CN110304978B - High-mechanical-property low-impedance high polymer bonded explosive and preparation method thereof - Google Patents
High-mechanical-property low-impedance high polymer bonded explosive and preparation method thereof Download PDFInfo
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- CN110304978B CN110304978B CN201910734485.XA CN201910734485A CN110304978B CN 110304978 B CN110304978 B CN 110304978B CN 201910734485 A CN201910734485 A CN 201910734485A CN 110304978 B CN110304978 B CN 110304978B
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0066—Shaping the mixture by granulation, e.g. flaking
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
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Abstract
The invention relates to a high-mechanical-property low-impedance high polymer bonded explosive and a preparation method thereof, belonging to the technical field of composite energetic materials. The explosive is prepared from a polymer binding material polyurea, an energetic material and an explosive property improving agent in a certain ratio. The novel adhesive bi-component slow-reaction polyurea is introduced to effectively compound high-energy explosives and the like, so that the mechanical property of the energy-containing compound is obviously improved, and the problems of low adhesive force and high acoustic impedance of the conventional high-energy compound explosive are solved. The high-mechanical-property polymer bonded explosive disclosed by the invention improves the bonding strength among explosive components and between the explosive and surrounding containing materials, and has important application value for improving the mechanical property of an energy-containing compound and the comprehensive property of explosive loading. In addition, the explosive is prepared at normal temperature, does not generate waste water, waste liquid, waste gas and the like, and has the advantages of safety, environmental protection, simple process and the like.
Description
Technical Field
The invention relates to the technical field of composite energetic materials, in particular to a high-mechanical-property low-impedance high polymer bonded explosive and a preparation method thereof.
Background
The adhesive used for the high polymer bonded explosive is usually organic high polymer, and is mainly used as an adhesive component for bonding when used for a composite explosive, and also can be used as a desensitizer and an explosive carrier.
The traditional high polymer bonded explosive has a plurality of types of bonding agents, and can be roughly divided into three types according to the compound structure: the hydrocarbon type, the fluorocarbon type, and the energetic type. (1) Hydrocarbon type binders include vinyl addition polymers such as polyisobutylene, polystyrene, polyacrylic acid and vinyl acetate; polyvinyl alcohols and acetals thereof; polyphthalamides, linear polyesters, and the like. In addition, there are thermosetting resins such as unsaturated polyester resins, epoxy resins, phenol resins, and the like. The main problem with these binders is that they are sensitive to shock, impact and other such stimuli due to the mechanical properties of the polymers themselves, such as being hard, brittle, crunchy and the like. In the last 60 years, polyurethane is used as an adhesive of RDX and HMX, and the prepared PBX is in a rubber state and insensitive to impact, so that the problem of brittleness of the PBX is well solved. Thermoplastic polyurethanes have received increasing attention in replacing the binders in previous explosive formulations due to their excellent overall properties. (2) The fluorine-containing copolymers F2314, F2311, F2603, etc. belong to the fluorocarbon type, and have the main advantages of higher thermal stability and chemical stability, but the synthesis is difficult, the price is high, and the coating is easy to be debonded, and the fluorine-containing copolymers are mainly used in devices with higher requirements on heat resistance and stability. (3) The energetic type is mainly a high polymer containing nitryl, and contains energy, but has poor thermal stability, chemical stability and compatibility and higher sensitivity.
In conclusion, the mechanical properties of the explosives prepared by the traditional binding agents limit the performance of the high polymer composite explosives, and particularly, the adhesive force of the binding agents and the matrix is still insufficient under the action of external high impact. The material prepared by the traditional binder material has higher acoustic impedance, is easy to accept the impact energy transmitted from the outside under the action of external shock waves, reduces the difficulty of shock initiation of the material and influences the use safety of the material. In addition, in the production process of the high polymer bonded explosive, the environmental and safety problems of waste water, waste gas, waste liquid, complex process and the like still exist under most conditions.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a high-polymer bonded explosive with high mechanical property and low impedance, which is used for improving the mechanical property of an energy-containing compound and improving the comprehensive property of explosive loading.
The invention is realized by the following technical scheme:
a high-mechanical-property low-impedance high polymer bonded explosive is prepared from the following raw materials in parts by weight: 15-60 parts of polymer binding material polyurea, 40-85 parts of energetic material and 0-5 parts of explosive property improver; wherein, the polymer binding material polyurea and the energetic material are main materials, and the explosive property improver is an auxiliary material.
In the invention, a high-molecular bonding material, namely bi-component slow-reaction polyurea, is used as a high-molecular bonding agent, the bi-component slow-reaction polyurea is a macromolecular polymer with a urea bond obtained by the reaction of an isocyanate component and a curing agent (MOCA, MDBA, polyaspartate and the like), a catalyst or heating is not needed for the fast reaction, and the material has high solid content, does not contain volatile organic compounds and has slow reaction. And meanwhile, the urea bond has high strength, is very stable, has high ductility, excellent corrosion resistance and good mechanical property, is easy to absorb surrounding environment materials, and has high adhesive force. In addition, a large number of urea bonds exist in the polyurea molecules, and the contained hydrogen atoms can form coordination with a large number of nitroxides in the explosive molecules, so that the high polymer adhesive can be tightly combined with the explosive crystal, and the adhesive property with the explosive is obviously improved. The energetic material may be selected from any type of high explosive. In order to improve the performance of the explosive and the charge, the explosive performance improving agent is supplemented, for example, in order to reduce the sensitivity of the explosive, a small amount of the sensitivity reducing agent can be added, for example, in order to increase the explosion heat and the work capacity of the explosive, a high-energy additive can be added, for example, in order to prepare energetic compounds with different colors, a small amount of pigment can be added. The addition amount of the explosive property improving agent is not more than 5 percent.
As a preferred technical scheme, the energetic material is an elementary high explosive. Because the elementary substance high explosive contains nitro, the elementary substance high explosive is beneficial to interacting with polyurea to form stronger acid-base coordination according to an acid-base coordination theory, and the using effect is better.
As a preferred technical scheme, the single-substance high explosive is one or a mixture of RDX (hexogen), HMX (HMX) and CL-20 in any proportion.
As a preferred technical scheme, the explosive property improving agent is one or a mixture of a plurality of desensitizers, high-energy additives, plasticizers and pigments in any proportion.
As a preferable technical scheme, the desensitizer adopts graphite desensitizer or wax desensitizer.
As the preferred technical scheme, the graphite desensitizer adopts colloidal graphite, graphene and graphite fluoride; the wax desensitizer is paraffin.
Preferably, the high-energy additive is metal powder or metal hydride powder.
As the preferred technical scheme, the metal powder adopts magnesium powder, aluminum powder and titanium powder; the metal hydride powder adopts magnesium hydride powder and titanium hydride powder.
As a preferable technical scheme, DOA (dioctyl adipate) or DOS (dioctyl sebacate) is adopted as the plasticizer.
Further, the invention also provides a preparation method of the high-mechanical-property low-impedance high polymer bonded explosive, which comprises the following steps:
1) pouring the energetic material and the explosive property improver in the specified weight parts into a container, and stirring and mixing uniformly;
2) taking the specified weight part of the polymer binding material polyurea, firstly adding the component A into a container, stirring and mixing uniformly, then adding the component R into the container, and continuing stirring and mixing uniformly;
3) and pouring the mixture into the device or coating the mixture on the surface of the device, and curing at normal temperature to obtain the high polymer bonded explosive with high mechanical property and low impedance.
In the method, the component A of the high-molecular binding material polyurea is isocyanate, the component R is a curing agent, and the curing agent is MOCA (3, 3' -dichloro-4, 4' -diaminodiphenylmethane), MDBA (4, 4' -bis-sec-butyl aminodiphenylmethane) or polyaspartic acid ester.
Compared with the existing high-molecular bonded explosive, the high-molecular bonded explosive with high mechanical property and low impedance of the invention effectively compounds high-energy explosive and the like by introducing novel adhesive bi-component slow-reaction polyurea, thereby obviously improving the mechanical property of energy-containing compound and simultaneously solving the problems of low adhesive force and high acoustic impedance of the existing high-energy compound explosive. The high-mechanical-property polymer bonded explosive disclosed by the invention improves the bonding strength among explosive components and between the explosive and surrounding containing materials, and has important application value for improving the mechanical property of an energy-containing compound and the comprehensive property of explosive loading. The high-mechanical-property low-impedance high polymer bonded explosive can be prepared into a density of 1.2-1.6 g/cm by adjusting different proportions in the preparation process3Sound velocity of 1100m/s to 2500m/s, low acoustic impedance and adjustable power, and the explosive can meet the use requirement under the condition of high-speed impact. In addition, the high-mechanical-property low-impedance polymer bonded explosive is prepared at normal temperature, does not generate waste water, waste liquid, waste gas and the like, and has the advantages of safety, environmental protection, simple process and the like.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A high-mechanical-property low-impedance high polymer bonded explosive is prepared from the following raw materials in parts by weight: 60 parts of polymer binding material polyurea, 40 parts of energetic material and 0.3 part of explosive property improver; wherein the polymer binding material polyurea comprises 40 weight parts of isocyanate of component A and 20 weight parts of polyaspartic ester of component R; the energetic material adopts HMX (HMX); the explosive property improver adopts colloidal graphite.
The preparation method of the high-mechanical-property low-impedance high polymer bonded explosive comprises the following steps:
1) putting 40 parts by weight of HMX into a container at room temperature, adding 0.3 part by weight of colloidal graphite into the container, stirring and mixing uniformly by using a wood shovel, and passivating the HMX;
2) adding 40 parts by weight of isocyanate of the component A into a container, stirring and mixing uniformly by using a copper bar, then adding 20 parts by weight of polyaspartic ester of the component R into the container, and continuously stirring and mixing uniformly by using the copper bar;
3) and (3) drying the sand-blasted 45# steel box, pouring the mixture into the box, casting the mixture into tablets with the thickness of 5mm, and curing the tablets at normal temperature to obtain the high-mechanical-property low-impedance high polymer bonded explosive.
And (3) maintaining the composite explosive for 3 days, and then carrying out performance test on the composite explosive. The test result shows that the sound velocity of the composite explosive prepared by the formula is 1100m/s, and the density of the composite explosive is about 1.2g/cm3. The adhesion force between the steel wire and the 45# steel box matrix can reach 38.5MPa by using a pull-off method for field measurement. The explosive has low sound velocity, high adhesive force and excellent performance.
Example 2
A high-mechanical-property low-impedance high polymer bonded explosive is prepared from the following raw materials in parts by weight: 20 parts of polymer binding material polyurea, 75 parts of energetic material and 3 parts of explosive property improver; wherein the polymer binding material polyurea comprises 12 weight parts of isocyanate of component A and 8 weight parts of MOCA of component R; the energetic material adopts RDX (hexogen); the explosive property improver adopts paraffin.
The preparation method of the high-mechanical-property low-impedance high polymer bonded explosive comprises the following steps:
1) putting 75 parts by weight of RDX into a container at room temperature, adding 3 parts by weight of paraffin into the container, stirring and mixing uniformly by using a wood shovel, and passivating the RDX;
2) adding 12 parts by weight of isocyanate of the component A into a container, stirring and mixing uniformly by using a copper bar, then adding 8 parts by weight of MOCA of the component R into the container, and continuously stirring and mixing uniformly by using the copper bar;
3) and (3) drying the sand-blasted 45# steel die, pouring the mixture into the die, casting the mixture into tablets with the thickness of 5mm and powder columns with the thickness of phi 20mm multiplied by 20mm, and curing the mixture at normal temperature to obtain the high-mechanical-property low-impedance high polymer bonded explosive.
And (3) maintaining the composite explosive for 3 days, and then carrying out performance test on the composite explosive. The test result shows that the sound velocity of the composite explosive prepared by the formula is 2220m/s, and the density of the composite explosive is about 1.6g/cm3. The adhesion force between the steel and a 45# steel matrix can reach 10.8MPa by using a pull-open method for field measurement. The compression fracture strength of the grain was 20.4MPa, and the compression fracture strain was 3.05%. Has lower sound velocity, higher adhesive force and compressive strength and excellent mechanical property.
Example 3
A high-mechanical-property low-impedance high polymer bonded explosive is prepared from the following raw materials in parts by weight: 15 parts of polymer binding material polyurea, 60 parts of energetic material and 1.5 parts of explosive property improver; wherein the polymer binding material polyurea comprises 10 weight parts of isocyanate of component A and 5 weight parts of MDBA of component R; the energetic material adopts CL-20; the explosive property improver adopts graphene and DOA.
The preparation method of the high-mechanical-property low-impedance high polymer bonded explosive comprises the following steps:
1) at room temperature, putting 60 parts by weight of CL-20 into a container, adding 1 part by weight of graphene and 0.5 part by weight of DOA into the container, stirring and mixing uniformly by using a wood shovel, and passivating the CL-20;
2) adding 10 parts by weight of isocyanate of the component A into a container, stirring and mixing uniformly by using a copper bar, then adding 5 parts by weight of MDBA of the component R into the container, and continuously stirring and mixing uniformly by using the copper bar;
3) and (3) drying the sand-blasted 45# steel box, pouring the mixture into the box, casting the mixture into tablets with the thickness of 5mm, and curing the tablets at normal temperature to obtain the high-mechanical-property low-impedance high polymer bonded explosive.
And (3) maintaining the composite explosive for 3 days, and then carrying out performance test on the composite explosive. The test result shows that the sound velocity of the composite explosive prepared by the formula is 2500m/s, and the density of the composite explosive is about 1.53g/cm3. The explosive has low sound velocity, high adhesive force and excellent performance.
Example 4
A high-mechanical-property low-impedance high polymer bonded explosive is prepared from the following raw materials in parts by weight: 38 parts of polymer binding material polyurea, 85 parts of energetic material and 5 parts of explosive property improver; wherein the polymer binding material polyurea comprises 23 weight parts of isocyanate of component A and 15 weight parts of MOCA of component R; the energetic material adopts HMX; the explosive property improver adopts graphite oxide and aluminum powder.
The preparation method of the high-mechanical-property low-impedance high polymer bonded explosive comprises the following steps:
1) putting 85 parts by weight of HMX into a container at room temperature, adding 2 parts by weight of graphite oxide and 3 parts by weight of aluminum powder into the container, stirring and mixing uniformly by using a wood shovel, and passivating the HMX;
2) adding 23 parts by weight of isocyanate of the component A into a container, stirring and mixing uniformly by using a copper bar, then adding 15 parts by weight of MOCA of the component R into the container, and continuing stirring and mixing uniformly by using the copper bar;
3) and (3) drying the sand-blasted 45# steel box, pouring the mixture into the box, casting the mixture into tablets with the thickness of 5mm, and curing the tablets at normal temperature to obtain the high-mechanical-property low-impedance high polymer bonded explosive.
And (3) maintaining the composite explosive for 3 days, and then carrying out performance test on the composite explosive. The test result shows that the sound velocity of the composite explosive prepared by the formula is 2150m/s, and the density of the composite explosive is about 1.5g/cm3. The explosive has low sound velocity, high adhesive force and excellent performance.
Example 5
A high-mechanical-property low-impedance high polymer bonded explosive is prepared from the following raw materials in parts by weight: 30 parts of polymer binding material polyurea and 50 parts of energetic material; wherein the polymer binding material polyurea comprises 20 weight parts of isocyanate of component A and 10 weight parts of polyaspartic ester of component R; RDX is adopted as energetic material.
The preparation method of the high-mechanical-property low-impedance high polymer bonded explosive comprises the following steps:
1) at room temperature, 50 parts by weight of RDX is put into a container and stirred and mixed uniformly by a wood shovel;
2) adding 20 parts by weight of isocyanate of the component A into a container, stirring and mixing uniformly by using a copper bar, then adding 10 parts by weight of polyaspartic ester of the component R into the container, and continuously stirring and mixing uniformly by using the copper bar;
3) and (3) drying the sand-blasted 45# steel box, pouring the mixture into the box, casting the mixture into tablets with the thickness of 5mm, and curing the tablets at normal temperature to obtain the high-mechanical-property low-impedance high polymer bonded explosive.
And (3) maintaining the composite explosive for 3 days, and then carrying out performance test on the composite explosive. The test result shows that the sound velocity of the composite explosive prepared by the formula is 1560m/s, and the density of the composite explosive is about 1.3g/cm3. The explosive has low sound velocity, high adhesive force and excellent performance.
The above description is only for the preferred embodiment of the present invention, and the embodiment of the present invention is not limited by the above-described embodiment. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the spirit and scope of the principles of this invention.
Claims (9)
1. A high-mechanical-property low-impedance high polymer bonded explosive is characterized by being prepared from the following raw materials in parts by weight: 15-60 parts of polymer binding material polyurea, 40-85 parts of energetic material and 0-5 parts of explosive property improver; wherein the macromolecular binding material polyurea is macromolecular polymer with urea bonds obtained by the reaction of isocyanate and polyaspartic acid ester;
the preparation method comprises the following steps:
1) pouring the energetic material and the explosive property improver in the specified weight parts into a container, and stirring and mixing uniformly;
2) taking a specified weight part of the polymer binding material polyurea, firstly adding the component A into a container, stirring and mixing uniformly, then adding the component R into the container, and continuously stirring and mixing uniformly, wherein the component A is isocyanate and the component R is polyaspartic ester;
3) and pouring the mixture into the device or coating the mixture on the surface of the device, and curing at normal temperature to obtain the high polymer bonded explosive with high mechanical property and low impedance.
2. The high mechanical property low impedance high polymer bonded explosive of claim 1, wherein: the energetic material is a single high explosive.
3. The high mechanical property low impedance high polymer bonded explosive of claim 2, wherein: the single-substance high explosive is one or a mixture of RDX, HMX and CL-20 in any proportion.
4. The high mechanical property low impedance high polymer bonded explosive of claim 1, wherein: the explosive property improving agent is one or a mixture of a plurality of desensitizers, high-energy additives, plasticizers and pigments in any proportion.
5. The high mechanical property low impedance high polymer bonded explosive of claim 4, wherein: the desensitizer is graphite desensitizer or wax desensitizer.
6. The high mechanical property low impedance high polymer bonded explosive of claim 5, wherein: the graphite desensitizer adopts colloidal graphite, graphene and graphite fluoride; the wax desensitizer is paraffin.
7. The high mechanical property low impedance high polymer bonded explosive of claim 4, wherein: the high-energy additive adopts metal powder or metal hydride powder.
8. The high mechanical property low impedance high polymer bonded explosive of claim 7, wherein: the metal powder adopts magnesium powder, aluminum powder and titanium powder; the metal hydride powder adopts magnesium hydride powder and titanium hydride powder.
9. The high mechanical property low impedance high polymer bonded explosive of claim 4, wherein: the plasticizer is DOA or DOS.
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| CN109206283A (en) * | 2018-03-16 | 2019-01-15 | 湖北航天化学技术研究所 | Low Vulnerability Explosive of a kind of thermosetting property and preparation method thereof |
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| US5600088A (en) * | 1988-10-27 | 1997-02-04 | Aerojet General Corporation | Coatings for solid propellants |
| CN109206283A (en) * | 2018-03-16 | 2019-01-15 | 湖北航天化学技术研究所 | Low Vulnerability Explosive of a kind of thermosetting property and preparation method thereof |
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