CN116041720A - Anti-migration ferrocenyl dendritic polymer burning rate catalyst, and preparation method and application thereof - Google Patents
Anti-migration ferrocenyl dendritic polymer burning rate catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 239000000412 dendrimer Substances 0.000 title claims abstract description 34
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 34
- 238000013508 migration Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 acrylic ester compound Chemical class 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000004449 solid propellant Substances 0.000 claims abstract description 14
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 20
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- QJTJIQBSZLFWFS-UHFFFAOYSA-N 2,8-bis-Trifluoromethyl-4-quinoline carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC(C(F)(F)F)=NC2=C1C(F)(F)F QJTJIQBSZLFWFS-UHFFFAOYSA-N 0.000 claims description 5
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- AOCSUUGBCMTKJH-UHFFFAOYSA-N tert-butyl n-(2-aminoethyl)carbamate Chemical compound CC(C)(C)OC(=O)NCCN AOCSUUGBCMTKJH-UHFFFAOYSA-N 0.000 claims description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 230000005012 migration Effects 0.000 abstract description 6
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- UENTUGXRMBXNHU-UHFFFAOYSA-N amino perchlorate Chemical compound NOCl(=O)(=O)=O UENTUGXRMBXNHU-UHFFFAOYSA-N 0.000 abstract 1
- 238000012679 convergent method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 45
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 7
- 239000003380 propellant Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000015842 Hesperis Nutrition 0.000 description 1
- 235000012633 Iberis amara Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
- B01J31/064—Dendrimers
-
- 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
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses an anti-migration ferrocenyl dendritic polymer combustion speed catalyst, a preparation method and application thereof. The ferrocenyl dendritic polymer is prepared by a divergent-convergent method, specifically, a ferrocenyl compound is taken as a core, and the ferrocenyl compound reacts with an acrylic ester compound through an amino compound to form a branched structure, so that a plurality of ferrocenyl compounds are connected together to construct a dendritic structure. The ferrocenyl dendritic polymer provided by the invention has high migration resistance in a composite solid propellant, can reduce the thermal decomposition temperature of ammonium perchlorate and can improve the combustion rate of the amino perchlorate composite solid propellant.
Description
Technical Field
The invention belongs to a fuel rate catalyst in the field of aerospace energy catalysis, and particularly relates to an anti-migration ferrocenyl dendritic polymer fuel rate catalyst, a preparation method and application thereof.
Background
The composite solid propellant is an important power source of propellant systems of strategic missiles, rockets, aerospace craft and the like. The main components of the composition comprise: oxidizing agents, burn rate catalysts, metal fuels, crosslinking agents, binders, plasticizers, and the like. Among them, ammonium perchlorate has become one of the main candidates for an oxidizing agent in a composite solid propellant due to its good compatibility, high gas generation amount, and the like. Meanwhile, the content of the compound is 60-70% of that of the propellant. Thus, the efficiency of the thermal decomposition of ammonium perchlorate will directly affect the performance of the propellant. The ferrocene-based material is a common burning rate catalyst in the composite solid propellant, can greatly improve the burning rate and specific impulse, and can also reduce the burning pressure index. At present, the common commercial ferrocenyl burning rate catalyst is katoxine, but the stability of the composite solid propellant is seriously affected due to migration, volatilization and other conditions.
Disclosure of Invention
The invention provides a preparation method of a ferrocenyl dendritic polymer burning rate catalyst, which aims to solve the defects of the existing commercial burning rate catalyst, namely the katocine. The ferrocenyl dendritic polymer burn rate catalyst has excellent migration resistance and burn rate catalytic performance. It is capable of reducing the thermal decomposition temperature of ammonium perchlorate without migration and volatilization at 50 ℃ for a long period of time.
The invention aims at realizing the following technical scheme:
1. anti-migration ferrocenyl dendritic polymer burning rate catalyst
The ferrocenyl dendritic polymer burning rate catalyst takes a ferrocenyl compound as a core, and the ferrocenyl compound is connected through a branched structure formed by the reaction of an amino compound and an acrylic ester compound, so that a dendritic structure is constructed.
The ferrocenyl compound comprises ferrocenecarboxylic acid, ferrocenecarboxyl chloride, 1-ferrocenedicarboxylic acid and 1, 1-ferrocenedicarboxychloride.
The amino compound comprises N-Boc-ethylenediamine, propylenediamine and butylenediamine.
The acrylate compound comprises methyl acrylate, methyl methacrylate and hydroxyethyl acrylate.
2. Preparation method of anti-migration ferrocenyl dendritic polymer burning rate catalyst
1) Dispersing single-end protected amino compound in methanol in ice water bath, adding acrylic ester compound in a dropwise manner, stirring at room temperature for reaction, and removing excessive acrylic ester compound and methanol by rotary evaporation after the reaction is finished to obtain a first product;
2) Dissolving the first product in methanol, slowly dropwise adding an amino compound, and stirring at room temperature for reaction; after the reaction is finished, removing redundant amino compounds and methanol by rotary evaporation to obtain a second product;
3) Under the protection of argon, dissolving the second product in anhydrous dichloromethane, then adding an acid binding agent, slowly dropwise adding an anhydrous dichloromethane solution containing a single-functional ferrocenyl compound, stirring at room temperature for reaction, and after the reaction is finished, obtaining a third product through washing, column chromatography purification and drying;
4) Dissolving the third product in dichloromethane, slowly adding trifluoroacetic acid to remove tert-butoxycarbonyl in the third product, and removing excessive trifluoroacetic acid and dichloromethane by rotary evaporation to obtain a fourth product;
5) Under the protection of argon, dissolving the fourth product in anhydrous dichloromethane, adding an acid binding agent, dropwise adding an anhydrous dichloromethane solution containing a difunctional ferrocenyl compound, stirring at room temperature for reaction, and washing, purifying by column chromatography and drying after the reaction is finished to obtain the ferrocenyl dendritic polymer combustion speed catalyst.
In the step 1), the molar dosage of the acrylic ester compound is 5-10 times of that of the single-end protected amino compound;
in step 2), the molar amount of amino compound is 10-20 times that of the first product.
In the step 3), the mono-functional ferrocenyl compound is ferrocenecarboxylic acid or ferrocenecarboxchloride, and the molar dosage of the mono-functional ferrocenyl compound is 3-4 times that of the second product;
in the step 5), the difunctional ferrocenyl compound is 1, 1-ferrocene dicarboxylic acid or 1, 1-ferrocene dicarboxylic acid chloride, and the molar amount of the difunctional ferrocenyl compound is 1 time that of the fourth product.
3. Composite solid propellant
The composite solid propellant comprises the anti-migration ferrocenyl dendritic polymer burning rate catalyst.
4. Preparation method of composite solid propellant
1) Grinding ammonium perchlorate, adding a ferrocenyl dendritic polymer burning rate catalyst, and continuously grinding and uniformly mixing to obtain a fifth product;
2) And uniformly mixing hydroxyl-terminated polybutadiene and isophorone diisocyanate to obtain a sixth product, adding the fifth product into the sixth product in batches, uniformly stirring, recharging into a container, and curing for 7-10 days to obtain the composite solid propellant.
In the step 1), the mass part of the ammonium perchlorate is 60-70 parts, and the mass part of the ferrocenyl dendritic polymer burning-rate catalyst is 1-10 parts.
In the step 2), the weight portion of the hydroxyl-terminated polybutadiene is 10-30 portions, the weight portion of the isophorone diisocyanate is 1-10 portions, and the curing temperature is 50-80 ℃.
The beneficial effects of the invention are as follows:
the ferrocenyl dendritic polymer burning rate catalyst has higher ferrocene content, and can effectively improve the catalytic performance. Meanwhile, a large amount of amide groups can form acting forces such as hydrogen bonds with ammonium perchlorate and other additives, so that the combustion speed catalyst is not easy to migrate and volatilize under natural conditions.
Drawings
FIG. 1 is a schematic diagram of the migration of a ferrocenyl dendrimer burn rate catalyst prepared according to the present invention in a simulated propellant.
FIG. 2 is a thermal gravimetric graph of the ferrocenyl dendrimer burn rate catalyst prepared according to the present invention catalyzing the decomposition of ammonium perchlorate.
Detailed Description
The present invention will be described in more detail with reference to examples, but embodiments of the present invention are not limited thereto.
The implementation case of the invention is as follows:
example 1:
1) Under ice-water bath, 5mmol of N-Boc-ethylenediamine was dispersed in 30mL of methanol, 50mmol of methyl acrylate was added dropwise, and the reaction was stirred at 30℃for 24 hours. After the reaction was completed, excess methyl acrylate and methanol were removed by rotary evaporation to give a first product.
2) The first product was dissolved in methanol, and 100mmol of ethylenediamine was slowly added dropwise thereto, and the reaction was stirred at 30℃for 24 hours. After the reaction was completed, excess ethylenediamine and methanol were removed by rotary evaporation to obtain a second product.
3) Under the protection of argon, the second product is dissolved in anhydrous dichloromethane, 1mL of triethylamine is added as an acid binding agent, and an anhydrous dichloromethane solution containing 7.5mmol of ferrocene formyl chloride is slowly added dropwise, and the reaction is stirred at 30 ℃ for 24 hours. After the reaction, a third product is obtained by washing, column chromatography purification and drying.
4) The third product was dissolved in dichloromethane and 10mL of trifluoroacetic acid was slowly added to remove the protecting group t-butoxycarbonyl. Excess trifluoroacetic acid and dichloromethane were then removed by rotary evaporation to give the fourth product.
5) Under the protection of argon, the fourth product is dissolved in anhydrous dichloromethane, then 1mL of triethylamine is added as an acid binding agent, and then 2.5mmol of anhydrous dichloromethane solution containing 1, 1-ferrocene diformyl chloride is added dropwise, and the reaction is stirred at room temperature. After the reaction, the final product is obtained by washing, column chromatography purification and drying.
Example 2:
1) Under ice water bath, 5mmol of N-Boc-ethylenediamine was dispersed in 30mL of methanol, 50mmol of methyl methacrylate was added dropwise, and the reaction was stirred at 30℃for 24 hours. After the reaction was completed, excess methyl methacrylate and methanol were removed by rotary evaporation to give a first product.
2) The first product was dissolved in methanol, and 100mmol of propylenediamine was slowly added dropwise thereto, and the reaction was stirred at 30℃for 24 hours. After the reaction was completed, excess propylenediamine and methanol were removed by rotary evaporation to obtain a second product.
3) Under the protection of argon, the second product is dissolved in anhydrous dichloromethane, 1mL of triethylamine is added as an acid binding agent, and an anhydrous dichloromethane solution containing 7.5mmol of ferrocene formyl chloride is slowly added dropwise, and the reaction is stirred at 30 ℃ for 24 hours. After the reaction, a third product is obtained by washing, column chromatography purification and drying.
4) The third product was dissolved in dichloromethane and 10mL of trifluoroacetic acid was slowly added to remove the protecting group t-butoxycarbonyl. Excess trifluoroacetic acid and dichloromethane were then removed by rotary evaporation to give the fourth product.
5) Under the protection of argon, the fourth product is dissolved in anhydrous dichloromethane, then 1mL of triethylamine is added as an acid binding agent, and then 2.5mmol of anhydrous dichloromethane solution containing 1, 1-ferrocene diformyl chloride is added dropwise, and the reaction is stirred at room temperature. After the reaction, the final product is obtained by washing, column chromatography purification and drying.
Example 3:
1) Under ice water bath, 5mmol of N-Boc-ethylenediamine was dispersed in 30mL of methanol, 50mmol of hydroxyethyl acrylate was added dropwise, and the reaction was stirred at 30℃for 24 hours. After the reaction was completed, excess hydroxyethyl acrylate and methanol were removed by rotary evaporation to give a first product.
2) The first product was dissolved in methanol, and 100mmol of diethylenetriamine was slowly added dropwise thereto, and the reaction was stirred at 30℃for 24 hours. After the reaction was completed, excess diethylenetriamine and methanol were removed by rotary evaporation to give a second product.
3) Under the protection of argon, the second product is dissolved in anhydrous dichloromethane, 1mL of triethylamine is added as an acid binding agent, and an anhydrous dichloromethane solution containing 7.5mmol of ferrocene formyl chloride is slowly added dropwise, and the reaction is stirred at 30 ℃ for 24 hours. After the reaction, a third product is obtained by washing, column chromatography purification and drying.
4) The third product was dissolved in dichloromethane and 10mL of trifluoroacetic acid was slowly added to remove the protecting group t-butoxycarbonyl. Excess trifluoroacetic acid and dichloromethane were then removed by rotary evaporation to give the fourth product.
5) Under the protection of argon, the fourth product is dissolved in anhydrous dichloromethane, then 1mL of triethylamine is added as an acid binding agent, and then 2.5mmol of anhydrous dichloromethane solution containing 1, 1-ferrocene diformyl chloride is added dropwise, and the reaction is stirred at room temperature. After the reaction, the final product is obtained by washing, column chromatography purification and drying.
Example 4:
1) After grinding 1.62 g of ammonium perchlorate, 0.06 g of ferrocenyl dendrimer burn rate catalyst was added. And (5) continuously grinding and uniformly mixing to obtain a fifth product.
2) A sixth product was obtained by uniformly mixing 0.24 g of hydroxyl-terminated polybutadiene and 0.04 g of isophorone diisocyanate. And adding the fifth product into the sixth product in batches, stirring uniformly, filling into a transparent glass tube, and curing at 70 ℃ for 7 days to obtain the composite solid propellant.
3) 1.62 g of ammonium perchlorate is ground and added in portions to a mixture of 0.24 g of hydroxyl-terminated polybutadiene and 0.04 g of isophorone diisocyanate, and then stirred well and then charged into a glass tube containing the sixth product. The migration was recorded weekly by placing it at 50℃and the results are shown in FIG. 1.
Example 5:
1) 0.95 g of ammonium perchlorate is ground, then 0.05 g of dendritic polymer taking ferrocene as a branching unit is added, and grinding and mixing are continued to be uniform.
2) 1.00 g of ammonium perchlorate are ground without adding a catalyst for accelerating combustion as reference.
3) The weight loss at 50-500 ℃ was recorded by using a thermogravimetric instrument, and the specific data is shown in fig. 2.
Example 6:
1) 0.97 g of ammonium perchlorate is ground, then 0.03 g of dendritic polymer taking ferrocene as a branching unit is added, and grinding and mixing are continued to be uniform.
2) 1.00 g of ammonium perchlorate are ground without adding a catalyst for accelerating combustion as reference.
3) The loss of weight at 50-500℃was recorded by using a thermogravimetric instrument.
Claims (10)
1. The anti-migration ferrocenyl dendritic polymer burning rate catalyst is characterized in that the ferrocenyl dendritic polymer burning rate catalyst takes a ferrocenyl compound as a core, and the ferrocenyl compound is connected through a branched structure formed by the reaction of an amino compound and an acrylate compound, so that a dendritic structure is constructed.
2. The anti-migration ferrocenyl dendrimer combustion catalyst according to claim 1, wherein the ferrocenyl compound comprises ferrocenecarboxylic acid, ferrocenecarboxylic acid chloride, 1-ferrocenedicarboxylic acid and 1, 1-ferrocenedicarboxylic acid chloride.
3. An anti-migration ferrocenyl dendrimer burn rate catalyst according to claim 1, wherein the amino compound comprises N-Boc-ethylenediamine, propylenediamine and butylenediamine.
4. The anti-migration ferrocenyl dendrimer combustion catalyst according to claim 1, wherein the acrylate compound comprises methyl acrylate, methyl methacrylate and hydroxyethyl acrylate.
5. A method for preparing an anti-migration ferrocenyl dendrimer combustion catalyst according to any one of claims 1 to 4, wherein the preparation method comprises the following steps:
1) Dispersing single-end protected amino compound in methanol in ice water bath, adding acrylic ester compound in a dropwise manner, stirring at room temperature for reaction, and removing excessive acrylic ester compound and methanol by rotary evaporation after the reaction is finished to obtain a first product;
2) Dissolving the first product in methanol, slowly dropwise adding an amino compound, and stirring at room temperature for reaction; after the reaction is finished, removing redundant amino compounds and methanol by rotary evaporation to obtain a second product;
3) Under the protection of argon, dissolving the second product in anhydrous dichloromethane, then adding an acid binding agent, slowly dropwise adding an anhydrous dichloromethane solution containing a single-functional ferrocenyl compound, stirring at room temperature for reaction, and after the reaction is finished, obtaining a third product through washing, column chromatography purification and drying;
4) Dissolving the third product in dichloromethane, slowly adding trifluoroacetic acid to remove tert-butoxycarbonyl in the third product, and removing excessive trifluoroacetic acid and dichloromethane by rotary evaporation to obtain a fourth product;
5) Under the protection of argon, dissolving the fourth product in anhydrous dichloromethane, adding an acid binding agent, dropwise adding an anhydrous dichloromethane solution containing a difunctional ferrocenyl compound, stirring at room temperature for reaction, and washing, purifying by column chromatography and drying after the reaction is finished to obtain the ferrocenyl dendritic polymer combustion speed catalyst.
6. The method for preparing the anti-migration ferrocenyl dendrimer fuel rate catalyst according to claim 5, wherein in the step 1), the molar amount of the acrylate compound is 5-10 times that of the single-end protected amino compound;
in step 2), the molar amount of amino compound is 10-20 times that of the first product.
7. The method for preparing the anti-migration ferrocenyl dendrimer fuel rate catalyst according to claim 5, wherein in the step 3), the mono-functionalized ferrocenyl compound is ferrocenecarboxylic acid or ferrocenecarboxchloride, and the molar amount of the mono-functionalized ferrocenyl compound is 3-4 times that of the second product;
in the step 5), the difunctional ferrocenyl compound is 1, 1-ferrocene dicarboxylic acid or 1, 1-ferrocene dicarboxylic acid chloride, and the molar amount of the difunctional ferrocenyl compound is 1 time that of the fourth product.
8. A composite solid propellant comprising an anti-migration ferrocenyl dendrimer burn rate catalyst according to claim 1 or 5.
9. A method of preparing a composite solid propellant according to claim 8, comprising the steps of:
1) Grinding ammonium perchlorate, adding a ferrocenyl dendritic polymer burning rate catalyst, and continuously grinding and uniformly mixing to obtain a fifth product;
2) And uniformly mixing hydroxyl-terminated polybutadiene and isophorone diisocyanate to obtain a sixth product, adding the fifth product into the sixth product in batches, uniformly stirring, recharging into a container, and curing for 7-10 days to obtain the composite solid propellant.
10. The preparation method and the application of the ferrocenyl dendritic polymer burning-rate catalyst according to claim 9, wherein in the step 1), the mass portion of ammonium perchlorate is 60-70 portions, and the mass portion of the ferrocenyl dendritic polymer burning-rate catalyst is 1-10 portions.
In the step 2), the weight portion of the hydroxyl-terminated polybutadiene is 10-30 portions, the weight portion of the isophorone diisocyanate is 1-10 portions, and the curing temperature is 50-80 ℃.
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