RU2375386C1 - Method of making water-resistant composite object (versions) and composite object, made using said method - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: one version of the method of making an object involves preparation of a hydrophobisation complex modifying additive through intense mixture of aqueous solutions of sodium tripolyphosphate, sodium adipate, potassium polymethylsiloconate and phosphogypsum with subsequent in situ obtaining of calcium polymethylsiliconate and an antifoaming agent, its mixture until obtaining a homogeneous mass with hardening water and with intense mixture with gypsum binder (high-strength, construction, anhydrous binder, their mixture) and, if necessary, with crushed filler and moulding the object. Other versions of the method of making water-resistant composite objects and the obtained composite object are also presented.

EFFECT: increased durability and improved operational characteristics of the objects.

7 cl, 11 ex, 2 tbl

Description

The invention relates to the chemical industry and the building materials industry, as well as to the field of various decorative products and, in particular, to obtain gypsum-polymer products.

Gypsum as anhydrite or hemihydrate for a long time is, thanks to its ability to bind to water, a valuable raw material with many interesting properties, for example, slight shrinkage, fire resistance, and is also characterized by a neutral pH during curing. Also, flue gas desulfurization currently produces large quantities of gypsum, which may be acceptable to the environment.

The disadvantage of bound gypsum mortar, gypsum flooring and gypsum coatings, however, is, for example, the relatively low water resistance of these systems.

From SU 1191437, 11/15/1985, a method is known for manufacturing a composite material from a gypsum mixture, including mixing finely ground gypsum binder, methyl cellulose, a retarder (one of the group: carboxymethyl cellulose, sodium tripolyphosphate, nitrilomethylphosphonic acid or its salt, borax, fodder yeast autolysate, forage yeast copolymer acid with formaldehyde) and an aqueous solution of a surfactant (one of the group: primary or secondary alkyl sulfates, sulfonol). At the same time, hemi-dispersed calcium sulfate hemihydrate or anhydrite is used as a gypsum binder, they are mixed with methyl cellulose, a setting retarder and an aqueous solution of a surfactant with a concentration of 20-30 wt.% In a ratio of 3.76: 1: 0.2: 0 , 04 to 37.8: 1: 2: 0.2 and finely ground to a residue on a sieve 02 of 0.5-30 wt.%, And then the resulting mixture is introduced into a finely ground gypsum binder in an amount of 1-6 wt.%. This method allows to increase the water holding capacity of the gypsum mixture.

From SU 1616977, 12/30/1990, a method is known for producing composites based on a gypsum binder (α- or β-hemihydrate of calcium sulfate grade G-6) from a mixture containing this gypsum binder, Na-carboxymethyl cellulose, sodium tripolyphosphate, anionic surfactant and mineral filler, while it contains solid ground lignosulfonates as an anionic filler of a surfactant, and concrete or kaolin as a mineral filler. The gypsum slurry obtained from this mixture has increased viability, and the water-holding ability is in the range of 99.0-99.2%.

From SU 1728160, 04/23/1992, a method for producing a structural and heat-insulating material based on a gypsum binder is known. The structural and heat-insulating composition contains, as a lime-containing regulator, the setting of sludge from the galvanic wastewater in the following ratio of components, wt.%: Gypsum gypsum - 23.7-36.0, skok (by dry weight) 2.58-3.8, sediment galvanic wastewater 6.5-7.0, urea 0.12-0.3, water 54.0-65.2. The material has a density of 500-700 kg / m ³ , compressive strength 1.55-1.7 MPa, bending 0.6-1.1 MPa, c.k.k. 1.2-1.65, shrinkage 0.1-0.7%, drying time 22-30 hours, has a reduced shrinkage.

From RU 2260572, 09/20/2005, it is known a composite product obtained on the basis of a gypsum binder and additives for modifying gypsum, in particular, the product is obtained from a mixture containing in wt.%:

1. gypsum binder - semi-aquatic gypsum 70 2. gypsum modification additive thirty

In this case, the addition of the following composition (% by weight):

1. hydraulic binder, portland cement 87.9 2. active mineral component, silica fume 10 3. polycarboxylate-based superplasticizer one 4. moderator gypsum hardening, natural tartaric acid 0.1 5. water soluble cellulose ether, hydroxyethyl cellulose one

The resulting composition has increased frost resistance and strength, therefore, the scope of use is expanding due to the possibility of perceiving large external loads and mixtures, while the value of the specific surface of the additive is 4000 m ² / kg. Thus, the technological characteristics are significantly improved.

From RU 2084416, 07/20/1997 there is also known a method of manufacturing decorative building products and / or decorative coatings by mixing with water a binder containing Portland cement clinker, a solid modifier consisting of an organic water-reducing substance and a hardening accelerator, active mineral additives and / or fillers and gypsum , pigments, fillers, functional additives, aging the resulting mixture, followed by its laying, molding, compaction and heat treatment, and the mixture obtained after mixing is kept for to achieve a constant concentration of the organic water-reducing component of the modifier in the liquid phase of the mixture. In the known method using a modifier containing as an organic water-reducing component polycondensate of naphthalenesulfonic acid with formaldehyde, and sodium sulfate in a ratio by weight of 15: 1 - 1: 1, respectively; hardening accelerators, for example, aluminum sulfate and / or retarders, for example, lactones and / or hydrophobizing additives, for example, higher fatty acids and their salts and / or sealing additives, for example, iron (III) sulfate or silica fume, are used as functional additives ; at least a component from the group is used as active mineral additives: blast furnace granulated slag, fly ash, natural pozzolans (slopes, volcanic ash), at least a component from the group is used as fillers: limestone, white quartz sand, carbonate sand. The known method allows to increase the strength of decorative concrete and its resistance to physical and chemical aggression of the environment, to prevent the formation of fading, to form and for a long time to maintain distinct relief, color and tonal contrasts on the surface of products and / or coatings.

From RU 2160239, 10.12.2000, a method is known for manufacturing architectural and construction products by mixing in a mixer a gypsum binder, a structure-forming additive, an amino aldehyde group resin, an acid hardener and a filler, followed by molding of the product and its exposure, the components of the mixture are used in the following ratios, wt.% : filler 22.0-45.0, fibrous material 2.0-8.0, structure-forming additive 0.6-6.5%, resin of the aminoaldehyde group 15.0-30.0, acid hardener 0.3-1, 5, gypsum binder - the rest, and the amount is sour hardener is preliminarily determined by the acid pH of the mixture, the value of which is set in the range of 2.5-3.5, while first the resin and the structure-forming additive are loaded into the inactive mixer, then it is turned on and the entire volume of the filler is fed immediately for 45-75 s - gypsum binder. After that, the acid hardener is loaded into the working mixer and all the components of the mixture are subjected to additional mixing for 25-35 s, after which the composition is poured into molds and after 15-20 minutes after pouring, after the product has set, they are unformed and sent to ripen. Products are kept at a temperature of 15-20 ° and humidity not more than 80% for 5-7 days or subjected to heat treatment at 60-70 ° for 12-14 hours. Fibrous material may be introduced into the mixture. The technical result is to increase the uniformity of the mixture, its workability and increase the strength of the hardened composition.

The technical task of the claimed invention is to increase the strength, water resistance, frost resistance of the product, as well as reducing water absorption and erosion of gypsum products under the influence of water flows, which generally leads to increased durability of products based on gypsum binder.

The stated technical problem is achieved by the claimed group of inventions, which includes a method for producing a waterproof composite product based on a gypsum binder (and its variants) and the composite gypsum product obtained by a method that is one of the inventions of the claimed group.

So, the stated technical problem is achieved by the method of producing a waterproof composite product based on a gypsum binder, including the preliminary preparation of a hydrophobizing complex modifying additive, its subsequent mixing to obtain a homogeneous mass with mixing water with intensive mixing and a gypsum binder selected from the group including construction, high strength gypsum binder, anhydrite binder, their mixture and, if necessary, with crushed filler and further form the product, while the hydrophobizing additive is prepared with vigorous stirring of aqueous solutions of sodium tripolyphosphate, sodium adipate, potassium polymethylsiliconate and phosphogypsum, to obtain calcium polymethylsiliconate and antifoam in situ.

The technical problem is also achieved in another way to obtain a water-resistant composite product based on a gypsum binder, including preliminary preparation of a paste-like plasticizing additive, its subsequent mixing with vigorous stirring until a homogeneous mass with mixing water and a gypsum binder selected from the group comprising building, high-strength gypsum binder , anhydrite binder, their mixture and, if necessary, with crushed filler and further molding of the product, while m plasticizing additive is prepared with vigorous stirring of aqueous solutions of sodium polycarboxylate, urea, sodium gluconate and powdered calcium hydroxide.

The technical problem is also achieved by another method that is included in the claimed group of inventions, and which is a method of obtaining a waterproof composite product based on a gypsum binder, including the preliminary preparation of a hydrophobizing complex additive and a paste-like plasticizing additive, their subsequent mixing in a ratio of 1: 1 to obtain a multifunctional additive modifying, mixing the resulting additive with vigorous stirring until a homogeneous mass with mixing water I and a gypsum binder, selected from the group including building, high-strength gypsum binder, anhydrite binder, their mixture, and also, if necessary, with crushed filler and subsequent molding of the product, while the hydrophobizing additive is prepared with vigorous stirring of aqueous solutions of sodium tripolyphosphate, sodium adipate, as well as potassium polymethylsiliconate and phosphogypsum, to obtain in situ calcium polymethylsiliconate and antifoam tributyl phosphate, and the plasticizing additive is prepared with vigorous stirring AANII aqueous sodium polycarboxylate, urea, sodium gluconate and calcium hydroxide powder.

When implementing all the variants of the method for producing the waterproof gypsum binder composite product according to the invention, crushed carbonate filler, for example limestone, sand, dolomite flour, aluminosilicate filler, for example aluminosilicate sand, gneiss or granite screenings, finely ground expanded clay, silica-containing filler is used as filler rocks, such as silica sand, silica dust.

The stated technical problem is also achieved by the invention, which is included in the claimed group of inventions, which is a product from a composite gypsum material based on a gypsum binder, obtained by one of the methods of the claimed group and made from a composition comprising a gypsum binder, an additive, if necessary, ground filler and water at the following ratio of components in wt.%:

Gypsum binder 20.0-90.0 Additive 1.8-9.0 Filler 0.00-60.0 Water rest

while as an additive, the composition contains a hydrophobic complex modifying additive composition in wt.%:

sodium tripolyphosphate 0.5-3.5 sodium adipates 0.35-2.5 potassium polymethylsiliconate 10.0-22.5 phosphogypsum 4.0-47.0 tributyl phosphate antifoam 0.04-0.2 water rest

or a paste-like plasticizing additive composition in wt.%:

sodium polycarboxylate 4,5-14,0 urea 2.4-4.5 sodium gluconate 0.005-0.04 powdered calcium hydroxide 48.0-80.0 water rest

or a mixture of these hydrophobizing and plasticizing additives in a ratio of 1: 1 to obtain a multifunctional additive.

In the claimed group of the invention, tributyl phosphate is used as a defoamer, building gypsum binder (high strength gypsum binder), for example, grades G7 (G-16), anhydrite gypsum binder, for example, AG-200 binder, are used as a gypsum binder.

The following are specific examples illustrating the invention, but not limiting it, while in examples 1-10, tributyl phosphate is used as a defoamer, G16 grade gypsum binder is used as a gypsum binder, tributyl phosphate is used as a defoamer in examples 1-10 gypsum binder - gypsum binder grades G7.

EXAMPLE 1. In a container, a gypsum modifying additive was preliminarily prepared by mixing 80 g of potassium polymethylsiliconate solution (40 g of dry basic substance) and 15 g of phosphogypsum, stirring was continued until a colloidal compound of calcium polymethylsiliconate was formed, and 100 g of a solution containing 300 g / l of urea (30.0 g), 120 g of a solution containing 380 g / l of sodium poly-R-carboxylate (45.6 g), 20 g of a solution containing 600 g / l of sodium tripolyphosphate (12 g), 30 g of a solution containing 300 g / l sodium adipate (9.0 g) and 0.5 g of antifoam - three butyl phosphate. Got a product - a modifying additive weighing 360.5 g, containing 140 g of dry matter.

In another container, a pasty plasticizer was previously prepared by mixing 150 g of a solution containing 380 g / l sodium poly-R-carboxylate (57 g), 100 g of a solution containing 300 g / l of urea (30 g), and 5 g of a solution containing 100 g / l sodium gluconate (0.5 g), 1000 g of powdered calcium hydroxide was added to the resulting solution with stirring until a uniform, paste-like suspension was obtained. In total, a paste-like plasticizer of 1255 g; including 167.5 g of water.

The obtained water-repellent additive and a paste-like plasticizer were mixed in equal masses with constant stirring to obtain an even mass of suspended multifunctional gypsum modifying additive. A total of 1615 g of additives was obtained; including 388 g of water.

A gypsum modifying additive in an amount of 807.5 g was placed in a container with 1000 g of water and 5000 g of gypsum binder grade G16 were successively added with vigorous stirring, obtaining a homogeneous, easily moving suspension with stirring, and 5000 g of quartz sand to a homogeneous mass.

Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Measured according to GOST, the spread of the composite mass and the setting time of the suspension at a water-gypsum ratio (W / D) of 0.23.

Upon hardening of the product and prototypes, they were tested for resistance to erosion, water absorption, water resistance, compressive and bending strength and frost resistance according to GOST 23789-79, 10060.0-95, 8462-85. The test results are shown in table.2 (at the end of the description).

Gypsum binder - 5000 g - 41.7% Quartz sand - 5000 g - 41.7% Modifying additive - 807.5 g. - 6.8% Water - 1140 g - 9.6%

The composition of the complex water-repellent component: Calcium Polymethylsiliconate - 26.3% Sodium Tripolyphosphate - 3.3% Sodium adipate - 2.5% Antifoam agent - 0.14% Water - the rest The composition of the paste plasticizer: Calcium hydroxide - 79.6% Sodium Poly-R-Carboxylate - 4.5% Urea - 2.4% Sodium Gluconate - 0.04% Water - the rest The composition of the suspended multifunctional gypsum modifying additive: Calcium hydroxide - 30.9% Calcium Polymethylsiliconate - 2.9% Sodium Tripolyphosphate - 0.37% Sodium adipate - 0.28% Antifoam agent - 0.02% Sodium Poly-R-Carboxylate - 1.7% Urea - 0.9% Sodium Gluconate - 0.01% Water - the rest

EXAMPLE 2. A hydrophobizing complex component was preliminarily prepared by mixing 160 g of a solution of potassium polymethylsiliconate (80 g) and 200 g of phosphogypsum, 60 g of a solution containing 100 g / l sodium tripolyphosphate (6 g), 5 g of a solution containing 300 g / l adipate sodium (1.5 g) and 0.5 g (0.5 g) antifoam tributyl phosphate, mixing was carried out until the formation of a colloidal compound of calcium polymethylsiliconate. A total of 425.5 g of water repellent solution was obtained; including water 137.5 g

In another container, a pasty plasticizer was previously prepared by mixing 150 g of a solution containing 380 g / l sodium poly-R-carboxylate (57 g), 100 g of a solution containing 300 g / l of urea (30 g), and 5 g of a solution containing 100 g / l sodium gluconate (0.5 g), 1000 g of powdered calcium hydroxide was added to the resulting solution with stirring until a uniform, paste-like suspension was obtained. In total, a paste-like plasticizer of 1255 g; including 167.5 g of water.

The obtained hydrophobic complex component and paste-like plasticizer were mixed in equal volumes with constant stirring until a uniform mass of suspended multifunctional gypsum modifying additive was obtained. In total, a gypsum modifying additive turned out to be 1680.5 g; including 305 g of water.

A gypsum modifying additive in the amount of 840 g was placed in a container with 1000 g of water, and 5000 g of gypsum binder grade G7 were successively added with vigorous stirring, obtaining a homogeneous, easily moving suspension, and 5000 g of limestone sand until a homogeneous mass. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. The spread of the composite mass and the setting time according to GOST of the suspension were measured at a water-gypsum ratio (W / D) of 0.23.

Upon hardening of the product and prototypes, they were tested for resistance to erosion, water absorption, water resistance, compressive and bending strength and frost resistance according to GOST 23789-79, 10060.0-95, 8462-85. The test results are shown in table.2.

Gypsum binder - 5000 g - 41.7% Limestone sand - 5000 g - 41.7% Modifying additive - 840 g. - 7.0% Water - 1150 g - 9.59% The composition of the complex water-repellent component: Calcium Polymethylsiliconate - 35.2.0% Sodium Tripolyphosphate - 1.4% Sodium adipate - 0.35% Antifoam agent - 0.12% Water rest

The composition of the paste plasticizer: Calcium hydroxide - 79.7% Sodium Poly-R-Carboxylate - 4.5% Urea - 2.4% Sodium Gluconate - 0.04% Water - the rest The composition of the suspended multifunctional gypsum modifying additive: Calcium hydroxide - 29.8% Calcium Polymethylsiliconate - 4.46% Sodium Tripolyphosphate - 0.18% Antifoam agent - 0.03% Sodium Poly-R-Carboxylate - 1.7% Urea - 0.9% Sodium adipate - 0.04% Sodium Gluconate - 0.02% Water - the rest

EXAMPLE 3. A complex water-repellent component was preliminarily prepared by mixing 80 g of a solution of potassium polymethylsiliconate (40 g) and 150 g of phosphogypsum, 60 g of a solution containing 100 g / l sodium tripolyphosphate (6 g), 5 g of a solution containing 300 g / l sodium adipate (1.5 g) and 0.5 g (0.5 g) antifoam tributyl phosphate, stirring was carried out until the formation of a colloidal compound of calcium polymethylsiliconate. In total, a water-repellent solution of 295.5 g was obtained; including water 197.5

The resulting complex water-repellent component in an amount of 148 g was placed in a container with 600 g of water, and 5000 g of a gypsum binder grade G16 were successively added with vigorous stirring, obtaining a homogeneous, easily-moving suspension with stirring. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Further, as in example 1.

Gypsum binder - 5000 g 85.5% Water repellent component - 148 g 2.5% Water - 698 g 11.9% The composition of the complex water-repellent component: Calcium Polymethylsiliconate - 30.4% Sodium Tripolyphosphate - 2.0% Sodium adipate - 0.5 Antifoam agent - 0.17% Water - the rest

EXAMPLE 4. A complex water-repellent component was preliminarily prepared by mixing 180 g of a solution of potassium polymethylsiliconate (90 g) and 250 g of phosphogypsum, 100 g of a solution containing 100 g / l sodium tripolyphosphate (10 g), 10 g of a solution containing 300 g / l sodium adipate (3 g) and 0.5 g (0.5 g) antifoam, mixing was carried out until the formation of a colloidal compound of calcium polymethylsiliconate. In total, a solution of water-repellent 540.5 g was obtained; including water 357 g

The resulting hydrophobizing additive in an amount of 270 g was placed in a container with 600 g of water, and 5000 g of a gypsum binder grade G 7 were successively added with vigorous stirring to obtain a homogeneous, easily moving suspension with stirring. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Further, as in example 1.

Gypsum binder - 5000 g 82.7% Water-repellent additive - 270 g. 4,5% Water - 778 g 12.9 The composition of the complex water-repellent component: Calcium Polymethylsiliconate - 31.4% Sodium Tripolyphosphate - 1.82% Sodium adipate 0.55% Antifoam agent - 0.09% Water - the rest

EXAMPLE 5. A complex water-repellent component was preliminarily prepared by mixing 500 g of a solution of potassium polymethylsiliconate (250 g) and 400 g of phosphogypsum, 200 g of a solution containing 100 g / l sodium tripolyphosphate (20 g), 10 g of a solution containing 300 g / l sodium adipate (3 g) and 0.5 g (0.5 g) antifoam, mixing was carried out until the formation of a colloidal compound of calcium polymethylsiliconate. In total, a solution of water-repellent 1110.5 g was obtained; including water 687

The obtained water-repellent component in an amount of 278 g was placed in a container with 800 g of water and 5000 g of a gypsum binder was successively added with vigorous stirring to obtain a homogeneous, easily moving suspension with stirring. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Further, as in example 1.

Gypsum binder - 5000 g 80.0% Water-repellent additive - 278 g. 4.4% Water - 972 g 15.5% The composition of the complex water-repellent component: Magnesium Polymethylsiliconate - 36.0% Sodium Tripolyphosphate - 1.8% Sodium adipate - 0.27% Antifoam agent - 0.04% Water - the rest

EXAMPLE 6. In a container, a pasty plasticizer was preliminarily prepared by mixing 750 g of a solution containing 380 g / l sodium poly-R-carboxylate (285 g), 300 g of a solution containing 300 g / l of urea (90 g) and 5 g of a solution containing 20 g / l of calcium gluconate (0.1 g), to the resulting solution was added with stirring 1000 g of powdered calcium hydroxide to obtain a uniform pasty suspension. In total, a paste-like plasticizer of 2055 g was obtained; including 680 g of water.

The resulting paste-like plasticizer in an amount of 210 g was placed in a container with 1 l of water and 5000 g of gypsum binder grade G10 were successively added with vigorous stirring, obtaining a homogeneous, easily-moving suspension with stirring, and 5000 g of aluminosilicate sand to a homogeneous mass. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Further, as in example 1.

Gypsum binder - 5000 g - 44.3% Silica sand - 5000 g - 44.3% Pasty plasticizer - 210 g - 1.86% Water - 1070 g - 9.5% The composition of the paste plasticizer Calcium hydroxide - 48.7% Sodium Poly-R-Carboxylate - 13.9% Urea - 4.38% Sodium Gluconate - 0.005% Water - the rest

EXAMPLE 7. In a container, a pasty plasticizer was preliminarily prepared by mixing 750 g of a solution containing 380 g / l sodium poly-R-carboxylate (285 g), 300 g of a solution containing 300 g / l of urea (90 g), 25 g of a solution containing 20 g / l of calcium gluconate (0.5 g), to the resulting solution was added with stirring 1000 g of powdered calcium hydroxide to obtain a uniform paste-like suspension. In total, a paste-like plasticizer of 2075 g was obtained; including 699.5 g of water.

The resulting paste-like plasticizer in an amount of 210 g was placed in a container with 500 g of water and 5000 g of a gypsum binder grade G16 were successively added with vigorous stirring, obtaining a homogeneous, easily-moving suspension with stirring to a homogeneous mass. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Further, as in example 1.

Gypsum binder - 5000 g - 86.5% Pasty plasticizer - 210 g - 3.6% Water - 1070 g - 9.8% The composition of the paste plasticizer: Calcium hydroxide - 48.2% Sodium Poly-R-Carboxylate - 13.7% Urea - 4.3% Sodium Gluconate - 0.02% Water - the rest

EXAMPLE 8. In a container, a pasty plasticizer was preliminarily prepared by mixing 750 g of a solution containing 380 g / l sodium poly-R-carboxylate (285 g), 300 g of a solution containing 300 g / l of urea (90 g) and 25 g of a solution containing 20 g / l of calcium gluconate (0.5 g), to the resulting solution was added with stirring 1000 g of powdered calcium hydroxide to obtain a uniform pasty suspension. In total, a paste-like plasticizer of 2100 g was obtained; including 710 g of water.

The resulting paste-like plasticizer in an amount of 630 g was placed in a container with 1.4 l of water, and with vigorous stirring, 5000 g of a gypsum binder were successively added, obtaining a homogeneous, easily moving suspension, and 15000 g of quartz sand with a uniform mass. Thus prepared suspension mass of the composite material was poured into the shapes of the products and the forms of the test samples. Further, as in example 1.

Gypsum binder - 5000 g - 22.5% Quartz sand - 15000 g - 67.4% pasty plasticizer - 630 g - 2.8% Water - 1400 g - 7.3% The composition of the paste plasticizer: Calcium hydroxide - 48.2% Sodium Poly-R-Carboxylate - 13.7% Urea - 4.3% Sodium Gluconate - 0.02% Water - the rest

EXAMPLE 9. A complex water-repellent component was preliminarily prepared by mixing 200 g of a solution of potassium polymethylsiliconate (100 g) and 250 g of phosphogypsum, 100 g of a solution containing 100 g / l sodium tripolyphosphate (10 g), 50 g of a solution containing 300 g / l sodium adipate (15 g) and 0.5 g (0.5 g) antifoam tributyl phosphate, mixing was carried out until the formation of a colloidal compound of calcium polymethylsiliconate. In total, a solution of a hydrophobizing agent of 600.5 g was obtained; including water 355.0 g

In another container, a pasty plasticizer was previously prepared by mixing 250 g of a solution containing 380 g / l sodium poly-R-carboxylate (95 g), 200 g of a solution containing 300 g / l of urea (60 g) and 25 g of a solution containing 20 g / l of calcium gluconate (0.5 g), 1000 g of powdered calcium hydroxide was added to the resulting solution with stirring until a uniform, paste-like suspension was obtained. In total, a paste-like plasticizer of 1475 g; including 319.5 g of water.

The resulting complex water-repellent component and a paste-like plasticizer were mixed in equal masses with stirring until a uniform mass of suspended multifunctional gypsum modifying additive was obtained. In total, a gypsum modifying additive turned out to be 2075.5 g; including 674.5 g of water.

A gypsum modifying additive in an amount of 1030 g was placed in a container with 1000 g of water, and 5000 g of gypsum binder grade G16 were successively added with vigorous stirring, obtaining a homogeneous, easily moving suspension, and 5000 g of limestone sand to a homogeneous mass with stirring. Further, as in example 1.

Gypsum binder - 5000 g - 40.4% Limestone sand - 5000 g - 40.4% Modifier 1030 g - 8.3% Water - 1337 g - 10.8% The composition of the complex water-repellent component: Calcium Polymethylsiliconate - 36.6% Sodium Tripolyphosphate - 1.66% Sodium adipate - 2.5% Antifoam agent - 0.08% Water - the rest The composition of the paste plasticizer: Calcium hydroxide - 48.2% Sodium Poly-R-Carboxylate - 13.7% Urea - 4.3% Sodium Gluconate - 0.02% Water - the rest The composition of the suspended multifunctional gypsum modifying additive: Calcium hydroxide 23.9% Calcium Polymethylsiliconate 4.3% Sodium Tripolyphosphate 0.24% Sodium adipate 0.16% Antifoam agent 0.01% Sodium Poly-R-Carboxylate 2.23% Urea 1.41% Sodium Gluconate 0.01% Water rest

EXAMPLE 10. A complex water-repellent component was preliminarily prepared by mixing 200 g of a solution of potassium polymethylsiliconate (100 g) and 250 g of phosphogypsum, 100 g of a solution containing 100 g / l sodium tripolyphosphate (10 g), 50 g of a solution containing 300 g / l sodium adipate (15 g), and 0.5 g (0.5 g) of antifoam tributyl phosphate, mixing was carried out until the formation of a colloidal compound of calcium polymethylsiliconate. In total, a solution of a hydrophobizing agent of 600.5 g was obtained; including water 355 g

In another container, a pasty plasticizer was previously prepared by mixing 250 g of a solution containing 380 g / l sodium poly-R-carboxylate (95 g), 200 g of a solution containing 300 g / l of urea (60 g), and 50 g of a solution containing 20 g / l calcium gluconate (1 g) to the resulting solution was added with stirring 1000 g of powdered calcium hydroxide to obtain a uniform paste-like suspension. In total, a pasty plasticizer of 1500 g was obtained; including 344 g of water.

The obtained complex water-repellent component and paste-like plasticizer were mixed in equal volumes with constant stirring until a uniform mass of suspended multifunctional gypsum modifying additive was obtained. In total, a gypsum-modifying additive turned out to be 2100.5 g; including 699 g of water.

A gypsum modifying additive in an amount of 1030 g was placed in a container with 1 liter of water, and with vigorous stirring, 10,000 g of gypsum binder grade G7 were successively added, obtaining a homogeneous, easily moving suspension with stirring. Further, as in example 1.

Gypsum binder - 10,000 g - 80.8% Modifying additive - 1030 g. - 8.3% Water - 1340 g - 10.8% The composition of the complex water-repellent component: Calcium Polymethylsiliconate - 36.6% Sodium Tripolyphosphate - 1.7% Sodium adipate - 2.5% Antifoam agent - 0.08% Water - the rest The composition of the paste plasticizer: Calcium hydroxide - 66.7% Sodium Poly-R-Carboxylate - 13.7% Urea - 4.3% Sodium Gluconate - 0.02% Water - the rest The composition of the suspended multifunctional gypsum modifying additive: Calcium hydroxide - 28.9% Calcium Polymethylsiliconate - 4.3% Sodium Tripolyphosphate - 0.20% Sodium adipate - 0.35% Antifoam agent 0.01% Sodium Poly-R-Carboxylate 2.24% Urea 1.40% Sodium Gluconate 0.01% Water rest

EXAMPLE 11 (control). Portland cement is loaded into the grinder in the amount of 82% of the total weight of the prepared gypsum modifying additive, the active mineral component is fine quartz sand - 10%, sodium carboxylate in the amount of 2%, tartaric acid - 1%, water-soluble cellulose ether (MC) - 5%. The material in the form of a dry mixture was ground for 3 hours to a fineness of particles with a specific surface area of 4900 cm ² / g. After cooling, the additives were used to prepare the gypsum slurry. To 5000 g of gypsum binder grade G16 was added 500 g of the obtained preliminary modifying gypsum additive 5000 g of quartz sand and 2000 ml of water. W / D = 0.4. The suspension was mixed to a homogeneous mass, then it was poured into the forms of the products and experimental test samples. The tests were performed as described in example 1. The results are shown in table.2.

The compositions of the gypsum modifying additives used in examples 1-10 are shown in table 1.

Table 1
Composition Examples №№ The content of components,% Gypsum binder Filler - sand Modifying additive Complex-
idrophobic
component Pasty
plasticizer Water Quartz Limestone Aluminosilicate one. 42.3 42.3 - - 6.8 - - 8.5 2. 41.7 - 41.7 - 7.0 - - 9.6 3. 85.5 - - - - 2.5 - 11.9 four. 82.7 - - - 4,5 - 12.9 5. 80.0 - - - - 4.4 - 15,5 6. 44.3 - - 44.3 - 1.86 - 9.5 7. 86.5 - - 3.6 - - 9.8 8. 22.5 67.4 - - - - 2,8 7.3 9. 40,4 40,4 - - - - 8.3 10.8 10. 80.8 - - - 8.3 - - 10.8 eleven. 32,0 32,0 - 10.0 - - 16,0

The test results of gypsum concrete samples using gypsum modifying additives are given in table 2

table 2
Properties of the composite material according to the invention №№ CM Suspension Spray The depth of erosion by a jet of water surface with a diameter of 2 mm for 4 days. on the surface of a hardened concrete sample Water absorption,% Water resistance coefficient, Cr Volumetric density, kg / m ³ Strength, MPa Frost resistance cycles compression bend one. 210 0.5 1,1 0.94 2250.0 48.5 19.5 one hundred 2. 212 0.6 1,1 0.95 2255.0 48,2 20,0 one hundred 3. 210 0.6 1,0 0.95 2200.0 48.3 19.3 one hundred four, 215 0.7 1,2 0.96 2215.0 49.0 20.5 one hundred 5. 200 0.8 1.3 0.93 2080.0 47.9 18.5 75 6. 195 0.9 1,2 0.94 2050.0 47.3 18.3 75 7. 230 0.5 1,0 0.90 2180.0 50,0 22.0 one hundred 8. 190 0.9 1,1 0.95 2030.0 48.0 18.6 75 9. 195 1,2 1,0 0.96 2045.0 48.9 18.9 75 10 190 1,1 1,1 0.94 2048.0 47.9 17.5 75 eleven 160 10.8 8.4 0.65 1870.0 23.0 7.8 fifty

Thus, the invention allows to increase the plasticity of pouring suspensions, strength, water resistance, frost resistance and durability, to reduce water absorption and erosion of products under the influence of water flows.

In addition, the advantages of the proposed invention include the cost-effectiveness of preparation of the additive (there is no need to use the laborious, metal-intensive and energy-intensive process of grinding the starting components), the simplicity of the preparation operations.

Claims (7)

1. A method of obtaining a waterproof composite product based on a gypsum binder, including the preliminary preparation of a hydrophobizing complex modifying additive, its subsequent mixing to obtain a homogeneous mass with mixing water with intensive mixing and a gypsum binder selected from the group comprising building gypsum binder, high-strength gypsum binder , anhydrite binder, their mixture and, if necessary, with crushed filler and molding of the product, while hydrophobizing The casing is prepared with vigorous stirring of aqueous solutions of sodium tripolyphosphate, sodium adipate, potassium polymethylsiliconate and phosphogypsum, to obtain calcium polymethylsiliconate and antifoam in situ. 2. A method of obtaining a water-resistant composite product according to claim 1, characterized in that the filler uses ground carbonate filler, aluminosilicate filler, silica filler from rocks. 3. A method of obtaining a waterproof composite product based on a gypsum binder, including the preliminary preparation of a paste-like plasticizing additive, its subsequent mixing to obtain a homogeneous mass with mixing water with intensive mixing and a gypsum binder selected from the group including building gypsum binder, high-strength gypsum binder, anhydrite binder, their mixture and, if necessary, with crushed filler and further molding of the product, while plasticizing additive prepared with vigorous stirring aqueous solutions of sodium poly-R-carboxylate (sodium polycarboxylate), urea, sodium gluconate and powdered calcium hydroxide. 4. A method of obtaining a water-resistant composite product according to claim 3, characterized in that the crushed carbonate filler, aluminosilicate filler, silica filler from rocks are used as filler. 5. A method of obtaining a waterproof composite product based on a gypsum binder, including the preliminary preparation of a hydrophobizing complex modifying additive and a pasty plasticizing additive, their subsequent mixing in a ratio of 1: 1 to obtain a multifunctional modifying additive, mixing the resulting additive with intensive mixing with mixing water and gypsum a binder selected from the group comprising building gypsum binder, high strength gypsum binder, anhydrite binder it, their mixture, and, if necessary, with ground filler and subsequent molding of the product, while the hydrophobizing additive is prepared with vigorous stirring of aqueous solutions of sodium tripolyphosphate, sodium adipinate, as well as potassium polymethylsiliconate and phosphogypsum, to obtain in situ calcium polymethylsiliconate and antifoam, and a plasticizing additive is prepared with vigorous stirring of aqueous solutions of sodium polycarboxylate, urea, sodium gluconate and powdered calcium hydroxide. 6. A method of obtaining a water-resistant composite product according to claim 5, characterized in that the crushed carbonate filler, aluminosilicate filler, silica filler from rocks are used as filler. 7. A product from a composite gypsum material obtained by the method according to one of claims 1 to 6 and made from a composition comprising a gypsum binder, an additive, optionally ground filler and water in the following ratio of components, wt.%:
Gypsum binder 20.0-90.0 Additive 1.8-9.0 Filler 0.00-60.0 Water Rest
while as an additive, the composition contains a hydrophobic complex modifying additive composition, wt.%:
Sodium Tripolyphosphate 0.5-3.5 Sodium adipates 0.35-2.5 Potassium Polymethylsiliconate 10.0-22.5 Phosphogypsum 4.0-47.0 Antifoam agent 0.04-0.2 Water Rest
or pasty plasticizing additive composition, wt.%:
Sodium Polycarboxylate 4,5-14,0 Urea 2.4-4.5 Sodium Gluconate 0.005-0.04 Powdered Calcium Hydroxide 48.0-80.0 Water Rest
or a mixture of these hydrophobizing and plasticizing additives in a ratio of 1: 1 to obtain a multifunctional additive.