CN103288839B - Chromatographic separation method and quantitative detection method of CL-20 (hexaazaisowurtzitane) and three intermediates CL-20 - Google Patents
Chromatographic separation method and quantitative detection method of CL-20 (hexaazaisowurtzitane) and three intermediates CL-20 Download PDFInfo
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- CN103288839B CN103288839B CN201310213952.7A CN201310213952A CN103288839B CN 103288839 B CN103288839 B CN 103288839B CN 201310213952 A CN201310213952 A CN 201310213952A CN 103288839 B CN103288839 B CN 103288839B
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Abstract
The invention discloses a chromatographic separation method and a quantitative detection method of CL-20 (hexaazaisowurtzitane) and three intermediates of CL-20. In the chromatographic separation method, a filler of a chromatographic column used is octyl silane bonded silica gel, a mobile phase is a mixed solution including a formic acid aqueous solution and acetonitrile which are in a volume ratio of (20-25):(75-80), and the volume ratio of formic acid to water in the formic acid aqueous solution is (0.1-0.4):100. The quantitative detection method disclosed by the invention comprises the steps of separating four components by using the chromatographic separation method and then detecting the contents of the four components by using an ultraviolet detector, wherein the detection wavelength is 212nm. The chromatographic separation method and the quantitative detection method are high in accuracy, strong in repeatability, and simple and convenient to operate.
Description
Technical field
The invention belongs to explosive wastewater technical field, be specifically related to a kind of method of sharp separation and mensuration CL-20 and intermediate thereof.
Background technology
Hexanitrohexaazaisowurtzitane (CL-20) is energy density the most much higher ring nitramine cage type single chmical compound explosive up to now; with reference to figure 6; the synthetic method of CL-20 is mainly divided into three steps; correspondingly can produce three kinds of intermediates: HBIW (HBIW), tetra-acetylated dibenzyl hexaazaisopen wootz alkyl (TADB) and tetraacetylhexaazaisowurtzitane (TAIW), be specially:
1st step is initial feed by benzylamine and oxalic dialdehyde, is condensed into intermediate HBIW;
2nd step HBIW takes off benzyl through catalytic hydrogenolysis and generates intermediate TADB;
Direct nitrated TADB or TADB of 3rd step obtains TAIW again through nitrated generation CL-20 through secondary hydrogenolysis;
May remaining a small amount of HBIW, TADB and TAIW in final product CL-20.
Therefore, need be separated to obtain highly purified CL-20 to final product, and reaction product
The detection of intermediates content remaining in CL-20 is also monitoring building-up process and the key parameter evaluating CL-20 purity.
Prior art being separated mainly for CL-20 and its intermediate TADB, TAIW, and independent analysis is only done for HBIW, concrete feature is:
(1) because HBIW and other component polarity difference are too large, by the restriction of chromatographic column filler, moving phase, Four composition flash liberation cannot be realized.
(2) in the chromatographic column filler of existing report, HBIW only can wash-out be out under tetrahydrofuran (THF)-water (volume ratio 90:10) binary mobile phase.And the chromatographic peak profile of detector display is very poor, illustrate that chromatographic column filler is low to its inferior separating effect, post effect, when foundation component strength of signal is on the detector quantitative in addition, the signal background that moving phase tetrahydrofuran (THF) tool is stronger, quantitative sensitivity is lower.
(3) two-step approach separation of C L-20 and three kind of intermediate, the test period is long, can not realize flash liberation, and quantitative system error is large.
In order to prepare high pure component and to each measured portions, being necessary to find a kind of separation simply, quickly and accurately and the method for quantitatively CL-20 and intermediate thereof, just can realizing the separation of CL-20 and 3 kind of intermediate and quantitative by chromatographic run.
Summary of the invention
An object of the present invention is the chromatography separating method providing a kind of CL-20 and its three kinds of intermediates, completes being separated of CL-20 and its three kinds of intermediates with a step.
For this reason, the filler of the chromatography separating method chromatographic column used of CL-20 provided by the invention and its three kinds of intermediates is octyl silane group silica gel, moving phase is the mixed solution of aqueous formic acid and acetonitrile, and the volume ratio of aqueous formic acid and acetonitrile is (20 ~ 25): (75 ~ 80), in aqueous formic acid, the volume ratio of formic acid and water is: (0.1 ~ 0.4): 100.
The volume ratio of described aqueous formic acid and acetonitrile is 20:80,22:78 or 25:75.
Another object of the present invention is to the quantitative detecting method that a kind of CL-20 and its three kinds of intermediates are provided.
CL-20 provided by the present invention and the quantitative detecting method of its three kinds of intermediates first utilize above-mentioned chromatography separating method to be separated four kinds of components, then utilizes UV-detector to detect the content of four kinds of components.
The determined wavelength of UV-detector is 212nm.
The method for quick of CL-20 provided by the invention and its intermediate, presenting property of peak is good, resolving power is high, repeatability by force simple and efficient to handle, chromatographic run can realize being separated and assay of CL-20 and its 3 kinds of intermediates, save experimentation cost, be convenient to promote, the building-up process for CL-20 monitors and production quality control provides effective guarantee.
Accompanying drawing explanation
Fig. 1 is that the volume ratio of formic acid and water in embodiment 1 gets 0.1:100, and the absorption value of CL-20 is the stratographic analysis collection of illustrative plates of 0.2 ~ 0.7;
Fig. 2 is that the volume ratio of formic acid and water in embodiment 2 gets 0.2:100, and the absorption value of CL-20 is the stratographic analysis collection of illustrative plates of 0.2 ~ 0.7;
Fig. 3 is that the volume ratio of formic acid and water in embodiment 3 gets 0.3:100, and the absorption value of CL-20 is the stratographic analysis collection of illustrative plates of 0.2 ~ 0.7;
Fig. 4 is the stratographic analysis collection of illustrative plates that embodiment 4 increases each intermediates content in CL-20;
Fig. 5 is comparative example stratographic analysis collection of illustrative plates;
Fig. 6 is the synthetic method flow chart of steps of Hexanitrohexaazaisowurtzitane.
Embodiment
Separation of the present invention and quantitative detecting method mainly carry out on liquid chromatograph, sample enters octyl silane group silica gel chromatographic column, particular flow phase (acetonitrile, aqueous formic acid) carry out isocratic elution, because each component is different from the effect of chromatographic column filler, isolate three kinds of intermediates and CL-20 successively, then flow through detector signal quantification of intensities according to each separated portion.Adopt the method can realize effectively being separated of CL-20 and three kinds of intermediates and quantitatively.
Below the embodiment that contriver provides, to be further explained explanation to technical scheme of the present invention.
Embodiment 1:
The laboratory apparatus of this embodiment:
Waters1525 type high performance liquid chromatograph, binary gradient pump, 100 μ l automatic samplers, Waters2998 type diode-array detector; Column oven, Empower chromatographic working station.
The test condition of this embodiment:
Chromatographic column: Sun Fire
tMc8(3.5 μm, 4.6 × 150mm);
Column temperature: 26 DEG C;
Flow velocity: 1ml/min;
UV-detector wavelength: 212nm;
The A phase of moving phase is chromatographically pure level acetonitrile, and B phase is formic acid: water=0.1:100(V/V), A phase: B phase=75:25(V/V);
Utilize moving phase to prepare the solution of testing sample, the absorption value of CL-20 is 0.2 ~ 0.7; Sampling volume: 10 μ l; After instrument stabilizer, sample introduction, draws the percentage contents of each component by area percentage method.
The testing sample separation detection result of this embodiment as shown in Figure 1.
Embodiment 2:
This embodiment difference from Example 1 is: the A phase of moving phase is chromatographically pure level acetonitrile, and B phase is formic acid: water=0.2:100(V/V), A phase: B phase=78:22(V/V).
The separation detection result of this embodiment testing sample as shown in Figure 2.
Embodiment 3:
This embodiment difference from Example 1 is: the A phase of moving phase is chromatographically pure level acetonitrile, and B phase is formic acid: water=0.3:100(V/V), A phase: B phase=80:20(V/V).
The separation detection result of this embodiment testing sample as shown in Figure 3.
Embodiment 1-3 to CL-20 and intermediates content as shown in table 1 through liquid-phase chromatographic analysis result.
Table 1
| Embodiment | HBIW(%) | TADB(%) | TAIW(%) | CL-20(%) |
| 1 | 2.11 | 8.78 | 4.02 | 85.09 |
| 2 | 2.08 | 8.49 | 4.68 | 84.75 |
| 3 | 1.77 | 9.62 | 3.78 | 84.63 |
Embodiment 4:
This embodiment laboratory apparatus used is with embodiment 1, and test condition is with described in embodiment 2, and difference is: the content increasing three kinds of intermediates in testing sample.
Its separating and measuring result as shown in Figure 4, when comparison diagram 1 ?4 can illustrate that in testing sample, three kinds of intermediates content are different, separating effect and peak shape all has obvious display.
Comparative example:
The testing sample of this embodiment is pure intermediate HBIW, and testing conditions is:
Chromatographic column: Sun Fire
tMc18(3.5 μm, 4.6 × 150mm),
Column temperature: 25 DEG C,
Flow velocity: 1ml/min,
UV-detector wavelength: 241nm,
The A phase of moving phase is chromatographically pure level tetrahydrofuran (THF), and B phase is water, and A phase: B phase=90:10(V/V);
Moving phase is utilized to prepare the solution of testing sample, sampling volume: 10 μ l;
After instrument stabilizer, sample introduction.
As shown in Figure 5, compared with result shown in Fig. 1, this embodiment selects tetrahydrofuran (THF) as moving phase to separating and measuring result, can produce system peak interference chromatographic determination.
In addition, when utilizing the chromatographic condition of this comparative example to carry out the separation detection of CL-20 and three kind of intermediate, under CL-20 and TADB is just in time overshadowed in tetrahydrofuran (THF) system peak, TAIW on a column without reserve, does not go out peak.And the moving phase selected by embodiment 1 had both overcome the interference of system peak, effectively improved peak shape, ensured the tolerance range of measurement result.And a chromatographic run can be realized, the separation of four kinds of components is with quantitative.
Claims (3)
1. the chromatography separating method of a CL-20 and its three kinds of intermediates; described three kinds of intermediates are: HBIW, tetra-acetylated dibenzyl hexaazaisopen wootz alkyl and tetraacetylhexaazaisowurtzitane; it is characterized in that; in the method, the filler of chromatographic column used is octyl silane group silica gel; moving phase is the mixed solution of aqueous formic acid and acetonitrile; and the volume ratio of aqueous formic acid and acetonitrile is (20 ~ 25): (75 ~ 80), in aqueous formic acid, the volume ratio of formic acid and water is: (0.1 ~ 0.4): 100.
2. the chromatography separating method of CL-20 as claimed in claim 1 and its three kinds of intermediates, it is characterized in that, the volume ratio of described aqueous formic acid and acetonitrile is 20:80,22:78 or 25:75.
3. a quantitative detecting method for CL-20 and its three kinds of intermediates, described three kinds of intermediates are: HBIW, tetra-acetylated dibenzyl hexaazaisopen wootz alkyl and tetraacetylhexaazaisowurtzitane, is characterized in that, comprise the following steps:
The CL-20 described in claim 1 or 2 is utilized to be separated four kinds of components with the chromatography separating method of its three kinds of intermediates;
Afterwards, utilize the content of UV-detector to four kinds of components to detect, and determined wavelength is 212nm.
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| CN1052483C (en) * | 1995-02-01 | 2000-05-17 | 旭化成工业株式会社 | Hexaazaisowurtzitane derivative and process for producing same |
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