CN104950056A - Nitrine nitramine absorbing medicine sample preparing method - Google Patents
Nitrine nitramine absorbing medicine sample preparing method Download PDFInfo
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Abstract
The invention discloses a nitrine nitramine absorbing medicine sample preparing method. The method comprises the following steps that nitrine nitramine absorbing medicine with 20%-40% of water is subjected to rolling for two times, a flake-shaped sample is processed, the thickness of the sample is not larger than 2 mm, the medicine material is plasticized and dense, the water is reduced by ranging from 1% to 3%, the residual water is dried under the temperature of 55 DEG C, the flake-shaped sample is processed into a strip with the size no larger than the size of 1 mm*5 mm, the appropriate strip is weighed, an organic component comprising nitrocotton is soaked by using a good solvent, the nitrocotton is separated out by adding the appropriate amount of water, the other components are remained in the solution, after filtering is carried out, filter liquor is a sampling solution, and the next step quantitative analysis can be carried out on the organic component of the nitrine nitramine absorbing medicine according to the conventional method. Due to the even sample, on the premise of guaranteeing the detecting result, the sampling amount is decreased, and the amount of the organic solvent used for preparing the sampling solution is reduced. The preparing method has the advantages that the sampling cycle is short, and the waste solvent generating amount is low. The method can be also used for a sample preparing method for other absorbing medicine samples containing NC.
Description
Technical field
The invention belongs to explosive wastewater measured portions and analyze detection field, relate generally to a kind of explosive wastewater sample preparation methods, particularly relate to a kind of nitrine nitramine and absorb medicine sample preparation methods.
Background technology
Nobel in 1888 with 60% nitrocotton (NC) absorb 40% nitroglycerine (NG), make NG and absorb medicine, then make double-base propellant through series of process.NC is high molecular polymer, and its plasticizing must by means of low molecule solution.NG is not still containing energy component, or the low molecule solution plastifier of NC, adds the intermolecular distance of NC, improves the compliance of NC strand and reduce intermolecular Van der Waals force, making it dissolve plasticizing, become the strong solution of polymkeric substance.This strong solution improves glass temperature and the flow temperature of spice, under certain External Force Acting, is conducive to machine-shaping.
Triazo-compound, many azide compounds are until full nitrogen type extrahigh energy compound is one of direction of energetic material development.Nitrine nitramine (1,5-diazido-3-nitro aza-pentane is called for short DIANP) is the same with NG, is in a liquid state at normal temperatures, not only containing energy, also has very strong molten ability of moulding NC.Current DIANP, as novel energetic plasticiser, replaces part NG, is used successfully to some new modified propellant powder products of batch production.
For reasons such as safety in production and economic supports, DIANP and NG is produced by different manufacturers: first production of units NG, because pure NG can not transport, absorbing medicine with moisture NG being made in NG absorption with NC, being transported to the second unit producing DIANP, moisture NG is absorbed medicine and adds aqueous dispersion by second unit again, add the components such as DIANP to stir, make moisture DIANP and absorb medicine, be transported to the third unit producing propellant powder, the third unit adds respective components more inward and produces relevant modification propellant powder product.In this whole process, first unit, second unit need to detect NG and absorb medicine component concentration, and second unit, the third unit all need to detect the component concentration that DIANP absorbs medicine.
For accurate detected components content, need technique and the physical and chemical state of understanding spice.
First the manufacture process that classical NG absorbs medicine is introduced: be suspended in by NC in dispersion medium, by methods such as injection, stirrings, each component macroscopically evenly and in accurate measurement mixed, and strong bonded, this process is called absorption.
In NG and NC contact, infiltration and dispersion process, NG molecule permeates in NC strand, and with the functional group on chain, solvation occurs.NC is more much bigger than NG, its movement velocity is very slow, after there is solvation, NC occurs swelling, thus reduce macromolecular intermolecular force, and have the large molecule of small part to be separated to enter in solvent and to dissolve, namely there is small part NC to be dissolved in NG and (dissolve plasticizing completely, when manufacturing propellant powder, by what complete in spice calendering and forming process).
Containing the moisture of about 90% in the medicine slurry of good absorbing.Moisture in medicine slurry can be divided into free water, physical bond water and materialization Bound moisture.Free water refers to not combination between spice, is suspended in top layer, can filters by simple method after spice sedimentation.Physical bond water refers to the moisture infiltrated in medicine slurry hole or kapillary, and this part water just can major part be extruded under certain extruding.Materialization Bound moisture depends on the planar water that hydrogen bond or other intermolecular force combines.Expelling water operation makes free water, most of water drive of physical bond water is removed.Moisture in medicine slurry is driven away to 20% ~ 40% by a general expelling water machine.Medicine slurry now can transport as absorption medicine product.
It is similar that the manufacturing process of DIANP absorption medicine and classical NG absorb medicine manufacturing process.Second unit absorbs in medicine at the moisture NG purchased and adds water, and disperses, add the function ingredients such as DIANP and stir, each component macroscopically evenly and is in accurate measurement mixed in stirred tank, and strong bonded.Equally, containing the moisture of about 90% in the DIANP medicine slurry of good absorbing, the moisture centrifugal dehydration in being starched by medicine with an expelling water machine is to 20% ~ 40%.Medicine slurry now can absorb medicine product as DIANP and transport.DIANP is as in the effect of plastifier in spice and the moisture existence in spice etc., and it is closely similar that DIANP absorption medicine and NG absorb medicine.
NG or DIANP absorbs the whole technological process that medicine manufactures, and along with much physics, chemical process, is summed up, is substantially divided into Four processes: the dispersion of component; The diffusion of component; Liquid component is to the adhesion of NC and infiltration; Solvent is to the dissolving of NC.If disperse uneven, uniformity of mixture is just very poor.The mixed liquors such as such as NG, DIANP disperse insufficient can be formed " micelle " when contacting with NC, and when NG, DIANP content is higher, whole micelle is translucent colloidal particle.This micelle viscosity is large, not easily under the effect of external force, is dispersed into thinner particle.The existence of micelle has a strong impact on component in micelle and H
2the further mixing of other component such as O, diffusion and dissolving, should avoid in production.Namely but due to spice itself, the absorption medicine macroscopically mixed, with the naked eye observable goes out translucent " micelle " that on microcosmic (0.2g level) exists a greater number, is namely uneven at 0.2g horizontal absorption medicine.Absorb the H of in medicine 20% ~ 40%
2o also counteracts that further dissolving and the plasticizing of NC and NG, DIANP.In addition, DIANP absorbs H in medicine
2o content is high, and each pot of material centrifugal expelling water, packaging respectively, finally absorbs medicine quality by each pot and be added, dispatch from the factory as large quantities of, so for large quantities of material, and wherein each junior unit (each pot) H
2o content is obviously different, namely concerning H large quantities of
2o is obviously uneven.In a word, on a microscopic level (0.2g level), it is uneven for absorbing each component in medicine, so when sampling detection, requirement sample quarterlies, sampling amount is comparatively large, and sampling spot is more, and during detection, sample size is also relatively large.
NG absorbs medicine and occurs comparatively early, is use vapor-phase chromatography detection level.Representative for ensureing sampling, the thermal conductivity detector (TCD) sensitivity of gas chromatography is lower in addition, so generally large quantities of NG is absorbed medicine repeatedly sample quarterlies, sieves, dries, therefrom take 2g, with Solvent Extract methods, prepare sample solution.Shortcoming is, gas chromatography can only detect gaseous material, need the component transient evaporation to be measured made by high temperature in sample, it will be separated by the chromatographic column of higher temperature (the low component condensation easily making to have gasified of chromatogram column temperature) by the component of gasification one by one.The high temperature of vaporizer, chromatographic column makes NG be very easy to decompose, Interference Detection, so have employed the means such as lower gasification temperature (175 DEG C ~ 210 DEG C), lower column temperature (140 DEG C ~ 190 DEG C), short column (500mm) and high flow rate of carrier gas (80mL/min ~ 200mL/min), reduce heating temperature and the heated time of NG.Even if but like this, still there is the accident in inserting needle gasification moment NG blast.On the other hand, the means such as short column and high flow rate of carrier gas, the NG residence time in the chromatography column can be shortened, but make separation efficiency reduce simultaneously, be unfavorable for being separated the many samples of detected components, and Novel emission medicine is due to the increase of request for utilization, component gets more and more, and the application of gas chromatography in new product is restricted.
Liquid chromatography can avoid high temperature to the thermostimulation of sample, carries out separation and detection at normal temperatures after sample dissolution with solvents, the detection of be applicable to very much the being heated components such as labile NG, DIANP.Liquid chromatograph is ripe and market-oriented, and current each explosive wastewater Physico-chemical tests room is all equipped with liquid chromatograph.The quantitative detection of current DIANP sterling, DIANP absorption medicine, the modified double base propellant powder containing DIANP, the modification triple-base propellant containing DIANP all adopts liquid phase chromatography.
What be all equipped with is UV-detector for the liquid chromatograph overwhelming majority of current explosive wastewater physics and chemistry room, this mainly because: most Small molecular organic component that need detect by chromatogram in explosive wastewater, all contain-NO
2,-N
3, phenyl ring, unsaturated double-bond etc. have the functional group of uv absorption; UV-detector is highly sensitive, to containing absorption official can the detection limit of material of figure very low, the slight change of component can be observed; UV-detector is sturdy, easily safeguard.
The quantitative principle of UV-detector is: the light of a branch of specific wavelength is by detection cell, and the sample that a part of light is detected in pond absorbs, and a part of light transmission detection cell is responded to by detecting device.The intensity of light of detecting device by sensing, and the intensity of initial light, calculate the absorbance of sample.
In formula: A is absorbance; I
0for the light of specific wavelength is by the intensity before detection cell; I
tfor the light of specific wavelength is by the intensity after detection cell.
Then foundation law of light absorption A=KcL (in formula: K is absorptivity, is constant; C is the concentration of test substance in solution; L is that light is by light path during detection cell) determine the concentration of sample solution in detection cell.
When sample overrich, A=KcL formula is no longer set up, namely will no longer linearly between the c of sample and absorbance A, the content of object in the A calculation sample that can not provide according to detecting device again, otherwise will produce very big error.The part that even some liquid chromatograph A exceeds 1 does not show concrete numerical value, and now chromatogram will occur " tack peak ", the light as 95% is absorbed by solution to be measured, and only have the light of 5% to be responded to by detecting device, then A should be " 1.3 ", and instrument only shows " 1 ".In addition A relative error 0.434 time is minimum, think and ensure the accuracy of testing result, absorbance should control below 0.9 by general detection as far as possible.
Prepare the DIANP solution of a series of variable concentrations, detect with the 1120LC of Agilent company of the U.S. and the Rrostar HPLC of U.S.'s Varian respectively, when the concentration of known DIANP is within the scope of 0.1 ~ 1mg/mL, instrumental response value A is between 0.1 ~ 0.9.Be 15% calculating with DIANP content in sample, if sampling amount is 2g, then need dilution constant volume to be 300mL ~ 3000mL, and general conventional sense needs at least to detect two Duplicate Samples, each like this sample can need the organic solvent of 600mL ~ 6000mL to dissolve.Can find out, the shortcoming of this operation is: organic solvent use amount is many, detected after containing can spent organic solvent amount too large.And so sampling amount is defined as 2g, be because absorb medicine after sieving and drying, its component skewness on microcosmic, sampling amount can make testing result have more representativeness greatly a bit.
On the other hand, original sample preparation methods overlong time.The former preparation process of sample is as follows:
(1) overall material is about 1kg with repeatedly sample quarterlies, then rubbing crosses 3mm and 2mm double deck screen (sieve and about need 0.5hr);
(2) get 2mm screen overflow and be about 10g, be put in 55 DEG C of baking ovens and dry moisture (about needing 4hr);
(3) take 2g (accurately to 0.0001g) and dry rear sample in 1000mL volumetric flask, add about 800mL acetone, put into magnetic stirring bar, the whole component of stirring and dissolving;
(4) the about 150mL that dropwise adds water separates out NC (whole process magnetic stirring bar stirs);
(5) separate out magnetic stirring bar with magnet, add water 1000mL volumetric flask constant volume;
(6) leave standstill more than 2hr, make most NC sedimentation;
(7) draw about 5mL supernatant liquid with syringe, filter, filtrate is sample solution;
(8) press each component concentration preparing standard solution in sample simultaneously, detect with liquid chromatograph (joining UV-detector), calculate component concentration in sample by external standard method.
DIANP absorbs moisture in medicine and differs greatly, and detecting so be not suitable for directly preparing sample solution with moisture absorption medicine (wet basis), is all get butt to carry out measured portions.Sieved and baking step by sample, the homogeneity that DIANP absorbs medicine can be improved a little, make testing result can represent overall material, but the obvious shortcoming brought is that the sample preparation time is oversize: sieve 0.5hr, dry 4hr.
Drying time is long is what to be caused by the reason of two aspects:
(1) DIANP, NG have the trend of heat resolve, so oven temperature can not higher than 55 DEG C (DIANP, NG be low volatilyty liquid materials, are not suitable for vacuumizing method), the volatilization of temperature low moisture is slow;
(2) DIANP absorbs containing free water, physical bond water and materialization Bound moisture in medicine, and 55 DEG C can only be dried in fact except whole free waters and most physical bond water, and intermolecular interaction makes the more difficult volatilization of materialization Bound moisture, so drying time is long.
In sum, can find out that current DIANP absorbs the measured portions of medicine and has that the sample preparation time is long, solvent-oil ratio is large, produce containing can the shortcomings such as waste liquid is many.
The sample preparation time is long, causes sense cycle long, makes total ton DIANP absorb medicine and can not enter next operation in time, and for manufacturer and use producer, DIANP absorbs parking of medicine and there is obvious potential safety hazard.Project team wishes to improve preparation method for this reason, shortens preparation time, reduces solvent-oil ratio.
Summary of the invention
DIANP absorb medicine sense cycle length be due to sample preparation consuming time caused by: principal element is that sample contains very uneven moisture, need low temperature baking water, and moisture is combined closely, dries very slow in order to obtain butt sample with spice; Secondary cause is that other component is also uneven, so need to sieve.Sieve and dry and approximately need 4.5hr.
Absorb defect or the deficiency of medicine sample preparation methods for DIANP in above-mentioned prior art, the object of the invention is to, provide a kind of and have fast, accurately, low energy consumption, environmental protection sample preparation methods.
In order to realize above-mentioned task, the present invention takes following technical solution:
(1) medicine sample 2 ~ 3kg plough groove type calender will be absorbed with a collection of nitrine nitramine and roll 2 times, rolling temperature 85 ~ 95 DEG C, be processed into the sheet sample that thickness is not more than 2mm, nitrocellulose and nitrine nitramine and other solvent is made to occur deeply to act on, spice plasticizing and closely knit, the moisture in sample reduces to 1 ~ 3% by original 20% ~ 40%;
(2) sheet sample is dried residual moisture in not higher than the baking oven of 55 DEG C;
(3) sheet sample after oven dry is treated to the slice being not more than 1mm × 5mm;
(4) take the slice 0.2g (being accurate to 0.0001g) handled well, soak with good solvent, dissolve the organic component comprising NC;
(5) adding suitable quantity of water makes NC separate out, and Small molecular organic component to be measured still stays in the solution, and filtrate is sample solution;
(6) preparing standard solution, with liquid phase chromatography test samples solution and standard solution, calculates DIANP by external standard method and absorbs each component concentration in medicine.
Although at high temperature carry out in calender line, because whole calendering is no more than 10min, so NG, DIANP obviously do not decompose.DIANP of the present invention absorbs medicine sample preparation methods, the advantage that the sample preparation time is short, sample homogeneity is good had:
(1) DIANP absorbs medicine on plough groove type calender, be subject to the extruding of calender two Kun, heat (85 ~ 95 DEG C) and external force effect under, most of moisture is purged, and after rolling 2 times, moisture becomes 1% ~ 3% from 20% ~ 40%, NC and NG, DIANP and other solvent act on further simultaneously, physicochemical change occurs, and absorb medicine dry, mixing gradually, plasticizing and closely knit, whole process about needs 5 ~ 10min;
(2) roll the spice after 2 times due to residual moisture in spice little, so greatly can shorten drying time, drying time is about 1hr;
(3) high temperature (85 ~ 95 DEG C) can make that the movement velocity of NC macromolecular chain segment increases, molecular flexibility increases, also can accelerate the dissolving of NG, DIANP equal solvent low molecule system, so the large molecule of NC and solvent molecule relative diffusion rates accelerate, improve solubility property, mix very soon.
In microcosmic (0.2g) aspect, the DIANP of " component is uneven " absorbs medicine, uniform in macroscopically (in the actual production of propellant powder) component, the moisture in spice is driven away by moulding process, spice plastifies under higher pressure and temperature, makes the powder column with certain geometrical shape, certain size and compact structure.
The object that component detects should be the component concentration reacting overall material, too should not be entangled with the component concentration of the sample compared with small scale.So want large for material sampling amount uneven in microcosmic point, testing result be made to reflect overall material situation, and can significantly reduce for uniform material sampling amount.
Quantification range due to liquid chromatography (UV-detector) makes sample to be configured to lean solution, so sampling amount is greatly just meaned need to use more multi-solvent preparation sample solution, produces more containing energy solvent slop.If the homogeneity of material can be improved, just can reduce sampling amount, also just can use solvent less.
The DIANP absorption medicine rolling 2 times through high temperature becomes even, therefore can reduce sampling amount, only need less solvent to dissolve accordingly, make sample solution.After rolling process sample preparation, single sample only needs to take 0.2g (being diluted to 100mL) and detects, and testing result can represent material by the gross.
Therefore replace sieving, drying the preparation carrying out sample by High Temperature High Pressure calendering, by sieving in former method sample preparation, drying 4.5hr used, shorten to about 1.1hr.In addition, rolling process makes sample homogeneity obtain the change of matter, and therefore obviously can reduce the sampling amount for detecting, the organic solvent amount accordingly for extracting dissolving significantly reduces, containing becoming 200mL from original 2000mL by solvent slop.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment 1
It is that (component is NC, NG, C by the NG of outsourcing absorption medicine that certain DIANP absorbs medicine
2, for transportation safety also containing 20% ~ 40% water) in add water dispersed with stirring in a kettle., then add the components such as DIANP, DNT and continue to stir and evenly mix, each component of absorption medicine macroscopically evenly and is in accurate measurement mixed, and strong bonded.Containing the moisture of about 90% in the medicine slurry of good absorbing, the moisture centrifugal dehydration in being starched by medicine with an expelling water machine becomes DIANP to 20% ~ 40% and absorbs medicine product.
DIANP has the advantages that to decompose before vapourizing temperature point, so the detection that DIANP absorbs the organic molecule components such as DIANP in medicine at present adopts liquid chromatography external standard method, adopt the preparing of sample sieve, method that 55 DEG C dry.Sieve, drying time more than 4.5hr, and like this sample composition of preparation is still uneven in microcosmic point (0.2g level), causes sampling amount comparatively large (2g), testing result just can be made to react the composition situation of material by the gross.The UV-detector be equipped with due to liquid chromatograph is not suitable for detecting strong solution, and need lean solution 2g sample being made into 1000mL, the quantity of solvent of consumption is large, generation containing can waste liquid many.Therefore the preparation of sample is carried out in the rolling process preparation that the present invention proposes DIANP absorption medicine.This preparation method is few (calendering is no more than 10min, and residual moisture is dried and is no more than 1hr) consuming time not only, and makes the homogeneity of sample obtain the improvement of matter, and therefore can reduce sampling amount is 0.2g, and correspondingly solvent slop generation decreases 10 times.
The operation steps of the present embodiment is as follows:
(1) from the DIANP absorption medicine spice of moisture 20% ~ 40%, 2 ~ 3kg is got by inquartation, 2 times are rolled with calender, temperature 85 ~ 95 DEG C, the calendering time is about 10min, be processed into the sheet sample that thickness is not more than 2mm, make the moisture in sample become 1% ~ 3%, NC and DIANP and other solvent there is deeply effect, plasticizing, closely knit;
(2) sheet sample is placed on about 1hr in 55 DEG C of baking ovens, drives away the residual moisture in sample;
(3) sheet sample is treated to the slice being not more than 1mm × 5mm;
(4) accurately take the slice 0.2g (being accurate to 0.0001g) handled well, be placed in 100mL volumetric flask, add about 80mL acetone, put into magnetic stirring bar, stirring and dissolving comprises the organic component of NC;
(5) dropwise adding 15mL water makes NC separate out (whole process still stirs with magnetic stirring bar), and with magnet sucking-off magnetic stirring bar, and rinse stirring rod with 2mL water, the water of flushing is incorporated in volumetric flask, then the constant volume that adds water;
(6) leave standstill more than 2hr, make most NC sedimentation;
(7) draw about 5mL supernatant liquid with syringe, filter, filtrate is sample solution;
(8) preparing standard solution, with liquid chromatographic detection standard solution and sample solution, calculates by external standard method the content that DIANP absorbs medicine small molecular organic component.
As can be seen from above step: the sample preparation time of rolling process obviously shortens, shorten to 1.1hr (calendering+dry) from the 4.5hr (sieve+dry) of former method; Sample weighting amount is reduced to 0.2g from the 2g of former method, and when sample solution concentration is constant, sample preparation solvent for use becomes 100mL from the 1000mL of former method.
Rolling process sample preparation has short, advantage that solvent-oil ratio is few consuming time, but the accuracy that the prerequisite that all these advantages can realize must be testing result can not lower than former method.Seminar has carried out following experiment and has verified new preparation process for this reason.
1. former preparation method sample sample weighting amount determines test
Because it is obviously uneven that moisture DIANP absorbs medicine component (0.2g level) on microcosmic, generally passes through to increase the methods such as sampling amount when detecting uneven material, make testing result can reflect material overall condition.
The DIANP of certain crowd moisture 20% ~ 40% is absorbed medicinal repeatedly sample quarterlies and is about 1kg, then rubbing crosses 3mm and 2mm double deck screen, gets 2mm screen overflow and is about 10g, is put in 55 DEG C of baking ovens and dries moisture.Take each 6 of 0.2g, 0.5g, 1.0g, 1.5g, 2.0g (being all accurate to 0.0001g) sample respectively, all be mixed with the sample solution that DIANP content is 0.2g/L, DIANP content is detected by liquid phase chromatography, experiment with computing standard deviation RSD (n=6), the results are shown in Table 1 respectively.Because detection method, detecting instrument, operator are identical, if sample is uniform, with the increase of sample weighting amount, the RSD of testing result and extreme difference can not obviously reduce, and as can be seen from Table 1 as sample weighting amount >=1.5g, RSD, testing result extreme difference (maximal value-minimum value) obviously diminish and tend to definite value, illustrate sampling amount at least should more than 1.5g time, testing result could represent overall material.Require in product specification that the content detection of the components such as DIANP need make two Duplicate Samples, franchise≤0.5% of Duplicate Samples.From the extreme difference value of table 1, when sample weighting amount is 2.0g, extreme difference value is 0.3%, and illustrate that the difference of the testing result of Duplicate Samples is now below 0.3%, the collimation of two testing results is better, product specification requirement can be met, so the sample weighting amount that former method for making sample is determined is 2.0g.Table 1 data also further demonstrate that, in 0.2g level, sample is uneven.Although the unevenness in this degree is footy concerning large-scale production, material can be made evenly real gradually by the production technology in later stage, but be need to pay attention to concerning detection, even can be with and serve contradiction: sample weighting amount is very few, testing result can not react the situation of overall physics; Sample weighting amount is comparatively large, again due to the restriction of detecting instrument, more solvent must be used to dilute, make solvent slop treatment capacity excessive.Because sampling amount during such propellant powder finished product detection is 0.2g, so wish the preparation method absorbing medicine by improving DIANP, make spice enough even, also can reach sampling amount is 0.2g.
The former preparation method's sample weighting amount of table 1 determines test
2. roll pass and determine test
The object of sieve, drying obtains uniform not aqueous specimen comparatively speaking, but for the amount that instrument can bear, the homogeneity of sample still not.And the absorption medicine of Microinhomogeneity is when producing propellant powder, the even of the microcosmic point of component being reached completely by operations such as calenderings, so use for reference propellant powder production technology, iting is desirable to prepare the uniform sample for detecting on microcosmic by rolling process.Rolling temperature when producing propellant powder is 85 ~ 95 DEG C, so seminar also adopts this rolling temperature to prepare sample.More Multi-example is more even for calendering pass, but considers time cost, so wish that calendering pass is better less.
Certain crowd of DIANP is absorbed medicine roll respectively 0,1,2,3 time (after having rolled, putting into 55 DEG C of oven for drying moisture).6 points got respectively at random by often kind of sample rolled, and make sample solution respectively.Operation steps is: weigh the sample that 0.2g (being accurate to 0.0001g) rolls, dried, and with acetone solution, adds water and separates out NC, and constant volume, to 100mL, filters and makes sample solution.Detect by liquid chromatography external standard method, testing result lists in table 2.As can be seen from Table 2, when after calendering 2 times, RSD, extreme difference are tending towards definite value, meet the requirement of product specification.So finally determine that rolling temperature is 85 ~ 95 DEG C, calendering pass is 2.From practical operation situation, the whole calendering time is no more than 10min, and high temperature calendering can extrude the most water absorbed in medicine, and the oven dry of residual moisture is no more than 1hr, and the T.T. of therefore rolling process sample preparation shortens greatly than former method.
Table 2 rolls pass and determines test
3. roll preparation method sample volume and determine test
During the uniform propellant powder sample of general conventional sense, sample weighting amount is about 0.2g, is diluted to 100mL.So seminar wishes that DIANP absorbs the sampling amount of medicine also at about 0.2g.
Sample is prepared by rolling process.Take each 6 of 0.1g, 0.2g, 0.5g, 1.0g, 1.5g (being all accurate to 0.0001g) sample respectively, all be mixed with the sample solution that DIANP content is 0.2g/L, DIANP content is detected by liquid chromatography external standard method, experiment with computing standard deviation RSD (n=6), the results are shown in Table 3 respectively.Because detection method, detecting instrument, operator are identical, if sample is uniform, with the increase of sample weighting amount, the RSD of testing result and extreme difference can not obviously reduce.As can be seen from Table 3 when sample weighting amount is increased to 1.5g from 0.1g, RSD is reduced to 0.9% by 1.5%, testing result extreme difference (maximal value-minimum value) is reduced to 0.3% by 0.5%, substantially the change on the same order of magnitude is belonged to, namely along with the increase of sample weighting amount, the change that data do not have matter is detected.Now consider testing cost again, can think when sample weighting amount is chosen as 0.2g, can meet the requirement of product specification to Duplicate Samples franchise, also can save time cost, and reduce solvent slop.Can find out on the other hand, when the sample weighting amount of calendering preparation method is 0.2g and the representative that takes 2.0g of former method be on close level, overall material level can be represented.
Table 3 rolls preparation method sample weighting amount and determines test
4. two kinds of sample preparation method testing results when sample weighting amount is identical
Certain DIANP is absorbed medicinal two kinds of distinct methods and carries out sample preparation (sampling amount is 0.2g, and equal constant volume is 100mL), detect definite value by liquid chromatography external standard method, detect 3 batches altogether, often criticize detection 6 Duplicate Samples.The testing result absorbing the most difficult DIANP of mixing and DNT in medicine is listed in table 4.As can be seen from Table 4: when sampling amount is 0.2g, the RSD (n=6) of the testing result of preparation method of the present invention (calendering, baking water) can control 0.97% ~ 1.33%, and extreme difference is 0.32% ~ 0.39%, and precision is better; Former preparation method (sieve, dry water) is uneven due to sample itself, and the RSD (n=6) making testing result is 7.28% ~ 12.53%, and extreme difference is 1.99% ~ 4.41%, and precision is poor.Precision is well the prerequisite ensureing that accuracy in detection is high, therefore, when sample weighting amount is 0.2g, adopt method of the present invention (calendering, dry water law) to prepare sample and carry out DIANP when absorbing the quantitative detection of medicine, precision is better, can quote testing result by the mode that 2 parallel results are average.Detection data from table 4 also can be found out when adopting multidraw to detect (n=6), even if the precision of former preparation method (sieve, oven drying method) testing result is bad, but the average content of 6 sample average content and method of the present invention, 2 samples conforms to, when illustrating that dispersion degree due to uneven the caused testing result of sample is larger, multidraw method can be adopted to carry out detecting and quoting average result.
The detection data of absorption medicine sample prepared by table 4 two kinds of methods
5. the expelling water Effect disquisition of two kinds of preparation methods
Moisture in spice is divided into free water, physical bond water and materialization Bound moisture.Free water refers to not combination between spice, is suspended in top layer, can filters by simple method after spice sedimentation.Physical bond water refers to the moisture infiltrated in medicine slurry hole or kapillary, and this part water just can major part be extruded under certain extruding.Materialization Bound moisture depends on the planar water that hydrogen bond or other intermolecular force combines.Preparation method of the present invention and former preparation method are all the moisture in spice will be driven away completely, then carry out quantitatively butt spice.Can observe from table 4, legal system of the present invention is for the testing result of sample
substantially all higher than the testing result numerical value of former preparation method, conjecture is likely because former preparation method (sieve, dry water), moisture in sample can not be driven away completely, therefore detect the moisture in the spice after two kinds of preparation method's expelling waters respectively with Karl_Fischer method.Detect 5 batches of spices altogether, often criticize and prepare expelling water by two kinds of methods, often criticize detection 6 Duplicate Samples, sample weighting amount is 2g, detects data in table 5.
The expelling water Effect disquisition of table 5 two kinds of preparation methods
As can be seen from Table 5, after preparation method of the present invention (calendering, oven dry) expelling water, in sample, water content detection result is 0.06% ~ 0.12%, after former preparation method (sieve, dry) expelling water, sample water content detection result is 0.76% ~ 1.16%, illustrate that the inventive method is more effective than former preparation method's expelling water, former preparation method can not discharge the materialization Bound moisture in sample completely.Because actual spice adopts High Temperature High Pressure to carry out expelling water, so inventive samples preparation method testing result is closer to product actual conditions, preparation method component testing result of the present invention listed in what table 4 also can be interpreted as thus micro-higher than former preparation method.It can also be seen that from table 5 data, when sample weighting amount is 2g, former preparation method moisture data extreme difference is obviously greater than preparation method of the present invention, further illustrates the sample that the standby sample of legal system of the present invention prepared than former method even.
Conclusion: by above several test, can find out: the method for the invention (calendering, oven dry) prepares sample, relative to former preparation method (sieve, dry), the homogeneity of sample has had the improvement of matter, even if so sampling amount is 0.2g, the preci-sion and accuracy of testing result also can be ensured.And sample prepared by former preparation method (sieve, oven drying method), due to the unevenness of essence, for ensureing that sample detection result can represent overall material, take mode (the single sample 2g strengthening sampling amount, make 2 Duplicate Samples), make the whole preparation process not only cycle long (sieve, dry need 4.5hr), and need to dilute sample with a large amount of solvents.The materialization Bound moisture in sample can not be discharged in addition due to former preparation method completely, make testing result more on the low side than actual sample.Therefore, can think that the method for the invention (calendering, oven dry) is prepared sample and had preparation time short (calendering, oven dry need 1.1hr), produces solvent slop few (being 1/10th of former method), more can react overall material situation than former preparation method.
Claims (3)
1. nitrine nitramine absorbs a medicine sample preparation methods, and it is characterized in that, the method comprises the following steps:
Step one, medicine sample 2 ~ 3kg plough groove type calender will be absorbed with a collection of nitrine nitramine and roll 2 times, rolling temperature 85 ~ 95 DEG C, be processed into the sheet sample that thickness is not more than 2mm, nitrocellulose and nitrine nitramine and other solvent is made to occur deeply to act on, spice plasticizing and closely knit, the moisture in sample reduces to 1 ~ 3% by original 20% ~ 40%;
Step 2, dries the residual moisture in sample in not higher than the baking oven of 55 DEG C;
Step 3, is treated to the slice being not more than 1mm × 5mm by sheet sample;
Step 4, takes the slice that 0.2g (being accurate to 0.0001g) handles well, soaks with good solvent, dissolves the organic component comprising nitrocotton;
Step 5, add suitable quantity of water and nitrocotton is separated out, and Small molecular organic component to be measured still stays in the solution, filtrate is sample solution, and namely available liquid phase chromatography carries out the quantitative test of next step nitrine nitramine absorption medicine Small molecular organic component.
2. the method for claim 1, is characterized in that, described in be not more than 1mm × 5mm fine strip shape sample also can carry out the preparation of sample solution with such as soxhlet extraction method, high temperature high pressure enclosed extracting method.
3. the method for claim 1, is characterized in that, described good solvent can dissolve nitrocotton and small organic molecule to be measured, can also dissolve each other with water, is the organic solvents such as acetone, tetrahydrofuran, dimethyl formamide, dimethyl sulfoxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114112754A (en) * | 2021-11-19 | 2022-03-01 | 西安近代化学研究所 | Device and method for determining curing time of small columnar three-base propellant based on nitrocotton plastic dissolving effect value |
| CN114136822A (en) * | 2021-11-19 | 2022-03-04 | 西安近代化学研究所 | Device and method for screening nitroguanidine emission medicine plasticizer based on curing rate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106808A (en) * | 1986-10-16 | 1988-04-27 | Wnc-硝基化学有限公司 | The method for making of propelling charge |
| CN1047072A (en) * | 1989-05-11 | 1990-11-21 | Wnc-氮化学有限公司 | The preparation method of triple-base propellant and device |
| US6171530B1 (en) * | 1996-07-26 | 2001-01-09 | Cordant Technologies Inc. | Process for the manufacture of high performance gun propellants |
-
2015
- 2015-07-14 CN CN201510412524.6A patent/CN104950056B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87106808A (en) * | 1986-10-16 | 1988-04-27 | Wnc-硝基化学有限公司 | The method for making of propelling charge |
| CN1047072A (en) * | 1989-05-11 | 1990-11-21 | Wnc-氮化学有限公司 | The preparation method of triple-base propellant and device |
| US6171530B1 (en) * | 1996-07-26 | 2001-01-09 | Cordant Technologies Inc. | Process for the manufacture of high performance gun propellants |
Non-Patent Citations (3)
| Title |
|---|
| 杨建兴 等: "含RDX的叠氮硝胺发射药热分解与燃烧性能", 《含能材料》 * |
| 贾林 等: "ASE-HPLC检测某型号球形发射药中的叠氮硝胺、硝化甘油、Ⅱ号中定剂含量的研究", 《分析测试技术与仪器》 * |
| 贾林 等: "叠氮硝胺对硝基胍发射药热行为的影响", 《火炸药学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114112754A (en) * | 2021-11-19 | 2022-03-01 | 西安近代化学研究所 | Device and method for determining curing time of small columnar three-base propellant based on nitrocotton plastic dissolving effect value |
| CN114136822A (en) * | 2021-11-19 | 2022-03-04 | 西安近代化学研究所 | Device and method for screening nitroguanidine emission medicine plasticizer based on curing rate |
| CN114136822B (en) * | 2021-11-19 | 2023-07-18 | 西安近代化学研究所 | Curing rate-based screening device and method for nitroguanidine emission medicinal plasticizer |
| CN114112754B (en) * | 2021-11-19 | 2023-07-18 | 西安近代化学研究所 | Device and method for determining curing time of small columnar three-base propellant based on nitrocotton plastic dissolving effect value |
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