SU857170A1 - Method of producing modified oxide filler - Google Patents

Description

I

The invention relates to the production of modified oxide fillers based on mixed oxides TiO2 SiO2 modified with organic core fillers, which can be used as pigments and thickeners in paint and varnish materials and lubricants, as well as fillers for silicone rubbers.

A known method for producing a modified OXYGEN filler by the interaction of silicon-containing oxide — silicon dioxide with organochlorosilane or aminoethoxyorganosilane L5 j “

The disadvantage of lime 1x fillers is their low thickening ability when used as thickeners for lubricants and paints and varnishes and low opacity in pigment coatings.

The purpose of the invention is to increase the thickening properties of the filler and

improvement of hiding power when receiving pigment coatings based on it. This goal is achieved by obtaining a highly dispersed Ti02 SiO oxide with a T: Si ratio of (1: 4) - (1: 100) as a silicon oxide containing organochlorosilane or aminosulfioxyorganosilane when preparing a modified OXYGEN filler by reacting silicon-containing oxide.

Smetana oxide-S1 O get. by hydrolysis of a homogeneous mixture of vapors of titanium tetrachloride and silicon tetrachloride in an air-hydrogen flame. This forms a highly dispersed product containing S.I-0-TI titanosiloxane groups. with a specific surface of 125-240 m / g

The presence of titanosiloxane bonds is confirmed by the absorption band 950 of the IR spectrum of the oxide. The intensity of the absorption band depends 3 on the ratio of Ti / Si, which is regulated by the ratio of silicon and titanium chlorides in the mixture, of the vapors fed to the hydrolysis. This ratio is in the range of 1/1 to 1/100, which makes it possible to obtain a titanosiloxane oxide with a Ti / Si ratio adjustable in the range, advantageously about 1/4 to 1/100. The resulting mixed oxide is treated with vapors of organosilicon compounds, ds replacing hydroxyl groups, HMeronoiXCH on the surface of the oxide, to organosilicon groups. Replacement completeness is controlled according to IR spectra. As organosilicon compounds using dimethylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane or aminophenylmetry lendiethoxysilane. The preparation of the modified oxide fillers is carried out in the following sequence. A mixture of titanium chloride and vapor vapors is fed to the burner together with hydrogen and air. At the exit of the burner in a high-temperature flame, hydrolysis of the chlorides produces a mixed oxide Ti02 which is caught by the cyclone. The mixed oxide is loaded into a reactor equipped with a stirrer and electric heating. At the appropriate temperature (20-320 ° C), vapors of the organosilicon compound are fed into the reactor in a stream of nitrogen. The unreacted silane vapor, together with the hydrogen chloride formed in the reaction results, is removed in a stream of nitrogen. Water vapor is fed to the reactor to hydrolyze the residual S1C1 bonds. The drying of the final product and the final removal of gaseous products is carried out at a temperature of 200-40 sPc. The thermal and hydrolytic stability of the silicon-modifying organic groups is estimated by the change in the IR spectra of the modified oxides after heat treatment and boiling in water. Example I. A mixed oxide obtained by the hydrolysis of the removal of titanium chloride and silicon (SICl 1/115) in an air-hydrogen flame is treated with dimethyldi / chlorosilane vapors, taken in an amount of 18 wt.% In nitrogen at 20-2 04 After removal of unreacted Chlorosilane vapor product is treated with water vapor for hydrolysis of residual SiCl bonds and heated at. In the final product, the Ti / Si ratio is 1/100, which is explained by a lower, conversion of SiCl4B oxide, compared to TICK. In the IR spectrum of the product, there is an absorption band of 950 cm, corresponding to the Ti-0-Si titanosiloxane bond, and an absorption band of 2980 cm, respectively; corresponding methyl groups. The product is heat resistant to 380-390 ° C. in the air and up to 540–550 ° C in a nitrogen atmosphere, hydrolytically stable by boiling in water for 50 hours, the splitting off of the orgs groups does not occur. The specific surface area of the obtained modified mixed oxide was 240, the content of the organic part was 3.7 May,%. Example 2. A mixed oxide obtained by hydrolyzing a mixture of silicon chloride and titanium vapor (T Cl4 / SiCl1 1/23) in an air-hydrogen flame is treated at a temperature in a nitrogen atmosphere with methyl chlorosilane vapor, taken in an amount of 15% by weight of oxide. After stripping off the unreacted chlorosilane vapor, the product is treated with water vapor to hydrolyze the residual SiCl bonds and is heated under nitrogen at 300 ° C for one hour. In the final product, the Ti / Si ratio is 1/20. In the IR spectrum of the product, an absorption band is observed, 950 cm, corresponding to the TiOSI titanosiloxane bond, and an absorption band of 2890 cm, corresponding to methyl groups. The product is heat-scrubbed up to 400 ° C in air and up to 550 ° C in a nitrogen atmosphere, hydrolytically stable at boiling water in water for 50 hours. The specific surface of the oxide obtained, the organic part content is 3% by weight. Example 3. Mixed oxide obtained} B | 1Y by hydrolysis of a mixture of titanium chlorides "a and silicon (Ti / Si 1/64) in an air-hydrogen flame, treated with trim1 tylchlorosilane vapor at a temperature of 70-75 C in the atmosphere

five .

nitrogen. Consumption of trimethylchlorosilane 12 wt.%.

Removal of unreacted vapors of silane and hydrogen chloride carried out by cr- at a temperature. In the final product, the Ti / Si ratio is 1/55.

In the IR spectrum of the product, there is an absorption band of 950, corresponding to the titanosiloxane bond of j TiOSi, and an absorption band of 2980 cm, corresponding to methyl groups.

The product is thermally stable up to air and up to 530 under nitrogen, hydrolytically stable by boiling in water for 50 hours. The surface area of the obtained oxide is 190 m / g, containing organic parts of 4.2 wt.%.

Example 4. A mixed oxide obtained by hydrolysis of a mixture of silicon chloride and titanium chlorides (1/12) in air-hydrogen flames is treated with diphenyldichlorosilane vapor at 320 ° C in a nitrogen atmosphere. The consumption of diphenyldichlorosilane 20% by weight of oxide. After removal of unreacted silane vapors, the product is treated with vapor water | to hydrolyze the residual SiCl bonds and heat in an azo / ta atmosphere at 300 ° C for an hour. In the final product, the Tl / Si ratio is 1 / 10.4.

In the infrared spectrum of the product, there is an absorption band of 950 absorption bands in the region of 3000-3100 cm, characteristic of the C – H stretching vibrations of the phenyl ring.

The product is heat resistant up to 500 C / in the air and up to 600 C in a nitrogen atmosphere, hydrolytically stable at

70 "

boiling in water for 20 hours. The surface area of the obtained oxide is 160 mog, the organic content is 5.8 wt.%.

Example 5. A mixed oxide obtained by hydrolysis of a mixture of titanium and silicon (TICl4 / SiC ij 1 / 4.8) is treated with pairs of aphenylmethylenemethyldiethoxysmane vapor under nitrogen at a temperature of 2 hours, followed by removing the silane vapor and heating the product at 1 h. Consumption of silane 30% by weight of silane. The ratio Ti / Sl in the final product is 1/4.

In the IR spectrum of the product, along with a band of 950 cm, there are bands at 3430 cm corresponding to the vibrations of the N – H bond, in the region of SOE2800, belonging to the C – H bonds of the methyl, methylenose, and phenyl groups.

The product is thermally stable up to 200 ° C in air and under a nitrogen atmosphere, hydrolytically stable by boiling in water for 120 hours. The specific surface area of the obtained oxide is 125, the organic content is 4.7 wt.%.

The thickening ability of the fillers is evaluated by the kinematic viscosity of 5% suspensions of the fillers in n-butyl alcohol, and measured on the VIS-1 viscometer. Investigate the modified filler obtained in example 2 (the ratio of 11: Si is equal to ISO), as well as aerosil with a specific surface of 175 m / g n Methyl Aero (the product of the treatment of Aerosil with dimethyldichlorosilane). The results of the analysis are shown in Table I.

Table

Modified 4.46. 6.44 oxide 4.29 4.53 Aerosil 3.89 4.29 Methyl Aero 10.0 14.43 22.08 5.24 8.11 9.85 5.12 5.95 8.04 7 From the table it can be seen which thickens the ability of the modified naphtha on the basis of a mixed oxide to be substantially higher than for aerosil n methylaosyl. The hiding power of various samples of modified mixed oxides is determined by comparison with the hiding power in the coating composition, including the following components, m.ch.: Test material 5,0 Chevno-formaldehyde resin brand K-411-021,5 Polyvinyl butyral Mar LA 0.5 Ethanol 40,0 These coatings are used, for example, to make a bleaching layer of magnetic paper.

Modified mixed

The test results show that the modified mixed oxides make it possible to create high-quality coatings with a minimum mass and

thickness.

table 2

Thus, the proposed method makes it possible to obtain a modification of fillers based on mixed oxides TiOjj-SiO, possessing increased thickening properties. Suspension coatings are prepared by dispersing its components in a laboratory ball mill for 5 hours. Then the suspensions are applied on black paper on a laboratory irrigation installation. During coating, a successive decrease in their mass is carried out by diluting the suspensions with alcohol. After fabrication and drying of samples of coatings, their colorimetric characteristics are measured on an ND-K6 color meter, a shading value of D E is calculated with respect to a white color meter standard, and the minimum thickness and weight of coatings are determined, providing a shading value of no more than 4-6 NBS units, which is corresponds to the minimum threshold of the eye sensitivity of the average observer, Table 2 shows the characteristics of the tested samples and the results of the tests.

and improved hiding power when receiving pigment coatings.

Claims (1)

1. Debt. et al. Siliconic liquid rubber and materials based on them. L., Khimi, 1975, p.35 (prototype).