Polyester derivative as well as preparation method and application thereof

Abstract

The invention discloses a polyester derivative with a structure shown in a formula (I) as well as a preparation method and application thereof, and the preparation method of the polyester derivative comprises the following steps: adding 2, 3-dimethylol-2, 3-dinitro-1, 4-butanediol, fatty acid, a dehydrating agent and a catalyst into an organic solvent, and carrying out esterification reaction in a nitrogen atmosphere to obtain the polyester derivative. And after the reaction is finished, purifying to obtain the polyester derivative. The polyester derivative is used for coating AP, and the hygroscopicity and the high-temperature decomposition temperature of AP are effectively reduced. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a compound, in particular to a polybasic ester derivative and a preparation method and application thereof. Background Art

[0002] Ammonium perchlorate has high hygroscopicity, deliquescent and agglomerating properties. When dry ammonium perchlorate (AP) is placed in a constant temperature and humidity environment, its quality will first increase and then decrease (the increase is due to hygroscopicity, and the decrease is due to deliquescent property), and the sample will agglomerate after absorbing moisture. AP can reduce sensitivity, hygroscopicity and agglomeration hardness through coating and modification, thereby improving the safety of use. Modification and coating can also increase the decomposition heat release and reduce the decomposition temperature.

[0003] Polyester compounds obtained by esterification of alcohol compounds containing multiple hydroxyl groups with acids are unstable as coating agents for AP, and ester compounds as coating agents for ammonium perchlorate will reduce the energy of the entire system. Summary of the invention

[0004] Purpose of the invention: The first purpose of the present invention is to provide a polyester derivative which can reduce the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate and is stable without reducing the energy of the ammonium perchlorate system; the second purpose of the present invention is to provide a method for preparing the polyester derivative; the third purpose of the present invention is to provide the use of the polyester derivative in reducing the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate.

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

[0006]

[0007] Wherein, R is the carbon chain of fatty acid.

[0008] The R is CH2=C(CH3)-, n-CH3(CH2) 12 -, CH3(CH2)7CH=CH(CH2)7-, CH3(CH2)7CH=CH(CH2) 11 -, p-NO2C6H4-, and the corresponding derivatives are 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-α-methylacrylate, 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 tetra-4-nitrocinnamate.

[0009] The preparation method of the polyol ester derivatives of the present invention comprises the following steps: adding 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol, fatty acid, dehydrating agent and catalyst into an organic solvent to carry out esterification reaction under nitrogen atmosphere, and purifying after the reaction to obtain the polyol ester derivatives.

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

[0011] Preferably, the purification is as follows: pouring the reaction solution into crushed ice, stirring until crystals are completely precipitated, filtering, dissolving the filter cake with ether, filtering, distilling the filtrate under reduced pressure to dryness, precipitating crystals, and finally recrystallizing with methanol to obtain the product.

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

[0013] Preferably, the dehydrating agent is dicyclohexylcarbodiimide, and the usage amount 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 98.0-99.0%.

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

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

[0018] The polyester derivatives of the present invention are used in reducing the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate.

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

[0020] Preferably, the coating is performed by adding a polyester derivative and ammonium perchlorate into 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 temperature of the reduced pressure distillation is 40-50°C.

[0022] Invention mechanism: 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol and organic acid (formic acid, acetic acid and higher fatty acid) undergo esterification reaction to obtain corresponding polyester derivatives. The ester compound of 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol has the characteristic of non-hygroscopicity. The ester compound is a hindered ester with strong thermal stability. It contains nitro groups in the structure and can maintain a high energy of the ammonium perchlorate system, so it can be used as an excellent modifier for AP.

[0023] Five polyester derivatives of the present invention, 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-α-methylacrylate, 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 tetra-4-nitrocinnamate, are respectively added with 5% of the modifier to modify AP, and then DSC characterization and hygroscopicity test are carried out. It is found that the high-temperature decomposition temperature and hygroscopicity of the modified samples are greatly reduced, and the modified samples can be used as an excellent modified substance 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 tetra-α-methylacrylate, 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 tetra-4-nitrocinnamate were used to coat AP, respectively. The maximum moisture absorption rate of AP was reduced from 5.51% to 1.89%, 1.95%, 2.90%, 1.65% and 2.66%, respectively. The high-temperature decomposition temperature of AP was reduced from 437.0℃ to 326.8℃, 422.8℃, 426.5℃, 423.8℃ and 365.5℃, respectively. The improvement effect was significant. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The H NMR spectrum of the polyol derivative 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-α-methylacrylate prepared in Example 1;

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

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

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

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

[0030] Figure 6 The infrared spectra of the polyester derivatives prepared in Examples 1 to 5;

[0031] Figure 7 It is a line graph showing the relationship between moisture absorption rate of pure AP and AP coated with five kinds of polyester derivatives prepared in Examples 1 to 5 and time;

[0032] Figure 8 The DSC curves of pure AP and AP coated with five kinds of polyester derivatives prepared in Examples 1 to 5 are shown. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is further described below in conjunction with embodiments.

[0034] Example 1

[0035] The polyol derivative of the present invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-α-methylacrylate, and its preparation method comprises 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-methylacrylic acid to a clean and dry round-bottom flask, add 10 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30°C;

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

[0038] (3) introducing nitrogen to exhaust the air in the device, sealing it, maintaining the temperature at 20-30° C., and reacting for 6 days;

[0039] (4) After the reaction is completed, the solution is poured into ice water and stirred for 15 min. After the precipitate is completely precipitated, it is filtered, and 10 ml of ether is added to the filter cake to dissolve it. The insoluble matter is filtered out, and the filtrate is evaporated to precipitate crystals. The crystals are dissolved in methanol and recrystallized to obtain a pure product.

[0040] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-α-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, 1454cm -1 : NO stretching vibration.

[0041] Example 2

[0042] The polyol derivative of the present invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetramyristate, and its preparation method comprises 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, dry round-bottom flask, add 20 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30°C;

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

[0045] (3) introducing nitrogen to exhaust the air in the device, sealing it, maintaining the temperature at 20-30° C., and reacting for 7 days;

[0046] (4) After the reaction is completed, the solution is poured into ice water and stirred for 15 min. After the precipitate is completely precipitated, it is filtered, and 20 ml of ether is added to the filter cake to dissolve it. The insoluble matter is filtered out, and the filtrate is evaporated to precipitate crystals. The crystals are dissolved in methanol and recrystallized to obtain a 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, 1471cm -1 : NO stretching vibration.

[0048] Example 3

[0049] The polyol derivative of the present invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraoleate, and its preparation method comprises 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, dry round-bottom flask, add 20 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30°C;

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

[0052] (3) introducing nitrogen to exhaust the air in the device, sealing it, maintaining the temperature at 20-30° C., and reacting for 7 days;

[0053] (4) After the reaction is completed, the solution is poured into ice water and stirred for 15 min. After the precipitate is completely precipitated, it is filtered, and 20 ml of ether is added to the filter cake to dissolve it. The insoluble matter is filtered out, and the filtrate is evaporated to precipitate crystals. The crystals are dissolved in methanol and recrystallized to obtain a 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 polyol derivative of the present invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraerucate, and its preparation method comprises 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, dry round-bottom flask, add 20 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30°C;

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

[0059] (3) introducing nitrogen to exhaust the air in the device, sealing it, maintaining the temperature at 20-30° C., and reacting for 7 days;

[0060] (4) After the reaction is completed, the solution is poured into ice water and stirred for 15 min. After the precipitate is completely precipitated, it is filtered, and 20 ml of ether is added to the filter cake to dissolve it. The insoluble matter is filtered out, and the filtrate is evaporated to precipitate crystals. The crystals are dissolved in methanol and recrystallized to obtain a pure product.

[0061] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetraerucate 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, 1471cm -1 : NO stretching vibration.

[0062] Example 5

[0063] The polyol derivative of the present invention is 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol tetra-4-nitrocinnamate, and its preparation method comprises 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, dry round-bottom flask, add 50 ml of N,N-dimethylformamide, stir, and set the temperature to 20-30°C;

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

[0066] (3) introducing nitrogen to exhaust the air in the device, sealing it, maintaining the temperature at 20-30° C., and reacting for 10 days;

[0067] (4) After the reaction is completed, the solution is poured into ice water and stirred for 15 min. After the precipitate is completely precipitated, it is filtered, and 20 ml of ether is added to the filter cake to dissolve it. The insoluble matter is filtered out, and the filtrate is evaporated to precipitate crystals. The crystals are dissolved in methanol and recrystallized to obtain a pure product.

[0068] 2,3-Dihydroxymethyl-2,3-dinitro-1,4-butanediol tetrakis 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 : CH stretching vibration of benzene ring, 1518cm -1 : NO stretching vibration.

[0069] Performance Testing

[0070] The polyester derivatives prepared in Examples 1 to 5 are respectively used for coating perchloric acid, and the application method comprises the following steps:

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

[0072] (2) Heat the flask in a water bath at 40-50°C with stirring for 10 min until the ammonium perchlorate and the polyester derivative are completely dissolved;

[0073] (3) The solution was subjected to reduced pressure distillation at 40-50° C., the stirring speed was set to 500-750 r / min, the vacuum degree was set to 0.08-0.09 MPa, and after the solvent was evaporated, the power of the water bath and the vacuum pump was turned off;

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

[0075] Moisture absorption rate test: Take 0.5g of dry ammonium perchlorate and place it in a culture dish. Place the culture dish in a constant temperature and humidity atmosphere. Record the mass change every 12 hours and calculate the relationship between moisture absorption rate and time. The test results are as follows: Figure 1 shown.

[0076] High temperature decomposition temperature test: The dried coated ammonium perchlorate was subjected to DSC test at a temperature range of 50-500°C and a heating rate of 10°C / min to obtain a DSC curve; the test results are as follows: Figure 2 shown.

[0077] Depend on Figure 7 and 8 It can be obtained that the maximum moisture absorption rate of ammonium perchlorate after being coated with the polyester derivative prepared in Example 1 is 1.89%, and the high-temperature decomposition peak temperature is 326.8°C; the maximum moisture absorption rate of ammonium perchlorate after being coated with the polyester derivative prepared in Example 2 is 1.95%, and the high-temperature decomposition peak temperature is 422.8°C; the maximum moisture absorption rate of ammonium perchlorate after being coated with the polyester derivative prepared in Example 3 is 2.90%, and the high-temperature decomposition peak temperature is 426.5°C; the maximum moisture absorption rate of ammonium perchlorate after being coated with the polyester derivative prepared in Example 4 is 1.65%, and the high-temperature decomposition peak temperature is 423.8°C; the maximum moisture absorption rate of ammonium perchlorate after being coated with the polyester derivative prepared in Example 5 is 2.66%, and the high-temperature decomposition peak temperature is 365.5°C.

[0078] The maximum moisture absorption rate of ammonium perchlorate without any treatment is 5.51%, and the high temperature decomposition temperature is 437.0° C. In contrast, the polyester derivatives prepared in Examples 1 to 5 coated with ammonium perchlorate significantly reduced the moisture absorption and high temperature decomposition peak of ammonium perchlorate. Reducing the moisture absorption is beneficial to the energy release during the decomposition of ammonium perchlorate, and reducing the decomposition temperature is beneficial to increasing the energy release rate of ammonium perchlorate under certain temperature conditions.

Claims

1. A polyester derivative, characterized in that: Its structural formula is: Wherein, R is the carbon chain end of the fatty acid.

2. The polyol derivative according to claim 1, characterized in that: The R is CH2=C(CH3)-, n-CH3(CH2) 12 -, CH3(CH2)7CH=CH(CH2)7-, CH3(CH2)7CH=CH(CH2) 11 -or p-NO2C6H4-.

3. A method for preparing a polyester derivative according to claim 1 or 2, characterized in that: The following steps are involved: 2,3-dihydroxymethyl-2,3-dinitro-1,4-butanediol, fatty acid, dehydrating agent and catalyst are added to an organic solvent to carry out esterification reaction under a nitrogen atmosphere, and the polyester derivative is obtained by purification after the reaction is completed.

4. The method for preparing a polyol ester derivative according to claim 3, characterized in that: The reaction temperature is 20-30°C.

5. The method for preparing a polyol ester derivative according to claim 3, characterized in that: The purification is as follows: pouring the reaction solution into crushed ice, stirring until crystals are completely precipitated, filtering, dissolving the filter cake with ether, filtering, distilling the filtrate under reduced pressure to dryness, precipitating crystals, and finally recrystallizing with methanol to obtain the product.

6. Use of the polyester derivative according to claim 1 or 2 in reducing the hygroscopicity and high-temperature decomposition temperature of ammonium perchlorate.

7. The use according to claim 6, characterized in that: The application method is: coating the polyol derivatives on the surface of ammonium perchlorate.

8. The use according to claim 7, characterized in that: The coating process comprises the following steps: adding the polyester derivative and ammonium perchlorate into a solvent, dissolving, distilling under reduced pressure, and drying to obtain modified ammonium perchlorate.

9. The use according to claim 8, characterized in that: The solvent is methanol.

10. The use according to claim 8, characterized in that: The dissolving temperature is 40-50°C.

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