RU2494131C1 - Polymeric polyurethane composition and multilayer material based thereon - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to polymer compositions for producing multilayer materials meant for making inflatable rescue equipment, including inflatable stairs for aircraft. The polymeric polyurethane composition contains a polyurethane polymer, filler - titanium dioxide and a fire-retardant - antimony trioxide, and additional filler in form of a layered nanosilicate which is organically modified with imidazole, and decabromodiphenyl oxide as a fire-retardant. Content of the organic modifier in the layered nanosilicate is at least 100% of the cationic volume capacity of the layered nanosilicate. The polymer composition can additionally contain polyisocyanate and ethyl acetate. The multilayer material contains a high-strength textile base coated with layers of said polymeric polyurethane composition on the front and back sides. The textile base used is a textile made from high-modulus SVM threads with density of 70-80 g/m² and breaking strength on the base and filling of at least 1200 kg/cm². The multilayer material has density of 220-270 g/m² and is air-tight and self-extinguishing.

EFFECT: obtaining a polyurethane composition and a multilayer material based on said composition, having high fire-safety (self-extinction), air-tightness, low density and hardness.

7 cl, 2 tbl, 5 ex

Description

The present invention relates to the field of polymer compositions for the production of multilayer materials for the manufacture of inflatable rescue equipment, including inflatable shells of passenger ramps of aircraft.

Known polymer compositions and materials for inflatable shells of rescue ramps based on a fabric substrate coated with a polyurethane coating (US patent No. 554628, 554629).

A disadvantage of the known materials is their low strength properties and hydrogen tightness - up to 10 l / (m ² · day).

Known self-extinguishing (flame retardant) elastic composition based on thermoplastic polyurethane - 30 ÷ 50%, flame retardants 50-70% and solvent tetrahydrofuran - 100% nylon fabric. Woven materials based on this composition are intended for the manufacture of clothes of astronauts, containers and other space containers (US patent No. 4284682).

The disadvantages of materials based on the specified polymer composition are increased gas permeability and insufficient heat resistance.

Known polymer compositions based on polyurethane combined with nanoparticles, including organically modified quaternary ammonium compounds SiO ₂ , CaCO ₃ , etc. Compositions are designed to produce films, film adhesives, abrasion-resistant coatings of organic glasses, etc. (patent applications US No. US 2010/0288963, US 2007/0292623, US 2009/0280329, US 2011/0159281, US 2011/0046286).

None of the above compositions can be used to obtain self-extinguishing multilayer materials of increased tightness of inflatable rescue equipment.

The closest adopted for the prototype is a polyurethane composition and a multilayer material based on it, intended for the manufacture of shells of aircraft - airships, balloons, etc.

The polymer composition consists of three different formulations, parts by weight:

- recipe No. 1 (adhesive layer):

polyurethane - 25

ethyl acetate - 75

Recipe No. 2 (sealing layer)

polyvinyl chloride - 100

polyurethane - 10 ÷ 15

plasticizer - 55 ÷ 65

flame retardant - 14 ÷ 18

stabilizer - 2 ÷ 4

filler - 15 ÷ 29

modifier - 1.5 ÷ 17

Recipe No. 3 (protective layer)

polyvinyl chloride - 100

plasticizer - 55 ÷ 65

stabilizer - 2 ÷ 4

filler - 94.1 ÷ 98.2

modifier - 1.5 ÷ 17

A multilayer material is obtained by successively applying layers on a doctor blade to a polyester fabric with a density of 100-150 g / m ² and a warp and weft strength of at least 80 kg / cm ² (RF patent No. 2228850).

The disadvantages of the polymer composition and the multilayer material of the prototype are large:

- the complexity of manufacturing polymer compositions (3 different formulations);

- the weight of the multilayer material is 380 ÷ 420 g / m ² ;

- smoke generation - in combustion mode> 110.

An object of the invention is the creation of a polymeric polyurethane composition and a multilayer material based on it, having increased fire safety (self-extinguishing), tightness, low density and rigidity.

To solve the technical problem, a polymer polyurethane composition was proposed, including a polyurethane polymer, a filler - titanium dioxide and a flame retardant - antimony trioxide, which additionally contains layered nanosilicate organically modified with imidazole, and decabromodiphenyl oxide as a flame retardant in the following ratio of components, wt.h. .:

polyurethane polymer one hundred antimony trioxide 18 ÷ 25 decabromodiphenyl oxide 10 ÷ 15 titanium dioxide 15 ÷ 20 organically modified layered nanosilicate imidazole 2.5 ÷ 3.5

The content of the organomodifier in the layered nanosilicate organomodified with imidazole is at least 100% of the cationic volumetric capacity of the layered nanosilicate.

A multilayer material, including a high-strength woven base with layers of the polymer polyurethane composition of the proposed composition combined with a solvent and hardener deposited on it from the front and back side. ≈

Ethyl acetate is used as a solvent, and polyisocyanate is used as a hardener in the following ratio of components, parts by weight:

polyisocyanate 10 ÷ 15 ethyl acetate 150 ÷ 200

The multilayer material as a woven base contains a fabric of high-modulus CBM threads with a density of 70-80 g / m ² and tensile strength along the warp and weft of at least 1200 kg / cm ² .

The multilayer material has a low density of 220-270 g / m ² , mainly 230-240 g / m ² , is sealed and self-extinguishing.

As the polyurethanes in the present invention, any rolled polyurethanes based on polyesters can be used, but the best result is obtained using polyurethanes SKU-8A and SKU-8TB.

During the development of the polymer composition, it was found that gas permeability depends on the geometry (structure) and the amount of filler, as well as on the level of interaction at the filler-polymer interface. A filler in the form of flakes is a layered nanosilicate organically modified with imidazole with a high level of interaction with the polymer, which significantly increases the tightness of the polymer coating composition, as the gas path increases. In turn, an increase in tightness has a positive effect on reducing the combustibility of the material, since the rate of gas evolution during a fire is reduced.

In the proposed polymer composition as an organically modified nanosilicate used layered nanosilicate, organically modified by imidazole, obtained by the method protected by RF patent No. 2433954. The method includes dispersing smectite clay in a 1M aqueous solution of sodium salt,

separation of impurities, processing of the obtained product with a compound containing organic cations, isolation, washing and drying of the modified nanosilicate, while the amount of compound containing organic cations is calculated by the formula.

$$m_{OK}=\frac{Wc*Vc*KOE}{\mathrm{one}000*\mathrm{one}00}*\frac{M_{OK}}{W_{OK}}$$

where m _OK is the mass of the organic cation in commodity form, g, W _C is the solids content in the suspension of nanosilicate, g / l, V _C is the volume of suspension, l, CFU is the cation exchange capacity of the feedstock, mEq / 100 g, M _OK is the molar mass of the organic cation, g / mol, W _OK is the mass content of the basic substance in the form of an organic cation, fractions of a unit, and the modified nanosilicate is dried at a temperature of 100-120 ° С.

The use of flame retardants decabromodiphenyl oxide in conjunction with antimony trioxide (synergistic effect), allows to reduce the total concentration of the dispersed phase in the composition. In turn, this has a positive effect on reducing stiffness and increasing tightness and, accordingly, increasing fireproof properties.

A high concentration of dispersed filler leads to an increase in the rigidity of the material, therefore, a lower concentration of dispersed fillers is selected, in comparison with the prototype.

The preferred content of the organic modifier in the nanosilicate is at least 100% of the cation exchange capacity of the layered nanosilicate. This is due to the fact that such a content will sufficiently increase the interlayer distance of the nanosilicate and accelerate its interaction with the polymer.

The composition obtained after rolling has a long viability and can be transported. At the place of manufacture of the multilayer material before use, the composition is combined with a solvent - ethyl acetate and a hardener - polyisocyanate in predetermined proportions.

The multilayer material is obtained by the method of spreading, that is, by repeatedly applying thin layers of the polymer composition, combined with a solvent and hardener, to the fabric base, which ensures the formation of a polymer coating with less defects due to overlapping defects of the previous layer with each subsequent application of the layer of the polymer composition. This reduces the permeability of the material by increasing the true contact area of the fabric and the polymer composition. In addition, during the manufacturing process, the proposed material is vulcanized, which also contributes to a decrease in permeability due to the formation of a spatially structured network in the polymer coating.

The proposed composition allows you to create a multilayer material with a low density, since it does not require coating with different formulations and large thickness.

The invention is illustrated by the following examples:

Example 1. The preparation of the polymer polyurethane composition 100 wt.h. polyurethane polymer (SKU-8A (TU 38 103209)) combined with 15 parts by weight titanium dioxide (GOST 3808), with flame retardants (antimony trioxide (TU 48-14-1) 18 parts by weight and decabromodiphenyl oxide (TU 6-47-49) 15 parts by weight) and 3 parts by weight of an organically modified layered nanosilicate imidazole by rolling for 10 minutes The result was a polymeric polyurethane composition (plastic compound).

Laminate preparation

In the manufacture of a multilayer material, the polymer composition was combined in a glue mixer with a solvent of 150 wt.h. ethyl acetate (GOST 8981) and mixed until homogeneous. After this was added a hardener - 10 parts by weight polyisocyanate (TU 113-03-38-106), was stirred and kept for 10-15 minutes. The resulting composition was spread by thinning with thinning, followed by drying of each layer on the front and back sides of the base, made of fabric of technical CBM (TU 17-0001040-6-105) with a surface density of 70 g / m ² , twist 100 ± 10 cr / m from threads of linear density 14.3 tex. The weight gain on the front side was 60 g / m ² , on the wrong side - 120 g / m ² . Then, the resulting multilayer material was vulcanized at a temperature of 160 ° C for 6 minutes.

Examples 2, 3, 4, 5.

The manufacturing technology of the multilayer material according to examples 2, 3, 4 and 5 is similar to example 1.

The compositions of the multilayer material are shown in table 1, and the properties are shown in table 2.

Tests: hydrogen permeability - according to the method of M383AG 405629-86; combustibility - according to the AP-25 method (adj. F, part 1); stiffness (elasticity) - according to GOST 8977; density according to GOST 17073.

As can be seen from the data of table 2, the proposed material has a hydrogen permeability reduced by more than 2–3 times compared to the prototype, 1.5–1.8 times reduced elasticity (stiffness), and has a 1.5–2 times superior smoke generation, with a decrease in density of 1.6 times.

Thus, the use of a multilayer material based on the proposed composition for the manufacture of inflatable rescue equipment allows to increase their reliability and service life, reduce the complexity of manufacturing and, accordingly, their cost.

Table 1 No. p / p Laminate components The content of the examples, mass.h one 2 3 four 5 one UHM technical fabric, density, g / m 70 70 80 70 70 2 Polymer composition: Polyurethane SKU8A one hundred - one hundred - one hundred SKU8TB (TU38 103468) - one hundred - one hundred - antimony trioxide eighteen 25 twenty 22 25 decabromodiphenyl oxide fifteen 10 fifteen 12 10 titanium dioxide fifteen twenty 17 fifteen fifteen layered nanosilicate, organically modified imidazole 2,5 2,5 3,5 3.0 2.7 3 polyisocyanate 10 fifteen fifteen 10 12 ethyl acetate 150 180 150 200 150

table 2 The name of the properties of the multilayer material Examples of the invention Prototype one 2 3 four 5 Tightness (Hydrogen permeability), l / (m ² · day) 0.1 0.3 0.15 0.5-1.0 0.4-0.5 0.6-2.5 Smoke in mode * Combustion D ₂ / D ₄ 34/54 - - 10/60 8/55 13/118 Pyrolysis D ₂ / D ₄ 6/22 - - - 8/30 53/74 Density, g / m ² 230 240 240 250 230 380-420 Rigidity, gf 9.0 9.1 9.1 9.0 9.0 16 * Note: for 2 (D ₂ ) and 4 (D ₄ ) seconds of burning

Claims (7)

1. Polymeric polyurethane composition, including polyurethane polymer, filler - titanium dioxide and flame retardant - antimony trioxide, characterized in that the filler composition further comprises a layered nanosilicate organically modified by imidazole, and as a flame retardant - decabromodiphenyl oxide in the following ratio, wt.h. .:
polyurethane polymer one hundred antimony trioxide 18 ÷ 25 decabromodiphenyl oxide 10 ÷ 15 titanium dioxide 15 ÷ 20 layered nanosilicate, organically modified imidazole 2.5 ÷ 3.5 2. The polymer polyurethane composition according to claim 1, characterized in that the content of the organo modifier in the layered nanosilicate modified by imidazole is at least 100% of the cationic volumetric capacity of the layered nanosilicate. 3. A multilayer material, including a high-strength woven base with layers of polymer polyurethane composition deposited on it from the front and the wrong side, characterized in that as the polymer polyurethane composition, the composition according to claims 1 and 2, combined with a solvent and hardener, is used. 4. The multilayer polymer material according to claim 3, characterized in that ethyl acetate is used as a solvent, and polyisocyanate is used as a hardener in the following ratio of components, parts by weight:
polyisocyanate 10 ÷ 15 ethyl acetate 150 ÷ 200 5. A multilayer material according to claims 3 and 4, characterized in that a fabric of high modulus CBM threads with a density of 70-80 g / m ² and tensile strength along the warp and weft of at least 1200 kg / cm ^{2 is} used as the woven base. 6. The multilayer material according to any one of claims 3 to 5, characterized in that it has a density of 220-270 g / m ² . 7. The multilayer material according to any one of claims 3 to 6, characterized in that it is sealed and self-extinguishing.