High calorific value pyrophoric borane ion salt, its preparation method and application

Abstract

The present application relates to the chemical technology field, especially to a high calorific value self-ignition borane ion salt and its preparation method and application. The present application constructs borane cation skeleton and introduces carbon-carbon unsaturated bond by innovatively, uses the electron cloud delocalization effect of unsaturated bond to control the electronic structure of the molecule, reduces the activation energy of oxidation reaction, so as to give the borane ion salt high oxidation activity and self-ignition characteristics, so that it can contact with fuming nitric acid, hydrogen peroxide with a concentration greater than 90% or nitrogen tetraoxide and other strong oxidizing agents to ignite instantly without external ignition source, and still maintains the high calorific value advantage of borane molecule. The results of the examples show that the high calorific value self-ignition borane has a mass calorific value greater than 48.5 kJ / g, and after contacting with red fuming nitric acid, the self-ignition delay time is less than 70 ms; after contacting with 90% H2O2 solution, the self-ignition delay time is not more than 50 ms.

Description

Technical Field

[0001] This invention relates to the field of chemical technology, and in particular to a high-calorific-value self-igniting boron ion salt, its preparation method, and its application. Background Technology

[0002] Spontaneously combustible materials are capable of ignition upon contact with external oxidizers and are crucial as fuels and propellants in aerospace applications. Currently used spontaneously combustible fuels are highly toxic and carcinogenic hydrazine derivatives, spurring research into cleaner and safer spontaneously combustible fuels.

[0003] Conventional borane ion salts are a class of cleaning materials with extremely high calorific value, but they do not have the ability to spontaneously combust. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a high-calorific-value, self-igniting borane ion salt, its preparation method, and its application. The borane ion salt provided by this invention possesses both high calorific value and self-ignition properties.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a high-calorific-value, self-igniting borane ionic salt, composed of cage-like borane anions and cations; the cations have carbon-carbon unsaturated bonds; the cage-like borane anions include B... 10 H 10 2- Or B 12 H 12 2- The cation has the structure shown in any one of Formulas 1 to 3: Formula 1 Formula 2 Formula 3; Among them, R1 to R3 are -CH3、 or And has at least one of the latter two groups, R4 to R6 are or n1 to n6 are integers from 1 to 3.

[0006] Preferably, the cation has any one of the following structures: Formula 1-1 Formula 1-2 Formula 1-3 Formula 1-4 Formulas 1-5 Formulas 1-6 Formula 2-1 Equation 2-2 Formula 3-1 Equation 3-2.

[0007] Preferably, for combustion tests using an oxygen bomb calorimeter, the heat of combustion of the high-calorific-value self-igniting borane is greater than 48.5 kJ / g under 3 MPa oxygen conditions.

[0008] Preferably, the ignition delay time for spontaneous combustion after contact with fuming nitric acid is less than 70 ms.

[0009] Preferably, the ignition delay time for spontaneous combustion after contact with a 90% H2O2 solution does not exceed 50 ms.

[0010] The present invention provides a method for preparing the high-calorific-value self-igniting borane ion salt described above, comprising the following steps: mixing an aqueous solution containing cage-like borane anions with an aqueous solution containing cations, performing a metathesis reaction, separating the solid and liquid phases, and obtaining the high-calorific-value self-igniting borane ion salt.

[0011] Preferably, the aqueous solution containing cage-like borane anions is obtained by passing an aqueous solution of dodecylhydrododecoborate or decahydrodecaboorate through an acidic cation exchange resin.

[0012] Preferably, the dodecylborate comprises one or more of sodium dodecylborate, potassium dodecylborate, bis(tetraethylammonium) dodecylborate, and bis(triethylammonium) dodecylborate. The decahydrodeborate includes one or more of sodium decahydrodeborate, potassium decahydrodeborate, bis(tetraethylammonium) decahydrodeborate, and bis(triethylammonium) decahydrodeborate.

[0013] Preferably, the aqueous solution containing cations is obtained by dissolving the corresponding organic amine in water.

[0014] This invention provides the application of the high calorific value self-igniting borane ion salt described in the above-described scheme or the high calorific value self-igniting borane ion salt prepared by the preparation method described in the above-described scheme in propellants.

[0015] This invention provides a high-calorific-value, self-igniting borane ionic salt. By innovatively constructing a borane cation skeleton and introducing carbon-carbon unsaturated bonds, this invention utilizes the unique electron cloud delocalization effect of unsaturated bonds to significantly regulate the electronic structure of the molecule, lowering the activation energy of the oxidation reaction. This endows the borane ionic salt with extremely high oxidation reactivity and self-ignition properties, allowing it to react violently and instantaneously with strong oxidants such as fuming nitric acid, hydrogen peroxide with a concentration greater than 90%, or nitrogen tetroxide without an external ignition source, while maintaining the high calorific value of the borane molecule. The results of the embodiments show that the high-calorific-value, self-igniting borane has a calorific value greater than 48.5 kJ / g, and after contact with red fuming nitric acid, the self-ignition delay time is less than 70 ms; after contact with a 90% H₂O₂ solution, the self-ignition delay time is no more than 50 ms. Detailed Implementation

[0016] This invention provides a high-calorific-value, self-igniting borane ionic salt, composed of cage-like borane anions and cations; the cations have carbon-carbon unsaturated bonds; the cage-like borane anions include B... 10 H 10 2- Or B 12 H 12 2- The cation has the structure shown in any one of Formulas 1 to 3: Formula 1 Formula 2 Formula 3; Among them, R1 to R3 are -CH3、 or And has at least one of the latter two groups, R4 to R6 are or n1 to n6 are integers from 1 to 3.

[0017] In this invention, n1 to n6 can be 1, 2 or 3 independently.

[0018] In this invention, the cation has any one of the following structures: Formula 1-1 Formula 1-2 Formula 1-3 Formula 1-4 Formulas 1-5 Formulas 1-6 Formula 2-1 Equation 2-2 Formula 3-1 Equation 3-2.

[0019] This invention constructs a borane cation skeleton and introduces carbon-carbon unsaturated bonds. By utilizing the unique electron cloud delocalization effect of unsaturated bonds, the electronic structure of the molecule is significantly regulated, reducing the activation energy of the oxidation reaction. This endows borane ionic salts with extremely high oxidation reactivity and self-ignition properties, enabling them to spontaneously ignite instantly upon contact with strong oxidants such as fuming nitric acid, hydrogen peroxide with a concentration greater than 90%, or dinitrogen tetroxide without the need for an external ignition source. At the same time, it maintains the advantage of the high calorific value of the borane molecule.

[0020] In this invention, for combustion tests of an oxygen bomb calorimeter, the heat of combustion of the high-calorific-value self-igniting borane is greater than 48.5 kJ / g under 3 MPa oxygen conditions.

[0021] The high-calorific-value self-igniting borane ion salt exhibits an ignition delay time of less than 70 ms after contact with fuming nitric acid; and an ignition delay time of no more than 50 ms after contact with a 90% H2O2 solution.

[0022] The present invention provides a method for preparing the high-calorific-value self-igniting borane ion salt described above, comprising the following steps: mixing an aqueous solution containing cage-like borane anions with an aqueous solution containing cations, performing a metathesis reaction, separating the solid and liquid phases, and obtaining the high-calorific-value self-igniting borane ion salt.

[0023] Unless otherwise specified, all raw materials used in this invention are commercially available products well known in the art.

[0024] In this invention, the aqueous solution containing cage-like borane anions is preferably obtained by passing an aqueous solution of dodecylhydrododecoborate or decahydrodecaboorate through an acidic cation exchange resin.

[0025] In this invention, the dodecylhydroborate preferably includes one or more of sodium dodecylhydroborate, potassium dodecylhydroborate, bis(tetraethylammonium) dodecylhydroborate, and bis(triethylammonium) dodecylhydroborate; the decahydroborate preferably includes one or more of sodium decahydroborate, potassium decahydroborate, bis(tetraethylammonium) decahydroborate, and bis(triethylammonium) decahydroborate. This invention does not have special requirements for the acidic cation exchange resin; any acidic cation exchange resin well-known in the art is acceptable. In the embodiments of this invention, a cation exchange resin acidified with hydrochloric acid is specifically used.

[0026] In this invention, the aqueous solution containing cations is obtained by dissolving the corresponding organic amine in water. This invention does not impose a specific limit on the concentration of the aqueous solution containing cations; complete dissolution is sufficient.

[0027] In this invention, the organic amine corresponding to the cation is preferably prepared using methods well known in the art. The method for preparing the organic amine corresponding to the cation preferably includes the following steps: dissolving an organic amine raw material and a haloalkane having carbon-carbon unsaturated bonds in a polar organic solvent to carry out a substitution reaction, thereby obtaining the organic amine corresponding to the cation.

[0028] In this invention, the organic amine raw material and the halogenated hydrocarbon having carbon-carbon unsaturated bonds are determined according to the structure of the cation.

[0029] For example, when the cation has the structure shown in Formula 1, the organic amine raw material is at least one of ethyl / propane / butane / pentaneamine, allylamine / allylamine / allylamine, propargylamine / propargylamine / propargylamine; the haloalkane with carbon-carbon unsaturated bonds is one of 3-chloro / bromo / iodopropene, 3-chloro / bromo / iodopropyne, 4-chloro / bromo / iodobutyne, 4-chloro / bromo / iodobutene, 5-chloro / bromo / iodopentene, and 5-chloro / bromo / iodopentyne. Specific substances need to be determined by reverse calculation based on Formula 1.

[0030] When the cation has the structure shown in Formula 2, the organic amine raw material is triethylenediamine, and the halogenated hydrocarbon with carbon-carbon unsaturated bonds is one of 3-chloro / bromo / iodopropene, 3-chloro / bromo / iodopropyne, 4-chloro / bromo / iodobutyne, 4-chloro / bromo / iodobutene, 5-chloro / bromo / iodopentene, and 5-chloro / bromo / iodopentyne. Specific substances need to be determined by reverse calculation based on Formula 2.

[0031] When the cation has the structure shown in Formula 3, the organic amine raw material is hexamethylenetetramine, and the halogenated hydrocarbon with carbon-carbon unsaturated bonds is one of 3-chloro / bromo / iodopropene, 3-chloro / bromo / iodopropyne, 4-chloro / bromo / iodobutyne, 4-chloro / bromo / iodobutene, 5-chloro / bromo / iodopentene, and 5-chloro / bromo / iodopentyne. Specific substances need to be determined by reverse calculation based on Formula 3.

[0032] In this invention, the molar ratio of the organic amine raw material to the haloalkane with carbon-carbon unsaturated bonds is preferably 1:1 to 3, and in specific embodiments it can be 1:1, 1:2, or 1:3. In this invention, the substitution reaction is preferably carried out at a temperature of 60°C for 24 hours.

[0033] After the substitution reaction is completed, the present invention preferably filters and washes the resulting reaction product to obtain the organic amine corresponding to the cation.

[0034] After obtaining an aqueous solution containing cage-like borane anions and an aqueous solution containing cations, the present invention mixes the aqueous solution containing cage-like borane anions and the aqueous solution containing cations, performs a metathesis reaction, and separates the solid and liquid to obtain the high-calorific-value self-igniting borane ion salt.

[0035] In this invention, the cage-like borane anions and cations are mixed in stoichiometric ratio.

[0036] In this invention, the temperature of the metathesis reaction is preferably room temperature (without additional heating or cooling); the time of the metathesis reaction is preferably 2 hours; and the metathesis reaction is preferably carried out under stirring conditions.

[0037] After the metathesis reaction is completed, the present invention preferably filters, washes and dries the product system sequentially to obtain the high-calorific-value self-igniting borane ion salt.

[0038] This invention provides the application of the high calorific value self-igniting borane ion salt described in the above-described scheme or the high calorific value self-igniting borane ion salt prepared by the preparation method described in the above-described scheme in propellants.

[0039] The following detailed description, in conjunction with embodiments, illustrates the high calorific value self-igniting boron ion salt, its preparation method, and its applications provided by the present invention. However, these descriptions should not be construed as limiting the scope of protection of the present invention.

[0040] Example 1 (1) Dissolve 11 mmol of bromopropene and 10 mmol of diallylamine in 200 mL of acetonitrile, heat to 60 °C and stir thoroughly. After the reaction is completed for 24 h, collect the product by vacuum distillation to obtain triallylamine, and dissolve it in water to obtain an aqueous solution containing cations.

[0041] (2) Sodium dodecylborate is passed through a cation exchange resin acidified with hydrochloric acid to obtain dodecylborate (H2B). 12 H 12 ), to obtain an aqueous solution containing anions.

[0042] (3) The aqueous solution containing 20 mmol of the cation in step (1) was placed into the aqueous solution containing 10 mmol of the anion in step (2), and the reaction was stirred for 2 h. After filtration, washing and drying, high-calorific-value auto-igniting borane was obtained.

[0043] Example 2 (1) Dissolve 11 mmol of bromopropyne and 10 mmol of diacetylacetylamine in 200 mL of acetonitrile, heat to 60 °C and stir thoroughly. After the reaction is completed for 24 h, collect the product by vacuum distillation to obtain triallylamine, and dissolve it in water to obtain an aqueous solution containing cations.

[0044] (2) Sodium dodecylborate is passed through a cation exchange resin acidified with hydrochloric acid to obtain dodecylborate (H2B). 12 H 12 ), to obtain an aqueous solution containing anions.

[0045] (3) The aqueous solution containing 20 mmol of the cation in step (1) was placed into the aqueous solution containing 10 mmol of the anion in step (2), and the reaction was stirred for 2 h. After filtration, washing and drying, high-calorific-value auto-igniting borane was obtained.

[0046] Example 3 (1) Dissolve 22 mmol of bromopropyne and 10 mmol of triethylenediamine in 200 mL of acetonitrile, heat to 60 °C and stir thoroughly. After the reaction is completed for 24 h, filter and wash to obtain N,N-dipropynetriethylenediamine, and dissolve it in water to obtain an aqueous solution containing cations.

[0047] (2) Sodium dodecylborate is passed through a cation exchange resin acidified with hydrochloric acid to obtain dodecylborate (H2B). 12 H 12 ), to obtain an aqueous solution containing anions.

[0048] (3) The aqueous solution containing 10 mmol of the cation in step (1) was placed into the aqueous solution containing 10 mmol of the anion in step (2), and the reaction was stirred for 2 h. After filtration, washing and drying, high-calorific-value auto-igniting borane was obtained.

[0049] Example 4 (1) Dissolve 11 mmol of bromopropyne and 10 mmol of hexamethylenetetramine in 200 mL of acetonitrile, heat to 60 °C and stir thoroughly. After the reaction is completed for 24 h, filter and wash to obtain N-propynetriethylenediamine, and dissolve it in water to obtain an aqueous solution containing cations.

[0050] (2) Sodium dodecylborate is passed through a cation exchange resin acidified with hydrochloric acid to obtain dodecylborate (H2B). 12 H 12 ), to obtain an aqueous solution containing anions.

[0051] (3) The aqueous solution containing 10 mmol of the cation in step (1) was placed into the aqueous solution containing 10 mmol of the anion in step (2), and the reaction was stirred for 2 h. After filtration, washing and drying, high-calorific-value auto-igniting borane was obtained.

[0052] Example 5 The preparation method of high-calorific-value self-igniting borane is the same as in Example 1, except that sodium dodecyl hydrogen borate is replaced by sodium decahydroborate in (2).

[0053] Example 6 The preparation method of high-calorific-value self-igniting borane is the same as in Example 2, except that sodium dodecyl hydrogen borate is replaced by sodium decahydroborate in (2).

[0054] Example 7 The preparation method of high-calorific-value self-igniting borane is the same as in Example 3, except that sodium dodecyl hydrogen borate is replaced by sodium decahydroborate in (2).

[0055] Example 8 The preparation method of high-calorific-value self-igniting borane is the same as in Example 4, except that sodium dodecyl hydrogen borate is replaced by sodium decahydroborate in (2).

[0056] Comparative Example 1 The fuel anion is B. 12 H 12 2- The cation is tripropylamine.

[0057] Comparative Example 2 The fuel anion is B. 12 H 12 2- The cation is hexamethylenetetramine.

[0058] Comparative Example 3 The fuel anion is B. 10 H 10 2- The cation is tripropylamine.

[0059] Constant-volume combustion and calorific value test: Take 0.1 g of the borane ion salt prepared in the examples and comparative examples, and test the calorific value of the sample in an oxygen atmosphere of 3 MPa using a constant-volume combustion device.

[0060] Spontaneous combustion performance test: Take 20 mg of the borane ion salt prepared in the examples and comparative examples as fuel, put it into a sample cell with a diameter of 1 cm and a depth of 2.5 mm, add 10 μL of fuming nitric acid drop by drop using a pipette, and use a high-speed camera to take pictures and record the time from the droplet contacting the sample to the appearance of flame.

[0061] Take 20 mg of the borane ion salt prepared in the examples and comparative examples as fuel, place it in a sample cell with a diameter of 1 cm and a depth of 2.5 mm, add 10 μL of 90% H2O2 dropwise using a pipette, and use a high-speed camera to film and record the time from the droplet contacting the sample to the appearance of flame.

[0062] The properties of each borane ion salt are shown in Table 1.

[0063] Table 1. Composition, calorific value, and natural properties of the borane ion salts in the examples and comparative examples.

[0064] As shown in Table 1, the borane ion salts prepared in Examples 1-8 of this invention have high calorific values, exceeding 48.5 kJ / g under 3 MPa oxygen conditions. By introducing carbon-carbon unsaturated bonds into the cations, the prepared borane ion salts exhibit self-ignition properties. Upon contact with red fuming nitric acid, the self-ignition delay time is less than 70 ms; upon contact with a 90% H₂O₂ solution, the self-ignition delay time does not exceed 50 ms. In contrast, the borane ion salts prepared in Comparative Examples 1-3 lack carbon-carbon unsaturated bonds and therefore do not possess self-ignition capability.

[0065] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A high-calorific-value, self-igniting borane ion salt, characterized in that, It is composed of cage-like borane anions and cations; the cations have carbon-carbon unsaturated bonds; the cage-like borane anions include B 10 H 10 2- Or B 12 H 12 2- The cation has the structure shown in any one of Formulas 1 to 3: Formula 1 Formula 2 Formula 3; Among them, R1 to R3 are -CH3、 or And has at least one of the latter two groups, R4 to R6 are or n1 to n6 are integers from 1 to 3.

2. The high-calorific-value, self-igniting borane ion salt according to claim 1, characterized in that, The cation has any one of the following structures: Formula 1-1 Formula 1-2 Formula 1-3 Formula 1-4 Formulas 1-5 Formulas 1-6 Formula 2-1 Equation 2-2 Formula 3-1 Equation 3-2.

3. The high-calorific-value, self-igniting borane ion salt according to claim 1, characterized in that, For combustion tests using an oxygen bomb calorimeter, the heat of combustion of the high-calorific-value self-igniting borane is greater than 48.5 kJ / g under 3 MPa oxygen conditions.

4. The high-calorific-value, self-igniting borane ion salt according to claim 1, characterized in that, Upon contact with fuming nitric acid, the ignition delay time for spontaneous combustion is less than 70 ms.

5. The high-calorific-value, self-igniting borane ion salt according to claim 1, characterized in that, After contact with a 90% H2O2 solution, the ignition delay time for spontaneous combustion does not exceed 50 ms.

6. The method for preparing the high-calorific-value self-igniting borane ionic salt according to any one of claims 1 to 5, characterized in that, Includes the following steps: An aqueous solution containing cage-like borane anions is mixed with an aqueous solution containing cations, and a metathesis reaction is carried out. After solid-liquid separation, the high-calorific-value self-igniting borane ion salt is obtained.

7. The preparation method according to claim 6, characterized in that, The aqueous solution containing cage-like borane anions is obtained by passing an aqueous solution of dodecylhydrododecoborate or decahydrodecaboorate through an acidic cation exchange resin.

8. The preparation method according to claim 7, characterized in that, The dodecyl dodecyl borate includes one or more of sodium dodecyl dodecyl borate, potassium dodecyl dodecyl borate, bis(tetraethylammonium) dodecyl borate, and bis(triethylammonium) dodecyl borate. The decahydrodeborate includes one or more of sodium decahydrodeborate, potassium decahydrodeborate, bis(tetraethylammonium) decahydrodeborate, and bis(triethylammonium) decahydrodeborate.

9. The preparation method according to claim 5, wherein the aqueous solution containing cations is obtained by dissolving the corresponding organic amine in water.

10. The use of the high calorific value self-igniting borane ion salt according to any one of claims 1 to 5 or the high calorific value self-igniting borane ion salt prepared by the preparation method according to any one of claims 6 to 9 in propellants.

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