UA81093C2 - Swelling flameproof dye - Google Patents

Abstract

Swelling flameproof dye comprises, in weight %: plastified polyvinylacetate dispersion - 20-25, pentaerythritol - 8, ammonium polyphosphate - 8-10, titanium dioxide - 2, zinc phosphate - 8-10, thermalexpanding graphite - 8-12, ammonia water - 3-5, hardened fine-disperse carbamideformaldehyde resin - 6-8, tetramethylthiuramdisulphide (preservative) -0.01, dipropyleneglycol butyl ether (coalescent) - 1.0-1.25, sodium tripolyphosphate - 0.5 and water - to 100. The dye allows to increase flameproof protection and heat-insulating ability.

Description

Description of the invention

The invention relates to paint and varnish materials, namely to fire-resistant water-emulsion paints and can be used for internal and external works on wood, plaster, polyurethane foam, cardboard and metal structures in construction, aviation, railway transport and in other areas where protection of the surfaces of such products is required from fire

Fire-resistant coatings have a fire-resistant effect when protecting easily combustible surfaces (wood, cardboard) and a heat-insulating effect when protecting metal and other hard-to-burn surfaces in order to increase their 70 degree of fire resistance in the event of a fire. The principle of the protective effect of most coatings is to reduce the depth and speed of heating of the surface receiving protection.

The decisive factor that determines the effectiveness of the fireproof action of the coating is its heat-insulating ability, which largely depends on the thickness of the coating.

However, an excessive increase in the thickness of the coating can negatively affect its operational properties. 12 From this point of view, the most promising are the intumescent fire protection coatings, which have a relatively small thickness, which significantly increases in fire conditions under the influence of high temperatures.

The known composition of the intumescent fire-resistant paint based on carbamide-formaldehyde resin as a binder, which includes ammonium polyphosphate, dicyandiamide, pentaerythritol, kaolin, glass fiber and water Patent

RF Mo20283481I.

Ureaformaldehyde resin is used as a carbonizing component that forms "pincoke" as a result of combustion.

However, the preparation of such a composition must be carried out immediately before applying the coating, which is non-technological, and the use of dicyandiamide leads to the release of toxic substances during combustion.

A well-known composition of intumescent fire-resistant paint, which includes (95 mass): c o graphite, which thermally expands 10-15; liquid glass 70-80; sodium silicofluoride 5-10. co

As a result of the action of fire, thermally expanding graphite swells the coating, reducing its density from 1810 kg/m Z F to З15 kg/m3 and the coefficient of thermal conductivity from 0.436 to 0.132 W/m.K and, accordingly, provides an increase in the fire resistance of steel structures up to 120 minutes | "Fireproof compositions based on liquid glass and expanding graphite". Gvozdeva 0. "Building materials" 2004, Mo4, P.33-35.1. "-

Despite the high degree of fire protection, these compositions have a number of significant disadvantages. Applied as

Because the binding liquid glass does not provide sufficient adhesion to metal surfaces, and the high alkalinity of the liquid glass accelerates the corrosion of the metal, in addition, the specified compositions have low viability and require their preparation immediately before applying to the substrate.

The closest to the invention in technical terms is the intumescent fire retardant paint, which contains (95 mass): "

Pentaerythritol 8.0-15.0; - with poly ammonium phosphate 20.0-25.0; h » sodium polyphosphate 0.1-0.5; Melamine 10.0-15.0;

Dispersion of low molecular weight acrylic polymer 0.1-0.5;

Unplasticized polymer dispersion with vinyl versatate 18.0-22.0; bo Sodium carboxymethyl cellulose 0.2-0.4; sha Derivatives of isothiazolone 0.1-0.3;

Titanium dioxide 4.0-8.0; o Silicone defoamer 0.5-1.0;

I«e) 50 2,2,A-trimethyl-1,3-pentadiol monoisobutyrate 0.2-0.5;

Butyl cellosolve 0.3-0.87; c» Chloroparaffin or phosphate plasticizer 2.0-5.0;

Silicon dioxide 0.5-1.0;

Water up to 100.

GF) The paint has satisfactory water resistance (2.1 g/m?) and fire-retardant properties, which are expressed in an increase in the swelling factor (up to 32) and a stronger swollen layer (Russian Patent Mo2225423).

The disadvantages of the known composition are insufficient adhesion and corrosion resistance of the coating.

The basis of the invention is the task of increasing adhesion, increasing the swelling ratio and adding 60 anti-corrosion properties to the paint.

The task is solved by the fact that the intumescent fireproof paint includes an aqueous dispersion of polymers, pentaerythritol, ammonium polyphosphate, titanium dioxide, metal phosphate, preservative, coalescent and water, contains as an aqueous dispersion of polymers - plasticized polyvinyl acetate dispersion, as metal phosphate - zinc phosphate and sodium tripolyphosphate as a preservative - tetramethylthiuram disulfide, as a coalescent - butyl bo ether of dipropylene glycol and additionally heat-expanding graphite, ammonia water and hardened finely dispersed -D-

urea-formaldehyde resin with the following ratio of components (95 mass):

Plasticized polyvinyl acetate dispersion 20-25

Pentaerythritol 8

Ammonium polyphosphate 8-10

Titanium dioxide 2

Zinc phosphate 8-0

Thermally expanding graphite 8-12

Ammonia water 3-5

Cured fine-dispersed carbamide-formaldehyde resin 6-8

Tetramethylthiuram disulfide (preservative) 0.01

Dipropylene glycol butyl ether (coalescent) 1.0-1.25

Sodium tripolyphosphate 0.5

Water up to 100

The general features of the invention in comparison with the known are the use of an aqueous polymer dispersion as a binder and pentaerythritol as a swelling catalyst. as a gas generator - ammonium polyphosphate, as a white pigment titanium dioxide, as a surface-active substance - tripolyphosphosphate sodium, as well as 2o Preservative, coalescent and water.

The invention differs from the known application of the foaming component - heat-expanding graphite (8-1296 mass) as a carbonizer and gas generator - cured finely dispersed urea-formaldehyde resin (6-895 mass) as an anti-corrosion additive - zinc phosphate (8-1095 mass .) and as a pH regulator - aqueous ammonia 20905th (3-5905 mass). with

Plasticized polyvinyl acetate dispersion - 509o-water emulsion of polyvinyl acetate, plasticized with dibutyl phthalate. Milk-white liquid. (8)

Polyvinyl acetate is a chemical compound with the general formula:

ISN.-CH(OSOSN)-1,

It is used in adhesive and paint compositions. ("Encyclopedia of polymers", M., "Soviet social encyclopedia", 1972, vol. 1, pp. 386-389).

Pentaerythritol (2,2-dimethylol-1,3-propanediol) is a white crystalline powder. Me)

Chemical compound of the general formula: o sno "- z no-ny-s-sn.-on so sno "

It is used in the paint industry for the production of varnishes. ("Chemical encyclopedic dictionary"

M. "Soviet Encyclopedia", 198Zr. P.427). o, c Ammonium polyphosphate is a white crystalline powder, which is a mixture of ammonium phosphates with different degrees of polycondensation. A chemical compound of the general formula: и? (MNa)dak" RaOzpa, where n » 200 is the number of phosphorus atoms in the TU 6-47-18-91-911 molecule.

Titanium dioxide is a white powder. Chemical compound of the general formula: so tio" - Used as a component of enamels, glazes, filler and pigment for rubber, plastics and paint materials ("Chemical encyclopedic dictionary", M., "Soviet encyclopedia", 1983, p. 581). o Zinc phosphate - white powder. Chemical compound of the general formula: со 020 2(РО)о-ХНоО, where x is 2-4.

It is used as a corrosion inhibitor in paint coatings. ("Protection of metal from corrosion with paint and varnish coatings", M., "Khimiya", 1987, p. 60-611.

Thermally expanding graphite is a powder of natural graphite (carbon modification) intercalated with mineral acids. The coefficient of volumetric expansion at a temperature above 200 9C is 150-300dm Z/kg (TU U 14.5-30969031-001-20021.

GF) Ammonia water (Nashatyr alcohol) - an aqueous solution of ammonia (2095). Chemical compound of the general formula: 7 MnNaoN "Fire hazard of substances and materials used in the chemical industry", M, "Khimiya", 197Or., pp. 42-43).

Cured fine-dispersed urea-formaldehyde resin (polymethylene urea) is a white, fine-dispersed powder insoluble in water and other solvents. Chemical compound of the general formula: (SoNAM2O)

It is used as part of water-dispersion paints, polymer materials and paper (TU 3.01 of Ukraine 013-93 "Polymer filler").

Tetramethylthiuram disulfide (preservative) - aqueous dispersion with an active substance content of 4995 wt. The active substance is tetramethylthiuram disulfide, for example, (commercial product Priventol A 2-0 of the company I! apekh a.v.

Germany). It is possible to use other preservatives that do not impair the biocidal effect. Tetramethylthiuram disulfide is a chemical compound of the general formula: сн | Z Z re Zh. isn» ns n 57 from SNU

Butyl ether of dipropylene glycol (coalescent) is a transparent liquid, soluble in water up to 595 (for example, a commercial product of OUMAMOY ORiV of the firm UOMU, USA). It is allowed to use other coalescents that do not impair the quality of the product.

Dipropylene glycol butyl ether is a chemical compound of the general formula: pttry tent ton ton» on o-sn--sn-snA-СНa

Sodium tripolyphosphate is a white powder, a chemical compound of the general formula:

MaBRzOcho

It is used as a suspending and peptizing additive to detergent solutions. ("Chemical Encyclopedic Dictionary", M, "Soviet Encyclopedia", 198Zr. P.3651.

Water is a transparent, colorless liquid, a chemical compound with the general formula: no.

The invention is illustrated by the following examples. high school

Example 1. In a mixer with a capacity of 40 dm? equipped with two 2-shaped paddle stirrers and an electromechanical drive, load sequentially (at ambient temperature): water in i) amount of 5.52 kg, thermally expanding graphite - 2.0 bkg, ammonia water - 0.82 kg, start mixing and load : pentaerythritol - 1.b5kg, titanium dioxide - 0.4kg, zinc phosphate - 1.85kg, ammonium polyphosphate - 1.85kg, cured finely dispersed urea formaldehyde resin - 1.44kg. co

The mixture is stirred for 1-1.5 hours until a homogeneous mobile mass is reached. After mixing, the mass in the amount of 15.13 kg (taking into account 3905 losses) is unloaded from the mixer and loaded into a disc grinder (p-1500-300O0rpm). Av

Crushed mass in the amount of 14.9 kg (taking into account 195 losses) is loaded into a paddle mixer with a capacity of 40 dm, mixing is started and plasticized polyvinyl acetate dispersion is loaded in the amount of 4.32 kg, -- heated tripolyphosphate - 0.07 kg, mixed for 20-30 minutes and loaded butyl ether (ee) of dipropylene glycol in the amount of 0.17 kg, tetramethylthiuram disulfide - 0.0015 kg, stir for 10-15 minutes and discharge 18.9 kg (taking into account 3905 losses) of intumescent fire-retardant paint. The resulting paint is tested for swelling, corrosion resistance and adhesion. "

The swelling ratio is determined as the ratio of the average thickness of the coating after thermal action (500 2) to the initial thickness of the dried coating according to the following method. - s Equipment and materials: h 1. Laboratory muffle furnace, which provides heating to a temperature of 500-520. 2. Sheet steel plates of the Ovkp brand according to GOST 16523, size 70x15 mm and thickness 0.5-1 mm. 3. Possible solution of soda ash. 4. INTROMET F-2 thickness gauge. so 5. Metal laboratory spires. - 6. Rod applicator. 7. Caliper. at 8. Zxikator. at 50 Preparation for the test

Plates for coating are prepared in accordance with GOST 8832. Fireproof paint is applied to one side of a plate with a thickness of 2.5 mm and dried at a temperature of 20--22C for 24 hours, and the thickness of the coating is measured with an INTROMET F-2 thickness gauge.

The coated plate is placed in a muffle furnace, preheated to a temperature of 500-52C, and kept at 22 for 30 minutes. Then the plate is removed from the muffle furnace and cooled in a desiccator to temperature

GF) of the environment. After cooling, measure the thickness of the swollen coating in millimeters with a caliper with a measurement error of -0.05mm. on Processing and processing of results

The swelling ratio (K) is calculated according to the formula: 60 K- po/pi where M. is the thickness of the coating before thermal action in mm. n" - coating thickness after thermal action in mm.

Adhesion is determined according to GOST 15140.

Corrosion resistance is determined according to GOST 9,403. because Table 1 shows examples of intumescent fire-retardant paint with different content of components within the limits of the invention and outside the limits.

Table 2 shows examples that illustrate the dependence of adhesion, corrosion resistance, and swelling multiplicity on the content of components under the conditions of the invention and prototype.

Examples 2-3 are performed under the conditions of example 1, with the only difference that the plasticized polyvinyl acetate dispersion is loaded in the lower - 2095 wt. and the upper - 2595 mass. limit values. The obtained fire-retardant paints are characterized by significant adhesion, corrosion resistance and swelling multiplicity (at least 40).

Examples 4-5 are performed under the conditions of example 1, with the only difference that the plasticized polyvinyl acetate dispersion is loaded in example 4 below the lower, and in example 5 above the upper limit values. In the case of 7/0 example 4, the coating does not pass the corrosion resistance test and is characterized by low adhesion, and in the case of example 5, the swollen layer is not strong enough.

Examples 6-7 are performed in the conditions of example 1, with the only difference that ammonium polyphosphate is loaded in example b below the lower, and in example 7 above the upper limit values. In the case of example b, the swelling ratio is significantly reduced (to 28), and in example 7, the increase in the content of ammonium polyphosphate does not lead to a 7/5 significant increase in the swelling ratio and is economically impractical.

Examples 8-9 are performed in the conditions of example 1, with the only difference that zinc phosphate in example 8 is loaded below the lower, and in example 9 above the upper limit values. In the case of example 8, the adhesion and corrosion resistance of the coating is reduced, and in the case of example 9, the swelling ratio is significantly (up to 30) reduced.

Examples 10-11 are performed under the conditions of example 1, with the only difference that thermally expanding graphite in example 10 is loaded below the lower, and in example 11 above the upper limit values. In the case of example 10, the swelling factor is reduced (to 24), and in the case of example 11, the paint does not pass the corrosion resistance test.

Examples 12-13 are performed in the conditions of example 71, with the only difference that in example 12 ammonia water is loaded below the lower, and in example 13 above the upper limit values. In the case of example 12, the surface adhesion and corrosion resistance of the coating decreases, and in the case of example 13, the paint has a sharp, unpleasant smell of ammonia, which worsens its organoleptic properties.

Examples 14-15 are performed under the conditions of example 1, with the only difference that in the case of example 14, the cured finely dispersed urea formaldehyde resin is loaded below the lower, and in example 15 above the upper limit values. In the case of example 14, the thixotropic properties of the paint deteriorate, which complicates its application, and in the case of example 15, the paint has a very thick consistency.

Examples 16-17 are carried out in the conditions of example 1, with the only difference that in example 16 the butyl ether of Me dipropylene glycol (coalescent) is loaded below the lower, and in example 17 above the upper limit values. In the case of example 16, the adhesion and multiplicity of swelling decreases, and in the case of example 17, the plasticity of the paint deteriorates, which makes it difficult to apply. --

The fire-retardant paint obtained under the conditions of the prototype has low adhesion and cannot withstand corrosion resistance tests.

Thus, the use of the invention allows: - to increase the swelling rate of the fire-resistant coating; - add anti-corrosion properties to the paint; "- to improve the adhesion of the fireproof coating to the metal substrate. from seams 1I51 11515118 8 yur from polyInIL-acetate dispersion - 5 Pen elutes 0180 80 in 80 80 in 80 80 80/80 80 8980 80 8080 80. o (8 Polyphosphate ammonium 090 90 90 90 90/60 20/90/90 9090 90 909090 90. o (B Foofatsyn 00090 90 90 90 90/90 90/60/2090 090 90 90 90/90/9090.

Fo | ben MOM Mom m mov ooo heat-expandable od 52 carbam iodoformaldehyde resin

I vni y y ays B yo SYA Bai ke (preservative) di-propylene glycol 60 (coalescent) 100 | 100) 100 | 100 | 100.) 100 | 100 | 100 100 | 100 100 1100 100 100 | 100 100 100 b5

Table 2

GOST 15140, points of |595 mass solution within 24 hours at a swelling temperature of 20s) 59000 Vyshevyryudvanya 00000000 21111180 Withstands weathering.у/:.:/11111111111ю11 shishshshishsh nnyy 180000 Evurmuyevyryudvanya 00000000

NAME NAME LAST GENDER GENDER GENDER THREADS AND BUBBLES 1109 Detection 10000000 5708 Eroding 10000000 coating 11009 Detection 10000008 - stains and stains and NN PE PO 61111101 Withstands fading. 1/11:11/1111

We are responsible for the partial exfoliation of the Ge coating)

The composition of the intumescent fire-retardant paint, taken at the average values of the content of the components | Patent of the Russian Federation

Mo2225423). co

Claims (1)

Formula of the invention (22) "c) Intumescent fire-retardant paint, which contains an aqueous polymer dispersion, pentaerythritol, ammonium polyphosphate, titanium dioxide, metal phosphate, preservative, coalescent and water, which differs in that as an aqueous - polymer dispersion contains plasticized polyvinyl acetate dispersion, as metal phosphate - zinc phosphate and (ee) sodium tripolyphosphate, as a preservative - tetramethylthiuram disulfide, as a coalescent - butyl ether of dipropylene glycol and additionally contains heat-expanding graphite, ammonia water and cured fine-dispersed carbamide formaldehyde resin with the following ratio of components, by weight: " plasticized polyvinyl acetate dispersion 20-25 ssh with pentaerythritol 8 s ammonium polyphosphate 8-10 u? titanium dioxide 2 zinc phosphate 8-0 heat-expanding graphite 8-12 (Fe) ammonia water 3-5 - solidified finely dispersed urea formaldehyde resin 6-8 tetramethylthiuram disulfide 0.01 (ав) dipropylene glycol butyl ether 1.0-1.25 o 50 sodium tripolyphosphate 0.5 water to 100. this" Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2007, M 19, 26.11.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. name) 60 b5