RU2709106C1 - Method of producing poly(organo)(hydroxy)siloxanes with a given degree of polycondensation - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to chemistry and technology of producing poly(organo)(hydroxy)siloxanes with given degrees of polycondensation. Disclosed is a method of producing poly(organo)(hydroxy)siloxanes of general formula {[RRSiO][RSiO][OH]} with a given degree of condensation of "n" organo-trialkoxysilane, where a=0.3–0.8 is molar number of difunctional links; b=0.1–0.2 – molar amount of trifunctional links, c=0.1–0.132 – molar amount of OH groups, including acidohydrolytic copolycondensation of individual organotrialkoxysilanes or mixtures thereof of general formula RSi(OR)with one or mixture of diorganocyclosiloxanes of general formula [RRSiO], where m=3–6, where R=CH, CH; R=CH; R=R=CH, CH, CHF, CH, in molar ratio of reagents RSi(OR): RRSiO-link=1:2÷5, glacial acetic acid taken in an amount required to provide an "n" condensation degree on organo-trialkoxysilane not greater than 0.833, in the presence of catalytic amounts of concentrated sulfuric acid from 1.7 to 3.1 wt%, wherein the process is carried out at temperature of 85÷100 °C for 2–3 hours with subsequent stepwise increase of temperature of mixture to 120 °C with distillation of alcohol and its acetate to achieve a given organo(trialkoxy)silane condensation, returning the distilled products to the cooled reaction mass, adding demineralized water in an amount calculated by the equation m=yƒ-2x, (where m, y, x is molar quantity of water, alkoxysilane and acetic acid respectively, ƒ – functionality of alkoxysilane), required for complete hydrolysis of alkoxy groups, followed by neutralization of reaction mass, filtration of mixture and removal of volatile substances, wherein output of poly(organo)(hydroxy)siloxanes is not less than 97.8 wt%.EFFECT: disclosed method is easy to implement and environmentally friendly, and the obtained poly(organo)(hydroxy)siloxanes are used for processing molds to simplify extraction of articles from seats in the bus and polymer industry.4 cl, 8 ex

Description

The claimed invention relates to chemistry and technology for producing poly (organo) (hydroxy) siloxanes [D _a T _b (O _0.5 H) _c ] with predetermined degrees of polycondensation, where a = 0.3-0.8 is the molar amount of difunctional units ; b = 0.1-0.2 is the molar amount of trifunctional units, c = 0.1-0.132 is the molar amount of OH groups. The scope of such polysiloxanes is extensive and is determined by the ability of the ≡SiOH groups contained in their composition to thermally and / or catalytically condense with each other with the formation of thermo-, water- and chemically resistant polymers. Poly (organo) (hydroxy) siloxanes cured in a thin layer form polymer films with high release properties, which is why they are used for processing molds in the tire and polymer industries to simplify removal of products from nests.

Poly (organo) (hydroxy) siloxanes also readily enter the condensation reaction with various organic oligomers to form block copolymers, thereby increasing their thermal, water, light and chemical resistance.

In 1949, USSR author's certificate No. 77924 was obtained (IPC C08G 83/04, B29C 33/64, 1949) which proposes a method for producing lubricants for vulcanization forms, which are emulsions of silicone oils in water. Silicone oil is obtained by hydrolysis of a mixture of methylchlorosilanes resulting from the interaction of methyl chloride with silicon with aqueous solutions of alcohols or acetone. For the preparation of silicone oil, both the entire mixture of methyl chlorosilanes formed and its individual fractions can be used. When the emulsion is applied to the hot surface of the mold, water evaporates, and oil inert to rubber forms a thin liquid protective film on the metal surface of the mold, which prevents the product from vulcanizing to the mold.

The formation of a large amount of hydrogen chloride during the hydrolysis of chlorosilanes is the most significant drawback of this method; in addition, additional special processing equipment is required to remove and neutralize hydrogen chloride. And to wash silicone oil to a neutral environment, you need to use a huge amount of water, usually 8-10 times the size in relation to the oil.

A known method of producing polysiloxanes with alkoxyl terminal groups by the interaction of dialkyl and / or diarylcyclotrisiloxanes and / or tetrasiloxanes and / or dimethyldichlorosilane hydrolyzate with diorganodi and / or organotrialkoxysilanes and / or hexaalkoxysilysilane C at a temperature of 50-200 ° C. Potassium silanolate, potassium and sodium hydroxides, potassium methoxide and butoxide, tertiary amines and tetramethylammonium hydroxide were used as a polymerization catalyst. The molar ratio of alkoxy to siloxane varies from 1: 1 to 1: 100 (GB Patent No. 792470, IPC C08G 77/00, 1958).

There is also a method for producing linear and branched polydiorganosiloxanes with alkoxy groups at the ends by copolymerization of diorganocyclo-siloxanes with diorganodi and / or organotrialkoxysilanes, respectively, at a temperature of 150 ° C for 5 hours in the presence of a potassium dimethylsilanolate catalyst (US Patent No. 290074949 M, / 08, C08G 77/00, C08G 77/045, C08G 77/18, 1959).

The disadvantages of these methods include:

- the formation of low molecular weight products due to the cleavage of diorganocyclosiloxanes up to diorganodialkoxysilanes, the removal of which requires a distillation step, which reduces the yield of the target product - polydiorganosiloxane with alkoxy groups at the ends;

- the increased content of alkoxy groups in such polydiorganosiloxanes makes their thermal curing impossible, which significantly narrows the scope of their application.

In patent RU No. 2524342 (IPC C08G 77/06, C08G 77/18, C08G 77/16, 2014) we proposed a method for producing poly (organo) (alkoxy) - (hydroxy) siloxanes with a given degree of polycondensation (n≤1) acidohydrolytic polycondensation (AGPK) of individual alkoxy (organo) silanes or mixtures thereof. The equations for calculating the amount (x) of carboxylic acid necessary for the synthesis of poly (organo) -hydroxysiloxane (n <1), polyorganosiloxane (n = 1) and poly (organo) alkoxysiloxane (n <1) are given. For the synthesis of poly (organo) alkoxysiloxane with a value (n <1) from an individual alkoxy (organo) silane or a mixture of monomers with the same functionality (ƒ), the equation has the form - x = n⋅ƒ⋅y / 2, where x is the molar amount of carbon acid, y is the molar amount of alkoxysilane.

A known method of producing thermosetting homofunctional polycondensation of oligo- and polyelementoorganospirocyclosiloxanols with a uniform distribution of Q- and D-units and a high degree of polycondensation n≥90%, which synthesize acidohydrolytic copolycondensation (AHPC) of one of the tetraalkenes of Si or Si (tetraalkoxides) or mixtures thereof with an individual diorganodialkoxysilane (source of the D-link) and / or with individual diorganocyclosiloxane (the source of the D-link) and / or their mixtures in the presence of a catalyst - one of the strongest mines eral acids (Patent RU №2647586, IPC C08G 77/06, C08G 77/08, C08G 77/16, C08G 77/58, 2017), which is accepted by us as a prototype.

However, oligo- and polyelementoorganospirocyclosiloxanols [D _x Q (O _1/2 H) _y ] _z have rigid structures and are used only for impregnation of porous materials and cannot be used as release agents and coatings.

The objective of the present invention is to develop a universal technologically simple and environmentally friendly method for producing poly (organo) (hydroxy) siloxanes [D _a T _b (O _1/2 H) _c ] with specified degrees of polycondensation "n" not exceeding 0.833 from available raw materials possessing high stability during storage and reproducibility of physico-chemical properties. As the source of the trifunctional unit T, individual organotrialkoxysilanes or a mixture of the general formula R ¹ Si (OR ² ) _{3 is used} , as the source of the difunctional unit D, individual diorganocyclosiloxanes or a mixture of the general formula [R ³ R ⁴ SiO] _m , where m = 3 -6; R ² = CH ₃ , C ₂ H ₅ ; R ³ = CH ₃ ; R ¹ = R ⁴ = CH ₃ , C ₂ H ₃ , C ₃ H ₄ F ₃ , C ₆ H ₅ .

To solve this problem, a method for producing poly (organo) (hydroxy) siloxanes of the general formula {[R ¹ R ² SiO] _a [R ³ SiO _3/2 ] _b [O _1/2 H] _c } with a given degree of condensation by organotrialkoxysilane is proposed "N", where a = 0.3-0.8 is the molar number of difunctional units; b = 0.1-0.2 - the molar amount of three functional units, c = 0.1-0.132 - the molar amount of OH groups, including acidohydrolytic copolycondensation of individual organo-trialkoxysilanes or their mixtures of the general formula R ¹ Si (OR ² ) ₃ with one or a mixture of diorganocyclosiloxanes of the general formula [R ³ R ⁴ SiO] _m , where m = 3-6; R ² = CH ₃ , C ₂ H ₅ ; R ³ = CH ₃ ; R ¹ = R ⁴ = CH ₃ , C ₂ H ₃ , C ₃ H ₄ F ₃ , C ₆ H ₅ , with a molar ratio of reagents R ¹ Si (OR ² ) ₃ : R ³ R ⁴ SiO link = 1: 2 ÷ 5, glacial acetic acid, taken in the amount necessary to ensure the degree of condensation "n" on organotrialkoxysilane, not exceeding a value of 0.833, in the presence of catalytic amounts of concentrated sulfuric acid from 1.7 to 3.1% of the mass., The process being at a temperature of 85 ÷ 100 ° C for 2-3 hours, followed by a stepwise increase in the temperature of the mixture to 120 ° C with distillation of alcohol and its acetate to achieve a predetermined organol condensation ialcoxysilane, by returning the distilled products to the cooled reaction mass, by adding demineralized water in an amount calculated according to the equation m = уƒ-2х (where m is the molar amount of water, у is the molar amount of alkoxysilane, x is the molar amount of alkoxysilane, ƒ is the functionality of alkoxysilane ), necessary for the complete hydrolysis of residual alkoxy groups, subsequent neutralization of the reaction mass with excess calcium carbonate, filtering the mixture, and removing 50 mm volatile in a vacuum. Hg at a temperature of not more than 50 ° C from the target product, while the yield of poly (organo) (hydroxy) siloxanes is at least 97.8% of the mass. and their actual value of the degree of condensation "n ¹ " is calculated by the equation n ¹ = 1-m ¹ / уƒ, where m ¹ is the molar amount of hydroxyl groups in the product, determined by Fischer titration.

The process is carried out as follows: in a flask equipped with a stirrer, a thermometer, a reflux condenser, an individual organotrialkoxysilane or a mixture of organotri-alkoxysilanes and an individual organocyclo-siloxane or a mixture of organocyclo-siloxanes are used at a molar ratio of reactants R ¹ Si (OR ² ) ₃ : R ³ R ⁴ SiO-unit = 1: 2 ÷ 5 and carboxylic acid in an amount calculated according to the equation given by us in RU patent No. 2524342, according to which (x = n⋅ƒ⋅y / 2), where x is the molar amount of carboxylic acid, y is the molar amount of alkoxysilane , n - step polycondensation, ƒ - alkoxysilane functionality. It is known that the degree of polycondensation "n" is determined by the amount of organic acid taken into the reaction, which in turn significantly affects the quality of the final polymer product. Thus, organotrialkoxysilanes under the conditions of controlled hydrolytic polycondensation (AGPK) form soluble and subject to further processing polyorganosilsesesquioxanes exclusively with their degree of polycondensation n≤0.833. With a higher degree of polycondensation, unstable products are formed that are prone to gelation (Abstract of dissertation for the degree of Candidate of Chemical Sciences. Controlled acid-hydrolytic polycondensation of alkoxy (organo) silanes and siloxanes. A.G. Ivanov, M., 2013). Based on this, a prerequisite in the claimed process for the production of poly (organo) (hydroxy) silanes is the choice of such an amount of organic acid that the degree of polycondensation "n" on organotrialkoxysilane does not exceed 0.833, given that diorganocyclo-siloxane already has a degree of condensation (n = 1) .

The process is carried out in the presence of catalytic amounts of concentrated sulfuric acid (1.7 ÷ 3.1% wt.)

At the first stage, under the action of the catalyst at a temperature of 85 ÷ 100 ° C for 2-3 hours, the opening of diorganocyclosiloxane and partial condensation with trifunctional alkoxysilane occurs. To achieve a given degree of condensation (n≤0.833), the ester and alcohol formed during AGPA are distilled off by organotrialkoxysilane, and a further temperature rise to 120 ° C is carried out stepwise with a temperature step of 5 ° C, increasing the temperature to the next stage as the distillation ceases. The product obtained at this stage is a poly (organo (alkoxy) siloxane of the general formula [D _a T _b (O _0.5 R ⁴ ) _c ] or {[R ¹ R ² SiO] _a [R ³ SiO _3/2 ] _b [O _1/2 R ⁴ ] _c }.

Then, the distilled fraction is completely returned to the reaction mixture, cooled to 30 ° С, distilled water is added in an amount necessary for complete hydrolysis of the residual alkoxy groups, which is calculated by the obtained equation m = уƒ-2х (where m is the molar amount of water) mix for 2 hours, turn off the stirrer and stand for 12 hours. At the end of the exposure, add a seven-fold molar excess of chalk in relation to the amount of sulfuric acid and mix until it is completely neutralized for 2 hours. After which the reaction mass is filtered, the ester with alcohol is removed from the filtrate in a rotary evaporator at a temperature of not more than 50 ° C under a vacuum of 50 mm. Hg and get poly (organo (hydroxy) siloxane [D _a T _b (O _0.5 H) _c ] or {[R ¹ R ² SiO] _a [R ³ SiO _3/2 ] _b [O _1/2 H] _c }, with a given degree of polycondensation by organotrialkoxysilane n≤0.833. To ensure that the hydrolysis of the alkoxy groups was complete and the formed silanol groups did not undergo condensation, which leads to an increase in the degree of condensation of poly (organo (hydroxy) siloxane, a control analysis is carried out to determine molar amount (m ¹ ) of hydroxyl groups in the product by Fischer titration, based on which its fact is calculated the natural degree of condensation "n ¹ " according to the equation n ¹ = 1-m ¹ / yƒ.

The composition of the obtained poly (organo (hydroxy) siloxanes and distilled products is studied by GLC, ¹ H NMR and ²⁹ Si spectroscopy.

The gelation time of poly (organo (hydroxy) siloxanes is determined on a polymerization tile at a temperature of 200 ± 3 ° C.

Implementation of the proposed synthesis method:

- provides a high yield of poly (organo (hydroxy) siloxanes, not less than 97.8% of the mass .;

- provides high stability of poly (organo (hydroxy) siloxane during storage and uniform distribution of D- and T-links in it;

- makes it possible to adjust the gelation time of poly (organo (hydroxy) siloxane, which depends on its degree of condensation;

- eliminates the use of solvent and water for washing.

The high stability of the poly (organo (hydroxy) siloxane in the proposed method is due to the use of the calculated amount of organic acid in the synthesis to ensure the degree of condensation of organotrialkoxysilane n≤0.833, previously described by us (patent RU No. 2524342), and the estimated amount of water required for the complete hydrolysis of alkoxy -groups in poly (organo) (alkoxy) silane with the aim of converting it into poly (organo (hydroxy) siloxane, according to the equation m = уƒ-2х. To evaluate the completeness of the hydrolysis reaction, the formula n ¹ = 1-m ¹ / yƒ is given for defined Nia actual degree of condensation of poly (organo (hydroxy) siloxane of organotrialkoxysilanes, which depends on the molar amount of the hydroxyl groups of (m ¹⁾ in the product is determined by titration according to Karl Fischer.

The advantage of the proposed method for producing poly (organo- (hydroxy) siloxanes is the possibility of using methyltriethoxysilane as a cheap available feedstock - a waste product of methylsilane production (source of the T-unit), and methylphenylcyclosiloxanes (source of the D-unit) obtained by AGPH of methylphenyl diethoxysilanes, which are also synthesized based on the waste methyltriethoxysilane and chlorobenzene by the Grignard reaction.This not only reduces the cost of the product, but also solves the problem of the practical disposal of waste tonnage production wah.

A detailed description of the method is given in the following examples:

Example 1

35.6 g (y = 0.2 mol) of MeSi (OC ₂ H ₅ ) ₃ , 29.6 g (0.1 mol) (Me ₂ SiO) ₄ , 15.0 g (x = 0.25 mol) are loaded into a flask equipped with a stirrer, thermometer, reflux condenser ) glacial acetic acid (the required amount for the condensation of MeSi (OC ₂ H ₅ ) ₃ to the degree of 0.833), 1.36 ml of 94.7% sulfuric acid (0.024 mol of H ₂ SO ₄ ) and the reaction mixture is heated to 85 ° C. After stirring at this temperature for 2 hours, the volatile products are distilled off - 33.5 g, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° C, 1.8 g (m) of demineralized water are added, calculated according to the equation m = yƒ-2x, stirred for 2 hours and kept for 12 hours without stirring. At the end of the exposure, 16.8 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (38.04 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and obtain 42.9 g of a clear liquid, a poly (methyl) (hydroxy) siloxane. The yield of 97.8% of the mass. According to a study of the compositions of the distillate and the product by GLC, it was found that the distillation contains 57.62% of the mass. ethyl acetate, 42.14% of the mass. ethanol and 0.24% of the mass. water, and the product is 5.3% of the mass. (Me ₂ SiO) ₄ . NMR ¹ H-spectroscopy registers a trace amount of SiOC H ₂ CH ₃ (δ = 3.74 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts of Me ₂ Si O- (δ = -19.82 and -22.43 ppm) and Me Si O _3/2 - (δ = -57.21 ÷ -59, 13 ppm), the ratio of the values of their integrated intensities is 2. The average composition of the product, determined by the integrated intensities of chemical shifts (δ) of these silicon atoms and the result of Fischer titration, has the form: [Me ₂ SiO] _0.4 [MeSiO _{3 / 2} ] _0.2 [O _1/2 H] _0.1 or [D _0.4 T _0.2 (O _0..5 H) _0.1 ], and the degree of polycondensation by organotrialkoxysilane n ¹ = 0.833. Gelling time is 17 minutes.

Example 2

17.8 g (y = 0.1 mol) of MeSi (OC ₂ H ₅ ) ₃ , 40.8 g (0.1 mol) of [PhSi (Me) O] ₃ , 6 are charged into a flask equipped with a stirrer, thermometer, reflux condenser. , 0 g (x = 0.1 mol) of glacial acetic acid (the necessary amount for the condensation of MeSi (OC ₂ H ₅ ) ₃ to the degree of 0.667), 1.02 ml of 94.7% sulfuric acid (0.018 mol of H ₂ SO ₄ ) and heat the reaction mixture to 90 ° C. After stirring at this temperature for 2 hours, volatile products are distilled off - 13.3 g, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° C, 1.8 g (m) of demineralized water are added, calculated according to the equation m = yƒ-2x, stirred for 2 hours and incubated for 12 hours without stirring. At the end of the exposure, 12.6 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (17.8 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and get 47.6 g of a clear liquid - poly (methyl) (phenyl) (hydroxy) siloxane. The yield of 98.3% of the mass .. According to a study of the composition of the distillate and product by GLC, it was found that the distillation contains 48.50% of the mass. ethyl acetate, 51.22% of the mass. ethanol and 0.28% of the mass. water, and the product is 13.42% of the mass. [PhSi (Me) O] ₃ . ¹ H NMR spectroscopy records the trace amount of SiOC H ₂ CH ₃ (δ = 3.76 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts Ph Si (Me) O- (δ = -20.89 and -32.64 ppm) and Me Si O _3/2 - (δ = -57.88 ÷ - 59.98 ppm), the ratio of the values of their integrated intensities is 3. The average composition of the product, determined by the integrated intensities of the chemical shifts (δ) of these silicon atoms and the result of the Fischer titration, has the form: [PhSi (Me) O] _0.3 [ MeSiO _3/2 ] _0.1 [O _1/2 H] _0.102 or [D ₀ , ₃ T _0.1 (O _0.5 H) _1.02 ], and the degree of polycondensation by organotrialkoxysilane n ¹ = 0.660. Gelling time - 192 minutes.

Example 3

In a flask equipped with a stirrer, a thermometer, a reflux condenser, 14.8 g (y = 0.1 mol) of ViSi (OCH ₃ ) ₃ , 37.0 g (0.1 mol) (Me ₂ SiO) ₅ , 6.0 g (x = 0.1 mol) of glacial acetic acid (the required amount for the condensation of ViSi (OCH ₃ ) ₃ to the degree of 0.667), 0.68 ml of 94.7% sulfuric acid (0.012 mol of H ₂ SO ₄ ) and the reaction mixture is heated to 85 ° FROM. After stirring at this temperature for 2 hours, volatile products are distilled off - 10.6 g, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° C, 1.8 g (m) of demineralized water are added, calculated according to the equation m = yƒ-2x, stirred for 2 hours and kept for 12 hours without stirring. At the end of the exposure, 8.4 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (13.5 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and get 44.4 g of a clear liquid - poly (methyl) (vinyl) (hydroxy) siloxane. Yield 98.9% of the mass. According to a study of the composition of the distillate and the product by GLC, it was found that the distillation contains 53.48% of the mass. methyl acetate, 46.4% by weight. methanol and 0.12% of the mass. water, and the product is 4.27% of the mass. (Me ₂ SiO) ₅ and 8.99% of the mass. (Me ₂ SiO) ₅ . NMR ¹ H-spectroscopy does not detect SiOC H ₃ (δ = 3.5 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts of Me ₂ Si O- (δ = -21.89 and -22.65 ppm) and Vi Si O _3/2 - (δ = -81.1 ÷ 83.72 m. e.), the ratio of the values of their integrated intensities is 5. The average composition of the product, determined by the integrated intensities of the chemical shifts (δ) of these silicon atoms and the Fischer titration, has the form: [Me ₂ SiO] _0.5 [ViSiO _3/2 ] _0.1 [O _1/2 H] _0.1 or [D _0.5 T _0.1 (O _0.5 H) _0.1 ], and the degree of polycondensation by organotrialkoxysilane n ¹ = 0.667. The gelation time is 113 minutes.

Example 4

In a flask equipped with a stirrer, a thermometer, a reflux condenser, 21.8 g (у = 0.1 mol) of CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 37.6 g (0.1 mol) of [ViSi (Me) O ] _4, 6.0 g (x = 0.1 mol) of glacial acetic acid (the amount required for condensation of CF ₃ CH ₂ CH ₂ Si (OCH _{3) 3} equal to 0.667 degrees), 0.68 ml of 94.7% sulfuric acid ( 0.012 mol of H ₂ SO ₄ ) and heat the reaction mixture to 85 ° C. After stirring at this temperature for 2 hours, volatile products are distilled off - 10.6 g, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° C, 1.8 g (m) of demineralized water are added, calculated according to the equation m = yƒ-2x, stirred for 2 hours and kept for 12 hours without stirring. At the end of the exposure, 8.4 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (13.5 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and get 52.2 g of a clear liquid - poly (methyl) (vinyl) (3-trifluoropropyl (hydroxy) siloxane. Yield 97.8% of the mass. According to a study of the compositions of the distillation and product by GLC, it was found that the distillation contains 53.44% wt% methyl acetate, 46.38% wt% methanol and 0.18% wt water, and the product 10.70 wt% [ViSi (Me) O] _4. NMR ¹ H spectroscopy does not detect SiOC H ₃ (δ = 3.5 ppm) in the composition of the product On the ²⁹ Si NMR spectrum of the product, chemical shifts ViSi (Me) O- (δ = -32.73 and -35.91 ÷ -36.74 ppm) and CF ₃ CH ₂ CH ₂ Si O _3/2 - (δ = -60.23 ÷ -62.71 ppm), the ratio of the values of their integral intensities is 4. Average s the product residue, determined by the integrated chemical shift intensities (δ) of these silicon atoms and the Fischer titration result, has the form: [ViSi (Ме) O] _0.4 [CF ₃ CH ₂ CH ₂ SiO _3/2 ] _0.1 [O _{1 / 2} H] _0.1 or [D _0.4 T _0.1 (O _0.5 H) _0.1 ], and the degree of polycondensation by organotrialkoxysilane n ¹ = 0.667. The gelation time is 98 minutes.

Example 5

To a flask equipped with a stirrer, a thermometer, a reflux condenser, 35.6 g (у = 0.2 mol) of MeSi (OC ₂ H ₅ ) ₃ , 29.6 g (0.1 mol) (Me ₂ SiO) ₄ , 14 are charged , 0 g (x = 0.23 mol) of glacial acetic acid (the required amount for the condensation of MeSi (OC ₂ H ₅ ) ₃ to the degree of 0.778), 1.36 ml of 94.7% sulfuric acid (0.024 mol of H ₂ SO ₄ ) and heat the reaction mixture to 85 ° C. After stirring at this temperature for 2 hours, volatile products — 30.7 g — are distilled off, raising the temperature. stepwise up to 120 ° C in 2 hours. All the distillation is returned to the reaction mixture, cooled to 30 ° C, add 2.52 g (m) demineralized water calculated according to the equation m = yƒ-2x, stirred for 2 hours and kept for 12 hours without stirring. At the end of the exposure, 16.8 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (37.19 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and get 43.3 g of a clear liquid - poly (methyl) (hydroxy) siloxane. The yield of 98.0% of the mass. According to a study of the compositions of the distillate and the product by GLC, it was found that the distillation contains 54.15% of the mass. ethyl acetate, 45.58% of the mass. ethanol and 0.27% of the mass. water, and the product is 9.87% of the mass. (Me ₂ SiO) ₄ . NMR ¹ H-spectroscopy registers a trace amount of SiOC H ₂ CH ₃ (δ = 3.75 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts of Me ₂ Si O- (δ = -19.82 and -22.53 ppm) and Me Si O _3/2 - (δ = -57.43 ÷ -58, 92 ppm), the ratio of the values of their integrated intensities is 2. The average composition of the product, determined by the integrated intensities of the chemical shifts (δ) of these silicon atoms and the Fischer titration, has the form: [Me ₂ SiO] _0.4 [MeSiO _{3 / 2} ] _0.2 [O _1/2 H] _0.132 or [D _0.4 T _0.2 (O _0.5 N) _0.132 ], and the degree of polycondensation by organotrialkoxysilane n ¹ = 0.780. The gelation time is 41 minutes.

Example 6

39.6 g (y = 0.2 mol) of PhSi (OCH ₃ ) ₃ , 62.4 g (0.1 mol) of [CF ₃ CH ₂ CH ₂ Si (Me) O] ₄ are charged into a flask equipped with a stirrer, thermometer, reflux condenser. , 14.4 g (x = 0.24 mol) of glacial acetic acid (the required amount for the condensation of PhSi (OCH ₃ ) ₃ to the degree of 0.8), 1.36 ml of 94.7% sulfuric acid (0.024 mol of H ₂ SO ₄ ) and heat the reaction mixture to 100 ° C. After stirring at this temperature for 3 hours, the volatile products are distilled off - 25.4 g, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° C, 2.16 g (m) of demineralized water, calculated by the equation m = yƒ-2x, are added, stirred for 2 hours and incubated for 12 hours without stirring. At the end of the exposure, 16.8 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (29.2 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and 87.5 g of a clear liquid are obtained - poly (methyl) (3-trifluoropropyl) (phenyl) (hydroxy) siloxane. Yield 98.0% by weight. According to a study of the compositions of the distillate and the product by GLC, it was found that the distillate contains 53.44% of the mass. methyl acetate, 46.38% of the mass. methanol and 0.18% of the mass. water, and the product is 6.70% of the mass. [CF ₃ CH ₂ CH ₂ Si (Me) O] ₄ . NMR ¹ H-spectroscopy does not detect SiOC H ₃ (δ = 3.5 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts of CF ₃ CH ₂ CH ₂ Si (Me) O- (δ = -20.58 and -22.71 ppm) and Ph Si O _3/2 - (δ = - 74.6 ÷ -79.9 ppm), the ratio of the values of their integrated intensities is 2. The average composition of the product, determined by the integrated intensities of the chemical shifts (δ) of these silicon atoms and the result of the Fischer titration, has the form: [CF ₃ CH ₂ CH ₂ Si (Me) O] _0.4 [PhSiO _3/2 ] _0.2 [O _1/2 H] _0.12 or [D _0.4 T _0.2 (O _0.5 H) _0.12 ] and the degree of polycondensation of organotrialkoxysilane n ¹ = 0,800. Gelling time is 85 minutes.

Example 7

13.6 g (0.1 mol) of MeSi (OCH ₃ ) ₃ , 24.0 g (0.1 mol) of PhSi (OC ₂ H ₅ ) ₃ (y = 0) are charged into a flask equipped with a stirrer, thermometer, reflux condenser , 2 mol), 46.8 g (0.1 mol) [CF ₃ CH ₂ CH ₂ Si (Me) O] ₃ , 43.0 g (0.1 mol) [ViSi (Me) O] ₅ 15.0 g (x = 0.25 mol) of glacial acetic acid (the required amount for the condensation of both organoalkoxysilanes to the degree of 0.833), 1.36 ml of 94.7% sulfuric acid (0.024 mol of H ₂ SO ₄ ) and the reaction mixture is heated to 95 ° C. After stirring at this temperature for 2 hours, volatile products, 29.3 g, are distilled off, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° C, 1.8 g (m) of demineralized water are added, calculated according to the equation m = yƒ-2x, stirred for 2 hours and incubated for 12 hours without stirring. At the end of the exposure, 16.8 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (33.8 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and 108.9 g of a clear liquid are obtained - poly (methyl) (vinyl) (3-trifluoropropyl) (phenyl) (hydroxy) siloxane. The yield of 98.7% of the mass. According to a study of the composition of the distillate and product by GLC, it was found that the distillation contains 54.29% of the mass. methyl acetate, 4.73% of the mass. methanol, 40.83% of the mass. ethanol and 0.15% of the mass. water, and the product is 2.23% of the mass. [CF ₃ CH ₂ CH ₂ Si (Me) O] ₃ and 5.55% by weight. [ViSi (Me) O] ₅ . NMR ¹ H-spectroscopy registers a trace amount of only SiOC H ₂ CH ₃ (δ = 3.77 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts ViSi (Me) O- (δ = -34.48 and -35.88 ÷ -36.67 ppm), CF ₃ CH ₂ CH ₂ Si (Me) O- (δ = -9.54 and -22.71 ppm), Me Si O _3/2 - (δ = -57.76 ÷ -59.34 ppm) and Ph Si O _3/2 - (δ = -73.4 ÷ -78.3 ppm). The average composition of the product, determined by the integrated intensities of chemical shifts (δ) of silicon atoms and the Fischer titration result, has the form: [ViSi (Me) O] _0.5 [CF ₃ CH ₂ CH ₂ Si (Me) O] _0.3 [ MeSiO _3/2 ] _0.1 [PhSiO _3/2 ] _0.1 [O _1/2 H] _0.1 or [D _0.8 T _0.2 (O _0..5 H) _0.1 ], and the degree of polycondensation of organotrialkoxysilane n ¹ = 0.833. Gelling time is 56 minutes.

Example 8

In a flask equipped with a stirrer, thermometer, reflux condenser, load 19.0 g (0.1 mol) of ViSi (OC ₂ H ₅ ) ₃ , 26.0 g (0.1 mol) of CF ₃ CH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ (y = 0.2 mol), 54.4 g (0.1 mol) [PhSi (Me) O] ₄ , 22.2 g (0.1 mol) [Me ₂ SiO] ₃ 14.4 g (x = 0.24 mol) of glacial acetic acid (the required amount for the condensation of both organoalkoxysilanes to the degree of 0.800), 1.36 ml of 94.7% sulfuric acid (0.024 mol of H ₂ SO ₄ ) and the reaction mixture is heated to 100 ° C. After stirring at this temperature for 3 hours, volatile products are distilled off - 32.0 g, increasing the temperature stepwise to 120 ° C in 2 hours. All distillation is returned to the reaction mixture, cooled to 30 ° С, 2.16 g (m) of demineralized water, calculated by the equation m = yƒ-2x, are added, stirred for 2 hours and incubated for 12 hours without stirring. At the end of the exposure, 16.8 g of chalk is added and stirred until the sulfuric acid is completely neutralized - 2 hours. The whole mass is filtered off, the ester with alcohol (37.6 g) is removed from the filtrate in a rotary evaporator at a temperature of 50 ° C in a vacuum of 50 mm. Hg and 99.4 g of a clear liquid are obtained - poly (methyl) (phenyl) (vinyl) (3-trifluoropropyl) (hydroxy) siloxane. The yield of 98.9% of the mass .. According to a study of the composition of the distillate and product by GLC, it was found that the distillation contains 55.85% of the mass. ethyl acetate, 43.88% of the mass. ethanol and 0.27% of the mass. water, and the product is 1.06% of the mass. [Me ₂ SiO] ₃ and 8.49% of the mass. [PhSi (Me) O] ₄ . NMR ¹ H-spectroscopy registers a trace amount of SiOC H ₂ CH ₃ (δ = 3.77 ppm) in the composition of the product. On the ²⁹ Si NMR spectrum of the product, chemical shifts of Me ₂ SiO- (δ = -9.78 and -21.88 ÷ -22.67 ppm), PhSi (Me) O- (δ = -30.41 and -33.87 ppm), Vi Si O _3/2 - (δ = -81.1 ÷ -83.72 ppm) and CF ₃ CH ₂ CH ₂ Si O _3/2 - (δ = -60.73 ÷ -62.54 ppm). The average product composition, determined by the integrated intensities of chemical shifts (δ) of silicon atoms and the Fischer titration result, has the form: [Me ₂ SiO] _0.3 [PhSi (Me) O] _0.4 [ViSiO _3/2 ] _0.1 [CF ₃ CH ₂ CH ₂ SiO _3/2 ] _0.1 [O _1/2 H] _0.12 or [O _0.6 T _0.2 (O _0.5 N) _0.12 ], and the degree of polycondensation by organotrialkoxysilane n ¹ = 0.800 . Gelling time is 293 minutes.

The experimental data illustrate the complete convergence of the given “p” and actual “n ¹ ” degrees of polycondensation in the proposed method for producing poly (organo (hydroxy) siloxanes, which confirms the ability to predict and prevent an unpredictable process - gelling, which is a serious technological problem.

Claims (4)

1. The method of obtaining poly (organo) (hydroxy) siloxanes of the General formula {[R ¹ R ² SiO] _a [R ³ SiO _3/2 ] _b [O _1/2 H] _c } with a given degree of condensation by organotrialkoxysilane "n" where a = 0.3-0.8 is the molar amount of difunctional units; b = 0.1-0.2 is the molar amount of trifunctional units, c = 0.1-0.132 is the molar amount of OH groups, including acidohydrolytic copolycondensation of individual organotrialkoxysilanes or mixtures thereof of the general formula R ¹ Si (OR ² ) ₃ with one or a mixture of diorganocyclo-siloxanes of the general formula [R ³ R ⁴ SiO] _m , where m = 3-6, where R ² = CH ₃ , C ₂ H ₅ ; R ³ = CH ₃ ; R ¹ = R ⁴ = CH ₃ , C ₂ H ₃ , C ₃ H ₄ F ₃ , C ₆ H ₅ , with a molar ratio of reagents R ¹ Si (OR ² ) ₃ : R ³ R ⁴ SiO unit = 1: 2 ÷ 5, glacial acetic acid, taken in the amount necessary to ensure the degree of condensation "n" on organotrialkoxysilane not exceeding 0.833, in the presence of catalytic amounts of concentrated sulfuric acid from 1.7 to 3.1% wt., The process being at a temperature of 85-100 ° C for 2-3 hours, followed by a stepwise increase in the temperature of the mixture to 120 ° C with distillation of alcohol and its acetate to achieve a given organ condensation o (trialkoxy) silanes, returning the distilled products to the cooled reaction mass, adding demineralized water in an amount calculated by the equation m = yƒ-2x (where m is the molar amount of water, y is the molar amount of alkoxysilane, x is the molar amount of acetic acid, ƒ - alkoxysilane functionality), necessary for the complete hydrolysis of residual alkoxy groups, subsequent neutralization of the reaction mass with excess calcium carbonate, filtration of the mixture, and removal of 50 mm Hg volatile in a vacuum. at a temperature of not more than 50 ° C from the target product, while the yield of poly (organo) (hydroxy) siloxanes is not less than 97.8% by weight, and the value of its actual degree of condensation "n ¹ " is calculated by the equation n ¹ = 1- m ¹ / yƒ, where m ¹ is the molar amount of hydroxyl groups in the product, determined by Fischer titration. 2. The method of producing poly (organo) (hydroxy) siloxanes according to claim 1, characterized in that a stepwise increase in temperature to 120 ° C is carried out with a temperature step of 5 ° C, increasing the temperature to the next stage as the distillation ceases. 3. The method of producing poly (organo) (hydroxy) siloxanes according to claim 1, characterized in that the reaction mass is neutralized by a seven-fold molar excess of calcium carbonate relative to the amount of sulfuric acid for 2 hours. 4. The method of producing poly (organo) (hydroxy) siloxanes according to claim 1, characterized in that the waste material used for production of methylsilane is methyltriethoxysilane.