CN115322059B - Application of CAU-1 metal organic framework material as nitrate compound stabilizer - Google Patents
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Abstract
The invention discloses an application of a CAU-1 metal organic framework material as a nitrate compound stabilizer. The application is that the compound is used as a nitrate compound stabilizer. The nitrate energetic material is widely applied to various propellants, and can spontaneously decompose to generate nitrogen dioxide which further promotes nitrate decomposition. The CAU-1 series metal organic framework material can effectively remove nitrogen dioxide, thereby realizing the stabilization effect on nitrate energetic materials. Aniline or urea compounds and derivatives thereof are traditional nitrate stabilizers, and the stabilizers have toxicity or reaction products thereof have toxicity, thus bringing about safety problems for operators and environment. In the invention, the CAU-1 series metal organic framework material belongs to low-toxicity non-amine compounds, is safer and more environment-friendly, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of nitrate compound stabilization, and particularly relates to an application of a CAU-1 series metal organic framework material as a nitrate compound stabilizer.
Background
The storage properties of a solid propellant refer to the ability of the solid propellant to maintain its physical and chemical properties under storage conditions without changing beyond the allowable range, also known as stability or aging of the solid propellant. The nitrate is of the formula R-O-NO 2 Is an organic compound of the class (C). In the field of solid propellants, common nitrate-based energetic compounds are nitroglycerin and nitrocellulose. Under normal storage conditions, the nitrate component (nitroglycerin or nitrocellulose) of the solid propellant will slowly decompose to produce NO 2 ，NO 2 Further catalyzing the accelerated decomposition of the nitrate component results in reduced stability of the propellant, ultimately resulting in reduced shelf life of the propellant. Thus, in propellants containing nitrate components, the addition of a stabilizer is required. The stabilizer does not inhibit the thermal decomposition of the nitrate itself, but eliminates NO 2 Thereby reducing NO 2 To nitric acidCatalysis of the ester component. At present, conventional nitrate stabilizers are largely classified into aromatic amines and urea derivatives. In fact, conventional stabilizers are either toxic themselves, or contain toxic or carcinogenic impurities, or they produce toxic or carcinogenic products during the aging process of the propellant.
In order to develop low-toxicity non-amine substances capable of replacing the traditional stabilizer, researchers at home and abroad have conducted a great deal of research work.
Katoh et al [ Propellants Explos. Pyrotech.2007,32 (4), 314-321] investigated the effect of five conventional stabilizers and three phenolic compounds on NC isothermal exothermic behavior under an oxygen atmosphere. They found that these substances had a stabilizing effect on NC, but the stabilization mechanism of conventional stabilizers and phenolic compounds was different. Phenolic compounds are lower than traditional stabilizers in terms of increasing the extent of induction period.
Frys et al [ Propellants Explos. Pyrotech.2011,36 (4), 347-355] studied epoxy-based oils as stabilizers. The epoxy-based oil compound has a certain stabilizing effect, but is inferior to AK-II.
Krumlinde et al [ Propellants Explos. Pyrotech.2017,42 (1), 78-83] evaluated the stabilizing effect of five phenolic derivatives on NC, found that the phenolic derivative No. 5 had a better effect.
Dejeaifve et al [ Propellants Explos. Pyrotech.2018,43 (8), 831-837; propellants Explos. Pyrotech.,2020,45 (8), 1185-1193] screened over 80 non-amine compounds, four phenolic derivatives were found to be equivalent or superior to AK-II in stabilizing NG.
The patent [ CN201910389371.6, CN201910392460.6, CN201910406598.7] discloses a preparation method of fullerene (C60) derivatives and an effect on nitrocotton.
Metal Organic Frameworks (MOFs) materials are organic-inorganic hybrid materials with one-dimensional, two-dimensional or three-dimensional structures assembled from metal ions and organic ligands through coordination bonds. MOFs have excellent performance in many fields of application, particularly in gas adsorption and separation. However, to date, no published report has been made on the use of MOFs materials as stabilizers for nitrate compounds.
Document [ Angew.chem.int.ed.2009,48,5163-5166 ]]CAU-1 of tetrahedral structure is reported to be composed of eight rings of Al in quasi-body-centered cubic 8 (OH) 4 (OCH 3 ) 8 With 12 2-amino-terephthalic acids (H) 2 BDC-NH 2 ) Ion-linked structure (see fig. 3 a). Two micropores exist in the structure of CAU-1, with diameters of 1nm and 0.45nm, respectively.
Document [ chem. Eur. J.2011,17,6462-6468]It is reported that 2, 5-dihydroxy-terephthalic acid is used to replace 2-amino-terephthalic acid and aluminum chloride to synthesize a MOF material with a CAU-1 structure, namely CAU-1- (OH) 2 。
Document [ ACS appl. Mater. Interfaces 2018,10,3160-3163 ]]Three MOF materials having the structure of CAU-1, namely CAU-1-OH (or BIT-72), CAU-1-CH, were reported to be synthesized from 2-hydroxy-terephthalic acid, 2-methyl-terephthalic acid and 2, 5-dimethyl-terephthalic acid instead of 2-amino-terephthalic acid, with aluminum chloride 3 (or BIT-73) and CAU-1- (CH) 3 ) 2 (or BIT-74).
Document [ Inorg. Chem.2016,55,7425-7431]It is reported that MOF material CAU-20 having one-dimensional pore structure was synthesized from aluminum nitrate and 2, 5-dihydroxyp-benzoquinone (as shown in fig. 3 b). The pore diameter of the material is 0.9nm, and the specific surface area reaches 1440m 2 /g。
The literature [ Nature Materials,2007,6 (10), 760-764] reports the synthesis of porous MOF material MIL-110 from aluminum nitrate and 1,3, 5-trimesic acid, with a one-dimensional pore diameter of 1.6nm (as shown in FIG. 3 c).
Document [ chem. Commun.,2012,48,9486-9488]It was reported that the specific surface area of porous MOF material CAU-6 (as shown in FIG. 3 d) different from CAU-1 was synthesized from aluminum chloride and 2-aminoterephthalic acid and was up to 620m 2 /g。
Document [ PNAS,2009,106 (49) 20637-20640]Magnesium MOF-74 synthesized from magnesium nitrate and 2, 5-dihydroxyterephthalic acid was reported to have a one-dimensional pore structure (see fig. 3 e). Mg, co, ni, fe, mn MOF-74 series material in CO 2 The adsorption aspect shows good performance.
Document [ chem. Eur. J.2004,10,1373-1382]Empty spaces of MIL-53 aluminum-based MOFs were reportedAnd (3) an inter-structure. It is made of AlO 4 (OH) 2 Octahedral and terephthalic ligands (H) 2 BDC) are connected into a chain, and are further built into a one-dimensional pore canal (shown in fig. 3 f).
Document [ Science,295 (5554), 469-472] reports IRMOF series materials constructed from zinc oxide secondary building blocks and terephthalic acid and its derivatives into a series of MOFs materials of similar spatial topology (see figure 3 g). The series of materials have very good gas adsorption performance.
Literature [ chem. Mate. 2009,21,5783-5791] reports a porous material MILs-120 synthesized from aluminum nitrate and 1,2,4, 5-benzenetetracarboxylic acid (see fig. 3 h). The material has certain performance in the aspect of hydrogen adsorption.
Document [ J.AM.CHEM.SOC.2006,128,10223-10230; chem. Mater.2012,24,2462-2471] reports the synthesis of MIL-96 porous materials from aluminum nitrate and 1,3, 5-trimesic acid (see FIG. 3 i). It was found that MOFs (MIL-100 and MIL-110) with different structures can be synthesized by appropriately changing the synthesis conditions and the same raw materials.
However, to date, no published report has been made on the use of MOFs materials as stabilizers for nitrate compounds. Due to amino functions (NH) 2 -R) and NO 2 As a result, nitrite carcinogens may be generated, so that organic ligands containing amino functions are excluded in the use of MOFs as nitrate stabilizers.
Disclosure of Invention
The invention provides the application of CAU-1 series metal organic frame materials as the nitrate energetic material stabilizer in order to overcome the important problem that the traditional stabilizer has toxicity.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the application of CAU-1 series metal organic frame material as nitrate compound stabilizer is that the CAU-1 series metal organic frame material is composed of organic carboxylic acid ligand containing hydroxy functional group on benzene ring, aluminum ion and methoxy.
The organic carboxylic acid ligand with hydroxyl functional group is 2-hydroxy-terephthalic acid [ H ] 2 BDC-OH]2, 5-dihydroxy-terephthalic acid [ H ] 2 BDC(OH) 2 ]At least one or two of them.
The CAU-1 series metal organic framework material is free of amino functional groups.
The CAU-1 series metal organic framework material is Al 8 (OH) 4 (OCH 3 ) 8 (BDC(OH) 2 ) 6 CAU-1- (OH) for short 2 。
The CAU-1 series metal organic framework material is Al 8 (OH) 4 (OCH 3 ) 8 (BDC-OH) 6 Abbreviated as CAU-1-OH or BIT-72.
Compared with the prior art, the invention has the advantages that:
(1) The CAU-1 series metal organic framework material does not use organic carboxylic acid ligand containing amino functional groups, thereby avoiding generating nitrite type cancerogenic substances and reducing the possibility of generating toxicity.
(2) The CAU-1 series metal organic framework material has a micropore structure, and can effectively adsorb nitrogen dioxide generated by decomposing the nitrate compounds, thereby improving the stability of the nitrate compounds.
(3) The CAU-1 series metal organic framework material contains hydroxyl functional groups, so that the elimination capability of nitrogen dioxide can be remarkably improved.
Drawings
Figure 1 XRD patterns of example 1 and example 2CAU-1 series metal-organic framework materials.
FIG. 2 Nitrogen dioxide breakthrough curves for example 1 and example 2CAU-1 series metal organic framework materials.
FIG. 3 is a schematic three-dimensional structure of nine MOFs.
Detailed Description
The technical features of the present invention will be described with reference to the following specific experimental schemes and drawings, but the present invention is not limited thereto. The test methods described in the examples below, unless otherwise specified, are all conventional; the apparatus and materials are commercially available unless otherwise specified.
Example 1
Weighing and weighing4.35g (18 mmol) of aluminum trichloride hexahydrate and 1.09g (6 mmol) of 2-hydroxy-terephthalic acid were placed in a 100mL reaction vessel, 55mL of anhydrous methanol was added, and the reaction vessel was sealed after complete dissolution, reacted at 125℃for 5 hours, and then cooled naturally to room temperature. The product is centrifugally washed for three times by water, then is centrifugally washed for three times by DMF, and finally is centrifugally washed for three times by ethanol, and is dried in vacuum at 100 ℃ to obtain the target product: CAU-1 series metal organic framework materials with monohydroxy modification, al 8 (OH) 4 (OCH 3 ) 8 (BDC-OH) 6 Abbreviated as CAU-1-OH or BIT-72.
The prepared samples were determined to be CAU-1-OH or BIT-72 using powder XRD testing, see FIG. 1.
The penetration test is adopted to test that CAU-1-OH eliminates NO 2 See fig. 2. Through calculation, the CAU-1-OH can be obtained to eliminate NO 2 Is 198mg/g.
Example 2
4.35g (18 mmol) of aluminum trichloride hexahydrate and 1.19g (6 mmol) of 2, 5-dihydroxy-terephthalic acid were weighed into a 100mL reaction vessel, 55mL of anhydrous methanol and 0.16g of sodium hydroxide were added, stirred to dissolve completely, then the reaction vessel was sealed, reacted at 125℃for 5 hours, and then cooled naturally to room temperature. The product is centrifugally washed for three times by water, then is centrifugally washed for three times by DMF, and finally is centrifugally washed for three times by ethanol, and is dried in vacuum at 100 ℃ to obtain the target product: CAU-1 series metal organic framework material with dihydroxy modification, al 8 (OH) 4 (OCH 3 ) 8 (BDC(OH) 2 ) 6 CAU-1- (OH) for short 2 。
Powder XRD test was used to determine that the prepared sample was CAU-1- (OH) 2 See fig. 1.
CAU-1- (OH) was tested using the penetration test 2 NO elimination 2 See fig. 2. Through calculation, CAU-1- (OH) is obtained 2 NO elimination 2 The amount of (C) was 544mg/g.
Comparative example 1
4.35g (18 mmol) of aluminum trichloride hexahydrate and 1.08g (6 mmol) of 2-methyl-terephthalic acid were weighed out55mL of absolute methanol is added into a 100mL reaction kettle, stirred to be completely dissolved, then the reaction kettle is sealed and reacted for 5 hours at 125 ℃, and then the reaction kettle is naturally cooled to room temperature. The product is centrifugally washed for three times by water, then is centrifugally washed for three times by DMF, and finally is centrifugally washed for three times by ethanol, and is dried in vacuum at 100 ℃ to obtain the target product: CAU-1 series metal organic framework materials with monomethyl modification, al 8 (OH) 4 (OCH 3 ) 8 (BDC-CH 3 ) 6 Abbreviated as CAU-1-CH 3 Or BIT-73.
Determination of the prepared sample as CAU-1-CH by powder XRD test 3 Or BIT-73.
CAU-1-CH was tested using the penetration test 3 NO elimination 2 Is a penetration curve of (a). Through calculation, CAU-1-CH is obtained 3 NO elimination 2 The amount of (C) was 19mg/g.
Comparative example 2
4.35g (18 mmol) of aluminum trichloride hexahydrate and 1.16g (6 mmol) of 2, 5-dimethyl-terephthalic acid were weighed into a 100mL reaction vessel, 55mL of anhydrous methanol was added and stirred to dissolve completely, then the reaction vessel was sealed, reacted at 125℃for 5 hours, and then cooled naturally to room temperature. The product is centrifugally washed for three times by water, then is centrifugally washed for three times by DMF, and finally is centrifugally washed for three times by ethanol, and is dried in vacuum at 100 ℃ to obtain the target product: CAU-1 series metal organic framework material with dihydroxy modification, al 8 (OH) 4 (OCH 3 ) 8 (BDC-(CH 3 ) 2 ) 6 Abbreviated as CAU-1- (CH) 3 ) 2 Or BIT-74.
Determination of the prepared sample as CAU-1- (CH) by powder XRD test 3 ) 2 Or BIT-73.
CAU-1- (CH) was tested using the penetration test 3 ) 2 NO elimination 2 Is a penetration curve of (a). Through calculation, CAU-1- (CH) is obtained 3 ) 2 NO elimination 2 The amount of (C) was 25mg/g.
Comparative example 3
1.20g (3.2 mmol) of aluminum nitrate nonahydrate and 0.80g (4.8 mmol) of 3, 5-pyridinedicarboxylic acid (H) 2 PYDC) was placed in a 100mL reaction vessel, 2mL deionized water and 18mL N, N-Dimethylformamide (DMF) were added, stirred, then the reaction vessel was sealed, reacted at 120℃for 18 hours, and then naturally cooled to room temperature. Centrifuging and washing the product with DMF for three times, centrifuging and washing with ethanol for three times, and vacuum drying at 100 ℃ to obtain the target product: a metal organic framework material containing 3, 5-pyridine dicarboxylic acid, al (OH) PYDC, called CAU-10-PYDC for short.
The prepared sample was determined to be CAU-10-PYDC using powder XRD testing.
The penetration test is adopted to test that CAU-10-PYDC eliminates NO 2 Is a penetration curve of (a). Through calculation, the CAU-10-PYDC can eliminate NO 2 The amount of (C) was 9mg/g.
Comparative example 4
0.66g of aluminum nitrate nonahydrate, 0.30g of 1,3, 5-trimesic acid, 1mL of 4M nitric acid and 5mL of deionized water are weighed, placed in a 20mL reaction kettle, stirred, then the reaction kettle is sealed, reacted for 72 hours at 210 ℃, and then naturally cooled to room temperature. Centrifuging and washing the product with DMF for three times, centrifuging and washing with ethanol for three times, and vacuum drying at 100 ℃ to obtain the target product: MIL-110.
Powder XRD testing was used to determine that the sample prepared was MIL-110.
MIL-110 was tested for NO elimination using the penetration test 2 Is a penetration curve of (a). Calculated to obtain MOF-74 eliminating NO 2 The amount of (C) was 16mg/g.
Comparative example 5
0.7g of magnesium nitrate hexahydrate, 0.17g of 2, 5-dihydroxyterephthalic acid, 65mL of LDMF,4mL of ethanol and 4mL of deionized water are weighed, placed in a 100mL reaction kettle, stirred, then the reaction kettle is sealed, reacted for 26 hours at 125 ℃, and then naturally cooled to room temperature. Centrifuging and washing the product with DMF for three times, centrifuging and washing with ethanol for three times, and vacuum drying at 100 ℃ to obtain the target product: MOF-74.
The prepared sample was determined to be MOF-74 using powder XRD testing.
MOF-74 was tested for NO elimination using the penetration test 2 Is a penetration curve of (a). Calculated to obtain MOF-74 eliminating NO 2 The amount of (C) was 14mg/g.
Comparative example 6
3.75g (10 mmol) of aluminum nitrate nonahydrate and 1.66g (10 mmol) of terephthalic acid were weighed into a 100mL reaction vessel, 60mL of N, N-Dimethylformamide (DMF) was added, stirred to dissolve completely, then the reaction vessel was sealed, reacted at 150℃for 16 hours, and then cooled naturally to room temperature. Centrifuging and washing the product with DMF for three times, centrifuging and washing with ethanol for three times, and vacuum drying at 100 ℃ to obtain the target product: MIL-53 series aluminum-based metal organic frame materials without hydroxyl modification on benzene rings, al (OH) BDC, al-MIL-53 for short.
The prepared sample was determined to be Al-MIL-53 using powder XRD testing.
The penetration test is adopted to test that Al-MIL-53 eliminates NO 2 Is a penetration curve of (a). Through calculation, al-MIL-53 eliminating NO is obtained 2 The amount of (C) was 10mg/g.
Comparative example 7
0.073g (0.246 mmol) of zinc nitrate hexahydrate and 0.04g (0.24 mmol) of terephthalic acid were weighed and dissolved in 2ML of LDMF and 8ML of toluene, and 0.05ML of triethylamine and 5ML of toluene were slowly diffused into the above solution by a diffusion method to finally form a crystal precipitate, which was washed with ethanol to obtain IRMOF-1 (Zn (BDC).
The prepared sample was determined to be IRMOF-1 using powder XRD testing.
IRMOF-1 was tested for NO elimination using the penetration test 2 Is a penetration curve of (a). By calculation, IRMOF-1 elimination NO is obtained 2 The amount of (C) was 7mg/g.
Comparative example 8
3.2g (8.5 mmol) of aluminum nitrate nonahydrate and 0.5g (2 mmol) of 1,2,4, 5-phenyltetracarboxylic acid (H) 4 BTEC), 3.4mL NaOH solution (4M), 20mL deionized water were placed in a 100mL reaction kettle, stirred, then the reaction kettle was sealed, reacted at 210 ℃ for 24 hours, and then naturally cooled to room temperature. Centrifuging and washing the product with DMF for three times, centrifuging and washing with ethanol for three times, and vacuum drying at 100 ℃ to obtain the target product: MIL-120.
Powder XRD testing was used to determine that the sample prepared was MIL-120.
MIL-120 was tested for NO elimination using the penetration test 2 Is a penetration curve of (a). Through calculation, MIL-120 NO elimination is obtained 2 The amount of (C) was 10mg/g.
Comparative example 9
1.31g (3.5 mmol) of aluminum nitrate nonahydrate, 0.11g (0.5 mmol) of 1,3, 5-trimesic acid (H) 3 BTC), 5mL of deionized water was placed in a 30mL reaction kettle, stirred, then the reaction kettle was sealed, reacted at 210℃for 24 hours, and then naturally cooled to room temperature. Centrifuging and washing the product with DMF for three times, centrifuging and washing with ethanol for three times, and vacuum drying at 100 ℃ to obtain the target product: MIL-196.
Powder XRD testing was used to determine that the sample prepared was MIL-196.
MIL-196 was tested for NO elimination using a penetration test 2 Is a penetration curve of (a). Through calculation, MIL-196 eliminating NO is obtained 2 The amount of (C) was 9mg/g.
Detection of CAU-1 series aluminum-based metal organic framework material for NO elimination by penetration test method 2 Capacity, test conditions were as follows:
(1) The CAU-1 series aluminum-based metal organic frame material used about 0.6g of sample, mixed with 6g of quartz sand (particle size 40-70 mesh), and the sample mixture filled into a quartz tube fixed bed, wherein both sides of the sample mixture are respectively filled with 3g of quartz sand (particle size 20-40 mesh) and 1.5 g of quartz cotton. Filling sequential quartz wool-quartz sand-sample mixture-quartz sand-quartz wool.
(2) The nitrogen purging and degassing treatment temperature is 150 ℃, the degassing treatment time is 12 hours, the high-purity nitrogen is purged, and the nitrogen flow is 240ml/min;
(3) In the penetration test, a quartz tube fixed bed is placed into a constant temperature bath, and the test temperature is controlled at 25 ℃;
(4) Standard gas composition for penetration test: NO (NO) 2 Content 1000ppm, N 2 Balancing;
(5) Introducing standard gas into the treated quartz tube fixed bed at a flow rate of 100ml/min, and adopting NO 2 The detector detects the exhaust gas. When the detector displays NO 2 The test was stopped when the concentration reached 100ppm, at which time the breakthrough test time was recorded, divided by the degassing treatmentThe mass of the post-sample is the penetration time (min/g). Processing the data to obtain NO 2 The amount of elimination.
The data processing method is as follows:
description 1:1000ppm of NO 2 NO in standard gas 2 The content of (2) is 1000×10 -6 ×46g/mol(NO 2 Molecular weight)/(22.4L/mol= 2.0535 ×10) -3 g/L＝2.0535×10 -3 mg/mL
Description 2:
examples: when the standard gas passes through the fixed bed at a flow rate of 100ml/min, the penetration time is 1000min/g, and the NO 2 The total amount of the air is as follows:
(1000ppmNO 2 ×1000min/g)×100ml/min＝1×10 6 ppmNO 2 ·min/g×100ml/min
＝2.0535×10 -3 mg/mL×100ml/min×1000min/g＝205.35mg/g。
the penetration curve records the change value of the concentration of the tail gas in the penetration test process, and the penetration curve is integrated, and the integration is assumed to be 50000ppmNO 2 Min/g, reduced exhaust of NO 2 The amount of (2) is as follows:
50000ppmNO 2 ·min/g×100ml/min
＝50000ppmNO 2 ·min/g÷(1×10 6 ppmNO 2 ·min/g×100ml/min)×205.35mg/g×100ml/min＝10.27mg/g
sample actual elimination of NO 2 Quantity of =no 2 Introducing the total amount-tail gas to discharge NO 2 Is used in the amount= 205.35mg/g-10.27 mg/g= 195.08mg/g.
The toxicity of the CAU-1 series metal organic frame materials is detected by adopting an acute oral toxicity test, and the acute oral toxicity test method is carried out according to GB/T21603-2008, chemicals.
TABLE 1 detection results of CAU-1 series metal organic framework materials
The nitrate energetic material is widely applied to various propellants, and can spontaneously decompose to generate nitrogen dioxide which further promotes nitrate decomposition. The CAU-1 series metal organic framework material can effectively remove nitrogen dioxide, thereby realizing the stabilization effect on nitrate energetic materials. Aniline or urea compounds and derivatives thereof are traditional nitrate stabilizers, and the stabilizers have toxicity or reaction products thereof have toxicity, thus bringing about safety problems for operators and environment. In the invention, the CAU-1 series metal organic framework material belongs to low-toxicity non-amine compounds, is safer and more environment-friendly, and has wide application prospect.
Claims (3)
- Application of CAU-1 metal organic framework material as nitrate compound stabilizer; the CAU-1 series metal organic framework material consists of an organic carboxylic acid ligand containing hydroxyl functional groups on benzene rings, aluminum ions and methoxy groups; the organic carboxylic acid ligand containing hydroxyl functional groups is 2-hydroxy-terephthalic acid [ H ] 2 BDC-OH]2, 5-dihydroxy-terephthalic acid [ H ] 2 BDC(OH) 2 ]At least one or two of the following; the nitrate compound is one or two of nitroglycerin and nitrocellulose.
- 2. The use according to claim 1, characterized in that: the CAU-1 series metal organic framework material is Al 8 (OH) 4 (OCH 3 ) 8 (BDC(OH) 2 ) 6 CAU-1- (OH) for short 2 。
- 3. The use according to claim 1, characterized in that: the CAU-1 series metal organic framework material is Al 8 (OH) 4 (OCH 3 ) 8 (BDC-OH) 6 Abbreviated as CAU-1-OH or BIT-72.
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