CN116354779A

CN116354779A - AP compound and preparation method thereof

Info

Publication number: CN116354779A
Application number: CN202310246812.3A
Authority: CN
Inventors: 李娜; 赵凤起; 秦钊; 李辉; 张明; 张建侃; 刘鹤欣; 姜一帆; 蒋周峰
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2023-03-14
Filing date: 2023-03-14
Publication date: 2023-06-30

Abstract

The invention discloses a preparation method of an AP compound, which comprises the steps of dissolving AP, a catalyst and an energetic adhesive in a solvent, then performing ultrasonic dispersion to obtain a dispersion liquid, and performing spray drying on the dispersion liquid on a spray dryer to obtain the AP compound, wherein the AP compound comprises an AP/CuO/PAMMO compound and an AP/copper chromite/PBAMO compound. The AP compound of the invention greatly reduces the mechanical sensitivity of the AP compound on the premise of reducing the AP energy as much as possible at least, improves the safety of the AP compound and improves the thermal decomposition performance of the AP compound. The method is simple to operate, the solvent is easy to remove, mass production is amplified, and the prepared AP compound has good dispersibility and does not agglomerate.

Description

AP compound and preparation method thereof

Technical Field

The invention belongs to the field of energetic materials, and particularly relates to a preparation method of an ultrafine AP/CuO/PAMMO (3-methyl-3-azidomethyl oxybutane homopolymer) compound and an ultrafine AP/copper chromite/PBAMO (3, 3-bisazido methyl oxybutane homopolymer).

Background

Ammonium Perchlorate (AP) is used as an oxidant, has the advantages of larger formation enthalpy, more gas formation, stable performance, low cost, better compatibility with other components of the propellant, and the like, is a component part of energetic materials such as solid propellant, blasting explosive, gunpowder and the like, and is an important raw material of high-energy and high-combustion-speed solid propellant. One of the main ways to increase the burning rate of the propellant is to increase the content of the oxidant in the propellant formulation and add ultra-fine oxidant. The oxidizer particle size affects the propellant burn rate to a large extent. Research shows that after the superfine Ammonium Perchlorate (AP) is formed, the combustion speed of the prepared propellant is 5-10 times faster than that of the common propellant.

The superfine AP powder prepared by the superfine AP can greatly improve the burning speed and the energy density of the propellant, but researches show that the friction sensitivity of superfine AP particles is increased along with the reduction of the particle size, the impact sensitivity is also increased along with the reduction of the particle size, the mechanical sensitivity of the superfine AP is far higher than that of the common particle size AP, meanwhile, the caking phenomenon is easy to occur, the use effect is influenced more obviously especially in a damp and hot environment and in long-term storage, and unsafe factors are brought to the transportation, the storage and the use of the superfine AP.

At present, there are few reports on the degradation of superfine AP at home and abroad, the degradation treatment is carried out on large-particle AP, the adopted method is mainly coating degradation, the energetic material is coated or composited by using low-sensitivity substances to form composite particles, the effects of friction, impact, extrusion and the like among particles are reduced by utilizing the properties of the low-sensitivity substances, such as lubrication, heat insulation, buffering and the like, the probability of hot spot generation is reduced, and the aim of reducing the sensitivity of the energetic material can be achieved. The low sensitivity materials commonly used mainly comprise high molecular polymers (fluororubber, polyurethane, nitrocotton and the like), low sensitivity energetic materials (TATB and the like) and small molecular desensitizers (paraffin, stearic acid, graphite and the like).

Li Yu and the like study on the coating of the insensitive agent paraffin, the high polymer thermoplastic polyurethane and the like on the AP, and discover that the paraffin can completely coat the AP, thereby effectively reducing the mechanical sensitivity; the friction sensitivity of a typical cast PBX formulation using this degradent AP was also reduced from 82% to 0%. And S.Nandatopal and the like take a copolymer of hexafluoropropylene and vinylidene fluoride (HFP-VF) as a coating agent, the coating and degradation treatment is carried out on the AP by adopting a solvent-antisolvent method, the mechanical sensitivity of the coated AP is reduced along with the increase of the HFP-VF content, the friction sensitivity is unchanged, and the heat release quantity is correspondingly reduced. Liu Xuwang and the like prepare passivated AP by adopting a solvent method, and the impact sensitivity and the friction sensitivity of the passivated AP are greatly reduced, and the passivated AP can be found to greatly improve the safety performance of the formula after being applied to PBX explosives. However, the methods all adopt wet processes, the solid-liquid separation is difficult, and agglomeration and caking phenomena are easy to occur in the process of removing the solvent; the amount of modifier used is also large, which may lead to a decrease in the energy of the oxidant and the propellant, thus affecting the use.

Pei Hao and the like adopt trinitrotoluene (TNT) which is an energy-containing insensitive agent as a coating material in the paper of the university of Nanjing university of technology for superfine AP surface coating and performance research thereof in 2013, and adopt a solvent evaporation method to carry out surface coating on superfine AP, mainly research the influence of different TNT dosages on the friction sensitivity of the superfine AP, and the result shows that the friction sensitivity of the superfine AP coated by TNT is reduced, but the work of impact sensitivity change after TNT coating the superfine AP is not carried out. The preparation process of the method is complex and the sample dispersibility is poor. The particle size of the superfine AP coated particles increases with the increase of the TNT coating agent, and the particle size is difficult to control.

Disclosure of Invention

Aiming at the defects and shortcomings existing in the prior art, the AP compound and the preparation method thereof are provided.

In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:

a preparation method of the AP compound comprises the steps of dissolving AP, a catalyst and an energy-containing adhesive in a solvent, then performing ultrasonic dispersion to obtain a dispersion liquid, and performing spray drying on the dispersion liquid on a spray dryer to obtain the AP compound, wherein the AP compound comprises an AP/CuO/PAMMO compound and an AP/copper chromite/PBAMO compound.

Further, the mass ratio of the AP to the catalyst to the energy-containing adhesive is (8-10): 1-3): 2-3.

Further, the catalyst is nano copper oxide, the energetic binder is PAMMO, and the method comprises:

step 1: adding AP and PAMMO into a mixed solvent of distilled water and tetrahydrofuran, and stirring and dissolving to obtain a mixed solution;

and 2, adding nano copper oxide into the mixed solution, performing ultrasonic dispersion, and performing spray drying on the dispersion liquid on a spray dryer to obtain the superfine AP/CuO/PAMMO compound.

Further, the mass ratio of the AP to the nano copper oxide to the PAMMO is (8-10): 1-3): 2-3, the distilled water is 15-20 ml, and the tetrahydrofuran is 60-80 ml.

Further, the mass ratio of the AP to the nano copper oxide to the PAMMO is 8:2:3;

the reaction temperature of the step 1 and the step 2 is 20-35 ℃, the temperature of an air inlet of a spray dryer is 140-150 ℃, the feeding rate is 2-3 mL/min, and the flow rate of high-purity nitrogen is 300-350L/h.

Further, the catalyst is nano copper chromite, the energetic binder is PBAMO, and the method comprises:

step 1: adding AP into distilled water, stirring and dissolving, and then adding nano copper chromite for ultrasonic dispersion to obtain a mixed solution; wherein the dosage ratio of the AP to the nano copper chromite to the distilled water is 10:1.5 to 3g: 10-30 ml;

and 2, adding PBAMO into acetone, stirring and dissolving, adding the mixed solution in the step 1 for ultrasonic dispersion, and spray-drying the dispersion on a spray dryer to obtain the superfine AP/copper chromite/PBAMO compound.

Further, the mass ratio of the AP to the copper chromite to the PBAMO is (8-10): (1-3): (2-3), the distilled water is 15-30 ml, and the acetone is 60-90 ml.

Further, the mass ratio of the AP to the copper chromite to the PBAMO is 10 (1.5-3): 2;

the reaction temperature of the step 1 and the step 2 is 20-35 ℃, the air inlet temperature of the spray dryer is 120-130 ℃, the feeding rate is 3-4 mL/min, and the flow rate of high-purity nitrogen is 350-400L/h.

The AP compound prepared by the preparation method of the AP compound comprises an AP/CuO/PAMMO compound and an AP/copper chromite/PBAMO compound, wherein the particle size of the AP/CuO/PAMMO compound is 1-2 mu m, and the particle size of the AP/copper chromite/PBAMO compound is 1-3 mu m.

Compared with the prior art, the invention has the beneficial effects that:

(1) The AP compound of the invention comprises an AP/CuO/PAMMO compound and an AP/copper chromite/PBAMO compound, which not only can reduce the mechanical sensitivity of the AP, such as the ultra-fine AP/CuO/PAMMO compound reduces the friction sensitivity of 1.1 mu mAP by more than 18 percent and the impact sensitivity by more than 28 percent, but also can improve the thermal performance of the AP, such as the AP/CuO/PAMMO compound advances the low-temperature decomposition peak temperature and the high-temperature decomposition peak temperature of 1.1 mu mAP by 46.4 ℃ and 49.4 ℃ respectively.

(2) Compared with the AP coating sense-reducing method in the prior art, the method not only can ultrafine AP, but also can compound ultrafine AP with other materials.

Drawings

FIG. 1 is an SEM photograph of 1.1. Mu. MAP.

FIG. 2 is an SEM photograph of an AP/CuO/PAMMO composite prepared in example 1.

FIG. 3 is an SEM photograph of an AP/CuO/PAMMO composite prepared in example 2.

FIG. 4 is a DSC curve of 1.1 μmAP and AP/CuO/PAMMO complex.

FIG. 5 is an SEM photograph of 2.1. Mu. MAP.

FIG. 6 is an SEM photograph of an AP/copper chromite/PBAMO complex prepared in example 3.

FIG. 7 is an SEM photograph of an AP/copper chromite/PBAMO complex prepared in example 4.

Detailed Description

The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention, in order to better understand the essential characteristics of the present invention.

The AP compound of the invention is a compound obtained by adopting a spray drying technology to compound other materials while carrying out superfine treatment on the AP by the preparation method of the invention. The superfine process refers to preparing superfine material with particle diameter of 0.01-10 microns with certain technological equipment.

The preparation method of the AP compound comprises the steps of dissolving AP, a catalyst and an energetic binder in a solvent, then performing ultrasonic dispersion to obtain a dispersion liquid, and performing spray drying on the dispersion liquid on a spray dryer to obtain the AP compound, wherein the AP compound comprises an AP/CuO/PAMMO compound and an AP/copper chromite/PBAMO compound.

The catalyst comprises any one of nano copper oxide and nano copper chromite, and the energetic binder comprises any one of PAMMO (3-methyl-3-azidomethyloxetane homopolymer) and PBAMO (3, 3-diazidomethyloxetane polyether).

The mass ratio of the AP to the catalyst to the energy-containing adhesive is (8-10): 1-3): 2-3.

The nano copper chromite used in the invention is purchased through Beijing Inocover technology Co., ltd, and the granularity is 100-200 nm; PBAMO, relative molecular mass 3350, provided by western union recent chemistry research.

The used nano CuO is purchased by Beijing Inocover technology Co., ltd, and the granularity is 60-100 nm; PAMMO, relative molecular mass 3200, provided by the western union recent chemistry institute.

The AP compound prepared by the invention is subjected to mechanical sensitivity test:

in the invention, the explosion percentage of the explosive is measured by adopting an H3.5-10W drop hammer type impact sensitivity meter according to the 601.1 test method in GJB 772A-1997 standard. Drop weight mass: 10kg; dosage of: (50+ -1) mg; the test was divided into 2 groups of 25 hairs each, and a total of 50 hairs. Friction sensitivity test the percent explosion of the explosive samples was determined using a DM-l friction sensitivity meter according to the 602.1 test method in GJB 772A-1997 standard. Gauge pressure: 3.92MPa; swing angle: 90 ° ± 1 °; dosage of: (50+ -1) mg; 25 hairs per group, 50 hairs total.

Thermal properties of ultrafine AP/CuO/PAMMO composites

The thermal decomposition properties of the AP and AP complexes were determined using a DSC 204HP type differential scanning calorimeter from Netzsch, germany, under the conditions: the temperature is heated from room temperature to 450 ℃ at a heating rate of 10 ℃/min, and the temperature is controlled by N ₂ Under an atmosphere.

Example 1

The embodiment provides a preparation method of an AP/CuO/PAMMO compound, which comprises the following steps:

step 1: adding 8g of AP and 3g of PAMMO into a mixed solvent of 15mL of distilled water and 60mL of tetrahydrofuran, and stirring at 25 ℃ until the mixture is dissolved to obtain a mixed solution;

and 2, adding 2g of nano copper oxide into the mixed solution, performing ultrasonic dispersion for 30min at 25 ℃, and performing spray drying on the dispersion liquid on a spray dryer after uniform dispersion, wherein the temperature of an air inlet is 145 ℃, the feeding rate is 2.5mL/min, and the flow rate of high-purity nitrogen is 300L/h, so as to obtain gray AP/CuO/PAMMO composite powder.

Example 2

This example is identical to example 1, except that:

step 1: adding 8g of AP and 3g of PAMMO into a mixed solvent of 20mL of distilled water and 80mL of tetrahydrofuran, and stirring at 25 ℃ until the mixture is dissolved to obtain a mixed solution;

and 2, adding 2g of nano copper oxide into the mixed solution, performing ultrasonic dispersion for 30min at 25 ℃, and performing spray drying on the dispersion liquid on a spray dryer after uniform dispersion, wherein the temperature of an air inlet is 150 ℃, the feeding rate is 2mL/min, and the flow rate of high-purity nitrogen is 350L/h, so as to obtain gray AP/CuO/PAMMO composite powder.

Comparative example 1

The comparative example was an AP with a particle size of 1.1. Mu.m, which was not coated.

Comparative example 2

This comparative example differs from example 1 in that the mass ratio of AP, nano-copper oxide and PAMMO is 8:0.8:1.5.

FIGS. 1, 2 and 3 are scanning electron micrographs of the AP/CuO/PAMMO composites prepared in comparative example 1AP and examples 1 and 2, respectively. As is clear from the figure, agglomeration of 1.1. Mu.mAP was severe, the particle size of the AP/CuO/PAMMO composite prepared in example 1 was 1.21. Mu.m, and the particle size of the AP/CuO/PAMMO composite prepared in example 2 was 1.09. Mu.m, and the particle size distribution was uniform and controllable, and the particle dispersion was good and non-agglomerating.

The measured mechanical sensitivity data are shown in table 1:

TABLE 1 mechanical sensitivity data

Mechanical sensitivity	Comparative example 1	Example 1	Example 2	Comparative example 2
					Impact sensitivity (%)	28	19	20	25
Friction sensitivity (%)	88	71	72	80

As can be seen from the data in Table 1, the impact sensitivity and friction sensitivity of the AP/CuO/PAMMO composite are both greatly reduced compared with 1.1 mu mAP, and the safety is greatly improved. The friction sensitivity is reduced by more than 18%, the impact sensitivity is reduced by more than 28%, and the impact sensitivity and the friction sensitivity of the AP/copper chromite/PBAMO compound prepared in comparative example 2 are both smaller than those of 1.1 mu mAP, the friction sensitivity is reduced by 9.1%, and the impact sensitivity is reduced by 10.7%.

FIG. 4 shows DSC curves of the ultra-fine AP/CuO/PAMMO complex of example 1, 1.1. Mu. MAP, comparative example 1. As can be seen from fig. 4, the thermal decomposition process of 1.1 μmap can be divided into three stages: (1) When the temperature is raised to about 240 ℃, endothermic crystal form transformation occurs; (2) When the temperature is raised to about 290-310 ℃, an exothermic AP cryodecomposition process occurs; (3) When the temperature is raised to about 350-380 ℃, an exothermic AP pyrolysis process occurs. The overall thermal effect of AP thermal decomposition is exothermic.

The 1.1 mu mAP has a crystal form conversion peak temperature of 242.8 ℃, a low-temperature decomposition peak temperature of 309.2 ℃ and a high-temperature decomposition peak temperature of 387.5 ℃. The AP/CuO/PAMMO composites obtained in examples 1 and 2 had a crystal form conversion peak temperature of 247.1 ℃, a low temperature decomposition peak temperature of 262.8 ℃, a high temperature decomposition peak temperature of 338.1 ℃, and a low temperature decomposition peak temperature and a high temperature decomposition peak temperature advanced by 46.4 ℃ and 49.4 ℃ respectively from 1.1 μmap, indicating that the thermal decomposition properties of the ultrafine AP/CuO/PAMMO composites obtained in examples 1 and 2 were significantly better than 1.1 μmap. The superfine AP/CuO/PAMMO composite obtained in comparative example 2 has a crystal form conversion peak temperature of 249.4 ℃, a low-temperature decomposition peak temperature of 288.2 ℃, a high-temperature decomposition peak temperature of 349.3 ℃, and a low-temperature decomposition peak temperature and a high-temperature decomposition peak temperature which are respectively 21 ℃ and 38.2 ℃ earlier than those of 1.1 mu mAP, and the thermal decomposition performance is better than that of 1.1 mu mAP, but the thermal performance of 1.1 mu mAP is not improved greatly in examples 1 and 2.

Example 3

This example shows a method for preparing an AP/copper chromite/PBAMO complex comprising:

step 1: adding 10. 10gAP into 15mL of distilled water, stirring and dissolving, and then adding 1.5g of nano copper chromite, and performing ultrasonic dispersion at 25 ℃ for 30min to obtain a mixed solution;

and 2, adding 2.5g of PBAMO into 80mL of acetone, stirring for 20min at 25 ℃, adding the mixed solution in the step 1, performing ultrasonic dispersion for 30min at 25 ℃, and performing spray drying on the dispersion on a spray dryer, wherein the air inlet temperature is 120 ℃, the feeding rate is 3.5mL/min, and the high-purity nitrogen flow rate is 350L/h, so as to obtain gray AP/copper chromite/PBAMO composite powder.

Example 4

This embodiment differs from embodiment 3 in that:

step 1: adding 10gAP into 20mL of distilled water, stirring and dissolving, and then adding 2g of nano copper chromite, and performing ultrasonic dispersion at 25 ℃ for 30min to obtain a mixed solution;

and 2, adding 3g of PBAMO into 80mL of acetone, stirring for 20min at 25 ℃, adding the mixed solution in the step 1, performing ultrasonic dispersion for 30min at 25 ℃, and performing spray drying on the dispersion liquid on a spray dryer, wherein the air inlet temperature is 130 ℃, the feeding rate is 3mL/min, and the high-purity nitrogen flow rate is 400L/h, so as to obtain gray AP/copper chromite/PBAMO composite powder.

Comparative example 3

The comparative example was an ultra-fine AP having a particle diameter of 2.1. Mu.m, which was not coated.

Comparative example 4

This comparative example differs from example 2 in that the mass ratio of ultra-fine AP, copper chromite and PBAMO is 10:0.9:1.8.

FIGS. 5, 6 and 7 are scanning electron micrographs of the ultrafine AP of comparative example 3 and the AP/copper chromite/PBAMO complex prepared in examples 3 and 4, respectively. As is clear from the figure, agglomeration of 2.1. Mu.mAP was severe, and the AP/copper chromite/PBAMO composites prepared in examples 3 and 4 had particle sizes of 2.16 μm and 1.95. Mu.m, and were uniform in particle size distribution and non-agglomerated.

The measured mechanical sensitivity data are shown in table 2:

TABLE 2 mechanical sensitivity data

Mechanical sensitivity	Comparative example 3	Example 3	Example 4	Comparative example 4
					Impact sensitivity (%)	26	17	16	21
Friction sensitivity (%)	85	71	70	78

As can be seen from the data of Table 2, the impact sensitivity and the friction sensitivity of the ultrafine AP/copper chromite/PBAMO composite prepared in examples 3 and 4 are both greatly reduced compared with those of 2.1 μm ultrafine AP, the friction sensitivity is reduced by more than 16%, and the impact sensitivity is reduced by more than 34%; the AP/copper chromite/PBAMO composite prepared in comparative example 4 has smaller impact sensitivity and friction sensitivity than that of the AP with the thickness of 2.1 μm, the friction sensitivity is reduced by 8.2%, and the impact sensitivity is reduced by 19.2%.

The AP compound of the invention greatly reduces the mechanical sensitivity of the AP compound on the premise of reducing the AP energy as much as possible at least, improves the safety of the AP compound and improves the thermal decomposition performance of the AP compound. The method is simple to operate, the solvent is easy to remove, mass production is amplified, and the prepared AP compound has good dispersibility and does not agglomerate.

The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A preparation method of an AP compound is characterized by comprising the steps of dissolving AP, a catalyst and an energy-containing adhesive in a solvent, then performing ultrasonic dispersion to obtain a dispersion liquid, and performing spray drying on the dispersion liquid on a spray dryer to obtain the AP compound, wherein the AP compound comprises an AP/CuO/PAMMO compound and an AP/copper chromite/PBAMO compound.

2. The method for preparing an AP composite according to claim 1, wherein the mass ratio of the AP, the catalyst and the energy-containing binder is (8-10): (1-3): (2-3).

3. The method of preparing an AP composite according to claim 2, wherein the catalyst is nano copper oxide and the energetic binder material is PAMMO, the method comprising:

4. The method for preparing an AP composite according to claim 3, wherein the mass ratio of the AP to the nano copper oxide to the PAMMO is (8-10): (1-3): (2-3), the distilled water is 15-20 ml, and the tetrahydrofuran is 60-80 ml.

5. The method for preparing an AP composite according to claim 3, wherein the mass ratio of AP, nano copper oxide and PAMMO is 8:2:3;

6. The method of preparing an AP composite according to claim 1, wherein the catalyst is nano copper chromite and the energetic binder material is PBAMO, the method comprising:

7. The method for preparing an AP compound according to claim 6, wherein the mass ratio of the AP, the copper chromite and the PBAMO is (8-10): (1-3): (2-3), the distilled water is used in an amount of 15-30 ml, and the acetone is used in an amount of 60-90 ml.

8. The method for preparing an AP composite according to claim 7, wherein the mass ratio of the AP, the copper chromite and the PBAMO is 10 (1.5-3): 2;

9. An AP composite produced by the method for producing an AP composite according to any one of claims 1 to 8, comprising an AP/CuO/PAMMO composite and an AP/copper chromite/PBAMO composite, the AP/CuO/PAMMO composite having a particle size of 1 to 2 μm and the AP/copper chromite/PBAMO composite having a particle size of 1 to 3 μm.