JP2010202449A - Nitramine propellant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nitramine propellant composition which is low in combustion temperature and is excellent in mechanical properties while keeping the easiness of being handled and stored. <P>SOLUTION: The nitramine propellant composition contains: a component (a): cyclotrimethylene trinitramine; a component (b): a binder containing nitrocellulose; a component (c): nitroguanidine; and a component (d): and a plasticizer having nitric ester group, nitro group, nitramine group or azide group in a molecule. Wherein, the content of component (a) is 25-35 mass% in the nitramine propellant composition, the content of the component (b) is 100-150 pts.mass per 100 pts.mass component (a), the content of the component (c) is 30-90 pts.mass per 100 pts.mass component (a) and the content of the component (d) is 30-70 pts.mass per 100 pts.mass component (a). The binder of the component (b) is preferably one comprising nitrocellulose and polyvinyl pyrolidone. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a nitramine propellant composition used as an ammunition for a large-caliber tank gun, a field gun, and the like. More specifically, the present invention relates to a nitramine propellant composition that takes into account ease of handling and storage, has a low combustion temperature, and has excellent mechanical properties.

  Conventionally, a propellant called a LOVA propellant considering ease of handling and storage has been known. This LOVA propellant has the characteristics (LOVA property) that it is less sensitive to heat, flame, impact, friction, etc. than normal propellant, while it has proper performance such as ignitability and flammability when used. It is a propellant.

  As such propellants, the following propellants have been proposed. For example, a propellant containing a nitramine compound, nitrocellulose, and a plasticizer, containing 46 mass percent or more of the nitramine compound, and 99% of the total nitramine compound before mixing or mixing the propellant raw material has a particle size A nitramine propellant having an average particle size of 33 μm or less and an average particle size of 9 μm or less is known (see Patent Document 1).

  Moreover, 20-35 mass% of nitrocellulose, 16-30 mass% of a plasticizer, 46-64 mass% of a cyclic nitramine compound, 0-18 mass% of nitroguanidine, and 0-18 mass% of solid additives are contained. A nitramine propellant composition in which the ratio of each component is specified is known (see Patent Document 2).

  Furthermore, a propellant composition composed of oxygen-containing particles, a binder polymer, and a plasticizer is known (see Patent Document 3). The oxygen-containing particles are nitroguanidine or nitramine compounds such as cyclotrimethylenetrinitramine and cyclotetramethylenetetranitramine, the binder polymer is a cellulose derivative having a nitrate group such as nitrocellulose, and the plasticizer is an inert plasticizer. Or it is the combined use of an inert plasticizer and an active plasticizer, and the ratio of each component is specified. Specifically as this propellant composition, cyclotrimethylene trinitramine is 58% by mass, nitrocellulose is 21% by mass, nitroguanidine is 5% by mass, plasticizer is 15.5% by mass, and stabilizer is 0.5%. The mass% is set (Example 1 described on page 6 of Patent Document 3).

JP 2006-151791 A (pages 2 and 4) JP 2008-110892 A (second page and third page) JP 2000-272989 A (pages 2 and 6)

  Although the nitramine propellant described in Patent Document 1 has good LOVA properties and excellent flammability, it contains 46% by mass or more of cyclotrimethylenetrinitramine, which is a nitramine compound. There was a problem that the temperature was high and erosion occurred inside the gun barrel. Furthermore, since the ratio of nitrocellulose as a binder is small, there is a problem that the mechanical properties of the propellant are low.

  In addition, in the nitramine propellant composition described in Patent Document 2, 46% by mass or more of cyclotrimethylenetrinitramine, which is a nitramine compound, which has LOVA properties, is also present. High, there was a problem that erosion occurred inside the barrel.

  Furthermore, in the propellant composition described in Patent Document 3, the nitramine compound content is as high as 58% by mass although it has LOVA properties, and the combustion temperature is high, causing erosion on the inner surface of the gun barrel, There was a problem that the mechanical properties of the propellant were low because the ratio of nitrocellulose as a binder was as small as 21% by mass.

  Accordingly, an object of the present invention is to provide a nitramine propellant composition having a low combustion temperature and excellent mechanical properties while maintaining ease of handling and storage.

  As a result of diligent research focusing on the problems existing in the prior art, the present inventors combined cyclotrimethylene trinitramine, a binder containing nitrocellulose, nitroguanidine and an energy plasticizer, and in a specific blending ratio. By setting, the inventors have obtained knowledge that the problem can be solved and have completed the present invention.

  That is, the nitramine propellant composition of the first invention in the present invention comprises component (a) cyclotrimethylenetrinitramine, component (b) a binder containing nitrocellulose, component (c) nitroguanidine and component (d) molecule. It contains a plasticizer having a nitrate group, nitro group, nitramine group or azide group as a functional group. And while content of a component (a) is 25-35 mass% in a nitramine propellant composition, content of a component (b) is 100-150 mass parts with respect to 100 mass parts of a component (a), The content of the component (c) is 30 to 90 parts by mass and the content of the component (d) is 30 to 70 parts by mass.

In the nitramine propellant composition of the second invention, in the first invention, the component (b) comprises nitrocellulose and polyvinylpyrrolidone.
In the nitramine propellant composition of the third invention, in the second invention, the content of the polyvinylpyrrolidone is 10 to 30 parts by mass with respect to 100 parts by mass of nitrocellulose.

  The nitramine propellant composition according to a fourth aspect of the present invention is the component according to any one of the first to third aspects, wherein the component (b) and the component (d) with respect to the total amount of the component (a) and the component (c). The mass ratio of the total amount is 1.0: 0.7 to 1.0: 1.4.

According to the present invention, the following effects can be exhibited.
In the nitramine propellant composition of the present invention, the content of the component (a) is 25 to 35% by mass in the nitramine propellant composition, and the content of the component (b) with respect to 100 parts by mass of the component (a). The amount is set to 100 to 150 parts by mass, the content of component (c) is set to 30 to 90 parts by mass, and the content of component (d) is set to 30 to 70 parts by mass.

  In this way, the nitramine propellant composition uses cyclotrimethylene trinitramine as component (a) instead of nitroglycerin as an essential component, and the content of component (b) nitrocellulose is limited. Can be good. Moreover, since the reaction at the time of combustion of a propellant is an endothermic reaction, this nitroguanidine can suppress the raise of combustion temperature as a component (c). Furthermore, based on the property of the binder containing nitrocellulose as the component (b), and the property of the plasticizer as the component (d), mechanical properties such as the compressive strength of the propellant can be enhanced.

  Therefore, the nitramine propellant composition of the present invention has a low combustion temperature and excellent mechanical properties while maintaining ease of handling and storage.

Hereinafter, embodiments of the present invention will be described in detail.
[Nitramin propellant composition]
The nitramine propellant composition of the present embodiment (hereinafter also simply referred to as a propellant) is composed of component (a) cyclotrimethylenetrinitramine, component (b) a binder containing nitrocellulose, component (c) nitroguanidine and component ( d) A plasticizer having a nitrate group, nitro group, nitramine group or azide group as a functional group in the molecule is contained. And while content of a component (a) is 25-35 mass% in a nitramine propellant composition, content of a component (b) is 100-150 mass parts with respect to 100 mass parts of a component (a), The content of the component (c) is set to 30 to 90 parts by mass and the content of the component (d) is set to 30 to 70 parts by mass. In this way, by combining specific components and setting their content to a predetermined ratio, the ease of handling and storage of the propellant is maintained, the combustion temperature during propellant combustion is suppressed, and the propellant is further reduced. The mechanical properties of the molded product can be improved.
<Cyclotrimethylene trinitramine as component (a)>
First, cyclotrimethylenetrinitramine will be described. Cyclotrimethylenetrinitramine (1,3,5-trinitroperhydro-1,3,5-triazine or cyclotrimethylenetrinitroamine or RDX) is a cyclic nitramine compound and has a function of improving explosive power. It has a high energy and excellent combustibility. The average particle diameter of cyclotrimethylenetrinitramine is usually about 3 to 15 μm, preferably 5 to 10 μm. When the average particle diameter exceeds 15 μm, the propellant productivity tends to decrease, and when the average particle diameter is less than 3 μm, the availability and the dispersibility during the manufacture of the propellant tend to deteriorate. .

The content of cyclotrimethylenetrinitramine is 25 to 35% by mass, preferably 28 to 33% by mass in the nitramine propellant composition. When the content of cyclotrimethylenetrinitramine is more than 35% by mass, the combustion temperature at the time of combustion of the propellant becomes high and erosion occurs on the inner surface of the gun barrel. On the other hand, when the content is less than 25% by mass, the explosive power is lowered and the original function as a propellant cannot be exhibited.
<Binder of component (b)>
Next, the binder containing nitrocellulose as component (b) will be described. Nitrocellulose (nitrified cotton) is a component that functions as a binder (binder) for granulating (graining) a molded product of fuel and propellant. The nitrocellulose is a nitrate obtained by treating cellulose with a mixed acid of nitric acid and sulfuric acid.

  Nitrocellulose can be nitrated at three locations per unit glucose molecule, but it can be nitrified to various degrees, and the degree is distinguished by the nitrogen content. . The amount of nitrogen in the nitrocellulose is preferably 11.7 to 13.4% by mass, more preferably 12.2 to 13.4% by mass, and 12.6 to 13.2% by mass. It is particularly preferred. When the amount of nitrogen is less than 11.7% by mass, the combustibility of the propellant is lowered, and the nitrocellulose is too dissolved in the organic solvent and tends to be difficult to be formed into a granular shape. On the other hand, when the amount of nitrogen exceeds 13.4% by mass, the stability of the propellant with time decreases, and at the same time, nitrocellulose is difficult to dissolve in an organic solvent and tends to be difficult to be formed into granules. Indicates.

  The content of nitrocellulose in the binder is preferably 60 to 100% by mass, more preferably 75 to 100% by mass. When the content of nitrocellulose is less than 60% by mass, the content of nitrocellulose capable of exhibiting excellent mechanical properties and manufacturability is insufficient, and the mechanical properties of the propellant molding and the manufacturability of the propellant are lowered. Show the trend.

  The binder is preferably composed of the above nitrocellulose and polyvinylpyrrolidone in order to improve the function as a fuel and the function as a binder. This polyvinyl pyrrolidone will be described. By blending polyvinylpyrrolidone, the manufacturability when producing the propellant, particularly the dispersibility of each component, can be improved, and the mechanical properties of the propellant molding can be improved.

  The polyvinyl pyrrolidone used has a weight average molecular weight (mass average molecular weight) of about 10,000 to 1,500,000, preferably 30,000 to 100,000. If the weight average molecular weight is in the range of 10,000 to 1,500,000, the propellant manufacturability and the mechanical properties of the propellant molding are improved, and the weight average molecular weight of polyvinylpyrrolidone is 30,000 to 100,000. If it is within the range of 000, the manufacturability of the propellant and the mechanical properties of the propellant molding are greatly improved.

  By including a specific amount of polyvinyl pyrrolidone together with nitrocellulose as a binder, cyclotrimethylene trinitramine can be uniformly dispersed in the binder. In particular, when cyclotrimethylenetrinitramine is a fine particle, it is presumed that it greatly contributes to the improvement of its dispersibility and has a well-balanced good LOVA property and favorable mechanical properties.

  The content of polyvinylpyrrolidone in the binder is preferably 10 to 30 parts by mass, more preferably 10 to 15 parts by mass with respect to 100 parts by mass of nitrocellulose. If the content of polyvinylpyrrolidone is within the range of 10 to 30 parts by mass, the manufacturability of the propellant and the mechanical properties of the propellant molded product are improved. Furthermore, if the content of polyvinylpyrrolidone is in the range of 10 to 15 parts by mass, the manufacturability of the propellant and the mechanical properties of the propellant molding are greatly improved.

  As the binder, in addition to the above-mentioned nitrocellulose and polyvinylpyrrolidone, known binders such as cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate, carboxymethylcellulose, carboxymethylcellulose sodium salt, carboxymethylcellulose potassium salt, carboxymethylcellulose ammonium salt , Methylcellulose, ethylcellulose, hydroxyethylcellulose, ethylhydroxyethylcellulose, hydroxypropylcellulose, carboxymethylethylcellulose, microcrystalline cellulose and the like may be added as necessary from the viewpoint of mechanical properties and LOVA properties of the propellant molding. However, the content thereof is preferably 30 parts by mass or less with respect to 100 parts by mass of nitrocellulose, and when it exceeds 30 parts by mass, the mechanical properties of the propellant molded product tend to decrease.

Content of the binder containing a component (b) nitrocellulose is 100-150 mass parts with respect to 100 mass parts of component (a) cyclotrimethylene trinitramines, Preferably it is 100-120 mass parts. When content of a component (b) exceeds 150 mass parts, the LOVA property of a propellant will worsen. On the other hand, when the content of the component (b) is less than 100 parts by mass, the mechanical properties of the propellant molding are deteriorated.
<Nitroguanidine as component (c)>
Next, nitroguanidine [H ₂ NC (= NH) NHNO ₂ ] as the component (c) is a nitro compound, and has a function of lowering the combustion temperature of the propellant and improving the explosive power. Nitroguanidine can lower the combustion temperature during combustion of the propellant because the reaction during combustion of the propellant exhibits an endothermic reaction. The content of this nitroguanidine is 30 to 90 parts by mass, preferably 50 to 80 parts by mass with respect to 100 parts by mass of cyclotrimethylenetrinitramine. When the content of nitroguanidine exceeds 90 parts by mass, the manufacturability of the propellant deteriorates, and when the content of nitroguanidine is less than 30 parts by mass, the combustion temperature during combustion of the propellant is lowered. Can not be.
<Plasticizer of component (d)>
Next, the plasticizer of component (d) is a plasticizer having a nitrate group, nitro group, nitramine group or azide group as a functional group in the molecule (also referred to as an energy plasticizer). As well as the function of improving the manufacturability of the propellant and the mechanical properties of the propellant molding. As the energy plasticizer, any energy plasticizer that can improve explosive power and mechanical properties can be used. Examples of such energy plasticizers include diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate (TEGDN), butanediol dinitrate (BDDN), butanetriol trinitrate (BTTN), trimethylolethanetrinite. Plasticizers containing nitrate esters such as rate (TMETN) and trimethylolpropane trinitrate (TMPTN), and mixtures of bis-2,2-dinitropropyl acetal and bis-2,2-dinitropropyl formal (BDNPA / F) And plasticizers not containing nitrate esters such as nitratoethylnitramines (NENAs), glycidyl azide polymers (GAP), azido-acetic acid-2- (2-azido-acetoxy) -ethyl ester (EGBAA), etc. It is. These energy plasticizers can be used alone or in combination of two or more.

  Among these, a plasticizer which does not contain a nitrate ester having a high LOVA property is preferable, and a mixture of bis-2,2-dinitropropyl acetal and bis-2,2-dinitropropyl formal which is easy to obtain and handle. (BDNPA / F) and glycidyl azide polymer (GAP) are particularly preferred.

  As the plasticizer, in addition to the above-mentioned energy plasticizer, a known inert plasticizer may be added as needed from the viewpoint of LOVA properties and mechanical properties. Examples of the inert plasticizer include phthalic acid ester plasticizers such as dibutyl phthalate, dimethyl phthalate, and diethyl phthalate, oxy acid ester plasticizers such as acetyl triethyl citrate and acetyl tributyl citrate, phosphoric acid esters, and triacetin. . The content of these inert plasticizers is usually 20 parts by mass or less with respect to 100 parts by mass of the energy plasticizer. When this content exceeds 20 parts by mass, the explosive power of the propellant tends to decrease.

Content of an energy plasticizer is 30-70 mass parts with respect to 100 mass parts of cyclotrimethylenetrinitramines, Preferably it is 40-60 mass parts. When the content of the energy plasticizer exceeds 70 parts by mass, the manufacturability of the propellant is deteriorated. On the other hand, when the content of the energy plasticizer is less than 30 parts by mass, the explosive power of the propellant and the mechanical properties of the propellant molding are deteriorated.
<Ratio of component (a), component (b), component (c) and component (d)>
As described above, the component (a) and the component (c) improve the explosive power of the propellant, and particularly the component (c) can suppress the combustion temperature at the time of combustion of the propellant. In order to act synergistically, the mass ratio of component (a) to component (c) is preferably 1.0: 0.3 to 1.0: 0.9. When comprised in this way, the explosive power of a propellant can be raised further and the combustion temperature at the time of combustion of a propellant can fully be reduced. When the mass ratio is out of the range, the explosive power cannot be sufficiently improved and the combustion temperature cannot be sufficiently reduced.

  In addition, the component (b) and the component (d) can improve the manufacturability of the propellant and improve the mechanical properties of the propellant molding, but in order to exert their functions synergistically. In addition, the mass ratio of the component (b) to the component (d) is preferably 1.0: 0.3 to 1.0: 0.7. In this case, the manufacturability of the propellant can be further improved, and the mechanical properties of the propellant molding can be further improved. If the mass ratio is out of the range, it is impossible to sufficiently improve the manufacturability of the propellant and the mechanical properties of the propellant molding.

In addition, the mass ratio of the total amount of component (b) and component (d) to the total amount of component (a) and component (c) is 1.0: 0.7 to 1.0: 1.4. It is preferable that When comprised in this way, the effect of the ease of handling and preservation | save, and the fall of combustion temperature, and the effect of improvement of manufacturability and a mechanical physical property can be exhibited with sufficient balance. If the mass ratio is out of the range, the obtained effect tends to be unbalanced.
<Other ingredients>
In addition to the components (a), (b), (c) and (d), the nitramine propellant composition includes stabilizers and anti-inflammatory agents used in ordinary propellants as necessary. , Brighteners and the like. Examples of the stabilizer include diphenyl urea derivatives such as diphenyl urea, methyl diphenyl urea, ethyl diphenyl urea, diethyl diphenyl urea, dimethyl diphenyl urea, and methyl ethyl diphenyl urea, diphenyl amine derivatives such as diphenyl amine and 2-nitrodiphenyl amine, ethyl phenyl urethane, Examples thereof include phenylurethane derivatives such as methylphenylurethane, diphenylurethane derivatives such as diphenylurethane, and resorcinol. These compounds are used alone or as a mixture of two or more.

Among these compounds, since the melting point is 120 ° C. or higher, a diphenylurea derivative having a high effect of reliably capturing nitrogen oxides generated from nitrocellulose even at high temperatures, and suppressing the natural decomposition of nitrocellulose, Specifically, methyl diphenyl urea, diphenyl urea or dimethyl diphenyl urea is preferable, and methyl diphenyl urea or dimethyl diphenyl urea is particularly preferable. Examples of the flame retardant include potassium sulfate and potassium nitrate, and examples of the brightener include graphite and the content thereof is set according to a conventional method.
<Production method and molded product of nitramine propellant composition>
Next, the manufacturing method of a nitramine propellant composition is demonstrated.

  First, a predetermined amount of cyclotrimethylenetrinitramine, a binder containing nitrocellulose, nitroguanidine and an energy plasticizer, and if necessary, a stabilizer, a flame retardant and a brightening agent are weighed. After weighing, all components (raw materials) are put into a kneader, and an appropriate amount of organic solvent is added to the kneader and mixed uniformly to obtain a nitramine propellant composition. Subsequently, the obtained nitramine propellant composition is loaded into an extruder, applied with a predetermined pressure, and extruded through a die to be molded into a predetermined shape and size. Thereafter, the molded product of the nitramine propellant composition having a predetermined shape and size can be produced by cutting and drying.

  In addition, as the organic solvent used in the extrusion molding method, all those that dissolve or swell the binder containing nitrocellulose can be used. Examples of such an organic solvent include acetone, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, butyl acetate, diethyl ether, toluene, methyl ethyl ketone, and the like. These mixed solutions can also be used. In particular, acetone, ethyl alcohol, and diethyl ether are preferable in terms of excellent compatibility with nitrocellulose.

The molded product of the propellant can be appropriately sized and shaped according to the application. Examples of shapes include non-porous, single-hole, and porous tubes. Here, the single-hole tubular means a cylinder or hexagonal cylinder having one through-hole extending in the axial direction, and the porous tubular means a plurality (for example, 7, 19, and 37) extending in the axial direction. It is a cylindrical body or a hexagonal cylinder having a through hole.
[Summary of actions and effects exhibited by the embodiment]
In the nitramine propellant composition in the present embodiment, the content of the component (a) is 25 to 35% by mass in the nitramine propellant composition, and the component (b) with respect to 100 parts by mass of the component (a) The content of 100 to 150 parts by mass, the content of component (c) is set to 30 to 90 parts by mass, and the content of component (d) is set to 30 to 70 parts by mass.

  In this way, the propellant uses cyclotrimethylenetrinitramine as the component (a) instead of nitroglycerin as an essential component, and the content of nitrocellulose in the component (b) is limited. Handling during production and storage can be improved. Furthermore, nitroguanidine is blended as the component (c), and this nitroguanidine can suppress an increase in combustion temperature because the reaction during combustion of the propellant is an endothermic reaction. In addition, based on the properties of the binder containing nitrocellulose as the component (b) and the properties of the plasticizer as the component (d), mechanical properties such as compressive strength can be enhanced for the propellant molding.

  Therefore, the propellant has a low combustion temperature and excellent mechanical properties while maintaining ease of handling and storage. Since the combustion temperature can be suppressed in this way, it is possible to prevent erosion from occurring on the inner surface of a barrel such as a tank gun or a field gun.

  -When the binder of a component (b) consists of nitrocellulose and polyvinylpyrrolidone, the manufacturability of a propellant can be improved with the property as a binder of polyvinylpyrrolidone.

  -When the content of polyvinyl pyrrolidone is 10 to 30 parts by mass with respect to 100 parts by mass of nitrocellulose, the effect of polyvinyl pyrrolidone can be sufficiently enhanced, and the productivity of the propellant can be further improved.

  -The mass ratio of component (a) to component (c) is 1.0: 0.3 to 1.0: 0.9, so that the explosive power of the propellant is further increased, The combustion temperature can be sufficiently reduced.

  -The mass ratio of the component (b) and the component (d) is 1.0: 0.3 to 1.0: 0.7, so that the manufacturability of the propellant is further enhanced, and the projectile molding machine The physical properties can be further improved.

  The mass ratio of the total amount of component (b) and component (d) to the total amount of component (a) and component (c) is 1.0: 0.7 to 1.0: 1.4 Thus, the effect of easy handling and storage of the propellant and the reduction of the combustion temperature and the effect of improvement of the mechanical properties can be exerted in a balanced manner.

Hereinafter, the embodiment will be described more specifically with reference to examples and comparative examples. Abbreviations in Table 1 and Table 2 represent the following meanings.
RDX: Cyclotrimethylene trinitramine NC: Nitrocellulose NQ: Nitroguanidine GAP: Glycidyl azide polymer AKII: Methyldiphenylurea PVP: Polyvinylpyrrolidone CAB: Cellulose acetate butyrate BDNPA / F: Bis-2,2-dinitropropyl acetal Mixture with bis-2,2-dinitropropyl formal Next, a method for evaluating the characteristics of the nitramine propellant composition in Examples and Comparative Examples is shown below.
[LOVA characteristics]
A drop sensitivity test method for evaluating the LOVA property will be described. The drop sensitivity test was performed in accordance with the drop sensitivity test method defined in JIS K-4810 (explosives performance test method), and 1/6 explosion point was obtained and the corresponding grade was displayed. For LOVA, grade 5 or higher is a passing score.
[Combustion temperature]
A method for evaluating the combustion temperature will be described. The combustion temperature was calculated based on a thermal equilibrium calculation known in the art. In order to reduce the erosion generated on the inner surface of the gun barrel, it is preferable to lower the combustion temperature as much as possible. The combustion temperature calculated by thermal equilibrium calculation should be 2850K or less.
[Mechanical properties]
A compressive strength test method for evaluating mechanical properties will be described. The compressive strength test was performed using a tensile compression tester (AL-50kNB) manufactured by Minebea Co., Ltd. After a molded product of the nitramine propellant composition as a sample was placed on the center of the sample stage, the sample was compressed at a speed of 30 mm / min in the length direction to conduct a compression test. Then, the maximum load value and the compressibility were read from the stress strain curve, and the mechanical properties were evaluated. When shooting a tank gun, a field gun, etc., a large impact is given to the molded article of the nitramine propellant composition. Therefore, the molded product of the nitramine propellant composition is required to withstand the impact. In this test, it is necessary that the maximum load value is 23 MPa or more and the compression rate is 8.0% or more.
〔Manufacturability〕
A method for evaluating manufacturability will be described. The following evaluation criteria evaluated the ease of shaping | molding in the case of extruding the nitramine propellant composition of each Example and a comparative example with an extrusion molding apparatus, and the handleability at the time of conveying to a cutting machine.

(Double-circle): The flexibility of the extruding drug was high and it was able to handle very easily.
○: The extrudate was flexible and could be handled easily.
(Triangle | delta): The flexibility of an extruding medicine was scarce and it was necessary to handle it with care.

X: There was a problem in handling because the extrudate was not flexible and very brittle.
Regarding manufacturability, it is necessary to make ◎ or ○.
Hereinafter, an example and a comparative example will be described. In addition,% display is a mass reference | standard unless there is particular notice.
Example 1
A molded article of the nitramine propellant composition was produced by the method described below.

  As component (a) 30.0% cyclotrimethylenetrinitramine with an average particle size of 7 μm, as component (b) 33.0% nitrocellulose with 12.6% nitrogen, and as component (c) nitroguanidine 25 0.05% of glycidyl azide polymer having a weight average molecular weight of about 700 as component (d) and 1.0% of methyldiphenylurea as a stabilizer were mixed with 55% acetone and ethyl alcohol. -45% mixed solution was added and mixed uniformly with a so-called Werner mixer. The Werner-mixer is a device that stirs and mixes with stirring blades attached to a rotating shaft extending in the lateral direction.

  The resulting mixture was then loaded into an extruder. A 12.5 mm die and a 0.5 mm pin are attached to the extrusion apparatus in advance, and the mixture is extruded while passing through this die by applying pressure, and a 19-hole tubular cylinder having 19 through holes. Molded into medicine. This molded product was cut into a length of 10.0 mm and dried to obtain a molded product of a granular nitramine propellant composition. The productivity at that time was evaluated by the method described above.

Moreover, the LOVA property and combustion temperature by the said drop sensitivity test were calculated | required using the molded object of this nitramine propellant composition. Further, mechanical properties were evaluated by the compressive strength test. The test results are shown in Table 1. The combustion temperature is a calculated value calculated by performing a thermal equilibrium calculation known in the art.
(Examples 2 to 12)
Molded products of the nitramine propellant compositions of Examples 2 to 12 were produced in accordance with Example 1 with the compositions shown in Table 1. The LOVA property, combustion temperature, mechanical properties and manufacturability were determined in the same manner as in Example 1. The test results are shown in Table 1. The polyvinylpyrrolidone used for the production of the nitramine propellant composition is a grade product having an average molecular weight of about 50,000, and the mixture of bis-2,2-dinitropropyl acetal and bis-2,2-dinitropropyl formal is A grade product with a mass ratio of 1: 1.

表１の試験結果より次のようなことが明らかになった。

The test results in Table 1 revealed the following.

It was revealed that all of the nitramine propellant compositions shown in Examples 1 to 12 had no problems in LOVA properties and manufacturability. Moreover, it was confirmed that all the combustion temperatures are 2850K or less. Furthermore, in mechanical properties, all have a maximum load value of 25 MPa or more, and all have a compressibility of 8.5% or more, and it can be confirmed that there is no problem in mechanical properties. It was.
(Comparative Examples 1-8)
With the compositions shown in Table 2, molded articles of nitramine propellant composition (single base propellant) were produced in the same manner as in Example 1, and each characteristic was evaluated in the same manner as in Example 1. The results are shown in Table 2.

表２に示した結果から、シクロトリメチレントリニトラミンを２１質量％配合した比較例１では、火薬力が低く、ニトラミン発射薬としての機能を有さないことがわかった。すなわち、シクロトリメチレントリニトラミンの配合量は、少なくとも２５質量％が必要であることが明らかになった。その一方、シクロトリメチレントリニトラミンを４８質量％配合した比較例２では、燃焼温度が２９８５Ｋと高くなり、砲身内面にエロージョンを起こす可能性の高いことがわかった。シクロトリメチレントリニトラミンの配合量が多くなることによりニトロセルロースを含むバインダーの含有量が低下するため、機械的物性が低下することがわかった。すなわち、シクロトリメチレントリニトラミンの配合量は、３５質量％以下とする必要のあることが明らかになった。

From the results shown in Table 2, it was found that Comparative Example 1 containing 21% by mass of cyclotrimethylenetrinitramine has low explosive power and does not have a function as a nitramine propellant. That is, it was revealed that the amount of cyclotrimethylenetrinitramine is required to be at least 25% by mass. On the other hand, in Comparative Example 2 in which 48% by mass of cyclotrimethylenetrinitramine was blended, the combustion temperature was as high as 2985K, and it was found that there was a high possibility of causing erosion on the inner surface of the barrel. Since the content of the binder containing nitrocellulose is decreased by increasing the amount of cyclotrimethylenetrinitramine, it has been found that the mechanical properties are decreased. That is, it became clear that the amount of cyclotrimethylenetrinitramine needs to be 35% by mass or less.

  In Comparative Example 3 in which the content of the binder containing nitrocellulose was excessive, it was found that the LOVA property was lowered and the combustion temperature was increased, although there was no problem with mechanical properties and manufacturability. In Comparative Example 4 in which the content of the binder containing nitrocellulose was made too small, there was no problem with the LOVA property and the combustion temperature, but it was found that the mechanical properties were lowered because the effect as a binder was poor.

  In Comparative Example 5 in which the content of nitroguanidine was excessive, there was no problem with the LOVA property and the combustion temperature, but it was found that the productivity deteriorated because many powder components were blended. In Comparative Example 6 in which the content of nitroguanidine is excessively small, there is no problem with LOVA properties, manufacturability and mechanical properties, but the content of nitroguanidine decreases, so the problem of an increase in combustion temperature occurs. I understood.

  In Comparative Example 7 in which the content of the glycidyl azide polymer that is an energy plasticizer was excessive, there was no problem with the LOVA property and the combustion temperature, but it was found that the productivity deteriorates because many liquid components are blended. . In Comparative Example 8 in which the content of the glycidyl azide polymer, which is an energy plasticizer, was excessively small, it was found that although there was no problem with the LOVA property, the combustion temperature was high and the compression ratio was low.

  As described above, in contrast to Comparative Examples 1 to 8, the nitramine propellant compositions of Examples 1 to 12 can maintain ease of handling and storage, and at the same time, combustion during propellant combustion It was shown that the temperature was low and the mechanical properties of the propellant molding were excellent.

It should be noted that the above embodiment can be modified as follows.
-As the nitrocellulose of the component (b), it is possible to use a combination of a plurality of different nitrogen amounts.

  -As the energy plasticizer of component (d), a plasticizer having a nitrate group, nitro group, nitramine group or azide group as a functional group in the molecule is used in appropriate combination depending on the purpose. It can be configured to adjust the mechanical properties of the propellant molding.

Furthermore, the technical idea grasped from the embodiment will be described below.
The nitramine propellant according to any one of claims 1 to 4, wherein the mass ratio of the component (a) to the component (c) is 1.0: 0.3 to 1.0: 0.9. Composition. When constituted in this way, in addition to the effects of the invention according to any one of claims 1 to 4, the explosive power of the propellant can be further increased, and the combustion temperature at the time of combustion of the propellant can be sufficiently reduced. it can.

  The mass ratio of component (b) and component (d) is 1.0: 0.3 to 1.0: 0.7, The nitramine propellant according to any one of claims 1 to 4. Composition. When constituted in this way, in addition to the effects of the invention according to any one of claims 1 to 4, it is possible to further improve the manufacturability of the propellant and further improve the mechanical properties of the propellant molded product. it can.

Claims (4)

Component (a) cyclotrimethylene trinitramine, component (b) binder containing nitrocellulose, component (c) nitroguanidine and component (d) nitrate group, nitro group, nitramine group or azide group as functional groups in the molecule The content of component (a) is 25 to 35% by mass in the nitramine propellant composition, and the content of component (b) is 100 parts by mass of component (a). A nitramine propellant composition, wherein 100 to 150 parts by mass, the content of component (c) is 30 to 90 parts by mass, and the content of component (d) is 30 to 70 parts by mass. The nitramine propellant composition according to claim 1, wherein the component (b) comprises nitrocellulose and polyvinylpyrrolidone. The nitramine propellant composition according to claim 2, wherein a content of the polyvinyl pyrrolidone is 10 to 30 parts by mass with respect to 100 parts by mass of nitrocellulose. The mass ratio of the total amount of component (b) and component (d) to the total amount of component (a) and component (c) is 1.0: 0.7 to 1.0: 1.4. The nitramine propellant composition according to any one of claims 1 to 3.