SU1595855A1 - Method of producing dihydroxyorganosiloxanes with hydride groups at silicon atom - Google Patents

Abstract

The invention relates to methods for producing α, ω-dihydroxyorganosiloxanes with hydride groups at the silicon atom, which can be used to obtain block copolymers, sealants and modified polyorganosiloxanes used in rocket technology, aircraft manufacturing, electrical and automotive components. The invention allows to simplify the process and reduce its toxicity - eliminating the need to use an organic solvent and toxic pyridine, and there is no stage of washing the target product. α, ω-dihydroxyorganosiloxanes are obtained by co-hydrolysis at 0-10 ° C of methyl dichlorosilane with methyl / 3,3,3-trifluoropropyl / dichlorosilane, taken in an amount of at least 40 mol%, based on the reaction mixture, in the presence of an aqueous solution of sodium carbonate with the subsequent selection of the target product. The optimum concentration of sodium carbonate in the aqueous solution is 7-18%. 1 hp ff, 2 tab.

Description

(21) (22) (46)

it321711 / 23-05 12.08.87

09/30/90. Bul № 36 (72) E.P.Lebedev, G.I. Zayd, S.S.Lukashenko, V., A.Bylyev, A.K.Shakhmaeva, S.V.Avernov and R.A.Zakirov

(53) 678.8it (088.8)

(56) USSR Author's Certificate No. 529182, cl. With G 77/24, 1975 ..

(54) METHOD OF OBTAINING CO-DIHYDRO-XIORGANOSYLOXANES WITH HYDRIDE GROUPS AT SILICON ATOM

(57) The invention relates to methods for producing 0, (0-ligidroxy-organosiloxanes with hydride groups at the silicon atom, which can be used to obtain block copolymers, sealants and modified polyorganosiloxanes used in rocket technology, aircraft manufacturing, electrical engineering and automotive industries. The invention allows to simplify the process and reduce its toxicity - eliminating the need to use organic solvent and toxic pyridine, and there is no target washing step. product. (, ") - Dihydroxyorgano-siloxanes are obtained by hydrolysis at 0-10 ° C of methyldichlorosilane with methyl (3,3,3-trifluoropropyl) dichlorosilane, taken in an amount of at least 40 mol.% calculated on the reaction mixture, in the presence of an aqueous solution of sodium carbonate, followed by isolation of the desired product. The optimal concentration of chatri carbonate in the native solution is 1% fp. table 2.

(L

This invention relates to methods for producing β-dihydroxyorganosiloxanes with hydride groups at the silicon atom, which can be used to obtain block copolymers, sealants and modified polyorganosiloxanes used in rocket technology, aircraft manufacturing, electrical engineering and automotive engineering.

The aim of the invention is to simplify the process and reduce its toxicity.

D1, OZ-Dihydroxyorganosiloxanes (c /, DOS) were prepared as follows.

An aqueous solution of sodium carbonate (NagCO,) is charged to the reactor, while

 taken in an amount of e to provide a 1.2% excess of the calculated amount to neutralize the released hydrogen chloride, and water in an amount to obtain a 7-18% solution. A mixture of methyldichlorosilane (MDHS) and methyl (3,3,3-trifluoropropyl) dichlorosilane (MTFDS), taken in a mass ratio, providing a content in the target product of at least 40 mol.% In - typhtopropyl-: siloxane units. After the completion of the feeding of chlorosilanes, the reaction mixture is stirred for another 30 minutes at room temperature. Hydrolyzate

sd

about sd

00

ate

separated from the water-salt layer and dried over calcium chloride (CaC.1). A transparent, light yellow, odorless product is obtained.

PRI me R 1. In a three-necked flask equipped with a stirrer, cooling, thermometer and addition funnel, load a solution of 61 g Ca2. With Oz. In 280 g of water. When a mixture consisting of 100 g (98.5 mol. o) MTFDS and 0.83 g (1.5 mol.) MDCS is added dropwise while stirring evenly with stirring. After the completion of the dropping, the reaction mixture is over- (kept for another 30 minutes at 25 ° C. After the first hydrolyzate is separated from the water-lobe layer and dried over Ca. 7.3 mm (93%) of the desired product is absorbed. Example 2. Under the conditions of Example 1 to a solution of 13P, 5gMa2COz in 600 g of water, a mixture consisting of 200 g (92 mol) of MTTPHLC and 9.47 g (8 mol.%) MDCS was added dropwise. After the completion of the addition, the reaction mixture was stirred for another 30 minutes at. drying and separation from CaClg gives 150 g (96%) of the desired product,

Example Under the conditions of Example 1, a mixture consisting of 100 g (85 mol.%) Of MTTDS and 9.6 g (15 mol.%) Of MDCS was added dropwise to a solution of 70.9 g in 330 g of water. After the completion of the dropping, the reaction mixture was stirred for another 30 minutes at 25 ° C. After drying, 78.4 g (98%) of the desired product are obtained.

An example. Under the conditions of example 1, a mixture consisting of 100 g (70 mol.%) MTFDS and 23.36 g (30 mol.%) MDHS was added dropwise to a solution of 86.11 g in g of water at 5 ° C. At the end of the addition, the mixture is stirred for another 30 minutes at. After drying, 83.5 g (9b%) of the desired product are obtained.

PRI me R 5 (control). Under the conditions of Example 1, a mixture consisting of 70 g (50 mol.%) Of MTFPACS and 38.15 (50 mol.% MDCS) was added dropwise to a solution of 84 g in 650 g of water at 15 ° C. After the completion of the addition, the mixture was stirred for another 30 minutes After drying, 59.1 g (84.4%) of product are obtained.

PRI me R 6 (control). Under the conditions of Example 1, a mixture consisting of 20 g (30 mol.%) MTFPACS and 25.4 g (70 mol.%) Was added dropwise in 530 g of water at 5 ° C into a solution of 40.12 g of CaO3.

five

0

five

0

35

40

50

MDHS. Upon completion of the addition, the mixture is stirred for another 30 minutes at. 15.47 g (55.2%) of the desired product are obtained.

Example7. Under the conditions of example 1, 50 g (49.25 mol.%) MTFPAC and 0.415 g (50.75 mol.%) MDHS were added dropwise with stirring to a solution of 30.5 g of 138.94 g of water at 5 ° C. At the end of the dropping, the mixture is stirred for another 30 minutes at 25 ° C. 37.1 g (98%) of the desired product are obtained. Example B, CONDITIONS of Example 1, to a solution of 84 g of Na-gCO3 in 1116 g of water was added dropwise a mixture of 70 g (50 mol,%) MTFDS and 38.15 g / 50 mol%) MDHS. At the end of the pack, the mixture is stirred for another 30 minutes at 25 ° C. After drying, 64.63 g (92–3%) of the desired product is obtained.

- Example 9. In the conditions of Example 1, a solution consisting of 70 g (40 mol.%) MTFDS and 57.22 g (60 mol.%) MDHS was added dropwise to a solution of 84.9 g in 765 g of water. Upon completion of the addition, the mixture is stirred for another 30 minutes at. Get 89.2 (94%) of the desired product.

The composition of the obtained products was studied by means of IR spectroscopy, gel chromatographic method (VOers gel chromatograph,), volumetric method, IMC method. The content of hydroxyl groups was determined by the Grignard method. The molecular weight was determined by an ebuliometric method.

I

In all the compounds obtained in Examples 1-9, absorption bands are identified that correspond to the connections:

-SiO - 1050-1080 cm;

-SiCHb - 1250, 790 cm;

-51CH, 1200 cm;

-SiCH i -890;

-SiH - 2180 cm;

-SiOH-825, 870, 3200-3500,

3700 cm

Gelchromatographic data allow us to conclude that the synthesized Oi, C0-DOS are homogeneous and do not contain impurities of the products of separate condensation of the initial monomers. According to the volumetric analysis data, the hydride rpi / nn content at the Si atom in 1P-DOS is in the range of 0.01 to 0.44%.

55

h 51.595855

In tab. Table 1 lists the conditions for the preparation and, SO-DOS in examples 1-9, and Table 2 shows their properties.

The method does not require the use of the following selection of the target product, characterized in that, in order to simplify the process and reduce its toxicity, as a fluororg 7 - - "- - f t V iv -fvi-xl X IFIl b. ID f I Ci

methyl solvent (3.3,38 of the target product,

Claims (2)

1. The method of obtaining h, 63-dihydroxy organosiloxanes with hydride groups at the silicon atom with hydrolysis at 0-1 ° C methyldichlorosilane with fluorine-anodichlorosilane in the presence of a hydrogen chloride acceptor with trifluoropropyl) dichlorosilane in an amount of at least kO Moldova calculated per reaction mixture, and as JO of the hydrogen chloride acceptor is an aqueous solution of sodium carbonate. 2. The method according to claim 1, characterized in that, in order to ensure effective separation of the organic layer, 7-18% is used. an aqueous solution of sodium carbonate. Partial gelation. the following isolation of the target product, characterized in that, in order to simplify the process and reduce its toxicity, as fluorine ft V iv -fvi-lllX X IFIl b. ID f I Ci nodichlorosilane using methyl (3.3,3 dichlorosilane use methyl (3.3,3 trifluoropropyl) dichlorosilane in an amount of at least kO mol per the reaction mixture, and as hydrogen chloride acceptor - an aqueous solution of sodium carbonate. 2. A method according to claim 1, characterized in that, in order to ensure effective separation of the organic layer, 7-18% is used. an aqueous solution of sodium carbonate. Table 1 Spreadsheets  The massar molecule is determined by an ebuliometric method. Continued table. 2