm, from 0.5 to 1 g of zirconium tetrachloride and the required amount of alkaline salt of carboxylic acid, and then the reactor was tightly closed.

In the solid-phase mechanical activation of a mixture of ZrCl₄and alkali metal salts of carboxylic acids are formed powder white or light gray in color.

The zirconium carboxylates of the reaction mixtures were isolated by extraction with an organic solvent. Upon receipt of tetracarboxylates zirconium (RCOO)₄Zr to shorten the duration of the process reactor mechanically activated mixture of powders ZrCl₄and alkali metal salts of carboxylic acids after a short mechanical activation were subjected to a short heat treatment (heated to 120-150°).

The products obtained were identified by the methods of x-ray phase analysis (XRD), differential thermal analysis (DTA), infrared spectroscopy (IRS), elemental analysis and test experiments on the oligomerization of ethylene in LAO using isolated from the reaction mixture of carboxyla the basic zirconium as the basis of the catalysts for the oligomerization of ethylene.

XRD was carried out on the device DRONE 1.0 CuK_α-radiation, Ni filter at a sampling rate of 10°/min. Thermograms were obtained using the device Derivatograph Q-1500 D firm "MOM". IR spectra were recorded on instruments "Specord M82 or UR-20 dried in vaseline oil (capillary layer on the KBr Windows).

Elemental analysis was carried out as follows: alkali metal was determined by alkaline photometry, chlorine by titration on Folgard, zirconium-titration using Arsenazo-III" on the calibration curve.

In the x ray powder patterns of the initial powders are lines indicating ZrCl₄and alkaline salt of carboxylic acid. After mechanical activation on the vibrating mill for 5-15 minutes line characterizing initial reagents in Liberman, disappear, a broad band corresponding to amalfitani products mechanical activation reagents. After completion of the reaction on the diffraction intensity of the bands characterizing the amorphous phase decreases significantly, you receive a number of lines corresponding to the presence of chlorides of alkali metals LiCl, NaCl or KCl.

Comparison of the IR spectra of the initial reagents, the mechanically activated powder mixtures of reagents and selected reaction products confirms the fact of a complete expenditure of initial reagents and the formation of zirconium carboxylates.

The invention is also confirmed by sdaetsa (but not limited to) the following examples.

Example 1. Getting somelanguage Zirconia.

In an inert atmosphere in the reactor with a volume of 200 cm³download 1 g (4.29 mmol) of zirconium tetrachloride, 1.89 g (17.16 mmol) somelanguage sodium (molar ratio NaOCOC₃H₇/ZrCl₄=4.0) and activating the nozzle (40 steel balls with a diameter of 12 mm). Mass activating the nozzle 300, the Ratio of nozzle:useful load = 104:1. The reactor is closed and subjected to vibration with a frequency of 20 Hz and amplitude of 20 mm at a temperature of 20°C for 30 minutes. Then the reactor is heated to 150°C. At temperatures of 100-130°there was a significant self-heating of the reaction mass in the control sample.

From the reactor the reaction mass together with a trigger nozzle is discharged into the extractor (flat-bottomed three-neck thick-walled glass flask of 1 l equipped with a stirrer in the form of a frame). There is added 250 ml of dry toluene. The mixture is stirred for 30 minutes, the liquid is separated from the balls by decantation in a container with a glass filter with a pore size less than 0.1 mm filtered solution in the cube vacuum column volume of 0.5 l and then completely distilled off toluene. From the cube speakers remove waxy solid product in the amount of 1.64, the Output 87.2 wt.% from theoretically expected output Zr(EA₃H₇)₄. The analysis found: content of circa the Oia 19.94 wt.% (calculated - 20.75 wt.%). The chlorine content of 0.32 wt.%. This corresponds to a mixture of products containing 96.5 wt.% Zr(EA₃H₇)₄and 3.5 wt.% Zr(EA₃H₇)₃Cl. In the sediment on the filter was found 0.979 g NaCl (97.6 wt.% chlorine in the calculation of the original ZrCl₄).

Example 2. In the reactor of 200 cm³download 1 g (4.29 mmol) of zirconium tetrachloride and 2.13 g (17.15 mmol) of sodium salt of 2.2-dimethylpropionic acid (molar ratio) NaOCOC₄H₉=4/0 and 40 steel balls with a diameter of 12 mm Weight activating the nozzle 300 gliotoxin nozzle: useful load = 96:1. The reactor is closed and subjected to vibration with a frequency of 20 Hz and amplitude of 20 mm at a temperature of 20°C for 120 minutes

From the reactor the reaction mass with balls unloaded into the extractor and the zirconium carboxylate emit similar to that described in example 1.

Output 1.041 g (49.0 wt.% per Zr(OCOC₄H₉)₄).

The zirconium content in the product - 18.17 wt.% (calculated at 18.38 wt.%). The chlorine content in the product - 0.18 wt.%.

Example 3. In the reactor of 200 cm³download 2.1 g (9 mmol) of zirconium tetrachloride, 2.85 g (36 mmol) of sodium acetate and 30 steel balls with a diameter of 12 mm Weight activating the nozzle 225, the Ratio of nozzle:useful load = 45:1. The reactor is closed and subjected to vibration with a frequency of 20 Hz and amplitude of 20 mm at a temperature of 20&x000B0; C for 15 minutes.

After the reaction mass from the reactor together with balls unloaded into a steel Cup with a volume of 250 ml, remove the beads from the reaction mass, a portion of the reaction mass (8.26 g) are loaded into a quartz tube with an inner diameter of 4.5 mm, compacted glass rod, tube close refinished glass tube and heated the bottom of the tube up to 200°With (local heat pulse). Immediately after that there is the emergence of autothermal process - zone heating extends from the bottom of the heated end of the tube to the top of the reaction mixture. When this is heated filled with a mixture of parts of the tube to ˜95°C. test-tube reaction mass discharged in the extractor, add to it 100 ml of diethyl ether, stirred for 30 minutes, loaded into two plastic tubes with a diameter of 5 cm with traffic (comparable amounts) and centrifuged at a centrifugal acceleration, equivalent to 1000 g.

After that, the solution of zirconium acetate in diethyl ether is separated from the precipitates by decantation, combine, download cube of laboratory distillation with a volume of 250 ml and distilled diethyl ether.

From the cube speakers extract 1.98 g of zirconium acetate. Output 88.5 wt.% in the calculation of the original ZrCl₄. The zirconium content in the product 27.07 wt.% (calculated 27.83 wt.%).

The content of the Laura in the product 0.61 wt.%.

Example 4. In the reactor of 200 cm³download 0.26 g (1.11 mmol) of zirconium tetrachloride, 1.39 g (4.7 mmol) of potassium palmitate (the molar ratio of C₁₅H₃₁COOR/ZrCl₄=4.0) and 30 steel balls with a diameter of 12 mm Weight activating the nozzle 225, the Ratio of nozzle:useful load = 136:1. The reactor is closed and subjected to vibration with an operating frequency of 50 Hz and amplitude of 20 mm at a temperature of 20°C for 180 minutes. Then the reactor is heated to 150°C. From the reaction products similar to those described in example 1 extraction with isopentane selected 1.06, palmitate zirconium (86 wt.% in the calculation of the original ZrCl₄). The zirconium content 8.07 wt.% (calculated 8.191 wt.%). The chlorine content of 0.2 wt%..

Examples 5-14 show the influence of the nature of the alkali metal salts of carboxylic acids, conditions of mechanical activation and thermal treatment of the reaction mixture at the exit of zirconium carboxylates (table). The totality of the results obtained shows that the patented invention improves the selectivity and to simplify the technological process of obtaining zirconium carboxylates, to resolve the allocation of large amounts of corrosive hydrogen chloride.

Described techniques and examples (decision) demonstrate, but do not exhaust the possibilities of the developed method.

1. The method of producing zirconium carboxylates interaction of zirconium tetrachloride with carboxyl derivatives of the General formula RCOOM wherein R is a linear or branched aliphatic radical C_nH_2n+1or the remainder of the unsaturated acids, where n=0-16, and M is a proton or a cation of an alkali metal, characterized in that compounds RCOOM use alkali metal salts of aliphatic or unsaturated acids, the interaction of zirconium tetrachloride with these compounds is carried out in the solid phase in the absence of solvent under mechanical activation at a molar ratio ZrCl₄:RCOOM in the range 1<m<4,5, where m is a whole or fractional number, followed by extraction of the formed zirconium carboxylate organic solvent.

2. The method according to claim 1, characterized in that the mechanical activation of the mixture is carried out in a reactor of stainless steel using as a trigger nozzle steel balls with a diameter of 5-15 mm eccentric vibrating ball mill with an operating frequency of 5-50 Hz and amplitude of 5 to 20 mm at a temperature of 10-40°for 15-180 min with a ratio of mass activating the nozzle to the mass of the payload within (50-150):1.

3. The method according to claim 1, characterized in that the mechanical activation of a mixture of zirconium tetrachloride with messageselena salt of carboxylic acid in the solid phase is carried out with the use of the device for dispersing solid materials energonapryazhennosti 0.5 to 100 kW/kg, selected from the group which includes vibrating ball bead, planetary, drums, abrasive or coffee mills, cage mills, mixers and extruders.

4. The method according to claim 1, characterized in that, with the aim of reducing the duration of the process the reaction mixture was activated for 15-180 minutes, before allocating products are heated to 150°C.

5. The method according to claim 1, characterized in that the heat treatment of mechanically activated mixtures spend local thermal pulse, providing further autothermal self-propagating chemical reaction on the whole reaction mixture.