CN102500292B

CN102500292B - Preparation method of amino-containing energetic material graded microspheres

Info

Publication number: CN102500292B
Application number: CN201110309082.4A
Authority: CN
Inventors: 胡长文; 黄兵; 曹敏花
Original assignee: Beijing Institute of Technology BIT
Current assignee: Beijing Institute of Technology BIT
Priority date: 2011-10-13
Filing date: 2011-10-13
Publication date: 2014-04-09
Anticipated expiration: 2031-10-13
Also published as: CN102500292A

Abstract

The invention relates to a preparation method of amino-containing energetic material graded microspheres, belonging to the technical field of micro-nanomaterials. The preparation method comprises the steps of: dissolving urea in absolute ethanol at room temperature, then adding a surfactant, and stirring to obtain a solution; adding a precursor to the solution, stirring, transferring to a stainless steel autoclave, then sealing the autoclave, placing in a blast oven, carrying out an amination reaction between ammonia gas generated in the reaction between urea and ethanol and the precursor, after the reaction is finished, naturally precipitating, separating out a solid product, repeatedly and alternately washing the solid product with ultrapure water and absolute ethanol for multiple times, and drying to obtain amino-containing energetic material graded microspheres. The prepared graded microspheres are uniform in size and single in morphology and have the diameter of 10-150 mu m; the product yield generally reaches more than 70%; and the method has the advantages of mild reaction conditions, high yield, easiness in industrialization, low cost and easiness in product size and morphology control, and is suitable for organic low-molecular-weight substances.

Description

Preparation method with amino energetic material classification micron ball

Technical field

The present invention relates to the preparation method with amino energetic material classification micron ball, belong to micro Nano material technical field.

Background technology

The three-dimensional classification micro-/ nano spherical structure being assembled by nanoscale construction unit, due to its interesting geometric configuration, unique physics and chemistry character and in the potential use in the fields such as catalysis, optics, electronics and magnetic, arouse widespread concern.Therefore, the three-dimensional classification micro-/ nano spherical structure of a lot of inorganic material, as Fe ₂o ₃, CaCO ₃, BaCO ₃, BaSO ₄, Ni (OH) ₂deng (Angew.Chem, Int.Ed., 2003,42,980; J.Am.Chem.Soc., 2005,127,3596; J.Am.Chem.Soc., 2006,128,15714), all can obtain by the whole bag of tricks, and aspect magnetic and chemical property, show good character.For organic micromolecule compound, they are connected with Van der Waals force or other weak intermolecular force, make the preparation of organic hierarchy more difficult compared with the inorganic hierarchy of covalent bond effect.Based on the above fact, although obtaining significant progress aspect the pattern control of organic molecule nearly ten years, so far seldom relevant for the report, particularly classification micro-/ nano spherical structure of organic molecule hierarchy.For most simple substance energetic material, be all attributable to organic molecule kind, the particularity of this class material makes many preparation methods in organic molecule field can not directly be introduced into use, and hierarchy is difficult to be produced especially.In field of inorganic materials, " wet chemistry method " is the important method of preparation classification micron ball structure, has with low cost, mild condition, the feature such as simple to operate, is easy to the size of material and pattern to regulate and control, and is applicable to large-scale production.

Summary of the invention

The object of the invention is in order to propose the preparation method with amino energetic material classification micron ball.

The object of the invention is to be achieved through the following technical solutions.

The preparation method of the energetic material classification micron ball that band of the present invention is amino, described energetic material is 2,6-diaminourea-3,5-dinitro pyrazine (ANPZ, C ₄h ₄o ₄n ₆), 1,3-diaminourea-2,4,6-trinitrobenzen (DATB, C ₆h ₅o ₆n ₅) or 1,3,5-triamido-2,4,6-trinitrobenzen (TATB, C ₆h ₆o ₆n ₆) in a kind of; The method adopts the solvent thermal reaction that ethanol is solvent, at the ammonia and the precursor nitro compound that produce by urea alcoholysis, react, and under the effect of surfactant " soft template ", through direct solvent heat treatment, in nontoxic ethanol system, complete aminating reaction, prepare the different morphologies structure with amino energetic material, under soft template auxiliary, controlled the pattern that generates object product; Concrete steps are:

1) under room temperature, urea is dissolved in absolute ethyl alcohol, then adds surfactant, stir, obtain solution;

2) precursor is joined to step 1) in the solution that obtains, at 30～60 ℃, stir until precursor dissolves, obtain yellow transparent solution, transferred in the stainless steel autoclave of teflon lined, then autoclave sealing is put into convection oven, oven temperature is 100～140 ℃, ammonia and precursor generation aminating reaction that urea and ethanol synthesis generate, reaction time is 3～12h, after completion of the reaction, natural sedimentation is also isolated solid product, with ultra-pure water and absolute ethyl alcohol, repeatedly alternately wash for several times, remove surfactant and other mineral products, at 80～100 ℃, dry 6～8h obtains the energetic material classification micron ball of object product band amino, the yield of product generally can reach more than 70%, its size uniform, pattern is single, the diameter of product micron ball is 10～150 μ m.

Above-mentioned surfactant is a kind of in following material: molecular weight is non-ionic macromolecule compound polyvinylpyrrolidone (the PVP-K30, (C of K30 level ₆h ₉nO) n), quaternary cationics softex kw (CTAB, C ₁₆tMABr, C ₁₆h ₃₃(CH ₃) ₃nBr), anion surfactant Aerosol OT (AOT, C ₂₀h ₃₇naO ₇s), anionic (SDS, C ₁₂h ₂₅sO ₄na), nonionic surface active agent polyethylene glycol (PEG-Mw, H (OCH ₂cH ₂) nOH, Mw=400,1500,2000,6000,10000,20000), nonionic polyethylene oxygen-polypropylene oxygen-polyethylene oxygen triblock polymer (Pluronic, EO _xpO _yeO _x, Mw=5800,12600), nonionic surface active agent polyoxyethylene sorbitan fatty acid ester (Tween-X, X=20,60,80).

Above-mentioned steps 1) in, the mol ratio of urea, absolute ethyl alcohol and surfactant is 8～16: 850: 1～320.

Above-mentioned steps 2) precursor and step 1 in) mol ratio of middle absolute ethyl alcohol is 0.2～1: 850; Precursor is 2,6-dimethyl-3,5-dinitro pyrazine (DMDP, C ₆h ₆o ₆n ₄), 2,3,4,6-tetranitroaniline (TNA, C ₆h ₃o ₈n ₅) or 1,3,5-triethoxy-2,4,6-trinitrobenzen (TETNB, C ₁₂h ₁₅o ₉n ₃) in a kind of.

Beneficial effect

The energetic material classification micron ball of band amino prepared by the present invention, size uniform, pattern are single, and the diameter of product micron ball is 10～150 μ m; The yield that the method obtains product generally can reach more than 70%; Reaction condition is gentle, and is suitable for small molecule organic compound, method high yield of the present invention, easily realize industrialization, cost is low, and size and pattern are easily controlled.

Accompanying drawing explanation

Fig. 1 a is the SEM figure of the ANPZ of embodiment 1 preparation;

Fig. 1 b is the SEM figure of the ANPZ of embodiment 1 preparation;

Fig. 1 c is the SEM figure of the ANPZ of embodiment 2 preparations;

Fig. 1 d is the SEM figure of the ANPZ of embodiment 2 preparations;

Fig. 2 is the SEM figure of the DATB of embodiment 3 preparations;

Fig. 3 is the SEM figure of the TATB of embodiment 4 preparations;

Fig. 4 is the XRD figure of ANPZ;

Fig. 5 is the FT-IR figure of ANPZ;

Fig. 6 is ANPZ's ¹h-NMR figure;

Fig. 7 is the XRD figure of DATB;

Fig. 8 is the FT-IR figure of DATB;

Fig. 9 is DATB's ¹h-NMR figure;

Figure 10 is the MS figure of DATB;

Figure 11 is the XRD figure of TATB;

Figure 12 is the FT-IR figure of TATB;

Figure 13 is that the diameter of DATB classification micron ball is the SEM figure of 150 μ m.

The specific embodiment

Below in conjunction with embodiment, the present invention will be further described.

Embodiment 1

2,6-diaminourea-3,5-dinitro pyrazine (ANPZ, C ₄h ₄o ₄n ₆) preparation of classification micron ball, concrete steps are:

1) under room temperature, 0.48g (8mmol) urea is dissolved in 50mL absolute ethyl alcohol, then adds 0.222g (monomer molar number is 2mmol) surfactant PVP-K30, stir, obtain pale yellow solution;

2) by 0.046g (0.2mmol) precursor 2,6-dimethyl-3,5-dinitro pyrazine (DMDP, C ₆h ₆o ₆n ₄) join step 1) in the solution that obtains, at 35 ℃, stir until DMDP dissolves completely, obtain yellow transparent solution, transferred in the stainless steel autoclave of teflon lined, then autoclave sealing is put into convection oven, oven temperature is 120 ℃, ammonia and DMDP that urea alcoholysis produces react, reaction time is 9h, after completion of the reaction, natural sedimentation is also isolated solid product, with ultra-pure water and absolute ethyl alcohol, repeatedly alternately wash 6 times, remove surfactant and other mineral products, at 80 ℃, dry 8h obtains ANPZ micron ball, in DMDP, productive rate is 82.5%, its size uniform, pattern is single, the diameter of product classification micron ball is about 60 μ m, its SEM figure is as shown in a in Fig. 1 and b.

Embodiment 2

With embodiment 1, the difference is that autoclave sealing is put into oil bath pan, under stirring condition, be incubated 9h, obtain the ANPZ classification micron ball that size is about 10 μ m, less compared with the micron ball size of embodiment 1, its SEM figure is as shown in c in Fig. 1 and d.

Embodiment 3

1,3-diaminourea-2,4,6-trinitrobenzen (DATB, C ₆h ₅o ₆n ₅) preparation of classification micron ball, concrete steps are:

1) under room temperature, 0.48g (8mmol) urea is dissolved in 50mL absolute ethyl alcohol, then adds 0.222g (monomer molar number is 2mmol) surfactant PVP-K30, stir, obtain yellow solution;

2) by 0.055g (0.2mmol)

precursor

2,3,4,6-tetranitroaniline (TNA, C ₆h ₃o ₈n ₅) join step 1) in the solution that obtains, at 40 ℃, stir until TNA dissolves completely, obtain yellow transparent solution, transferred in the stainless steel autoclave of teflon lined, then autoclave sealing is put into convection oven, oven temperature is 100 ℃, ammonia and TNA that urea alcoholysis produces react, reaction time is 9h, after completion of the reaction, natural sedimentation is also isolated solid product, with ultra-pure water and absolute ethyl alcohol, repeatedly alternately wash 6 times, remove surfactant and other mineral products, at 80 ℃, dry 8h obtains DATB micron ball, in TNA, productive rate is 78.2%, its size uniform, pattern is single, the diameter of product classification micron ball is about 60～80 μ m, its SEM figure as shown in Figure 2.

Embodiment 4

1,3,5-triamido-2,4,6-trinitrobenzen (TATB, C ₆h ₆o ₆n ₆) preparation of classification micron ball, concrete steps are:

2) by 0.069g (0.2mmol) precursor 1,3,5-triethoxy-2,4,6-trinitrobenzen (TETNB, C ₁₂h ₁₅o ₉n ₃) join step 1) in the solution that obtains, at 30 ℃, stir until TETNB dissolves completely, obtain yellow transparent solution, transferred in the stainless steel autoclave of teflon lined, then autoclave sealing is put into convection oven, oven temperature is 120 ℃, ammonia and TETNB that urea alcoholysis produces react, reaction time is 9h, after completion of the reaction, natural sedimentation is also isolated solid product, with ultra-pure water and absolute ethyl alcohol, repeatedly alternately wash 6 times, remove surfactant and other mineral products, at 80 ℃, dry 8h obtains TATB micron ball, in TETNB, productive rate is 71.7%, its size uniform, pattern is single, the diameter of product classification micron ball is about 10～15 μ m, its SEM figure as shown in Figure 3.

The composition of ANPZ classification micron ball, DATB classification micron ball and TATB classification micron ball and structure by powder x-ray diffraction (XRD), infrared spectrum (FT-IR), proton magnetic spectrum ( ¹h-NMR), mass spectrum (MS) detects that to prove pure phase attached, if Fig. 4 is to Figure 12; Their micrometer structure pattern is proven by ESEM (SEM) means: diameter is the homogeneous classification micron ball of 10～80 μ m, if Fig. 1 is to Fig. 3, if increase presoma TNA concentration, the diameter of product D ATB classification micron ball can reach 150 μ m, as shown in figure 13.

By above-mentioned similar approach, can control and prepare other with specific dimensions and pattern and there is amino energetic material classification micron ball.

Claims

1. with the preparation method of amino energetic material classification micron ball, it is characterized in that concrete steps are:

2) precursor is joined to step 1) in the solution that obtains, at 30～60 ℃, stir until precursor dissolves, obtain yellow transparent solution, transferred in the stainless steel autoclave of teflon lined, then autoclave sealing is put into convection oven, oven temperature is 100～140 ℃, ammonia and precursor generation aminating reaction that urea and ethanol synthesis generate, reaction time is 3～12h, after completion of the reaction, natural sedimentation is also isolated solid product, with ultra-pure water and absolute ethyl alcohol, repeatedly alternately wash for several times, then at 80～100 ℃, be dried 6～8h, obtain with amino energetic material classification micron ball.

2. the preparation method of the amino energetic material classification micron ball of band according to claim 1, is characterized in that: energetic material is 2,6-diaminourea-3 5-dinitro pyrazine, 1,3-diaminourea-2,4,6-trinitrobenzen or 1,3,5-triamido-2, a kind of in 4,6-trinitrobenzen.

3. the preparation method of the amino energetic material classification micron ball of band according to claim 1, is characterized in that: the energetic material classification micron ball size uniform of the band amino obtaining, pattern are single, and the diameter of product micron ball is 10～150 μ m.

4. the preparation method of the amino energetic material classification micron ball of band according to claim 1, it is characterized in that: step 1) in surfactant be a kind of in following material: molecular weight is the non-ionic macromolecule compound polyvinylpyrrolidone of K30 level, quaternary cationics softex kw, anion surfactant Aerosol OT, anionic, nonionic surface active agent polyethylene glycol, nonionic polyethylene oxygen-polypropylene oxygen-polyethylene oxygen triblock polymer, nonionic surface active agent polyoxyethylene sorbitan fatty acid ester.

5. the preparation method of the amino energetic material classification micron ball of band according to claim 1, is characterized in that: step 2) in precursor be 2,6-dimethyl-3,5-dinitro pyrazine, 2,3,4,6-tetranitroaniline or 1,3,5-triethoxy-2, a kind of in 4,6-trinitrobenzen.

6. the preparation method of the amino energetic material classification micron ball of band according to claim 1, is characterized in that: step 1) in the mol ratio of urea, absolute ethyl alcohol and surfactant be 8～16: 850: 1～320.

7. the preparation method of the amino energetic material classification micron ball of band according to claim 1, is characterized in that: step 2) in precursor and step 1) mol ratio of middle absolute ethyl alcohol is 0.2～1: 850.

8. the preparation method of the amino energetic material classification micron ball of band according to claim 4, is characterized in that: nonionic surface active agent polyethylene glycol is PEG-Mw, H (OCH ₂cH ₂) nOH, Mw=400,1500,2000,6000,10000 or 20000.

9. the preparation method of the amino energetic material classification micron ball of band according to claim 4, is characterized in that: nonionic polyethylene oxygen-polypropylene oxygen-polyethylene oxygen triblock polymer is Pluronic, EO _xpO _yeO _x, Mw=5800 or 12600.

10. the preparation method of the amino energetic material classification micron ball of band according to claim 4, is characterized in that: nonionic surface active agent polyoxyethylene sorbitan fatty acid ester is Tween-X X=20,60 or 80.