A ricinoleic acid amide compound, a preparation method and a method for improving the performance of a propellant

Abstract

The application provides a ricinoleic acid amide compound, a preparation method and a method for improving propellant performance, and the method for improving propellant performance comprises the following steps: adding the ricinoleic acid amide compound into a solid propellant with a solid content greater than or equal to 90%, so as to be used as an additive for reducing the viscosity of a solid propellant slurry, improving the flow leveling property of the solid propellant slurry and improving the elongation at break of the solid propellant. The ricinoleic acid amide compound provided by the application can significantly improve the wetting state of solid particles and a binder system of the propellant, so that the solid particles are easily dispersed, the structural strength hindering the flow in the slurry is reduced, the yield value and the viscosity of the slurry are reduced, and the flow leveling index of the slurry is improved. In addition, the ricinoleic acid amide compound can realize dispersion of stress concentration at low temperature, and can improve the mechanical properties of the solid propellant while improving the process performance of the solid propellant.

Description

Technical Field

[0001] This invention belongs to the field of solid propellant technology, and relates to process aids for solid propellants, specifically to a castor oil amide compound, its preparation method, and a method for improving propellant performance. Background Technology

[0002] Composite solid propellants are composite material systems composed of high-energy oxidizers, metallic fuels, binders, curing agents, plasticizers, and various functional materials (such as bonding agents, process aids, and combustion catalysts). Their manufacturing process mainly includes three steps: slurry mixing, casting, and curing. Among these, propellant mixing and casting are processes carried out while the slurry is in a flowing state. Key process parameters such as the slurry's viscosity, yield value, and leveling index directly affect the mixing and casting processes of the propellant slurry.

[0003] In order to improve the process performance of propellant slurry, a small amount of process aids can usually be added to the propellant formulation. According to function, process aids mainly include: (1) particle interface performance improvement type, such as methyl stearate, methyl oleate, lecithin, British detergent, phosphorus-containing compounds and amide compounds (or polymers), which can increase the surface wetting of solid particles and reduce particle agglomeration. Among them, amide process aids mainly include amide compounds and polyamides, which have strong polarity in structure and are easy to migrate to the surface of ammonium perchlorate in the system, improving the interface performance between the binder and ammonium perchlorate. Although amide process aids can improve the process performance of HTPB propellant slurry, their application effect is not good in high solid content propellant formulations with solid content >90%. In addition, although amide compounds can reduce the viscosity of propellant, they will affect the mechanical properties of propellant. (2) delayed curing reaction type, such as cottonseed alcohol, styrene C-16, etc., can inhibit the catalytic effect of transition metal oxide burning rate catalysts on the curing reaction and prolong the pot life of slurry. (3) Diluting agents, such as styrene, can reduce the viscosity of the slurry to a certain extent when added in appropriate amounts.

[0004] In recent years, with the increasing demand for high-solids-content composite solid propellants and novel high-energy solid propellants, the requirements for the mechanical and processing properties of propellant slurries have become more stringent. Existing process aids are insufficient to meet the requirements of high-solids-content propellant and novel high-energy solid propellant formulations regarding both mechanical and processing properties. Therefore, there is an urgent need to develop multifunctional process aids that combine both processing and mechanical properties. Summary of the Invention

[0005] In view of the defects and deficiencies of the existing technology, one of the objectives of the present invention is to provide a castor oil amide compound, a preparation method and a method for improving propellant performance, thereby solving the technical problem that amide process aids in the prior art have poor application effects in high solid content propellant formulations with a solid content of ≥90%.

[0006] In view of the defects and deficiencies of the existing technology, another objective of the present invention is to provide a castor oil amide compound, a preparation method and a method for improving propellant performance, thereby solving the technical problem that amide process aids in the prior art are unable to simultaneously improve the process performance and mechanical properties of solid propellants.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] A method for improving propellant performance, the method comprising: adding a ricinoleic acid amide compound to a solid propellant with a solid content of ≥90%, as an adjuvant to reduce the viscosity of the solid propellant slurry, improve the leveling properties of the solid propellant slurry, and improve the elongation at break of the solid propellant; the chemical structural formula of the ricinoleic acid amide compound is shown in Formula I:

[0009]

[0010] The present invention also has the following technical features:

[0011] Specifically, the amount of the castor oil amide compound added to the solid propellant is 0.05–0.1 wt.%.

[0012] Specifically, the solid propellant is composed of the following raw materials: hydroxyl-terminated polybutadiene, dioctyl sebacate, toluene diisocyanate, triphenylbismuth, iron acetylacetone, ammonium perchlorate, octogen, and aluminum powder.

[0013] Specifically, the solid propellant, by mass percentage, is composed of the following raw materials: 5-8% hydroxyl-terminated polybutadiene, 3-5% dioctyl sebacate, 0.3-0.5% toluene diisocyanate, 0.02-0.05% triphenylbismuth, 0.01-0.05% ferric acetylacetone, 20-30% ammonium perchlorate, 30-50% octogen, and 20-30% aluminum powder.

[0014] Specifically, the preparation method of the ricinoleic acid amide compounds includes the following steps: N-oleo-1,3-propanediamine and ricinoleic acid are added to a reaction vessel, and the temperature is raised to 160-180°C under stirring and kept at a constant temperature for 1-3 hours. When no water is produced in the reaction, the temperature is lowered to 0-10°C using an ice-water bath. Then, acrylonitrile is added dropwise while maintaining the reaction temperature at 0-10°C. After the addition of 2-hydroxyethyl acrylate is completed, the temperature is raised to 60-80°C and kept at a constant temperature for 1-3 hours. After the reaction is completed, the resulting reaction product is distilled under reduced pressure to obtain the ricinoleic acid amide compounds.

[0015] Specifically, the molar ratio of N-oleo-1,3-propanediamine to ricinoleic acid is 1:(1 to 1.05).

[0016] Specifically, the molar ratio of N-oleo-1,3-propanediamine to acrylonitrile is 1:1.

[0017] The present invention also protects the castor oil amide compounds as described above.

[0018] The present invention also protects the preparation method of the castor oil amide compound as described above.

[0019] The beneficial technical effects of this invention compared to the prior art are as follows:

[0020] (I) The ricinoleic acid amide compounds provided by this invention can significantly improve the wetting state of the solid particles and binder system of the propellant, making the solid particles easier to disperse, reducing the structural strength that hinders flow inside the slurry, reducing the yield value and viscosity of the slurry, increasing the leveling index of the slurry, and improving the process performance of solid propellants. The ricinoleic acid amide compounds have good application effects in solid propellants with a solid content of ≥90%.

[0021] (II) The castor oil amide compounds provided by this invention can form ionic bonds with ammonium perchlorate through the orbital effect of nitrogen atoms, and introduce cyano groups with an inductive effect on solid fillers into the polyene-polyamine structure, thereby achieving dispersion of stress concentration at low temperatures. While improving the processing performance of solid propellants, they can also improve their mechanical properties; furthermore, the hydroxyl groups in their molecular structure can participate in the curing reaction, improving the interfacial adhesion between the solid filler and the binder matrix, further improving the mechanical properties of the solid propellant.

[0022] The technical solution of the present invention will be further described below with reference to the embodiments. Detailed Implementation

[0023] It should be noted that, unless otherwise specified, all raw materials used in this invention are those known in the art.

[0024] Following the above technical solutions, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0025] Example 1:

[0026] This embodiment provides a method for preparing ricinoleic acid amide compounds. The method specifically includes the following steps: 324.6 g (1 mol) of N-oleo-1,3-propanediamine and 298.5 g (1 mol) of ricinoleic acid are added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, and dehydration separator. The mixture is slowly heated to 160 °C under stirring and reacted at this temperature for 3 h. When no water is produced, the mixture is slowly cooled to 0 °C using an ice-water bath. Then, the dehydration separator is removed and a constant-pressure dropping funnel is installed. 53.1 g (1 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile addition is complete, the mixture is slowly heated to 60 °C and reacted at this temperature for 3 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 650.2 g of a pale yellow, oily, transparent liquid, with a yield of 98.8%.

[0027] In this embodiment, the final pale yellow, oily, transparent liquid product was analyzed, and its characterization data are as follows:

[0028] Infrared spectra (KBr, cm⁻¹): 3208, 3023, 2883, 2841, 2724, 1721, 1611, 1515, 1479, 1209, 1191, 953, 889;

[0029] 1H NMR spectrum 1 HNMR (400MHz, CDCl3, δ, ppm): 0.88s (6H, CH3), 1.26 ~ 1.40br. (48H, CH2), 1.54t (4H, CH2), 1.73d (2H, CH2), 2.13 ~ 2.16t (10H, CH2) 2),2.36t(2H,CH2),2.73t(2H,CH2),3.01t(4H,CH2),3.41~3.53dt(4H,CH2),4.77br.(1H,OH),5.36q(4H,CH);7.70s(1H,NH).

[0030] Carbon NMR Spectroscopy 13 C NMR (400MHz, CDCl3, δ, ppm): 14.1, 17.1, 22.5, 25.5, 27.7, 29.0, 29.3, 37.9, 40.7, 51.4, 55.7, 56.4, 71.7, 119.1, 126.9, 130.6, 133.2, 172.6.

[0031] Elemental analysis (%): C 76.62, H 12.08, N 6.28;

[0032] Hydroxyl value: 1.5182 mmol / g (theoretical value 1.5195 mmol / g).

[0033] Based on the above characterization data, the chemical structural formula of the product can be deduced as shown in Formula I:

[0034]

[0035] The compound is a castor oil amide compound, named (Z)-N-(3-((2-cyanoethyl)((Z)-octadecane-9-en-1-yl)amino)propyl)-12-hydroxyoctadecane-9-enamide.

[0036] Example 2:

[0037] This embodiment provides a method for preparing ricinoleic acid amide compounds. The method specifically includes the following steps: 324.6 g (1 mol) of N-oleo-1,3-propanediamine and 313.4 g (1.05 mol) of ricinoleic acid are added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, and dehydration separator. The mixture is slowly heated to 180 °C under stirring and reacted at this temperature for 1 h. When no water is produced, the mixture is slowly cooled to 0 °C using an ice-water bath. Then, the dehydration separator is removed and a constant-pressure dropping funnel is installed. 53.1 g (1 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile addition is complete, the mixture is slowly heated to 80 °C and reacted at this temperature for 2 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 647.6 g of a pale yellow, oily, transparent liquid, with a yield of 98.4%.

[0038] In this embodiment, the final obtained pale yellow oily transparent liquid product was analyzed, and its characterization data were consistent with those of Example 1.

[0039] Example 3:

[0040] This embodiment provides a method for preparing ricinoleic acid amide compounds. The method specifically includes the following steps: 324.6 g (1 mol) of N-oleo-1,3-propanediamine and 298.5 g (1 mol) of ricinoleic acid are added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, and dehydration separator. The mixture is slowly heated to 160 °C under stirring and reacted at this temperature for 3 h. When no water is produced, the mixture is slowly cooled to 0 °C using an ice-water bath. Then, the dehydration separator is removed and a constant-pressure dropping funnel is installed. 53.1 g (1 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile addition is complete, the mixture is slowly heated to 60 °C and reacted at this temperature for 2 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 641.7 g of a pale yellow, oily, transparent liquid, with a yield of 97.5%.

[0041] In this embodiment, the final obtained pale yellow oily transparent liquid product was analyzed, and its characterization data were consistent with those of Example 1.

[0042] Example 4:

[0043] This embodiment provides a method for preparing ricinoleic acid amide compounds. The method specifically includes the following steps: 324.6 g (1 mol) of N-oleo-1,3-propanediamine and 298.5 g (1 mol) of ricinoleic acid are added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, and dehydrator. The mixture is slowly heated to 170 °C under stirring and reacted at this temperature for 3 h. When no water is produced, the mixture is slowly cooled to 5 °C using an ice-water bath. Then, the dehydrator is removed and a constant-pressure dropping funnel is installed. 53.1 g (1 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile is added, the mixture is slowly heated to 80 °C and reacted at this temperature for 1 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 642.9 g of a pale yellow, oily, transparent liquid, with a yield of 97.7%.

[0044] In this embodiment, the final obtained pale yellow oily transparent liquid product was analyzed, and its characterization data were consistent with those of Example 1.

[0045] Example 5:

[0046] This embodiment provides a method for preparing ricinoleic acid amide compounds. The method specifically includes the following steps: 324.6 g (1 mol) of N-oleo-1,3-propanediamine and 298.5 g (1 mol) of ricinoleic acid are added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, and dehydration separator. The mixture is slowly heated to 170 °C under stirring and reacted at this temperature for 3 h. When no water is produced, the mixture is slowly cooled to 10 °C using an ice-water bath. Then, the dehydration separator is removed and a constant-pressure dropping funnel is installed. 53.1 g (1 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile is added, the mixture is slowly heated to 60 °C and reacted at this temperature for 1 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 639.0 g of a pale yellow, oily, transparent liquid, with a yield of 97.1%.

[0047] In this embodiment, the final obtained pale yellow oily transparent liquid product was analyzed, and its characterization data were consistent with those of Example 1.

[0048] Example 6:

[0049] This embodiment provides a method for preparing ricinoleic acid amide compounds. The method specifically includes the following steps: 324.6 g (1 mol) of N-oleo-1,3-propanediamine and 313.4 g (1.05 mol) of ricinoleic acid are added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, and dehydration separator. The mixture is slowly heated to 160 °C under stirring and reacted at this temperature for 2 h. When no water is produced, the mixture is slowly cooled to 5 °C using an ice-water bath. Then, the dehydration separator is removed, and a constant-pressure dropping funnel is installed. 53.1 g (1 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile is added, the mixture is slowly heated to 60 °C and reacted at this temperature for 1 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 645.6 g of a pale yellow, oily, transparent liquid, with a yield of 98.1%.

[0050] In this embodiment, the final obtained pale yellow oily transparent liquid product was analyzed, and its characterization data were consistent with those of Example 1.

[0051] Example 7:

[0052] This embodiment provides a method for improving propellant performance using ricinoleic acid amide compounds prepared in Examples 1 to 6. The specific process of this method is as follows: 0.05 wt.% of ricinoleic acid amide compounds are added to a solid propellant with a solid content of 90% as a bonding-type process aid to reduce the viscosity of the solid propellant slurry, improve the leveling properties of the solid propellant slurry, and improve the elongation at break of the solid propellant.

[0053] In this embodiment, the curing conditions used for testing process performance and mechanical properties were: curing time 180 h, curing temperature 50 °C. The basic formulation of the solid propellant is shown in Table 1.

[0054] Table 1. Solid propellant formulation composition of Example 7

[0055]

[0056]

[0057] Verification of the effect of Example 7:

[0058] The following results were obtained after adding 0.05 wt.% of ricinoleic acid amide compounds to the solid propellant formulation with a solid content of 90% shown in Table 1: The solid propellant with added ricinoleic acid amide process aids exhibited a falling ball viscosity range of 412 Pa·s after 1 hour, 1182 Pa·s after 6 hours, and a slurry leveling index of 1.58. Compared to the solid propellant without added ricinoleic acid amide process aids, the falling ball viscosity decreased by 10.43% after 1 hour, decreased by 6.19% after 6 hours, and increased the slurry leveling index by 41.07%. Furthermore, compared to the solid propellant without added ricinoleic acid amide process aids, the solid propellant with added ricinoleic acid amide process aids showed an increase in elongation at break of 9.12% at 20°C, an increase in elongation at break of 11.18% at 50°C, and an increase in elongation at break of 8.05% at -40°C. The above results demonstrate that using this castor oil amide compound as a process aid for solid propellants can significantly reduce slurry viscosity, significantly improve slurry leveling properties, and significantly increase elongation at break.

[0059] Example 8:

[0060] This embodiment provides a method for improving propellant performance using ricinoleic acid amide compounds prepared in Examples 1 to 6. The specific process of this method is as follows: 0.1 wt.% of ricinoleic acid amide compounds are added to a solid propellant with a solid content of 90% as a bonding-type process aid to reduce the viscosity of the solid propellant slurry, improve the leveling properties of the solid propellant slurry, and improve the elongation at break of the solid propellant.

[0061] In this embodiment, the curing conditions used for testing process performance and mechanical properties were: curing time 180 h, curing temperature 50 °C. The basic formulation of the solid propellant is shown in Table 2.

[0062] Table 2. Solid propellant formulation composition of Example 8

[0063]

[0064]

[0065] Effect verification of Example 8:

[0066] The following results were obtained after adding 0.1 wt.% of ricinoleic acid amide compounds to the solid propellant formulation with a solid content of 90% shown in Table 2: The solid propellant with added ricinoleic acid amide process aids exhibited a falling ball viscosity range of 383 Pa·s after 1 hour, 1075 Pa·s after 6 hours, and a slurry leveling index of 1.88. Compared to the solid propellant without added ricinoleic acid amide process aids, the falling ball viscosity decreased by 16.74% after 1 hour, decreased by 14.68% after 6 hours, and increased the slurry leveling index by 67.85%. Furthermore, compared to the solid propellant without added ricinoleic acid amide process aids, the solid propellant with added ricinoleic acid amide process aids showed an increase in elongation at break of 9.45% at 20°C, 12.44% at 50°C, and 9.44% at -40°C. The above results demonstrate that using this castor oil amide compound as a process aid for solid propellants can significantly reduce slurry viscosity, significantly improve slurry leveling properties, and significantly increase elongation at break.

[0067] Example 9:

[0068] This embodiment provides a method for improving propellant performance using ricinoleic acid amide compounds prepared in Examples 1 to 6. The specific process of this method is as follows: 0.08 wt.% of ricinoleic acid amide compounds are added to a solid propellant with a solid content of 90% as a bonding-type process aid to reduce the viscosity of the solid propellant slurry, improve the leveling properties of the solid propellant slurry, and improve the elongation at break of the solid propellant.

[0069] In this embodiment, the curing conditions used for testing process performance and mechanical properties were: curing time 180 h, curing temperature 50 °C. The basic formulation of the solid propellant is shown in Table 3.

[0070] Table 3. Solid propellant formulation composition of Example 9

[0071]

[0072] Verification of the effect of Example 9:

[0073] The following results were obtained after adding 0.08 wt.% of ricinoleic acid amide compounds to the solid propellant formulation with a solid content of 90% shown in Table 3: The solid propellant with added ricinoleic acid amide process aids exhibited a falling ball viscosity range of 405 Pa·s after 1 hour, 1155 Pa·s after 6 hours, and a slurry leveling index of 1.64. Compared to the solid propellant without added ricinoleic acid amide process aids, the falling ball viscosity decreased by 11.96% after 1 hour, decreased by 8.33% after 6 hours, and increased the slurry leveling index by 46.43%. Furthermore, compared to the solid propellant without added ricinoleic acid amide process aids, the solid propellant with added ricinoleic acid amide process aids showed an increase in elongation at break of 9.32% at 20°C, 12.12% at 50°C, and 9.07% at -40°C. The above results demonstrate that using this castor oil amide compound as a process aid for solid propellants can significantly reduce slurry viscosity, significantly improve slurry leveling properties, and significantly increase elongation at break.

Claims

1. A method for improving propellant performance, characterized in that, The method includes adding ricinoleic acid amide compounds to a solid propellant with a solid content of ≥90% as an adjuvant to reduce the viscosity of the solid propellant slurry and improve its flowability; The chemical structural formula of the castor oil amide compound is shown in Formula I: Formula I; The amount of the castor oil amide compound added to the solid propellant is 0.05–0.1 wt.%. The solid propellant is composed of the following raw materials: hydroxyl-terminated polybutadiene, dioctyl sebacate, toluene diisocyanate, triphenylbismuth, iron acetylacetone, ammonium perchlorate, octogen, and aluminum powder.

2. A method for improving propellant performance, characterized in that, The method includes adding ricinoleic acid amide compounds to solid propellants with a solid content of ≥90% as an additive to improve the elongation at break of the solid propellant; The chemical structural formula of the castor oil amide compound is shown in Formula I: Formula I; The amount of the castor oil amide compound added to the solid propellant is 0.05–0.1 wt.%. The solid propellant is composed of the following raw materials: hydroxyl-terminated polybutadiene, dioctyl sebacate, toluene diisocyanate, triphenylbismuth, iron acetylacetone, ammonium perchlorate, octogen, and aluminum powder.

3. The method for improving propellant performance as described in claim 1, characterized in that, The solid propellant, by mass percentage, is composed of the following raw materials: 5-8% hydroxyl-terminated polybutadiene, 3-5% dioctyl sebacate, 0.3-0.5% toluene diisocyanate, 0.02-0.05% triphenylbismuth, 0.01-0.05% ferric acetylacetone, 20-30% ammonium perchlorate, 30-50% octogen, and 20-30% aluminum powder.

4. The method for improving propellant performance as described in claim 1, characterized in that, The preparation method of the ricinoleic acid amide compounds specifically includes the following steps: N-oleo-1,3-propanediamine and ricinoleic acid are added to a reaction vessel, and the temperature is raised to 160-180°C under stirring and kept at a constant temperature for 1-3 hours. When no water is produced in the reaction, the temperature is lowered to 0-10°C using an ice-water bath. Then, acrylonitrile is added dropwise while maintaining the reaction temperature at 0-10°C. After the addition of 2-hydroxyethyl acrylate is completed, the temperature is raised to 60-80°C and kept at a constant temperature for 1-3 hours. After the reaction is completed, the obtained reaction product is distilled under reduced pressure to obtain the ricinoleic acid amide compounds.

5. The method for improving propellant performance as described in claim 4, characterized in that, The molar ratio of N-oleo-1,3-propanediamine to ricinoleic acid is 1:(1-1.05).

6. The method for improving propellant performance as described in claim 5, characterized in that, The molar ratio of N-oleo-1,3-propanediamine to acrylonitrile is 1:

1.

7. A ricinoleic acid amide compound, characterized in that, The chemical structural formula of the castor oil amide compound is shown in Formula I: Formula I.

8. A method for preparing the ricinoleic acid amide compound as described in claim 7, characterized in that, The method specifically includes the following steps: N-oleo-1,3-propanediamine and ricinoleic acid are added to a reaction vessel, and the temperature is raised to 160-180°C under stirring and kept at a constant temperature for 1-3 hours. When no water is produced in the reaction, the temperature is lowered to 0-10°C using an ice-water bath. Then, acrylonitrile is added dropwise while maintaining the reaction temperature at 0-10°C. After the addition of 2-hydroxyethyl acrylate is completed, the temperature is raised to 60-80°C and kept at a constant temperature for 1-3 hours. After the reaction is completed, the resulting reaction product is distilled under reduced pressure to obtain ricinoleic acid amide compounds.

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