A ferrocene-based hyperbranched polymer catalyst against migration, a preparation method thereof and application thereof
By preparing an anti-migration ferrocene-based hyperbranched polymer combustion rate catalyst, the migration problem of ferrocene-based combustion rate catalysts was solved, the catalytic efficiency was improved, and the thermal decomposition temperature of ammonium perchlorate was reduced, thus achieving safe and efficient catalytic performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ZHEJIANG UNIV
- Filing Date
- 2023-06-26
- Publication Date
- 2026-07-10
AI Technical Summary
Existing ferrocene-based combustion rate catalysts exhibit migration, which affects catalytic efficiency, and ultrafine ammonium perchlorate powder poses a hazard during preparation and storage.
A hyperbranched polymer combustion rate catalyst with anti-migration was prepared by using ferrocene-based compounds and amino compounds to form a hyperbranched structure through an amidation reaction. The catalyst's anti-migration ability and catalytic performance were improved by combining ammonium perchlorate and other additives to form hydrogen bonds and other forces.
This study achieved the long-term non-migration and non-volatilization of ferrocene-based hyperbranched polymer combustion rate catalyst at 50°C, thereby reducing the thermal decomposition temperature of ammonium perchlorate and improving catalytic efficiency.
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Abstract
Description
Technical Field
[0001] This invention relates to a combustion rate catalyst in the field of aerospace energy catalysis, specifically to an anti-migration ferrocene-based hyperbranched polymer combustion rate catalyst, its preparation method, and its application. Background Technology
[0002] Ammonium perchlorate, as one of the most common oxidizers in composite solid propellants, directly determines the final combustion of the propellant due to its thermal decomposition performance. Lowering the thermal decomposition temperature and increasing its thermal decomposition rate are considered effective ways to improve its thermal decomposition performance. Practice has shown that using ultrafine ammonium perchlorate or catalysts can significantly improve its thermal decomposition performance. However, ultrafine ammonium perchlorate powder is accompanied by many potential hazards during preparation and storage. Therefore, the use of catalysts has become the most common method. Since the catalyst content in composite solid propellants is relatively low, maximizing catalytic efficiency is crucial for catalyst design.
[0003] Over the past few decades, ferrocene-based compounds have attracted widespread attention as combustion rate catalysts. However, commonly used ferrocene-based combustion rate catalysts generally exhibit migration phenomena, such as n-butylferrocene, tert-butylferrocene, and catoxine. Summary of the Invention
[0004] To address the shortcomings of existing ferrocene-based combustion rate catalysts, this invention provides a method for preparing a migration-resistant ferrocene-based hyperbranched polymer combustion rate catalyst. The ferrocene-based hyperbranched polymer combustion rate catalyst exhibits excellent migration resistance and combustion rate catalytic performance. It can remain free from migration and volatilization for extended periods at 50°C, while simultaneously lowering the thermal decomposition temperature of ammonium perchlorate.
[0005] The objective of this invention is achieved through the following technical solution:
[0006] I. A Ferrocene-based Hyperbranched Polymer Combustion Rate Catalyst with Anti-migration
[0007] The ferrocene-based hyperbranched polymer combustion rate catalyst forms a hyperbranched structure through an amidation reaction using ferrocene-based compounds and amino compounds as monomers.
[0008] The ferrocene-based compounds include 1,1-ferrocene dicarboxylic acid or 1,1-ferrocene dicarboxylic chloride.
[0009] The amino compounds mentioned include tris(2-aminoethyl)amine.
[0010] II. A method for preparing a ferrocene-based hyperbranched polymer combustion rate catalyst with anti-migration properties
[0011] 1) The ferrocene-based compound and the catalyst were dissolved in N,N-dimethylformamide solvent, and the carboxyl group in the ferrocene-based compound was activated by stirring at room temperature for 30 min to obtain the first product;
[0012] 2) The amino compound was dispersed in N,N-dimethylformamide solvent and then slowly added dropwise to the first product. The reaction was stirred at room temperature. After the reaction was completed, deionized water was added to precipitate the product. After filtration, washing and vacuum drying, the ferrocene-based hyperbranched polymer combustion rate catalyst was obtained.
[0013] In 1), the molar amount of catalyst is 0.5-4 times that of the ferrocene-based compound;
[0014] In step 2), the molar amount of the amino compound is 0.5-2 times that of the ferrocene-based compound.
[0015] III. A composite solid propellant
[0016] The composite solid propellant includes the aforementioned anti-migration ferrocene-based hyperbranched polymer burning rate catalyst.
[0017] IV. A method for preparing a composite solid propellant
[0018] 1) Ammonium perchlorate and ferrocene-based hyperbranched polymer combustion rate catalyst were dissolved in N,N-dimethylformamide to obtain the second product;
[0019] 2) Under stirring conditions, the second product was slowly added dropwise to ethyl acetate. After the addition was complete, the third product was obtained by centrifugation, drying and sieving.
[0020] 3) After mixing hydroxyl-terminated polybutadiene and isophorone diisocyanate evenly, the fourth product is obtained. The third product is added to the fourth product in batches and stirred evenly before being filled into a container. After curing for 7-10 days, a composite solid propellant is obtained.
[0021] In step 1), the mass fraction of ammonium perchlorate is 60-70 parts, and the mass fraction of ferrocene-based hyperbranched polymer combustion rate catalyst is 1-10 parts.
[0022] In step 3), the mass fraction of hydroxyl-terminated polybutadiene is 10-30 parts, the mass fraction of isophorone diisocyanate is 1-10 parts, and the curing temperature is 50-80℃.
[0023] The beneficial effects of this invention are as follows:
[0024] The ferrocene-based hyperbranched polymer combustion rate catalyst of the present invention has a high ferrocene content, which can effectively improve catalytic performance. Simultaneously, the introduction of a large number of amide groups enables the formation of hydrogen bonds and other interactions with ammonium perchlorate and other additives, making the combustion rate catalyst of the present invention less prone to migration and volatilization under natural conditions. Attached Figure Description
[0025] Figure 1 This is a schematic diagram showing the migration of the ferrocene-based hyperbranched polymer combustion rate catalyst prepared in this invention in a simulated propellant.
[0026] Figure 2 Thermogravimetric curve of ammonium perchlorate decomposition catalyzed by the ferrocene-based hyperbranched polymer combustion rate catalyst prepared in this invention. Detailed Implementation
[0027] The present invention will be described in more detail below with reference to the embodiments, but the implementation of the present invention is not limited thereto.
[0028] The following are examples of implementations of the present invention:
[0029] Example 1
[0030] 1) Dissolve 1.1071 g of 1,1'-ferrocene dicarboxylic acid, 2.3393 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.1562 g of 4-dimethylaminopyridine, and 0.1570 g of 1-hydroxybenzotriazole in 40 mL of N,N-dimethylformamide solvent. Stir at room temperature to activate the carboxyl group in the ferrocene compound for 30 min to obtain the first product.
[0031] 2) 0.3129 g of tris(2-aminoethyl)amine was dispersed in 5 mL of N,N-dimethylformamide solvent, and then slowly added dropwise to the first product. The mixture was stirred and reacted at room temperature for 24 h. After the reaction was completed, deionized water was added to precipitate the product, and the ferrocene-based hyperbranched polymer combustion rate catalyst was obtained by filtration, washing, and vacuum drying.
[0032] Example 2
[0033] 1) Dissolve 1.1194 g of 1,1'-ferrocene dicarboxylic acid, 2.3298 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.1567 g of 4-dimethylaminopyridine and 0.1537 g of 1-hydroxybenzotriazole in 40 mL of N,N-dimethylformamide solvent, and stir at room temperature to activate the carboxyl group in the ferrocene compound for 30 min to obtain the first product.
[0034] 2) 0.4506 g of tris(2-aminoethyl)amine was dispersed in 5 mL of N,N-dimethylformamide solvent, and then slowly added dropwise to the first product. The mixture was stirred and reacted at room temperature for 24 h. After the reaction was completed, deionized water was added to precipitate the product, and the ferrocene-based hyperbranched polymer combustion rate catalyst was obtained by filtration, washing, and vacuum drying.
[0035] Example 3:
[0036] 1) Dissolve 1.1019 g of 1,1'-ferrocene dicarboxylic acid, 2.3452 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 0.1582 g of 4-dimethylaminopyridine and 0.1521 g of 1-hydroxybenzotriazole in 40 mL of N,N-dimethylformamide solvent, and stir at room temperature to activate the carboxyl group in the ferrocene compound for 30 min to obtain the first product.
[0037] 2) 0.5931 g of tris(2-aminoethyl)amine was dispersed in 5 mL of N,N-dimethylformamide solvent, and then slowly added dropwise to the first product. The mixture was stirred and reacted at room temperature for 24 h. After the reaction was completed, deionized water was added to precipitate the product, and the ferrocene-based hyperbranched polymer combustion rate catalyst was obtained by filtration, washing, and vacuum drying.
[0038] Example 4
[0039] 1) Dissolve 1.62 g of ammonium perchlorate and 0.10 g of ferrocene-based hyperbranched polymer combustion rate catalyst in 1 mL of N,N-dimethylformamide to obtain the second product.
[0040] 2) Under stirring conditions, the second product was slowly added dropwise to 30 mL of ethyl acetate. After the addition was completed, the third product was obtained by centrifugation, drying and sieving.
[0041] 3) Mix 0.24g of hydroxyl-terminated polybutadiene and 0.04g of isophorone diisocyanate evenly to obtain the fourth product. Add the third product in batches to the fourth product and stir evenly. Then fill the mixture into a transparent glass tube and cure it at 70°C for 7 days to obtain a composite solid propellant.
[0042] 4) Grind 1.62g of ammonium perchlorate and add it in batches to a mixture of 0.24g of hydroxyl-terminated polybutadiene and 0.04g of isophorone diisocyanate. Stir well and then fill the mixture into a glass tube containing the composite solid propellant. Place the tube at 50℃ and record its migration weekly. The results are as follows: Figure 1 As shown, after 28 days, no migration of the ferrocene-based hyperbranched polymer combustion rate catalyst was observed, and a clear interface was still visible.
[0043] Example 5
[0044] 1) Dissolve 1.60 g of ammonium perchlorate and 0.12 g of ferrocene-based hyperbranched polymer combustion rate catalyst in 1 mL of N,N-dimethylformamide to obtain the second product.
[0045] 2) Under stirring conditions, the second product was slowly added dropwise to 30 mL of ethyl acetate. After the addition was completed, the third product was obtained by centrifugation, drying and sieving.
[0046] 3) Mix 0.24g of hydroxyl-terminated polybutadiene and 0.04g of isophorone diisocyanate evenly to obtain the fourth product. Add the third product in batches to the fourth product and stir evenly. Then fill the mixture into a transparent glass tube and cure it at 70°C for 7 days to obtain a composite solid propellant.
[0047] 4) Grind 1.62g of ammonium perchlorate and add it in batches to a mixture of 0.24g of hydroxyl-terminated polybutadiene and 0.04g of isophorone diisocyanate. Stir well and then fill the mixture into a glass tube containing the composite solid propellant. Place the tube at 50°C and record its migration weekly.
[0048] The weight loss of the third product and pure ammonium perchlorate in Example 4 above was recorded using a thermogravimetric analyzer at 50-500°C. Specific data are as follows: Figure 2 As shown, the thermal decomposition endpoint temperature of pure ammonium perchlorate is 404℃, while the thermal decomposition endpoint temperature of ammonium perchlorate coated with ferrocene-based hyperbranched polymer drops to 335℃, exhibiting a significant catalytic effect.
[0049] The above embodiments are used to explain and illustrate the present invention, but not to limit the present invention. Any modifications and changes made to the present invention within the spirit and scope of the claims shall fall within the protection scope of the present invention.
Claims
1. A ferrocene-based hyperbranched polymer combustion rate catalyst with resistance to migration, characterized in that, The ferrocene-based hyperbranched polymer combustion rate catalyst forms a hyperbranched structure through an amidation reaction using ferrocene-based compounds and amino compounds as monomers; the amino compound is tris(2-aminoethyl)amine. The ferrocene-based compound is 1,1'-ferrocene dicarboxylic acid.
2. The method for preparing an anti-migration ferrocene-based hyperbranched polymer combustion rate catalyst according to claim 1, characterized in that, The preparation method includes the following steps: 1) The ferrocene-based compound and the catalyst were dissolved in N,N-dimethylformamide solvent, and the carboxyl group in the ferrocene-based compound was activated by stirring at room temperature to obtain the first product; 2) The amino compound was dispersed in N,N-dimethylformamide solvent and then added dropwise to the first product. The reaction was stirred at room temperature. After the reaction was completed, deionized water was added to precipitate the product. After filtration, washing and vacuum drying, the ferrocene-based hyperbranched polymer combustion rate catalyst was obtained.
3. The method for preparing an anti-migration ferrocene-based hyperbranched polymer combustion rate catalyst according to claim 2, characterized in that, In 1), the molar amount of catalyst is 0.5-4 times that of the ferrocene-based compound.
4. The method for preparing an anti-migration ferrocene-based hyperbranched polymer combustion rate catalyst according to claim 2, characterized in that, In step 2), the molar amount of the amino compound is 0.5-2 times that of the ferrocene-based compound.
5. A composite solid propellant, characterized in that, The catalyst includes the anti-migration ferrocene-based hyperbranched polymer combustion rate catalyst as described in claim 1.
6. The method for preparing a composite solid propellant according to claim 5, characterized in that, The preparation method includes the following steps: 1) Ammonium perchlorate and ferrocene-based hyperbranched polymer combustion rate catalyst were dissolved in N,N-dimethylformamide to obtain the second product; 2) Under stirring conditions, the second product was added dropwise to ethyl acetate. After the addition was complete, the third product was obtained by centrifugation, drying and sieving. 3) After mixing hydroxyl-terminated polybutadiene and isophorone diisocyanate evenly, the fourth product is obtained. The third product is added to the fourth product in batches and stirred evenly before being filled into a container. After curing for 7-10 days, a composite solid propellant is obtained.
7. The method for preparing a composite solid propellant according to claim 6, characterized in that, In step 1), the mass fraction of ammonium perchlorate is 60-70 parts, and the mass fraction of ferrocene-based hyperbranched polymer combustion rate catalyst is 1-10 parts.
8. The method for preparing a composite solid propellant according to claim 6, characterized in that, In step 3), the mass fraction of hydroxyl-terminated polybutadiene is 10-30 parts, the mass fraction of isophorone diisocyanate is 1-10 parts, and the curing temperature is 50-80℃.