Method for production of copper (ii) and zinc (ii) acetylacetonates

FIELD: production of high temperature superconductors.

SUBSTANCE: invention relates to electrochemical synthesis of metal β-diketonates, in particular acetylacetonates. Synthesis of Cu(II) and Zn(II) acetylacetonates in carried out by electrolysis of acetylacetone solution and base electrolyte in acetonitryl in ratio of (1:10):0.5:100, with electrodes made of metal presenting in produced acetylacetonate, at current density not more mA/cm2 by using pulse current. Pulse time is controlled by pulse forming unit connected in parallel to elecrtolyzer. As base electrolyte preferably lithium perchlorate or lithium chloride is used.

EFFECT: controlled process for production of metal acetylacetonates.

5 cl, 2 ex, 1 dwg

 

The invention relates to the synthesis of chemicals, namely, electrochemical synthesis β-diketonates metal. β-Diketonates metal, and especially the simplest of them is the acetylacetonates of the General formula (1):

where M is metal ion(II), are widely used in industry, for example, for the production of high-temperature superconductors (HTSC).

A method of obtaining β-diketonates of metals in aqueous solutions at high pH values, generated by the addition of ammonium hydroxide (Kuzmina N. calcium acetylacetonate. / Kuzmina N., Ciernikova M.V., Martynenko LI // inch. - 1990. - T.35. - VIP. - s). This method leads to the production of hydrated products, which restricts the use of these substances in production processes. Known mechano-chemical method of obtaining β-diketonates metal based on the mechanical impact, for example, in ball mill to mix β-diketonate sodium salt of the corresponding metal (A.P. Borisov of Mechanosynthesis acetylacetonates of 3d-metals. / A.P. Borisov, Petrov L.A., Matyushin E // Joh. - 1992. - T. - Issue 1. - p.15).

However, this method is sequential, provides for the separation of target products and raw materials and requires expensive equipment.

Some of these negotiatestream in an electrochemical method of producing acetylacetonate copper (II) electrolysis combined acetonitrile solutions of acetylacetone copper and steel electrodes (Wide V.L. and other Electrochemical synthesis of (3-diketonates of copper (II). // Joh. - 1996. - T.- V.2. - p.184-189). The disadvantage of this method is the application of a constant electric current, which leads to passivation of the copper electrode due to the adhesion of the formed precipitate.

Closest to the claimed is a method for acetylacetonates of rare earth elements (patent RF №2191190, IPC (7) C 07 F 5/00, C 07 C 49/92), including the synthesis of acetylacetonates of the rare earth elements of the General formula:

where Ln is a rare earth atom of the element by electrolysis of a solution of acetylacetone and lithium chloride in acetonitrile, taken in the ratio (1÷10):1:500, with rare earth metal anode and an inert cathode at a potential of the anode in the range of 0,5-1, using an asymmetric alternating current generated by including in the circuit a single semiconductor diode in series with the electrolytic cell, emitting the obtained solid product by washing with absolute alcohol, followed by drying.

The disadvantages of this method are its irrepressible, due to the impossibility of changing process parameters depending on the synthesis conditions without remounting electrical circuit.

The technical objective of the proposed technical solution is the creation of a managed JV is soba get acetylacetonates of metals.

To solve the technical problem is proposed synthesis of acetylacetonates of metals General formula (1), where M=Cu(II), Zn(II) to carry out the electrolysis of a solution of acetylacetone and background electrolyte in acetonitrile, taken in a certain ratio, the best of which are (1÷10):0,5:100, with electrodes of a suitable metal (M) at current density of not more than 10 mA/cm2using pulsed current time pulses regulate the use of block pulse shaping, connected in parallel to the electrolytic cell.

As a background electrolyte using lithium perchlorate or lithium chloride. The acetylacetone, background electrolyte and acetonitrile, taken in the ratio (1÷10):0,5:100, provide optimal conductivity.

Distinctive from the closest analogue (prototype) symptoms are:

- inclusion of the forming unit current pulses in parallel to the cell that allows you to change the parameters of the process depending on the material of the electrodes and the background electrolyte, setting the time of the cathodic and anodic pulses;

- the value of the current density is not more than 10 mA/cm2to avoid erosion of the electrodes, and therefore, contamination of the synthesis of metal electrodes (M).

The drawing shows a block diagram of the setup for the synthesis of acetylacetonates of Cu(II) and Zn(II). For Khujand is the implementation of the electrosynthesis constitute the electrical circuit, containing the electrolyzer 1, block pulse shaping 2, the constant current source 3, the oscilloscope 4, ammeter 5.

From the constant current source 3 meals are served in the shaping unit pulse 2, which govern the process in the electrolytic cell 5. Oscilloscope 4 and ammeter 3 are used to control synthesis parameters.

Example 1.

Synthesis acetylacetonate copper (II).

In the electrolytic cell 1 is placed 100 g of acetonitrile, 10 g of acetylacetone. As a background electrolyte add 0.5 g of lithium chloride. Immersed into the solution, the copper plate. The electrolytic cell 1 is connected according to the scheme (drawing). Electrolysis are within one hour, the current density of 10 mA/cm2to the unit pulse shaping 2, the time pulses of 5 s, which control the oscilloscope 4.

The results of the analysis are the following:

Calculated for Cu(AcAc)2)-ω(Cu)=24,78%; ω(ASAS)=75,22%.

Defined ω(Cu)=24,24%; ω(AcAc)=76,04%.

The IR spectrum of the synthesized compounds detected absorption bands 1592, 1537, 1516, 1258, 1178, 1002, 960, 930, 895 cm-1. In the visible region of the spectrum detected absorption band 15600 cm-1.

According to literature data the above is evidence that the obtained substance - acetylacetonate copper (II).

Example 2.

Synthesis of zinc acetylacetonate (II).

In the electrolytic cell 1 is placed 100 g of acetonitrile, 1 g acetylated is on. As a background electrolyte add 0.5 g of lithium perchlorate. Immersed into the solution of the zinc plate. The electrolytic cell 1 is connected to a source of electric pulses 2. Electrolysis are within one hour, the current density of 8 mA/cm2which is monitored by the ammeter time pulses of 5 s, which control the oscilloscope 4. The obtained precipitate was separated by filtration, washed with ethanol and dried to constant weight.

The results of the analysis of the obtained compound are:

Calculated for Zn(AcAc)2)-ω(Zn)=24.53%; ω(ASAS)=75,47%.

Defined ω(Zn)=24,42%; ω(AcAc)=76,05%.

The IR spectrum of the synthesized compounds detected absorption bands 1592, 1537, 1516, 1258, 1178, 1002, 960, 930, 895 cm-1. In the visible region of the spectrum detected absorption band 15600 cm-1.

According to literature data, the above is evidence that the substance is zinc acetylacetonate.

Compared with the prototype of the proposed method allows for controlled electrochemical synthesis of substances of the General formula (1), which ensures the purity of substances.

1. The method of obtaining acetylacetonates of Cu(II) and Zn(II), comprising the synthesis of acetylacetonates of metals General formula

where M is Cu(II), Zn(II), by electrolysis, using electricity is s, made of metal M, of a solution of acetylacetone and background electrolyte in acetonitrile, taken in a predetermined ratio, wherein the electrolysis is carried out at a current density of not more than 10 mA/cm2using a pulse current, the time pulses regulate the use of block pulse shaping, connected in parallel to the electrolytic cell.

2. The method according to claim 1, characterized in that as the background electrolyte using lithium perchlorate.

3. The method according to claim 1, characterized in that as the background electrolyte using lithium chloride.

4. The method according to claim 1 or 2, or 3, characterized in that the acetylacetone, background electrolyte in acetonitrile take in the ratio (1÷10):0,5:100.

5. The method according to claim 1 or 2, or 3, or 4, characterized in that the electrolysis is performed with the electrodes of the respective metals (M).



 

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