SU1120686A1 - Method of producing iodine-containing phthalocyanines - Google Patents

Abstract

METHOD OF OBTAINING IODSODER-. LONGER PHTHALOCYANINES, which means that phthalocyanine of the formula .gNg, where MH, Mg, Fe, Cu, Zn, and iodine are placed in two zones in one closed volume and heated in an inert atmosphere at a pressure of 10 -10 mm Hg . or in . a vacuum of 10 -10 mm Hg while maintaining the temperature of phthalocyanine 540-580 ° C and iodine 70-100 ° C for 30 minutes at a mass ratio of iodine and phthalocyanine 2-10: 1. (L N9 Od 00 a

Description

one

The invention relates to organic chemistry, specifically to methods for producing new iodine-containing phthalocyanines, which can be used to produce heat-resistant semiconductor materials with high electrical conductivity.

The composition of iodine-containing phthalocyanines corresponds to the general formula (MRc) .x (MPcf (r) J

where Mg; Fe; Si; Zn; .Ng; 0, 7,

They have semiconducting properties and are characterized by high heat resistance. Depending on the content of iodine, their electrical conductivity varies from 10 Ohms

A known method of producing iodine-containing nickel phthalocyanine by treating the starting nickel phthalocyanine with iodine in a solution of chlorobenzene or chloronaphthalene.

The disadvantage of this method is the very high electrical conductivity of the crystals (up to 1000 Ohm cm), which prevents the use of the product as a semiconductor material.

There is a method of iodizing films of nickel phthalocyanine with iodine vapor at 100–60 ° C.

The disadvantage of this method is low electrical conductivity (up to 2 Ohm-cm O and poor heat resistance of the product.

A known method for iodination of a finely dispersed polycrystalline powder of copper phthalocyanine in a vacuum of 10 mm Hg. in pairs or melt of iodine at 13-220С and at a ratio of iodine to copper phthalocyanine weights of two. The resulting product is a finely dispersed amorphous powder of the composition CoPc (1) where, 5, with an electrical conductivity of 10 ohm cm and heat resistance in vacuum of 100-200 ° C. Above this temperature, the product decomposes into copper phthalocyanine and iodine.

In a known manner, an amorphous product with an insufficiently high electrical conductivity and heat resistance is obtained.

The aim of the invention is to create a new method of obtaining new iodine-containing phthalocyanines with increased heat resistance, electrical conductivity and size of crystals.

62

The goal is achieved by the described method of obtaining new iodine-containing phthalocyanines of the specified formula, namely,

that phthalocyanine of the formula, where MH, Mg, Fe, Cu, Zn, and iodine are placed in two zones in one closed volume and heated in an inert atmosphere at a pressure of 10 10 mm Hg. while maintaining the temperature of phthalocyanine 540-580 ° C and iodine 70-100 s for 30 minutes at a mass ratio of iodine and phthalocyanine 2-10: 1.

The process is carried out at a temperature at a sublimation temperature of 450-480 ° C. When carrying out the process at temperatures below the sublimation temperature, the product has

low heat resistance (100-200 C). Iodization at 470–540 ° C does not allow obtaining a product of uniform composition, and a rise in temperature in excess of 580 ° C can lead to a partial decomposition of phthalocyanine. The optimum temperature range of the phthalocyanine zone is 540-580 ° C, in which the formation of a uniform target product occurs.

formulas characterized by high heat resistance in vacuum (540-580 ° С) and large size of crystals (10О, 2О, 02 mm). Its conductivity reaches 40

with, 7. Samples of iodine-containing phthalocyanines can also be obtained in the form of thin homogeneous films with a thickness of 1-5 microns. To this end, in the hot zone (540-580 ° C) ampoules

put the substrate of a material that does not react with iodine. To ensure uniformity of the deposited film, the entire substrate must be at the same temperature. The use of a melt of iodine for iodization leads to the preparation of samples in the form of plates, the shape of which is determined by the tube walls.

Example 1. In a clean cylindrical pyrex ampoule with a diameter of 10 mm and a length of 150 mm, 30 mg of phthalocyanine purified in two sublimations in the form of needle-shaped single crystals with dimensions are loaded separately from each other

tO-0.2-0.02 mm (on average) and polycristaptic iodine (60 mg). The ampoule is evacuated to the mercury column, filled with an inert gas to a pressure of 5 G 100 mm Hg, sealed off and placed in an oven. The furnace has separate sections for heating phthalocyanine and iodine. The temperature in the sections is regulated by thermostats with an accuracy of 1C. Phthalocyanine is heated to D0, iodine is heated to 30 minutes. The resulting product has the composition HjiPcIp, which is confirmed by elemental analysis data. Found,%: C 71,22; H 3.35; I 4.72. Calculated,%: C 71.19; H 3.34; I 4.71. The products stand up to a temperature of 540 ° C, the specific electrical conductivity at room temperature b 910 is the activation energy EZ 0.35 eV. The product yield is 30 mg (95.3%). Examples 2-10. Proceed as in example 1. The process parameters are listed in the table. Going beyond the boundaries of the parameters worsens the yield of the product (see Example 6). The structure of the compounds obtained was established on the basis of the following experimental data: elemental chemical analysis (see table); 6 a sharp increase in conductivity (by 10–15 orders of magnitude) of iodine-containing phtapo-cyanines compared to baseline ones; the absence of an intense EPR signal and, therefore, cations (MRs) in diamagnetic iodine-containing phthalocyanines; the appearance of a broad intense absorption band in the middle infrared region, due to the electronic transition between dication (MRc) and neutral molecules (MRc); a decrease in the intensity of the longwave absorption doublet (about 640 and 720 km) with increasing x, which is due to the increase in the proportion of dication (MRc) that do not absorb in this region; the absence of electronic absorption bands in the visible region characteristic of other possible forms of iodine (i ;, i ;, ip. Thus, using the proposed method allows iodine-containing phthalocyanines to be cured with high heat resistance, electrical conductivity in the form of large crystals.

Claims (1)

METHOD FOR PRODUCING IODOSODER-. LIVING PHALOCYANINES, which consists in the fact that the phthalocyanine of the formula MC ₃₂ H _d6 Ng, where M-H ₂ , Mg, Fe, Cu, Zn, and iodine are placed in two zones in one closed volume and heated in an inert atmosphere at a pressure of 10 -10 mmHg. or in . vacuum 10 ² -10 ' ³ mm Hg while maintaining the temperature of phthalocyanine 540-580 ° C and iodine 70-100 ° C for 30 minutes at a mass ratio of iodine and phthalocyanine 2-10: 1. 989021 Γ ^{, υ} AS I