METHOD OF PRODUCTION OF A BRANCHED ORGANOSILICONE POLYMEROUS POLYNUCLEAR ADSORBENT OF HIGH MOLECULAR TOXINS AND THIS ADSORBENT

Abstract

The synthesis of an organosilicone adsorbent, which can be used in medicine as an enterosorbent for the removal of organic and toxic metabolites from the body obtains a new branched organosilicone polymerous polynuclear adsorbent of high molecular toxins. According to the analysis by Si.sup.29NMR method, the adsorbent contains superpositions of at least three silicon signals with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and ratio of their integral intensities close to 2:2:1. This adsorbent has a high adsorption activity, and the synthesis of its obtaining can reduce labour costs, increase output of the target product in manufacture and reduce their self-cost/net-cost.

Claims

1. A method for obtaining of a branched polymerous polynuclear adsorbent of high molecular toxins, according to which the product of the hydrolysis of methyl trichlorosilane of a general formula (CH.sub.3SiO.sub.2Na).sub.n, is subjected to alkaline treatment until completion of the dissolution process, water is added to achieve a concentration of the product of the hydrolysis of methyl trichlorosilane not less than 250 g/l, which according to the analysis by Si.sup.29NMR method, comprises at least three superposition of silicon with values of chemical shifts 18 ppm, 26 ppm, 33 ppm, the product is processed with a solution of strong acid, ensuring formation of hydrogel, which, after completion of the polycondensation process is pulverized and treated with a dilute solution of strong acid, followed by washing with water until the neutral reaction and obtaining of the target product, which has the general empirical formula:
({CH.sub.3SiO(OH)}x.Math.(CH.sub.3SiO.sub.1.5)y.Math.(2H.sub.2O)z).sub.n, where xfrom 0.1 to 0.9; yfrom 0.9 to 0.1; zfrom 1.55 to 2.55, nmore than 2 and which according to the analysis by Si.sup.29NMR method contains superpositions of at least three silicon signals with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and ratio of their integral intensities close to 2:2:1.

2. The method of claim 1, by which after treatment with alkaline till completion of the dissolution process, water is added in ratio 1:0.3-0.4:0.7-2.

3. The method of claim 1, by which treatment with strong acid solution is carried out in a bulk ratio of components 5-10 to 1.

4. The method of claim 1, by which pulverized hydrogel is treated with a dilute solution of strong acid, having temperature not higher than 15 C. and concentration from 0.04 to 0.15 g.Math.equ/1.

5. A composition of branched polymerous polynuclear adsorbent of high molecular compounds of the general empirical formula,
({CH.sub.3SiO(OH)}x.Math.(CH.sub.3SiO.sub.1.5)y.Math.(2H.sub.2O)z).sub.n, where xfrom 0.1 to 0.9; yfrom 0.9 to 0.1; zfrom 1.55 to 2.55, nmore than 2 which is obtained by the method according to paragraphs 1-4 and which according to the analysis by Si.sup.29NMR method contains superpositions of at least three silicon signals with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and the ratio of their integral intensities close to 2:2:1.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0038] FIG. 1 is a graph illustration of infrared spectra confirming the branched organosilicone polymerous polynuclear compound of the invention.

[0039] FIG. 2 shows a graph illustration of analysis by the Si.sup.29NMR method.

DETAILED DESCRIPTION OF THE INVENTION

[0040] According to the claimed invention, in the beginning of the obtaining process of the product of the hydrolysis of methyl trichlorosilane of the general formula (CH.sub.3SiO.sub.2Na).sub.n, is subjected to alkaline treatment until the dissolution process is complete, water is added to achieve a concentration of the product of the hydrolysis of methyl trichlorosilane not less than 250 g/l, which according to the analysis by Si.sup.29NMR method, comprises at least three superposition of silicon with values of chemical shifts 18 ppm, 26ppm, 33 ppm. After, processing of the product is carried out by solution of strong acid, ensuring formation of hydrogel, which, after completion of the polycondensation is pulverized and treated with a dilute solution of strong acid, followed by washing with water until the neutral reaction and obtaining the target product, which has the general empirical formula:

({CH.sub.3SiO(OH)}x.Math.(CH.sub.3SiO.sub.1.5)y.Math.(2H.sub.2)z).sub.n,

where xfrom 0.1 to 0.9; yfrom 0.9 to 0.1; zfrom 1.55 to 2.55, nmore than 2
and which according to the analysis by Si.sup.29NMR method contains superpositions of at least three silicon signals with values of chemical shifts - 80 ppm, - 100 ppm, - 115 ppm, and ratio of their integral intensities close to 2:2:1.

[0041] It is advisable, after treatment with alkaline before completion of the dissolution process, to add water in ratio 1:0.3-0.4:0.7-2, and treatment with a strong acid solution to carry out in a volumetric ratio of components 5-10 to 1.

[0042] In addition, crushed hydrogel can preferably be treated with a dilute solution of strong acid, having temperature not higher than 15 C. and concentration from 0.02 to 0.2 g.Math.equ/1.

[0043] As conducted experiments show, as a result of synthesis at given temperature regime of the reaction mixture, the target product with the following physical and chemical properties, presented in Table 1 with a high sorption capacity to high molecular toxins (toxic agents), is formed.

TABLE-US-00001 TABLE 1 Influence of synthesis temperature on the appearance of the target product and its output Value of temperature of the synthesis Target Target No. of reaction of the product product experiment target product output, % properties 1 35 product has no form 2 30 3 25 30 5 amorphous mass 4 20 60 5 amorphous mass 5 15 70 5 Amorphous mass 6 10 70 5 weakly gel-like mass 7 9.5 78 5 Gel-likr mass 8 8 80 5 Stable gel-like mass 9 7 80 5 stable gel-like mass 10 6 85 5 stable gel-like mass 11 5.5 80 5 stable gel-like mass 12 5 80 5 stable gel-like mass 13 0 80 5 Stable gel-like mass

[0044] Compounds, synthesized according to the claimed method, are also a second aspect of the protection of the present invention.

[0045] Mentioned synthesized compounds have been analysed by Si.sup.29NMR method, for the content of water, silicon, carbon and hydrogen.

[0046] The adsorption activity (A) of the obtained target product has been determined by their ability to absorb Congo red and methyl orange from aqueous solution, as well as high molecular bacterial toxin.

[0047] Determination of the adsorption activity has been carried out according to methods, described in Patent RU 2293744.

[0048] Below, specific Examples of preferred embodiments of the synthesis of the target product with reference to the figure of drawings are given, where FIG. 1 provides experimental IR spectra of dehydrated hydrogels, obtained in accordance with the invention in the frequency range 400-1400.sup.1, where valent fluctuations of groups SiO(Si) are manifested, and FIG. 2data of the analysis of the compound, obtained according to the claimed technique by Si.sup.29NMR method.

Example 1

[0049] 100 liters of water were poured into the reactor and 12 liters of methyltrichlorosilane (MTCS) were added (about 15.24 kg) during stirring for 1 hour. The mixture was stirred for 30 minutes with the aid of a stirrer and then hydrochloric acid was separated by filtration during 15 min. After that, the cycle was repeated. In this process, the reaction mixture was heated to temperature of 60-70 C. The washing of the product, formed as a result of two cycles, was carried out in the same mode until the acidity of washing waters was equal to pH 5.0. 12.4 kg of the product of the hydrolysis of MTCS was obtained (output of about 80% by weight)

[0050] The resulting product of the hydrolysis of trichloromethylsilane was subjected to treatment with alkalinesodium hydroxidenot less than 97% in such a ratio of components' masses: for 1 fractional of the product of the hydrolysis not less than 10 weight fractions of sodium hydroxide until completion of the dissolution process, followed by addition of water to achieve concentration of the product of the hydrolysis of methyltrichlorosilane not less than 250 g/l.

[0051] 31 kg of hydrated product of the hydrolysis of MTCS, containing according to data of Si.sup.29NMR at least 3 types of silicon atoms and characterized by the presence of a superposition of three silicon signals with values of chemical shifts 18 ppm, 26 ppm, 33 ppm, and ratio of their integral intensities close to 2:2:1 is obtained.

[0052] After that, the resulting product was added with a solution of sulfuric acid (not less than 30%) of 3.4 liters. After 1.3 minutes, gel product (sedimentation) was obtained. After pulverizing and washing from acid to neutral washings, 37.2 kg of hydrogel polymeric organosilicone polynuclear adsorbent was obtained, which according to the analysis by Si.sup.29NMR method, comprises superposition of at least three silicon signals with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and ratio of their integral intensities close to 2:2:1.

[0053] The resulting product had a gelled/gel form of almost white colour; not soluble in water and organic solvents; had pH equal to 6.0; dry residue was 8.88%; silicon content was 3.94%; along with that adsorption activity was 3.0 mol/g.

Example 2

[0054] 200 liters of water were poured into the reactor and 25 liters of methyl trichlorosilane (MTCS) (about 31 kg) were added during stirring for 1 hour. The mixture was stirred for 50 minutes with the aid of a stirrer and then hydrochloric acid was separated by filtration for 30 min. After that, the cycle was repeated. In this process, the reaction mixture was heated to temperature of 60-70 C. The washing of the product, formed as a result of two cycles, was carried out in the same mode until the acidity of rinsing waters was equal to pH 5.5. 22 kg of the product of the hydrolysis of MTCS was obtained (output of about 70% by weight)

[0055] The resulting product of the hydrolysis of trichloromethylsilane was subjected to treatment with alkalinesodium hydroxidenot less than 97% in such a ratio of components' masses: for 1 fractional of the product of the hydrolysis not less than 10 weight fractions of sodium hydroxide until completion of the dissolution process, followed by addition of water to achieve concentration of the product of the hydrolysis of methyl trichlorosilane not less than 250 g/l.

[0056] 60 kg of hydrated product of the hydrolysis of MTCS, containing according to data of NMR Si.sup.29 at least 3 types of silicon atoms and characterized by the presence of a superposition of three silicon signals with values of chemical shifts 18 ppm, 26 ppm, 33 ppm, and ratio of their integral intensities close to 2:2:1 is obtained.

[0057] After that, the resulting product was added with a solution of sulfuric acid (not less than 30%) of 5 liters. After 1.5 minutes, gel product (sedimentation) was obtained. After pulverizing and washing from acid to neutral washings, 72.2 kg of hydrogel was obtained from polymerous organosilicone polynuclear adsorbent, which according to the analysis by Si.sup.29NMR method, comprises superposition of at least three silicon signals with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and ratio of their integral intensities close to 2:2:1.

[0058] The resulting product had a softgell form of almost white colour; not soluble in water and organic solvents; had pH equal to 6.3; dry residue was 8.9%; silicon content was 3.90%; along with that adsorption activity was 2.8 mol/g .

[0059] Thus, the indicated method allows to obtain an end- product, of a stabile composition, and which according to the analysis by Si.sup.29NMR method contains superpositions of at least three silicon signals with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and ratio of their integral intensities close to 2:2:1.

[0060] The chemical structure of the obtained branched organosilicone polymerous polynuclear compound is confirmed by infrared spectra, obtained in the frequency range from 400 to 1400 cm.sup.1, given in FIG. 1, which show valent fluctuations of groups SiO(Si), by Si.sup.29NMR method, which made it possible to distinguish between changes in the nature of the environment of resonant silicon atoms, a qualitative reaction to silicon, the method of elemental analysis, which indicates ratio of elements in the structure.

[0061] To show experimentally the structure of the globular matrix of the product, pore solvent water was removed by heating at 130 C. and recorded by IR. IR spectra in range 400-1400.sup.1 were recorded by Shimadzu spectrophotometer.

[0062] The resulting product had a slightly gel/gelled form of almost white colour; not soluble in water and organic solvents; had pH equal to 6.3; dry residue was 8.9%; silicon content was 3.90%; herewith adsorption activity was 2.8 mol/g.

[0063] As can be seen from FIG. 1, the experimental spectrum records three intensive absorption bands at 1003 cm.sup.1, 1132 cm.sup.1 and 1274 cm.sup.1. Frequencies in range 2800-3750 cm.sup.1 relate to valent fluctuations of SiOH groups. The presence in the spectrum of hydroxyl groups indicated the possibility of formation along with chemical bonds, intraglobular bonds. It is known that absorption bands of SiO bonds are in the range 900-1000 cm.sup.1, in three-dimensional absorption structures SiO-bonds are observed in range 1050-1200 cm.sup.1.

[0064] According to the data obtained from the analysis by Si.sup.29NMR method, shown in FIG. 2, the investigated compound contains at least three types of silicon atoms, characterized by the presence of superposition of three silicon signals (d and esynthesized compound, fxerogel of synthesized compound, and bmodel kubanpolymer, which contains a SiOSi dimer as a monomer component and is characterized by a single silicon signal) with values of chemical shifts 80 ppm, 100 ppm, 115 ppm, and ratio of their integral intensities close to 2:2:1.

[0065] Thus, it is confirmed that there is a dependency between the presence of three types of silicon atoms in the basic substance for synthesis of the final product, which indicates polynucleosis and branching, and allows the polymerization reaction to be carried out precisely at the expense of these groups and the structure of the final product (more negative values the chemical shift in comparison with the basic product (the product of the hydrolysis of methyl trichlorosilane) indicate polymerisation). Changes in the concentration parameters of the reaction, starting with the hydrolysis of MTCS, and ending with gel, will lead to a change in the structure of the finished product.

[0066] Studies of infrared spectra of the obtained compounds have been carried out. Frequencies in range 2800-3750cm.sup.1 of infrared spectra relate to valent fluctuations of SiOH groups and indicate the possibility of formation of intraglobular bonds along with the chemical bonds, that confirms the branched globular structure of the claimed compound.

[0067] More over, the globular structure is confirmed by studies in terms of determination of the pore size and specific surface area, and the adsorption activity of benzol, which are shown in Table 2.

TABLE-US-00002 TABLE 2 Capacity for benzol, g/cm.sup.3 Sample No. 1: synthesized organosilicone 0.73 Sample No. 2 synthesized organosilicone 0.83 activated charcoal (control, GOST) 0.46

[0068] The chemical structure of the claimed substance is also proved, using the elemental analysis by method of laser analysis of the elemental composition with the use of LEA-S500 apparatus, the results of which are given in Table 3.

[0069] As follows from Table 3, the proportion of silicon, carbon and hydrogen in the adsorbent according to the invention coincides with the calculated values of these figures. Thus, using the elemental analysis, the chemical structure of the declared adsorbent has been confirmed.

TABLE-US-00003 TABLE 3 Elemental composition of organosilicone sample Element C Si H Found, % 20.0 40.5 5.0 Calculated, % 18.0 41.8 4.5

[0070] Thus, ratio of elements: C 0.49: Si 1: H 0.12 corresponds to the declared empirical formula.

[0071] To confirm affinity of high molecular toxicagens, measurement of the adsorption activity for high molecular substancesimmunoglobulin G (more than 100,000 Da) and bacterial toxin (more than 10,000 Da) was performed.

[0072] The results are shown in Table 4.

TABLE-US-00004 TABLE 4 Comparative experimental data on the study of properties of the prototype and the claimed technical solution Name of indicators Prototype Claimed technical No. compared indicator solution indicator 1 Methylene blue 3.2 mol/g 3.2 mol/g 2 Immunoglobulin G 182.2 mol/g 336.4 mol/g 3 Bacterial toxin 6.22 mol/g 9.13 mol/g

[0073] As follows from the results of Table 4, the branched polymerous polynuclear adsorbent exhibits more signified activity in relation to high molecular compounds and exceeds such activity for the prototype in 1.5-1.83 times.