A polyester derivative, its preparation method and application

Abstract

This invention discloses a polyester derivative with the structure of formula (Ⅰ), its preparation method, and its application. The preparation method of the polyester derivative is as follows: 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol, fatty acid, dehydrating agent, and catalyst are added to an organic solvent and subjected to an esterification reaction under a nitrogen atmosphere. After the reaction is completed, the polyester derivative is purified to obtain the polyester derivative. The polyester derivative is used to coat AP, which effectively reduces the hygroscopicity and high-temperature decomposition temperature of AP.

Description

Technical Field

[0001] This invention relates to a compound, and more particularly to a polyester derivative thereof, its preparation method and application. Background Technology

[0002] Ammonium perchlorate (AP) exhibits high hygroscopicity, deliquescence, and agglomeration properties. When dry AP is placed in a constant temperature and humidity environment, its quality initially increases and then decreases (the increase is due to hygroscopicity, and the decrease is due to deliquescence), and the hygroscopic sample will clump. Coating and modification of AP can reduce its sensitivity, hygroscopicity, and agglomeration hardness, thereby improving its safety in use. Modification and coating can also increase the heat of decomposition and lower the decomposition temperature.

[0003] Polyester compounds obtained by esterification of alcohols containing multiple hydroxyl groups with acids are unstable as coating agents for ammonium perchlorate (AP), and the use of ester compounds as coating agents for ammonium perchlorate reduces the energy of the entire system. Summary of the Invention

[0004] Objectives of the Invention: The first objective of this invention is to provide a polyester derivative that can reduce the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate while maintaining stability and not reducing the energy of the ammonium perchlorate system; the second objective of this invention is to provide a method for preparing the polyester derivative; the third objective of this invention is to provide the application of the polyester derivative in reducing the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate.

[0005] Technical solution: The polyester derivatives of this invention have the following structural formula:

[0006]

[0007] Where R is the carbon chain of a fatty acid.

[0008] The R is CH2=C(CH3)- or n-CH3(CH2). 12 -, CH3(CH2)7CH=CH(CH2)7-, CH3(CH2)7CH=CH(CH2) 11 -、p-NO2C6H4-, the corresponding derivatives are 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraα-methacrylate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraerucate and 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra4-nitrocinnamate.

[0009] The preparation method of the polyester derivatives of the present invention includes the following steps: adding 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol, fatty acid, dehydrating agent and catalyst into an organic solvent and carrying out an esterification reaction under a nitrogen atmosphere, and purifying the polyester derivatives after the reaction is completed.

[0010] Preferably, the reaction temperature is 20–30°C and the reaction time is 6–10 days.

[0011] Preferably, the purification is performed as follows: the reaction solution is poured into crushed ice, stirred until the crystals are completely precipitated, filtered, the filter cake is dissolved in diethyl ether, filtered, the filtrate is evaporated to dryness under reduced pressure, the crystals are precipitated, and finally recrystallized with methanol to obtain the product.

[0012] Preferably, the organic solvent is N,N-dimethylformamide.

[0013] Preferably, the dehydrating agent is dicyclohexylcarbodiimide, and the amount used is 4.5 to 5.5 times the molar amount of 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol.

[0014] Preferably, the catalyst is 4-dimethylaminopyridine, and the amount used is 0.5 to 0.7 times the molar amount of 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol.

[0015] Preferably, the purity of the dicyclohexylcarbodiimide is 98.0% to 99.0%.

[0016] Preferably, the purity of the 4-dimethylaminopyridine is 98.5% to 99.5%.

[0017] Preferably, the fatty acid is α-methacrylic acid, myristic acid, oleic acid, erucic acid, or 4-nitrocinnamic acid.

[0018] The application of the polyester derivatives described in this invention in reducing the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate.

[0019] The application method is as follows: coating polyol derivatives onto the surface of ammonium perchlorate.

[0020] Preferably, the coating is performed by adding a polyester derivative and ammonium perchlorate to a solvent, dissolving, distilling under reduced pressure, and drying to obtain modified ammonium perchlorate.

[0021] Preferably, the solvent is methanol; the dissolution temperature is 40–50°C; and the vacuum distillation temperature is 40–50°C.

[0022] Mechanism of invention: 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol undergoes esterification with organic acids (formic acid, acetic acid, and higher fatty acids) to yield corresponding polyester derivatives. The esters of 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol are non-hygroscopic, are hindered esters with strong thermal stability, and contain a nitro group, which helps maintain the high energy of the ammonium perchlorate system, thus making them excellent modifiers for amino acids (APs).

[0023] The five polyester derivatives of this invention—2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraα-methacrylate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraerucate, and 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra4-nitrocinnamate—were used to modify AP at 5% of each derivative. DSC characterization and hygroscopicity testing were then performed on the modified samples. The results showed that the high-temperature decomposition temperature and hygroscopicity of the modified samples were significantly reduced, making them excellent modifiers for AP.

[0024] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The polyester derivatives are used to coat AP, which effectively reduces the hygroscopicity and high-temperature decomposition temperature of AP; (2) The polyester derivatives 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraα-methacrylate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristate, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate, 2,3-dihydroxymethyl 2,3-Dinitro-1,4-butanediol tetrasorcinate and 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-4-nitrocinnamate were used to coat AP, respectively. The maximum moisture absorption rate of AP decreased from 5.51% to 1.89%, 1.95%, 2.90%, 1.65%, and 2.66%, respectively, and the high-temperature decomposition temperature of AP decreased from 437.0℃ to 326.8℃, 422.8℃, 426.5℃, 423.8℃, and 365.5℃, respectively, showing significant improvement. Attached Figure Description

[0025] Figure 1 The 1H NMR spectrum of 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraα-methacrylate, a polyester derivative prepared in Example 1;

[0026] Figure 2The 1H NMR spectrum of the polyester derivative 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristic acid ester prepared in Example 2;

[0027] Figure 3 The 1H NMR spectrum of the polyester derivative 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate prepared in Example 3;

[0028] Figure 4 The 1H NMR spectrum of the polyester derivative 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetrasorcinate prepared in Example 4;

[0029] Figure 5 The 1H NMR spectrum of the polyester derivative 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-4-nitrocinnamate prepared in Example 5;

[0030] Figure 6 Infrared spectra of the polyester derivatives prepared in Examples 1-5;

[0031] Figure 7 Line graphs showing the moisture absorption rate versus time relationship between pure AP and AP coated with the five polyester derivatives prepared in Examples 1-5;

[0032] Figure 8 DSC curves of pure AP and AP coated with the five polyester derivatives prepared in Examples 1-5. Detailed Implementation

[0033] The technical solution of the present invention will be further described below with reference to the embodiments.

[0034] Example 1

[0035] The polyester derivative of this invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraα-methacrylate, and its preparation method includes the following steps:

[0036] (1) Add 0.24 g (1 mmol) of 2,3-dihydroxymethyl-2,3-nitro-1,4-butanediol and 0.43 g (5 mmol) of α-methacrylic acid to a clean and dry round-bottom flask, add 10 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30℃;

[0037] (2) Add 1.03g DCC (dicyclohexylcarbodiimide, 5mmol) and 67.8mg DMAP (4-dimethylaminopyridine, 0.6mmol) to a round-bottom flask, keep the temperature at 20-30℃, and stir until completely dissolved;

[0038] (3) Introduce nitrogen gas to purge the air from the apparatus, seal it, and maintain the temperature at 20-30°C for 6 days;

[0039] (4) After the reaction is complete, pour the solution into ice water and stir for 15 minutes. After the precipitate is completely precipitated, filter it, add 10 ml of diethyl ether to dissolve the filter cake, filter out the insoluble matter, evaporate the filtrate, precipitate crystals, dissolve in methanol and recrystallize to obtain the pure product.

[0040] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraα-methacrylate: 1 H NMR (400MHz, CDCl3): δ5.23, 5.16 (d, J = 12.4Hz, 8H), 2.94, 2.88, 2.83 (dd, J = 12.4Hz, 8H), 2.03 (s, J = 12.4Hz, 12H). IR: v (cm -1 ):2988,2901,1688,1454; 2988cm -1 2901cm -1 CH stretching vibration, 1688cm -1 C=O stretching vibration, 1454 cm -1 NO. Stretching vibration.

[0041] Example 2

[0042] The polyester derivative of this invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristate, and its preparation method includes the following steps:

[0043] (1) Add 0.24 g (1 mmol) of 2,3-dihydroxymethyl-2,3-nitro-1,4-butanediol and 1.14 g (5 mmol) of myristic acid to a clean and dry round-bottom flask, add 20 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30℃.

[0044] (2) Add 1.03g DCC (dicyclohexylcarbodiimide, 5mmol) and 67.8mg DMAP (4-dimethylaminopyridine, 0.6mmol) to a round-bottom flask, keep the temperature at 20-30℃, and stir until completely dissolved;

[0045] (3) Introduce nitrogen gas to purge the air from the apparatus, seal it, and maintain the temperature at 20-30°C for 7 days;

[0046] (4) After the reaction is complete, pour the solution into ice water and stir for 15 minutes. After the precipitate is completely precipitated, filter it, add 20 ml of diethyl ether to dissolve the filter cake, filter out the insoluble matter, evaporate the filtrate, precipitate crystals, dissolve in methanol and recrystallize to obtain the pure product.

[0047] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristate 1 H NMR (400MHz, CDCl3): δ4.50, 4.45, 4.36, 2.32 (dd, J = 12.4Hz, 8H), 2.39, 2.37, 2.35, (t, J = 12.4Hz, 8H), 1.71 ,1.68,1.66(tt,J=12.4Hz,8H),1.38~1.20(s,J=12.4Hz,80H),0.89,0.88,0.86(t,J=12.4Hz,12H).IR:v(cm -1 ):2988,2913,2847,1698,1471; 2988cm -1 2913cm -1 2847cm -1 CH stretching vibration, 1698cm -1 C=O stretching vibration, 1471 cm -1 NO. Stretching vibration.

[0048] Example 3

[0049] The polyester derivative of this invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate, and its preparation method includes the following steps:

[0050] (1) Add 0.24 g (1 mmol) of 2,3-dihydroxymethyl-2,3-nitro-1,4-butanediol and 1.41 g (5 mmol) of oleic acid to a clean and dry round-bottom flask, add 20 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30℃.

[0051] (2) Add 1.03g DCC (dicyclohexylcarbodiimide, 5mmol) and 67.8mg DMAP (4-dimethylaminopyridine, 0.6mmol) to a round-bottom flask, keep the temperature at 20-30℃, and stir until completely dissolved;

[0052] (3) Introduce nitrogen gas to purge the air from the apparatus, seal it, and maintain the temperature at 20-30°C for 7 days;

[0053] (4) After the reaction is complete, pour the solution into ice water and stir for 15 minutes. After the precipitate is completely precipitated, filter it, add 20 ml of diethyl ether to dissolve the filter cake, filter out the insoluble matter, evaporate the filtrate, precipitate crystals, dissolve in methanol and recrystallize to obtain the pure product.

[0054] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate 1H NMR (400MHz, CDCl3): δ5.42,5.41,5.39,5.37(dt,J=12.4Hz,8H),2.83,2.80,2.78,2.76(dd,J=12.4Hz,8H),2.38,2.36,2.34,(t,J=12.4Hz,8 H),2.05(dt,J=12.4Hz,16H),1.68,1.66,1.63(tt,J=12.4Hz,8H),1.40~1.15(s,J=12.4Hz,80H),0.89,0.88,0.86(t,J=12.4Hz,12H).IR:v(cm -1 ):2988,2916,2849,1691,1471; 2987cm -1 2922cm -1 2854cm -1 CH stretching vibration, 1707cm -1 C=O stretching vibration, 1455cm -1 NO. Stretching vibration.

[0055] Example 4

[0056] The polyester derivative of this invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetrasorcinate, and its preparation method includes the following steps:

[0057] (1) Add 0.24 g (1 mmol) of 2,3-dihydroxymethyl-2,3-nitro-1,4-butanediol and 1.69 g (5 mmol) of erucic acid to a clean and dry round-bottom flask, add 20 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30℃;

[0058] (2) Add 1.03g DCC (dicyclohexylcarbodiimide, 5mmol) and 67.8mg DMAP (4-dimethylaminopyridine, 0.6mmol) to a round-bottom flask, keep the temperature at 20-30℃, and stir until completely dissolved;

[0059] (3) Introduce nitrogen gas to purge the air from the apparatus, seal it, and maintain the temperature at 20-30°C for 7 days;

[0060] (4) After the reaction is complete, pour the solution into ice water and stir for 15 minutes. After the precipitate is completely precipitated, filter it, add 20 ml of diethyl ether to dissolve the filter cake, filter out the insoluble matter, evaporate the filtrate, precipitate crystals, dissolve in methanol and recrystallize to obtain the pure product.

[0061] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetrasorcinate 1H NMR (400MHz, CDCl3): δ5.42,5.38,5.37,5.36,5.33(dt,J=12.4Hz,8H),2.28,2.30,2.33(t,J=12.4Hz,8H),3.75,3.72,3.70,3.67(dd,J=12.4Hz, 8H),2.03(dt,J=12.4Hz,16H),1.67,1.65,1.62(tt,J=12.4Hz,8H),1.40 ~1.15(s,J=12.4Hz,112H),0.89,0.88,0.86(t,J=12.4Hz,12H).IR:v(cm -1 ):2988,2916,2849,1691,1471; 2988cm -1 2916cm -1 2849cm -1 CH stretching vibration, 1691cm -1 C=O stretching vibration, 1471 cm -1 NO. Stretching vibration.

[0062] Example 5

[0063] The polyester derivative of this invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-4-nitrocinnamate, and its preparation method includes the following steps:

[0064] (1) Add 0.24 g (1 mmol) of 2,3-dihydroxymethyl-2,3-nitro-1,4-butanediol and 0.965 g (5 mmol) of 4-nitrocinnamic acid to a clean and dry round-bottom flask, add 50 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30℃.

[0065] (2) Add 1.03g DCC (dicyclohexylcarbodiimide, 5mmol) and 67.8mg DMAP (4-dimethylaminopyridine, 0.6mmol) to a round-bottom flask, keep the temperature at 20-30℃, and stir until completely dissolved;

[0066] (3) Introduce nitrogen gas to purge the air from the apparatus, seal it, maintain the temperature at 20-30°C, and react for 10 days;

[0067] (4) After the reaction is complete, pour the solution into ice water and stir for 15 minutes. After the precipitate is completely precipitated, filter it, add 20 ml of diethyl ether to dissolve the filter cake, filter out the insoluble matter, evaporate the filtrate, precipitate crystals, dissolve in methanol and recrystallize to obtain the pure product.

[0068] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-4-nitrocinnamate 1 H NMR (400MHz, CDCl3): δ8.18, 8.15 (d, J = 12.4Hz, 8H), 8.03 (s, J = 12.4Hz, 8H), 7. 35,7.39(d,J=12.4Hz,8H),4.49,4.46,4.37,4.34(dd,J=12.4Hz,8H).IR:v(cm -1 ):2988,2901,1683,1629,1604,1518; 2988cm -1 2901cm -1 CH stretching vibration, 1683cm -1 C=O stretching vibration, 1629cm -1 1604cm -1 : Benzene ring CH stretching vibration, 1518 cm -1 NO. Stretching vibration.

[0069] Performance testing

[0070] The polyester derivatives prepared in Examples 1-5 were used for coating perchloric acid, and the application methods included the following steps:

[0071] (1) Take 0.6g of ammonium perchlorate and 0.03g of polyester derivative and add them to a clean flask, then add 20ml of methanol;

[0072] (2) Heat and stir the flask in a water bath at 40-50°C for 10 minutes until the ammonium perchlorate and polyester derivatives are completely dissolved.

[0073] (3) The solution is distilled under reduced pressure at 40-50℃, with the stirring speed set to 500-750 r / min and the vacuum degree set to 0.08-0.09 MPa. After the solvent has evaporated, the power supply to the water bath and vacuum water pump is turned off.

[0074] (4) The coated ammonium perchlorate was placed in a vacuum drying oven and dried for 6 hours to obtain the final coated ammonium perchlorate.

[0075] Moisture absorption rate test: 0.5g of dry ammonium perchlorate was placed in a petri dish, which was then placed in a constant temperature and humidity atmosphere. The mass change was recorded every 12 hours, and the relationship between moisture absorption rate and time was calculated. The test results are as follows: Figure 1 As shown.

[0076] High-temperature decomposition temperature test: The dried, coated ammonium perchlorate was subjected to DSC testing in the temperature range of 50–500℃, with a heating rate of 10℃ / min. The DSC curves were obtained. The test results are as follows: Figure 2 As shown.

[0077] Depend on Figure 7 and 8 The results show that the maximum moisture absorption rate of ammonium perchlorate coated with the polyester derivative prepared in Example 1 was 1.89%, and the high-temperature decomposition peak temperature was 326.8℃; the maximum moisture absorption rate of ammonium perchlorate coated with the polyester derivative prepared in Example 2 was 1.95%, and the high-temperature decomposition peak temperature was 422.8℃; the maximum moisture absorption rate of ammonium perchlorate coated with the polyester derivative prepared in Example 3 was 2.90%, and the high-temperature decomposition peak temperature was 426.5℃; the maximum moisture absorption rate of ammonium perchlorate coated with the polyester derivative prepared in Example 4 was 1.65%, and the high-temperature decomposition peak temperature was 423.8℃; and the maximum moisture absorption rate of ammonium perchlorate coated with the polyester derivative prepared in Example 5 was 2.66%, and the high-temperature decomposition peak temperature was 365.5℃.

[0078] Untreated ammonium perchlorate had a maximum hygroscopicity of 5.51% and a high-temperature decomposition temperature of 437.0℃. In contrast, the polyester derivatives prepared in Examples 1-5, after coating ammonium perchlorate, significantly reduced its hygroscopicity and high-temperature decomposition peak. Reduced hygroscopicity facilitates energy release during ammonium perchlorate decomposition, and lower decomposition temperature helps increase the rate of energy release under certain heating conditions.

Claims

1. A polyester derivative, characterized in that, The structural formula is: or 。 2. A method for preparing the polybasic ester derivative according to claim 1, characterized by, The method comprises the following steps: The esterification reaction is carried out by adding 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol, fatty acid, dehydrating agent and catalyst into an organic solvent under a nitrogen atmosphere, and the polybasic ester derivative is obtained by purification after the reaction is completed.

3. The method of claim 2, wherein the polybasic acid is a C4-Ci 8 carboxylic acid. The reaction temperature is 20-30 DEG C.

4. The method of claim 2, wherein the polybasic acid is a mixture of succinic acid and adipic acid. The purification is as follows: the reaction liquid is poured into crushed ice, stirring is carried out until the crystals are completely precipitated, filtration is carried out, the filter cake is dissolved with diethyl ether, filtration is carried out, the filtrate is distilled under reduced pressure until dry, the crystals are precipitated, and finally, the product is obtained by recrystallization with methanol.

5. The polybasic ester derivative of claim 1 is applied to reduce the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate.

6. Use according to claim 5, characterized in that, The application method is that the polyol derivative is coated on the surface of ammonium perchlorate.

7. Use according to claim 6, characterized in that, The coating is as follows: the polybasic ester derivative and ammonium perchlorate are added into a solvent, dissolved, distilled under reduced pressure, and dried to obtain modified ammonium perchlorate.

8. Use according to claim 7, characterized in that, The solvent is methanol.

9. Use according to claim 7, characterized in that, The dissolving temperature is 40-50 DEG C.

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