RU2556220C1 - Polyorganosiloxanes as base of foam-extinguishing compositions and method of obtaining thereof - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to polyorganosiloxanes, which are ultra-branched polymers, containing organosiloxane units, chemically grafted to silicon dioxide particles. Claimed is method of obtaining polyorganosiloxanes of general formula {[RO][(CH)SiO][RSiO][RSiO][RO][SiO]}, where Ris hydrogen, methyl, ethyl, propyl, acetyl; Ris methyl, ethyl, vinyl, octyl, phenyl, ethoxy; Ris methyl, ethyl, vinyl, octyl, phenyl, ethoxy; ([RO][SiO]) is particle of silicon dioxide, in which Ris Si(CH), Si(CH)O; f=1000-15000, with a:b:c:d:e=(0.005÷0.06):(10÷800):(0÷11):(0÷8):(0÷0.15), by interaction of some components, selected from: (A) polydiorganosiloxane of formula RO[(CH)SiO]R, where Ris hydrogen, methyl, ethyl, acetyl, m=8-500; (B) acetic acid; (C) organosiloxane of formula RSi(OR), where Ris methyl, ethyl, vinyl, oxtyl, phenyl, ethoxy, Ris methyl, ethyl, propyl; (D) organoacetoxysilane of formula RSi(O(O)CCH), where Ris methyl, ethyl, vinyl, octyl, phenyl, ethoxy; (E) silicon pyrogenic ioxide of formula {(SiO)(OR)(OH)}, where Ris Si(CH), Si(CH)O, e=0-0.15, g=0.05-0.25, f=1000÷15000, with surface 200-300 m/g, particle size 5-14 nm; with weight ratio A:B:C:D:E=100:(0÷23):(0÷6.1):(0÷10):(0.1÷7). Process is carried out at 50-130°C for 5-10 hours with following vacuum procession under reduced pressure and temperature 100-130°C to viscosity 30000-3000000 cPs. Polyorganosiloxanes obtained by claimed method are also claimed.EFFECT: claimed compounds can be applied in absence of catalyst with preservation of molecular structure of initial organosiloxanes and particles of silicon dioxide and can be applied as bases for highly effective foam-extinguishing compositions.5 cl, 11 ex

Description

The invention relates to the field of chemistry, in particular to polyorganosiloxanes, which are hybrid hyperbranched polymers containing organosiloxane blocks chemically grafted to silicon dioxide particles, and a method for their preparation. These products can be used as the basis of highly effective antifoam compositions.

It is known that polyorganosiloxanes of various composition and structure (PIC), mainly in a mixture with silicon dioxide, are widely used in various industries as antifoam, anti-foaming and anti-foaming additives. Scientific and technological research in this area has been going on for more than half a century until now.

In USSR author's certificate No. 1171473 (published on 08/07/1985), branched and cyclo-branched antifoam POSs are obtained by cohydrolyzing at 40-70 ° C catalytic (alkaline) products of a rearrangement of a mixture of linear and cyclic dimethylsiloxanes with tetraethoxysilane or polyethylsilylmethane and their subsequent . However, it should be noted that the target products exhibit low defoaming ability.

In the patent of the Russian Federation No. 2082725 (published on June 27, 1997), a method for producing PICs having enhanced anti-foaming properties is proposed. During the process, co-hydrolysis and polycondensation of the hydrolysis products of (CH ₃ ) ₂ SiCl ₂ , (CH ₃ ) ₃ SiCl and SiCl ₄ are carried out at a temperature of 40-70 ° C and maintaining the molar ratio of the last two compounds, respectively (0.02-0.03) ÷ (0.2-0.3) per 1 mol of the structural unit (CH ₃ ) ₂ SiO - products of hydrolysis of dimethyldichlorosilane. The synthesis is carried out in the presence of an excess of water and higher fatty alcohols of the C ₇ -C ₉ or C ₈ -C ₁₀ or 2-ethylhexyl alcohol fractions in an organic solvent medium, which, at the end of the reaction, is distilled off with the alcohols and returned to the process. Effect: simplification of technology and reduction of production waste to a volatile content of ≤5 wt. % The disadvantage of this method is the short period of action when extinguishing foam.

There are a number of inventions in which siloxane antifoaming agents, later used independently or as the basis of foam control compositions, are obtained by heating mixtures in the presence of alkaline catalysts, including linear or branched polydimethylsiloxanes with terminal Si (CH ₃ ) ₃ groups and with terminal OH groups ( I), polysiloxane resins (II), finely divided filler - crosslinked polyorganosiloxane or silicon dioxide (III), which in the presence of an alkaline catalyst is involved in the reaction with mations branching centers.

In the descriptions of inventions to US patents No. 3984200 (publ. 05/10/1976) and No. 5283004 (publ. 02/01/1994) proposed additional component (IV) of the reaction mixture is a polyoxyalkylene siloxane copolymer.

According to European application No. 0434060 (publ. 06/26/1991) as a component (III) forming the branching centers, use cross-linked viscous flowing PIC in the amount of 1.0-200 wt.h. per 100 parts by weight mixtures of component (I) with silica. For example, to obtain component (III), a linear POS with terminal hydroxyl groups is reacted with trialkoxysilane (R ¹ O) ₃ SiR ² , or with triacetoxysilane (CH ₃ COO) ₃ SiR ¹ , or with silicon alkyl trioximate (R ¹ R ² NO) ₃ SiR ³ , where R ¹ , R ² , R ³ are C ₁ ÷ C ₃ alkyls under the action of an organotin catalyst and atmospheric moisture. The use of component (III) allows to achieve a prolonged antifoam action.

In US patent No. 6512015 (publ. January 28, 2003), the most preferred is a silicone agent for the foam control composition obtained by heating from 50 ° C to 300 ° C a homogeneous mixture of polydimethylsiloxanes with terminal hydroxyl and trimethylsilyl groups of viscosity 1000-50000 mm ² / s with an alkyl polysilicate (methyl, ethyl or propyl polysilicate) and a catalyst - potassium silanolate. To obtain a stable antifoaming agent, at the end of the reaction, the catalyst is neutralized.

As the closest analogue selected US patent No. 4749740 (publ. 07/07/1988) of the corporation Dow Corning Kabushiki Kaisha, which most fully presents a method for the production of antifoam composition and its silicone base. The purpose of the invention is to obtain a silicone antifoam composition having a long functional effect sufficient for the successful production of liquid products that emit large volumes of foam during the process.

The method consists in the interaction of a mixture of the following reagents:

(I) two PIC linear structures of different viscosities (A) from 20 to 100,000 cSt at 25 ° C and (B) from 200 to several million cSt, with a content in the mixture (A) = 0-95 parts by weight, ( B) = 5-100 parts by weight and the sum of (A) + (B) = 100 parts by weight, with the most preferred viscosity of the mixture of components (A) and (B) from 1000 to 100000 cSt at 25 ° C. PIC - mainly polydimethylsiloxanes with terminal hydroxyl (B) and trimethylsilyl (A) groups;

(II) any reagent, in an amount of 0.5-20 wt.h. (preferably 1.0-7.0 parts by weight) per 100 parts by weight (I) selected from:

a) a monomer of the general formula R _a SiX _(4-a) , where R is an organic C ₁ -C ₅ , X is a hydrolyzable group, a≤1;

b) partially hydrolyzed condensate of monomer a);

c) a siloxane resin consisting of (CH ₃ ) ₃ SiO _0.5 and SiO ₂ units in a ratio of (0.4-1.2): 1.0;

d) a condensed resin c) with a) or b) monomer;

(III) finely divided filler - oxides of silicon, titanium, aluminum or a mixture of silicon oxide with aluminum oxide in an amount of 0.5-30 wt.h. (preferably silicon dioxide in an amount of 1.0-7.0 parts by weight);

(IV) an alkaline catalyst in an amount of 0.03-1.0 parts by weight per 100 parts by weight (I): hydroxides, alkoxides, alkali metal silanates, quaternary ammonium or phosphonium bases, metal salts of organic acids;

(V) PIC low viscosity (5-200 cSt at 25 ° C in an amount of 0-20 wt.h.). When using PICs with terminal OH groups, compounds with a viscosity of 10-50 cSt at 25 ° C in an amount of 1-10 parts by weight are preferred. per 100 parts by weight (I).

The process is carried out in an inert gas atmosphere with heating from 50 to 300 ° C and vigorous stirring of all reagents for 1-8 hours in a colloid mill, mixer and other homogenizing devices. At the end of the reaction, volatile by-products and unreacted substances are distilled off from the products at T = 180 ° C for one hour under reduced pressure of 40 mm Hg. Art. Get a mixed product without identification, with anti-foaming properties of long-acting. The siloxane agent can be used both independently and with other additives in the composition in the form of solutions or emulsions of the oil-in-water type.

It should be noted that the silicone mixture has a rather complex composition. The production method is carried out in a rather severe temperature regime and with the mandatory introduction of alkaline catalysts that require neutralization. To carry out the reaction, an inert gas atmosphere is necessary in order to eliminate the danger of explosion in case of contact of the resulting substances with air.

The use of alkaline catalysts and elevated temperatures, as a rule, leads to the rearrangement of the siloxane skeleton of the starting compounds, including the filler, with a change in the structure and composition of the polymer molecule, as well as the formation of significant quantities of cyclic products.

The authors were faced with the task of developing new polyorganosiloxanes used as the basis for antifoam compositions, which are hybrid hyperbranched polymers containing organosiloxane blocks chemically grafted to silicon dioxide particles, and a new method for producing these organopolysiloxanes under mild conditions.

As a result of scientific and experimental studies, new polyorganosiloxanes have been proposed that are used as the basis for antifoam compositions of the general formula:

{[R ¹ O _0.5 ] _a [(CH ₃ ) ₂ SiO] _b [R ² SiO _1.5 ] _c [R ³ SiO _1.5 ] _d [R ⁴ O _0.5 ] _e [SiO ₂ ] } _f ,

where R ¹ is hydrogen, methyl, ethyl, propyl, acetyl; R ² is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; R ³ is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; ([R ⁴ O _0.5 ] _e [SiO ₂ ]) is a silica particle in which R ⁴ is Si (CH ₃ ) ₃ , Si (CH ₃ ) ₂ O _0.5 ; f≈1000-15000, with the ratio of the numbers of links a: b: c: d: e = (0.005 ÷ 0.06) :( 10 ÷ 800) :( 0 ÷ 11) :( 0 ÷ 8) :( 0 ÷ 0 , 15) per SiO ₂ group, with viscosities of 30000-3000000 cPs, which are hybrid hyperbranched polymers containing organosiloxane blocks chemically grafted to silicon dioxide particles, and a new method for producing these organopolysiloxanes.

The method consists in the interaction of several components selected from: (A) a polydiorganosiloxane of the formula R ¹ O [(CH ₃ ) ₂ SiO] _m R ¹ , where R ¹ is hydrogen, methyl, ethyl, acetyl, m = 8-500; (B) acetic acid; (B) an organoalkoxysilane of the formula R ² Si (OR ³ ) ₃ , where R ² is methyl, ethyl, vinyl, octyl, phenyl, ethoxy, R ³ is methyl, ethyl, propyl; (D) an organoacetoxysilane of the formula R ⁴ Si (O (O) CCH ₃ ) ₃ , where R ⁴ is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; (E) pyrogenic silicon dioxide of the formula {(SiO ₂ ) (O _0.5 R ⁵ ) _e (O _0.5 H) _g } _f , where R ⁵ is Si (CH ₃ ) ₃ , Si (CH ₃ ) ₂ O _0.5 , e = 0-0.15, g = 0.05-0.25, f≈1000 ÷ 15000, with a surface of 200-300 m ² / g, particle size of 5-14 nm, with a mass ratio of A: B: C: D: D = 100: (0 ÷ 23) :( 0 ÷ 6.1) :( 0 ÷ 10) :( 0.1 ÷ 7). The process is carried out at a temperature of 50-130 ° C for 5-10 hours, followed by evacuation at reduced pressure and a temperature of 100-130 ° C to a viscosity of 30000-3000000 cps.

The synthesis of polyorganosiloxanes by the proposed method is shown in the examples below.

Example 1

200 g (0.090 mol) of α, ω-dihydroxy-polydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₃₀ H, 9.4 g (0.069 mol) of methyltrimethoxysilane are charged into the reactor, and the resulting reaction mass is heated with stirring for 5 hours at 100 ° C. Then, 4 g (0.067 mol) of acetic acid are added to it at 50 ° C and stirred for 2 hours at the same temperature, then heated to 110 ° C and stirred for 3 hours. Upon completion of heating, volatile reaction products are distilled off from the obtained polyorganosiloxane under vacuum at 100 mmHg century, gradually raising the temperature to 130 ° C until a product viscosity of 10,000 cps is reached. 10 g of modified pyrogenic silicon dioxide with a surface of 300 m ² / g of the formula {(SiO ₂ ) (O _0.5 Si (CH ₃ ) ₃ ) _0.03 (O _0.5 H) _0.05 } ₁₀₀₀ are introduced into the resulting product , with a particle size of 5 nm, carefully grind and conduct copolycondensation in vacuum at 40 mm RT. Art. and temperatures from 100 to 130 ° C until a viscosity of 200,000 cPs is reached. 205 g of product are obtained {[CH ₃ O] _0.02 [(CH ₃ ) ₂ SiO] ₁₆ [CH ₃ SiO _1.5 ] _0.4 ((CH ₃ ) ₃ SiO _0.5 ) _0.03 (SiO ₂ )} ₁₀₀₀ .

Example 2

The synthesis is carried out as in example 1. 200 g (0.30 mol) of α, ω-diethoxypolydimethylsiloxane of the formula C ₂ H ₅ O [(CH ₃ ) ₂ SiO] ₈ C ₂ H ₅ , 8.8 g (0.045 mol) are taken in the reaction ethyltriethoxysilane, 46 g (0.76 mol) of acetic acid, 5 g of fumed silica with a surface of 200 m ² / g of the formula {(SiO ₂ ) (O _0.5 H) _0.25 } ₁₅₀₀₀ , with a particle size of 14 nm. 155 g of product are obtained {[C ₂ H ₅ O _0.5 ] _0.03 [(CH ₃ ) ₂ SiO] ₂₉ [C ₂ H ₅ SiO _1.5 ] _0.5 (SiO ₂ )} ₁₅₀₀₀ with a viscosity of 30,000 cPz .

Example 3

The synthesis is carried out as in example 1. 200 g (0.053 mol) of α, ω-dimethoxypolydimethylsiloxane of the formula CH ₃ O [(CH ₃ ) ₂ SiO] ₅₀ CH ₃ , 11.6 g (0.049 mol) of octyltrimethoxysilane, 20 g (0 , 33 mol) of acetic acid, 5 g of fumed silica with a surface of 200 m ² / g of the formula {(SiO ₂ ) (OSi (CH ₃ ) ₂ ) _0.05 (O _0.5 H) _0.15 } ₁₅₀₀₀ , s particle size of 14 nm. 195 g of product are obtained {[CH ₃ O _0.5 ] _0.04 [(CH ₃ ) ₂ SiO] ₃₂ [C ₈ H ₁₇ SiO _1.5 ] _0.6 ((CH ₃ ) ₂ SiO) _0.05 ( SiO ₂ )} _15,000 with a viscosity of 300,000 cps.

Example 4

200 g (0.0054 mol) of α, ω-dihydroxypolydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₅₀₀ H are mixed with 10 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (О _{0, 5} Si (CH ₃ ) ₃ ) _0.15 (O _0.5 N) _0.10 } ₃₀₀₀ , with a particle size of 7 nm, and carefully rubbed on a three-roll paint grinder. The resulting mass is loaded into the reactor and 1.2 g (0.0054 mol) of methyltriacetoxysilane are added to it. Then the reaction mass is heated for 5 hours at 100 ° C. Upon completion of heating, the resulting polyorganosiloxane is evacuated at 10 mm Hg. century, gradually raising the temperature to 130 ° C until the viscosity of the product reaches 2,000,000 cps. 195 g of product are obtained {[HO _0.5 ] _0.005 [(CH ₃ ) ₂ SiO] ₁₆ [CH ₃ SiO _1.5 ] _0.03 ((CH ₃ ) ₃ SiO _0.5 ) _0.15 (SiO ₂ ) } ₃₀₀₀ .

Example 5

200 g (0.09 mol) of α, ω-dihydroxypolydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₃₀ H are thoroughly mixed on a three-roll paint sprayer with 14 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (O _0.5 Si (CH ₃ ) ₃ ) _0.05 (O _0.5 H) _0.05 } ₃₀₀₀ , with a particle size of 7 nm. The resulting mass is loaded into the reactor and 9.4 g (0.04 mol) of vinyl triacetoxysilane are added to it. The reaction mass is heated and incubated for 5 hours at 100 ° C. Then 5 g (0.034 mol) of vinyltrimethoxysilane are added to it and heated for 5 hours at 110 ° C. At the end of heating, the resulting polyorganosiloxane is evacuated at 40 mm Hg. century, gradually raising the temperature to 130 ° C until a product viscosity of 800,000 cps is reached. 202 g of product are obtained {[CH ₃ C (O) O _0.5 ] _0.01 [(CH ₃ ) ₂ SiO] ₁₂ [(CH ₂ = CH) SiO _1.5 ] _0.3 ((CH ₃ ) ₃ SiO _0.5 ) _0.05 (SiO ₂ )} ₃₀₀₀ .

Example 6

The synthesis is carried out according to example 5. Take 200 g (0,086 mol) of α, ω-di-acetoxypolydimethylsiloxane of the formula CH ₃ C (O) O [(CH ₃ ) ₂ SiO] ₃₀ (O) CCH ₃ , 2.2 g (0, 01 mol) methyltriacetoxysilane, 6.8 g (0.034 mol) phenyltrimethoxysilane, 14 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (O _0.5 H) _0.25 } ₃₀₀₀ , with particle size 7 nm. 210 g of product are obtained {[CH ₃ C (O) O _0.5 ] _0.05 [(CH ₃ ) ₂ SiO] ₁₀ [C ₆ H ₅ SiO _1.5 ] _0.15 [CH ₃ SiO _1.5 ] _0.04 (SiO ₂ )} _3,000 with a viscosity of 1,700,000 cps.

Example 7

The synthesis is carried out as in example 5. Take 200 g (0.09 mol) of α, ω-dihydroxypolydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₃₀ H, 20.0 g (0.071 mol) of phenyltriacetoxysilane, 2.4 g (0.011 mol) ) methyltripropoxysilane, 14 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (OSi (CH ₃ ) ₂ ) _0.02 (O _0.5 H) _0.05 } ₃₀₀₀ , with a particle size of 7 nm 212 g of product are obtained {[C ₃ H ₇ O _0.5 ] _0.02 [(CH ₃ ) ₂ SiO] ₁₂ [CH ₃ SiO _1.5 ] _0.05 [C ₆ H ₅ SiO _1.5 ] _{0, 30} ((CH ₃ ) ₂ SiO) _0.02 (SiO ₂ )} ₃₀₀₀ with a viscosity of 1,600,000 cps.

Example 8

The synthesis is carried out according to example 5. Take 200 g (0.09 mol) of α, ω-dihydroxypolydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₃₀ N, 7.2 g (0.031 mol) of ethyl triacetoxysilane, 12.2 g (0.052 mol) ) octyltrimethoxysilane, 14 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (O _0.5 Si (CH ₃ ) ₃ ) _0.1 (O _0.5 H) _0.15 } ₃₀₀₀ , with a particle size of 7 nm. 208 g of product are obtained {[CH ₃ O _0.5 ] _0.03 [(CH ₃ ) ₂ SiO] ₁₂ [C ₈ H ₁₇ SiO _1.5 ] _0.22 [C ₂ H ₅ SiO _1.5 ] _{0, 13} ((CH ₃ ) ₃ SiO _0.5 ) _0.1 (SiO ₂ )} ₃₀₀₀ with a viscosity of 1,700,000 cps.

Example 9

The synthesis is carried out according to example 5. Take 200 g (0.09 mol) of α, ω-dihydroxypolydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₃₀ H, 11.6 g (0.036 mol) octyltriacetoxysilane, 6.6 g (0.037 mol) ) methyltriethoxysilane, 14 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (O _0.5 H) _0.25 } ₃₀₀₀ , with a particle size of 7 nm. 208 g of product are obtained {[C ₂ H ₅ O _0.5 ] _0.05 [(CH ₃ ) ₂ SiO] ₁₂ [CH ₃ SiO _1.5 ] _0.16 [C ₈ H ₁₇ SiO _1.5 ] _{0, 15} (SiO ₂ )} _3,000 with a viscosity of 1,700,000 cps.

Example 10

The synthesis is carried out according to example 1. Take 300 g (0.13 mol) of α, ω-dihydroxypolydimethylsiloxane of the formula HO [(CH ₃ ) ₂ SiO] ₃₀ H, 11.0 g (0.053 mol) of tetraethoxysilane, 15 g (0.25 mol) ) acetic acid, 0.3 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (O _0.5 Si (CH ₃ ) ₃ ) _0.05 (O _0.5 H) _0.05 } ₃₀₀₀ , with a particle size of 7 nm. 301 g of product are obtained {[C ₂ H ₅ O _0.5 ] _0.03 [(CH ₃ ) ₂ SiO] ₇₈₀ [(C ₂ H ₅ O) SiO _1.5 ] ₁₁ ((CH ₃ ) ₃ SiO _{0, 5} ) _0.05 (SiO ₂ )} _3,000 with a viscosity of 2,000,000 cps.

Example 11

The synthesis is carried out as in example 4. Take 400 g (0.18 mol) of α, ω-dimethoxypolydimethylsiloxane of the formula CH ₃ O [(CH ₃ ) ₂ SiO] ₃₀ CH ₃ , 0.4 g of modified pyrogenic silicon dioxide with a surface of 260 m ² / g of the formula {(SiO ₂ ) (OSi (CH ₃ ) ₂ ) _0.1 (O _0.5 H) _0.05 } ₃₀₀₀ , with a particle size of 7 nm, 13.4 g (0.054 mol) of ethoxytriacetoxysilane. 395 g of product are obtained {[CH ₃ O _0.5 ] _0.06 [(CH ₃ ) ₂ SiO] ₈₀₀ [(C ₂ H ₅ O) SiO _1.5 ] ₈ ((CH ₃ ) ₂ SiO) _0.1 (SiO ₂ )} _3,000 with a viscosity of 3,000,000 cps.

All products obtained in the above examples dissolve well without gel or SiO ₂ particles, do not form a precipitate during storage, disperse well when emulsions are obtained, which indicates the homogeneity of the product and the absence of free SiO ₂ particles.

In contrast to the previously proposed methods for the synthesis of branched polyorganosiloxanes, the method we developed allows us to use the highly reactive starting reagents to form a branched structure of siloxane blocks and to graft them to particles of fumed silica in the absence of a catalyst while maintaining the molecular structure of the starting organosiloxanes and particles of silicon dioxide. This also eliminates the depolymerization reaction with the formation of volatile organocyclosiloxanes and allows you to control the branching and molecular weight of the grafted siloxane blocks.

Obtained by the proposed method, polyorganosiloxanes can be used as the basis of highly effective defoaming emulsions (mainly direct aqueous) of a wide range of applications. The content of the silicone part in the emulsion can vary in the range of 10-50 wt. % depending on specific consumer requirements. As emulsifiers, mixtures of various surfactants of both ionic and nonionic nature can be used. Advantageously, non-ethoxylated and ethoxylated esters of sorbitan and fatty acids, ethoxylated fatty acids, ethoxylated linear and branched alcohols with 10 to 20 carbon atoms can be used. The content of emulsifiers in the emulsion, as a rule, falls within the range of 2-10 wt. % In addition, in the emulsion, if necessary, may contain minor amounts of structuring additives (xanthan gum, cellulose ethers) and a preservative.

Claims (5)

1. The method of producing polyorganosiloxanes of the General formula:
{[R ¹ O _0.5 ] _a [(CH ₃ ) ₂ SiO] _b [R ² SiO _1.5 ] _c [R ³ SiO _1.5 ] _d [R ⁴ O _0.5 ] _e [SiO ₂ ] } _f ,
where R ¹ is hydrogen, methyl, ethyl, propyl, acetyl; R ² is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; R ³ is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; ([R ⁴ O _0.5 ] _e [SiO ₂ ]) is a silica particle in which R ⁴ is Si (CH ₃ ) ₃ , Si (CH ₃ ) ₂ O _0.5 ; f≈1000-15000, with the ratio of the numbers of links a: b: c: d: e = (0.005 ÷ 0.06) :( 10 ÷ 800) :( 0 ÷ 11) :( 0 ÷ 8) :( 0 ÷ 0 , 15) per 1 group of SiO ₂ , characterized in that the interaction of several components selected from: (A) a polydiorganosiloxane of the formula R ¹ O [(CH ₃ ) ₂ SiO] _m R ¹ , where R ¹ is hydrogen, methyl ethyl, acetyl, m = 8-500; (B) acetic acid; (B) an organoalkoxysilane of the formula R ² Si (OR ³ ) ₃ , where R ² is methyl, ethyl, vinyl, octyl, phenyl, ethoxy, R ³ is methyl, ethyl, propyl; (D) an organoacetoxysilane of the formula R ⁴ Si (O (O) CCH ₃ ) ₃ , where R ⁴ is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; (E) pyrogenic silicon dioxide of the formula {(SiO ₂ ) (O _0.5 R ⁵ ) _e (O _0.5 H) _g } _f , where R ⁵ is Si (CH ₃ ) ₃ , Si (CH ₃ ) ₂ O _0.5 , e = 0-0.15, g = 0.05-0.25, f≈1000 ÷ 15000, with a surface of 200-300 m ² / g, particle size 5-14 nm; when the mass ratio A: B: C: D: D = 100: (0 ÷ 23) :( 0 ÷ 6.1) :( 0 ÷ 10) :( 0.1 ÷ 7), at a temperature of 50-130 ° C for 5-10 hours, followed by evacuation under reduced pressure and a temperature of 100-130 ° C to a viscosity of 30000-3000000 cPs. 2. The method according to p. 1, characterized in that the components (A) and (C) are first mixed and heated at 100 ° C for 5 hours, then component (B) is added at a temperature of 50 ° C, the reaction mass 2 is mixed hours at this temperature and 3 hours at 110 ° C, the polycondensation product is evacuated, gradually raising the temperature to 130 ° C until a viscosity of 10,000 cPs is reached, then component (D) is introduced into it, it is thoroughly ground and copolycondensation is carried out in vacuum at a temperature of from 100 to 130 ° C until a viscosity of 30000-2000000 cps is achieved. 3. The method according to p. 1, characterized in that component (A) is thoroughly mixed with component (D), component (G) is introduced into the resulting mass and heated for 5 hours at a temperature of 100 ° C, after which the resulting product is vacuumized, gradually raising temperature up to 130 ° C until viscosity reaches 2000000-3000000 cPs. 4. The method according to p. 1, characterized in that components (A) and (D) are thoroughly mixed, component (G) is introduced and heated for 5 hours at 100 ° C, then component (B) is added, heated for 5 hours at 110 ° C, after which the resulting product is vacuumized, gradually raising the temperature to 130 ° C until a viscosity of 800000-1700000 cPs is reached. 5. Polyorganosiloxanes obtained by the method according to any one of paragraphs. 1-4, of the General formula:
{[R ¹ O _0.5 ] _a [(CH ₃ ) ₂ SiO] _b [R ² SiO _1.5 ] _c [R ³ SiO _1.5 ] _d [R ⁴ O _0.5 ] _e [SiO ₂ ] } _f ,
where R ¹ is hydrogen, methyl, ethyl, propyl, acetyl; R ² is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; R ³ is methyl, ethyl, vinyl, octyl, phenyl, ethoxy; ([R ⁴ O _0.5 ] _e [SiO ₂ ]) is a silica particle in which R ⁴ is Si (CH ₃ ) ₃ , Si (CH ₃ ) ₂ O _0.5 ; f≈1000-15000, with the ratio of the numbers of links a: b: c: d: e = (0.005 ÷ 0.06) :( 10 ÷ 800) :( 0 ÷ 11) :( 0 ÷ 8) :( 0 ÷ 0 , 15) per 1 group of SiO ₂ , with a viscosity of 30,000 to 3,000,000 cps.