RU2521043C2 - Composite material for manufacturing protective clothes - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the field of production of composite protective rubberised materials used for manufacturing protective clothes, and respiratory protection equipment for people, including self-rescuers, breathing bags of isolating gas masks. A composite material contains chlorosulphonated polyethylene, polychloropren, kaolin, titanium dioxide, a nanodisperse filling agent montmorillonite, modified with quaternary ammonium salts, chloroparaffin-470, antimony trioxide, decabromodiphenyl oxide, magnesium oxide, zinc oxide, thiuram D, captax, rosin, benzene and ethylacetate mixture and polyether or cotton-polyether, or viscose-polyamide.

EFFECT: material possesses higher strength with simultaneous protection against action of toxic and aggressive chemical substances and open fire.

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Description

The invention relates to the production of composite protective rubber materials used for the manufacture of protective clothing, as well as respiratory protective equipment for humans, including self-rescuers, breathing bags of insulating gas masks, which provide protection under the influence of toxic and aggressive chemicals and an open flame.

Known multilayer fire-retardant material made in the form of a package containing an outer layer of heat-resistant fibers, an intermediate heat-insulating layer, an inner layer of cotton fabric and a waterproofing layer located between the intermediate and outer layers, which contains a polymer composition including chlorosulfonated polyethylene, chloroprene rubber, kaolin, antimony trioxide, magnesium oxide, trichloroethyl phosphate and solvent - a mixture of butyl acetate and toluene in the ratio 1: 1 (US Pat. RU No. 2305036, IPC BV 25/04 (2006.01), about UBL. 27.08.2007 city).

A disadvantage of the known fire-retardant material is multilayer, which increases the mass of protective clothing made from it and reduces ergonomic indicators, as well as the use of a highly toxic and carcinogenic solvent toluene for dissolving the polymer composition.

Known fire retardant composition, fire retardant paste and method for producing fire retardant material (US Pat. RU No. 2285031, IPC S09K 21/14, publ. 10.10.2006,). The flame retardant composition contains chloroprene rubber, chloroparaffin, intercalated graphite, ammonium polyphosphate, kaolin and aerosil. Known material has flame retardant properties when exposed to an open flame and is used to protect electrical cables and cable lines. There are no data on protective properties when exposed to highly toxic liquid and gaseous accidentally chemically hazardous substances. 1.0 mm thick material is not suitable for the manufacture of personal protective equipment.

Known rubber fabric 8-77 TU 381051665-85, manufactured by UZEMIK (Ufa), which is a combined fabric art.66045 with one-sided rubber coating based on chloroprene and nitrile butadiene rubber, applied by calendering followed by vulcanization. Fabric 8-77 is fire-, explosion-proof, does not ignite on its own and is intended for the manufacture of protective clothing that protects against groundwater and lubricating oils.

A disadvantage of the known fabric is low fire resistance and lack of chemical protective properties.

Closest to the claimed invention is a composite material for the manufacture of protective clothing, containing a base fabric of non-combustible fiberglass plain weave, impregnated with a polymer composition including chlorosulfonated polyethylene, chlorobutyl and ethylene propylene diene rubber, decabromodiphenyl oxide, ammonium polyphosphate and alumina, titanium oxide, kaanol magnesium, zinc oxide, thiuram, captax, pigment and a mixture of solvents of gasoline and ethyl acetate (RU No. 2429974 C2, 09/27/2011, formula).

The proposed material differs from the known one in that it contains polyester, cotton-polyester or viscose-polyamide fabric as the base fabric in relation to the polymer composition (1: 1) - (1: 1,2), and the polymer composition additionally contains polychloroprene in ratio with chlorosulfonated polyethylene (1-3) :( 1-4), nanodispersed filler montmorillonite, modified with quaternary ammonium salts, chloroparaffin-470, antimony trioxide, rosin, a mixture of gasoline and ethyl acetate 1: 1, with a ratio of components indicated in the formula and gaining.

Identified distinguishing features in combination with other well-known distinguishing features give the material an increase in mechanical strength and resistance to liquid aggressive environments while maintaining resistance to open flames and resistance to highly toxic gaseous substances.

Polychloroprene (Baypren-210 from Lanxess AG or Nairit DP TU 6-01-1319-85) is a highly linear rubber soluble in organic solvents, characterized by high chemical resistance, excellent adhesion to many surfaces, including textile materials, good gas impermeability, not only at room temperature, but also at elevated temperature. Polychloroprene combines well with various elastomers, including chlorosulfonated polyethylene.

Chlorosulfonated polyethylene (TU 2211-063-56856807-05) has a unique combination of ozone and weather resistance, chemical, oil and gas resistance. Materials based on chlorosulfonated polyethylene have high gas impermeability, chemical resistance, resistance to oxidative degradation, frost resistance of minus 40 ° C, fire and heat resistance.

The combination of self-extinguishing polymers - polychloroprene and chlorosulfonated polyethylene with a group of flame retardants - chloroparaffin and antimony trioxide, which have a synergistic effect, and decabrom-diphenyl oxide, which emits bromine ions during combustion, which cause recombination of free radicals and thereby inhibit flame, provides resistance to open flame.

Montmorillonite modified with quaternary ammonium salts (MMT-15) is a nanodispersed filler from the group of natural layered silicates of magnesium and aluminum with an anisotropic, lamellar structure (silicate plates 1 nm thick and 70-150 nm in length). Modified montmorillonite combines with polymers and forms layered polymer nanocomposites that improve the complex properties of the polymer composition due to the lability of the layered structure that swells during intercalation (incorporation into the polymer system). The introduction of montmorillonite into the composite material reduces its combustibility due to an increase in the temperature of the onset of thermal deformation and an increase in coal residue, in combination with a finely divided filler kaolin increases the heat resistance of the material, reduces the anisotropy of shrinkage and warpage.

Rosin (GOST 19113-84) is a plasticizer and vulcanization accelerator of the polymer composition.

Gasoline C50 / 170, GOST 8505-80 or gasoline C280 / 120 TU 38.401-67-108-92, density at 20 ° C 690-0.730 g / cm ³ .

Ethyl acetate GOST 8981-78, density at 20 ° C 0.865-0.885 g / cm ³ .

The composition of the polymer composition also includes magnesium oxide, zinc oxide, thiuram D (tetraalkylthiuramdisulfide and captax (2-mercapto-benzothiazole).

Magnesium oxide (GOST 844-79) and zinc oxide (GOST 202-84) are vulcanizing agents and acceptors of hydrochloric acid, which reduces the adhesive properties of the polymer composition. Zinc oxide synergistically interacts with magnesium oxide, inhibiting the autocatalytic process of polychloroprene vulcanization.

Thiuram D (tetraalkylthiuramdisulfide) GOST 740-76 and captax (2-mercapto-benzthiazole) GOST 739-74 provide the maximum number of cross-linking of polychloroprene.

The invention is illustrated by the following examples.

Example 1

Composite material is made by the method of layer-by-layer deposition on the base fabric of the polymer composition — a solution of the rubber compound in an organic solvent, followed by heating of the material at a temperature of 70-80 ° C for 6 hours.

The rubber mixture for the polymer composition is made in a standard way on rollers PD 630 315/315 l, adding the ingredients in the following order:

- chlorosulfonated polyethylene - 75.0 parts by weight

- polychloroprene - 25.0 parts by weight

- chloroparaffin - 5.5 parts by weight

- antimony trioxide - 6.8 wt.h.

- kaolin - 10.0 parts by weight

- montmorillonite - 3.0 wt.h.

- titanium dioxide - 2.5 wt.h.

- DBDFO - 3.0 wt.h.

- magnesium oxide - 2.5 wt.h.

- zinc oxide - 1.0 wt.h.

- thiuram - 1.0 wt.h.

- captax - 0.2 wt.h.

- rosin - 1.0 wt.h.

- pigment yellow lightfast - 1 wt.h.

After rolling, the rubber mixture is removed from the rollers and cooled to room temperature.

The rubber mixture is loaded into an adhesive mixer, a mixture of gasoline and ethyl acetate in an amount of 530.0 parts by weight is added. and mixed until the rubber mixture is completely dissolved and a homogeneous dispersion forms. To dissolve the rubber mixture, a mixture of gasoline and ethyl acetate in a ratio of 1: 1 by weight is used.

The finished solution is applied to fabric art.80014 (100% polyester, surface density 120 g / m ² ) layer by layer on one or two sides on the IBO 3220 adhesive machine at a steam pressure of 2.0-2.1 kgf / cm in the steam plates of the adhesive machine ² .

The resulting composite material is wound on a seaming bobbin and heated at a temperature of 70-80 ° C for 6 hours.

The surface density of the obtained composite material is 259 g / m ² , the ratio of the base fabric and the polymer composition is 1: 1.2.

Example 2

According to the method specified in example 1, a composite material is made, including: chlorosulfonated polyethylene - 78.0 parts by weight, polychloroprene - 22.0 parts by weight, chloroparaffin - 6.5 parts by weight, antimony trioxide - 8, 0 parts by weight, kaolin - 12.5 parts by weight, montmorillonite - 4.0 parts by weight, titanium dioxide - 3.0 parts by weight, DBDFO - 3.5 parts by weight, magnesium oxide - 3.0 parts by weight, zinc oxide — 1.2 parts by weight, thiuram — 1.2 parts by weight, captax — 0.2 parts by weight, rosin — 1.3 parts by weight, pigment organic orange K grade B - 1 parts by weight, a mixture of gasoline and ethyl acetate - 560.6 parts by weight in the ratio 1: 1 and viscose-polyamide fabric art.66018 (50% viscose, 50% polyamide, surface density 100 g / m ² ).

The surface density of the obtained composite material is 210 g / m ² , the ratio of the base fabric and the polymer composition is 1: 1.1.

Example 3

According to the method specified in example 1, a composite material is made, including: chlorosulfonated polyethylene - 80.0 parts by weight, polychloroprene - 20.0 parts by weight, chloroparaffin - 7.5 parts by weight, antimony trioxide - 9, 4 parts by weight, kaolin - 15.0 parts by weight, montmorillonite - 5.0 parts by weight, titanium dioxide - 3.5 parts by weight, DBDFO - 4.0 parts by weight, magnesium oxide - 3.5 parts by weight, zinc oxide — 1.4 parts by weight, thiuram — 1.5 parts by weight, captax — 0.3 parts by weight, rosin — 1.6 parts by weight, pigment phthalocyanine Megaton blue AR-008 - 2 parts by weight, a mixture of gasoline and ethyl acetate - 590.0 parts by weight in a ratio of 1: 1 and cotton-polyester fabric art. 18012 (60% cotton, 40% polyester, surface density 150 g / m ² ).

The surface density of the obtained composite material is 300 g / m ² , the ratio of the base fabric and the polymer composition is 1: 1.

The stated dosage limits of chlorosulfonated polyethylene and polychloroprene are due to the fact that with an increase in the content of chlorosulfonated polyethylene in the polymer composition, its solubility in organic solvents decreases, with an increase in the content of polychloroprene in the polymer composition, stickiness of the material appears, which sticks when it is wound on a seaming bobbin.

An increase in the amount of montmorillonite in the polymer composition does not allow to obtain a homogeneous solution of the polymer composition in an organic solvent, with a decrease in the dosage of monmorillonite, the advantages of its use in the preparation of the composite material are reduced.

Samples of the composite material for the manufacture of protective clothing, obtained by the methods specified in examples 1, 2 and 3, were tested for breathability, resistance to gaseous substances - ammonia, chlorine, hydrogen sulfide, liquid aggressive environments - concentrated solutions of acid and alkali, resistance to exposure open flame, durability and frost resistance.

Determination of the protective properties of the composite material was carried out according to the "Methods for determining the time of protective action of personal protective equipment when exposed to vapors of chemically hazardous aggressive substances" OJSC "KazHimNII".

The resistance to open flame was determined according to GOST P 12.4.200-99 with a vertical arrangement of the sample and a horizontal arrangement of the burner.

The determination of air permeability was carried out on a test bench pneumometric control with a pressure meter PROMA-IDM.

Determination of tensile tensile strength was carried out according to GOST 30303-95 on a test machine "Schopper" head. No. 5549.

The following is a table of indicators of the properties of the inventive composite material for protective clothing.

Table Test Results of Composite Material for Protective Clothing Name of indicator Example 1 Example 2 Example 3 1 Weight 1 m ² material, g 259 210 300 2 Breathability, dm ³ / m ² · s 0 0 0 3 Resistance to gaseous substances, hour: - ammonia, concentration (685 ± 40) mg / l More than 24 More than 24 More than 24 - chlorine, concentration (287 ± 30) mg / l - hydrogen sulfide, conc. (1420 ± 40) mg / l 4 Resistance to open flame, s 12 s 10 s 15 s Residual burning, s Absent Absent Absent Residual decay, s Absent Absent Absent 5 Tensile strength tensile, H (kgf), based 890 (90.8) 850 (86.7) 900 (91.8) by duck 1060 (108.2) 600 (61.2) 480 (48.9) 6 Resistance to liquid aggressive media, min, sulfuric acid (concentration 96%) 270 240 280 caustic soda (concentration 40%) 360 360 360 8 Five-fold crushing at a temperature of minus 40 ° C No through destruction No through destruction No through destruction

The inventive composite material for protective clothing with a low surface density (not more than 300 g / m ² ) is characterized by high strength, provides a high level of protection when exposed to toxic highly concentrated fumes of ammonia, chlorine, hydrogen sulfide, concentrated solutions of acids and alkalis, an open flame.

Claims (1)

A composite material for the manufacture of protective clothing containing a base fabric impregnated with a polymer composition including chlorosulfonated polyethylene, kaolin, titanium dioxide, decabromodiphenyl oxide, magnesium oxide, zinc oxide, thiuram D, captax, pigment and a mixture of solvents of gasoline and ethyl acetate, characterized in that as the base fabric, it contains polyester, cotton polyester or viscose-polyamide fabric, taken in proportion to the polymer composition (1: 1) - (1: 1,2), and the polymer composition additionally contains polychloro ren in the ratio with chlorosulfonated polyethylene (1-3) :( 1-4), nanodispersed filler montmorillonite modified with quaternary ammonium salts, chloroparaffin-470, antimony trioxide, rosin, a 1: 1 mixture of gasoline and ethyl acetate in the following ratio of components, wt. h:
chlorosulfonated polyethylene 75.0-80.0 polychloroprene 20.0-25.0 kaolin 10.0-15.0 modified montmorillonite quaternary ammonium salts 3.0-5.0 titanium dioxide 2.5-3.5 chloroparaffin-470 5.5-7.5 antimony trioxide 6.8-9.4 decabromodiphenyl oxide 3.0-4.0 magnesium oxide 2.5-3.5 zinc oxide 1.0-1.4 tiuram D 1.0-1.5 captax 0.2-0.3 rosin 1.0-1.6 pigment 1.0-2.0 petrol 265-295 ethyl acetate 265-295.