The method of purification of alkyl compounds of non-transition elements of groups ii - vi of the periodic system from the admixture of alkyl halide by distillation and distillation column for its implementation

 

(57) Abstract:

The invention relates to the field of deep purification of organic compounds, in particular to the purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from the admixture of alkyl halide by rectification and improvement of distillation columns for its implementation. The method is carried out by continuous processing alkyl compounds in the process of rectification of metallic magnesium. Distillation column for purification of the above alkyl compounds from admixture of alkyl halide includes cube, rectificatory section, a cylinder, a condenser and contains an additional section, filled with a nozzle made of magnesium metal, which irreversibly binds to the admixture of alkyl halide in the non-volatile alkylsalicylate. 2 S. p. f-crystals, 1 Il., 3 table.

The invention relates to the field of deep purification of substances, in particular to the purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from primacy alkyl halide.

Alkyl compounds are formed non-transition elements of groups II-VI and are widely used for the growth and doping of semiconductor structures I purity: they severely limited the concentration of metal impurities ( 104-10-6wt.%), as well as oxygen and halogenated substances ( 10-2- 10-4wt.%).

Binding reagent in the synthesis of all alkyl compounds is an alkyl halide. For complete alkylation and enhance the yield of the target products this halogen-containing reagent is taken in excess. Ultimately, this leads to contamination of alkyl halide compounds with alkyl and makes necessary further purification of this mixture.

A known method of purification of alkyl compounds from alkyl halide by treatment containing this admixture product metal magnesium [1]. The method is implemented by heating of trimethylaluminum with magnesium flakes to a temperature of 40oC. this contained in the alkyl halide is bound magnesium in low volatile alkylhalogenide magnesium (Grignard reagent):

RX + Mg __ MgX, (1)

where

R is an alkyl radical (CH3C2H5and so on);

X is halogen (Cl, Br, J).

The target product is easily separated from the formed Grignard reagent in the process followed by simple distillation.

However, the described reaction proceeds effectively only at a high concentration of alkyl halide. As% approaches zero.

Low degree of purification is the main disadvantage of this method.

There is a method of deep cleaning alkyl compounds by distillation [2]. Rectification is carried out on Packed columns of periodic action. To protect alkyl compounds from oxidation and thermal decomposition of their rectification is carried out in an atmosphere of inert gas under reduced pressure.

On the basis of significant differences in volatility halide Akilov and obtained on the basis alkyl compounds expected high efficiency of this method. However, in practice this is implemented only for alkyl compounds, group IV (e.g., tetramethyl - or tetraethyl - tin or lead). These substances are fairly easy to clean by rectification method from the admixture of the corresponding halide Akilov (iodotope methyl or ethyl) to the content of 10-3- 10-4wt.%. Alkyl same compound II and VI groups III and V groups form with metal-halide alkilani molecular complexes:

RhE + RX __ RhE RX (2)

where

E - the element II-VI groups of the Periodic system;

h - stoichiometric ratio.

These complexes are thermally unstable and reversible rotting in prte throughout the process of evaporating device ( 10-1wt.%). As a result, the concentration of the alkyl halide is reduced very slowly and only at the end of the selection of the main fraction is possible to obtain a small amount of product with the content of this impurity level 1 - 510-2wt.%.

Low cleaning efficiency is the main disadvantage of this known method, selected as a prototype of the present invention as the most close to him on purpose and technical nature.

The problem solved by the invention is to increase the depth of the distillation purification of alkyl compounds from admixture of alkyl halide and improvement of distillation columns for its implementation.

The problem is solved in that in the known method of purification of alkyl compounds by distillation alkyl compound in the process of rectification continuously treated with metallic magnesium. For this purpose the upper part of the distillation column fill nozzle, made of magnesium (magnesium shavings or pellets). The admixture of alkyl halide is more volatile than the base material, and is concentrated in the upper part of the distillation column. Here she is actively vzaimodeistvuyushchego binding of additional quantities of alkyl halide with magnesium depth cleaning alkyl compounds of this impurity increases as compared to distillation purification by a known method (prototype), and compared to treatment with magnesium initial mixture in a known manner (similar).

Purification of alkyl compounds from admixture of alkyl halide according to the invention, carried out on a column, which is different from the known Packed distillation columns have additional sections filled with magnesium nozzle. Additional section is placed in the upper part of the column between the head of the capacitor and the primary rectificarse section. Diagram of a distillation column according to the invention shown in the drawing. Column consists of the lower cube 1, rectificarse section 2, filled prismatic mass transfer nozzle of nichrome, additional sections 3, filled with magnesium nozzle in the form of a spiral shavings, head of the capacitor consisting of the refrigerator 4 and valve phlegmy 5 and otbornye distillate 6 and cranes 7-12. Cube ratificirebisa and an additional section of the column is equipped with a resistive heater type 13-15. To control the hydrodynamic regime at the top and bottom placed counters drops of phlegmy 16, 17, and to maintain the temperature of thermocouple 18, 19. The pressure in the column was measured by the pressure gauge 20 and podderjivaet">

The technique works on the column was as follows: the column was pumped booster pump to a pressure of 0.1 mm RT.article Then in the cube columns were filled alkyl compound to be cleaned from the alkyl halide. The column was filled with an inert gas to the operating pressure, which is determined by the physico-chemical properties of the purified alkyl compounds (boiling point, and heat resistance). After that, he joined the electrical heating Cuba, rectificarse and additional sections through the refrigerator head condenser was supplied with running water and the column was introduced into a working mode. Within 3-5 h column worked in bestporno the mode in which the distillate from it was not shown. At this time, all of the condensate is returned to the column and interact therein alkyl halide with magnesium nozzle. This is followed by the selection of the pure product, which is collected in the receiving vial.

The method of purification of alkyl compounds from primacy alkyl halide by distillation with continuous processing of the product metal magnesium, and distillation column for its implementation, contains an additional section, filled with magnesium density - continuous processing of the purified alkyl compounds in the process of rectification of metal magnesium and an introduction to the additional column sections, filled with magnesium nozzle, where this processing, are essential features of the invention, for enhancing the purity of the target product by admixture of alkyl halide.

The following are specific embodiments of the invention.

Example 1. Purification of trimethylaluminum from impurities iodotope bromide.

Distillation purification of trimethylaluminum was carried out on a column whose schema described above. Height rectificarse section of the column was 150 cm, and the height of the additional sections - 50 cm Diameter of these sections was 25 mm Main ratificirebisa section columns filled prismatic nozzle, collapsed from nichrome wire. The element size of the nozzle was 3 3 3 mm. Additional section filled with magnesium shavings with the size of the individual elements 3 3 1 mm Cube of the column is filled to 2/3 of its volume and has a capacity of 3 liters of purified substances. The column efficiency, determined in a model mixture of benzene-dichloroethane, was 30 theoretical stages of separation.

Rectification of trimethylaluminum was carried out in an atmosphere of inert gas (argon) at a pressure of 760 mm RT.article and temperature 115-128oC. the so, to all the nozzle is uniformly moistened with phlegm and the rate of irrigation in the lower part of the column was 60 drops/min, and in the top - 40 drops/min Selection of distillate was started after 5 h of the column at the rate of 2 to 3 drops/min

The impurity content iodotope bromide in the source trimethylaluminum and the product purified according to the model, the prototype, and in accordance with the invention, are shown in table 1.

From the table it is seen that the invention provides a 20 - 30 times to reduce the impurity content iodotope bromide in comparison with the known purification methods.

Example 2. Cleaning diethylzinc from impurities iodine ethyl.

Cleaning of diethylzinc carried out as in example 1, but the process of rectification is carried out at a pressure of 150 mm RT.article and a temperature of 65 - 75oC.

The impurity content in the resulting product are shown in table 2.

From the table it is seen that the invention provides a 10 - 20 times to reduce the impurity content of iodine in ethyl diethylzinc compared with known methods.

Example 3. Purification of tetraethyl lead from the admixture of ethyl chloride.

Cleaning of tetraethyl lead was performed as in examples 1 and 2, but the process rectify the CSOs ethyl in the resulting product are shown in table 3.

The table shows that for tetraethyl lead, which is derived from the IV group, good results and conventional rectification (the prototype), since these compounds do not form complexes with metal-halide alkilani. However, in this case, the invention allows 5 times to increase the purity of tetraethyl lead in comparison with the prototype.

Thus, the invention can significantly improve the purity of the alkyl compounds according to their content of impurities alkyl halide.

1. The method of purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from the admixture of alkyl halide by distillation, characterized in that in the process of rectification alkyl connection continuously treated with metallic magnesium.

2. Distillation column for purification of alkyl compounds of non-transition elements of groups II-VI of the Periodic system from impurities alkyl halide, including cube, rectificatory section and the head of the capacitor, characterized in that it contains an additional section, filled with a nozzle made of magnesium metal, which is placed between rectificarse section and a cylinder capacitor.

 

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