SU372228A1 - ALL: SOBZZNAYA - Google Patents

Description

one

The invention relates to the synthesis of silicone monomers of the general formula

g: MN, (SNZ), 51K "(

where R and R are alkyl.

Y-aminopronyl triethoxysilane is known to be a good fit. The most convenient method for its preparation is hydrosilylation by addition of hydroalkoxysilanes and alkylhydroalkoxysilanes to allylamine in the presence of hydrochloric acid. However, to obtain satisfactory yields, very long boiling of the reagents is necessary (24-40 hours).

In order to simplify the process, a process has been proposed to be carried out in the presence of unsaturated esters, for example, vinyl ethyl, vinyl butyl, allyl acetate, allyl trifluoroacetate, in an amount of 0.1-5 wt. %

This makes it possible to shorten the duration of the synthesis by 1.5-2.5 times and thereby greatly simplify the method.

Example 1. In a flask with reflux condenser, a thermometer and a dropping funnel, 0.5 ml viil-n-butyl ether, 0.5 ml triethoxysilane and 0.2 ml 0.1 N are placed. solution of HaPtCle in isopropyl alcohol. The mixture heats up and darkens. Then a mixture of 10; 2 g is introduced through an addition funnel.

(0.18 mol) of allylamine and 31 g (0.19 mol) of triethoxysilane, and then the mixture is boiled. After 10 hours, the temperature in the mixture reaches 125 ° C. During distillation, 19 g (47.6%) of uZminopropyltriethoxysilane are obtained, t. Bales. 95-125 ° C / 10 mm Hg. Art., p. 201.4220, d f 0.950.

Example 2. Analogously to Example 1, the mixture was boiled for 12 hours. The temperature in the mixture reaches 130 ° C. 24 g (60.2%) of y-amino-propyl triethoxysilane are obtained.

Example 3. The experiment is carried out according to example 1,

but vinyl ethyl ether is added to the reaction mixture and boiled for 16 hours. The temperature in the mixture reaches 125 ° C. Output

y-aminopropyltriethoxysilane 56.3%.

Example 4. Analogously to example 1, but in the presence of allyl acetate, the mixture is boiled for 16 hours to 125 ° C. The yield of γ-aminopropyltriethoxysilia is 57.5%. Example 5. Analogously to Example 1, but in the presence of allyl trifluoroacetate, the mixture was boiled for 7 hours. The temperature reaches 125 ° C. Shnoiropltrpethoxysilane exit

49.5%.

Example 6. The experiment was carried out as in example 1, but 0.1 ml of vinyl-and-butyl ether was added to the reaction mixture and boiled for 16 hours at 125 ° C. The output of ammoniaopropyltranoxysilane 54.2%. Example 7. Analogously to example 1, but adding 0.2 ml of vinyl-to-butyl ether, the mixture is boiled for 18 hours to 125 ° C. The output of aminopropyltriethoxysilane 47.6%. Example 8. The test was carried out as in Example 1, but taking 1 ml of vinyl n-butyl ether. After 9 hours, the temperature reaches 125 ° C. The output of aminopropyltriethoxysilane 52.5%. After 12.5 hours, yield 67%. Example 9. A mixture of 31 g (0.19 mol) of triethoxysilane, 10.2 g (0.18 mol) of allylamine and 0.2 ml of 0.1 n. A solution of HaPtClg in isopropyl alcohol is heated to boiling. After 24 hours, the temperature in the mixture reaches 120 ° C. The output of aminopropyltriethoxysilane 57%. Example 10. Analogously to Example 9, the mixture was boiled for 16 hours. The temperature in the mixture reaches 102 ° C. The output of aminopropyltriethoxysilane 32.4%. Example 11. In a flask is placed 0.5 ml of vinyl-n-butyl ether, 0.5 ml of tributoxysilane and 0.2 ml of 0.1 n. a solution of HgPtCle in isopropyl alcohol. The mixture heats up. A mixture of 49.7 g (0.2 mol) of tributoxysilane and 10.2 g (0.18 mol) of allylamine is then added via an addition funnel and boiled. After 11.5 hours, the temperature reaches 125 ° C. During distillation, 34.2 g (56%) of Y-aminopropyltributoxysilane are obtained, t. Bale. 135- 137 ° C / 3 mm Hg. Art., p. 201.4318, df 0.9119. Paydeno: MKv 86.86. Calculated: MRn 86.98. Example 12. Analogously to example 10, but without the addition of vinyl - "- butyl ether, the mixture is boiled for 31.5 hours. The temperature reaches 125 ° C. The output of y-aminopropyltributoxysilane 54.3%. Example 13. In a flask is placed 0.5 ml of vinyl-n-butyl ether, 0.5 ml of methyldiethoxysilane and 0.2 ml of 0.1 n. solution of HaPtCU in isopropyl alcohol. The mixture warms up. Then, 10.2 g (0.18 mol) of allylamine and 25.5 g (0.19 mol) of methyldiethoxysilane are added via an addition funnel. After boiling for 12.5 hours, 13.9 g (40.5%) of methyl-α-aminopropyl diethoxysilane are obtained, t. Bale. 60-65 ° C / 2 mm Hg Art., p of 1.4271, df 0.9160. Example 14. A mixture of 10.2 g (0.18 mol) of allylamine, 25.5 g (0.19 mol) of methyldiethoxysilane and 0.2 ml of 0.1N. the solution of PHARCL was boiled for 12.5 hours. The yield of methyl-y-aminopropyldiethoxysilane 5.5 g (16%). Example 15. In a flask with reflux condenser, thermometer and addition funnel, 0.5 ml of allyl glycidyl ether, 0.5 ml of triethoxysilane and 0.2 ml of 0.1 N are placed. P2P1S1b solution in isopropyl alcohol. The mixture warms up. Then a mixture of 10.2 g of allylamine and 31 g of triethoxysilane was introduced through an addition funnel, boiled for 13.5 hours at 120 ° C, kept at this temperature for 0.5 hour and dispersed. The output of aminopropyltriethoxysilane 56%. The subject matter of the invention 1. A method for producing aminopropylalkoxysilanes by adding alkoxysilanes to allylamine in the presence of hydrochloric acid as a catalyst and isolating the desired product by known methods, characterized in that, in order to simplify the process, the process is carried out in the presence of unsaturated esters. 2. A method according to claim 1, characterized in that the unsaturated esters take in an amount of 0.1 to 5 weight. %