Quaternary ammonium salt speed reducer and synthesis method thereof

Abstract

The present invention discloses a quaternary ammonium salt rate reducer with a molecular formula of C 46 H 98 N2Cl2O8. The present invention also discloses a synthesis method of the quaternary ammonium salt rate reducer, which specifically includes the following process: using octadecyl halide and N,N,N',N'-tetramethyl-1,6-hexanediamine as raw materials, adding solvent A and a catalyst, heating and stirring evenly, after the reaction system is cooled to room temperature, adding a B solution of silver perchlorate, continuing to stir evenly, then filtering, collecting the obtained filtrate, distilling off solvent A and solvent B under reduced pressure, and washing with organic solvent C and water respectively, and then drying to obtain the quaternary ammonium salt product. The present invention solves the problems of the existing rate reducer such as easy moisture absorption, unfavorable process construction, and no energetic groups.

Description

Technical Field

[0001] The invention belongs to the technical field of quaternary ammonium salt synthesis, relates to a quaternary ammonium salt speed reducer, and also relates to a preparation method of the speed reducer. Background Art

[0002] Ammonium oxalate and quaternary ammonium salts are commonly used propellant combustion decelerators. Ammonium oxalate can produce NH 3 , thereby inhibiting the decomposition of ammonium perchlorate (AP) and reducing the burning rate of the propellant. 3 In addition, it can also form hydrogen bonds with the AP surface, reduce the high-temperature heat release of AP, and the generated free radical intermediates can inhibit the formation of perchloric acid shell on the AP surface, thereby inhibiting NH 3 desorption, therefore, quaternary ammonium salts have a higher deceleration efficiency. However, ammonium oxalate and quaternary ammonium salts do not have energetic groups, and while reducing the burning rate of the propellant, they will also greatly reduce the energy performance of the propellant. In order to improve the energy loss caused by the decelerator, the development of energetic decelerators has become a research hotspot. The energy level of quaternary ammonium salts can be improved by introducing groups such as tetrazine, tetrazole and furazan derivatives into quaternary ammonium salts, but these groups will bring some other problems, such as catalysis of the adhesive curing reaction, thereby increasing the viscosity of the slurry, shortening the applicable period of the slurry, etc. In addition, ammonium oxalate and quaternary ammonium salts containing anions such as chlorine and bromine have a strong affinity with water molecules, are easily soluble in water, and have strong hygroscopicity, which brings great inconvenience to the construction of the drug column. Therefore, the development of a quaternary ammonium salt substance that is insoluble in water, does not have hygroscopicity, and has energetic groups at the same time is of great significance for the development of high-performance solid propellants, and is an important technical problem currently faced. Summary of the invention

[0003] The invention aims to provide a quaternary ammonium salt speed reducer, which solves the problems of the existing speed reducers, such as easy hygroscopicity, disadvantageous for process construction and no energetic groups.

[0004] Another object of the present invention is to provide a method for synthesizing a quaternary ammonium salt speed reducer.

[0005] The first technical solution adopted by the present invention is that the quaternary ammonium salt speed reducer has a molecular formula of C 46 H 98 N 2 Cl 2 O 8 , the molecular structure is as follows:

[0006]

[0007] The second technical scheme adopted by the present invention is a method for synthesizing a quaternary ammonium salt speed reducer, which specifically comprises the following steps: taking halogenated octadecane and N,N,N',N'-tetramethyl-1,6-hexanediamine as raw materials, adding solvent A and a catalyst, heating and stirring evenly, adding silver perchlorate solution B after the reaction system is cooled to room temperature, continuing to stir evenly, then filtering, collecting the obtained filtrate, distilling off solvent A and solvent B under reduced pressure, washing with organic solvent C and water respectively, and then drying to obtain a quaternary ammonium salt product.

[0008] The second technical solution adopted by the present invention is also characterized in that:

[0009] The halogenated octadecane is chlorooctadecane or bromooctadecane, and the feeding molar ratio of the halogenated octadecane to N,N,N',N'-tetramethyl-1,6-hexanediamine is (2-3):1.

[0010] The solvent A is DMF, DMSO, benzene or toluene, and the feeding molar ratio of the solvent A to N,N,N',N'-tetramethyl-1,6-hexanediamine is (5-10):1.

[0011] The catalyst is KI or iodooctadecane, and the molar ratio of the catalyst to N, N, N', N'-tetramethyl-1, 6-hexanediamine as a raw material is (0.1-0.3):1. After adding the catalyst, the heating and stirring conditions in the reaction are 70°C to the boiling point of the solvent, and the reaction time is 20-48 hours.

[0012] The silver perchlorate solution B is one of the benzene, toluene or pyridine solutions of silver perchlorate, wherein the concentration of silver perchlorate is 3-8%, and the molar ratio of silver perchlorate to N,N,N',N'-tetramethyl-1,6-hexanediamine is (2.1-2.5):1. After adding the silver perchlorate, stirring is continued at room temperature for 10-60 minutes.

[0013] The organic solvent C is one of methanol, ethanol, ethyl acetate or dichloromethane.

[0014] The beneficial effects of the present invention are as follows:

[0015] 1. The quaternary ammonium salt synthesized by the present invention is a gemini quaternary ammonium salt, which is used as a speed reducer in solid propellants and has a good speed reduction effect.

[0016] 2. The quaternary ammonium salt synthesized by the present invention, wherein the energetic group is an anion ClO 4 - , when used as a rate reducer, can increase the propellant energy compared to non-energetic rate reducers.

[0017] 3. The quaternary ammonium salt synthesized by the present invention has no catalytic effect on the curing reaction of the adhesive and will not have an adverse effect on the original propellant processing process.

[0018] 4. The quaternary ammonium salt synthesized by the present invention is insoluble in water and non-hygroscopic. When used as a speed reducer, it is beneficial to the processing technology. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is the infrared spectrum of Example 2 of the synthesis method of the quaternary ammonium salt speed reducer of the present invention. DETAILED DESCRIPTION

[0020] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0021] The quaternary ammonium salt speed reducer of the present invention has the molecular formula of C 46 H 98 N 2 Cl 2 O 8 , its molecular structure is shown below:

[0022]

[0023] The synthesis method of a quaternary ammonium salt speed reducer specifically comprises the following steps: taking halogenated octadecane and N,N,N',N'-tetramethyl-1,6-hexanediamine as raw materials, adding a solvent A and a catalyst, heating and stirring for a certain time, adding a silver perchlorate solution B after the reaction system is cooled to room temperature, continuing to stir for a period of time, then filtering, collecting the obtained filtrate, distilling off the solvent A and B under reduced pressure, washing with an organic solvent C and water respectively, and then drying to obtain a quaternary ammonium salt product.

[0024] The halogenated octadecane is chlorooctadecane or bromooctadecane. The molar ratio of the halogenated octadecane to N,N,N',N'-tetramethyl-1,6-hexanediamine is (2-3):1.

[0025] The solvent A is one of DMF (dimethylformamide), DMSO (dimethyl sulfoxide), benzene or toluene, and the feeding molar ratio of the solvent A to N, N, N', N'-tetramethyl-1, 6-hexanediamine is (5-10):1.

[0026] The catalyst is KI or iodooctadecane, and the molar ratio of the catalyst to N, N, N', N'-tetramethyl-1,6-hexanediamine as the raw material is (0.1-0.3):1. After adding the catalyst, the heating and stirring conditions in the reaction are 70°C to the boiling point of the solvent, and the reaction time is 20-48h.

[0027] The silver perchlorate solution B is one of the benzene, toluene or pyridine solutions of silver perchlorate, wherein the concentration of silver perchlorate is 3-8%, the molar ratio of silver perchlorate to N,N,N',N'-tetramethyl-1,6-hexanediamine is (2.1-2.5):1, and stirring is continued at room temperature for 10-60 minutes after the addition of silver perchlorate.

[0028] The conditions for distilling out solvents A and B by reduced pressure distillation are general reduced pressure distillation, which is a basic experimental condition. For example, a rotary evaporator is used and the vacuum degree of the vacuum water pump is reduced to about -0.9 MPa until the solvent is completely dried.

[0029] The organic solvent C is methanol, ethanol, ethyl acetate or dichloromethane, and the amount used for each washing is 5 to 8 times the molar amount of N, N, N', N'-tetramethyl-1,6-hexanediamine, and the number of washings is 3 to 5 times;

[0030] The washing process uses deionized water to wash the product, the amount of each washing is 20 to 30 times the molar amount of N, N, N', N'-tetramethyl-1, 6-hexanediamine, and the washing times are 3 to 5 times.

[0031] The purpose of the drying conditions is to remove moisture and residual washing organic solvents. The drying temperature is 80 to 120° C. and the drying time is 4 to 24 hours.

[0032] The synthesis method of the quaternary ammonium salt speed reducer of the present invention has a purity of more than 98% and a yield of 90-98%. The quaternary ammonium salt N, N, N', N'-tetramethyl-N, N'-dioctadecyl hexamethylenediamine perchlorate provided by the present invention is insoluble in water, methanol, ethanol, ethyl acetate or dichloromethane, but soluble in DMF, DMSO, benzene or toluene. The intermediate product N, N, N', N'-tetramethyl-N, N'-dioctadecyl hexamethylenediamine chloride or bromide salt can be dissolved in hot water, DMF, DMSO, benzene or toluene, but insoluble in cold water, methanol, ethanol or ethyl acetate, but has a strong swelling absorption effect on these solvents, and can absorb solvents more than 5 times its own volume. When N, N, N', N'-tetramethyl-N, N'-dioctadecyl hexamethylenediamine chloride or bromide salt reacts with silver perchlorate in a solvent, a product and a silver halide precipitate are generated. After filtering out the silver halide, the solvent is evaporated to obtain the product quaternary ammonium salt. Therefore, solvent A is selected from DMF, DMSO, benzene or toluene; solvent C is selected from methanol, ethanol, ethyl acetate or dichloromethane to remove unreacted raw materials and intermediate products to obtain high-purity products; the main function of solvent B is to dissolve silver perchlorate and avoid the simultaneous precipitation of quaternary ammonium salt products when it is added into the reaction system.

[0033] Example 1

[0034] Add 2.2 mol of chlorooctadecane, 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, 5 mol of solvent DMF, and 0.2 mol of catalyst KI into a reactor, heat to 70°C and stir to react for 48 hours. After the reaction system cools to room temperature, add a 3% toluene solution of silver perchlorate by mass to make the molar amount of silver perchlorate added be 2.2 mol. Continue stirring for 10 minutes, then filter, collect the obtained filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure, wash the solid product obtained after the solvent is evaporated with 5 mol of methanol 5 times and 20 mol of water 5 times, respectively, and then dry at 80°C for 24 hours to obtain 800.9 g of quaternary ammonium salt product, with a yield of 91.2% based on N,N,N',N'-tetramethyl-1,6-hexanediamine and a product purity of 98.5%.

[0035] Example 2

[0036] Add 2.0 mol of octadecane bromide, 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, 8 mol of solvent DMSO, and 0.1 mol of catalyst octadecane iodide into a reactor, heat to 80°C and stir to react for 40 hours. After the reaction system cools to room temperature, add a 5% benzene solution of silver perchlorate by mass to make the molar amount of silver perchlorate added 2.1 mol. Continue stirring for 60 minutes, then filter, collect the obtained filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure, wash the solid product obtained after the solvent is evaporated with 6 mol ethanol 4 times and 25 mol water 4 times, respectively, and then dry at 100°C for 12 hours to obtain 807.9 g of quaternary ammonium salt product, with a yield of 92.0% based on N,N,N',N'-tetramethyl-1,6-hexanediamine and a product purity of 98.4%.

[0037] Figure 1 It is a quaternary ammonium salt speed reducer synthesized according to Example 2. Figure 1 As can be seen from the spectrum, at 3000cm -1 There is no absorption peak above, indicating that the molecule does not contain NH and OH groups. -1 There is no strong absorption peak, indicating that there is no C=O bond. 2916.5cm -1 The absorption peak and its shoulder peak and 2853.57cm -1 The absorption peak of —CH 3 , —CH 2 The existence of the base, 1473.19cm -1 The absorption peak is the stretching vibration absorption peak of the CN bond, and the shoulder peak here comes from the asymmetric shear vibration of the CH bond, 1092.25cm -1 and 624.75cm -1 It is ClO 4- The absorption peak is 717.57 cm -1 It is the CH in-plane swing absorption peak, which can indicate the existence of long-chain methylene.

[0038] The element analysis results of the sample of Example 2 are shown in Table 1. From the results in Table 1, it can be seen that the C, H, O, and N elements in the prepared product are in good agreement with the theoretical values. Figure 1 The infrared spectrum also shows that the product does not contain NH bonds, indicating that there are at least three substituents on the N atom in the product. The product was tested by ion chromatography to analyze the Br - The results show that the sample does not contain Br - , indicating that the precipitation reaction was relatively complete.

[0039] Table 1 Elemental analysis results of Example 2

[0040] element C H O N Theoretical content / % 62.91 11.25 14.57 3.19 Test results / % 62.91 11.16 14.49 3.20

[0041] The quaternary ammonium salt prepared by the present invention is used in the propellant for experiment. According to the standard of the Ministry of Aerospace Industry "Determination Method of Burning Rate, Burning Rate Pressure Index and Burning Rate Temperature Sensitivity Coefficient of Composite Solid Propellant Strips (Target Line Method)", the linear burning rate of the propellant is tested by the target line method. Taking the AP / Al / HTPB curing system = 68 / 18 / 14 as an example, the curing parameters TR = 0.9, MR = 0.3, and constant temperature curing at 70°C for 3 days. 3.0% ammonium oxalate, 0.4% comparative product, and 0.4% Example 2 product were added respectively, and the experimental results are shown in Table 2 below. The results of mechanical properties at room temperature are shown in Table 3. Explosive heat is the thermal effect of the deflagration process of solid propellant, which characterizes the energy performance of solid propellant. According to the "Test Methods for Explosive Agents Part 28: Adiabatic Calorimetry for Determination of Combustion Heat and Explosive Heat", the energy performance test of the experimental formula was carried out, and the results are shown in Table 4 below. Ammonium oxalate is hygroscopic, and water absorption will cause changes in the particle size of ammonium oxalate itself. In addition, moisture has a great influence on the curing process and the propellant processing process. In order to investigate the hygroscopicity of each substance, moisture absorption and weight gain experiments were carried out on three samples under saturated steam conditions at 25°C. The results are shown in Table 5 below.

[0042] Table 2 Burning rate test results

[0043]

[0044] Table 3 Mechanical properties at room temperature

[0045]

[0046] Table 4 Explosion heat test results

[0047]

[0048] Table 5 Water absorption test of samples

[0049]

[0050] As can be seen from the above results, the quaternary ammonium salt synthesized by the present invention has a good deceleration effect. As can be seen from the results of Table 2, compared with ammonium oxalate, the addition amount of 0.4% of the quaternary ammonium salt provided by the present invention can achieve the deceleration effect of ammonium oxalate with an addition amount of 3.0%. As can be seen from Table 3, the mechanical properties of the prepared propellant using the decelerator provided by the present invention are better than the ammonium oxalate formula. As can be seen from Table 4, in terms of energy, after adding the non-energetic quaternary ammonium salt of the comparative example, compared with the ammonium oxalate formula, the propellant energy has been reduced by 1.43%. This is because the basic formula itself is a negative oxygen balance, and the addition of the non-energetic quaternary ammonium salt decelerator, although the combustion itself can bring certain energy, and the amount is less than ammonium oxalate, the addition of the non-energetic quaternary ammonium salt further reduces the oxygen balance of the propellant, and the redox reaction of the propellant can be carried out more incompletely, thereby reducing the energy of the propellant. When adding the energetic quaternary ammonium salt provided by the present invention, compared with the use of ammonium oxalate, when the deceleration effect is basically the same, the propellant energy can be increased to a greater extent. As can be seen from Table 5, ammonium oxalate and halogenated quaternary ammonium salts have strong water absorption, and replacing the halide ions in the quaternary ammonium salt with ClO 4 - After that, quaternary ammonium salt does not have water absorption substantially, and its reason is that halogen ion can form hydrogen bond with water, and has stronger action force with water. In summary, the quaternary ammonium salt prepared by the present invention can be used as a speed reducer in solid propellant, and can bring greater improvement to the processing and performance of propellant.

[0051] Comparative Example

[0052] Add 2.0 mol of bromooctadecane, 1 mol of N, N, N', N'-tetramethyl-1,6-hexanediamine, 8 mol of solvent toluene, 0.1 mol of catalyst iodooctadecane into the reactor, heat to 80°C and stir for 40 hours to generate the product N, N, N', N'-tetramethyl-N, N'-dioctadecyl hexanediamine bromide salt. Distill off the solvent under reduced pressure to obtain a solid product. Although the obtained product can be dissolved in toluene, it dissolves slowly at room temperature, so a small amount of toluene can be used for washing to remove unreacted raw materials. After washing, the product is dried at 120°C for 24 hours to remove toluene, and 713.2 g of product is obtained, with a yield of 85.0%. The product purity is determined by liquid chromatography, and the product purity is 97.9%. Because the dissolution loss of part of the product will occur during the toluene washing process, the yield is low.

[0053] Example 3

[0054] Add 2.5 mol of octadecane bromide, 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, 10 mol of solvent benzene, and 0.2 mol of catalyst KI into a reactor, heat to 80°C, stir and reflux for reaction for 40 hours, and after the reaction system cools to room temperature, add a 5% benzene solution of silver perchlorate by mass to make the molar amount of silver perchlorate added be 2.3 mol, continue stirring for 30 minutes, then filter, collect the obtained filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure, wash the solid product obtained after the solvent is evaporated with 8 mol of ethyl acetate 3 times and 30 mol of water 3 times, respectively, and then dry at 100°C for 12 hours to obtain 809.7 g of quaternary ammonium salt product, with a yield of 92.2% based on N,N,N',N'-tetramethyl-1,6-hexanediamine and a product purity of 98.6%.

[0055] Example 4

[0056] Add 2.5 mol of octadecane bromide, 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, 10 mol of toluene solvent, and 0.2 mol of catalyst KI into a reactor, heat to 110°C, stir and reflux for reaction for 28 hours, and after the reaction system cools to room temperature, add a 5% toluene solution of silver perchlorate by mass to make the molar amount of silver perchlorate added be 2.3 mol, continue stirring for 30 minutes, then filter, collect the obtained filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure, wash the solid product obtained after the solvent is evaporated with 8 mol of dichloromethane 3 times and 30 mol of water 3 times, respectively, and then dry at 120°C for 4 hours to obtain 827.2 g of quaternary ammonium salt product, with a yield of 94.2% based on N,N,N',N'-tetramethyl-1,6-hexanediamine and a product purity of 98.5%.

[0057] Example 5

[0058] Add 2.8 mol of octadecane bromide, 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, 10 mol of solvent DMF, and 0.2 mol of catalyst KI to the reactor, heat to 150°C, stir and reflux for 20 hours, and after the reaction system cools to room temperature, add 5% pyridine solution of silver perchlorate to make the added molar amount of silver perchlorate 2.3 mol, continue stirring for 30 minutes, then filter, collect the obtained filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure, wash the solid product obtained after evaporating the solvent with 8 mol of ethanol 3 times and 30 mol of water 3 times, and then dry at 120°C for 4 hours to obtain 853.6 g of quaternary ammonium salt product, with a yield of 97.2% and a product purity of 98.4% based on N,N,N',N'-tetramethyl-1,6-hexanediamine. .

[0059] Example 6

[0060] Add 3.0 mol of octadecane bromide, 1 mol of N,N,N',N'-tetramethyl-1,6-hexanediamine, 10 mol of solvent DMF, and 0.3 mol of catalyst KI into a reactor, heat to 150°C, stir and reflux for reaction for 28 hours, and after the reaction system cools to room temperature, add a 5% toluene solution of silver perchlorate by mass to make the molar amount of silver perchlorate added be 2.5 mol, continue stirring for 30 minutes, then filter, collect the obtained filtrate, use a rotary evaporator to evaporate the solvent under reduced pressure, wash the solid product obtained after the solvent is evaporated with 8 mol of ethanol 3 times and 30 mol of water 3 times, respectively, and then dry at 120°C for 4 hours to obtain 860.6 g of quaternary ammonium salt product, with a yield of 98.0% based on N,N,N',N'-tetramethyl-1,6-hexanediamine and a product purity of 98.5%.

Claims

1. A quaternary ammonium salt speed reducer, characterized in that: The molecular formula is C 46 H 98 N2Cl2O8, the molecular structure is as follows: 。 2. The synthetic method of quaternary ammonium salt speed reducer according to claim 1, wherein: The specific process includes: taking halogenated octadecane and N,N,N',N'-tetramethyl-1,6-hexanediamine as raw materials, adding solvent A and catalyst, heating and stirring evenly, adding silver perchlorate solution B after the reaction system cools to room temperature, continuing to stir evenly, then filtering, collecting the obtained filtrate, distilling off solvent A and solvent B under reduced pressure, washing with organic solvent C and water respectively, and then drying to obtain a quaternary ammonium salt product; The solvent A is DMF, DMSO, benzene or toluene, and the molar ratio of solvent A to N,N,N',N'-tetramethyl-1,6-hexanediamine is (5-10):1; The catalyst is KI or iodooctadecane, and the molar ratio of the catalyst to N,N,N',N'-tetramethyl-1,6-hexanediamine as the raw material is (0.1-0.3):

1. After adding the catalyst, the heating and stirring conditions in the reaction are 70°C to the boiling point of the solvent, and the reaction time is 20-48h. The silver perchlorate solution B is one of benzene, toluene or pyridine solutions of silver perchlorate, wherein the concentration of silver perchlorate is 3-8%, the molar ratio of silver perchlorate to N,N,N',N'-tetramethyl-1,6-hexanediamine is (2.1-2.5):1, and stirring is continued at room temperature for 10-60 minutes after adding silver perchlorate.

3. The synthetic method of quaternary ammonium salt speed reducer according to claim 2, wherein: The halogenated octadecane is chlorooctadecane or bromooctadecane, and the feeding molar ratio of the halogenated octadecane to N,N,N',N'-tetramethyl-1,6-hexanediamine is (2-3):

1.

4. The synthetic method of quaternary ammonium salt speed reducer according to claim 2, wherein: The organic solvent C is one of methanol, ethanol, ethyl acetate or dichloromethane.

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