CN114014738B

CN114014738B - Combustible cartridge/box slurry formula and preparation method of combustible cartridge/box

Info

Publication number: CN114014738B
Application number: CN202111209319.1A
Authority: CN
Inventors: 杨伟涛; 胡睿; 杨建兴; 李曼曼; 肖霞; 梁磊
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2021-10-18
Filing date: 2021-10-18
Publication date: 2022-08-19
Anticipated expiration: 2041-10-18
Also published as: CN114014738A

Abstract

The invention provides a slurry formula of a combustible cartridge/box and a preparation method of the combustible cartridge/box. The disclosed formula comprises 100 parts of acrylic resin, 1-4 parts of photoinitiator, 40-100 parts of reactive diluent and 100-246 parts of explosive crystal, wherein the explosive crystal is one or a mixture of 1,3, 5-trinitro-1, 3, 5-triazacyclohexane and 1,3,5, 7-tetranitro-1, 3,5, 7-tetraazacyclooctane, the acrylic resin is epoxy acrylic resin, polyurethane acrylic resin or a mixture thereof, the photoinitiator is 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate, one or two mixture of 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the reactive diluent is one or mixture of 2- (2-ethoxyethoxy) ethyl acrylate and trimethylolpropane triacrylate. The formula disclosed by the invention can be used for 3D printing for preparation. The explosive power of the prepared combustible cartridge/box reaches 845J/g, the 5s explosion point is 356.6 ℃, the autoignition resistance temperature is more than 300s at 245 ℃, and the hygroscopicity is 0.5 percent under the conditions of 25 ℃ and 89 percent relative humidity.

Description

Combustible cartridge/box slurry formula and preparation method of combustible cartridge/box

Technical Field

The invention relates to a combustible cartridge/box technology, in particular to a combustible cartridge/box slurry formula suitable for a 3D printing process and a related preparation method.

Background

The combustible cartridge/box comprises a combustible cartridge and a combustible medicine box, both are made of combustible materials and are used for containing propellant powder or solid rocket engine igniter ignition powder, and the combustible cartridge/box can be completely burnt without residue in the process of launching or ignition.

The combustible cartridge/box manufactured by the prior art adopts nitrocotton as a main energy component and mainly adopts a suction filtration mould pressing preparation method. Because of the limitation of raw materials and preparation methods, the existing preparation of the combustible cartridge requires a processing and forming die, the flexibility of the preparation process is poor, the combustible cartridge is generally in a simple cylinder shape, and the product has poor heat resistance, low energy and high hygroscopicity.

Syal [ Syal R K, Narr P.Cook Off Study of Combustible Cartridge [ J ]. Defence Science Journal,2013,42(2): 113-.

Prune [ novel energetic fiber combustible cartridge performance study [ J ]. energetic material, 2009,17 (3): 334-338 parts replace inert fibers in the suction filtration cartridge by adding energy-containing fibers, so that the explosive power of the suction filtration cartridge is increased from 448.92J/g to 664.59J/g.

Tubelchang (Tubelchang, Zhanjun. a novel combustible ignition medicine box [ J ]. initiating explosive device, 1995(04):16-18.] designs a combustible ignition medicine box of a solid rocket engine containing 63% of nitrocotton, 24% of fiber paper board and 13% of latex by using the formula and the preparation method of a suction filtration combustible medicine box, but the ignition point of the nitrocotton is only 160-170 ℃.

The combustible cartridge is a porous composite material and is rich in water-absorbing fibers, so that the hygroscopicity of the combustible cartridge is high, and the influence of environment humidity on the hygroscopicity and the combustion completeness of the combustible cartridge is researched [ J ] fire explosive bulletin 2012(01):95-98 ], and the influence of the environment humidity on the hygroscopicity and the combustion completeness of the combustible cartridge is researched, so that the moisture absorption rate of the combustible cartridge reaches 1.99% under the conditions of 25 ℃ and 89% of relative humidity RH, and the burnout of the combustible cartridge is influenced.

Disclosure of Invention

In response to the shortcomings or drawbacks of the prior art, one aspect of the present invention is to provide a combustible cartridge/case slurry formulation.

The formula of the combustible cartridge/box provided by the invention comprises 100 parts of acrylic resin, 1-4 parts of photoinitiator, 40-100 parts of reactive diluent and 100-246 parts of explosive crystal;

the explosive crystal is selected from one or a mixture of 1,3, 5-trinitro-1, 3, 5-triazacyclohexane (RDX) and 1,3,5, 7-tetranitro-1, 3,5, 7-tetraazacyclooctane (HMX);

the acrylic resin is selected from one or a mixture of epoxy acrylic resin and polyurethane acrylic resin;

the photoinitiator is selected from one or a mixture of two of 2,4, 6-trimethyl benzoyl phenyl phosphonic acid ethyl ester (TPO-L) and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide (TPO);

the reactive diluent is selected from one or a mixture of two of 2- (2-ethoxyethoxy) ethyl acrylate and trimethylolpropane triacrylate (TMPTA).

Preferably, the mass ratio is as follows: 100 parts of acrylic resin, 2 parts of photoinitiator, 50 parts of reactive diluent and 152 parts of RDX crystal.

Optionally, the average particle size of the explosive crystals is in the range of 30-70 μm.

The invention also provides a preparation method of the combustible cartridge/box. The preparation method comprises the steps of taking the slurry formula as a raw material, and preparing the combustible cartridge/box by adopting a 3D printing process.

Further, the 3D printing process adopts an SLA printing process.

Optionally, the light source of the SLA printing process is a 405nm ultraviolet light source.

The invention can make the cartridge/box carry on 3D printing preparation by utilizing the printing prototype, adopt acrylate and contain the formulation of the crystal as the main component, has improved the heat-resisting time and energy (explosive power) of the flammable cartridge/box, and reduce its moisture absorption rate, the processing technology is simple at the same time, and the precision is high.

Drawings

FIG. 1 is a digital model of a combustible kit prepared in example 1; wherein, the left picture is the medicine box body, and the right picture is the medicine box cover.

FIG. 2 is a digital model of the combustible drug cartridge prepared in example 2; wherein, the left figure is the medicine box body, and the right figure is the medicine box cover.

Figure 3 is a digital model of the combustible cartridge prepared in example 3.

Figure 4 is a digital model of the combustible cartridge prepared in example 4.

Detailed Description

Unless otherwise defined, the terms, methods, or processes herein are understood or implemented using existing methods or processes as would be recognized by one of ordinary skill in the relevant art. The related 3D printing equipment in the market, in particular SLA 3D printing (photocuring molding technology) equipment provided with a 405nm ultraviolet light source is suitable for the invention.

The combustible cartridge/box of the invention comprises a cylindrical combustible drug shell, a bottle-shaped combustible shell, a box-shaped combustible drug box, and a combustible drug box with a cover or without a cover in an irregular shape. Specific examples are shown in fig. 1-4.

The average particle size refers to the average particle size detected by a laser method.

The present invention is further illustrated by the following examples, but is not limited thereto. The starting components used in the following examples are all commercially available products.

Example 1:

the formulation of this example is as follows: 100 parts of epoxy acrylic resin, 3 parts of TPO photoinitiator, 40 parts of 2- (2-ethoxyethoxy) ethyl acrylate reactive diluent and 100 parts of RDX crystal (average particle size is 30 mu m). The preparation steps are as follows:

(1) mixing all the components by a stirrer in a dark place for 1 hour at a rotating speed of 200 revolutions per second;

(2) pouring the uniformly mixed materials into a material groove of an SLA 3D printer (Form 3SLA printer of a Form labs model), wherein the laser wavelength of the printer is 405 nm;

(3) selecting a model of the combustible cartridge to be printed (model generated in the curca software), as shown in figure 1, using an SLA 3D printer for printing;

(4) taking down the printed cartridge from the forming platform, and cleaning by using ethanol or glycerol;

(5) the cartridge was placed under an ultraviolet curing lamp for 3 h.

Example 2:

unlike example 1, the formulation of this example is as follows: 60 parts of epoxy acrylic resin, 40 parts of polyurethane acrylic resin, 3 parts of TPO-L photoinitiator, 50 parts of trimethylolpropane triacrylate reactive diluent and 152 parts of RDX crystal (with the average particle size of 50 mu m).

The process differs from example 1 in that the model is shown in figure 2, which shows a combustible kit for a solid propellant engine igniter.

Example 3:

different from the embodiment 1, the mass ratio of the embodiment is as follows: 50 parts of epoxy acrylic resin, 4 parts of TPO-L photoinitiator, 40 parts of 2- (2-ethoxyethoxy) ethyl acrylate reactive diluent, 20 parts of trimethylolpropane triacrylate reactive diluent and 246 parts of RDX crystal (average particle size is 70 mu m).

The difference between the preparation process and the example 1 is that the model is a combustible cartridge for a countersink as shown in figure 3.

Example 4

Different from the embodiment 1, the formulation of the embodiment is as follows: 100 parts of polyurethane acrylic resin, 4 parts of TPO-L photoinitiator, 20 parts of 2- (2-ethoxyethoxy) ethyl acrylate reactive diluent, 20 parts of trimethylolpropane triacrylate reactive diluent and 100 parts of HMX crystal (average particle size of 10 mu m).

The preparation process is different from that of example 1 in that the model is a bottle-shaped semi-combustible cartridge as shown in figure 4.

The combustible cartridges/capsules prepared in the above examples were tested for 5s burst point, tensile strength and pyrotechnic power according to GJB5472 semi-combustible cartridge test method and GJB772A-97 gunpowder test method. The moisture absorption of the cartridge was measured at 25 ℃ and RH of 89%.

The results are shown in table 1, where: the reference sample is a combustible cartridge/box which is prepared by adopting a suction filtration method and is shown in figures 1-4, and the preparation raw material formula of each reference sample is as follows: NC 62%, kraft fiber 24.5%, and binder 13.5%; the coating is nitrocellulose varnish.

TABLE 1 comparison of heat resistance and energy power data for articles

As shown in Table 1, the results of 5s burst point, tensile strength, powder strength and moisture absorption rate measurements of the four comparative samples were the same. In addition to this, the present invention is,

the shape of the cartridge shown in fig. 1 corresponds to the comparative combustible cartridge in which the combustible central fire tube and the shell are respectively suction-filtered and molded, and the central fire tube and the shell are bonded by using an adhesive, and the central combustible fire tube and the shell are integrally printed by using the material and 3D printing technology of the invention.

The shape of the combustible medicine box of the igniter of the engine shown in the figure 2 is that the corresponding combustible medicine box of the comparison sample is manufactured by suction filtration mould pressing, the forming precision is +/-0.1 mm, the quality control is difficult, and the combustible medicine box is not suitable for the precision assembly of the engine, but the combustible medicine box of the igniter of the engine can be printed with the precision of +/-0.05 mm by adopting the materials and the 3D printing technology.

The shape of the cartridge shown in fig. 3 corresponds to the combustible cartridge of the comparative example, the combustible guide cylinder and the shell are respectively subjected to suction filtration and mould pressing, the combustible guide cylinder and the shell are bonded by using an adhesive, and the combustible guide cylinder and the shell are integrally printed by adopting the material and 3D printing technology in the invention.

The shape of the cartridge shown in fig. 4, corresponding to the combustible cartridge of the comparative sample, is prepared by suction filtration and mould pressing, but by adopting the material and 3D printing technology in the invention, three-dimensional printing can be realized without opening a mould.

Claims

1. The combustible cartridge/box slurry is characterized by comprising explosive crystals, acrylic resin, a photoinitiator and an active diluent, wherein the mass ratio of the components is as follows: 100 parts of acrylic resin, 1-4 parts of photoinitiator, 40-100 parts of active diluent and 100-246 parts of explosive crystal;

the explosive crystal is selected from one or a mixture of 1,3, 5-trinitro-1, 3, 5-triazacyclohexane and 1,3,5, 7-tetranitro-1, 3,5, 7-tetraazacyclooctane;

the photoinitiator is selected from one or a mixture of two of 2,4, 6-trimethylbenzoyl phenyl phosphonic acid ethyl ester and 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide;

the reactive diluent is selected from one or a mixture of 2- (2-ethoxyethoxy) ethyl acrylate and trimethylolpropane triacrylate.

2. Combustible cartridge/cartridge slurry according to claim 1, characterised in that the mass ratio is: 100 parts of acrylic resin, 2 parts of photoinitiator, 50 parts of reactive diluent and 152 parts of RDX crystal.

3. Combustible cartridge/cartridge slurry according to claim 1 or 2, characterized in that the average particle size of the explosive crystals is in the range of 30-70 μm.

4. A method for preparing a combustible cartridge/box, characterized in that the method comprises preparing a combustible cartridge/box by 3D printing process using the slurry of claim 1 or 2 as raw material.

5. The method according to claim 4, wherein the 3D printing process is an SLA printing process.

6. The method according to claim 5, wherein the light source of the SLA printing process is a 405nm ultraviolet light source.

7. A combustible cartridge/cartridge prepared according to the method of claim 4.