Oleic acid modified polyene polyamine compound, preparation method and application thereof

Abstract

The application provides an oleic acid modified polyene polyamine compound, a preparation method and application thereof, and a chemical structural formula of the compound is shown in formula I: in the formula, n is a positive integer greater than or equal to 1 and less than or equal to 10. The compound can improve the process performance of a solid propellant and also can improve the mechanical property 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 an oleic acid-modified polyene polyamine compound, its preparation method, and its application. Background Technology

[0002] 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 process, playing a decisive role in the propellant's structural integrity and the stability of its internal ballistic performance.

[0003] In order to improve the process performance of propellant slurry, domestic and foreign solid propellant technicians have improved the flowability and leveling properties of propellant slurry and extended the trial period of slurry by selecting appropriate process aids. 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, whose structure has strong polarity and is 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 and styrene C-16, can inhibit the catalytic effect of transition metal oxide combustion rate catalysts on the curing reaction and extend the pot life of the slurry. (3) Dilution type, such as styrene, can reduce the viscosity of the slurry to a certain extent when added in appropriate amounts. However, most of these process aids have a single function. While improving the process performance of the slurry, they can also affect other properties of the propellant. For example, the mechanical properties of propellants with good process performance may deteriorate, while those with good mechanical properties may not meet the process performance requirements.

[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, the purpose of this invention is to provide an oleic acid-modified polyene polyamine compound, its preparation method and its application, so as to solve the technical problem that process aids in the existing technology are unable to simultaneously improve the process performance and mechanical properties of solid propellants.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0007] An oleic acid-modified polyene polyamine compound, the chemical structural formula of which is shown in Formula I:

[0008] Formula I;

[0009] In the formula: n is a positive integer greater than or equal to 1 and less than or equal to 10.

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

[0011] Preferably, n is 1, 2 or 3.

[0012] This invention also protects a method for preparing the oleic acid-modified polyene polyamine compound as described above, the method specifically comprising the following steps: adding an ethyleneamine compound to a reaction vessel, cooling it to 0-5°C under stirring conditions via an ice bath, then adding acrylonitrile dropwise while maintaining the reaction temperature at 0-10°C; after the acrylonitrile dropwise addition is complete, raising the temperature to 60-80°C and reacting at a constant temperature for 1-3 hours; after the reaction is complete, cooling it to 30°C via a water bath, then adding oleic acid dropwise while maintaining the reaction temperature at 30-40°C; after the oleic acid dropwise addition is complete, raising the temperature to 40-50°C and reacting at a constant temperature for 6 hours; after the reaction is complete, distilling the resulting reaction product under reduced pressure to obtain the oleic acid-modified polyene polyamine compound.

[0013] Specifically, the ethyleneamine compounds are tetraethylenepentamine, diethylenetriamine, or triethylenetetraamine.

[0014] Specifically, the molar ratio of the ethyleneamine compound to acrylonitrile is 1:2.

[0015] Specifically, the molar ratio of the ethyleneamine compound to oleic acid is 1:(1-3).

[0016] The present invention also protects the use of the oleic acid-modified polyene polyamine compounds as described above in solid propellants.

[0017] Specifically, the method of this application includes adding oleic acid-modified polyene polyamine compounds to solid propellants as an adjuvant to reduce the viscosity of solid propellant slurry and improve the leveling properties of solid propellant slurry.

[0018] Specifically, the method of this application includes adding oleic acid-modified polyene polyamine compounds to solid propellants as an additive to improve the elongation at break of solid propellants.

[0019] Preferably, the amount of the oleic acid-modified polyene polyamine compound added to the solid propellant is 0.05 wt.%.

[0020] The beneficial technical effects of this invention compared to the prior art are as follows:

[0021] The oleic acid-modified polyene-polyamine compound 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 within the slurry, lowering the yield value and viscosity of the slurry, increasing the leveling index of the slurry, and improving the processing performance of the solid propellant. Simultaneously, this oleic acid-modified polyene-polyamine compound can form ionic bonds with ammonium perchlorate through the orbital effect of nitrogen atoms, and introduces cyano groups with an inductive effect on the solid filler into the polyene-polyamine structure, achieving stress concentration at low temperatures during dispersion. This improves both the processing performance and mechanical properties of the solid propellant. Furthermore, the hydroxyl groups in the compound's 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 oleic acid-modified polyene polyamine compounds. The method specifically includes the following steps: 189 g (1 mol) of tetraethylenepentamine is added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, constant pressure dropping funnel, and ice bath. The mixture is cooled to 0 °C under stirring conditions using an ice bath, and then 106 g (2 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile addition is complete, the temperature is slowly raised to 80 °C and maintained at this temperature for 3 h. After the reaction is complete, the temperature is lowered to 30 °C using a water bath, and then 847.38 g (3 mol) of oleic acid is slowly added dropwise while maintaining the reaction temperature at 30–40 °C. After the oleic acid addition is complete, the temperature is slowly raised to 50 °C and maintained at this temperature for 6 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 1127.5 g of a pale yellow, oily, transparent liquid, with a yield of 98.7%.

[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): 3411, 3265, 3154, 2988, 2923, 2832, 2165, 1620, 1558, 1448, 1311, 1095, 983, 891;

[0029] 1H NMR spectrum 1 HNMR (400 MHz, CDCl3, d , ppm): 0.87t (9H, CH3), 1.21t (6H, CH3), 1.24~1.31br (54H, CH2), 1.58t (6H, CH2), 2.16br (6H, CH2), 2.38br (6H, CH2), 3.29t (2H, NH), 3.41~4.22dt(4H, CH2),

[0030] 3.73q (2H, CH), 4.07s (4H, CH2), 5.36q (6H, CH); 7.22s (4H, NH2).

[0031] Carbon NMR Spectroscopy 13 CNMR (400 MHz, CDCl3, d , ppm): 14.2, 18.9, 22.7, 25.7, 27.5, 29.9, 31.9, 37.6, 46.4, 116.2, 130.6, 183.5.

[0032] Elemental analysis (%): C 70.85, H 11.38, N 8.94.

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

[0034] Formula I;

[0035] In this embodiment, n in formula I is 3, and its theoretical molecular formula is C. 65 H 125 N7O6 is an oleic acid-modified polyene polyamine compound.

[0036] Example 2:

[0037] This embodiment provides a method for preparing oleic acid-modified polyene polyamine compounds. The method specifically includes the following steps: 103.17 g (1 mol) of diethylenetriamine is added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, constant pressure dropping funnel, and ice bath. The mixture is cooled to 5 °C under stirring conditions using an ice bath, and then 106 g (2 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile is added, the temperature is slowly raised to 60 °C and maintained for 3 hours. After the reaction is complete, the temperature is lowered to 30 °C using a water bath, and then 282.5 g (1 mol) of oleic acid is slowly added dropwise while maintaining the reaction temperature at 30–40 °C. After the oleic acid is added, the temperature is slowly raised to 40 °C and maintained for 6 hours. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 482.8 g of a pale yellow, oily, transparent liquid, with a yield of 98.2%.

[0038] In this embodiment, the final pale yellow, oily, transparent liquid product was analyzed, and its characterization data are as follows:

[0039] Infrared spectra (KBr, cm⁻¹): 3405, 3251, 3172, 2985, 2927, 2830, 2155, 1650, 1554, 1449, 1312, 1098, 985, 894;

[0040] 1H NMR spectrum 1 HNMR (400 MHz, CDCl3, d, ppm): 0.82t (3H, CH3), 1.22t (2H, CH3), 1.24~1.33br (18H, CH2), 1.59t (3H, CH2), 2.18br (3H, CH2), 2.36br (2H, CH2), 3.26t (2H, NH), 3.39~4.18dt (4H, CH2), 3.73q (2H, CH), 4.11s (4H, CH2), 5.43q (6H, CH); 7.25s (4H, NH2).

[0041] Carbon NMR Spectroscopy 13 CNMR (400 MHz, CDCl3, d (ppm): 14.3, 18.4, 22.5,

[0042] 25.8, 27.2, 29.6, 31.6, 37.3, 46.3, 116.5, 130.5, 183.4.

[0043] Elemental analysis (%): C 67.85, H 10.66, N 14.53.

[0044] Based on the above characterization data, the chemical structural formula of the product can be deduced as shown in Formula I:

[0045] Formula I;

[0046] In this embodiment, n in formula I is 1, and its theoretical molecular formula is C. 27 H 51 N5O2 is an oleic acid-modified polyene polyamine compound.

[0047] Example 3:

[0048] This embodiment provides a method for preparing oleic acid-modified polyene polyamine compounds. The method specifically includes the following steps: 146.2 g (1 mol) of triethylenetetramine is added to a 1 L three-necked flask equipped with a mechanical stirrer, thermometer, constant pressure dropping funnel, and ice bath. The mixture is cooled to 5 °C under stirring conditions using an ice bath, and then 106 g (2 mol) of acrylonitrile is slowly added dropwise while maintaining the reaction temperature at 0–10 °C. After the acrylonitrile addition is complete, the temperature is slowly raised to 60 °C and maintained at this temperature for 3 h. After the reaction is complete, the temperature is lowered to 30 °C using a water bath, and then 564.9 g (3 mol) of oleic acid is slowly added dropwise while maintaining the reaction temperature at 30–40 °C. After the oleic acid addition is complete, the temperature is slowly raised to 50 °C and maintained at this temperature for 6 h. After the reaction is complete, the resulting reaction product is distilled under reduced pressure to obtain 801.6 g of a pale yellow, oily, transparent liquid, with a yield of 98.1%.

[0049] In this embodiment, the final pale yellow, oily, transparent liquid product was analyzed, and its characterization data are as follows:

[0050] Infrared spectra (KBr, cm⁻¹): 3402, 3253, 3151, 2983, 2928, 2831, 2151, 1658, 1552, 1444, 1309, 1098, 986, 896;

[0051] 1H NMR spectrum 1 HNMR (400 MHz, CDCl3, d , ppm): 0.81t (6H, CH3), 1.23t (6H, CH3), 1.24~1.31br (36H, CH2), 1.58t (6H, CH2), 2.16br. (3H, CH2), 2.33br. (4H, CH2), 3.28t (2H, NH), 3.38~4.14dt(4H, CH2),

[0052] 3.78q (2H, CH), 4.18s (4H, CH2), 5.49q (6H, CH); 7.31s (4H, NH2).

[0053] Carbon NMR Spectroscopy 13 CNMR (400 MHz, CDCl3, d (ppm): 14.2, 18.6, 22.3,

[0054] 25.5, 27.6, 29.4, 31.8, 37.5, 46.4, 116.3, 130.4, 183.6.

[0055] Elemental analysis (%): C 70.05, H 11.33, N 10.68.

[0056] Based on the above characterization data, the chemical structural formula of the product can be deduced as shown in Formula I:

[0057] Formula I;

[0058] In this embodiment, n in formula I is 2, and its theoretical molecular formula is C. 46 H 88 N6O4 is an oleic acid-modified polyene polyamine compound.

[0059] Example 4:

[0060] This embodiment describes the application of the oleic acid-modified polyene polyamine compound obtained in Example 1 in solid propellants. The specific method of this application includes adding 0.05 wt.% of the oleic acid-modified polyene polyamine compound to a solid propellant with a solid content of 90% as a bonding-type additive 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 were: curing time 168 hours and curing temperature 50°C. The basic formulation of the solid propellant is shown in Table 1.

[0062] Table 1. Composition of Solid Propellants

[0063]

[0064] Verification of the effect of Example 4:

[0065] The following results were obtained after adding 0.05 wt.% of oleic acid-modified polyene-polyamine compounds to the solid propellant formulation with a solid content of 90% shown in Table 1: The solid propellant with added oleic acid-modified polyene-polyamine compounds exhibited a falling ball viscosity range of 405 Pa·s after 1 hour and 1132 Pa·s after 6 hours, with a slurry leveling index of 1.65. Compared to the solid propellant without added oleic acid-modified polyene-polyamine compounds, the falling ball viscosity decreased by 4.93% after 1 hour and 4.51% after 6 hours, while the slurry leveling index increased by 47.32%. Furthermore, compared to the solid propellant without added oleic acid-modified polyene-polyamine compounds, the solid propellant with added oleic acid-modified polyene-polyamine compounds showed an 8.78% increase in elongation at break at 20°C, a 10.23% increase in elongation at break at 50°C, and a 7.14% increase in elongation at break at -40°C. The above results show that using this oleic acid-modified polyene polyamine compound as an additive for solid propellants can significantly reduce the viscosity of the propellant slurry, significantly improve the leveling properties of the propellant slurry, and significantly improve the elongation at break.

[0066] Example 5:

[0067] This embodiment describes the application of the oleic acid-modified polyene polyamine compound obtained in Example 2 in solid propellants. The specific method of this application includes adding 0.05 wt.% of the oleic acid-modified polyene polyamine compound to a solid propellant with a solid content of 90% as a bonding-type additive 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.

[0068] In this embodiment, the curing conditions used for testing process performance were: curing time 168 hours and curing temperature 50°C. The basic formulation of the solid propellant was exactly the same as that of the solid propellant in Example 4.

[0069] Verification of the effect of Example 5:

[0070] The following results were obtained after adding 0.05 wt.% of oleic acid-modified polyene-polyamine compounds to the solid propellant formulation with a solid content of 90% shown in Table 1: The solid propellant with added oleic acid-modified polyene-polyamine compounds exhibited a falling ball viscosity range of 378 Pa·s after 1 hour, a falling ball viscosity range of 1023 Pa·s after 6 hours, and a slurry leveling index range of 2.06. Compared with the solid propellant without added oleic acid-modified polyene-polyamine compounds, the falling ball viscosity decreased by 12.69% after 1 hour, decreased by 13.52% after 6 hours, and increased the slurry leveling index by 83.93%. Furthermore, compared with the solid propellant without added oleic acid-modified polyene-polyamine compounds, the solid propellant with added oleic acid-modified polyene-polyamine compounds showed an increase in elongation at break of 9.21% at 20°C, an increase in elongation at break of 11.46% at 50°C, and an increase in elongation at break of 8.53% at -40°C. The above results show that using this oleic acid-modified polyene polyamine compound as an additive for solid propellants can significantly reduce the viscosity of the propellant slurry, significantly improve the leveling properties of the propellant slurry, and significantly improve the elongation at break.

[0071] Example 6:

[0072] This embodiment describes the application of the oleic acid-modified polyene polyamine compound obtained in Example 3 in solid propellants. The specific method of this application includes adding 0.05 wt.% of the oleic acid-modified polyene polyamine compound to a solid propellant with a solid content of 90% as a bonding-type additive 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.

[0073] In this embodiment, the curing conditions used for testing process performance were: curing time 168 hours and curing temperature 50°C. The basic formulation of the solid propellant was exactly the same as that of the solid propellant in Example 4.

[0074] Verification of the effect of Example 6:

[0075] The following results were obtained after adding 0.05 wt.% of oleic acid-modified polyene-polyamine compounds to the solid propellant formulation with a solid content of 90% shown in Table 1: The solid propellant with added oleic acid-modified polyene-polyamine compounds exhibited a falling ball viscosity range of 386 Pa·s after 1 hour and 1096 Pa·s after 6 hours, with a slurry leveling index of 1.83. Compared to the solid propellant without added oleic acid-modified polyene-polyamine compounds, the falling ball viscosity decreased by 9.39% after 1 hour and by 7.35% after 6 hours, while the slurry leveling index increased by 63.39%. Furthermore, compared to the solid propellant without added oleic acid-modified polyene-polyamine compounds, the solid propellant with added oleic acid-modified polyene-polyamine compounds showed an increase in elongation at break of 9.65% at 20°C, 12.11% at 50°C, and 9.37% at -40°C. The above results show that using this oleic acid-modified polyene polyamine compound as an additive for solid propellants can significantly reduce the viscosity of the propellant slurry, significantly improve the leveling properties of the propellant slurry, and significantly improve the elongation at break.

Claims

1. An oleic acid-modified polyene polyamine compound, characterized in that, The chemical structural formula of the oleic acid-modified polyene polyamine compound is shown in Formula I: Formula I; In the formula: n is a positive integer greater than or equal to 1 and less than or equal to 10.

2. The oleic acid-modified polyene polyamine compound as described in claim 1, characterized in that, n is 1, 2, or 3.

3. A method for preparing oleic acid-modified polyene polyamine compounds as described in claim 1 or 2, characterized in that, The method specifically includes the following steps: adding an ethyleneamine compound to a reaction vessel, cooling it to 0–5°C under stirring conditions via an ice bath, then adding acrylonitrile dropwise while maintaining the reaction temperature at 0–10°C; after the acrylonitrile addition is complete, raising the temperature to 60–80°C and maintaining the temperature for 1–3 hours; after the reaction is complete, cooling it to 30°C via a water bath, then adding oleic acid dropwise while maintaining the reaction temperature at 30–40°C; after the oleic acid addition is complete, raising the temperature to 40–50°C and maintaining the temperature for 6 hours; after the reaction is complete, distilling the resulting reaction product under reduced pressure to obtain an oleic acid-modified polyene polyamine compound.

4. The method for preparing oleic acid-modified polyene polyamine compounds as described in claim 3, characterized in that, The ethyleneamine compounds mentioned are tetraethylenepentamine, diethylenetriamine, or triethylenetetraamine.

5. The method for preparing oleic acid-modified polyene polyamine compounds as described in claim 3, characterized in that, The molar ratio of the ethyleneamine compound to acrylonitrile is 1:

2.

6. The method for preparing oleic acid-modified polyene polyamine compounds as described in claim 3, characterized in that, The molar ratio of the ethyleneamine compound to oleic acid is 1:(1-3).

7. The application of the oleic acid-modified polyene polyamine compound as described in claim 1 or 2 in solid propellants.

8. The application as described in claim 7, characterized in that, The method of this application includes adding oleic acid-modified polyene polyamine compounds to solid propellants as an adjuvant to reduce the viscosity of solid propellant slurry and improve the leveling properties of solid propellant slurry.

9. The application as described in claim 7, characterized in that, The method of this application includes adding oleic acid-modified polyene polyamine compounds to solid propellants as an additive to improve the elongation at break of solid propellants.

10. The application as described in claim 8 or 9, characterized in that, The amount of the oleic acid-modified polyene polyamine compound added to the solid propellant is 0.05 wt.

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