1654
BELYAKOVA et al.
By the method of stopped flow [19, 20] we
was added dropwise 17.7 g of a solution of ethanol in
23 ml of solvent, and heating was continued. Then
from the mixture was distilled off the solvent with
hydrogen chloride until the temperature in the vapor
raised to 61°C. With ethyl formate the following
mixture was obtained (%): 15 ethyl formate, 20 etha-
nol, 3.7 vinyl-diethoxychlorosilane, 55.6 vinyltri-
ethoxysilane and 5.7 siloxanes. With methyl acetate
was obtained a mixture (%): 3.5 acetyl chloride, 11.4
methyl acetate, 11.6 ethanol, 6.4 vinyltrimethoxy-
silane, 19.6 vinyldiethoxychlorosilane, 44.5 vinyltri-
ethoxysilane and 3.7 siloxanes.
investigated the etherification of methyltrichlorosilane
and γ-methacryloxypropyltrichlorosilane with methyl
alcohol. We measured the rate constants of reactions of
MeSiCl3 and γ-methacryloxypropyltrichlorosilane with
methanol for the limiting stage of etherification, the
reaction (4) at 22°C. They are equal to 6.1 and
12.4 l mol–1 s–1, respectively. The rate constant for the
reaction of MeSiCl3 with ethanol, determined for the
limiting stage of etherification, the reaction (4), at 20°C,
is equal to 2.20 l mol–1 s–1 [1]. Thus, the reaction rate
constant of MeSiCl3 with MeOH is 2.8 times higher
than with EtOH.
Investigation of the kinetics of etherification by the
stopped flow method was carried out along the
technique [19].
EXPERIMENTAL
The GLC analysis of the reaction products is
carried out on a LKhM-72 chromatograph with a
detector on thermal conductivity. Solid carrier is
Chromaton N, stationary phase is PMS-20000 on
Chromaton N (15 wt % of the sobent). The column
2000×4 mm, the temperature of evaporator 390°C, of
detector 300°C, of column 40–200°C, the programmed
rate heating is 15 deg min–1. Carrier gas helium, flow
rate 60 ml min–1.
Reaction of vinyltriethoxysilane with dry HCl. Into
vinyltriethoxysilan containing 55.7% of vinyltri-
ethoxysilane, 5.7% of ethanol and 35% of siloxanes
was passed for 10 minutes dry HCl, the color of the
solution changed from colorless to orange, but after
2 days the mixture darkened. The mixture obtained had
the following composition (%): 17.7 vinyltriethoxy-
silane, 16.2 vinyldiethoxychlorosilane, 28.8 alcohol
and 30% siloxanes.
Etherification of methyltrichlorosilane in vapor
phase was carried out in a heated reactor equipped
with a receiver, a condenser and two evaporators.
Reagents were dosed from dropping funnels.
REFERENCES
1. Utkin, O.V., Pavlova, N.V., Kolobkov, V.S., and
Vasil’ev, O.A., Zh. Prikl. Khim., 1986, vol. 53, no. 3,
p. 653.
The influence of temperature, of reagents ratio, and
of iron chloride on the process of etherification was
carried out as follows. The synthesis was carried out in
a low-temperature bubbling apparatus of periodic
operation designed as a cylinder divided inside into
two section by a horizontal fluoroplastic plate with
holes (2% of its area), equipped with a jacket for
heating. In the lower part there was an input for dry
nitrogen. The rate of nitrogen flow in the apparatus is
0.5 m s–1. The upper part was fitted with a contact
thermometer, a reflux condenser cooled by dry ice
with acetone, and a dropping funnel. In the current of
nitrogen, to the chlorosilane loaded into the apparatus,
for 4–5 min was added ethanol from the dropping
funnel. Sampling was carried out from the apparatus
by capillary microsyringe each 5 min. The con-
centration of components was determined by GLC.
2. Kolobkov, V.S. and Utkin, O.V., Zh. Prikl. Khim., 1981,
vol. 54, no. 3, p. 671.
3. Andrianov, K.A., Metody elementoorganicheskoi
khimii. Kremnii (Methods in Organoelement Chemistry.
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13.Khananashvili, L.M., Vardosanidze, Ts.N., Makarash-
vili, E.G., Savushkina, V.I., and Lomtatidze, Z.Sh.,
The etherification of vinyltrichlorosilane with
distilling off boiling solvent was carried out by the
method described previously [16]. To the solution of
20 g of vinyltrichlorosilane in 14 ml of solvent at 40°C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 8 2009