CN115784824B - Nano SiO2Preparation method of coated pentaaminotetrazole - Google Patents
Nano SiO2Preparation method of coated pentaaminotetrazole Download PDFInfo
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- CN115784824B CN115784824B CN202211340894.XA CN202211340894A CN115784824B CN 115784824 B CN115784824 B CN 115784824B CN 202211340894 A CN202211340894 A CN 202211340894A CN 115784824 B CN115784824 B CN 115784824B
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- WURGAKORBPRKIL-UHFFFAOYSA-N tetrazolidine-1,2,3,4,5-pentamine Chemical compound NC1N(N)N(N)N(N)N1N WURGAKORBPRKIL-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 55
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims abstract description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000012047 saturated solution Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000005457 ice water Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 14
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000004913 activation Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000012933 kinetic analysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- -1 glyceryl ether Nitrate Chemical compound 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention discloses a preparation method of pentaamino tetrazole coated by nano SiO 2, which comprises the following specific steps: adding 5-aminotetrazole into a DMSO solution, sealing and preserving heat of a container by using a film, heating under the stirring condition, and continuously stirring after the 5-aminotetrazole is completely dissolved to prepare a 5-aminotetrazole saturated solution; adding SiO 2 into a container containing ethyl acetate, and carrying out ice water bath under the condition of stirring; slowly dripping the treated 5-aminotetrazole into cold ethyl acetate added with SiO 2 in a saturated manner, and continuously stirring to completely separate out the 5-aminotetrazole; carrying out suction filtration on the obtained suspension, and washing a filter cake with deionized water; and finally, drying the filter cake. The preparation method provided by the invention has the advantages of convenience in operation, high safety, good improvement effect and the like, the pyrolysis stability of the obtained sample in the range of 200-300 ℃ is improved, and favorable conditions can be provided for obtaining more stable combustion speed in the combustion stage.
Description
Technical Field
The invention relates to a preparation method of nano SiO 2 coated 5-aminotetrazole, in particular to a specific method for preparing a sample and selection of optimal process conditions and process parameters, and belongs to the field of energetic material pyrolysis research.
Background
The nano SiO 2 as a catalyst has the characteristics of large specific surface area, high surface energy, small particle size, strong adsorption capacity, high stability and the like. The nano SiO 2 is used for coating and modifying the energetic material, and can catalyze the pyrolysis process of the energetic material. However, the nano particles are easy to agglomerate, and are often agglomerated on the surface of the energetic material after being mixed with the energetic material, so that the catalytic performance of the nano particles is weakened.
At present, in the aspect of improving the catalytic performance of the catalyst, changing the contact mode of the catalyst and the energetic material is an effective method. The surface coating is a method commonly used at present, and the catalyst is coated on the surface of the energetic material by a certain means, or the energetic material is coated on the surface of the catalyst, so that the contact mode of the catalyst and the energetic material can be effectively changed, and the catalyst efficiency is improved.
In paper Size effect of silica nanoparticles on thermal decomposition of PMMA, zou et al add SiO 2 of different particle sizes to polymethyl methacrylate (PMMA) by vapor deposition, and the results show that SiO 2 has good catalytic effect on PMMA pyrolysis. However, the method has higher operating temperature of partial steps, and is not suitable for coating energy-containing materials. In the literature RDX@NEGEC and performance study of nano composite energetic materials prepared by an electrostatic spraying method, li Jiang et al use a cellulose glyceryl ether Nitrate (NGEC) as a coating layer to coat the black soljin (RDX) by an electrostatic drying spraying method, and achieve a good coating effect. However, the method needs to use a special instrument, and has high use cost.
Under the existing technical conditions, other coating methods such as a mechanical ball milling method, a freeze drying method, a sol-gel method and the like exist, but the problems of low efficiency or high cost and the like exist in the methods, so that the further application and development of the pentaaminotetrazole are limited.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of nano SiO 2 coated 5-aminotetrazole, and shows specific preparation methods of samples containing additives in different proportions as an application example.
The raw materials comprise the following components in percentage by mass: coating agent SiO 2 -1%, 5-aminotetrazole 95-99%, dimethyl sulfoxide (solvent) and ethyl acetate (non-solvent).
Preferably, the coating agent uses nano-sized SiO 2 with an average particle size within 100 nm.
Preferably, dimethyl sulfoxide (DMSO) is used as a solvent of the 5-aminotetrazole, and ethyl acetate is used as a non-solvent of the 5-aminotetrazole.
Preferably, the volume ratio (V DMSO:VH2O) of the dimethyl sulfoxide (DMSO) solution is 3-5.
Wherein, the structural formula of the 5-aminotetrazole is as follows:
the molecular weight is 85.07, the nitrogen content is 82.3 percent, and the combustion heat value is 208.7kJ/mol.
The preparation of the sample of the present invention comprises the steps of:
S1, adding 5-aminotetrazole into a DMSO solution, sealing and preserving heat by using a film, heating to 70 ℃ under the stirring condition, and continuously stirring for about 1h after the 5-aminotetrazole is completely dissolved to prepare a 5-aminotetrazole saturated solution;
S2, adding SiO 2 into a container filled with ethyl acetate, and carrying out ice-water bath for 1-1.5 h under the condition of stirring;
S3, slowly dripping the treated 5-aminotetrazole into cold ethyl acetate added with SiO 2 in a saturated manner, and continuously stirring for about 4 hours to completely separate out the 5-aminotetrazole;
s4, carrying out suction filtration on the obtained suspension, and washing a filter cake with deionized water;
s5, putting the filter cake into an electric heating oven, and drying at 50 ℃ for about 5 hours.
Preferably, in S2, the temperature of the SiO 2 ethyl acetate turbid liquid is reduced to be near 0 ℃ so that the temperature difference between the turbid liquid and a DMSO saturated solution of 5-aminotetrazole is near 70 ℃;
Preferably, in S3, the dropping rate of the saturated solution of 5-aminotetrazole is kept between 2 and 3ml/S;
preferably, in S3, after the saturated solution of 5-aminotetrazole is started to be added dropwise, the stirring speed is maintained at 1200 r/min-1300 r/min.
The invention has the remarkable advantages that:
1. According to the method, 5-aminotetrazole is subjected to surface coating, nano SiO 2 is used as an additive, DMSO is used as a solvent, and a sample with fine particles and symmetrical medicine bodies is obtained;
2. The sample prepared by the method has lower activation energy, and the fluctuation range of the activation energy of the obtained sample in the pyrolysis process at 200-300 ℃ is reduced compared with that of a pure 5-aminotetrazole product, which shows that the stability of the pyrolysis process is improved after the surface of the sample is coated by nano SiO 2.
Drawings
FIG. 1 shows TG-DTG curves of examples 1-3 of the invention.
FIG. 2 is a graph showing the activation energy profile obtained by KAS method treatment in the iso-conversion method in example 1 of the present invention.
FIG. 3 is a graph showing the activation energy profile obtained by KAS method treatment in the iso-conversion method in example 2 of the present invention.
FIG. 4 is a graph showing the activation energy profile obtained by KAS method treatment in the iso-conversion method in example 3 of the present invention.
FIG. 5 is a graph showing the change in the number of reaction stages obtained by the CR method in the single scan rate method at a temperature rise rate of 10k/min in example 1 of the present invention.
FIG. 6 is a plot of the change in the number of reaction stages of example 2 of the present invention at a rate of 10k/min rise in temperature by CR process in a single scan rate process.
FIG. 7 is a graph showing the change in the number of reaction stages obtained by the CR method in the single scan rate method at a temperature rise rate of 10k/min in example 3 of the present invention.
Detailed Description
The following examples are given to further illustrate the present invention, but the present invention is not limited to the following examples, and any simple changes or substitutions based on the spirit of the present invention shall fall within the scope of the present invention.
Example 1
The invention provides a method for coating 5-aminotetrazole by using nano SiO 2. The obtained sample comprises the following raw materials in percentage by mass: 99% of analytically pure 5-aminotetrazole and 2% of nano SiO. The preparation process specifically comprises the following steps:
S1, adding 5-aminotetrazole crystals into a dimethyl sulfoxide aqueous solution, heating and stirring to dissolve the crystals;
s2, after the 5-aminotetrazole is completely dissolved, carrying out heat preservation and stirring for 1h at 70 ℃ to prepare a saturated solution;
S3, adding nano SiO 2 into ethyl acetate, and carrying out ice-water bath on the suspension to enable the temperature to reach 0 ℃;
s4, dropwise adding the 5-aminotetrazole saturated solution into the cold suspension prepared in the S3 at a speed of 2-3 ml under the stirring condition, wherein the stirring speed is maintained at 1200r/min;
s5, stirring for 4 hours at a rotating speed of 1200r/min after the dripping is completed;
s6, carrying out suction filtration on the obtained turbid liquid to obtain a filter cake;
and S7, placing the sample into a baking oven at 50 ℃ to be dried for 5 hours until the weight is constant, and obtaining the improved sample.
Example 2
The invention provides a method for coating 5-aminotetrazole by using nano SiO 2. The obtained sample comprises the following raw materials in percentage by mass: and (3) the analytically pure 5-aminotetrazole is 97 percent and the nanometer SiO 2 percent. The preparation process specifically comprises the following steps:
S1, adding 5-aminotetrazole crystals into a dimethyl sulfoxide aqueous solution, heating and stirring to dissolve the crystals;
s2, after the 5-aminotetrazole is completely dissolved, carrying out heat preservation and stirring for 1h at 70 ℃ to prepare a saturated solution;
S3, adding nano SiO 2 into ethyl acetate, and carrying out ice-water bath on the suspension to enable the temperature to reach 0 ℃;
s4, dropwise adding the 5-aminotetrazole saturated solution into the cold suspension prepared in the S3 at a speed of 2-3 ml under the stirring condition, wherein the stirring speed is maintained at 1200r/min;
s5, stirring for 4 hours at a rotating speed of 1200r/min after the dripping is completed;
s6, carrying out suction filtration on the obtained turbid liquid to obtain a filter cake;
and S7, placing the sample into a baking oven at 50 ℃ to be dried for 5 hours until the weight is constant, and obtaining the improved sample.
Example 3
The invention provides a method for coating 5-aminotetrazole by using nano SiO 2. The obtained sample comprises the following raw materials in percentage by mass: 95% of analytically pure 5-aminotetrazole and 2% of nano SiO. The preparation process specifically comprises the following steps:
S1, adding 5-aminotetrazole crystals into a dimethyl sulfoxide aqueous solution, heating and stirring to dissolve the crystals;
s2, after the 5-aminotetrazole is completely dissolved, carrying out heat preservation and stirring for 1h at 70 ℃ to prepare a saturated solution;
S3, adding nano SiO 2 into ethyl acetate, and carrying out ice-water bath on the suspension to enable the temperature to reach 0 ℃;
S4, dropwise adding the 5-aminotetrazole saturated solution into the cold suspension prepared in the S3 at a speed of 2-3 ml under the stirring condition, wherein the rotating speed of a stirrer is 1200r/min;
s5, stirring for 4 hours at a rotating speed of 1200r/min after the dripping is completed;
s6, carrying out suction filtration on the obtained turbid liquid to obtain a filter cake;
and S7, placing the sample into a baking oven at 50 ℃ to be dried for 5 hours until the weight is constant, and obtaining the improved sample.
The three examples are subjected to non-isothermal thermogravimetric experiments with temperature rising rates of 5k/min, 10k/min, 15k/min and 20k/min, the experimental data are subjected to finishing, corresponding TG-DTG graphs are drawn, chemical kinetics analysis is carried out by using a KAS method in an equal conversion rate method and a CR method in a single scanning rate method, and reaction series models of three groups of samples at different temperature rising rates in a temperature range of 200-300 ℃ and average activation energy in a pyrolysis process are obtained.
The Coats-Redfern method (CR method) is a method of kinetic analysis using data from a non-isothermal thermogravimetric analysis curve (here, a TG curve) and is calculated to determine the number of reaction stages n of 5-aminotetrazole during pyrolysis using the following equation:
The Kissinger-Akahira-Sunose method (KAS method) is a common method among the isoconversion methods, which refers to a method of kinetic analysis using data at the same conversion (alpha) on a plurality of TG or DTG curves measured at different heating rates. The activation energy data in the pyrolysis process of the 5-aminotetrazole is determined in the calculation process by the following two formulas:
common thermal decomposition models are shown in the following table.
Wherein the average activation energy of the sample pyrolysis process added with nano SiO 2 (mass percent 1%) is 164.28kJ/mol, the average activation energy of the sample pyrolysis process added with nano SiO 2 mass percent 3%) is 168.62kJ/mol, and the average activation energy of the sample pyrolysis process added with nano SiO 2 (mass percent 5%) is 160.89kJ/mol. The corresponding reaction series model for the three groups of samples at different temperature rise rates is shown in the following table:
| Sample of | Optimal model |
| Pure 5-aminotetrazole | F3 |
| Example 1 | F2 |
| Example 2 | F2 |
| Example 3 | F2 |
The figure and the data show that the sample prepared by the method has lower activation energy, and the fluctuation amplitude of the activation energy of the obtained sample in the pyrolysis process at 200-300 ℃ is reduced compared with that of a pure 5-aminotetrazole product, which shows that the stability of the pyrolysis process is improved after the nano SiO 2 is used for surface coating.
Claims (4)
1. A preparation method of pentaamino tetrazole coated by nano SiO 2 is characterized by comprising the following specific steps:
S1, adding 5-aminotetrazole into a DMSO solution, sealing and preserving heat by using a film, heating up under the stirring condition, and continuously stirring for 1h after the 5-aminotetrazole is completely dissolved to prepare a 5-aminotetrazole saturated solution;
S2, adding SiO 2 into a container filled with ethyl acetate, and carrying out ice-water bath for 1-1.5 h under the condition of stirring;
S3, slowly dripping the treated 5-aminotetrazole into cold ethyl acetate added with SiO 2 in a saturated manner, and continuously stirring for 4 hours to completely separate out the 5-aminotetrazole;
s4, carrying out suction filtration on the obtained suspension, and washing a filter cake with deionized water;
s5, drying the filter cake;
In S1, heating 5-aminotetrazole to 70 ℃;
The volume ratio V DMSO:VH2O of the dimethyl sulfoxide DMSO solution is 3-5;
In S2, the temperature of the SiO 2 ethyl acetate turbid liquid is reduced to be near 0 ℃ so that the temperature difference between the turbid liquid and a DMSO saturated solution of 5-aminotetrazole reaches 70 ℃;
in S2, the rotational speed of the stirrer should be maintained at 1200-1300r/min.
2. The method for preparing the nano SiO 2 coated pentaamino tetrazole according to claim 1, wherein the nano SiO 2 coated pentaamino tetrazole comprises the following components: the coating agent comprises, by mass, 1% -5% of SiO 2% and 95% -99% of 5-aminotetrazole.
3. The method for preparing nano SiO 2 coated pentaaminotetrazole according to claim 1, wherein the average particle size of nano SiO 2 is within 100 nm.
4. The preparation method of nano SiO 2 coated pentaamino tetrazole according to claim 1, wherein in S5, the drying is specifically: the filter cake was placed in an electric oven and dried at 50 ℃ for 5h at a drying temperature of 50 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777457A (en) * | 2016-04-01 | 2016-07-20 | 中国工程物理研究院化工材料研究所 | Method for coating energetic crystal surfaces |
| CN109796292A (en) * | 2017-11-17 | 2019-05-24 | 南京理工大学 | The preparation method of superfine spherical shape TEX crystal |
| CN114315489A (en) * | 2021-12-13 | 2022-04-12 | 西安近代化学研究所 | Synthesis method of heat-resistant energy-containing material azide 5-aminotetrazole zinc energy-containing complex |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777457A (en) * | 2016-04-01 | 2016-07-20 | 中国工程物理研究院化工材料研究所 | Method for coating energetic crystal surfaces |
| CN109796292A (en) * | 2017-11-17 | 2019-05-24 | 南京理工大学 | The preparation method of superfine spherical shape TEX crystal |
| CN114315489A (en) * | 2021-12-13 | 2022-04-12 | 西安近代化学研究所 | Synthesis method of heat-resistant energy-containing material azide 5-aminotetrazole zinc energy-containing complex |
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