CN117903060A - Preparation method of polynitrobipyrazole compound - Google Patents
Preparation method of polynitrobipyrazole compound Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 230000001546 nitrifying effect Effects 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 16
- 235000011054 acetic acid Nutrition 0.000 claims description 14
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 239000003759 ester based solvent Substances 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 32
- 239000003795 chemical substances by application Substances 0.000 description 6
- YGAILVDTGIMZAB-UHFFFAOYSA-N 3-pyrazol-3-ylidenepyrazole Chemical compound N1=NC=CC1=C1N=NC=C1 YGAILVDTGIMZAB-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000802 nitrating effect Effects 0.000 description 5
- 238000006396 nitration reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 239000012442 inert solvent Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- FTBBGQKRYUTLMP-UHFFFAOYSA-N 2-nitro-1h-pyrrole Chemical class [O-][N+](=O)C1=CC=CN1 FTBBGQKRYUTLMP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005474 detonation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/91—Nitro radicals
- C07D233/92—Nitro radicals attached in position 4 or 5
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention belongs to the technical field of synthesis of synthetic energy materials, and particularly relates to a preparation method of a polynitrobipyrazole compound, which comprises the following steps: a) Feeding the biimidazole solution and a nitrifying reagent into a first reactor group, and obtaining a first reactor group product stream after reaction; b) The preparation method disclosed by the invention can be used for improving the reaction yield and efficiency, the reaction yield is far higher than that in the prior art, the yield reaches 90%, the preparation method is high in safety, the waste acid amount can be reduced, and the environmental-friendly disposal pressure is further reduced.
Description
Technical Field
The invention belongs to the technical field of synthesis of synthetic energy materials, and particularly relates to a preparation method of a polynitrobipyrazole compound.
Background
The energetic material refers to a compound which can generate a violent oxidation-reduction reaction and release a large amount of energy under the stimulation of certain external energy. In recent years, with the continuous pursuit of high-performance high-density energy materials, polynitrogen compounds represented by nitroazoles have been attracting more attention. The energy of the nitroazole energetic compound mainly comes from high-energy chemical bonds such as n-n bonds, c-n bonds, n-o bonds and the like contained in a ring structure and ring tension, has high nitrogen and low carbon and hydrogen, has higher density, is easier to reach oxygen balance, and is n2 with most combustion products being environment-friendly, thus being a novel high-energy compound.
Bisimidazoles have been widely studied as important constituent units of energetic materials due to their high positive enthalpy of formation of the cyclic framework, and the advantages of excellent thermal stability, more modification sites, low sensitivity and the like brought by conjugated systems. Wherein 4,4', 5' -tetranitro-2, 2' -biimidazole is a representative of polynitrobipyrazole energetic compounds, the density is 1.80g/cm <3>, the detonation velocity is 7840m/s, the detonation pressure is 27.6GPa, the formation enthalpy is 232kJ/mol, and the decomposition temperature is 290 ℃.
At present, three synthetic routes are mainly reported, namely, firstly, bipyrazole is used as a raw material, sodium nitrate/concentrated sulfuric acid is used as a nitration system, urea is used as a catalyst, and the reaction is carried out for 16 hours at 80 ℃, so that the yield is 51%; firstly, bipyrazole is used as a raw material, concentrated or fuming nitric acid/concentrated sulfuric acid is used as a nitration system, and the bipyrazole is prepared by reacting for 3-7 hours at 40-60 ℃ with the yield of 48%; the method is characterized in that bipyrazole is used as a raw material, fuming nitric acid/phosphorus pentoxide/polyphosphoric acid is used as a nitration system, and the reaction is carried out for 6 hours at 55 ℃, so that the yield is about 30%.
Besides, the patent CN 114835647A also discloses that a micro-channel reactor or a millimeter-level tubular reactor is adopted for the first time, bipyrazole is used as a raw material, concentrated nitric acid/concentrated sulfuric acid or nitrate/concentrated sulfuric acid is used as a nitration system to prepare 4,4', 5' -tetranitro-2, 2' -bipyrazole, and the yield is between 5 and 49 percent.
The above methods all need to solve the problem of low yield.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a polynitrobipyrazole compound. So as to achieve the purposes of improving the reaction yield and efficiency, realizing high safety of post-treatment, reducing the waste acid amount and further reducing the environmental protection disposal pressure.
The invention solves the technical problems by adopting the following technical scheme:
The invention aims to provide a preparation method of a polynitrobipyrazole compound,
The method comprises the following steps:
a) Feeding the biimidazole solution and a nitrifying reagent into a first reactor group, and obtaining a first reactor group product stream after reaction;
b) And feeding the first reactor group product stream and water into a second reactor group, cooling, diluting and neutralizing to obtain a second reactor group product stream, and carrying out aftertreatment to obtain the polynitrobipyrazole compound.
Further, the mole ratio of the biimidazole solution to the nitrifying agent is 1 (0.8-30).
Further, the first reactor set and the second reactor set each include at least one reactor.
Further, the first reactor set comprises a plurality of reactors connected in parallel and/or in series.
Further, the first reactor group comprises two parallel reactors, and at least one reactor is connected in series at the discharge end of the parallel reactors.
Further, the bisimidazole solution is 2,2 '-bisimidazole solution, the nitrifying reagent comprises nitric acid, and the prepared polynitrobispyrazole compound is 4,4',5 '-tetranitro-2, 2' -bisimidazole.
Further, also fed to the first reactor set in step a) is sulfuric acid, 2' -bisimidazole: nitric acid: the molar ratio of sulfuric acid is 1 (4-8): (4-10).
Further, step a) is performed in a solvent, wherein the solvent adopts one or more of benzene solvents, amide solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, sulfone or sulfoxide solvents, ether solvents, acid solvents, ester solvents or water.
Further, the solvent adopts one or more of dichloroethane, chloroform, dichloromethane, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, methyltetrahydrofuran, ethyl acetate, butyl acetate, formic acid, acetic acid, propionic acid, butyric acid and water.
Further, step a) is carried out in a solvent which is dichloroethane.
Further, the reaction temperature of step a) is from-50 ℃ to 200 ℃, the reaction time is from 1 second to 5 hours, the molar ratio of the first reactor group product stream to water in step b) is from 1 (1-100), the reaction temperature of step b) is from-50 ℃ to 100 ℃, and the reaction time is from 1 second to 5 hours.
Compared with the prior art, the invention has the beneficial technical effects that:
1. The preparation method can improve the reaction yield and efficiency, the reaction yield is far higher than that in the prior art, and the yield reaches 90%.
2. The preparation method provided by the invention has high safety, and can reduce the waste acid amount, thereby reducing the environmental protection disposal pressure.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention in order that the technical means thereof may be more clearly understood, and in order that the present invention may be more readily understood, its objects, features and advantages be more particularly described below.
Drawings
FIG. 1 is a schematic flow chart of example 1 of a process for preparing a polynitrobipyrazole compound according to the invention.
FIG. 2 is a schematic flow chart of examples 2 and 3 of a preparation method of a polynitrobipyrazole compound according to the invention.
FIG. 3 is a schematic flow chart of example 4 of a process for preparing a polynitrobipyrazole compound according to the invention.
Detailed Description
The technical scheme of the invention is further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or preferred value or example value, this is to be understood as equivalent to any range specifically disclosed by combining any upper or lower range limit or preferred value or example value. Unless otherwise indicated, the numerical ranges set forth herein are intended to include the endpoints of the ranges, and all integers and fractions within the range.
In addition, unless otherwise specifically indicated, the various raw materials, reagents, instruments and equipment used in the present invention may be obtained commercially or prepared by existing methods.
A process for the preparation of a polynitrobipyrazole compound comprising:
a) Feeding the biimidazole solution and a nitrifying reagent into a first reactor group, and obtaining a first reactor group product stream after reaction;
b) And feeding the first reactor group product stream and water into a second reactor group, cooling, diluting and neutralizing to obtain a second reactor group product stream, and carrying out aftertreatment to obtain the polynitrobipyrazole compound.
The reactor train consists of one or more reactors, in which the individual reactors may be identical or different and may be connected in series or in parallel. A reactor refers to a containment unit in which reactants are able to react. In the case of a microchannel reactor, a reactor may refer to a microchannel reaction module, and a microchannel reactor refers to a continuous flow reactor in which the equivalent diameter of the reaction channels is on the order of millimeters or less.
The polynitrobipyrazole compound is exemplified by 4,4', 5' -tetranitro-2, 2' -bisimidazole, and the structural formula is shown as follows:
A process for preparing 4,4', 5' -tetranitro-2, 2' -biimidazole comprising:
a) Feeding the 2,2' -biimidazole solution and a nitrifying reagent into a first reactor group, and obtaining a first reactor group product stream after reaction;
b) And feeding the first reactor group product stream and water into a second reactor group, cooling, diluting and neutralizing to obtain a second reactor group product stream, and then carrying out aftertreatment to obtain the 4,4', 5' -tetranitro-2, 2' -biimidazole compound.
Step a)
In step a), 2' -bisimidazole is fed with a nitration reagent to a first reactor set, after which a first reactor set product stream is obtained, wherein the feed is preferably a continuous feed.
In step a), the molar ratio of 2,2' -bisimidazole to nitrating agent may be 1 (0.8-30), for example ,1:0.9、1:1.0、1:1.05、1:1.1、1:1.2、1:1.5、1:1.7、1:2.0、1:2.2、1:2.5、1:2.7、1:3.0、1:3.2、1:3.5、1:3.7、1:4.0、1:4.2、1:4.5、1:4.7、1:5.0、1:5.2、1:5.5、1:5.7、1:6.0、1:6.2、1:6.5、1:6.7、1:7.0、1:7.2、1:7.5、1:7.7、1:8.0、1:8.2、1:8.5、1:8.7、1:9.0、1:9.2、1:9.5、1:9.7, is preferably 1 (4-20).
In the present application, in the case of continuous feeding, the molar ratio between the compounds is achieved by calculating the molar flow rate ratio of the materials at the time of addition, i.e., the ratio of the flow rates of the two substances in terms of moles of the substances per unit time. The person skilled in the art can calculate the molar flow rate ratio by multiplying the concentration (in molar concentration) of each substance by its flow rate and then determining the ratio of the two resulting values.
In the case of continuous feeding, the 2,2 '-bisimidazole and the nitrating agent can be fed simultaneously into the first reactor set, or the 2,2' -bisimidazole and/or the nitrating agent can be fed into the first reactor set at different time points and/or at different feeding points, respectively, so long as the two continuously flow out of the first reactor set after the first reactor set completes the reaction.
The reaction of step a) may be carried out over a wide temperature range, for example over a temperature range of from-50℃to 200℃for example ,-45℃、-40℃、-35℃、-30℃、-25℃、-20℃、-15℃、-10℃、-5℃、0℃、10℃、15℃、20℃、25℃、30℃、35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃、195℃.
Optionally, the 2,2 '-bisimidazole and the nitrating agent may be pre-cooled or pre-heated before they enter the first reactor set, thereby cooling or heating the stream of 2,2' -bisimidazole and nitrating agent to a reaction temperature close to or equal to step a). The pre-cooling or pre-heating means may employ any cooling or heating means known in the art.
The reaction time of step a) may be adjusted within a wide range, for example within a range of 1 second to 5 hours, for example 1 second, 2 seconds, 5 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 13 seconds, 15 seconds, 18 seconds, 20 seconds, 23 seconds, 25 seconds, 28 seconds, 30 seconds, 33 seconds, 35 seconds, 38 seconds, 40 seconds, 43 seconds, 45 seconds, 48 seconds, 50 seconds, 53 seconds, 55 seconds, 58 seconds, 1 minute, 1.3 minutes, 1.5 minutes, 1.8 minutes, 2.0 minutes, 2.3 minutes, 2.5 minutes, 2.8 minutes, 3.0 minutes, 3.3 minutes, 3.5 minutes, 3.8 minutes, 4 minutes, 4.5 minutes, 5 minutes, 5.5 minutes, 6.0 minutes, 6.5 minutes, 7.0 minutes, 7.5 minutes, 8.0 minutes, 8.5 minutes, 9.0 minutes, 9.5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 hours, 35 hours, 5 hours, 2.5 hours, 3.0, 4 hours, 3.5 hours.
The reaction time may be a residence time in the case of a continuous flow reactor, such as a microchannel reactor, a tubular reactor or a tubular packed reactor.
A tubular reactor refers to a continuous flow reactor in which the reaction channels are not filled with a filler and the equivalent diameter of the reaction channels is larger than that of the "microchannel reactor" described above. The tubular reactor of the present application encompasses straight tubular reactors and various bent tubular reactors, such as coil tubular reactors.
The tubular packing reactor refers to a continuous flow reactor in which a packing is packed in a reaction channel and the equivalent diameter of the reaction channel is larger than that of the above-mentioned "microchannel reactor". The tubular packed reactor of the present application encompasses straight tube packed reactors and various elbow packed reactors, such as coiled tube packed reactors.
In the case of continuous flow reactors, the term "residence time" is used to refer to the time taken for the various reactants participating in the reaction to simultaneously mix in the reactor to begin the reaction, and to leave the reactor after the reaction. The residence time can be calculated by the following method:
the residence time T s was calculated as follows:
Wherein: t s -residence time, seconds(s);
V-total reactor volume, mL;
q-total reaction mass flow rate, mL/min;
G i -mass flow rate of each reaction material, G/min;
ρ i -density of the respective reaction mass, g/mL.
Step a) is carried out in a solvent, for example by dissolving the reactants in an inert solvent, respectively. The inert solvent is not particularly limited as long as it does not adversely affect the progress of step a). For example, the inert solvent which can be used in the step a) may be any one or more selected from benzene-based solvents, amide-based solvents, hydrocarbon-based solvents, halogenated hydrocarbon-based solvents, sulfone-or sulfoxide-based solvents, ether-based solvents, acid-based solvents, ester-based solvents, or water; preferably, the inert solvent is selected from any one or more of 1, 2-dichloroethane, chloroform, dichloromethane, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, methyltetrahydrofuran, ethyl acetate, butyl acetate, formic acid, acetic acid, propionic acid, butyric acid and water.
The first reactor set of step a) may consist of one or more reactors, for example, may consist of one reactor or may consist of two, three, four, five or more reactors. The kind of the reactor herein is not particularly limited as long as production in a continuous manner can be achieved. For example, the reactor used herein may be selected from the group consisting of a microchannel reactor, a stirred tank reactor, a tubular reactor, and a tubular packed reactor. For example, the first reactor set is comprised of one or more microchannel reactors.
When the first reactor set consists of only one reactor, it may be a microchannel reaction module (also referred to herein as a microchannel reactor), a stirred tank reactor, a tubular reactor, or a tubular packed reactor.
When the first reactor set consists of more than one reactor, it may consist of one type of reactor in parallel or in series, for example of two, three, four, five or more microchannel reaction modules (or microchannel reactors) in parallel or in series, of two, three, four, five or more stirred tank reactors, tubular reactors or tubular packed reactors in parallel or in series; it may also consist of reactors of different types in parallel or in series, for example of microchannel reaction modules and tubular reactors in parallel or in series. From the point of view of the ease of operation of the process, it is possible to choose to consist of a type of reactor in parallel or in series, for example of two, three, four, five or more microchannel reaction modules in parallel or in series, or of two, three, four, five or more tubular reactors in parallel or in series. The reaction conditions in the respective reactors may be the same or different as long as they fall within the reaction condition ranges described herein.
When the first reactor set consists of more than one reactor in series, the reaction time of step a) is calculated as the time over all reactors in series. For example, in the case of using two or more continuous flow reactors in series, the reaction time (i.e. residence time) of step a) is calculated as the time over all continuous flow reactors in series.
When the first reactor group is composed of more than one reactor in parallel, the reaction time (or residence time) of each parallel line is calculated separately, and the reaction time (or residence time) of each parallel line satisfies the above range.
In step a), the first reactor set product stream refers to the entire stream exiting the first reactor set, including reaction products, unreacted reactants, optionally solvents, optionally salts resulting from the neutralization reaction, and the like.
Step b)
In step b), the first reactor set product stream is fed with water to a second reactor set, after which a second reactor set product stream is obtained, wherein the feed is preferably a continuous feed.
In step b), the molar ratio of the first reactor group product stream to water may be 1 (1-100), for example 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:60, 1:70, 1:80, 1:90, 1:99, preferably 1 (1-3).
The reaction of step b) may be carried out over a wide temperature range, for example in the range from-50℃to 100℃such as-45 ℃, -40 ℃, -35 ℃, -30 ℃, -25 ℃, -20 ℃, -15 ℃, -10 ℃, -5 ℃,0 ℃,10 ℃, 15 ℃, 20 ℃, 25 ℃,30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, preferably-20 ℃ to 20 ℃.
The reaction time of step b) may be adjusted over a wide range, for example, may be adjusted over a range of 1 second to 5 hours, for example, 1 second, 2 seconds, 5 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 13 seconds, 15 seconds, 18 seconds, 20 seconds, 23 seconds, 25 seconds, 28 seconds, 30 seconds, 33 seconds, 35 seconds, 38 seconds, 40 seconds, 43 seconds, 45 seconds, 48 seconds, 50 seconds, 53 seconds, 55 seconds, 58 seconds, 1 minute, 1.3 minutes, 1.5 minutes, 1.8 minutes, 2.0 minutes, 2.3 minutes, 2.5 minutes, 2.8 minutes, 3.0 minutes, 3.3 minutes, 3.5 minutes, 3.8 minutes, 4 minutes, 4.5 minutes, 5 minutes, 5.5 minutes, 6.0 minutes, 6.5 minutes, 7.0 minutes, 7.5 minutes, 8.0 minutes, 8.5 minutes, 9.0 minutes, 9.5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 hours, 35 hours, 5 hours, 2.5 hours, 3.0 hours, 3.8 hours, 4 hours.
The reaction time may be a residence time in the case of a continuous flow reactor, such as a microchannel reactor, a tubular reactor or a tubular packed reactor.
The second reactor set of step b) may consist of one or more reactors, for example, may consist of one reactor or may consist of two, three, four, five or more reactors. The kind of the reactor herein is not particularly limited as long as production in a continuous manner can be achieved. For example, the reactor used herein may be selected from the group consisting of a microchannel reactor, a stirred tank reactor, a tubular reactor, and a tubular packed reactor. For example, the second reactor set is comprised of one or more microchannel reactors.
When the second reactor set consists of only one reactor, it may be a microchannel reaction module (also referred to as a microchannel reactor in the present application), a stirred tank reactor, a tubular reactor or a tubular packed reactor.
When the second reactor set consists of more than one reactor, it may consist of one type of reactor in parallel or in series, for example of two, three, four, five or more microchannel reaction modules (or microchannel reactors) in parallel or in series, of two, three, four, five or more stirred tank reactors, tubular reactors or tubular packed reactors in parallel or in series; it may also consist of reactors of different types in parallel or in series, for example of microchannel reaction modules and tubular reactors in parallel or in series. From the point of view of the ease of operation of the process, it is possible to choose to consist of a type of reactor in parallel or in series, for example of two, three, four, five or more microchannel reaction modules in parallel or in series, or of two, three, four, five or more tubular reactors in parallel or in series. The reaction conditions in the respective reactors may be the same or different as long as they fall within the reaction condition ranges described herein.
When the second reactor set consists of more than one reactor in series, the reaction time of step b) is calculated as the time over all reactors in series. For example, in the case of using two or more continuous flow reactors in series, the reaction time (i.e., residence time) of step b) is calculated as the time over all continuous flow reactors in series.
When the second reactor group is composed of more than one reactor in parallel, the reaction time (or residence time) of each parallel line is calculated separately, and the reaction time (or residence time) of each parallel line satisfies the above range.
In step b), the second reactor set product stream refers to the entire stream exiting the second reactor set, including reaction products, unreacted reactants, optionally solvent, optionally salts resulting from the neutralization reaction, and the like.
Example 1:
the reaction scheme is shown in FIG. 1, a pre-configured 25 wt% concentration acetic acid solution of 2,2 '-biimidazole and fuming nitric acid are respectively heated to 80 ℃ through two parallel micro-channel reactors (with the volume of about 8.5 mL) at the feeding speed of 10g/min and 5g/min, and then the 2,2' -biimidazole acetic acid solution and fuming nitric acid are simultaneously fed into the other micro-channel reactor (with the volume of about 8.5 mL) for rapid mixing reaction at 80 ℃ to obtain a first reactor group product stream.
The first reactor set product stream (15 g/mL) and water (50 g/mL) were then simultaneously fed into one microchannel reactor (volume about 8.5 mL) of the second reactor set, cooled down to about 20deg.C, neutralized to obtain a second reactor set product stream, further cooled to about 0deg.C, a significant amount of yellow solids precipitated, post-treated, suction filtered, and dried to obtain 4,4', 5' -tetranitro-2, 2' -biimidazole compound in a yield of 47%.
The acetic acid solution feed rate, nitric acid feed rate, water feed rate, 2' -biimidazole of this example were set to: the HNO 3 molar ratio, reaction temperature and residence time were subjected to adjustment tests, as shown in the following table 1, to obtain the yields under the corresponding parameters.
TABLE 1
Note that: the mass fraction of the a2, 2' -biimidazole acetic acid solution is 25%, b is 90% HNO 3, c is 65% HNO 3
Example 2:
The reaction scheme is shown in FIG. 2, a pre-configured 25 wt% concentration acetic acid solution of 2,2 '-biimidazole and fuming nitric acid are respectively heated to 80 ℃ through two parallel micro-channel reactors (with the volume of about 8.5 mL) at the feeding speed of 10g/min and 5g/min, then the 2,2' -biimidazole acetic acid solution and fuming nitric acid are simultaneously fed into the other micro-channel reactor (with the volume of about 8.5 mL) for rapid mixing reaction at 80 ℃, and then the mixture is reacted through a coil reactor (with the residence time of 5 min) at the same temperature, so that a first reactor group product stream is obtained.
The first reactor group product stream (15 g/mL) and water (50 g/mL) are simultaneously fed into a micro-channel reactor (volume of about 8.5 mL) of a second reactor group, the temperature is reduced at 20 ℃ for neutralization to obtain a second reactor group product stream, the second reactor group product stream is further cooled to 0 ℃, a large amount of yellow solid is separated out, and the product stream is subjected to suction filtration after post-treatment and dried to obtain the 4,4', 5' -tetranitro-2, 2' -biimidazole compound, wherein the yield is 73%.
The acetic acid solution feed rate, nitric acid feed rate, water feed rate, 2' -biimidazole of this example were set to: the HNO 3 molar ratio, reaction temperature and residence time were subjected to adjustment tests, as shown in the following table 2, to obtain the yields under the corresponding parameters.
TABLE 2
Note that: the mass fraction of the a2, 2' -biimidazole acetic acid solution is 25 percent
Example 3:
The reaction scheme is shown in FIG. 2. The pre-prepared dichloroethane solution of 2,2 '-biimidazole and fuming nitric acid with the concentration of 25 wt% are respectively heated to 80 ℃ by two parallel micro-channel reactors (with the volume of about 8.5 mL) at the feeding speed of 10g/min and 5.3g/min, then the 2,2' -biimidazole acetic acid solution and fuming nitric acid are simultaneously fed into the other micro-channel reactor (with the volume of about 8.5 mL) to be rapidly mixed and reacted at 80 ℃, and then reacted by a coil reactor (with the residence time of 10 min) at the same temperature, so that a first reactor component stream is obtained.
The first reactor group product stream (15.3 g/mL) and water (50 g/mL) are simultaneously fed into a micro-channel reactor (volume of about 8.5 mL) of a second reactor group, the temperature is reduced at 20 ℃ for neutralization to obtain a second reactor group product stream, the second reactor group product stream is further cooled to 0 ℃, a large amount of yellow solid is separated out, and the 4,4', 5' -tetranitro-2, 2' -biimidazole compound is obtained through suction filtration after post treatment and drying, and the yield is 67%.
The 2,2 '-biimidazole solution feed rate, solvent, nitric acid feed rate, water feed rate, 2' -biimidazole in this example were: the HNO 3 molar ratio, reaction temperature and residence time were subjected to adjustment tests, as shown in the following table 3, to obtain the yields under the corresponding parameters.
TABLE 3 Table 3
Note that: the mass fraction of the a2, 2' -biimidazole acetic acid solution is 25 percent
Example 4:
The reaction scheme is shown in fig. 3, concentrated nitric acid and concentrated sulfuric acid are respectively fed through a micro-channel reactor (volume is about 8.5 mL) according to a certain proportion, the temperature is raised to 80 ℃, meanwhile, a pre-prepared dichloroethane solution with 25 weight percent concentration of 2,2' -biimidazole is heated to 80 ℃ through the micro-channel reactor (volume is about 8.5 mL), then the two materials are simultaneously fed into another micro-channel reactor (volume is about 8.5 mL), the two materials are rapidly mixed and reacted at 80 ℃, and then the mixture is reacted through a coil reactor (residence time is 5 min) at the same temperature, so that a first reactor component product stream is obtained.
The first reactor group product stream (24.6 g/mL) and water (50 g/mL) are then simultaneously fed into one microchannel reactor (volume of about 8.5 mL) of a second reactor group, the second reactor group product stream is obtained by cooling and neutralizing at 20 ℃, the second reactor group product stream is further cooled to 0 ℃ and a large amount of yellow solid is separated out, and the 4,4', 5' -tetranitro-2, 2' -biimidazole compound is obtained by suction filtration after post-treatment and drying, and the yield is 78%.
The 2,2 '-biimidazole solution feed rate, nitric acid feed rate, sulfuric acid feed rate, water feed rate, 2' -biimidazole in this example were: the HNO 3：H2SO4 molar ratio, reaction temperature and residence time were subjected to adjustment tests, as shown in the data in table 4 below, to obtain the yields under the corresponding parameters.
TABLE 4 Table 4
Note that: the mass fraction of the a2, 2' -biimidazole acetic acid solution is 25%, b is 90% HNO 3, c is 65% HNO 3
The foregoing embodiment numbers of the present invention are merely for the purpose of description, and do not represent the advantages or disadvantages of the embodiments.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and many forms may be made by those having ordinary skill in the art without departing from the spirit of the present invention and the scope of the claims, which are to be protected by the present invention.
Claims (10)
1. A process for the preparation of a polynitrobipyrazole compound, comprising the steps of:
a) Feeding the biimidazole solution and a nitrifying reagent into a first reactor group, and obtaining a first reactor group product stream after reaction;
b) And feeding the first reactor group product stream and water into a second reactor group, cooling, diluting and neutralizing to obtain a second reactor group product stream, and carrying out aftertreatment to obtain the polynitrobipyrazole compound.
2. A process for the preparation of a polynitrobipyrazole compound according to claim 1, wherein: the mole ratio of the biimidazole solution to the nitrifying reagent is 1 (0.8-30).
3. A process for the preparation of a polynitrobipyrazole compound according to claim 1, wherein: the first reactor set and the second reactor set each comprise at least one reactor.
4. A process for the preparation of a polynitrobipyrazole compound according to claim 3 wherein: the first reactor set comprises a plurality of reactors connected in parallel and/or in series.
5. A process for the preparation of a polynitrobipyrazole compound according to claim 4 wherein: the first reactor group comprises two parallel reactors, and at least one reactor is connected in series with the discharge end of the parallel reactors.
6. A process for the preparation of a polynitrobipyrazole compound according to claim 2 or 5, wherein: the bisimidazole solution adopts 2,2 '-bisimidazole solution, the nitrifying reagent comprises nitric acid, and the prepared polynitrobispyrazole compound is 4,4',5 '-tetranitro-2, 2' -bisimidazole.
7. A process for the preparation of a polynitrobipyrazole compound according to claim 6 wherein: also fed to the first reactor set in step a) is sulfuric acid, 2' -bisimidazole: nitric acid: the molar ratio of sulfuric acid is 1 (4-8): (4-10).
8. A process for the preparation of a polynitrobipyrazole compound according to claim 6 or 7, wherein: step a) is carried out in a solvent which adopts one or more of benzene solvents, amide solvents, hydrocarbon solvents, halogenated hydrocarbon solvents, sulfone or sulfoxide solvents, ether solvents, acid solvents, ester solvents or water.
9. A process for the preparation of a polynitrobipyrazole compound according to claim 8 wherein: the solvent is one or more of dichloroethane, chloroform, dichloromethane, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, methyltetrahydrofuran, ethyl acetate, butyl acetate, formic acid, acetic acid, propionic acid, butyric acid and water.
10. A process for the preparation of a polynitrobipyrazole compound according to claim 1, wherein: the reaction temperature of step a) is-50 ℃ to 200 ℃, the reaction time is 1 second to 5 hours, the molar ratio of the first reactor group product stream to water in step b) is 1 (1-100), the reaction temperature of step b) is-50 ℃ to 100 ℃, and the reaction time is 1 second to 5 hours.
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