RU2540976C2 - Light-weight rubber-polymer material for manufacturing protective clothes and method of obtaining thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: material includes chlorosulphonated polyethylene, filling agents (kaolin, titanium dioxide), fire retardant (decabromodiphenyloxide), vulcanising agents (magnesium oxide, zinc oxide) vulcanisation accelerators (thiuram D, 2-metcaptobenzothiazole), additionally contains fluralit (nanopolytetrafluoroethylene), nanoadditive "Cloisite 30B", polychloroprene, chloroparaffin-470, antimony trioxide, rosin, mixture of nefras and ethylacetate in ratio 1:1 and textile base - technical polyether fabric, or cotton-polyether fabric, or fibreglass fabric. Method of manufacturing light-weight rubber-polymer material includes application of rubber-polymer composition on textile base on adhesive spreading machine IVO 3220 with steam pressure in steam stoves of adhesive spreading machines 2.0-2.1 kgf/cm².

EFFECT: manufacturing light-weight rubber-polymer material, providing protection against impact of toxic, aggressive chemical substances and open fire.

2 cl, 1 tbl, 3 ex

Description

The invention relates to protective rubberized materials used for the manufacture of protective clothing, respiratory protective equipment, including self-rescuers, which provide protection against toxic, aggressive chemicals and open flames.

Known multilayer textile fabric for the manufacture of elastic containers (tanks), tents, tarpaulins, overalls (patent RU No. 2113354, IPC B32B 27/10, publ. 06/20/1998). Cloth with a layer of fabric, on one side of which there is a rubber layer, and on the other side of the fabric layer is a synthetic polymer film. The synthetic polymer film is made of polyvinylidene fluoride and is located between two rubber layers. Thanks to this arrangement of the polymer layer, a stable protection is achieved against all types of exposure to chemical poisonous substances and chemicals, and the elasticity of the textile fabric is increased.

The disadvantages of this multilayer textile fabric for the manufacture of elastic containers (tanks), tents, tarpaulins, overalls are its flammability, insufficient adhesion of the rubber layers to the polyvinylidene fluoride film and the complex manufacturing technology.

Known universal protective material for the manufacture of protective clothing (patent RU No. 2375192, IPC B32B 25/00, publ. 10.12.2009). The material contains a layer of textile base in the form of a polyamide, polyester, aramid or polyolefin fabric, rubberized on both sides with layers of a composition based on chlorosulfonated polyethylene, polychloroprene rubber, butyl rubber or a fluorine-containing polymer composition. The inner layer is made of butyl rubber.

The disadvantages of a universal protective material for the manufacture of protective clothing are its combustibility and high surface density, which leads to a heavier protective clothing.

Known multilayer fire-retardant material (patent RU No. 2305036, IPC B32B 25/04 (2006.01), published on 08.27.2007), 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 located between intermediate and outer layers - a waterproofing layer that contains a polymer composition including chlorosulfonated polyethylene, chloroprene rubber, kaolin, antimony trioxide, magnesium oxide, trichloroethyl phosphate and a solvent - a mixture of butyl acetate and toluene in 1: 1 ratio.

The disadvantages of the known fire-retardant material are its multi-layering, 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, to dissolve the polymer composition.

The closest technical solution is a multifunctional lightweight rubberized protective material based on a polymer composition (patent RU No. 2429974, IPC C09K 21/14, publ. 09/27/2011), including chlorosulfonated polyethylene, chlorobutyl and ethylene propylene diene rubber, antipyrating group, vulcanizing agents, ingredients, providing the necessary physical and mechanical properties, in the following ratio of components, parts by weight:

- chlorosulfonated polyethylene - 60.0-80.0;

- chlorobutyl rubber - 15.0-30.0;

- ethylene propylene diene rubber - 0.5-10;

- decabromodiphenyl oxide, ammonium polyphosphate and aluminum hydroxide (from 1: 5: 5 to 5: 1: 5) - 33.0;

- titanium oxide - 3.0-6.0;

- kaolin - 3.0-9.0;

- zinc oxide - 1.2-2.0;

- magnesium oxide - 4.0-6.0;

- captax - 0.2-1.2;

- thiuram - 1.4-2.2;

- solvent - a mixture of ethyl acetate and nefras (1: 2);

- textile basis - fiberglass.

The disadvantage of a multifunctional lightweight rubberized protective material is its increased stiffness, as a result of which its operational properties are deteriorated and the scope is limited.

The technical task of the invention is the creation of lightweight rubber-polymer material for the manufacture of protective clothing with a surface density of up to 250 g / m ² , which provides protection against highly concentrated vapors of toxic chemicals (chlorine, ammonia, hydrogen sulfide), resistance to open flame, high mechanical strength, frost resistance based on textile materials of various nature.

The technical result is achieved in that a lightweight rubber-polymer material for the manufacture of protective clothing, including chlorosulfonated polyethylene, fillers (kaolin, titanium dioxide), flame retardant (decabromodiphenyl oxide), vulcanizing agents (magnesium oxide, zinc oxide), vulcanization accelerators (thiuram D, captax), additionally contains fluralite (nanopolytetrafluoroethylene), Cloisite 30B nanoadditive, polychloroprene, chloroparaffin-470, antimony trioxide, rosin, a 1: 1 mixture of nephras and ethyl acetate and a textile base - techno fabric ical polyester, cotton-polyester cloth and glass fiber cloth with a ratio of the base fabric and the polymeric composition (1: 1) - (1: 1.2) with the following ratio of components in the polymer composition, in parts by weight .:

- chlorosulfonated polyethylene - 35.2-50.0;

- fluralite (nanopolytetrafluoroethylene) - 2.2-5.0;

- nanoadditive "Cloisite 30B" - 2.9-6.4;

- polychloroprene - 20.0-25.0;

- kaolin - 10.0-15.0;

- 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;

- thiuram D - 1.0-1.5;

- captax - 0.2-0.3;

- rosin - 1.0-1.6;

- pigment - 1.0-2.0;

- a mixture of nephras and ethyl acetate (1: 1) - 520-610.

A distinctive feature of the proposed lightweight rubber-polymer material for the manufacture of protective clothing is the presence of fluralite (nanopolytetrafluoroethylene), Cloisite 30B nanoparticles, polychloroprene (PCP) and chlorosulfonated polyethylene (ChSPE) in the ratio (1: 4) - (1: 3), rosin, chloroparaffin-470, antimony trioxide, a mixture of nephras and ethyl acetate in a 1: 1 ratio and the textile base - technical polyester fabric, cotton-polyester and fiberglass fabric with a ratio of base fabric and polymer composition (1: 1) - (1: 1,2).

Fluralite (nanopolytetrafluoroethylene) according to TU 2213-001-42515356-2005 is an ultrafine powder with low molecular weight. A feature of this material is the granule size of 100-900 nanometers. The effect of the use of this material is reflected primarily on such characteristics as the coefficient of friction, wear and heat resistance.

In addition, fluralite is inert to almost all chemicals and solvents, resistant to ultraviolet and atmospheric effects, does not absorb moisture.

Cloisite 30B nanoadditive is an imported product (England) consisting of nanosized organically modified layered silicates of magnesium and aluminum.

Cloisite 30B nanoadditive increases tensile strength, improves barrier properties with respect to moisture, solvents, chemical vapors, gases and odors. The lamellar structure of the Cloisite 30B nanoadditive enhances the barrier properties of the material.

Polychloroprene according to 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 temperatures. Polychloroprene combines well with various elastomers, including chlorosulfonated polyethylene.

Chlorosulfonated polyethylene according to 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 chemical resistance, high gas impermeability, resistance to oxidative degradation, frost resistance up to minus 40 ° C, fire and heat resistance.

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

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

Thiuram D (tetramethylthiuramdisulfide) according to GOST 740-76 and captax (2-mercapbenzothiazole) according to GOST 739-74 provide the maximum number of cross-links of polychloroprene.

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

Nefras C50 / 170 according to GOST 8505-80 or Nefras C2 80/120 according to TU 38.401-67-108-92, density at 20 ° C from 0.69 to 0.73 g / cm ³ .

Ethyl acetate according to GOST 8981-78, density at 20 ° C from 0.86 to 0.88 g / cm ³ .

The inventive lightweight rubber-polymer material for the manufacture of protective clothing has protective properties when exposed to toxic highly concentrated vapors of ammonia, chlorine, hydrogen sulfide, as well as concentrated solutions of acids and alkalis, resistance to open flames, maintains elasticity, integrity after abrasion at ambient temperature and after repeated crushing at a temperature of minus 40 ° C.

The invention is illustrated by the following examples.

Example 1

Lightweight rubber-polymer material for the manufacture of protective clothing is produced by the method of layer-by-layer deposition on a fabric base of a polymer composition — a solution of the rubber mixture in organic solvents, followed by heating of the material at a temperature of 70-80 ° C for 6 hours.

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

- chlorosulfonated polyethylene - 35.2;

- polychloroprene - 13.3;

- fluralite (nanopolytetrafluoroethylene) - 2.2;

- nanoadditive "Cloisite 30B" - 6.4;

- chloroparaffin - 7.0;

- antimony trioxide - 8.5;

- kaolin - 10.3;

- titanium dioxide - 4.4;

- decabromodiphenyl oxide - 4.8;

- magnesium oxide - 3.4;

- zinc oxide - 1.0;

- thiuram D - 0.3;

- captax - 0.4;

- rosin - 1.6;

- pigment yellow lightfast - 1.2.

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 nefras and ethyl acetate 520 parts by weight is added portionwise. and mixed until the rubber mixture is completely dissolved and a homogeneous dispersion forms. To dissolve the rubber mixture, a mixture of nefras and ethyl acetate in a volume ratio of 1: 1 is used.

The finished composition is applied to a technical polyester fabric, art. 56341 (100% polyester, surface density 93 g / m ² ), layered on one side on the IVO 3220 glue spreading machine at a steam pressure of 2.0-2.1 kgf / cm ² in the steam plates of the glue spreading machine.

The obtained lightweight rubber-polymer protective 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 lightweight rubber-polymer material for the manufacture of protective clothing is 200-220 g / m ² .

Example 2

By the method specified in example 1, make lightweight rubber-polymer material for the manufacture of protective clothing, including, by weight:

- chlorosulfonated polyethylene - 40.2;

- polychloroprene - 12.5;

- fluralite (nanopolytetrafluoroethylene) - 2.6;

- nanoadditive "Cloisite 30B" - 3.9;

- chloroparaffin - 6.2;

- antimony trioxide - 7.9;

- kaolin - 10.9;

- titanium dioxide - 3.9;

- decabromodiphenyl oxide - 3.2;

- magnesium oxide - 3.7;

- zinc oxide - 1.3;

- thiuram D - 0.5;

- captax - 0.7;

- rosin - 1.5;

- pigment organic orange K, grade B - 1.0;

- a mixture of nephras and ethyl acetate (1: 1) - 580.0;

- fiberglass fabric brand E2 / 1-80-P-76/100 (surface density 90 g / m ² ).

As in example 1, the polymer composition is applied in layers on one side.

The surface density of the obtained lightweight rubber polymer material for the manufacture of protective clothing is 230 g / m ² .

Example 3

By the method specified in example 1, make lightweight rubber-polymer material for the manufacture of protective clothing, including, by weight:

- chlorosulfonated polyethylene - 43.0;

- polychloroprene - 11.5;

- fluralite (nanopolytetrafluoroethylene) - 5.0;

- nanoadditive "Cloisite 30B" - 2.9;

- chloroparaffin - 5.3;

- antimony trioxide - 6.9;

- kaolin - 7.70;

- titanium dioxide - 2.9;

- decabromodiphenyl oxide - 2.0;

- magnesium oxide - 4.2;

- zinc oxide - 3.7;

- thiuram D - 1.5;

- captax - 1.6;

- rosin - 0.8;

- phthalocyanine pigment "Megaton blue AR-008" - 1.0;

- a mixture of nephras and ethyl acetate (1: 1) - 610.0;

- Cotton-polyester fabric "Panacea Cotton Rich 150", art. 18012 (60% cotton, 40% polyester, surface density 150 g / m ² ).

The polymer composition is applied in layers on both sides.

The surface density of the obtained lightweight rubber polymer material for the manufacture of protective clothing is 250 g / m ² .

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 rubber mixture, its solubility in organic solvents decreases, with an increase in the content of polychloroprene in the polymer composition, the material sticks together when it is wound on a seaming bobbin.

An increase in the amount of fluralite (nanopolytetrafluoroethylene) in the rubber compound does not allow a uniform solution of the rubber compound in an organic solvent to be obtained. Reducing the dosage of fluralite (nanopolytetrafluoroethylene) reduces the fire resistance of lightweight rubber-polymer material for the manufacture of protective clothing.

Samples of lightweight rubber-polymer 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 acids and alkalis), stability to the effects of open flame, strength and frost resistance.

The properties of the inventive lightweight rubber-polymer material for the manufacture of protective clothing are presented in the table.

Table Name of indicator Example 1 Example 2 Example 3 1. The basis The fabric is technical polyester, an art. 56341 Fiberglass fabric E2 / 1-80-P-76/100 Fabric cotton-polyester "Panacea Cotton Rich 150", art. 18012 2. The surface density, g / m ² 200 230 250 3. Breathability, dm ³ / m ² · s 0 0 0 4. Resistance to gaseous substances: - ammonia, conc. (685 ± 40) mg / l, hour More than 24 More than 24 More than 24 - chlorine, conc. (2875 ± 30) mg / l, hour More than 24 More than 24 More than 24 - hydrogen sulfide, conc. (1420 ± 40) mg / l, hour More than 24 More than 24 More than 24 5. Resistance to open flame, s 360 600 400 Residual burning, s Absent Absent Absent Residual decay, s Absent Absent Absent 6. Tensile strength tensile: - based, H (kgf) 870 (88.8) 880 (89.8) 890 (90.8) - duck, H (kgf) 1030 (105.1) 580 (59.2) 470 (47.9) 7. Resistance to liquid aggressive media: - sulfuric acid (conc. 96%), min 1440 1440 1440 - caustic soda (conc. 40%), min 1440 1440 1440 8. Fivefold crushing at a temperature of minus 40 ° C No through destruction No through destruction No through destruction

Determination of the protective properties of lightweight rubber-polymer material for the manufacture of protective clothing was carried out according to the methodology of OAO KazKhimNII "Method for determining the time of protective action of personal protective equipment when exposed to vapors of chemically dangerous aggressive substances.

The resistance to open flame was determined according to GOST R 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 "PROMAIDM".

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

The inventive lightweight rubber-polymer material for the manufacture of protective clothing with a density of up to 250 g / m ^{2 is} characterized by high strength and fire resistance, a high level of protection when exposed to toxic highly concentrated vapors of ammonia, chlorine, hydrogen sulfide, concentrated solutions of acids, alkalis and open flame.

Claims (2)

1. Lightweight rubber-polymer material for the manufacture of protective clothing, including chlorosulfonated polyethylene, pigment, fillers - kaolin, titanium dioxide, flame retardant - decabromodiphenyl oxide, vulcanizing agents - magnesium oxide, zinc oxide, vulcanization accelerators - thiuram D, captax, additionally contains fluralite - nanopolygraph Cloisite 30B nanoadditive, polychloroprene, chloroparaffin-470, antimony trioxide, rosin, a 1: 1 mixture of nephras and ethyl acetate, and the textile base - technical polyester fabric or chlorine fabric optical-polyester or fiberglass fabric in the following ratio of components in the rubber-polymer composition, parts by weight:
- chlorosulfonated polyethylene - 35.2-50.0;
- polychloroprene - 20.0-25.0;
- fluralite-nanopolytetrafluoroethylene - 2.2-5.0;
- nanoadditive "Cloisite 30В" - 2.9-6.4;
- chloroparaffin-470 - 5.5-7.5;
- antimony trioxide - 6.8-9.4;
- kaolin - 10.0-15.0;
- titanium dioxide - 2.5-3.5;
- decabromodiphenyl oxide - 3.0-4.0;
- magnesium oxide - 2.5-3.5;
- zinc oxide - 1.0-1.4;
- thiuram D - 1.0-1.5;
- captax - 0.2-0.3;
- rosin - 1.0-1.6;
- pigment - 1.0-2.0;
- a mixture of nephras and ethyl acetate (1: 1) - 520.0-610.0. 2. A method of manufacturing a lightweight rubber-polymer material for the manufacture of protective clothing according to claim 1, comprising preparing a rubber-polymer mixture by rolling the components by sequentially feeding them to rollers ПД 630 315/315 l, dissolving the rubber-polymer mixture in organic solvents - a mixture of nefras and ethyl acetate in the ratio 1: 1 in the glue mixer, applying the rubber-polymer composition to the textile base on the IVO 3220 glue machine with steam pressure in the steam plates of the glue machine 2.0-2.1 kgf / cm, n winding on a seaming bobbin and drying at a temperature of 70-80 ° C for 6 hours.