CN112125768B - polycarbonate-AlH3Double-shell compound, preparation method and application - Google Patents

polycarbonate-AlH3Double-shell compound, preparation method and application Download PDF

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CN112125768B
CN112125768B CN202010932943.3A CN202010932943A CN112125768B CN 112125768 B CN112125768 B CN 112125768B CN 202010932943 A CN202010932943 A CN 202010932943A CN 112125768 B CN112125768 B CN 112125768B
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alh
polycarbonate
shell
double
shell structure
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CN112125768A (en
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蒋周峰
赵凤起
安亭
李辉
杨燕京
张明
张建侃
李娜
姜一帆
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0091—Elimination of undesirable or temporary components of an intermediate or finished product, e.g. making porous or low density products, purifying, stabilising, drying; Deactivating; Reclaiming
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
    • C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention discloses a polycarbonate-AlH3Double-shell compound, preparation method and application thereof, and polycarbonate-AlH3The composite with the double-shell structure comprises an inner core, a first shell layer wrapping the inner core and a second shell layer wrapping the first shell layer from inside to outside; the inner core is alpha-AlH3A core, the first shell layer is Al2O3The second shell layer is a polycarbonate layer. And alpha-AlH obtained by the acid washing method3/Al2O3In contrast, the double-shell structure compound alpha-AlH synthesized by the method3/Al2O3The thermal stability of the/PC is obviously improved.

Description

polycarbonate-AlH3Double-shell compound, preparation method and application
Technical Field
The invention relates to polycarbonate-AlH3Double-shell compound, preparation method and application, and double-shell structure can significantly improve alpha-AlH3Thermal stability of (3).
Background
Hydrogen is introduced in the combustion process of the solid propellant, so that the average relative molecular mass of the fuel gas can be effectively reduced; meanwhile, the high combustion heat value of the hydrogen is beneficial to improving the temperature of the combustion chamber and the specific impulse. Aluminum trihydride is a light metal hydride with a relatively high hydrogen content, up to 10.08%, has a hydrogen storage density of 148g/L, twice that of liquid hydrogen (70.8g/L), has a higher heat of combustion value than aluminum powder, and is an ideal solidA propellant fuel. At present, AlH3A total of 7 different crystal forms include: alpha, alpha', beta, gamma, delta, epsilon and zeta, wherein the thermodynamic property of the alpha crystal form is relatively stable, and the alpha crystal form is the only crystal form with application value in the solid propellant formula. However, currently α -AlH is to be substituted3The solid propellant is applied to the solid propellant, and the decomposition phenomenon existing in the range of room temperature and the process temperature of the solid propellant needs to be solved.
Disclosure of Invention
The invention aims to provide polycarbonate-AlH3Double-shell structure compound, preparation method and application thereof for improving AlH3Thermal stability of (2).
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
polycarbonate-AlH3The composite with the double-shell structure comprises an inner core, a first shell layer wrapping the inner core and a second shell layer wrapping the first shell layer from inside to outside;
the kernel is alpha-AlH3A core, the first shell layer is Al2O3The second shell layer is a polycarbonate layer.
Optionally, the diameter of the inner core is 200 nm-40 um; the thickness of the first shell layer is 5-30 nm; the thickness of the second shell layer is 1-15 nm.
Optionally, carbonate-AlH3The preparation method of the double-shell structure compound comprises the following steps:
cleaning alpha-AlH with dilute hydrochloric acid solution3Obtaining alpha-AlH3/Al2O3Core/shell materials of construction, alpha-AlH3/Al2O3And stirring and dispersing the core/shell structure material and the polycarbonate in an organic solvent to obtain the core/shell structure material.
Optionally, the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min.
Optionally, the polycarbonate is bisphenol a polycarbonate, molecular weight 45000;
α-AlH3/Al2O3the mass ratio of the core/shell structure material to the polycarbonate is (3-15) to (2-4).
Optionally, the stirring and dispersing time is 4-12 h.
polycarbonate-AlH3Method for preparing double-shell structure compound, washing alpha-AlH with dilute hydrochloric acid solution3Obtaining alpha-AlH3/Al2O3Core/shell materials of construction, alpha-AlH3/Al2O3And stirring and dispersing the core/shell structure material and the polycarbonate in an organic solvent to obtain the core/shell structure material.
Optionally, the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min; the polycarbonate was bisphenol a polycarbonate, molecular weight 45000; alpha-AlH3/Al2O3The mass ratio of the core/shell structure material to the polycarbonate is (3-15) to (2-4); the stirring and dispersing time is 4-12 h.
Optionally, the preparation method specifically comprises: (1) obtaining alpha-AlH by acid washing3/Al2O3：α-AlH3Adding diluted acid solution for cleaning, filtering, cleaning with volatile organic solvent for 3 times, and freeze drying to obtain off-white powder sample alpha-AlH3/Al2O3(ii) a (2) Polymer-AlH3Preparing a double-shell structure compound: dispersing 80-200 mg of polycarbonate in a trichloromethane solvent, and stirring for dissolving; 300mg of alpha-AlH3/Al2O3Adding the raw materials into the solution, stirring and dispersing for 4 to 12 hours, filtering, washing for 3 times by using trichloromethane, and finally freeze-drying to obtain an off-white powder sample polycarbonate-AlH3A double shell structured composite.
The polycarbonate-AlH of the invention3Double-shell structure compound or polycarbonate-AlH3polycarbonate-AlH prepared by preparation method of double-shell-layer structure compound3Use of a double shell structure composite for the preparation of a solid propellant fuel.
The invention has the advantages and positive effects that:
alpha-AlH of the invention3/Al2O3The alpha-AlH is further improved on the basis of the acid pickling treatment method by the aid of the/PC double-shell structure compound3Purpose of thermal stability, alpha-AlH obtained by synthesis3/Al2O3The PC double-shell structure compound can be used as a solid propellant fuel, the preparation process of the double-shell structure is carried out at normal temperature, and the preparation method is safe and reliable and is suitable for large-scale production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a schematic view of the alpha-AlH of the present invention3/Al2O3SEM pictures of core/shell structures;
FIG. 2 is a schematic view of the alpha-AlH of the present invention3/Al2O3XRD pattern of core/shell structure;
FIG. 3 shows α -AlH prepared in example 13/Al2O3SEM image of/PC double-shell structure compound;
FIG. 4 shows α -AlH prepared in example 13/Al2O3Thermal stability curve of PC double shell structure compound at 60 deg.C;
FIG. 5 is an X-ray photoelectron spectrum of a composite of α -AlH3/Al2O3/PC double-shell structure;
FIG. 6 shows the peak spectrum of O1s of the alpha-AlH 3/Al2O3/PC double-shell structure composite.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The invention designs and synthesizes alpha-AlH3/Al2O3Double-shell structure composite of/PC. The PC has good heat resistance and can improve alpha-AlH3The compatibility of the alpha-AlH can also be obviously improved, and the alpha-AlH is beneficial to promoting the thermal stability of the alpha-AlH3Research on the practical application of the solid propellant.
The PC material used in the invention is specifically bisphenol A polycarbonate, and the molecular weight is 45000.
polycarbonate-AlH3The composite with the double-shell structure comprises an inner core, a first shell wrapping the inner core and a second shell wrapping the first shell from inside to outside; the inner core is alpha-AlH3A core with a first shell layer of Al2O3The second shell layer is a polycarbonate layer. The diameter of the inner core is 200 nm-40 um; the thickness of the first shell layer is 5-30 nm; the thickness of the second shell layer is 1-15 nm.
In order to further improve the alpha-AlH based on acid pickling passivation3The invention provides an alpha-AlH3/Al2O3A double-shell structure compound of PC and a synthetic method thereof.
In order to achieve the aim, the invention provides alpha-AlH3/Al2O3The synthetic method of the double-shell structure compound of the/PC comprises the following steps:
(1) obtaining alpha-AlH by acid washing3/Al2O3：
Firstly, preparing a dilute acid solution with a volume fraction of 10%; secondly, taking a certain amount of synthesized alpha-AlH3Adding into dilute acid solution, stirring for a certain time, filtering, washing with volatile organic solvent for 3 times, and freeze drying to obtain off-white powder sample.
(2)α-AlH3/Al2O3Preparation of/PC double-shell structure compound
Firstly, 200mgPC is taken to be dispersed in a trichloromethane solvent, and stirred and dissolved; then 300mg of alpha-AlH is taken3/Al2O3Adding the mixture into the solution, stirring and dispersing for 4-12 h, filtering, washing for 3 times by using trichloromethane, and finally freeze-drying to obtain an off-white powder sample.
α-AlH3/Al2O3Obtaining a shell structure:
washing of alpha-AlH by dilute hydrochloric acid solution3Obtaining alpha-AlH3/Al2O3The specific data for studying the relationship between the dilute hydrochloric acid concentration, the cleaning time and the first shell thickness for the core/shell structure material are shown in table 1:
TABLE 1
Dilute hydrochloric acid concentration (V%) Cleaning time (min) Al2O3Layer thickness (nm)
5 6 5
10 6 12
8 5 13
12 7 16
α-AlH3/Al2O3The SEM and XRD patterns of the core/shell structure are shown in FIGS. 1 and 2.
α-AlH3/Al2O3Specific examples of/PC double shell composites are given in example 1 and example 2:
example 1:
(1) obtaining alpha-AlH by acid washing3/Al2O3
Firstly, preparing a dilute hydrochloric acid solution with the volume fraction of 10%; secondly, taking a certain amount of synthesized alpha-AlH3Adding into dilute hydrochloric acid solution, stirring for 5min, filtering, and cleaning with ethanolWashed 3 times and finally freeze dried to obtain an off-white powder sample.
(2)α-AlH3/Al2O3Preparation of/PC double-shell structure compound
Firstly, 80mg of polycarbonate is dispersed in a chloroform solvent and stirred for dissolution; then 300mg of alpha-AlH is taken3/Al2O3Adding into the mixture, stirring and dispersing for 6h, filtering and washing with chloroform for 3 times, and finally freeze-drying to obtain an off-white powder sample.
Example 1 preparation of alpha-AlH3/Al2O3The structure and the thermal stability of the/PC double-shell structure compound are characterized in that:
α-AlH3/Al2O3an SEM image of the/PC double-shell structure composite is shown in FIG. 3, the morphology of the composite is bulk particles, and alpha-AlH is illustrated in the coating process3The morphology of (a) is not changed. Thermal stability characterization experiments were performed under vacuum at 60 ℃, as shown in fig. 4: as can be seen from this, the alpha-AlH3/Al2O3As a control, the thermal stability, alpha-AlH, was measured as the percentage decomposition at the same constant temperature time3/Al2O3The thermal stability of the/PC double-shell structure compound is obviously higher than that of alpha-AlH3/Al2O3。
α-AlH3/Al2O3The qualitative characterization of the components of the/PC double-shell structure composite is shown in FIG. 5 and FIG. 6;
FIG. 5 is an X-ray photoelectron spectrum of a composite of α -AlH3/Al2O3/PC double-shell structure, wherein FIG. 5 shows that the surface of a sample contains a large amount of O and C elements;
fig. 6 is a peak spectrum diagram of O1s of the α -AlH3/Al2O3/PC double-shell-layer-structure composite, and the peak positions of O1s in fig. 6 are 532.77eV and 535.77eV, which correspond to O ═ C and O-C in the PC molecular structure, respectively, and verify that a PC molecular layer exists on the surface of the composite.
Example 2:
(1) obtaining alpha-AlH by acid washing3/Al2O3
Firstly, preparing a dilute hydrochloric acid solution with the volume fraction of 5%; secondly, the first step is to carry out the first,taking a certain amount of synthesized alpha-AlH3Adding into dilute hydrochloric acid solution, stirring for 5min, filtering, washing with ethanol for 3 times, and freeze drying to obtain off-white powder sample.
(2)α-AlH3/Al2O3Preparation of/PC double-shell structure compound
Firstly, 200mg of polycarbonate is dispersed in a chloroform solvent, and is stirred and dissolved; then 300mg of alpha-AlH is taken3/Al2O3Adding into the mixture, stirring and dispersing for 6h, filtering and washing with chloroform for 3 times, and finally freeze-drying to obtain an off-white powder sample.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (6)

1. polycarbonate-AlH3The double-shell structure compound is characterized in that the compound comprises an inner core, a first shell wrapping the inner core and a second shell wrapping the first shell from inside to outside;
the kernel is a-AlH3A core, the first shell layer is Al2O3The second shell layer is a polycarbonate layer;
carbonate-AlH3The preparation method of the double-shell structure compound comprises the following steps: cleaning alpha-AlH with dilute hydrochloric acid solution3Obtaining alpha-AlH3/Al2O3Core/shell materials of construction, alpha-AlH3/Al2O3Stirring and dispersing the core/shell structure material and the polycarbonate in an organic solvent to obtain the core/shell structure material;
the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min;
the polycarbonate was bisphenol a polycarbonate, molecular weight 45000; alpha-AlH3/Al2O3The mass ratio of the core/shell structure material to the polycarbonate is (3-15) to (2-4);
the diameter of the inner core is 200 nm-40 um; the thickness of the first shell layer is 5-30 nm; the thickness of the second shell layer is 1-15 nm.
2. The polycarbonate-AlH of claim 13The double-shell structure compound is characterized in that the stirring and dispersing time is 4-12 hours.
3. polycarbonate-AlH3The preparation method of the double-shell structure compound is characterized in that the polycarbonate-AlH3The double-shell structure compound is the polycarbonate-AlH as described in claim 1 or 23A double shell structure compound; cleaning alpha-AlH with dilute hydrochloric acid solution3Obtaining alpha-AlH3/Al2O3Core/shell materials of construction, alpha-AlH3/Al2O3And stirring and dispersing the core/shell structure material and the polycarbonate in an organic solvent to obtain the core/shell structure material.
4. The polycarbonate-AlH of claim 33The preparation method of the double-shell structure compound is characterized in that the concentration of the dilute hydrochloric acid solution is 5-12V%, and the cleaning time is 6-7 min;
the polycarbonate was bisphenol a polycarbonate, molecular weight 45000;
α-AlH3/Al2O3the mass ratio of the core/shell structure material to the polycarbonate is (3-15) to (2-4);
the stirring and dispersing time is 4-12 h.
5. The polycarbonate-AlH of claim 33The preparation method of the double-shell structure compound is characterized by comprising the following steps:
(1) obtaining a-AlH by acid washing3/Al2O3：a-AlH3Adding diluted acid solution for cleaning, filtering, cleaning with volatile organic solvent for 3 times, and freeze drying to obtain off-white powder sample a-AlH3/Al2O3；
(2) Polymer-AlH3Preparing a double-shell structure compound: dispersing 80-200 mg of polycarbonate in a trichloromethane solvent, and stirring for dissolving; 300mg ofα-AlH3/Al2O3Adding the raw materials into the solution, stirring and dispersing for 4 to 12 hours, filtering, washing for 3 times by using trichloromethane, and finally freeze-drying to obtain an off-white powder sample polycarbonate-AlH3A double shell structured composite.
6. The polycarbonate-AlH of claim 1 or 23Double shell structure composite or polycarbonate-AlH according to any of claims 3 to 53polycarbonate-AlH prepared by preparation method of double-shell-layer structure compound3Use of a double shell structure composite for the preparation of a solid propellant fuel.
CN202010932943.3A 2020-09-08 2020-09-08 polycarbonate-AlH3Double-shell compound, preparation method and application Active CN112125768B (en)

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US20140141089A1 (en) * 2009-02-11 2014-05-22 Colorado School Of Mines Nanoparticles, Compositions Thereof, and Methods of Use, and Methods of Making the Same

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