JPH0648878A - Explosive composition - Google Patents

Abstract

PURPOSE:To improve detonation velocity as the explosive performance of a plastic-bonded explosive by incorporating polymer azide having higher energy than glycidylazide polymer into the binder. CONSTITUTION:This explosive compsn. consists of the main component of an explosive compd. and a binder component. This explosive compd. is cyclotrimethylene trinitroamine and/or cyclotetramethylene tetranitroamine. The binder component consists of (A) polymer azide, (B) bis(2,2-dinitropropyl) acetal/formal, trimethylolethane trinitrate and/or diethylene glycol dinitrate, (C) crosslinking agent, and (D) hardening agent. The amt. of the binder is 15-30wt.% of the whole compsn. As for the polymer azide, 3,3-bisazide methyloxoethane (BAMO)/tetrahydrofuran copolymer having hydroxyl groups as end groups, or BAMO/3-azide-methyl-3-methyloxoethane copolymer is preferable.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to explosive compositions. More specifically, it relates to an explosive containing a high-energy binder, particularly a plastic bonded explosive (PBX) used for explosives of warheads and the like.

[0002]

2. Description of the Related Art As a conventional explosive composition, trinitrotoluene is used as a base and cyclotrimethylenetrinitramine (RDX) or cyclotetramethylenetetranitramine (HMX) is hardened with wax, or RDX or HM.
So-called plastic bonded explosive (PBX) containing X as a main component and polyethylene glycol (PEG), trimethylolpropane (TMP), tolylene diisocyanate (TDI), or hexamethylene diisocyanate (HMDI) and dioctyl adipate (DOA) as binders )It has been known.

More recently, the latter PBX has a glycidyl azide polymer (GAP) in the binder component.
Are known (US Pat. No. 5,061,330).

[0004]

Among such known explosive compositions, those which are hardened with wax or the like raise the temperature to dissolve the wax, and the RDX or HMX powder is mixed therein and cooled. Because of the volume reduction during cooling,
Voids called cast holes are easily formed. Therefore, it is difficult to increase the packing density of the composition, and the performance as an explosive, especially the high explosive speed, cannot be obtained. In addition, PBX that is hardened with a binder can be cast and is highly safe during manufacturing, but it is necessary to increase the mixing ratio of the binder, and as a result, there is a limit to the detonation speed as explosive performance. Therefore, there has been a strong demand for a PBX having a higher explosion performance.

[0005]

DISCLOSURE OF THE INVENTION As a result of earnest studies on an explosive composition satisfying such requirements, the present inventor has focused on an azide polymer having higher energy than GAP, and contains it in a binder. The inventors have found that a high explosion speed can be achieved by doing so, and completed the present invention.

That is, the present invention comprises a main component comprising an explosive compound of RDX and / or HMX, (A) an azide polymer, and (B) bis (2,2-dinitropropyl) acetal / formal (BDNPA / F). ), Trimethylolethane trinitrate (TMETN) and diethylene glycol dinitrate (DEGNN), and at least one selected from the group consisting of (C) a cross-linking agent and (D) a binder component. And the amount of the binder is 15 to 30% by weight of the total composition.

RDX and HMX as the main components used in the explosive composition of the present invention may be used alone,
You may mix.

Further, the particle diameters of RDX and HMX can be appropriately selected, but they affect not only the explosive performance but also the manufacturability. In other words, the single use of particles with a particle size exceeding 200 μm
Explosion performance is inferior, and single use of particles with a small particle size such as 20 μm or 3 μm can be expected to have a high explosion speed, but it is difficult to manufacture. Therefore, it is desirable to mix particles having a particle diameter of 200 μm and those having a particle diameter of 20 μm, or mixing particles having a particle diameter of 200 μm, and those having a particle diameter of 20 μm and 3 μm. The mixing ratio is, for example, 200 μm / 20.
In μm, it is 65/35 (weight ratio, the same applies hereinafter) to 80/20, and preferably 70/30 to 77/23. At 200 μm / 20 μm / 3 μm, it is 70/22/8 to 77/20/3.

Further, the proportion of RDX and / or HMX in the whole composition is preferably 70 to 85% by weight.

The binder component used in the explosive composition of the present invention comprises (A) an azide polymer, (B) a nitro plasticizer selected from a specific compound group, (C) a cross-linking agent and (D) a curing agent. If necessary, it contains a small amount of stabilizer and curing catalyst.

A suitable azide polymer is 3,3-bisazidomethyl oxetane / having a terminal hydroxyl group.
Tetrahydrofuran copolymer (BAMO / THF copolymer) or 3,3-bisazidomethyloxetane / 3-azidomethyl-3-methyloxetane copolymer (BAMO / AMMO copolymer) having a terminal hydroxyl group may, for example, be mentioned.

For BAMO / THF copolymers:
Any BAMO / THF molar ratio can be selected, but PB
X, that is, 7/3 to 4/6 as explosives in the casting method
(Molar ratio, the same applies hereinafter), preferably 7/3 to 6/4. If it exceeds 7/3, the viscosity is high and the ratio of the binder to the entire composition is high, so that higher performance cannot be expected. Also, if the ratio is less than 4/6, the amount of inert THF component is large, and thus high performance cannot be achieved. Furthermore, the molecular weight is 10
Those of 00 to 3000 are preferable.

Next, also for the BAMO / AMMO copolymer, the BAMO / AMMO molar ratio is from 7/3 to 7 in terms of the viscosity during production and the energy level of the composition.
4/6 is preferable. The molecular weight is also selected in the range of 1000 to 3000.

Since all of these polymers have urethane bonds at the terminals with the curing agent, they must have hydroxyl groups.

The amount of the azide polymer (A) used is appropriately 50 to 60% by weight based on the whole binder component. If it is less than 50% by weight, the main components are RDX and HMX.
If it exceeds 60% by weight, the amount of the plasticizer is reduced, the viscosity as a binder becomes high, and the productivity is deteriorated, which is not preferable.

The nitro plasticizer (B) used in the binder component of the present invention means the above-mentioned BDNPA / F and TMET.
It is a particular compound selected from the group consisting of N and DEGDN. These are used alone or in combination of two or more. The amount is 35 to 6 with respect to 100 parts by weight of the azide polymer (A).
0 parts by weight is preferred. If the amount is less than 35 parts by weight, the viscosity as a binder becomes high, which hinders casting. Also, 60
If it exceeds the amount by weight, it separates from the composition.

Suitable crosslinkers (C) are trimethylolpropane (TMP) and 3,3-bisazidomethyloxetane / tetrahydrofuran copolymer (BTT) having three terminal hydroxyl groups. The latter is more preferable in consideration of the physical properties of the explosive composition.

The amount of the cross-linking agent (C) used is usually expressed as a ratio with the azide polymer (A). That is, it is the number of moles of the hydroxyl group of (C) / the number of moles of the hydroxyl group of {(C) + (A)}. This display is 0.05 to 0.5, preferably 0.1 to 0.5
It is in the range of 0.3. If it is less than 0.05, the so-called cross-linking degree is so small that the physical properties of the composition deteriorate over time. On the other hand, if it exceeds 0.5, the degree of cross-linking is large, resulting in a composition that is hard and lacks flexibility, and neither of them can be applied.

As the curing agent (D), for example, an isocyanate compound such as hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI) or tolylene diisocyanate (TDI) is used.
The ratio of the curing agent (D) to the azide polymer (A) is usually isocyanate / hydroxyl group = 0.8 to 1.2 in terms of the molar ratio of the isocyanate group and the hydroxyl group. If it is less than 0.8, the explosive after curing is too soft, and it is difficult to mold it into an arbitrary shape. On the other hand, if it exceeds 1.2, unreacted isocyanate remains, and the explosive performance and physical properties of the composition deteriorate.

The stabilizer used as an optional component in the present invention is, for example, ethyl centrallite, and the curing catalyst is, for example, dibutyltin dilaurate (D
BTDL), triphenylbismuth (TPB) and the like. 0.5% by weight in the composition
It is the following.

In the present invention, the amount of the binder is 15 to 30% by weight of the total composition. If it is less than 15% by weight, casting is impossible, and if it exceeds 30% by weight, high explosive charges cannot be obtained.

In a known manner from the explosive composition of the present invention,
For example, an explosive can be manufactured by three steps of mixing, casting, and curing.

[0023]

The explosive composition of the present invention can be safely cast, and the explosive obtained has a high detonation velocity of over 7900 m / s.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 An explosive having the composition shown in Table 1 was produced as follows. (A)
BAMO / THF copolymer 16.5% by weight, (B) TME
TN 9.7% by weight, (C) TMP 1.1% by weight at a pressure of 8 Torr
The mixture was mixed at a temperature of 57 ° C for 25 minutes. Then, 70.0 wt% of HMX (particle size 200 μm / particle size 20 μm = 77/23 weight ratio) was added and mixed at the same pressure and temperature for 46 minutes. Then, (D)
Add 2.7% by weight of IPDI and add 2 more at the same pressure and temperature.
Mix for 5 minutes. Then, the mixture was transferred to a casting hopper that had been preheated to 57 ° C, and cast into a casting container at a pressure of 10 Torr and a temperature of 25 ° C. Then, the casting container was transferred to a curing bath and cured at 57 ° C. for 7 days. The explosive thus obtained was tested. The results are shown in Table 1. The test contents in Table 1 are shown below.

Manufacturability: Judgment was made based on whether or not an explosive which can be safely produced without containing bubbles and in which the binder and the powder are not separated can be produced.・ Explosion speed test A sample was injected into a 32A carbon steel tube with a length of 200 mm and the explosion speed was measured using the ion gap method.・ Drop sensitivity test In accordance with JIS K 4810, the 1/6 explosion point was determined, and the drop height was used to indicate the grade.・ Friction sensitivity test In accordance with JIS K 4810, find the 1/6 explosion point and load at that time (k
It is indicated by grade from gf).

Examples 2 and 3 Explosives having the compounding compositions shown in Table 1 were produced in the same manner as in Example 1. The same test as in Example 1 was conducted for each explosive, and the results are shown in Table 1. The RDX of Example 3 is
A mixture of 200 μm / 20 μm = 70/30 weight ratio was used.

[0028]

[Table 1]

Comparative Example 1 PEG (molecular weight: 1500) was used in place of the azide polymer used in the present invention, and the composition shown in Table 2 was used.
The explosive was manufactured according to The same test as in Example 1 was conducted on the explosive, and the results are shown in Table 2.

Comparative Example 2 An explosive was produced in accordance with Example 1 using GAP (molecular weight: 2100, number of hydroxyl groups: 2) instead of the azide polymer used in the present invention and having the composition shown in Table 2. Further, the same test as in Example 1 was conducted on the explosive, and the results are shown in Table 2.
It was shown to.

[0031]

[Table 2]

Claims (3)

[Claims] 1. A main component comprising an explosive compound of cyclotrimethylenetrinitramine and / or cyclotetramethylenetetranitramine, and (A) an azide polymer,
(B) one or more selected from the group consisting of bis (2,2-dinitropropyl) acetal / formal, trimethylolethanetrinitrate and diethylene glycol dinitrate, (C) a crosslinking agent and (D) An explosive composition containing a binder component consisting of a curing agent, and the amount of the binder being 15 to 30% by weight of the total composition. 2. The azide polymer is a 3,3-bisazidomethyloxetane / tetrahydrofuran copolymer having a terminal hydroxyl group or a 3,3-bisazidomethyloxetane / 3-azidomethyl-3-methyloxetane copolymer having a terminal hydroxyl group. The explosive composition of claim 1, wherein: 3. The explosive composition according to claim 1, wherein the cross-linking agent is trimethylolpropane or a 3,3-bisazidomethyloxetane / tetrahydrofuran copolymer having three terminal hydroxyl groups.