CN106631809A - Green synthesis method for preparing nitroalkanes by oxime oxidation - Google Patents
Green synthesis method for preparing nitroalkanes by oxime oxidation Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
Abstract
The invention belongs to the field of organic chemical industries, and provides a green synthesis method for preparing nitroalkanes by oxime oxidation. At the temperature of 55 to 120 DEG C and under the pressure of 0 to 1.0 MPa, oxime, a solvent and hydrogen peroxide are reacted for 20 to 200min in the presence of certain amounts of nanoporous skeleton metal hybrid catalysts and cocatalysts, a reaction liquid is subjected to membrane separation, the catalysts can be repeatedly used for more than 7 times, and distilled to obtain nitroalkane products, the purity of the products is not less than 99%, and the yield of the products is not less than 95%. Furthermore, the green synthesis method for preparing nitroalkanes by the oxime oxidation disclosed by the invention is a green synthesis method of nitroalkanes, and suitable for large-scale industrialized production.
Description
Technical field
A kind of oxime oxidation prepares the green synthesis method of nitroparaffins.The present invention relates to a kind of green syt of nitroparaffins
Method, and in particular to oxidation reaction.
Technical background
Nitroparaffins are mainly used as organic synthesis raw material, solvent and explosive etc., can produce nearly 2000 kinds of derivatives.Its
Purposes is related to the states such as medicine, agricultural chemicals, explosive, dyestuff, reagent, solvent, surfactant, extractant, emulsifying agent and lubricant
The economic every profession and trade of the people (《Finely and specialty chemicals》The 1st phase of volume 13 in 2005,27-30 page).By nitroparaffins and and aldehydes
Condensation, and then reduction treatment, can be obtained many broad-spectrum amino alcohol products, be nitroparaffins most industrial application value
One of aspect (《Gas chemical industry》2006 volume 31,64-66 page).
The industrialized preparing process of nitroparaffins mainly has 3 kinds：The displacement of vaporphase nitration method, liquid-phase nitration method and nitrite
Method.Vaporphase nitration method is that low-carbon alkanes and nitric acid react at high temperature, is mainly used in below C4 low-carbon alkanes nitrification and produces nitro
Methane, nitroethane and nitropropane etc..The method conversion ratio is higher, but side reaction is more, selective relatively low, it is difficult to obtain higher
Purity nitroparaffins product (《Scientific and technical innovation and application》6th phase in 2016,1-3 page).Liquid-phase nitration method be mainly used in C4 with
On alkane and alkene nitrification, equally there is also the problems referred to above (《Finely with special chemicals》The 1st phase of volume 13,27-30 page；
WO2009129099).Nitroparaffin generated and mainly displacement reaction with halogenated alkane and nitrite in nitrite displacement method there is
Hydrocarbon, although process is simple, reaction temperature is low, equipment corrosion is little, and product chooses, but the substantial amounts of abraum salt of meeting by-product cannot be located
Reason, very big pollution is caused to environment, at the same the source of raw material also have certain limitation (《Liaoning chemical industry》5th phase in 1996,
40-41 page；KR2011117954).
Constantly study recently as the technology of ketone or aldehyde ammonia oximate, the technique for synthesizing ketoxime or aldoxime reaches its maturity, by
Oxime oxidative synthesis correspondence nitroparaffins are increasingly becoming study hotspot.Zolfigol and Keana et al. are respectively with sodium hypochlorite, smelly
Oxygen and chlorine are aoxidized to oxime, but product is chloro nitroparaffins, needs further to reduce generation nitroparaffins
(Journal of the Iranian Chemical Society, 8 (4) 1058-1062；2011, Pure and Applied
Chemistry, 62 (2), 201-205；1990).Ballistreri in 1996 et al. is with [BzOMoO (O2)2]-But 4N+(Benz-
Mo) acetophenone oxime is aoxidized for catalyst, yield is 90%, but the catalyst synthesis for using is difficult, it is expensive, no
Amplify (Synlett, (11), 1093-1094 beneficial to industry；1996).D Subhas Bose et al. potassium hydrogen persulfate, acetonitrile
Aldoxime is aligned with phosphate buffer solution to be aoxidized, 1- nitrohexanes yield 70%, but this reaction response thing is various, post processing
Complicated (Synthetic Communications, 28 (24), 4531-4535 (1998)).Backstrom in 2008 et al. is with mistake
Boratex is oxidant, in glacial acetic acid 1- phenylpropyl alcohol ketoximes is oxidized into 1- nitrobenzene propane, (the Journal of of yield 45%
Physical Organic Chemistry, 21 (7-8), 603-613；2008).George in 2010 et al. is in the same way
4- heptanone oximes are oxidized into 4- nitroheptanes, conversion ratio is 55% (Synlett, (4), 337-339；1992)；The same year,
Methyln-hexyl ketone oxime is oxidized to 2- nitrooctanes by Durchschein et al. in glacial acetic acid again with four water sodium perborate as oxidant,
Conversion ratio is 36% (Green Chenistry, 12 (4), 616-619；2010).This several oxime is direct oxidation into nitroparaffins
Experimental technique is relatively low due to yield, and catalyst activity is low, short life, it is difficult to reuse.Therefore develop new catalyst system and catalyzing with
Technique, improves its conversion ratio with the difficult point and emphasis that are selectively research.
In sum, nitroparaffins are prepared by direct oxidations such as Green Oxidant such as hydrogen peroxide by oxime and has no document report
Road, the method is the synthetic route of an atom economy, meets environmental protection theory, and industrial applications prospect is good.For this purpose, this
It is bright that hydrogen peroxide is catalyzed directly to oxime oxygen with the nano-pore framework metal hydridization oxidation catalyst of our independent developments and co-catalyst
Change reaction, in high yield high selectivity and synthesizing nitryl alkane, product purity >=99%, yield >=97%.Avoid traditional mode of production
A large amount of abraum salts that the displacement of technique nitrite is produced, the HTHP, equipment corrosion, pollution in alkane nitration reaction is big, dangerous
Property it is big the problems such as, be the good low-carbon green environmental protection synthesizing nitryl alkane new technology of a kind of novelty, practicality.
The content of the invention
The purpose of the present invention, there is provided oxime oxidation prepares the green synthesis method of nitroparaffins.
Its synthetic route is as follows：
Under 55～120 DEG C and 0～1.0MPa pressure, oxime, solvent and hydrogen peroxide are in a certain amount of nano-pore bone for the present invention
20～200min, reactant liquor Jing UF membranes, the repeatable profit of catalyst are reacted in the presence of frame metal hybrid catalyst and co-catalyst
With more than 7 times, rectifying obtains nitroparaffins product, product purity >=99%, yield >=95%.
Co-catalyst be sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus, ammonium carbonate, ammonium hydrogen carbonate, ammoniacal liquor, liquefied ammonia,
Lithia, sodium oxide molybdena, potassium oxide, magnesia, calcium oxide, barium monoxide, lithium hydroxide, NaOH, potassium hydroxide, hydroxide
Magnesium, calcium hydroxide, barium hydroxide, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, monoethanolamine, diethanol amine and
One of triethanolamine.
Oxime is acetoxime, diacetylmonoxime, 2 pentanone oxime, isopropyl methyl ketoxime, propione oxime, methyl-n-butyl ketone oxime, 4- methyl -2-
Pentanone oxime, cyclopentanone oxime, 1- methylcyclopentanone oximes, 2- methylcyclopentanone oximes, 3- methylcyclopentanone oximes, cyclohexanone oxime, 2- methyl
Cyclohexanone oxime, acetophenone oxime, formaldoxime, acetaldoxime, propionaldoxime, hutanal oxime, isobutyl aldoxime, valeraldehyde oxime, isovaleraldehyde oxime, just
One of hexanal oxime, dissident's aldoxime, hexahydrobenzaldehyde oxime and benzaldoxime.
Hydrogen peroxide and oxime mol ratio are 0.1: 1～4: 1, and the amount of catalyst is the 0.001～10% of material total amount, nano-pore
Framework metal hybrid catalyst and co-catalyst weight ratio are 1: 0.01～1: 1.
Required solvent is one of methyl alcohol, ethanol, propyl alcohol, isopropanol, the tert-butyl alcohol and acetonitrile or its aqueous solution, in its aqueous solution
Moisture weight percentage composition is 0.1%～50%；Oxime and solvent molar ratio are 1: 0.1～1: 30.
Specific embodiment
Specific examples below is used for further illustrating the present invention.
The preparation method of used catalyst is with reference to our unit patent applied for CN201510866441.4.
Embodiment 1, embodiment 2 and embodiment 3 are that catalyst reuses experiment.
Embodiment 1：
To be used with measuring pump A, hydrogen peroxide (content is 70%) 97g after the blended device mixing of acetoxime 73g and methyl alcohol 160g
Measuring pump B is continuously added to carry in V-ZSM-5 catalyst 3g (silicon metal ratio is 30), the reactor of sodium carbonate 0.003g, temperature
60 DEG C, pressure 0.01MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 2- nitropropane 85.9g, and yield is
96.5%, purity is 99.2%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction, V-ZSM-5 catalysis
Agent obtains 2.87g after filtering.
Embodiment 2：
The V-ZSM-5 catalyst of above-mentioned recovery is carried out by above-mentioned experiment proportioning to repeat experiment, is reused 8 times, yield
More than 95%, the 9th experiment, conversion ratio is down to 92%, and the 10th experiment, conversion ratio is down to 87%.
Embodiment 3：
With measuring pump A, hydrogen peroxide after the blended devices of diacetylmonoxime 87g and tert-butyl alcohol 74g are mixed (content is 27.5%)
125g measuring pump B, it is added continuously to Zr-V-ZSM-5 catalyst (silicon metal ratio be 50) 14g, saleratus 0.3g
In reactor, 65 DEG C of temperature, pressure 0.05MPa, the reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 2- nitrobutanes
99.9g, yield 97%, purity is 99%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction.
Embodiment 4：
The Zr-V-ZSM-5 catalyst that embodiment 3 is reclaimed is carried out repeating experiment by above-mentioned experiment proportioning, reuses 8
Secondary, more than 95%, the 10th experiment, conversion ratio is down to 91.5% to yield, and the 10th experiment, conversion ratio is down to 88.6%.
Embodiment 5：
Measuring pump A, hydrogen peroxide will be used after mixing with the blended device of 2 pentanone oxime 101g, propyl alcohol 600g (water content 30%)
(content is 50%) 34g measuring pump B are continuously added to V-Mo-SBA-15 catalyst (silicon metal ratio is 65) 0.1g, carbonic acid
In the reactor of ammonium 0.1g, 75 DEG C of temperature, pressure 0.15MPa.The reaction clear liquid that UF membrane goes out rectifying 2- nitre Jing after precipitation deamination
Base pentane 55.6g, yield is 87%, and purity is 99.3%., unreacted oxime and solvent it is recovered after return proceed amidoxime
Change reaction.
Embodiment 6：
The V-Mo-SBA-15 catalyst that embodiment 5 is reclaimed is carried out repeating experiment by above-mentioned experiment proportioning, reuses 7
Secondary, more than 95%, the 8th experiment, conversion ratio is down to 92.8% to yield, and the 9th experiment, conversion ratio is down to 87.3%.
Embodiment 7：
By the blended device mixing measuring pump A of isopropyl methyl ketoxime 101g and isopropanol 30g, hydrogen peroxide, (content is
30%) 23g measuring pumps B is continuously added to molybdenum doping micropore-mesopore composite catalyst (silicon metal ratio is 32) 13.8g, oxygen
In changing the reactor of sodium 0.15g, 80 DEG C of temperature, pressure 0.5MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 2-
Nitro -3- methyl-butan 22.8g, yield is 97.6%, and purity is 99.1%, unreacted oxime and solvent it is recovered after return
Proceed oxidation reaction.
Embodiment 8：
Measuring pump A, hydrogen peroxide will be used after the blended device mixing of propione oxime 101g and ethanol 115g (water content 1.5%)
(content is 70%) 185g measuring pump B are continuously added to titanium vanadium doping mesopore-macropore composite catalyst that (silicon metal ratio is
70) in 0.4g, the reactor of magnesia 0.1g, 105 DEG C of temperature, pressure 0.95MPa.The reaction clear liquid Jing precipitations that UF membrane goes out take off
Rectifying after ammonia obtains 3-Nitropentane 111.3g, and yield is 95.2%, and purity is 99%, unreacted oxime and solvent it is recovered after
Return proceeds oxidation reaction.
Embodiment 9：
(will be contained with measuring pump A, hydrogen peroxide after the blended device mixing of methyl-n-butyl ketone oxime 115g and methyl alcohol 640g (water content 5%)
Measure and be continuously added to V-Mo-MCM-41 (silicon metal ratio is 25) 3.95g lithium hydroxide 0.16g for 70%) 73g measuring pumps B
Reactor in, 100 DEG C of temperature, pressure 0.6MPa.The reaction clear liquid that UF membrane goes out obtains 2- nitrohexanes Jing after precipitation
124.5g, purity is 99.2%, and yield is 95.1%, and unreacted oxime and recovered rear return of solvent proceed oxidation instead
Should.
Embodiment 10：
By with measuring pump A, hydrogen peroxide, (content is after the mixing of 4-methyl-2 pentanone oxime 115g and tert-butyl alcohol 59g blended devices
50%) 170g measuring pumps B be continuously added to zirconium it is doped meso-porous-macropore composite catalyst (silicon titanium ratio be 55) 8.5g, potassium hydroxide
In the reactor of 0.1g, 72 DEG C of temperature, pressure 0.3MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtain 2- nitros-
4- methylpentane 125.9g, yield is 96.1%, and purity is 99.1%, returns after unreacted oxime and solvent recovery and proceeds
Oxidation reaction.
Embodiment 11：
(will be contained with measuring pump A, hydrogen peroxide after the blended device mixing of cyclopentanone oxime 99g and acetonitrile 1130g (water content 15%)
Measure for 30%) 90g, with measuring pump B and be continuously added to zirconium vanadium doping micropore-mesopore composite catalyst (silicon metal ratio is 75)
In 2.3g, the reactor of calcium hydroxide 1g, temperature 70 C, pressure 0.65MPa.Reaction clear liquid rectifying Jing after precipitation that UF membrane goes out
Nitrocyclopentane 110g, yield is 95.8%, and purity is 99.2%.After unreacted cyclohexanone and solvent recovery return continue into
Row oxidation reaction.
Embodiment 12：
By with measuring pump A, hydrogen peroxide, (content is after the mixing of 1- methylcyclopentanone oximes 113g and ethanol 345g blended devices
50%) 81.6g measuring pumps B is continuously added to Ti-V-SBA-15 catalyst (silicon metal ratio is 55) 3.8g, liquefied ammonia 0.2g
In reactor, 95 DEG C of temperature, pressure 0.8MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 122.8g, and yield is
95.3%, purity is 99%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction.
Embodiment 13：
With measuring pump A, hydrogen peroxide after the blended devices of cyclohexanone oxime 113g and methyl alcohol 460g are mixed (content is 50%)
122g measuring pump B are continuously added to V-Mo-ZSM-5 catalyst (silicon metal ratio is 75) 10g, the reactor of liquefied ammonia 0.35g
In, 120 DEG C of temperature, pressure 0.95MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 122.5g, and yield is 95%,
Purity is 99.1%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction.
Embodiment 14：
By with measuring pump A, hydrogen peroxide, (content is after the mixing of 2- methylcyclohexanone oximes 127g and acetonitrile 460g blended devices
30%) 73.6g measuring pumps B is continuously added to V-Zr-MCM-41 catalyst (silicon metal ratio is 35) 13g, dimethylamine 0.3g
Reactor in, 110 DEG C of temperature, pressure 0.8MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 88.3g, yield
For 95%, purity is 99%, unreacted oxime and solvent it is recovered after return and proceed oxidation reaction.
Embodiment 15：
With measuring pump A, hydrogen peroxide after the blended devices of acetophenone oxime 135g and ethanol 138g are mixed (content is 50%)
27.2g measuring pump B are continuously added to titanium vanadium doping mesopore-macropore composite catalyst (silicon metal ratio is 40) 11.8g, ethamine
In the reactor of 0.2g, 88 DEG C of temperature, pressure 0.75MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 57.2g,
Yield is 95.2%, and purity is 99%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction.
Embodiment 16：
(will be contained with measuring pump A, hydrogen peroxide after the blended device mixing of formaldoxime 45g and tert-butyl alcohol 600g (water content 45%)
Measure and be continuously added to molybdenum vanadium doping micropore-mesopore composite catalyst for 70%) 77g measuring pumps B (silicon metal ratio is 50)
In 4.3g, the reactor of triethylamine 0.1g, temperature 60 C, pressure 0.8MPa.Reaction clear liquid rectifying Jing after precipitation that UF membrane goes out
Nitromethane 58.8g, yield is 96.5%, and purity is 99.1%.Unreacted first oxime and solvent it is recovered after return continue into
Row oxidation reaction.
Embodiment 17：
With measuring pump A, hydrogen peroxide after the blended devices of acetaldoxime 59g and isopropanol 270g are mixed (content is 50%)
91.8g measuring pump B be continuously added to Ti-Mo-MCM-41 catalyst (silicon metal ratio be 58) 1.6g, monoethanolamine 0.4g it is anti-
In answering kettle, 75 DEG C of temperature, pressure 0.5MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 1- nitroethane 71.3g,
Yield is 95.1%, and purity is 99%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction.
Embodiment 18：
Measuring pump A, hydrogen peroxide (content will be used after the blended device mixing of propionaldoxime 73g and propyl alcohol 210g (water content 20%)
For 27.5%) 170g measuring pumps B be continuously added to V-Mo-MCM-41 (silicon titanium ratio be 42) 46g, magnesium hydroxide 0.2g it is anti-
In answering kettle, 80 DEG C of temperature, pressure 0.7MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 1- nitropropane 84.9g,
Yield is 95.5%, and purity is 99%, returns after unreacted oxime and solvent recovery and proceeds oxidation reaction.
Embodiment 19：
Measuring pump A, hydrogen peroxide (content will be used after the blended device mixing of butyl aldoxime 87g and acetonitrile 120g (water content 10%)
It is continuously added to titanium doped mesoporous macropore composite catalyst (silicon metal ratio is 30) catalyst for 70%) 106g measuring pumps B
In 3g, the reactor of triethanolamine 0.5g, 85 DEG C of temperature, pressure 0.62MPa.The reaction clear liquid that UF membrane goes out is obtained Jing after precipitation
1- nitrobutane 98.6g, yield is 95.8%, and purity is 99%, and unreacted oxime and recovered rear return of solvent proceed
Oxidation reaction.
Embodiment 20：
By valeraldehyde 101g and tert-butyl alcohol 200g, ((content is for the blended device mixing measuring pump A of aqueous 15%), hydrogen peroxide
27.5%) 300g measuring pumps B is continuously added to molybdenum doping micropore-mesopore composite catalyst (silicon metal ratio is 30) 3g, carbon
In the reactor of sour hydrogen ammonium 0.1g, 80 DEG C of temperature, pressure 0.55MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation is obtained
1- nitro pentane 111.2g, yield is 95.1%, and purity is 99%, unreacted oxime and solvent it is recovered after return continue into
Row oxidation reaction.
Embodiment 21：
(will be contained with measuring pump A, hydrogen peroxide after the blended device mixing of dissident's aldoxime 115g and methyl alcohol 350g (water content 25%)
Measure and the reaction with Mo-MCM-41 (silicon metal ratio is 85) 9g, NaOH 0.5g is continuously added to for 30%) 80g measuring pumps B
In kettle, 95 DEG C of temperature, pressure 0.6MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation deamination obtains 1- nitro isohexanes
87.1g, yield is 95%, and purity is 99.1%, returns after unreacted oxime is recovered and proceeds oxidation reaction.
Embodiment 22：
(will be contained with measuring pump A, hydrogen peroxide after the blended device mixing of isobutyl aldoxime 100g and propyl alcohol 260g (water content 35%)
Measure and be continuously added to catalyst Ti zirconium doped micropore-composite mesoporous catalyst (silicon metal ratio for 50%) 102g measuring pumps B
For in 65) 4.5g, the reactor of ammoniacal liquor 0.6g, 85 DEG C of temperature, pressure 0.3MPa.The reaction clear liquid that UF membrane goes out essence Jing after precipitation
1- nitro iso-butane 98.4g are evaporated, purity is 99.1%.Yield is 95.6%, returns after unreacted oxime is recovered and proceeds
Oxidation reaction.
Embodiment 23：
Measuring pump A, hydrogen peroxide will be used after the blended device mixing of hexahydrobenzaldehyde oxime 127g and ethanol 300g (water content 5%)
(content is 30%) 34g measuring pump B, be continuously added to Ti-Mo-ZSM-5 catalyst 15g (silicon metal ratio be 90) 3.6g,
In the reactor of ammonium hydrogen carbonate 0.1g, 95 DEG C of temperature, pressure 0.75MPa, the reaction clear liquid that UF membrane goes out essence Jing after precipitation deamination
Evaporate and obtain cyclohexyl nitromethane 40.7g, yield 95%, purity is 99.2%, unreacted oxime and solvent it is recovered after return
Proceed oxidation reaction.
Embodiment 24：
With measuring pump A, hydrogen peroxide after the blended devices of benzaldoxime 121g and tert-butyl alcohol 300g are mixed (content is 30%)
17g, the reactor with V-SBA-15 catalyst (silicon metal ratio be 30) 10g, calcium oxide 0.3g is continuously added to measuring pump B
In, 105 DEG C of temperature, pressure 0.5MPa.The reaction clear liquid that UF membrane goes out rectifying Jing after precipitation obtains 1- nitro -1- phenylmethanes
19.5g, yield is 95%, and purity is 99%, and unreacted oxime and recovered rear return of solvent proceed oxidation reaction.
Any those skilled in the art, without departing from the spirit and scope of the present invention, should make
Various modifications and change.Therefore protection scope of the present invention should be considered as appended claims limited range.
Claims (5)
1. a kind of oxime oxidation prepares the green synthesis method of nitroparaffins, it is characterized by：In 55～120 DEG C and 0～1.0MPa pressures
Under power, oxime, solvent and hydrogen peroxide react 20 in the presence of a certain amount of nano-pore framework metal hybrid catalyst and co-catalyst
～200min, reactant liquor Jing UF membranes, catalyst is repeatable to be utilized more than 7 times, and rectifying obtains nitroparaffins product, product purity
>=99%, yield >=95%.
2. a kind of oxime oxidation as claimed in claim 1 prepares the green synthesis method of nitroparaffins, it is characterised in that：It is described to help
Catalyst be sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus, ammonium carbonate, ammonium hydrogen carbonate, lithia, sodium oxide molybdena, potassium oxide,
Magnesia, calcium oxide, barium monoxide, lithium hydroxide, NaOH, potassium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, ammonia
One of water, liquefied ammonia, methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, monoethanolamine, diethanol amine and triethanolamine.
3. a kind of oxime oxidation as claimed in claim 1 prepares the green synthesis method of nitroparaffins, it is characterised in that：Oxime is third
Ketoxime, diacetylmonoxime, 2 pentanone oxime, isopropyl methyl ketoxime, propione oxime, methyl-n-butyl ketone oxime, 4-methyl-2 pentanone oxime, cyclopentanone
Oxime, 1- methylcyclopentanone oximes, 2- methylcyclopentanone oximes, 3- methylcyclopentanone oximes, cyclohexanone oxime, 2- methylcyclohexanone oximes, benzene second
Ketoxime, formaldoxime, acetaldoxime, propionaldoxime, hutanal oxime, isobutyl aldoxime, valeraldehyde oxime, isovaleraldehyde oxime, n-hexyl aldehyde oxime, isocaproaldehyde
One of oxime, hexahydrobenzaldehyde oxime and benzaldoxime.
4. a kind of oxime oxidation as claimed in claim 1 prepares the green synthesis method of nitroparaffins, it is characterised in that：Hydrogen peroxide
It is 0.1: 1～4: 1 with oxime mol ratio, the amount of catalyst is the 0.001～10% of material total amount, and nano-pore framework metal hydridization is urged
Agent and co-catalyst weight ratio are 1: 0.01～1: 1.
5. a kind of oxime oxidation as claimed in claim 1 prepares the green synthesis method of nitroparaffins, it is characterised in that：It is required molten
Agent is one of methyl alcohol, ethanol, propyl alcohol, isopropanol, the tert-butyl alcohol and acetonitrile or its aqueous solution, and moisture weight percentage contains in its aqueous solution
Measure as 0.1%～50%；Oxime and solvent molar ratio are 1: 0.1～1: 30.
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| CN108178731A (en) * | 2018-01-19 | 2018-06-19 | 广州印田新材料有限公司 | One kettle way prepares the green synthesis method of AMP-95 |
| CN110003013A (en) * | 2019-03-26 | 2019-07-12 | 山东理工大学 | Catalytic distillation prepares the green method of nitroparaffins |
| CN111939952A (en) * | 2020-08-21 | 2020-11-17 | 中国科学院兰州化学物理研究所 | Hierarchical pore catalyst and preparation method and application thereof |
| CN114634416A (en) * | 2022-04-14 | 2022-06-17 | 河北旭阳能源有限公司 | Preparation method of 2-chloro-2-nitropropane |
| CN115709061A (en) * | 2022-11-26 | 2023-02-24 | 神马实业股份有限公司 | Preparation method and application of porous boron-molybdenum-doped silicon-based material |
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| CN111939952A (en) * | 2020-08-21 | 2020-11-17 | 中国科学院兰州化学物理研究所 | Hierarchical pore catalyst and preparation method and application thereof |
| CN111939952B (en) * | 2020-08-21 | 2022-04-19 | 中国科学院兰州化学物理研究所 | Hierarchical pore catalyst and preparation method and application thereof |
| CN114634416A (en) * | 2022-04-14 | 2022-06-17 | 河北旭阳能源有限公司 | Preparation method of 2-chloro-2-nitropropane |
| CN115709061A (en) * | 2022-11-26 | 2023-02-24 | 神马实业股份有限公司 | Preparation method and application of porous boron-molybdenum-doped silicon-based material |
| CN115709061B (en) * | 2022-11-26 | 2024-02-06 | 神马实业股份有限公司 | Preparation method and application of porous boron-molybdenum doped silicon-based material |
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