Oleic acid amide compound, preparation method and method for improving performance of propellant

Abstract

The application provides an oleic 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 oleic acid amide compound into a solid propellant with a solid content greater than or equal to 90% as an additive for reducing the viscosity of a solid propellant slurry and improving the flow leveling property of the solid propellant slurry. The oleic acid amide compound of 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. The application effect of the oleic acid amide compound in the solid propellant with a solid content greater than or equal to 90% is good.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of solid propellant, and relates to a process additive of solid propellant, in particular to an oleic acid amide compound, a preparation method and a method for improving the performance of propellant. BACKGROUND

[0002] The solid propellant is a composite material system composed of high-energy oxidizer, metal fuel, binder, curing agent, plasticizer and various functional materials (such as bonding agent, process additive, combustion catalyst, etc.), and its manufacturing process mainly includes three processes of mixing, pouring and curing of propellant slurry. Among them, the mixing and pouring of propellant are process procedures carried out in the flow state of propellant slurry, and the key process parameters such as the viscosity, yield value and flow index of propellant slurry directly affect the mixing and pouring process of propellant slurry.

[0003] In order to improve the process performance of propellant slurry, a small amount of process additive can usually be added to the propellant formula. According to the function, the process additive mainly includes: (1) the process additive for improving the particle interface performance, such as methyl stearate, methyl oleate, lecithin, British detergent, phosphorus-containing compound and amide compound (or polymer) etc., which can increase the wetting of solid particle surface and reduce the particle agglomeration. Among them, the amide process additive mainly includes amide compound and polyamide, and its structure has strong polarity and is easy to migrate to the surface of ammonium perchlorate in the system, so as to improve the interface performance of the binder and ammonium perchlorate. Although the amide process additive can improve the process performance of HTPB propellant slurry, its application effect is not good in the high solid content propellant formula with solid content > 90%. (2) The process additive for delaying the curing reaction, such as cotton alcohol and dioxane C-16, which can inhibit the catalytic effect of transition metal oxide type burning rate catalyst on the curing reaction, and prolong the pot life of propellant slurry. (3) The dilution type process additive, such as styrene, which can reduce the viscosity of propellant slurry to a certain extent.

[0004] At present, with the increasing demand for the application of high solid content composite solid propellant and the use of various new materials in propellant formula, the good process performance of propellant slurry is more important, and the existing process additive is difficult to meet the requirements of high solid content propellant formula on the process performance of propellant slurry. Therefore, in order to meet the requirements of high solid content propellant on the process performance of propellant slurry, it is urgent to develop a process additive with better performance. SUMMARY

[0005] In view of the defects and deficiencies in the prior art, the purpose of the present application is to provide an oleic acid amide compound, a preparation method and a method for improving the performance of propellant, which solves the technical problem that the amide process additive in the prior art has poor application effect in the high solid content propellant formula with solid content ≥ 90%.

[0006] To solve the above technical problems, the present application adopts the following technical solutions to achieve the purpose:

[0007] A method for improving the performance of propellant by using oleic acid amide compound, the method comprising: adding oleic acid amide compound in solid propellant with solid content greater than or equal to 90% as an additive for reducing the viscosity of solid propellant slurry and improving the flow leveling of solid propellant slurry; the chemical structure of the oleic acid amide compound is shown as formula I:

[0008]

[0009] The present application also has the following technical features:

[0010] Specifically, the amount of oleic acid amide compound added in the solid propellant is 0.05-0.1wt.%.

[0011] Specifically, the solid propellant is composed of the following raw materials: hydroxyl-terminated polybutadiene, dioctyl sebacate, toluene diisocyanate, triphenyl bismuth, iron acetylacetone, ammonium perchlorate, octogen and aluminum powder.

[0012] Specifically, the solid propellant is composed of the following raw materials in mass percentage: hydroxyl-terminated polybutadiene 5-8%, dioctyl sebacate 3-5%, toluene diisocyanate 0.3-0.5%, triphenyl bismuth 0.02-0.05%, iron acetylacetone 0.01-0.05%, ammonium perchlorate 20-30%, octogen 30-50%, and aluminum powder 20-30%.

[0013] Specifically, the preparation method of the oleic acid amide compound comprises the following processes: adding N-oleyl-1,3-propanediamine and oleic acid into a reaction container, heating to 160-180℃ under stirring and constant temperature reaction for 1-3h, when no water is produced in the reaction, cooling to 0-10℃ by ice water bath; then adding 2-hydroxyethyl acrylate dropwise, maintaining the reaction temperature at 0-10℃; after the addition of 2-hydroxyethyl acrylate is completed, heating to 60-80℃ and constant temperature reaction for 1-3h; after the reaction is completed, the obtained reaction product is distilled under reduced pressure to obtain the oleic acid amide compound.

[0014] Specifically, the molar ratio of N-oleyl-1,3-propanediamine to oleic acid is 1:(1-1.05).

[0015] Specifically, the molar ratio of N-oleyl-1,3-propanediamine to 2-hydroxyethyl acrylate is 1:1.

[0016] Specifically, the reaction container is a 1L three-necked flask equipped with mechanical stirring, thermometer and water separator.

[0017] The application also protects the oleic acid amide compound as described above.

[0018] The application also protects the preparation method of the oleic acid amide compound as described above.

[0019] Compared with the prior art, the application has the following beneficial technical effects:

[0020] The oleic acid amide compound of the application can significantly improve the wetting state of the solid particles and the binder system of the propellant, so that the solid particles are easily dispersed, the structural strength that hinders the flow in the propellant is reduced, the yield value and the viscosity of the propellant are reduced, and the flow leveling index of the propellant is improved. The application effect of the oleic acid amide compound in the solid propellant with a solid content greater than or equal to 90% is good.

[0021] The technical solutions of the application are further described below in combination with examples. DETAILED DESCRIPTION

[0022] It should be noted that all the raw materials used in the application are known raw materials in the art unless otherwise specified.

[0023] In accordance with the above technical solutions, the specific examples of the application are given below. It should be noted that the application is not limited to the following specific examples, and any equivalent transformation made on the basis of the technical solutions of the application falls within the protection scope of the application.

[0024] Example 1

[0025] The example gives a preparation method of an oleic acid amide compound, which specifically includes the following processes: 324.6 g (1 mol) of N-oleyl-1,3-propanediamine and 282.5 (1 mol) of oleic acid are added to a 1L three-necked flask equipped with a mechanical stirrer, a thermometer and a water separator, and slowly heated to 160℃ under stirring and kept at this temperature for 3h. When no water is generated in the reaction, an ice water bath is used to slowly cool it to 0℃. Then, the water separator is removed and a constant pressure dropping funnel is installed, and 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added while maintaining the reaction temperature at 0-10℃. After the addition of 2-hydroxyethyl acrylate is completed, the temperature is slowly raised to 60℃ and kept at this temperature for 3h. After the reaction is completed, the obtained reaction product is distilled under reduced pressure to obtain 693.8 g of a light yellow transparent liquid with a yield of 98.4%.

[0026] In the example, the finally obtained light yellow transparent liquid product is analyzed, and the characterization data are as follows:

[0027] IR (KBr, cm"1): 3103, 3065, 2871, 2854, 2735, 1711, 1605, 1509, 1485, 1216, 1185, 956, 887;

[0028] NMR of hydrogen 1 HNMR (400MHz, CDC13, δ, ppm): 0.88s (3H, CH3), 1.27~1.39br. (40H, CH2), 1.53t (4H, CH2), 1.73t (4H, CH2), 2.13~2.16br. (12H, CH2), 2.36~2.49br. (2H, CH2), 3.01t (2H, CH2), 3.42~3.54dt (4H, CH2), 4.22t (2H, CH2), 4.89s (1H, OH), 5.36q (2H, CH).

[0029] NMR of carbon 13 C NMR (400MHz, CDC13, δ, ppm): 14.1, 22.7, 25.6, 27.7, 29.3, 29.7, 31.9, 36.5, 40.7, 51.9, 53.1, 56.9, 61.1, 64.1, 130.6, 171.0;

[0030] Elemental analysis (%): C 74.89, H 12.05, N 3.92;

[0031] Hydroxyl value: 1.4175 mmol / g (theoretical value 1.4181 mmol / g).

[0032] According to the above characterization data, the chemical structure of the product is shown as Formula I:

[0033]

[0034] The compound is an oleic acid amide compound, which is named as 3-(((Z)-octadec-9-en-1-yl) (3-oleic amide propyl) amino) propanoic acid-2-hydroxyethyl ester.

[0035] Example 2:

[0036] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following steps: 324.6 g (1 mol) of N-oleyl-1, 3-propylenediamine and 296.6 (1.05 mol) of oleic acid are added into a 1L three-necked flask which is provided with a mechanical stirrer, a thermometer and a water separator, the temperature is slowly increased to 180 DEG C under stirring, and the reaction is kept at 180 DEG C for 1 h, when no water is generated in the reaction, the temperature is slowly decreased to 0 DEG C through an ice water bath, then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is kept at 0-10 DEG C, after the 2-hydroxyethyl acrylate is added, the temperature is slowly increased to 80 DEG C, and the reaction is kept at 80 DEG C for 2 h, and after the reaction is completed, the reaction product is distilled under reduced pressure, and 692.47 g of a yellowish transparent oily liquid is obtained, and the yield is 98.2 %.

[0037] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0038] Embodiment 3

[0039] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following steps: 324.6 g (1 mol) of N-oleyl-1, 3-propylenediamine and 296.6 (1.05 mol) of oleic acid are added into a 1L three-necked flask which is provided with a mechanical stirrer, a thermometer and a water separator, the temperature is slowly increased to 180 DEG C under stirring, and the reaction is kept at 180 DEG C for 1 h, when no water is generated in the reaction, the temperature is slowly decreased to 0 DEG C through an ice water bath, then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is kept at 0-10 DEG C, after the 2-hydroxyethyl acrylate is added, the temperature is slowly increased to 80 DEG C, and the reaction is kept at 80 DEG C for 2 h, and after the reaction is completed, the reaction product is distilled under reduced pressure, and 692.47 g of a yellowish transparent oily liquid is obtained, and the yield is 98.2 %.

[0040] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0041] Embodiment 4

[0042] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following steps: 324.6 g (1 mol) of N-oleyl-1, 3-propylenediamine and 282.5 (1 mol) of oleic acid are added into a 1L three-necked flask which is provided with mechanical stirring, a thermometer and a water separator, the temperature is slowly increased to 170 DEG C under stirring, and the reaction is kept at 170 DEG C for 3h, when no water is generated in the reaction, the temperature is slowly decreased to 5 DEG C through an ice water bath, then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is maintained at 0-10 DEG C, after the 2-hydroxyethyl acrylate is added, the temperature is slowly increased to 80 DEG C and kept at 80 DEG C for 1h, and after the reaction is completed, the obtained reaction product is distilled under reduced pressure, and 685.4 g of a yellowish transparent oily liquid is obtained, and the yield is 97.2 %.

[0043] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0044] Embodiment 5

[0045] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following steps: 324.6 g (1 mol) of N-oleyl-1, 3-propylenediamine and 282.5 (1 mol) of oleic acid are added into a 1L three-necked flask which is provided with mechanical stirring, a thermometer and a water separator, the temperature is slowly increased to 170 DEG C under stirring, and the reaction is kept at 170 DEG C for 3h, when no water is generated in the reaction, the temperature is slowly decreased to 10 DEG C through an ice water bath, then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is maintained at 0-10 DEG C, after the 2-hydroxyethyl acrylate is added, the temperature is slowly increased to 60 DEG C and kept at 60 DEG C for 1h, and after the reaction is completed, the obtained reaction product is distilled under reduced pressure, and 688.2 g of a yellowish transparent oily liquid is obtained, and the yield is 97.6 %.

[0046] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0047] Embodiment 6

[0048] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following steps: 324.6 g (1 mol) of N-oleyl-1, 3-propylenediamine and 296.6 (1.05 mol) of oleic acid are added into a 1L three-necked flask which is provided with a mechanical stirrer, a thermometer and a water separator, the temperature is slowly increased to 160 DEG C under stirring, and the reaction is kept at 160 DEG C for 2 hours, when no water is generated in the reaction, the temperature is slowly decreased to 5 DEG C through an ice water bath, then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is maintained at 0-10 DEG C, after the 2-hydroxyethyl acrylate is added, the temperature is slowly increased to 60 DEG C, and the reaction is kept at 60 DEG C for 1 hour, after the reaction is completed, the reaction product is distilled under reduced pressure, and 684.7 g of a yellowish transparent oily liquid is obtained, and the yield is 97.1 %.

[0049] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0050] Embodiment 7

[0051] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following steps: 324.6 g (1 mol) of N-oleyl-1, 3-propylenediamine and 296.6 (1.05 mol) of oleic acid are added into a 1L three-necked flask which is provided with a mechanical stirrer, a thermometer and a water separator, the temperature is slowly increased to 160 DEG C under stirring, and the reaction is kept at 160 DEG C for 2 hours, when no water is generated in the reaction, the temperature is slowly decreased to 5 DEG C through an ice water bath, then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is maintained at 0-10 DEG C, after the 2-hydroxyethyl acrylate is added, the temperature is slowly increased to 60 DEG C, and the reaction is kept at 60 DEG C for 1 hour, after the reaction is completed, the reaction product is distilled under reduced pressure, and 684.7 g of a yellowish transparent oily liquid is obtained, and the yield is 97.1 %.

[0052] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0053] Embodiment 8

[0054] The embodiment provides a preparation method of an oleic acid amide compound, and the method specifically comprises the following process: 324.6 g (1 mol) of N-oleyl-1,3-propylene diamine and 296.6 (1.05 mol) of oleic acid are added into a 1L three-necked flask provided with a mechanical stirrer, a thermometer and a water separator, the temperature is slowly increased to 180 DEG C under stirring, and the reaction is kept at 180 DEG C for 2 hours; when no water is generated in the reaction, the temperature is slowly decreased to 10 DEG C through an ice water bath; then the water separator is removed, a constant pressure dropping funnel is installed, 116.1 g (1 mol) of 2-hydroxyethyl acrylate is slowly added, and the reaction temperature is kept at 0-10 DEG C; after the addition of the 2-hydroxyethyl acrylate is completed, the temperature is slowly increased to 60 DEG C, and the reaction is kept at 60 DEG C for 2 hours; after the reaction is completed, the obtained reaction product is distilled under reduced pressure, and 688.9 g of a yellowish transparent oily liquid is obtained, and the yield is 97.7%.

[0055] In the embodiment, the finally obtained yellowish transparent oily liquid product is analyzed, and the characterization data is consistent with that of the embodiment 1.

[0056] Embodiment 9

[0057] The embodiment provides a method for improving the performance of a propellant by using the oleic acid amide compound prepared in the embodiments 1 to 8, and the specific process is as follows: 0.05-0.1 wt.% of the oleic acid amide compound is added into a solid propellant with a solid content of 90%, so as to be used as a process additive for reducing the viscosity of the solid propellant slurry and improving the flow leveling property of the solid propellant slurry.

[0058] In the embodiment, the curing conditions for testing the process performance are as follows: the curing time is 180 hours, and the curing temperature is 50 DEG C. The basic formula of the solid propellant is shown in Table 1.

[0059] Table 1, the formula composition of the solid propellant

[0060]

[0061] Effect verification of the embodiment 9:

[0062] After adding 0.05-0.1 wt.% of the oleic acid amide compound to the solid propellant formulation with a solid content of 90% shown in Table 1, the results are as follows: the solid propellant with the added oleic acid amide process additive has a 1h after-ball drop viscosity ranging from 374 Pa·s to 398 Pa·s, a 6h after-ball drop viscosity ranging from 963 Pa·s to 1075 Pa·s, and a slurry flow leveling index ranging from 1.65 to 1.98; compared with the solid propellant without the added oleic acid amide process additive, the 1h after-ball drop viscosity is reduced by 6.57-12.21%, the 6h after-ball drop viscosity is reduced by 9.13-18.59%, and the slurry flow leveling index is increased by 47.32-76.79%. The above results show that the oleic acid amide compound used as the process additive of the solid propellant can significantly reduce the slurry viscosity and significantly improve the slurry flow leveling.

Claims

1. A method of improving the performance of a propellant, characterized in that, The method comprises: adding an oleic acid amide compound into a solid propellant with a solid content of 90% or more as an additive for reducing the viscosity of the solid propellant slurry and improving the flow leveling property of the solid propellant slurry; The chemical structural formula of the oleic acid amide compound is shown as Formula I: Formula I; The adding amount of the oleic acid amide compound in 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, triphenyl bismuth, iron acetylacetone, ammonium perchlorate, octogen and aluminum powder.

2. The method of improving propellant performance according to claim 1, wherein The solid propellant is composed of the following raw materials in mass percentage: 5-8% of hydroxyl-terminated polybutadiene, 3-5% of dioctyl sebacate, 0.3-0.5% of toluene diisocyanate, 0.02-0.05% of triphenyl bismuth, 0.01-0.05% of iron acetylacetone, 20-30% of ammonium perchlorate, 30-50% of octogen and 20-30% of aluminum powder.

3. The method of improving propellant performance according to claim 1, wherein The preparation method of the oleic acid amide compound specifically comprises the following process: adding N-oleyl-1,3-propanediamine and oleic acid into a reaction container, heating to 160-180°C under stirring and keeping the temperature constant for 1-3 hours, cooling to 0-10°C by using an ice water bath when no water is generated in the reaction, then adding 2-hydroxyethyl acrylate dropwise while maintaining the reaction temperature at 0-10°C, heating to 60-80°C after the addition of 2-hydroxyethyl acrylate is completed and keeping the temperature constant for 1-3 hours, and distilling the obtained reaction product under reduced pressure to prepare the oleic acid amide compound.

4. The method of improving propellant performance according to claim 3, wherein The molar ratio of the N-oleyl-1,3-propanediamine and the oleic acid is 1: (1-1.05).

5. The method of improving propellant performance according to claim 4, wherein The molar ratio of the N-oleyl-1,3-propanediamine and the 2-hydroxyethyl acrylate is 1:

1.

6. The method of improving propellant performance according to claim 3, wherein The reaction container is a 1L three-necked flask provided with a mechanical stirrer, a thermometer and a water separator.

7. An oleic acid amide compound, characterized by, The chemical structural formula of the oleic acid amide compound is shown as Formula I: Formula I.

8. A method for producing the oleic acid amide compound according to claim 7, characterized by, The method specifically comprises the following process: adding N-oleyl-1,3-propanediamine and oleic acid into a reaction container, heating to 160-180°C under stirring and keeping the temperature constant for 1-3 hours, cooling to 0-10°C by using an ice water bath when no water is generated in the reaction, then adding 2-hydroxyethyl acrylate dropwise while maintaining the reaction temperature at 0-10°C, heating to 60-80°C after the addition of 2-hydroxyethyl acrylate is completed and keeping the temperature constant for 1-3 hours, and distilling the obtained reaction product under reduced pressure to prepare the oleic acid amide compound.

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