RU2244703C1 - Stabilizer of chemical resistance of blasting powders, solid rocket propellants and gas-generating compositions based on nitro-cellulose and a method of their treatment - Google Patents

Abstract

FIELD: separation of materials by size.

SUBSTANCE: the invention is pertinent to the field of blasting powders, solid rocket propellants and gas-generating compositions based on nitro-cellulose and used in the barrel and rocket systems, and also in the fire-extinguishing systems, in fire extinguisher, for opening and inflation of the sea life saving means, for an automobile air-safety bags, pneumatic means and for other purposes requiring fast and safe creation by gases of positive pressure or volume. The offered stabilizer of r blasting powders, solid rocket propellants and gas-generating compositions based on nitro-cellulose represents itself the boric acid either phosphorous acid, or organic acid or its salt out of a row of derivatives of the benzoic and dibasic aliphatic acids - oxalic and succinic acids. The invention also offers a method of treatment of the indicated substances with the stabilizer of chemical resistance. Introduction of the offered stabilizers in compositions of blasting powders, solid rocket propellants and gas-generating compositions based on nitro-cellulose in amount of 0.1 up to 35 % of their weight ensures required chemical resistance of the treated substances and safe ecology. At that the invention allows to achieve an increase of the index of a flame extinguishing, ballistic performances, phlegmatization, a considerable change of temperature and increase of volumes of the formed gases. Besides the use of offered stabilizers of chemical resistance at treatment of the indicated substances ensures a heightened antioxidative, anti ozonating, light-, radio-, thermo-bioresistance at improvement of ecology in the process of production, storing, usage and reprocessing and utilization of blasting powders, solid rocket propellants and gas-generating compositions based on nitro-cellulose.

EFFECT: the invention ensures required chemical resistance of the treated substances and safe ecology.

4 cl, 1 tbl

Description

The invention relates to the field of gunpowders, solid rocket fuels and gas-generating compositions based on nitrocellulose, which are used in barrel and rocket systems, as well as in fire extinguishing systems, in fire extinguishers, for deployment and inflation of emergency rescue equipment, for automobile safety bags, pneumatic devices and for other purposes that require quick and safe creation of gas pressure, volume.

It is known that at present stabilization of gunpowder, solid rocket fuels and gas-generating compositions based on nitrocellulose is carried out by treatment with N-nitrosodiphenylamine, alkylated diphenylurea derivatives (centralites), diphenylamine in concentrations of 0.2-4 wt.% (RU 2093500 C1.1997; RU 2026276 C1, 1995; RU 21998870 C2; US 3917767, 1975; RU 2140893 C1, 1999; RU 2117649 C1, 1998).

Dioxinaphthalenes, their esters and homologs, and disalicylidene-1,2-propanediamine are effective time stabilizers of combustible rocket fuel. Effective thermal stabilizers are long-chain aliphatic amines, preferably with a number of carbon atoms of 10-40, formaldimines, condensation products of triethanolamine with alcohols or fatty acids (Ya. M. Pushkin. Liquid and solid chemical rocket fuels. - M., Nauka, 1978, p. .162-164).

A disadvantage of the known stabilizers of gunpowder, solid rocket fuels and gas-generating compositions based on nitrocellulose is that N-nitrosodiphenylamine, centralites and diphenylamine form toxic substances during the preparation, storage, use, processing and disposal of these gas-forming substances, while the stabilizers themselves belong to various hazard classes (Harmful substances in industry. Edited by N.V. Lazarev, “Chemistry”, 1969).

In addition, the assortment of known stabilizers of substances based on nitrocellulose is insufficient, which did not allow to obtain a variety of composite materials, gunpowder, solid rocket fuels, gas-generating compositions with desired properties without introducing additional components. In addition, the formation of toxic nitroso compounds in nitrocellulose compositions dramatically limits their civilian use.

As the closest analogue to the proposed group of inventions, the chemical stability stabilizer of powders and fuels based on nitrocellulose — diphenylamine and a method for treating powders and fuels based on nitrocellulose using diphenylamine (“Brief Encyclopedic Dictionary. Condensed Energy Systems”, as amended by B) can be adopted. .P. Zhukova, M., “Janus-K”, 2000, p. 408).

The objective of the present invention is to improve the quality of gunpowders, solid rocket fuels and gas-generating compositions based on nitrocellulose, as well as their properties and ecology in the process of obtaining, storage, use, processing and disposal due to the universality of the properties of the introduced substances, which allow to refuse the introduction of additional additives, and also obtaining gunpowders, solid rocket fuels, gas-generating compounds with desired properties and at the same time increase the range of substances used to stabilize things PTS on the basis of nitrocellulose.

The solution to this problem is achieved by using as a stabilizer gunpowder, solid rocket fuels and gas generating compositions based on nitrocellulose inorganic acids, or organic acids, or their salts.

A stabilizer of gunpowders, solid rocket fuels and gas-generating compounds based on nitrocellulose is proposed, which is boric or phosphorous acid, or an organic acid and its salt of the formula (I):

Where:

R = -H, -OH, -COOH, -COONa,

R ₁ = —H, —OH, —COOH, —COONH ₄ , —COONa,

R ₂ = —H, —OH, —COOH, —COONa, the remainder of the compounds of formula

in which R ₁ and R have the above meanings, or formulas (II):

Where:

R = -OH, -OK, -ONH ₄ , -ONa,

R _l = - bond or - C ₂ H ₄ ,

R ₂ = absent or means H ₂ O or 2H ₂ O.

This invention is based on the totality of the obtained experimental data, theoretical representations of organic, inorganic and physical chemistry, which allows us to reasonably predict and calculate the compositions of the components of the systems and their ratios necessary for the optimal process taking into account the requirements for them. Until now, it was believed that acids accelerate the decomposition of nitrocellulose (L. A. Smirnov. “Equipment for the production of ballistic gunpowder by screw technology and charges from them,” edited by L.V. Zabelina, M., 1997). This circumstance determined the main direction in conducting studies on the stabilization and search for components of nitrocellulose materials, which excluded the use of acids as stabilizers and components of gas generators, additives for changing the properties of composite materials, such as nitrocellulose gunpowder, solid rocket fuels and gas generating compositions.

However, as a result of tests on the chemical resistance of nitrocellulose using a number of organic and inorganic acids and their salts, it was found that certain acids do not contribute to the decomposition of nitrocellulose, but stabilize it. Based on existing ideas that the process of decomposition of nitrocellulose proceeds according to a radical, ion-radical, ion mechanism (L. A. Smirnov. “Equipment for the production of ballistic defects by screw technology and charges from them”, edited by L. V. Zabelina, M ., 1997), and the experimental data obtained, we can conclude that it is possible to stabilize nitrocellulose at a certain stage of its destruction and use for this purpose the substances responsible for the inhibition of each of these pathways, or use one substance, The ability to stabilize the nitrocellulose in all stages of its expansion.

One of the properties of many of the proposed substances is their relatively low decomposition temperature and relatively high ignition temperature with the formation of a significant amount of gases, while part of the energy (temperature) will be spent on the decomposition of these substances, which will reduce the total (total) temperature of the resulting gases with a simultaneous increase their volumes (due to gases generated as a result of thermal decomposition and combustion of substances), which will lead to a smooth and rapid increase in pressure in the boundary confined space (volume) and the rapid outflow of gases formed in the direction of lower pressure, which is very important when shooting from barrel and missile systems, since such a (uniform and smooth) increase in pressure will avoid strong (loud), sharp sound pops (noise) , reduce muzzle pressure, and also for the same reasons, reduce the wall thickness of barrels, missiles, shells, as well as change the material from which they are made, while improving ballistic and other characteristics of these systems and reduce reduction of visible flame emissions (mainly due to the absence of solid incandescent particles in the emissions).

The proposed substances capable of forming crystalline hydrates contribute to lowering the moisture content of composite materials. Moreover, the crystalline hydrates themselves during thermolytic decomposition will significantly reduce the total (total) temperature of the gases formed (RU 2151135 C1; Bull. No. 17 from 06/20/2000).

Some substances at the same time have antiseptic, antibacterial, antifungal, anti-mold action (Bioorganic chemistry, 2nd ed., Revised and add. - M .: Medicine, 1991. - 528 s; Rukhadze E.G. et al. “Insects and rodents - destroyers of materials and technical devices. ”M., 1983, pp. 252-258), which leads to improved operational properties of materials and their biostability.

In addition, substances with different enthalpies contribute to the creation of composite materials with desired properties.

It is known to use oxalic sodium or ammonium, as well as a double sodium-ammonium salt as a means to destroy a muzzle flame (G. Cast and L. Metz. Chemical studies of explosives and igniters. - Translated from German, M. - L., ed. ONTI, 1934, p. 161).

It is also known to use oxalic ammonium as a component of a gas generating composition based on potassium nitrate (RU 2151135 C1; Bull. No. 17 dated 06/20/2000).

In addition, the use of oxalic, succinic, phosphorous, boric, phthalic, benzoic, salicylic acids and their salts in pharmacy is known as analytical reagents, drugs of external and internal antiseptic, antirheumatic, analgesic, antipyretic, antifungal action (Belikov V.G. Special Pharmaceutical Chemistry. Part 2. Editor VN Boranenkova, 1996, 608 pp .; Bioorganic Chemistry. 2nd ed., revised and enlarged - M .: Medicine, 1991. - 528 pp.), methylene disalicylic acid and its salts as a drug to combat Bole plants, destroying rust, controlling insects and rodents, molds, for coating photographic materials, additives to feed, as analytical reagents (I. M. Korenman. Organic reagents in inorganic analysis. Reference book. M: “Chemistry”, 1980, p. 448; Salinas F. Quim anal., 1975, V.29, p. 288, 307; US patent, CL 424-230 (A 23 K 1/00, No. 3493663, claimed 05.27.66, publ. . 03.02.70); English Patent No. 7744286, dated 01.02.56; US patent No. 2940895, from 14.06.60; Kuhn Martin "Farbe und Lack" 1963, 69, No. 4, S.275-278; Rukhadze EG and others. “Insects and rodents-destroyers of materials and technical devices”, Moscow, 1983, p. 252-258).

Preferred acids and salts of the compounds of formula (I) are:

- 5,5'-метилендисалициловая кислота,when R = -OH, R ₁ = -COOH, R ₂ =

- 5,5'-methylendisalicylic acid,

- диаммонийная соль 5,5′-метилендисациловой кислоты,when R = -OH, R ₁ = -COONH ₄ , R ₂ =

- diammonium salt of 5,5′-methylene disacic acid,

- динатриевая соль 5,5′- метилендисациловой кислоты,at R = -OH, R ₁ = - COONa, R ₂ =

- disodium salt of 5,5′-methylene disacic acid,

when R = -COOH, R ₁ = -COOH, R ₂ = H - orthophthalic acid,

at R = H, R ₁ = —COOH, R ₂ = —COOH — isophthalic acid,

at R = -COOH, R ₁ = H, R ₂ = -COOH - terephthalic acid,

at R = —COONa, R ₁ = H, R ₂ = —COONa is the disodium salt of terephthalic acid,

at R = H, R ₁ = —COONa, R ₂ = —COONa is the disodium salt of metaphthalic acid,

at R = —COOH, R ₁ = —OH, R ₂ = H — salicylic acid,

when R = —OH, R ₁ = —COONa, R ₂ = H — sodium salt of salicylic acid,

at R = —COOH, R ₁ = —H, R ₂ = —H — benzoic acid,

when R = -COONa, R ₁ = -H, R ₂ = -H - sodium salt of benzoic acid,

at R = —COOH, R ₁ = —H, R ₂ = —OH — para-hydroxybenzoic acid,

at R = —H; R ₁ = —COOH; R ₂ = —OH — meta-hydroxybenzoic acid.

Preferred acids and salts of the compounds of formula (II) are:

when R = -OH, R ₁ = - bond, - oxalic acid,

when R = —OH, R ₁ = - bond, R ₂ = 2H ₂ O - oxalic acid, 2-aqueous,

when R = -OK, R ₁ = - bond, - potassium oxalate,

when R = -ONa, R ₁ = - bond, - sodium oxalate,

when R = —ONH ₄ , R ₁ = —bond, R ₂ = H ₂ O — oxalic ammonium, 1-aqueous,

at R = —OH, R ₁ = —C ₂ H ₄ — succinic acid.

A method for treating gunpowders, solid rocket fuels and gas-generating compositions based on nitrocellulose using the above chemical stability stabilizer by introducing it in an amount of 0.1-35% by weight of the processed substances is also proposed.

New and non-obvious is the establishment that the introduction of these acids or their salts in the composition of nitrocellulose powders, as well as solid rocket fuels and gas-generating compositions based on them in the amount of 0.1-35% of their mass provides the required chemical resistance. At the same time, an improvement in the rate of flame suppression, ballistic characteristics, phlegmatization, a significant change in temperature and an increase in the volume of formed gases are achieved. In addition, the use of these compounds in the treatment of nitrocellulose powders, solid rocket fuels, gas generating compositions provides antioxidant, antiozonant, light, radio, heat and biostability and ecology.

The following examples illustrate but do not limit the present invention. In all examples, the samples were prepared according to the well-known classical technology.

A stabilizer sample taken with an accuracy of 0.0001 g is dissolved in 50 ml of ethyl acetate (EA), then 5 g of nitrocellulose substance is poured, with a nitrogen content of at least 212.0 ml of NO / g (taking into account humidity = 57.3 wt.%) . The resulting mixture is periodically stirred for 24-28 hours until a homogeneous mass is formed. The mass is poured over the surface of the mold and dried. The obtained nitrocellulose film is cut into strips and its chemical resistance is determined according to OST B 84-2085-92 (at a temperature of 110 ° C and 125 ° C) and other characteristics. The test results are shown in table 1.

As a result of the tests, the effectiveness of chemical resistance stabilizers was shown when introduced into pyroxylin or compositions based on it in an amount of 0.1 to 35% by weight, while the required stability of all nitrocellulose compositions was achieved with an improvement in the rate of flame retardation, ballistic characteristics, and phlegmatization, significant changes in temperature and increase in gas volumes. In addition, the use of these compounds in the processing of gunpowder, solid rocket fuels, gas-generating compounds based on nitrocellulose provides antioxidant, antiozonant, light, radio, thermal, biostability and ecology in the process of obtaining, storage, use, processing and disposal of nitrocellulose materials. The results obtained make it possible to use these substances not only as stabilizers of chemical resistance, but also as components for the creation of new formulations of nitrocellulose powders, solid rocket fuels and gas-generating compositions, since they have unique properties that can be used to create new various composite materials with specified properties.

Table 1 Nitrocellulosic material Stabilizer Content, wt.% Toxic substances Chemical resistance 1 2 3 4 5 pyroxylin Diphenylamine 0.5 N nitrosodiphenylamine high ballitis Diphenylamine 1 N nitrosodiphenylamine high cordite Diphenylamine 2,5 N nitrosodiphenylamine high Pyroxylin * 5,5'-methylendisalicylic acid 0.5 Not detected high ballitis oxalic acid 2-aqueous 0.8 Not detected high cordite terephthalic acid 5 Not detected high pyroxylin boric acid 2 Not detected sat. ballitis phosphorous acid 3 Not detected sat. cordite salicylic acid twenty Not detected high pyroxylin succinic acid 10 Not detected high ballitis oxalic acid 25 Not detected high Cordite ammonium oxalate, 1-aqueous fifteen Not detected high Pyroxylin ** benzoic acid 0.5 Not detected high Ballistitis *** terephthalic acid disodium salt 5 Not investigated high cordite 5.5'-methylendisalicylic acid diammonium salt thirty Not detected high * - the following substances were tested under experimental conditions: diammonium salt of 5,5'-methylendisalicylic acid, salicylic acid, succinic acid, oxalic acid, oxalic acid 2-hydrous, potassium oxalate, sodium oxalate, sodium salt of salicylic acid. ** - in the conditions of the experiment (at a temperature of 110 ° C) the following substances were tested: sodium salt of benzoic acid, para-hydroxybenzoic acid, meta-hydroxybenzoic acid. *** - the following substances were tested under experimental conditions: disodium salt of 5,5'-methylendisalicylic acid, disodium salt of metaphthalic acid.

Claims (4)

1. The stabilizer of chemical resistance of gunpowder, solid rocket fuel and gas-generating composition based on nitrocellulose, which is boric or phosphorous acid, or an organic acid or its salt of the formula (I)

Where R = —H, —OH, —COOH, —COONa R ₁ = —H, —OH, —COOH; -COONH ₄ , -COONa, R ₂ = —H, —OH, —COOH, —COONa, the remainder of the compounds of formula

in which R ₁ or R have the above meanings, or formula (II)

Where R = -OH, -OK, -ONH ₄ , -ONa, R ₁ = - bond or - C ₂ H ₄ , R _{2 is} absent or means H ₂ O or 2H ₂ O. 2. The chemical stability stabilizer according to claim 1, characterized in that the organic acid or its salt of the formula (I) are when R = —OH, R ₁ = —COOH, R ₂ =

-5,5'-methylendisalicylic acid, at R = —OH; R ₁ = —COONH ₄ ; R ₂ =

the diammonium salt of 5.5 'methylene disalicylic acid, when R = —OH, R ₁ = —COONa, R ₂ =

disodium salt 5.5'- methylenedisalicylic acid when R = -COOH, R ₁ = -COOH, R ₂ = H - orthophthalic acid, at R = —H; R ₁ = —COOH, R ₂ = —COOH — isophthalic acid, at R = —COOH, R ₁ = —H, R ₂ = —COOH — terephthalic acid, when R = -COONa, R ₁ = -H, R ₂ = -COONa is the disodium salt of terephthalic acid, when R = -H, R ₁ = -COONa, R ₂ = -COONa is the disodium salt of metaphthalic acid, at R = —COOH, R ₁ = —OH, R ₂ = —H — salicylic acid, at R = —OH, R ₁ = —COONa, R ₂ = —H — sodium salt of salicylic acid, at R = —COOH, R ₁ = —H, R ₂ = —H — benzoic acid, when R = —COONa, R ₁ = —H, R ₂ = —H — sodium salt of benzoic acid, at R = —COOH, R ₁ = —H; R ₂ = —OH — para-hydroxybenzoic acid, when R = —H, R ₁ = —COOH, R ₂ = —OH — meta-hydroxybenzoic acid. 3. The stabilizer of chemical resistance according to claim 1, characterized in that the preferred organic acid or its salt of the formula (II) are when R = —OH, R ₁ = —bond, - oxalic acid, at R = —OH; R ₁ = - bond, R ₂ = 2Н ₂ О - oxalic acid, 2-aqueous, when R = -OK, R ₁ = -link, - potassium oxalate, when R = -ONa, R ₁ = -bond, - sodium oxalate, when R = - ONH ₄ ; R ₁ = - bond, R ₂ = H ₂ O - oxalic ammonium, 1-aqueous, at R = —OH; R ₁ = —C ₂ H ₄ - succinic acid. 4. The method of processing gunpowder, solid rocket fuel and a gas-generating composition based on nitrocellulose using a chemical resistance stabilizer, characterized in that the chemical resistance stabilizer according to claim 1 is used as a chemical stability stabilizer according to claim 1 in an amount of 0.1-35% by weight of the processed powder , solid rocket fuel and gas-generating composition based on nitrocellulose.