CN113214271A - Continuous preparation method of micron granular CL-20/HMX eutectic - Google Patents
Continuous preparation method of micron granular CL-20/HMX eutectic Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
Abstract
The invention provides a continuous preparation method of CL-20/HMX eutectic micron particles, belonging to the technical field of energetic materials. The method for preparing the eutectic crystal provided by the invention introduces microchannel crystals into the traditional solvent/non-solvent method to realize the efficient mixing of the solution and the non-solvent, ensures the uniformity of heat and mass transfer, accurately regulates and controls the concentration and the supersaturation degree, can effectively overcome the main technical difficulties of the traditional solvent/non-solvent method and the amplification process thereof, is easy for the continuity of the preparation process and has strong regulation and control on the appearance and the particle size. The method not only effectively overcomes the inherent defects of the traditional solvent/non-solvent method, but also has the advantages of easy amplification and serialization of the process, strong adjustability of process parameters, easy obtainment of the CL-20/HMX eutectic with controllable particle size and morphology, further improvement of the comprehensive performance of the eutectic by controlling the morphology and the particle size, and the like.
Description
Technical Field
The invention belongs to the technical field of energetic materials, relates to a eutectic material, and particularly relates to a continuous preparation method of a micron granular CL-20/HMX eutectic.
Background
The pharmaceutical co-crystal has remarkable effect in improving the solubility, the dispersibility and the hygroscopicity of active components, improving the stability and the bioavailability of the medicament and the like. With the introduction, researchers introduce eutectic technology into the field of energetic materials, rapidly attract wide attention, and become one of the ten popular technologies in 2013. The results of the last decade study preliminarily show that: the eutectic technology has an outstanding effect on adjusting the physical and chemical properties, the thermal properties, the safety and the detonation properties of the energetic material, such as density, melting point, decomposition temperature, sensitivity, detonation velocity, detonation pressure and the like, and some energetic materials even have gene mutation to cause the performance of the energetic material to have mutation, such as the eutectic density is higher than that of a single component, and the eutectic sensitivity is lower than that of a single component, so that the performance of the energetic material is obviously adjusted. Therefore, the appearance and development of the eutectic technology in the field of energetic materials provides a new strategy for constructing a novel energetic material from a molecular scale and regulating and controlling the contradiction between the explosive energy and the safety, opens up a new direction for developing the energetic material, and has important significance and great military application value for promoting the development of the energetic material and improving the performance of weaponry.
Through the development of the last decade, researchers have obtained a series of eutectic energetic materials based on 2,4, 6-trinitrotoluene (TNT), Benzotrifuroxan (BTF), hexanitrohexaazaisowurtzitane (CL-20), octogen (HMX) and the like. About 20 energetic-energetic eutectics and about 40 energetic-non-energetic eutectics are reported at present, wherein the CL-20/HMX eutectic is a star in the energetic material of the eutectic due to the excellent combination of properties. A great deal of reports are available about the preparation method of the CL-20/HMX eutectic material.
Bolton et al reported the co-crystal for the first time in 2012, using a slow solvent evaporation method, but the resulting CL-20/HMX co-crystal was impure, accompanied by approximately 15% of β -HMX, β -and e-CL-20. Then they use CL-20/HMX eutectic as seed Crystal and adopt solvent mediated co-crystallization method to obtain pure CL-20/HMX eutectic [ Crystal Growth & Design,2012,12(9):4311-4314 ]. However, this method has a small preparation amount (milligram), a complicated process and many uncontrollable factors, so that researchers have searched for other preparation methods in subsequent work. For example, Gao et al synthesized nano CL-20/HMX eutectic by ultrasonic spray assisted electrostatic adsorption [ Journal of Materials Chemistry A,2014,2(47):19969-19974 ]; preparing micron-scale and nano-scale CL-20/HMX eutectic crystals [ Scientific Reports,2014,4:6575] by utilizing a spray flash technology, Spitzer and the like; qiu et al obtained nano-sized CL-20/HMX eutectic [ CrytEngComm,2015,17(22): 4080-; a spray drying method is adopted, and An and the like are used for preparing the CL-20/HMX eutectic microspheres with the diameter of 0.5-5 mu m. The microspheres are formed by aggregation of flaky eutectic crystals with the thickness of less than 100nm [ Journal of nanomaterials,2017,2017:1-7 ]; ghosh et al propose a process for the preparation of coarse particles of a CL-20/HMX eutectic by evaporation of the solvent from a saturated solution of CL-20 and HMX (molar ratio 2:1) in the presence of a high-boiling nonsolvent, giving a prismatic lamellar eutectic [ Crystal Growth & Design,2018,18(7):3781-3793] with a thickness of about 30 μm. It can be found that this process actually combines evaporative crystallization and solvent/non-solvent crystallization; under the condition of existence of trace solvent, obtaining CL-20/HMX eutectic ultrafine particles (energetic material, 2020,28(2): 137-144) with the particle size of less than 1 mu m by an ultra-efficient mixing technology; zhang et al prepared a CL-20/HMX micro eutectic [ CrystEngComm,2020,22(1):61-67] by taking CL-20 and HMX nanoparticles as raw materials and adopting a solvothermal method.
From the above reports, it can be seen that the preparation of the CL-20/HMX co-crystal has attracted the attention of researchers, and the proposed methods have advantages and disadvantages. In view of the potential hazards associated with high explosive CL-20 and HMX, such as being relatively sensitive to friction, shock, heat and static electricity, the present inventors believe that the solvent/non-solvent process should be more suitable for preparing the CL-20/HMX co-crystal because of its simplicity, ease of use and safety characteristics. However, the conventional solvent/non-solvent method has the defects of temperature and concentration gradient, difficulty in controlling supersaturation degree in the process amplification process, difficulty in rapidly increasing and decreasing temperature, poor uniformity of mass and heat transfer and the like, and the problems caused by the defects are as follows: (1) solutes are easy to crystallize respectively, and pure eutectic crystals are difficult to obtain; (2) the particle size distribution of the sample is wide; (3) the reproducibility of the experiment was poor.
Therefore, how to provide a new preparation method of the CL-20/HMX eutectic crystal becomes a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to solve the technical problems and provide a continuous preparation method of micron granular CL-20/HMX eutectic. The preparation method introduces the microchannel crystallization technology into the solvent/non-solvent method, not only overcomes the inherent defects of the traditional solvent/non-solvent method, but also provides a preparation technology which is easy to amplify and continue for the CL-20/HMX eutectic crystal, and provides a material basis for the practical application of the preparation technology.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a continuous preparation method of micron granular CL-20/HMX eutectic crystals comprises the following steps:
1) building a microchannel crystallization device;
2) selecting a solvent and a non-solvent based on the solubility of CL-20 and HMX;
3) according to the molar ratio of CL-20 to HMX in the CL-20/HMX eutectic of 2:1 weighing eutectic components, adding the eutectic components into a certain amount of solvent, and fully dissolving to form transparent solution;
4) adjusting the concentration of the eutectic component solution in the step 3), the flow rate ratio of the solution to the non-solvent or adding a crystal growth control agent to regulate and control the morphology and the granularity of the CL-20/HMX eutectic;
5) the crystallized sample was filtered, washed and dried to obtain the CL-20/HMX co-crystal.
In order to overcome the defects in the existing CL-20/HMX eutectic preparation and consider the problems of amplification and continuous production of a cocrystallization process, the invention innovatively introduces a microchannel crystallization technology into the traditional solvent/non-solvent method to realize the efficient mixing of a solution and a non-solvent, ensure the uniformity of heat and mass transfer, accurately regulate and control the concentration and the supersaturation degree, can effectively overcome the main technical difficulties of the traditional solvent/non-solvent method and the amplification process thereof, is easy to realize the continuity of the preparation process and has strong regulation and control on the appearance and the particle size.
In addition, the method can also provide technical support for the amplified preparation of the CL-20/HMX eutectic by the design of the micro-channel crystallization device, such as the high-efficiency assembly of a multi-channel micro-fluidic chip or a plurality of groups of single-channel chips. Therefore, the preparation method disclosed by the invention is expected to provide a new way for the amplified preparation of the CL-20/HMX eutectic and provide a material basis for the practical application of the CL-20/HMX eutectic. By regulating and controlling the main parameters involved in the technology, the CL-20/HMX eutectic with adjustable particle size and morphology can be obtained, and then the micron-sized granular CL-20/HMX eutectic is obtained, so that the comprehensive performance of the micron-sized granular CL-20/HMX eutectic is further improved. The preparation method can also be popularized to other eutectic energetic materials, and the eutectic energetic materials are promoted to be widely applied to the military fields of conventional weapons, propellants and the like.
Further, the types of the micro-channel in step 1) include a cross-shaped channel, a T-shaped channel or a Y-shaped channel, and preferably, the cross-shaped channel.
Further, the material of the microchannel in the step 1) is selected from optical glass, a high polymer material or stainless steel, and preferably the material is optical glass.
Further, the inner diameter of the pipe of the microchannel in the step 1) is micrometer to millimeter level, and the length of the crystallization pipeline is centimeter level.
Further, when the microchannel crystallization device is built in the step 1), the polytetrafluoroethylene hose is selected as the connecting pipe, and the power pump is a peristaltic pump or a laminar flow pump.
Further, the solvent used in the step 2) is DMSO, acetone, ethyl acetate, -butyrolactone and the like, and the non-solvent is ultrapure water, CH2Cl2Petroleum ether or alkanes.
Further, the concentration of the eutectic component solution in the step 4) is adjustable between 0.08 and 0.25mol/L, and the flow rate ratio of the solution to the non-solvent is 1: 2. 1: 4. 1:6 or 1: 8.
furthermore, the crystal growth control agent in the step 4) can be selected from anhydrous citric acid, maleic acid and the like, and the dosage of the additive is 1 wt% or 2 wt% of the mass of the CL-20.
Further, the detergent in step 5) may be a non-solvent such as ultrapure water, dichloromethane, petroleum ether or alkanes.
Further, the drying in the step 5) may be achieved by natural drying at normal temperature, freeze drying at low temperature, microwave drying, supercritical drying, infrared drying, or spray drying.
The invention has the following beneficial effects:
the invention introduces the microchannel crystallization technology into the solvent/non-solvent method to realize the high-efficiency mixing of the solution and the non-solvent, ensure the uniformity of heat and mass transfer, and accurately regulate and control the concentration and the supersaturation degree, not only can overcome the inherent defects of the traditional solvent/non-solvent method, but also can provide a preparation technology which is easy to amplify and continue for CL-20/HMX eutectic crystal, and provide a material basis for the practical application thereof. The preparation technology has strong controllability of main parameters, and is easy to obtain the CL-20/HMX eutectic with controllable particle size and shape, so that micron particles of the CL-20/HMX eutectic are obtained, and the comprehensive performance of the micron particles is further improved. The preparation technology can also be popularized to other eutectic energetic materials, and the eutectic energetic materials are promoted to be widely applied to the military fields of conventional weapons, propellants and the like.
Drawings
FIG. 1 is a diagram of a microchannel type (left) and microchannel crystallization apparatus (right), in which the diameter of the tube is 1.5mm and the length of the tube in which co-crystallization occurs is 9 cm;
FIG. 2 is XRD patterns of examples 1, 2, 3, 4 and comparative examples 5, 6 with starting materials and based on single crystal structure simulation;
FIG. 3 is a Scanning Electron Microscope (SEM) comparison of the raw materials of examples 1, 2, 3, 4 and comparative examples 5, 6; (a) raw material CL-20; (b) raw material HMX; (c) example 1; (d) example 2; (e) example 3; (f) example 4; (g) comparative example 5; (h) comparative example 6;
FIG. 4 shows the results of thermal performance tests of the materials of examples 1, 2, 3 and 4 and comparative examples 5 and 6.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail with reference to the following embodiments. It is to be noted that the following examples are only for explaining and illustrating the present invention and are not intended to limit the present invention. The invention is not limited to the embodiments described above, but rather, may be modified within the scope of the invention.
Example 1
1.0950g of CL-20 and 0.3700g of HMX (molar ratio of CL-20 to HMX 2:1) were dissolved in 10mL of DMSO with ultrasonic agitation at 25 ℃ to form a homogeneous solution. 1 mL-min by peristaltic pump-1The solution was pumped into the left horizontal channel of the cross microchannel at a flow rate of 3mL min-1Pumping non-solvent ultra-pure water into the upper and lower vertical channels simultaneously. The solution and ultrapure water were rapidly mixed at the cross and flowed into the collector via the right horizontal channel. And filtering the suspension in the collector, washing the suspension for 3-5 times by using ultrapure water to remove the solvent, and performing vacuum freeze drying to obtain a white powder sample.
Example 2
1.0950g of CL-20 and 0.3700g of HMX (molar ratio of CL-20 to HMX 2:1) were dissolved in 20mL of DMSO with ultrasonic agitation at 25 ℃ to form a homogeneous solution. The solution was pumped at 1 mL. min by a peristaltic pump-1Is pumped into the left horizontal channel of the cross microchannel at a flow rate of 1mL min-1Pumping non-solvent ultra-pure water into the upper and lower vertical channels simultaneously. The solution and ultrapure water were rapidly mixed at the intersection and flowed into the collector via the right horizontal channel. And filtering the suspension in the collector, washing the suspension for 3-5 times by using ultrapure water to remove the solvent, and performing vacuum freeze drying to obtain a white powder sample.
Example 3
1.0950g of CL-20 and 0.3700g of HMX (molar ratio of CL-20 to HMX 2:1) were dissolved in 30mL of DMSO with ultrasonic agitation at 25 ℃ to form a homogeneous solution. The solution was pumped at 1 mL. min by a peristaltic pump-1Pumping the non-solvent ultrapure water into the left horizontal channel of the cross-shaped microchannel at a flow rate of 4 mL/min-1Is pumped into the upper and lower vertical channels simultaneously. The solution and ultrapure water were rapidly mixed at the intersection and flowed into the collector via the right horizontal channel. And filtering the suspension in the collector, washing the suspension for 3-5 times by using ultrapure water to remove the solvent, and performing vacuum freeze drying to obtain a white powder sample.
Example 4
1.0950g of CL-20 and 0.3700g of HMX (the molar ratio of CL-20 to HMX is 2:1) are dissolved in 10mL of DMSO under ultrasonic stirring at 25 ℃ to form a homogeneous solution, and a crystal growth control agent, maleic acid, is added in an amount of 1 wt% of the mass of CL-20. The solution was pumped at 1 mL. min by a peristaltic pump-1Pumping the non-solvent ultrapure water into the left horizontal channel of the cross-shaped microchannel at a flow rate of 4 mL/min-1And simultaneously pumping into an upper vertical channel and a lower vertical channel. The solution and ultrapure water were rapidly mixed at the intersection and flowed into the collector via the right horizontal channel. And filtering the suspension in the collector, washing the suspension for 3-5 times by using ultrapure water to remove the solvent, and performing vacuum freeze drying to obtain a white powder sample.
Comparative examples 5 and 6 use a conventional solvent/non-solvent process, with comparative example 5 being a forward addition and comparative example 6 being a reverse addition.
Comparative example 5
1.0950g of CL-20 and 0.3700g of HMX (molar ratio of CL-20 to HMX 2:1) were dissolved in 10mL of DMSO with ultrasonic agitation at 25 ℃ to form a homogeneous solution. While stirring at a constant temperature (25 ℃ C.) at a speed of 2 mL/min-120mL of ultrapure water at 25 ℃ was added dropwise to the solution to obtain a suspension. And filtering the suspension, washing the suspension for 3-5 times by using ultrapure water to remove the solvent, and drying the suspension in vacuum to obtain a white powder sample.
Comparative example 6
1.0950g of CL-20 and 0.3700g of HMX (molar ratio of CL-20 to HMX 2:1) were dissolved in 10mL of DMSO with ultrasonic agitation at 25 ℃ to form a homogeneous solution. The solution was stirred at a constant temperature (25 ℃) and at a speed of 1 mL/min (r: 260rpm)-1Was dropped into 20mL of ultrapure water to obtain a suspension. And finally, filtering the suspension, washing the suspension for 3-5 times by using ultrapure water to remove the solvent, and drying the suspension in vacuum to obtain a white powder sample.
Structural and performance testing
Fig. 2 is an XRD pattern of examples 1, 2, 3, 4 and comparative examples 5, 6 with the starting material and based on single crystal structure simulation. The simulated spectra were based on the CL-20/HMX eutectic single crystal structure (CCDC: 875458) and were simulated using the Reflex module in Materials Studio. The XRD spectra of examples 1, 2, 3, 4 and comparative examples 5, 6 are very similar and agree well with the simulated XRD spectra. In addition, it is well consistent with the new peaks reported by Bolton et al (10.9 °, 13.2 °, 16.3 °, 26.1 ° and 29.7 °) [ Crystal Growth & Design,2012,12(9): 4311-.
FIG. 3 is a Scanning Electron Microscope (SEM) image of the starting material, examples 1, 2, 3, 4 and comparative examples 5, 6. It can be seen that the raw material CL-20 is spindle-shaped, the raw material HMX is granular, the grain sizes of the two are dozens of microns to more than one hundred microns, and the grain size of the CL-20/HMX obtained by adopting microchannel crystallization is greatly reduced. The initial concentration of CL-20 in example 1 was 0.25mol-1The flow rate ratio of solution to non-solvent is 1: 6. the CL-20/HMX eutectic obtained under the condition is a square particle with regular appearance, the particle length is 5-15 mu m, and the thickness is about 5 mu m; the initial concentration of CL-20 in example 2 was 0.125mol-1The flow rate ratio of solution to non-solvent is 1: 2. the appearance part of the CL-20/HMX eutectic obtained under the condition is in a flower cluster shape, and the part is in a sheet shape (the thickness is 200-600 nm). The flower-like crystals (about 20 to 30 μm in diameter) are actually assembled from plate-like crystals; the initial concentration of CL-20 in example 3 is 0.083mol-1The flow rate ratio of solution to non-solvent is 1: 8. the CL-20/HMX eutectic obtained under these conditions has a few lamellar crystals interspersed among the oblong particles. The thickness of the rectangular particles is about 3 μm, and the thickness of the flaky crystals is in submicron order. The initial concentration of CL-20 in example 4 is 0.25mol-1The flow rate ratio of solution to non-solvent is 1:8, adding 1 wt% of maleic acid. The CL-20/HMX eutectic obtained under the condition is granular, the size is 5-14 mu m, the grain size distribution is uniform, and the surface of a sample is regular and smooth. From these four examples, it can be seen that the morphology and particle size of the CL-20/HMX co-crystal can be controlled by solution concentration and flow rate ratio of solution to non-solvent. Due to the strength and direction of hydrogen bonds between molecules of the CL-20/HMX eutectic and the lattice stacking mode, the CL-20/HMX eutectic is very easy to form flaky crystals in the crystallization process. While the plate-shaped crystal is highThe fracture easily occurs in the shearing mixing process, thereby influencing the application performance of the explosive in the mixed explosive. Furthermore, continuous preparation technology of nano CL-20/HMX eutectic is reported in the literature [ Journal of Materials Chemistry A,2014,2(47): 19969-19974; scientific Reports,2014,4:6575 (1-6); journal of Nanomaterials,2017,2017:1-7]However, it is difficult to achieve the desired solid loading in practical formulations. Therefore, the invention successfully realizes the preparation of the micron-sized granular CL-20/HMX eutectic by adjusting the concentration of the solution in the microchannel crystallization and the flow rate ratio of the solution to the non-solvent. Examples 2 and 4 both yielded microparticles of the CL-20/HMX co-crystal.
To illustrate the advantages of microchannel crystallization techniques for making eutectic energetic materials by comparison, fig. 2(g, h) shows comparative example 5 and comparative example 6, i.e., CL-20/HMX eutectic morphologies prepared by a conventional solvent/non-solvent process. It can be seen that the appearance of the sample is mainly flaky and the particle size distribution range is wide no matter the positive addition or the negative addition is adopted.
FIG. 4 shows the results of thermal performance tests of the materials of examples 1, 2, 3 and 4 and comparative examples 5 and 6. Compared with the raw materials CL-20 and HMX, the thermal decomposition behavior of the CL-20/HMX eutectic is obviously different, a crystal transformation peak and a melting peak disappear, only a very sharp exothermic peak is observed, the exothermic peak temperature is between 240 and 246 ℃, and the exothermic peak temperature is very close to that of the micro-nano eutectic reported in the literature [ Crystegcomm, 2020,22(1): 61-67; journal of materials Chemistry A,2014,2(47):19969 and 19974. The decomposition heat release of the prepared CL-20/HMX eutectic is within a very narrow temperature range (within 5 ℃), and is far lower than that of raw materials CL-20 (230-254.6 ℃) and HMX (281.0-290.7 ℃), which shows that the energy release efficiency is greatly improved. The one-step weight loss on the TG curve also indicates high sample purity, which is consistent with XRD analysis results.
Impact sensitivity and friction sensitivity are important parameter indexes for measuring the safety of the explosive. According to the method of GJB 5891.22-2006, the impact sensitivity of a sample is tested by adopting a BFH-PEx type light drop hammer impact sensitivity tester of Aidiselen (Beijing) science and technology Limited, the drop hammer mass is 2kg, the sample amount of each sample is (30 +/-1) mg, and each group of samples is tested for 30 times; according to the GJB 5891.24-2006 method, a light friction sensitivity tester FSKM-10L model of Aidiselen (Beijing) science and technology Limited is adopted to test the friction sensitivity of the samples, the amount of each sample is (20 +/-1) mg, and 30 samples are tested in each group. To illustrate the effect of morphology and particle size on sensitivity, the starting material and the two typical morphologies of the CL-20/HMX co-crystal, i.e. the floral-like shape obtained in example 1 and the square-like shape obtained in example 2, were tested in the same manner and the results are given in table 1. It can be seen that the impact sensitivity of the floral cluster eutectic is lower than that of the starting material, and the friction sensitivity is between the two starting materials, i.e. lower than CL-20 and higher than HMX. When the morphology of the CL-20/HMX eutectic is regulated to be regular square particles (the length is 5-15 mu m, the thickness is about 5 mu m), the sensitivity performance of the CL-20/HMX eutectic is better improved, and the impact sensitivity (>20J) and the friction sensitivity (168N) are lower than those of raw material HMX (14.4J and 144N). The sensitivity test result shows that the sensitivity of the obtained micron-sized granular CL-20/HMX eutectic is further improved based on the regulation and control effect of the microchannel crystallization technology on the morphology and the granularity, and the safety performance of the CL-20/HMX eutectic is greatly improved.
TABLE 1 sensitivity contrast test
| Examples of the invention | Sensitivity to impact (J) | Degree of friction (N) |
| Starting material CL-20 | 10 | 80 |
| Feedstock HMX | 14.4 | 144 |
| Example 1 | 18 | 96 |
| Example 2 | >20 | 168 |
Claims (10)
1. A continuous preparation method of micron granular CL-20/HMX eutectic is characterized by comprising the following steps:
1) building a microchannel crystallization device;
2) selecting a solvent and a non-solvent based on the solubility of CL-20 and HMX;
3) weighing eutectic components according to the molar ratio of CL-20 to HMX in the CL-20/HMX eutectic of 2:1, adding the eutectic components into a certain amount of solvent, and fully dissolving to form a transparent solution;
4) adjusting the concentration of the eutectic component solution in the step 3), controlling the flow rate ratio of the solution and the non-solvent or adding a crystal growth control agent, and adjusting and controlling the morphology and the granularity of the CL-20/HMX eutectic;
5) the crystallized sample was filtered, washed and dried to obtain the CL-20/HMX co-crystal.
2. The method according to claim 1, wherein the type of the microchannel in step 1) comprises a cross-shaped, T-shaped or Y-shaped channel, preferably a cross-shaped channel.
3. The preparation method according to claim 1, wherein the material of the microchannel in step 1) is selected from optical glass, polymer material or stainless steel, preferably optical glass.
4. The preparation method according to claim 1, wherein the tube inner diameter of the microchannel in step 1) is selected to be in the micrometer to millimeter level, and the length of the crystallization tube is selected to be in the centimeter level.
5. The preparation method according to claim 1, wherein a polytetrafluoroethylene hose is selected as a connecting pipe when the microchannel crystallization device is built in the step 1), and a peristaltic pump or a laminar flow pump is selected as a power pump.
6. The method according to claim 1, wherein the solvent in step 2) is DMSO, acetone, ethyl acetate or butyrolactone, and the non-solvent is ultrapure water, CH2Cl2Petroleum ether or alkanes.
7. The method according to claim 1, wherein the concentration of the eutectic composition solution in step 4) is 0.08 to 0.25mol/L, and the flow rate ratio of the solution to the non-solvent is 1:2, 1:4, 1:6, or 1: 8.
8. The method for preparing the crystalline growth controlling agent according to claim 1, wherein the crystalline growth controlling agent in the step 4) comprises anhydrous citric acid or maleic acid, and the additive amount thereof is 1 wt% or 2 wt% of the mass of CL-20.
9. The preparation method according to claim 1, wherein the washing agent used in the step 5) is a non-solvent, and comprises ultrapure water, dichloromethane, petroleum ether or alkanes.
10. The preparation method according to claim 1, wherein the drying of step 5) comprises normal temperature natural drying, low temperature freeze drying, microwave drying, supercritical drying, infrared drying or spray drying.
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| CN116553985A (en) * | 2022-01-27 | 2023-08-08 | 中国工程物理研究院化工材料研究所 | Synchronous regulation and control method for HMX quality, granularity and distribution thereof based on additive-ultrasonic combined technology |
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