CN104280470B - The method of intermediate in liquid chromatogram measuring LLM-105 production waste water - Google Patents
The method of intermediate in liquid chromatogram measuring LLM-105 production waste water Download PDFInfo
- Publication number
- CN104280470B CN104280470B CN201410453230.3A CN201410453230A CN104280470B CN 104280470 B CN104280470 B CN 104280470B CN 201410453230 A CN201410453230 A CN 201410453230A CN 104280470 B CN104280470 B CN 104280470B
- Authority
- CN
- China
- Prior art keywords
- waste water
- llm
- liquid
- standard
- dmp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention relates to a kind of methods that liquid chromatogram measuring LLM 105 produces intermediate in waste water, belong to chemical analysis field.Steps are as follows for the method：Step 1: the standard solution of DCP, DMP and ANPZ standard substance is prepared with liquid chromatogram mobile phase respectively；Step 2: the production waste water of the LLM 105 is cleaned with filtering with microporous membrane, liquid chromatographic detection sample is obtained；Step 3: carrying out liquid-phase chromatographic analysis to the standard solution, standard curve is drawn；Step 4: using liquid-phase chromatographic analysis, contrast standard curve determination LLM 105 to produce the intermediate in waste water respectively in the sample.The method can accurately detect LLM 105 and produce intermediate related substance DCP, DMP and ANPZ micro in waste water, and the repeatability of quantitative analysis results is good, has filled up the defect of the prior art.
Description
Technical field
The present invention relates to a kind of productions of liquid chromatogram measuring 2,6- diamino -3,5- dinitro -1- oxygen pyrazines (LLM-105)
The method of intermediate, belongs to chemical analysis field in waste water.
Background technology
2,6- diamino -3,5- dinitro -1- oxygen pyrazines (LLM-105) are a kind of energetic material of suitable insensitiveness, energy
It is higher by 20% than photoacoustic spectroscopy (TATB), it is the 81% of octogen (HMX), there is good thermostability.Existing skill
In art, with 2,6- dichloropyrazines (DCP) for starting material, it can be synthesized through methoxylation, nitrification, amination and oxidation four-step reaction
LLM-105, specific building-up process are as follows：
The first step, methoxylation：DCP → DMP (2,6- dimethoxy-pyrazine), chemical equation is as follows：
Ice water washing is added into the mother liquor after reaction, product DMP is precipitated, methoxylation waste liquid is obtained by filtration, is i.e. DMP is useless
DMP is washed with water in liquid, obtains methoxylation waste water, i.e. tri- times washings of DMP；
Second step, nitrification：DMP → DMDNP (2,6- dimethoxy -3,5- dinitros pyrazine)
Ice water washing is added into the mother liquor after reaction, product DMDNP is precipitated, nitrification waste liquid is obtained by filtration, is washed with water
DMDNP obtains nitration waste water；
Third step, amination：DMDNP → ANPZ (2,6- diamino -3,5- dinitros pyrazine)
It is directly filtered after the completion of reaction, obtains product ANPZ and amination waste liquid, i.e. three times scrub raffinates of amination, be washed with water
ANPZ obtains amination waste water, i.e. amination little water washs mother liquor；
4th step, nitrogen oxidation：ANPZ→LLM-105；
LLM-105 crude products are directly obtained by filtration after reaction, after filtering, solvent C F3CO2It is useless that nitrogen oxidation is obtained after H is recovered
Liquid, after dimethyl sulfoxide (DMSO) (DMSO) recrystallizing and refining LLM-105, washing obtains nitrogen oxidation waste water.
In the synthetic method of the LLM-105, waste liquid and waste water can be all generated per single step reaction, in order to carry out subsequent processing
Work, needs to produce the type and content of midbody compound in waste water to LLM-105 and is measured, collect the first step and
Third step generate waste water, altogether there are four types of：DMP waste liquids, tri- times washings of DMP, three times scrub raffinates of amination and amination minute quantity
Water washing mother liquor carries out class to tri- kinds of ingredients of midbody compound DCP, DMP and ANPZ in four kinds of waste water water samples respectively
The analysis of type and constituent content.
Currently, the detection method of midbody compound mainly has ultraviolet spectrophotometry, thin layer in LLM-105 production waste water
Chromatography, dead-stop titration, gas chromatography and Mass Spectrometry etc..Ultraviolet spectrophotometry is the classical method of comparison,
But sensitivity is not high, has extremely similar absorption peak since LLM-105 produces intermediate in waste water, be easy to cause interference, no
It is analyzed while conducive to multicomponent intermediate.Thin-layered chromatography high sensitivity, selectivity are good, but poor repeatability, and detect step
It is rapid cumbersome.Dead-stop titration agents useful for same toxicity is big, and technology is difficult to grasp, and what is measured is organic in LLM-105 production waste water
The total amount of object can not distinguish the type of the intermediate in LLM-105 production waste water, also not be suitable for LLM-105 production waste water
The analysis of multicomponent intermediate materials.Intermediate boiling point in LLM-105 production waste water is above 300K, is difficult in general pillar
It regasifies, therefore gas chromatography is same as gas chromatography mass spectrometry method not applicable.LLM-105 produces the intermediate connection in waste water
NO2And NH2When, very low, connection NO is responded after ionization2It when with-OMe, is less susceptible to be ionized, therefore passes through mass spectrographic method
Also unworkable.
Since LLM-105 productions waste water is various, matrix is complicated, and the physicochemical property difference of each ingredient is larger, especially
Intermediate in the LLM-105 production waste water content in waste water is relatively low, and various methods described above can not detect LLM-
Micro intermediate composition in 105 production waste water, therefore, there is presently no a kind of effective methods can detect LLM-105
Produce the micro intermediate composition in waste water.
Invention content
It can not be to DCP, DMP and ANPZ for the method for the intermediate in waste water in existing measurement LLM-105 production processes
The defect accurately detected, the purpose of the present invention is to provide a kind of liquid chromatogram measuring LLM-105 to produce among in waste water
The method of body, the method have the tool that detection sensitivity is high, it is accurate to quantify, can provide intermediate in LLM-105 production waste water
The advantages of body type and monomer component content.
To achieve the purpose of the present invention, the technical solution of use is as follows：
A kind of method that liquid chromatogram measuring LLM-105 produces intermediate in waste water, the waste water is with 2,6- dichloro pyrroles
Piperazine is starting material, when producing LLM-105 through methoxylation, nitrification, amination and oxidation four-step reaction, methoxylation and aminating reaction production
Raw waste water, specially：DMP waste liquids, tri- times washings of DMP, three times scrub raffinates of amination and amination little water wash mother liquor, point
Other tri- kinds of ingredients of DCP, DMP and ANPZ in four kinds of waste water carry out the analysis of concrete type and monomer component content；Institute
It is as follows to state method and step：
Step 1: preparing standard solution
Tri- kinds of standard substances of DCP, DMP and ANPZ are weighed respectively, are 1 with volume ratio:1 acetonitrile and the mixed solution of water are matched
Standard solution is made；
Step 2: processing waste water
Four kinds of waste water is subjected to filtering with microporous membrane with the filter membrane of aperture≤0.45pm respectively, is collected filtered molten
Liquid is used as liquid chromatographic detection sample；
Step 3: drawing standard curve
DCP, DMP and ANPZ standard solution made from step 1 are detached and surveyed respectively with the external standard method of liquid chromatogram
It is fixed, the peak area at each peak is measured, using peak area as ordinate, a concentration of abscissa draws the standard of DCP, DMP and ANPZ respectively
Curve obtains the linear equation and linearly dependent coefficient of standard curve；The analysis condition of the liquid chromatography such as the following table 1 institute
Show, the stationary phase of reverse-phase chromatographic column is that octadecyl is chemically bonded facies pattern silica gel (ODS)；
1 liquid-phase chromatographic analysis condition of table
Step 4: measuring intermediate in LLM-105 production waste water
According to the corresponding liquid-phase chromatographic analysis condition of each standard solution in table 1, step 2 is handled useless
Water sample is measured with liquid chromatogram respectively, obtains the type and content of wherein intermediate.
To reduce detection error, preferably standard solution is synchronized with the processing of step 2 wastewater sample using same procedure
It after processing, then carries out step 3 and draws standard curve, specific processing method is as follows：
DCP, DMP and ANPZ standard solution are filtered processing with the filter membrane of aperture≤0.45pm respectively, collect filtering
Solution afterwards is used as liquid chromatographic detection sample.
By the standard solution sample replication 5 times of 2 various concentrations, can investigate the method for the invention precision and
Accuracy.
Standard substance (reference material, RM) of the present invention is that one kind having determined that there are one tools or more
The substance or material of a sufficiently uniform characteristic value measure " measurer " in industry, in calibration measurement instrument and dress as analysis
It sets, evaluate the operating technology level for measuring analysis method, measurement of species or material property value and examining analysis personnel, and in life
The fields such as quality control of product play indispensable role during production.
External standard method of the present invention is one of common method of Instrumental Analysis, is one kind of comparison method.Compared with internal standard method,
External standard method is not added to standard substance in sample, is individually surveyed under chromatographic condition identical with sample
It is fixed, obtained chromatographic peak area is compared with the chromatographic peak area of tested component the content for acquiring tested component.
Advantageous effect
1. the present invention provides a kind of method that liquid chromatogram measuring LLM-105 produces intermediate in waste water, the method is used
In the wastewater sample analysis containing DCP, DMP and ANPZ, the separating effect and linear relationship of DCP, DMP and ANPZ are good, measure
Relative error is not higher than 1%, and the analytic variance of 5 measurement is respectively less than 2%, and quantitative accurate, liquid chromatogram is to DCP, DMP and ANPZ
Monitoring lower-cut up to 0.001mg/L, high sensitivity；
2. the method that the present invention provides intermediate in a kind of liquid chromatogram measuring LLM-105 production waste water, in the method
The content replication of intermediate DCP, DMP and ANPZ 2 times in LLM-105 production waste water, the repeatability of quantitative analysis results is good
It is good；
3. the method that the present invention provides intermediate in a kind of liquid chromatogram measuring LLM-105 production waste water, the method and
LLM-105 productions waste water COD measurement result compares, and the scaling results of the two are consistent, but COD detection methods can only provide organic matter
Total content cannot provide the concrete type and monomer component content of intermediate in LLM-105 production waste water, the method for the invention
Intermediate DCP, DMP and ANPZ in waste water can not only be produced to LLM-105 and carry out qualitative analysis, and can to each component into
Row quantitative analysis.
Description of the drawings
Fig. 1 is the canonical plotting of DCP.
Fig. 2 is the liquid chromatogram of DCP standard substances.
Fig. 3 is the canonical plotting of DMP.
Fig. 4 is the liquid chromatogram of DMP standard substances.
Fig. 5 is the canonical plotting of ANPZ.
Fig. 6 is the liquid chromatogram of ANPZ standard substances.
Specific implementation mode
With reference to specific embodiment, the present invention is described further.
With 2,6- dichloropyrazines (DCP) for starting material, can be closed through methoxylation, nitrification, amination and oxidation four-step reaction
At LLM-105, specific building-up process is as follows：
The first step, methoxylation：DCP → DMP (2,6- dimethoxy-pyrazine), chemical equation is as follows：
Wherein, the dosage of various materials is as follows：DCP：20kg, the sodium methoxide (NaOCH of technical grade3)：78.7kg, analysis are pure
Methanol (CH3OH)：16.7kg (22L), product DMP yield：80%；
Ice water is added into the mother liquor after reaction to wash, the volume ratio of ice water and mother liquor is 3:1, product DMP, filtering is precipitated
Methoxylation waste liquid, i.e. DMP waste liquids are obtained, DMP is washed with water, obtains methoxylation waste water, i.e. tri- times washings of DMP；
Second step, nitrification：DMP → DMDNP (2,6- dimethoxy -3,5- dinitros pyrazine)
Wherein, the dosage of various materials is as follows：DMP：10kg, the concentrated sulfuric acid (H2SO4)：100L, concentrated nitric acid (HNO3)：
19.5kg (13L), product DMDNP yield：60%；
Ice water is added into the mother liquor after reaction to wash, the volume ratio of ice water and mother liquor is 3:1, product DMDNP, mistake is precipitated
Filter obtains nitrification waste liquid, and DMDNP is washed with water, obtains nitration waste water；
Third step, amination：DMDNP → ANPZ (2,6- diamino -3,5- dinitros pyrazine)
Wherein, the dosage of various materials is as follows：DMDNP：10kg, acetonitrile (CH3CN)：42.7L, percentage by volume 25%
~28% ammonium hydroxide (NH3·H2O)：8.7L, product ANPZ yield：90%；
It is directly filtered after the completion of reaction, obtains product ANPZ and amination waste liquid, i.e. three times scrub raffinates of amination, be washed with water
ANPZ obtains amination waste water, i.e. amination little water washs mother liquor；
4th step, nitrogen oxidation：ANPZ→LLM-105；
Wherein, the dosage of various materials is as follows：ANPZ：3kg, the H that percentage by volume is 30%2O2：6L, trifluoroacetic acid
(CF3CO2H)：20L, product LLM-105 yield：90%；
LLM-105 crude products are directly obtained by filtration after reaction, after filtering, solvent C F3CO2It is useless that nitrogen oxidation is obtained after H is recovered
Liquid, after dimethyl sulfoxide (DMSO) (DMSO) recrystallizing and refining LLM-105, washing obtains nitrogen oxidation waste water.
In the synthetic method, waste water can be all generated per single step reaction, in order to carry out subsequent processing work, is needed to LLM-
The type and content of midbody compound are measured in 105 production waste water, collect the first step and third walks the useless of generation
Water, altogether there are four types of：DMP waste liquids, tri- times washings of DMP, three times scrub raffinates of amination and amination little water wash mother liquor, respectively
Tri- kinds of ingredients of midbody compound DCP, DMP and ANPZ in four kinds of waste water water samples are carried out with point of type and constituent content
Analysis.
Embodiment 1
One, DCP ingredients are analyzed as follows：
Step 1: preparing standard solution
The DCP for weighing 0.0250g is positioned in the volumetric flask of 25mL, and it is 1 then to use volume ratio:1 acetonitrile and water it is mixed
Close the standard that solution is configured to a concentration of 1 μ g/mL, 3 μ g/mL, 10 μ g/mL, 30 μ g/mL, 100 μ g/mL and 300 μ g/mL respectively
Solution, successively standard specimen serial number 1-1#, 1-2#, 1-3#, 1-4#, 1-5# and 1-6#；
Step 2: the synchronization process of waste water and standard solution
The DCP standard solution that step 1 is prepared and the filter membrane that four kinds of waste water is respectively 0.45pm with aperture are carried out
Filtering with microporous membrane collects filtered solution and is used as liquid chromatographic detection sample；
Step 3: drawing standard curve
It is detached and is measured with the external standard method of liquid chromatogram, concrete operations are：It is with syringe that step 2 is processed
DCP standard solution samples are full of the sample amounts pipe of sampling valve, and inject liquid chromatograph, the DCP chromatographic peaks face recorded
Product, using DCP mass concentrations as abscissa, the peak area of DCP is ordinate, draws the standard curve of DCP, obtains standard curve
Linear equation and linearly dependent coefficient；The liquid-phase chromatographic analysis condition of DCP is as shown in table 1, and reverse-phase chromatographic column type is stationary phase
It is chemically bonded facies pattern silica gel (ODS) for octadecyl；
Step 4: measuring intermediate in LLM-105 production waste water
The wastewater sample that step 2 is handled is determined with the liquid-phase chromatographic analysis condition of DCP standard solution in table 1
Property and quantitative analysis；
Wherein, the standard curve of DCP standard solution is shown in Fig. 1, and liquid chromatogram is shown in Fig. 2, the chromatographic peak for being DCP in box,
Standard curve determination the results are shown in Table 2；To the sample replication 5 times of standard specimen serial number 1-2# and 1-4# in standard solution, investigate
The preci-sion and accuracy of the method, the results are shown in Table 3；The wastewater sample quantitative analysis results are shown in Table 4.
2 DCP standard curve determination results of table
3 preci-sion and accuracy test result of table
The analysis data of table 2 and table 3 illustrate that the correlation coefficient r of the calibration curve of DCP is 0.99995, and linear relationship is good
Good, the relative error that standard specimen measures is 1%, and the analytic variance of 5 measurement is respectively less than 2%, quantitative accurate, in liquid product
The Monitoring lower-cut of DCP is up to 0.001mg/L, high sensitivity.
4 LLM-105 of table produces wastewater sample measurement result
The analysis data of table 4 illustrate, compound DCP assays in the four kinds of waste water generated in LLM-105 production processes
As a result the repeatability of 2 replications, quantitative analysis results is good；Compare with COD measurement results, COD can only provide organic matter
Total content cannot provide compound DCP concrete types and content, and the method for the present invention can not only be to the compound DCP in waste water
It is qualitative, and the content of DCP can be measured, and the result of quantitative analysis is accurate.
Two, DMP ingredients are analyzed as follows：
Step 1: preparing standard solution
The DMP for weighing 0.0250g is positioned in the volumetric flask of 25mL, and it is 1 then to use volume ratio:1 acetonitrile and water
Mixed solution is configured to the mark of a concentration of 1 μ g/mL, 3 μ g/mL, 10 μ g/mL, 30 μ g/mL, 100 μ g/mL and 300 μ g/mL respectively
Quasi- solution, successively standard specimen serial number 2-1#, 2-2#, 2-3#, 2-4#, 2-5# and 2-6#；
Step 2: the synchronization process of waste water and standard solution
The DMP standard solution that step 1 is prepared and the filter membrane that four kinds of waste water is respectively 0.45pm with aperture are carried out
Filtering with microporous membrane collects filtered solution and is used as liquid chromatographic detection sample；
Step 3: drawing standard curve
It is detached and is measured with the external standard method of liquid chromatogram, concrete operations are：It is with syringe that step 2 is processed
DMP standard solution samples are full of the sample amounts pipe of sampling valve, and inject liquid chromatograph, record obtained DMP chromatographic peaks
Area, using DMP mass concentrations as abscissa, the peak area of DMP is ordinate, draws the standard curve of DMP, obtains standard curve
Linear equation and linearly dependent coefficient；The liquid-phase chromatographic analysis condition of DMP is as shown in table 1, and reverse-phase chromatographic column type is to fix
It is mutually that octadecyl is chemically bonded facies pattern silica gel；
Step 4: measuring intermediate in LLM-105 production waste water
The wastewater sample that step 2 is handled is determined with the liquid-phase chromatographic analysis condition of DMP standard solution in table 1
Property and quantitative analysis；
Wherein, the standard curve of DMP standard solution is shown in Fig. 3, and liquid chromatogram is shown in Fig. 4, the chromatographic peak for being DMP in box,
Standard curve determination the results are shown in Table 5, to the sample replication 5 times of standard specimen serial number 2-2# and 2-4# in standard solution, investigate
The preci-sion and accuracy of the method the results are shown in Table 6, and the wastewater sample quantitative analysis results are shown in Table 7.
5 DMP standard curve determination results of table
6 preci-sion and accuracy test result of table
The analysis data of table 5 and table 6 illustrate that the correlation coefficient r of the calibration curve of DMP is 0.99870, and linear relationship is good
Good, the relative error that standard specimen measures is not higher than 1%, and the analytic variance of 5 measurement is respectively less than 2%, quantitative accurate, in liquid product
DMP Monitoring lower-cut up to 0.001mg/L, high sensitivity.
7 LLM-105 of table produces wastewater sample measurement result
The analysis data of table 7 illustrate, compound DMP assays in the four kinds of waste water generated in LLM-105 production processes
As a result the repeatability of 2 replications, quantitative analysis results is good；Compare with COD measurement results, COD can only provide organic matter
Total content cannot provide compound DMP concrete types and content, and the method for the present invention can not only be to the compound DMP in waste water
It is qualitative, and the content of DMP can be measured, and the result of quantitative analysis is accurate.
Three, ANPZ ingredients are analyzed as follows：
Step 1: preparing standard solution
The ANPZ for weighing 0.0250g is positioned in the volumetric flask of 25mL, and it is 1 then to use volume ratio:1 acetonitrile and water
Mixed solution is configured to the standard solution of a concentration of 1 μ g/mL, 3 μ g/mL, 10 μ g/mL, 30 μ g/mL and 100 μ g/mL respectively, according to
Secondary standard specimen serial number 3-1#, 3-2#, 3-3#, 3-4# and 3-5#；
Step 2: the synchronization process of waste water and standard solution
By step 1 prepare ANPZ standard solution and four kinds of waste water respectively with aperture be 0.45pm filter membrane into
Row filtering with microporous membrane collects filtered solution and is used as liquid chromatographic detection sample；
Step 3: drawing standard curve
It is detached and is measured with the external standard method of liquid chromatogram, concrete operations are：It is with syringe that step 2 is processed
ANPZ standard solution samples are full of the sample amounts pipe of sampling valve, and inject liquid chromatograph, record obtained ANPZ chromatographies
Peak area, using ANPZ mass concentrations as abscissa, the peak area of ANPZ is ordinate, draws the standard curve of ANPZ, is marked
The linear equation and linearly dependent coefficient of directrix curve；The liquid-phase chromatographic analysis condition of ANPZ is as shown in table 1, reverse-phase chromatographic column type
It is that octadecyl is chemically bonded facies pattern silica gel for stationary phase；
Step 4: measuring intermediate in LLM-105 production waste water
The wastewater sample that step 2 is handled is determined with the liquid-phase chromatographic analysis condition of ANPZ standard solution in table 1
Property and quantitative analysis；
Wherein, the standard curve of ANPZ standard solution is shown in that Fig. 5, liquid chromatogram are shown in Fig. 6, the chromatography for being ANPZ in box
Peak, standard curve determination the results are shown in Table 8；To the sample replication 5 times of standard specimen serial number 3-2# and 3-4# in standard solution, examine
The preci-sion and accuracy of the method is examined, the results are shown in Table 9, and the wastewater sample quantitative analysis results are shown in Table 10.
8 ANPZ standard curve determination results of table
9 preci-sion and accuracy test result of table
The analysis data of table 2 and table 3 illustrate that the correlation coefficient r of the calibration curve of ANPZ is 0.99995, and linear relationship is good
Good, the relative error that standard specimen measures is not higher than 1%, and the analytic variance of 5 measurement is respectively less than 2%, quantitative accurate, in liquid product
ANPZ Monitoring lower-cut up to 0.001mg/L, high sensitivity.
10 LLM-105 of table produces wastewater sample measurement result
The analysis data of table 10 illustrate that compound ANPZ is containing measurement in the four kinds of waste water generated in LLM-105 production processes
Determine 2 replications of result, the repeatability of quantitative analysis results is good；Compare with COD measurement results, COD can only provide organic
Object total content cannot provide compound ANPZ concrete types and content, and the method for the invention can not only be to the change in waste water
It is qualitative to close object ANPZ, and the content of ANPZ can be measured, and the result of quantitative analysis is accurate.
Claims (3)
1. a kind of method of intermediate in liquid chromatogram measuring LLM-105 productions waste water, it is characterised in that：The method step is such as
Under：
Step 1: preparing standard solution
Tri- kinds of standard substances of DCP, DMP and ANPZ are weighed respectively, are 1 with volume ratio:1 acetonitrile and the mixed solution of water are configured to
Standard solution；
Step 2: processing waste water
LLM-105 productions waste water is subjected to filtering with microporous membrane with the filter membrane of aperture≤0.45pm respectively, is collected filtered molten
Liquid is used as liquid chromatographic detection sample；
Step 3: drawing standard curve
DCP, DMP and ANPZ standard solution are detached and measured respectively with the external standard method of liquid chromatogram, measures the peak at each peak
Area, using peak area as ordinate, a concentration of abscissa draws the standard curve of DCP, DMP and ANPZ respectively, obtains standard song
The linear equation and linearly dependent coefficient of line；The analysis condition of the liquid chromatography is as shown in table 1 below；
1 liquid-phase chromatographic analysis condition of table
Step 4: measuring intermediate in LLM-105 production waste water
According to the corresponding liquid-phase chromatographic analysis condition of each standard solution in table 1, the wastewater sample is used into liquid phase respectively
Chromatography is measured, and obtains the type and content of wherein intermediate.
2. the method for intermediate, feature in a kind of liquid chromatogram measuring LLM-105 productions waste water according to claim 1
It is：After standard solution and the processing of step 2 wastewater sample are synchronized processing using same procedure, then carries out step 3 and paint
Standard curve processed.
3. the method for intermediate, feature in a kind of liquid chromatogram measuring LLM-105 productions waste water according to claim 2
It is：Synchronization processing method is as follows：
DCP, DMP and ANPZ standard solution are filtered processing with the filter membrane of aperture≤0.45pm respectively, collected filtered
Solution is used as liquid chromatographic detection sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410453230.3A CN104280470B (en) | 2014-09-05 | 2014-09-05 | The method of intermediate in liquid chromatogram measuring LLM-105 production waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410453230.3A CN104280470B (en) | 2014-09-05 | 2014-09-05 | The method of intermediate in liquid chromatogram measuring LLM-105 production waste water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104280470A CN104280470A (en) | 2015-01-14 |
| CN104280470B true CN104280470B (en) | 2018-08-24 |
Family
ID=52255558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410453230.3A Active CN104280470B (en) | 2014-09-05 | 2014-09-05 | The method of intermediate in liquid chromatogram measuring LLM-105 production waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104280470B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108120773A (en) * | 2017-12-07 | 2018-06-05 | 西安近代化学研究所 | Separation, the quantitative approach of a kind of 1- oxygen -2,6- diamino -3,5- dinitros pyrazine and its impurity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8663406B1 (en) * | 2006-10-02 | 2014-03-04 | The United States Of America As Represented By The Secretary Of The Army | Melt cast insensitive eutectic explosive |
| CN103694181A (en) * | 2013-11-29 | 2014-04-02 | 西安近代化学研究所 | Synthetic method of 2, 6-diamino-3, 5-binitropyrazine-1-oxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8071813B2 (en) * | 2007-05-03 | 2011-12-06 | Lawrence Livermore National Security, Llc | Methods of using ionic liquids having a fluoride anion as solvents |
-
2014
- 2014-09-05 CN CN201410453230.3A patent/CN104280470B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8663406B1 (en) * | 2006-10-02 | 2014-03-04 | The United States Of America As Represented By The Secretary Of The Army | Melt cast insensitive eutectic explosive |
| CN103694181A (en) * | 2013-11-29 | 2014-04-02 | 西安近代化学研究所 | Synthetic method of 2, 6-diamino-3, 5-binitropyrazine-1-oxide |
Non-Patent Citations (4)
| Title |
|---|
| 1．氧．2，6．二氨基．3，5．二硝基吡嗪(LLM-105)的合成;刘进全等;《化学通报》;20060228(第2期);全文 * |
| Crystal Structure, Safety Performance and Density-Functional Theoretical Investigation of 2,6-Diamino-3,5-dinitropyrazine-1-oxide (LLM-105);MA, Hai-Xia等;《Chinese Journal of Chemistry》;20081231;第26卷;全文 * |
| Scale-up synthesis and characterization of 2,6-diamino-3,5-dinitropyrazine-1-oxide;Hai-bin WANG等;《Defence Technology》;20140731;第1-6页 * |
| The Synthesis of Amino and Nitro-Substituted Heterocycles as Insensitive Energetic Materials;P. F. Pagoria等;《U.S. Department of Energy》;20010823;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104280470A (en) | 2015-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A novel and simple spectrophotometric method for detection of nitrite in water | |
| CN108802256B (en) | Method for detecting content of monoethanolamine | |
| Ranyuk et al. | Rational design of aminoanthraquinones for colorimetric detection of heavy metal ions in aqueous solution | |
| CN102520079B (en) | Method for rapidly measuring content of solanesol in tobaccos by using UPLC (Ultra Performance Liquid Chromatography) | |
| CN109406690B (en) | Method for detecting related substances in chloral hydrate | |
| CN110609100A (en) | Method for simultaneously detecting 6 organic acids in compound acidifier by gas chromatography | |
| CN107247103A (en) | A kind of method of thiocarbamide content in utilization HPLC external standard methods thiocarbamide synthesis | |
| CN101726533A (en) | Rapid and sensitive method for detecting melamine | |
| CN103115994B (en) | Method for rapidly measuring Cr(III) and Cr(VI) ion in tipping paper for cigarette | |
| CN104280470B (en) | The method of intermediate in liquid chromatogram measuring LLM-105 production waste water | |
| CN111413432B (en) | Method for detecting trace PFOA (perfluorooctanoic acid) in fluorine-containing polymer emulsion product | |
| CN113533548A (en) | Method for detecting 1-vinyl imidazole in chemical products | |
| CN104237405B (en) | The method of TATB synthetic intermediate and product in liquid chromatogram measuring waste water | |
| CN105158372A (en) | Method for determining urocanic acid and ethyl ester thereof in cosmetics | |
| CN101025407A (en) | Analytical method for determining micro moisture in cyclopropyl amine by gas phase chromatography | |
| CN106872629B (en) | A kind of method of three nitrogen amidine contents in measurement dairy products | |
| CN103558174A (en) | Method for measuring content of cresol in lysol by utilizing ultraviolet spectrophotometry | |
| CN106053698A (en) | Quantitative analysis method for ethylenediamine sulfate | |
| CN109387588B (en) | Separation method of water-soluble ultraviolet absorbent and application thereof | |
| CN112578037A (en) | Method for detecting content of hexaketal in ulipristal acetate intermediate I | |
| CN110646531A (en) | Ion chromatography quantitative analysis method for raw material diethanolamine in reaction liquid for synthesizing iminodiacetic acid by dehydrogenation of diethanolamine | |
| CN109507327B (en) | Quantitative determination of TNT content by GC-AED independent calibration curve method (CIC method) | |
| CN109521120B (en) | Quantitative determination of DNTF content by GC-AED independent calibration curve method (CIC method) | |
| CN104297379B (en) | The method of high performance liquid chromatography-internal mark method determination pyrogallic acid content | |
| CN110618227B (en) | Method for detecting dicyandiamide content in cyanamide solution by using HPLC method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |