Amine mechanical enhancer as well as synthesis method and application thereof

Abstract

The invention discloses an amine mechanical enhancer as well as a synthesis method and application thereof, alkyl thioether diketone is taken as a raw material and reacts with p-aminodiphenylamine to obtain alkyl thioether di (anilino) imine, and then the alkyl thioether di (anilino) imine is subjected to catalytic hydrogenation reaction through a palladium-carbon catalyst to obtain the amine sulfur-containing mechanical enhancer. The synthesized amine sulfur-containing mechanical reinforcing agent has a good anti-aging effect and can be used for improving the mechanical property of a solid propellant, inhibiting embrittlement and increasing the tensile strength and the ductility.

Description

Technical Field

[0001] The invention belongs to the field of functional materials and relates to an amine mechanical enhancer and a synthesis method and application thereof. Background Art

[0002] Mechanical enhancers are one of the indispensable main functional additives in high-solid content and high-energy propellant products. Their use can greatly increase the service life of the propellant and improve the mechanical properties of the propellant. Adding mechanical enhancers to the solid propellant formula can effectively improve the brittleness of the propellant matrix and increase the tensile strength and elongation.

[0003] According to their chemical structure, mechanical enhancers can be divided into amines, phenols, heterocyclics, phosphites, and other types. Among them, amine mechanical enhancers are one of the most commonly used enhancers, mainly used to inhibit the propellant from becoming brittle and causing the mechanical properties to decline and affect its use. Its disadvantage is that it is highly polluting. According to the structure, it can be further divided into phenylnaphthylamines, ketoamines, diphenylamine derivatives, and p-phenylenediamine derivatives. P-phenylenediamine is currently the most important and largest-producing type of amine mechanical enhancer. Its main varieties include 4010NA (N-isopropyl-N'-phenyl p-phenylenediamine), 4020 (N-(1,3-dimethylbutyl)-N'-phenyl p-phenylenediamine), 4030 (N,N'-di(1,4-dimethylpentyl) p-phenylenediamine), etc. Its molecular structure is as follows:

[0004]

[0005] Amine mechanical enhancers are used in solid propellants to improve the brittleness of propellants, but the tensile strength and elongation decrease, and the overall mechanical properties are not good. It is urgent to develop new mechanical enhancers that can increase the tensile strength and elongation while suppressing the embrittlement of propellants. Summary of the invention

[0006] In view of the deficiencies in the prior art, the purpose of the present invention is to provide an amine mechanical enhancer and a synthesis method and application thereof, so as to solve the problems that the application of the existing amine mechanical enhancers to solid propellants will lead to a decrease in tensile strength and elongation, and poor comprehensive mechanical properties. The present invention combines an amine structure with a vulcanization structure to produce a synergistic effect during the application process, thereby achieving the goal of suppressing the embrittlement of the solid propellant while improving its tensile strength and elongation.

[0007] In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve the above problems:

[0008] An amine mechanical enhancer, the structural formula of which is shown in (I):

[0009]

[0010] Wherein R is an alkyl group, including methyl, ethyl, propyl, butyl, and pentyl.

[0011] The synthesis method of the amine mechanical enhancer comprises the following steps:

[0012] Step 1, adding alkyl sulfide diketone and p-aminodiphenylamine to toluene, adding 4A molecular sieve, and reflux reaction at a temperature of 110-115° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing toluene by vacuum distillation to obtain alkyl sulfide di(aniline)imine;

[0013] Step 2, adding the alkyl sulfide di(aniline)imine obtained in step 1 and the palladium-carbon catalyst into methanol, introducing hydrogen, and reacting at a temperature of 30-35° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing methanol by vacuum distillation to obtain an amine-based sulfur-containing mechanical enhancer.

[0014] The present invention also includes the following technical features:

[0015] Specifically, in step 1, the molar ratio of alkyl sulfide diketone to p-aminodiphenylamine is 1:2-3, and the feed ratio of alkyl sulfide diketone to toluene is 1 mol:600 ml.

[0016] Specifically, in step 2, the molar ratio of alkyl sulfide di(aniline)imine to palladium-carbon catalyst is 1:0.04-0.06, and the feed ratio of alkyl sulfide di(aniline)imine to methanol is 1 mol:600 ml.

[0017] Specifically, in step 1, the alkyl sulfide diketone includes methyl sulfide diketone; and the alkyl sulfide di(aniline)imine includes methyl sulfide di(aniline)imine.

[0018] Specifically, the molar ratio of methyl sulfide diketone to p-aminodiphenylamine is 1:2.2, and the feed ratio of methyl sulfide diketone to toluene is 1 mol:600 ml.

[0019] Specifically, the molar ratio of the methyl sulfide di(aniline)imine to the palladium-carbon catalyst is 1:0.05, and the feed ratio of the methyl sulfide di(aniline)imine to methanol is 1 mol:600 ml.

[0020] Specifically, in step 2, the amine-based sulfur-containing mechanical enhancer obtained includes methyl sulfide bis(diphenylamino)amine.

[0021] The amine mechanical reinforcing agent synthesized by the synthesis method of the amine mechanical reinforcing agent is used as a mechanical reinforcing agent in solid propellants.

[0022] Compared with the prior art, the present invention has the following technical effects:

[0023] (1) The amine-containing sulfur mechanical enhancer of the present invention has both amine and sulfurized structures, and can produce synergistic effects when used in propellants. (2) The preparation process of the amine-containing sulfur mechanical enhancer of the present invention is simple, safe and reliable. (3) The amine-containing sulfur mechanical enhancer of the present invention can effectively improve the mechanical properties of solid propellants. Compared with the amine-containing mechanical enhancer 4010NA, the embrittlement parameter is reduced from 29.32 to 24.57; under low temperature conditions (-40°C), the tensile strength is increased from 22.9MPa to 25.1MPa, and the elongation is increased from 2.03% to 3.98%; under high temperature conditions (50°C), the tensile strength is increased from 0.97MPa to 1.12MPa, and the elongation is increased from 17.2% to 31.5%. DETAILED DESCRIPTION

[0024] The present invention provides an amine mechanical enhancer and a synthesis method and application thereof, wherein the synthesis route is:

[0025]

[0026] The sulfodialkyl alcohol is used as the raw material, and reacts with p-aminodiphenylamine under the catalysis of p-toluenesulfonic acid to obtain an amine sulfur-containing mechanical enhancer.

[0027] The amine sulfur-containing mechanical enhancer of the present invention has a structure as shown in (I):

[0028]

[0029] Wherein R is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, etc.

[0030] The method for synthesizing the amine sulfur-containing mechanical enhancer of the present invention comprises the following steps:

[0031] Step 1, using alkyl sulfide diketone as a raw material, adding alkyl sulfide diketone and p-aminodiphenylamine into toluene, adding 4A molecular sieve, and reflux reaction at a temperature of 110-115° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing toluene by vacuum distillation to obtain alkyl sulfide di(aniline)imine, wherein the molar ratio of alkyl sulfide diketone to p-aminodiphenylamine is 1:2-3, and the feed ratio of alkyl sulfide diketone to toluene is 1 mol:600 ml.

[0032] Step 2, adding the alkyl sulfide di(aniline)imine and palladium carbon catalyst obtained in step 1 into methanol, introducing hydrogen, and reacting at a temperature of 30-35° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing methanol by reduced pressure distillation to obtain an amine sulfur-containing mechanical enhancer, wherein the molar ratio of the alkyl sulfide di(aniline)imine and the palladium carbon catalyst is 1:0.04-0.06, and the feed ratio of the alkyl sulfide di(aniline)imine to the methanol is 1 mol:600 ml.

[0033] Preferably, the synthesis method of the amine sulfur-containing mechanical enhancer comprises the following steps:

[0034] (1) Using methyl sulfide diketone as a raw material, methyl sulfide diketone and p-aminodiphenylamine are added to toluene, and 4A molecular sieve is added. The temperature is 110-115° C. for reflux reaction. After the reaction is completed, it is naturally cooled to room temperature, filtered, and toluene is removed by vacuum distillation to obtain methyl sulfide di(aniline)imine, wherein the molar ratio of methyl sulfide diketone to p-aminodiphenylamine is 1:2.2, and the feed ratio of methyl sulfide diketone to toluene is 1 mol:600 ml.

[0035] (2) adding the methyl sulfide di(aniline)imine obtained in step (1) and the palladium-carbon catalyst to methanol, introducing hydrogen, and reacting at a temperature of 30 to 35° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing methanol by reduced pressure distillation to obtain methyl sulfide di(aniline)amine, wherein the molar ratio of methyl sulfide di(aniline)imine to the palladium-carbon catalyst is 1:0.05, and the feed ratio of methyl sulfide di(aniline)imine to methanol is 1 mol:600 ml.

[0036] The amine mechanical reinforcing agent synthesized by the invention is used as a mechanical reinforcing agent in solid propellants.

[0037] 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 changes made on the basis of the technical solution of this application fall within the protection scope of the present invention.

[0038] Embodiment 1:

[0039] This embodiment provides an amine mechanical enhancer and a synthesis method thereof, comprising the following steps:

[0040] (1) Preparation of methyl sulfide di(anilino)imide

[0041] Under stirring, at a temperature of 20°C to 25°C, 1 mol of methyl sulfide diketone, 2.2 mol of p-aminodiphenylamine, 4A molecular sieves, and 600 ml of toluene were added to the reaction flask in sequence, and refluxed at 110 to 115°C for dehydration until the solvent in the water separator became transparent. The mixture was naturally cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure to remove toluene to obtain 376.6 g of methyl sulfide di(anilino)imine with a yield of 78.68%.

[0042] (2) Preparation of methyl sulfide bis(diphenylamino)amine

[0043] Under stirring, 0.5 mol of methyl sulfide di(aniline)imine, 0.025 mol of palladium-carbon catalyst and 300 ml of methanol were added to the reaction flask in sequence at a temperature of 20°C to 25°C, hydrogen was introduced, and the reaction was carried out at a temperature of 30 to 35°C. After the reaction was completed, it was naturally cooled to room temperature, filtered, and methanol was removed by distillation under reduced pressure to obtain 233.4 g of a bright yellow viscous liquid with a yield of 96.79%.

[0044] (3) Structural identification:

[0045] Infrared spectrum: IR (KBr, cm -1 ),υ:3428(-NH), 3095(CH), 1590(C=C), 662(CS);

[0046] NMR spectrum: 1 H NMR(DMSO,500MHz),δ:7.79(s,2H,2NH),7.40(m,4H,4CH),7.08(m,4H,4CH),7.06(m,4H,4CH),7.02(m,2H,2CH) ,6.63(m,4H,4CH),4.57(s,2H,2NH),3.00(m,2H,2CH),2.73(m,4H,2CH2),2.48(m,4H,2CH2),1.24(s,3H,2CH3). 13 C NMR (DMSO, 125MHz), δ: 142.4(CH), 137.1(CH), 130.8(CH), 129.6(CH), 121.9(CH), 121.1(CH), 120.6(CH), 118.6(CH), 59.0(CH), 41.0(CH2), 20.0(CH3).

[0047] Elemental analysis: Molecular formula C 30 H 34 N4S;

[0048] Theoretical value (%): C 74.65, H 7.10, N 11.61;

[0049] Found (%): C 74.62, H 7.01, N 11.59.

[0050] The above structural identification data confirmed that the obtained substance was indeed methyl sulfide bis(diphenylamino)amine.

[0051] Embodiment 2:

[0052] This embodiment provides an amine mechanical enhancer and a synthesis method thereof, comprising the following steps:

[0053] (1) Preparation of methyl sulfide di(anilino)imide

[0054] Under stirring, at a temperature of 20°C to 25°C, 1 mol of methyl sulfide diketone, 2 mol of p-aminodiphenylamine, 4A molecular sieves, and 600 ml of toluene were added to the reaction flask in sequence, and refluxed at 110 to 115°C for dehydration until the solvent in the water separator became transparent. The mixture was naturally cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure to remove toluene to obtain 359.8 g of methyl sulfide di(aniline)imine with a yield of 75.17%.

[0055] (2) Preparation of methyl sulfide bis(diphenylamino)amine

[0056] Under stirring, at a temperature of 20°C to 25°C, 0.5 mol of methyl sulfide di(aniline)imine, 0.02 mol of palladium-carbon catalyst and 300 ml of methanol were added to the reaction flask in sequence, and hydrogen was introduced to react at a temperature of 30 to 35°C. After the reaction was completed, it was naturally cooled to room temperature, filtered, and methanol was removed by distillation under reduced pressure to obtain 229.7 g of a bright yellow viscous liquid with a yield of 95.26%.

[0057] Embodiment 3:

[0058] This embodiment provides an amine mechanical enhancer and a synthesis method thereof, comprising the following steps:

[0059] (1) Preparation of methyl sulfide di(anilino)imide

[0060] Under stirring, at a temperature of 20°C to 25°C, 1 mol of methyl sulfide diketone, 2.4 mol of p-aminodiphenylamine, 4A molecular sieves, and 600 ml of toluene were refluxed and dehydrated at 110-115°C until the solvent in the water separator became transparent. The mixture was naturally cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure to remove toluene to obtain 376.3 g of methyl sulfide di(aniline)imine with a yield of 78.62%.

[0061] (2) Preparation of methyl sulfide bis(diphenylamino)amine

[0062] Under stirring, 0.5 mol of methyl sulfide di(aniline)imine, 0.025 mol of palladium-carbon catalyst and 300 ml of methanol were added to the reaction flask in sequence at a temperature of 20°C to 25°C, hydrogen was introduced, and the reaction was carried out at a temperature of 30 to 35°C. After the reaction was completed, it was naturally cooled to room temperature, filtered, and methanol was removed by distillation under reduced pressure to obtain 233.2 g of a bright yellow viscous liquid with a yield of 96.71%.

[0063] Embodiment 4:

[0064] This embodiment provides an amine mechanical enhancer and a synthesis method thereof, comprising the following steps:

[0065] (1) Preparation of methyl sulfide di(anilino)imide

[0066] Under stirring, at a temperature of 20°C to 25°C, 1 mol of methyl sulfide diketone, 2.6 mol of p-aminodiphenylamine, 4A molecular sieves, and 600 ml of toluene were added to the reaction flask in sequence, and refluxed at 110 to 115°C for dehydration until the solvent in the water separator became transparent. The mixture was naturally cooled to room temperature, filtered, and the filtrate was distilled under reduced pressure to remove toluene to obtain 376.5 g of methyl sulfide di(aniline)imine with a yield of 78.66%.

[0067] (2) Preparation of methyl sulfide bis(diphenylamino)amine

[0068] Under stirring, 0.5 mol of methyl sulfide di(aniline)imine, 0.02 mol of palladium-carbon catalyst and 300 ml of methanol were added to the reaction flask in sequence at a temperature of 20°C to 25°C, hydrogen was introduced, and the reaction was carried out at a temperature of 30 to 35°C. After the reaction was completed, it was naturally cooled to room temperature, filtered, and methanol was removed by distillation under reduced pressure to obtain 231.5 g of a bright yellow viscous liquid with a yield of 96.01%.

[0069] Application of the amine sulfur-containing mechanical enhancer of the present invention:

[0070] The amine sulfur-containing mechanical enhancer of the present invention can be used to improve the mechanical properties of solid propellants, inhibit embrittlement, and increase tensile strength and elongation.

[0071] Table 1 Tensile strength and embrittlement parameters of solid propellants

[0072]

[0073] Compared with the traditional amine mechanical enhancer 4010NA, the embrittlement parameter decreased by 16.2%, the low-temperature tensile strength increased by 9.6%, and the elongation increased by 96.1%; the high-temperature tensile strength increased by 15.5%, and the elongation increased by 83.1%, indicating that amine sulfur-containing mechanical enhancers have good application effects in solid propellants and can effectively improve their mechanical properties.

Claims

1. An amine mechanical enhancer, characterized in that: Its structural formula is shown in (I): Wherein R is an alkyl group, including methyl, ethyl, propyl, butyl, and pentyl.

2. The method for synthesizing the amine mechanical enhancer according to claim 1, characterized in that: The following steps are involved: Step 1, adding alkyl sulfide diketone and p-aminodiphenylamine to toluene, adding 4A molecular sieve, and reflux reaction at a temperature of 110-115° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing toluene by vacuum distillation to obtain alkyl sulfide di(aniline)imine; Step 2, adding the alkyl sulfide di(aniline)imine obtained in step 1 and the palladium-carbon catalyst into methanol, introducing hydrogen, and reacting at a temperature of 30-35° C. After the reaction is completed, naturally cooling to room temperature, filtering, and removing methanol by vacuum distillation to obtain an amine-based sulfur-containing mechanical enhancer.

3. The method for synthesizing an amine mechanical enhancer according to claim 2, characterized in that: In the step 1, the molar ratio of alkyl sulfide diketone to p-aminodiphenylamine is 1:2-3, and the feed ratio of alkyl sulfide diketone to toluene is 1 mol:600 ml.

4. The method for synthesizing an amine mechanical enhancer according to claim 2, characterized in that: In the step 2, the molar ratio of alkyl sulfide di(aniline)imine to the palladium-carbon catalyst is 1:0.04-0.06, and the feed ratio of alkyl sulfide di(aniline)imine to methanol is 1 mol:600 ml.

5. The method for synthesizing an amine mechanical enhancer according to claim 2, characterized in that: In the step 1, the alkyl sulfide diketone includes methyl sulfide diketone; and the alkyl sulfide di(anilino)imine includes methyl sulfide di(anilino)imine.

6. The method for synthesizing an amine mechanical enhancer according to claim 5, characterized in that: The molar ratio of the methyl sulfide diketone to p-aminodiphenylamine is 1:2.2, and the feed ratio of the methyl sulfide diketone to toluene is 1 mol:600 ml.

7. The method for synthesizing an amine mechanical enhancer according to claim 5, characterized in that: The molar ratio of the methyl sulfide di(aniline)imine to the palladium-carbon catalyst is 1:0.05, and the feed ratio of the methyl sulfide di(aniline)imine to methanol is 1 mol:600 ml.

8. The method for synthesizing an amine mechanical enhancer according to claim 7, characterized in that: In the step 2, the obtained amine sulfur-containing mechanical enhancer includes methyl sulfide bis(diphenylamino)amine.

9. Use of the amine mechanical reinforcing agent synthesized by the synthesis method of the amine mechanical reinforcing agent according to claim 2 as a mechanical reinforcing agent in solid propellants.

Images