CN113754506B - Nano core-shell combustion catalyst and preparation method thereof - Google Patents
Nano core-shell combustion catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a nano core-shell combustion catalyst and a preparation method thereof, wherein the nano core-shell combustion catalyst comprises the following steps: the method comprises the following steps: taking cis-5-norbornene-exo-2, 3-dicarboxylic anhydride, hexanediol, p-toluenesulfonic acid and dichloromethane to obtain a dibromide monomer sample; taking pure triamine, cis-5-norbornene-exo-2, 3-dicarboxylic anhydride and a toluene solvent to obtain a cross-linking agent; and preparing the nanometer core-shell combustion catalyst by taking the dibromide monomer, the catalyst and copper sulfate or palladium acetate. The method has the advantages and positive effects of solving two problems that the agglomeration phenomenon of metal active molecules and the shell thickness cannot be accurately controlled. The dibromide monomer with an active center at the end is synthesized through ring-opening metathesis polymerization reaction, and then a cross-linking agent is added for further cross-linking to form the combustion catalyst with a compact shell structure consisting of linear macromolecular arms and a core containing a ligand structure, the particle size of the combustion catalyst is nano-sized, the activity is high, the catalytic combustion efficiency is high, and the preparation method is favorable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of gunpowder and explosive combustion catalysis, and particularly relates to a nano core-shell combustion catalyst and a preparation method thereof.
Background
The nanometer combustion catalyst has the advantages of small particle size, large specific surface area, high catalytic activity and the like, and is one of the hot spots of research in the field of explosives and powders, and the nanometer combustion catalyst is internationally researched and developed as a fourth generation catalyst. However, during the preparation and use of the nano-catalyst, the specific surface is reduced due to easy agglomeration of nano-particles, thereby affecting the catalytic performance of the nano-catalyst.
Ammonium Perchlorate (AP) is a commonly used oxidizer in solid propellants, the properties of which play a crucial role in the combustion performance of solid propellants. The best way to adjust the combustion performance of solid propellants at present is to add a small amount of combustion catalyst. At present, the common combustion catalysts mainly comprise metal simple substance catalysts, inorganic metal oxides, energetic catalysts, bimetallic catalysts and the like.
In recent years, the assembly of nanomaterials has become an important means for preparing novel multifunctional nanomaterials, and the nanomaterials with core-shell structures are receiving the attention of researchers. The core-shell structure material is a multi-stage nano structure formed by coating a nano-scale shell layer on the surface of a core which is nano or micron particles. The catalyst is prepared into the core-shell type nano composite, and the inner core is used as the catalyst of the carrier supporting shell layer, so that the nano particles can be effectively prevented from agglomerating, the specific surface area is increased, the contact sites between the catalyst and reactants are increased, and the catalytic activity is improved.
Disclosure of Invention
The invention aims to overcome the defects of the conventional combustion catalyst and provides a nano core-shell combustion catalyst and a preparation method thereof, which can improve the activity of the nano core-shell combustion catalyst, and have the advantages of high catalytic efficiency, simple preparation process and low cost.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for preparing a nano core-shell combustion catalyst, comprising the steps of:
step one, dispersing cis-5-norbornene-exo-2, 3-dicarboxylic anhydride into hexanediol, heating and stirring until the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is completely dissolved; then adding p-toluenesulfonic acid, carrying out vacuum reaction, cooling the solution to room temperature after the reaction is finished, diluting and washing the solution by using ethyl acetate and sodium bicarbonate aqueous solution, collecting an organic layer, and carrying out reduced pressure evaporation to obtain a diol monomer sample;
dissolving a diol monomer sample in dichloromethane to form a solution, adding carbon tetrabromide, cooling in an ice water bath, dropwise adding triphenylphosphine, taking out the mixture from the ice water bath, heating and stirring after dropwise adding, and filtering to remove the solvent to obtain a dibromide monomer sample;
step three, adding N-Boc-2-bromoethylamine, sodium azide and tripropylamine into a reactor containing a DMF solution, adding copper bromide and pentamethyldiethylenetriamine, stirring at constant temperature, washing, filtering and drying to obtain a light yellow solid sample, namely triazolamine;
step four, removing the triazolylamine protected by the Boc by trifluoroacetic acid, and drying in vacuum to obtain pure triamine; dissolving pure triamine and cis-5-norbornene-exo-2, 3-dicarboxylic anhydride in a toluene solvent to obtain a cross-linking agent;
step five, adding the dibromide monomer sample obtained in the step two and the Grubbs catalyst into a dichloromethane solvent to form a solution, and quickly stirring for reaction; and adding the crosslinking agent and the hexafluorophosphate solution obtained in the step four into the solution, simultaneously adding copper sulfate or palladium acetate, stirring, washing and filtering to obtain the nano core-shell combustion catalyst.
Preferably, in the first step, the mass volume ratio of the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to hexanediol is 0.2 to 0.7g; the mass ratio of the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to the p-toluenesulfonic acid is 2-7; the mass volume ratio of the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to the ethyl acetate is 0.2-0.7g; the volume ratio of the ethyl acetate to the sodium bicarbonate aqueous solution is 1; the concentration of the sodium bicarbonate aqueous solution is 3-6 wt%;
in the second step, the mass volume ratio of the diol monomer to the dichloromethane is 0.2-0.7g; the molar ratio of the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride to carbon tetrabromide is 1; the mass ratio of the diol monomer to the carbon tetrabromide is 2-7; the mass volume ratio of the diol monomer to the triphenylphosphine is 0.2-0.7g.
Preferably, in the third step, the molar ratio of N-Boc-2-bromoethylamine to sodium azide to tripropylamine is 3-5; the mass volume ratio of the N-Boc-2-bromoethylamine to the DMF solution is 1-1.5g; the mass ratio of the N-Boc-2-bromoethylamine to the copper bromide to the pentamethyl diethylenetriamine is 10-15, and the mass ratio of the N-Boc-2-bromoethylamine to the copper bromide to the pentamethyl diethylenetriamine is 0.4-0.6;
in the fourth step, the mass ratio of the pure triamine to the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is 1-3; the mass volume ratio of the pure triamine to the toluene is 0.1-0.3g.
Preferably, in the fifth step, the mass volume ratio of the dibromide monomer sample to the Grubbs catalyst is 30-50mg; the mass volume ratio of the dibromide monomer sample to the dichloromethane solvent is 30-50mg; the mass ratio of the dibromide monomer sample to the cross-linking agent is 6-10; the mass volume ratio of the dibromide monomer sample to the hexafluorophosphate solution is 30-50mg; the mass ratio of the dibromide monomer sample to the copper sulfate is 3-5; the concentration of the hexafluorophosphate solution is 50-70 wt%; the mass ratio of the dibromide monomer sample to the palladium acetate is 3-5.
Preferably, the copper sulfate is nano copper sulfate, and the palladium acetate is micro palladium acetate.
Preferably, in the first step, the heating temperature is 40-60 ℃, the stirring mode is magnetic stirring, the rotating speed is 200-450 r/min, and the vacuum reaction time is 30-45 min.
Preferably, in the second step, the cooling temperature in the ice-water bath is 0 ℃; the heating temperature is 20-30 ℃; the stirring mode is glass rod stirring or magnetic stirring; the filtration mode is reduced pressure filtration.
Preferably, in the third step, the constant temperature is 20-30 ℃; the filtration mode is reduced pressure filtration; the drying mode is vacuum heating drying or water bath oven drying; in the fourth step, the vacuum drying temperature is 50-60 ℃.
Preferably, in the fifth step, the rapid stirring mode is magnetic stirring, the stirring speed is 450-600 r/min, and the stirring time is 45-60 min; the filtration mode is reduced pressure filtration.
The invention also provides a nano core-shell combustion catalyst prepared by the preparation method of the nano core-shell combustion catalyst.
The invention at least comprises the following beneficial effects: compared with the prior art, the method has the advantages and positive effects of solving two problems that the agglomeration phenomenon of metal active molecules and the shell thickness cannot be accurately controlled. The method has the advantages that the problem of reduction of catalytic activity caused by agglomeration and sintering of metal nano particles is avoided through interaction of modified metal carriers, the activity and the efficiency are high, specifically, a dibromide monomer with an active center at the tail end is synthesized through ring-opening metathesis polymerization, a cross-linking agent is added for further cross-linking, and the combustion catalyst with a compact shell structure consisting of linear macromolecular arms and a core containing a ligand structure is formed.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a reaction scheme of step one and step two of the present invention;
FIG. 2 shows the reaction schemes of step three and step four of the present invention.
FIG. 3 is a DSC curve of a mixture of a nano core-shell combustion catalyst of the present invention and Ammonium Perchlorate (AP).
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a preparation method of a nanometer core-shell combustion catalyst comprises the following steps:
step one, dispersing 0.5g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride into 20mL of hexanediol, heating to 40 ℃, and magnetically stirring at 300r/min until the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is completely dissolved; then adding 60mg of p-toluenesulfonic acid, carrying out vacuum reaction for 30min, after the reaction is finished, cooling the solution to room temperature, diluting and washing the solution with 10mL of ethyl acetate and 10mL of sodium bicarbonate aqueous solution (with the concentration of 5 wt%), collecting an organic layer, and carrying out reduced pressure evaporation to obtain a glycol monomer sample;
step two, dissolving 0.5g of diol monomer sample in 10mL of dichloromethane to form a solution, adding 50mg of carbon tetrabromide, cooling in an ice-water bath at 0 ℃, dropwise adding 4mL of triphenylphosphine, taking out from the ice-water bath, heating to 30 ℃, stirring by adopting magnetic stirring, and filtering under reduced pressure to remove the solvent to obtain a dibromide monomer sample;
step three, adding 1.3g of N-Boc-2-bromoethylamine, 1.5g of sodium azide and 300mg of tripropylamine into a reactor containing 15mL of DMF solution, adding 36mg of copper bromide and 50mg of pentamethyldiethylenetriamine, stirring at constant temperature of 20 ℃, washing, filtering under reduced pressure, and drying in a water bath oven to obtain a light yellow solid sample, namely triazolylamine;
step four, removing the Boc protected triazolylamine (0.5 g) by using 4mL of trifluoroacetic acid, and performing vacuum drying at 60 ℃ to obtain pure triamine; dissolving 0.2g of pure triamine and 0.7g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride in 15mL of toluene solvent to obtain a crosslinking agent;
step five, adding 40mg of the dibromide monomer sample obtained in the step two and 50 mu L of Grubbs catalyst into 4mL of dichloromethane solvent to form a solution, and magnetically stirring at 600r/min for 45min to react; and then adding 14mg of the cross-linking agent obtained in the fourth step and hexafluorophosphate (10 mu L, the concentration is 60 wt%) into the solution, and simultaneously adding 40mg of copper sulfate, stirring, washing and filtering to obtain the nano core-shell combustion catalyst.
DSC test was performed using the mixture of the nano core-shell combustion catalyst prepared in example 1 and Ammonium Perchlorate (AP), as shown in FIG. 3, at a temperature rise rate of 10 deg.C. Min -1 Next, DSC measurements were performed on AP and the core-shell combustion catalyst/AP mixture. As can be seen from the figure, the addition of the core-shell combustion catalyst has almost no influence on the crystal form transformation of AP, but has obvious catalytic action on low-temperature and high-temperature decomposition, the peak value of the low-temperature decomposition is reduced from 294.5 ℃ to 285.8 ℃, and the peak temperature of the high-temperature decomposition is reduced from 418.4 ℃ to 354.5 ℃, and is reduced by 63.9 ℃.
The burning rates of AP and core-shell catalyst/AP (physical mixture) at different pressures were also tested, as shown in Table 1:
TABLE 1
The burning rate and the pressure index of the core-shell catalyst/AP are greatly changed, the burning rate is greatly improved, and the pressure index is reduced, which shows that the core-shell catalyst has strong catalytic action on AP burning.
Example 2:
a preparation method of a nanometer core-shell combustion catalyst comprises the following steps:
step one, dispersing 0.5g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride into 20mL of hexanediol, heating to 40 ℃, and magnetically stirring at 350r/min until the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is completely dissolved; then adding 0.06g of p-toluenesulfonic acid, carrying out vacuum reaction for 45min, after the reaction is finished, cooling the solution to room temperature, diluting and washing the solution with 10mL of ethyl acetate and 10mL of sodium bicarbonate aqueous solution (with the concentration of 5 wt%), collecting an organic layer, and carrying out reduced pressure evaporation to obtain a diol monomer sample;
step two, dissolving 0.5g of diol monomer sample in 10mL of dichloromethane to form a solution, adding 0.04g of carbon tetrabromide, cooling in an ice-water bath at 0 ℃, dropwise adding 4mL of triphenylphosphine, taking out from the ice-water bath, heating to 30 ℃, stirring by adopting magnetic stirring after dropwise adding, and removing the solvent by reduced pressure filtration to obtain a dibromide monomer sample;
step three, adding 1.2g of N-Boc-2-bromoethylamine, 1.5g of sodium azide and 0.04g of tripropylamine into a reactor containing 12mL of DMF solution, adding 0.035g of copper bromide and 0.05g of pentamethyldiethylenetriamine, stirring at constant temperature of 25 ℃, washing, filtering under reduced pressure, and drying in a water bath oven to obtain a light yellow solid sample, namely triazolylamine;
step four, removing the Boc protected triazolylamine (0.5 g) by using 4mL of trifluoroacetic acid, and carrying out vacuum drying at 50 ℃ to obtain pure triamine; dissolving 0.2g of pure triamine and 0.7g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride in 15mL of toluene solvent to obtain a crosslinking agent;
step five, adding 0.5g of the dibromide monomer sample obtained in the step two and 50 mu L of Grubbs catalyst into 5mL of dichloromethane solvent to form a solution, and magnetically stirring for 50min at 500r/min to react; then adding 0.015g of the cross-linking agent obtained in the fourth step and hexafluorophosphate (10 mu L, the concentration is 60 wt%) into the solution, simultaneously adding 0.04g of palladium acetate, stirring, washing and filtering to obtain the nano core-shell combustion catalyst;
while embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (1)
1. An application of a nanometer core-shell combustion catalyst in catalyzing ammonium perchlorate combustion is characterized in that,
at a temperature rise rate of 10 ℃ min -1 The DSC test is carried out on the mixture of the nano core-shell combustion catalyst and the ammonium perchlorate, the addition of the core-nano core-shell combustion catalyst has obvious catalytic action on the low-temperature and high-temperature decomposition of the ammonium perchlorate, the peak value of the low-temperature decomposition is reduced from 294.5 ℃ to 285.8 ℃, and the peak temperature of the high-temperature decomposition is reduced from 418.4 ℃ to 354.5 ℃ and is reduced by 63.9 ℃;
the preparation method of the nanometer core-shell combustion catalyst comprises the following steps:
step one, dispersing 0.5g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride into 20mL of hexanediol, heating to 40 ℃, and magnetically stirring at 300r/min until the cis-5-norbornene-exo-2, 3-dicarboxylic anhydride is completely dissolved; then adding 60mg of p-toluenesulfonic acid, reacting for 30min in vacuum, after the reaction is finished, cooling the solution to room temperature, diluting and washing the solution with 10mL of ethyl acetate and 10mL of sodium bicarbonate aqueous solution, collecting an organic layer, and evaporating under reduced pressure to obtain a diol monomer sample; the concentration of the aqueous sodium bicarbonate solution was 5wt%;
step two, dissolving 0.5g of diol monomer sample in 10mL of dichloromethane to form a solution, adding 50mg of carbon tetrabromide, cooling in an ice-water bath at 0 ℃, dropwise adding 4mL of triphenylphosphine, taking out the mixture from the ice-water bath, heating to 30 ℃, stirring by adopting magnetic stirring, and filtering under reduced pressure to remove the solvent to obtain a dibromide monomer sample;
step three, adding 1.3g of N-Boc-2-bromoethylamine, 1.5g of sodium azide and 300mg of tripropylamine into a reactor containing 15mL of DMF solution, adding 36mg of copper bromide and 50mg of pentamethyldiethylenetriamine, stirring at constant temperature of 20 ℃, washing, filtering under reduced pressure, and drying in a water bath oven to obtain a light yellow solid sample, namely triazolamine;
step four, removing 0.5g of Boc protected triazolylamine by using 4mL of trifluoroacetic acid, and drying in vacuum at 60 ℃ to obtain pure triamine; 0.2g of pure triamine and 0.7g of cis-5-norbornene-exo-2, 3-dicarboxylic anhydride were dissolved in 15mL of toluene solvent to obtain a crosslinking agent;
step five, adding 40mg of the dibromide monomer sample obtained in the step two and 50 muL of the Grubbs catalyst into 4mL of dichloromethane solvent to form a solution, and magnetically stirring for 45min at the speed of 600r/min to react; and adding 14mg of the cross-linking agent obtained in the fourth step and 10 muL of hexafluorophosphate with the concentration of 60wt% into the solution, simultaneously adding 40mg of copper sulfate, stirring, washing and filtering to obtain the nano core-shell combustion catalyst.
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