CN104950056B - A kind of nitrine nitramine absorbs medicine sample preparation methods - Google Patents
A kind of nitrine nitramine absorbs medicine sample preparation methods Download PDFInfo
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Abstract
The invention discloses a kind of nitrine nitramine absorbs medicine sample preparation methods, aqueous 20%～40% nitrine nitramine is absorbed medicine calendering and is processed into the sheet sample that thickness is not more than 2mm for twice by the method first, spice becomes to plastify and closely knit, moisture is reduced to 1%～3%, dry residual moisture in 55 DEG C, sheet sample is processed as the no more than slice of 1mm × 5mm, weigh appropriate slice sample, soak organic component including nitrocotton for the dissolving with good solvent, plus suitable quantity of water makes nitrocotton separate out, other components remain in solution, after filtration, filtrate is sample solution, the nitrine nitramine that next step can be carried out according to a conventional method absorbs the quantitative analyses of organic component in medicine.Because sample is more uniform, can ensure testing result accuracy on the premise of the amount of down-sampling, reduce the organic solvent amount for preparing sample solution.This sample preparation methods has the advantages that sample preparation cycle is short, solvent slop yield are few.This method also can be used as the sample preparation methods of other absorption medicines containing NC.
Description
Technical field
The invention belongs to explosive wastewater measured portions analysis detection field, relate generally to a kind of explosive wastewater sample preparation methods,
More particularly, to a kind of nitrine nitramine absorbs medicine sample preparation methods.
Background technology
Nobel absorbs 40% nitroglycerine (NG) with 60% nitrocotton (NC) within 1888, makes NG and absorbs medicine, then
Make double-base propellant through series of process.NC is high molecular polymer, and its plasticizing must be by means of low molecule solution.NG
Still do not contain energy component, or the low molecule solution plasticizer of NC, increased the intermolecular distance of NC, improve NC strand
Compliance and the intermolecular Van der Waals force of minimizing, so as to dissolving plasticizing, become the concentrated solution of polymer.This concentrated solution improves
The vitrification point of spice and flow temperature, under certain external force acts on, are conducive to machine-shaping.
Azido compound, many azide compounds until full nitrogen type extrahigh energy compound be energetic material development direction it
One.Nitrine nitramine (1,5- diazido -3- nitro aza-pentane, abbreviation DIANP) as NG, is in a liquid state, no at normal temperatures
But containing energy, also there is the very strong molten ability moulding NC.DIANP, as new energetic plasticiser, replaces part NG, successfully uses at present
In some new modified propellant powder products of batch production.
For the reason such as safety in production and economic support, DIANP is from NG by different manufacturer's production：First production of units
NG, because pure NG can not transport, makes aqueous NG absorption medicine with being absorbed NG with NC, transports the second unit producing DIANP, second
Aqueous NG absorption medicine is added water dispersion by unit again, adds the components such as DIANP to stir, and makes aqueous DIANP and absorbs medicine, transports
Arrive the third unit producing propellant powder, the third unit is added respective components more inward and produced related modified propellant powder product.Whole at this
During, first unit, second unit need to detect that NG absorbs medicine constituent content, and second unit, the third unit are required for detecting that DIANP inhales
Receive the constituent content of medicine.
For accurate detected components content it is to be understood that the technique of spice and physical and chemical state.
The NG introducing classics first absorbs the manufacture process of medicine：NC is suspended in disperse medium, by injection, stirring etc.
Method makes each component macroscopically mix uniformly and in accurate measurement, and strong bonded, and this process is referred to as absorbing.
NG contacted with NC, infiltrate with diffusion process in, NG molecule permeates in NC strand, and sends out with the functional group on chain
Raw solvation.NC is more much bigger than NG, and its movement velocity is very slow, and after there is solvation, NC occurs swelling, thus reducing macromole
Molecular separating force, and have small part macromole to be segregated into being dissolved in solvent, that is, have small part NC to be dissolved in NG (completely
Dissolving plasticizing, is when manufacturing propellant powder, by complete in spice calendering and forming process).
90% about moisture is contained in the medicine slurry of good absorbing.Moisture in medicine slurry can be divided into free water, physical bond water and
Materialization combines water.Free water refers to be not bound with and spice between, is suspended in top layer after spice sedimentation, permissible with simple method
Filter.Physical bond water refers to the moisture of infiltration in medicine slurry hole or capillary tube, and this part water just can be big under certain extruding
Part is extruded.Materialization refers to the absorption water combining by hydrogen bond or other molecular separating force with reference to water.Expelling water operation make free water,
Most of water drive of physical bond water is removed.A general expelling water machine drives away the moisture in medicine slurry to 20%～40%.Now
Medicine slurry can as absorb medicine product be transported.
It is similar that the NG of manufacturing process and classics that DIANP absorbs medicine absorbs medicine manufacturing process.Second unit is aqueous purchase
NG absorbs in medicine and adds water, and disperses in stirred tank, adds the stirring of the function ingredients such as DIANP, so that each component is macroscopically uniformly counted
Amount mixes exactly, and strong bonded.Equally, contain 90% about moisture in the DIANP medicine slurry of good absorbing, with once
Expelling water machine is by the moisture centrifuge dehydration in medicine slurry to 20%～40%.Medicine slurry now can absorb medicine product as DIANP and enter
Row transport.As plasticizer at the aspect such as the effect in spice and the moisture existence in spice, DIANP absorbs medicine to DIANP
Closely similar with NG absorption medicine.
NG or DIANP absorbs the whole technical process that medicine manufactures, and along with many physics, chemical process, is summed up, base
Originally it is divided into Four processes：The dispersion of component；The diffusion of component；Liquid component is to the adhesion of NC and infiltration；The dissolving to NC for the solvent.
If dispersion is uneven, uniformity of mixture is just very poor.The mixed liquors such as such as NG, DIANP disperse insufficient when contacting with NC
Can be formed " micelle ", when NG, DIANP content is higher, whole micelle is translucent colloidal particle.This micelle viscosity is big, is difficult
It is dispersed into thinner granule in the presence of external force.The presence of micelle has a strong impact on component and H in micelle2Other component such as O
Mixing further, diffusion and dissolving, should avoid in production.But due to spice itself, macroscopically mix homogeneously
Absorption medicine, with the naked eye can observe on microcosmic (0.2g level) and there is greater number of translucent " micelle ", that is, exist
0.2g horizontal absorption medicine is uneven.Absorb in medicine 20%～40% H2O also counteracts that NC and NG, DIANP's is further
Dissolving and plasticizing.In addition, DIANP absorbs H in medicine2O content is high, and each pot of material is centrifuged expelling water, packaging respectively, finally by each pot
Absorb medicine quality to be added, dispatch from the factory as large quantities of, so for large quantities of materials, wherein each junior unit (each pot) H2O contains
Amount is substantially different, i.e. H for large quantities of2O is substantially uneven.In a word, on a microscopic level (0.2g level),
It is uneven for absorbing each component in medicine, so in sampling detection it is desirable to use sample quarterlies, sampling amount is larger, sample point
More, during detection, sample size is also relatively large.
NG absorbs medicine and occurs relatively early, is to use gas chromatography detection level.For ensureing to sample representative, gas phase color in addition
The thermal conductivity detector (TCD) sensitivity of spectrum is relatively low, so general absorb the multiple sample quarterlies of medicine by large quantities of NG, sieves, dries, from
In weigh 2g, with organic solvent extraction, prepare sample solution.Shortcoming is that gas chromatogram can only detect gaseous material, needs to pass through
High temperature makes the component transient evaporation to be measured in sample, and it will be separated one by one by the component of gasification by the chromatographic column of higher temperature
(the low group segregation junction easily making to have gasified of chromatogram column temperature).Vaporizer, the high temperature of chromatographic column make NG be very easy to decompose, and do
Disturb detection, so employing relatively low gasification temperature (175 DEG C～210 DEG C), relatively low column temperature (140 DEG C～190 DEG C), short column
(500mm) heating temperature and the heated time of NG with means such as high flow rate of carrier gass (80mL/min～200mL/min), are reduced.But
Even if so, still there is the accident of moment NG blast that gasifies in inserting needle.On the other hand, the handss such as sub and high flow rate of carrier gas of short column
Section, can shorten the NG time of staying in the chromatography column, but so that separation efficiency is reduced simultaneously, be unfavorable for more than separation detection component
Sample, and novel emission medicine is due to the increase of use requirement, component gets more and more so that application in new product for the gas chromatogram
It is restricted.
Liquid chromatograph can avoid the thermostimulation to sample for the high temperature, and sample is with being separated at normal temperatures after solvent dissolving and being examined
Survey, be especially suitable for the detection of the components such as labile NG, DIANP of being heated.Chromatograph of liquid is ripe and market-oriented, at present respectively
Explosive wastewater Physico-chemical tests room has been equipped with chromatograph of liquid.DIANP sterling, DIANP absorb medicine, the modification pair containing DIANP at present
Base propellant powder, the detection by quantitative of the modified triple-base propellant containing DIANP all adopt liquid chromatography.
The most all outfits of the chromatograph of liquid of current explosive wastewater physics and chemistry room are UV-detector, this be mainly because
For：In explosive wastewater, most small molecule organic components that need to be detected with chromatograph, all contain-NO2、-N3, phenyl ring, unsaturated double-bond
Etc. the functional group having uv absorption；UV-detector sensitivity is high, very low to the detection limit containing the material absorbing sense figure, can see
Examine the slight change of component；Sturdy, the easy maintenance of UV-detector.
The quantitative principle of UV-detector is：The light of a branch of specific wavelength passes through detection cell, and a part of light is detected in pond
Sample absorb, a part of light transmission detection cell sensed by detector.The intensity of the light by sensing for the detector, and initially
The intensity of light, calculates the absorbance of sample.
In formula：A is absorbance；I0Light for specific wavelength passes through the intensity before detection cell；ItLight for specific wavelength passes through
Intensity after detection cell.
Then according to law of light absorption A=KcL (in formula：K is specific absorbance, is constant；C is test substance in solution
Concentration；L is that light passes through 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, that is, will be no longer linear between the c of sample and absorbance A, no
The content of object in sample can be calculated further according to the A that detector is given, otherwise will produce very big error.Even some liquid phase colors
The part that spectrometer A exceeds 1 does not show concrete numerical value, now will appear from " tack peak " on chromatogram, and such as 95% light is by be measured molten
Liquid absorbs, and only 5% light is sensed by detector, then A should be " 1.3 ", and instrument only shows " 1 ".In addition A is when 0.434
Relative error is minimum, so for the accuracy ensureing testing result, general detection should try one's best by absorbance control 0.9 with
Under.
Prepare a series of DIANP solution of variable concentrations, use respectively in the 1120LC and the U.S. watt of Agilent company of the U.S.
The Rrostar HPLC detection of peace it is known that when the concentration of DIANP is in the range of 0.1～1mg/mL instrumental response value A 0.1～
Between 0.9.With in sample DIANP content be 15% calculating, if sampling amount be 2g, need dilute constant volume be 300mL～
3000mL, and general conventional sense needs at least to detect two Duplicate Samples, so each sample may require that 600mL～6000mL
Organic solvent dissolved.As can be seen that the shortcoming of this operation is：Organic solvent usage amount is many, detected after contain can give up
Organic solvent amount is too big.And so sampling amount is defined as 2g, be because absorbing medicine after sieving and drying, its component is on microcosmic
Skewness, it is more representative that sampling amount can make greatly testing result have more a bit.
On the other hand, original sample preparation methods overlong time.The former preparation process of sample is as follows：
(1) by overall material multiple sample quarterlies about 1kg, then rubbing is crossed 3mm and 2mm double deck screen and (is sieved and about need
0.5hr)；
(2) take 2mm oversize about 10g, be put in 55 DEG C of baking ovens and dry moisture (about needing 4hr)；
(3) weigh after 2g (accurately to 0.0001g) is dried sample to 1000mL volumetric flask, plus 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, 1000mL volumetric flask is added water constant volume；
(6) stand more than 2hr, make most NC sedimentations；
(7) draw about 5mL supernatant liquid with syringe, filter, filtrate is sample solution；
(8) press each constituent content preparing standard solution in sample simultaneously, detected with chromatograph of liquid (joining UV-detector),
Calculate constituent content in sample with external standard method.
DIANP absorbs moisture in medicine and differs greatly, so being not suitable for the directly preparation examination of aqueous absorption medicine (wet basis)
Sample solution is detected, is all to take butt to carry out measured portions.Sieved by sample and baking step, can somewhat improve DIANP
Absorb medicine uniformity so that testing result can represent entirety material, but the obvious shortcoming brought be the sample preparation time too
Long：Sieve 0.5hr, and 4hr is dried.
The reason drying time length is by two aspects causes：
(1) DIANP, NG have the trend of heat resolve, so oven temperature is not above at 55 DEG C, (DIANP, NG are low
Volatile liquid material, is not suitable for vacuumizing method), the volatilization of temperature low moisture is slow；
(2) DIANP absorbs in medicine and combines water containing free water, physical bond water and materialization, and 55 DEG C can only be dried in fact except complete
The free water in portion and most physical bond water, intermolecular interaction makes materialization combine the more difficult volatilization of water, so drying time is long.
In view of the foregoing it is apparent that the measured portions that current DIANP absorbs medicine have sample preparation time length, solvent consumption
The shortcomings of amount is big, the waste liquid containing energy of generation is many.
The sample preparation time is long, leads to detection cycle length so that several tons of DIANP absorb medicine and can not timely enter next work
Sequence, for manufacturer with using for producer, DIANP absorbs parking of medicine and there is obvious potential safety hazard.For this project team
Wish to improve preparation method, shorten preparation time, reduce solvent-oil ratio.
Content of the invention
It is because sample preparation takes that DIANP absorbs medicine detection cycle length：Principal element is that sample contains very not
Uniform moisture, needs low temperature to dry water to obtain butt sample, and moisture and spice is tightly combined, and dry very slow；Secondary because
Element is that other components are also uneven, so needing to sieve.Sieve and drying takes around 4.5hr.
Absorb defect or the deficiency of medicine sample preparation methods for DIANP in above-mentioned prior art, the purpose of the present invention exists
In providing and a kind of there are quick, accurate, low energy consumption, the sample preparation methods of environmental protection.
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 to roll 2 times, rolling temperature 85～
95 DEG C, it is processed into the sheet sample that thickness is not more than 2mm, make nitrocellulose occur deeply to make with nitrine nitramine and other solvent
With spice plastifies and closely knit, and the moisture in sample is reduced to 1～3% by original 20%～40%；
(2) sheet sample is dried in not higher than 55 DEG C of baking oven residual moisture；
(3) sheet sample after drying is processed as the no more than slice of 1mm × 5mm；
(4) weigh the slice 0.2g (being accurate to 0.0001g) handling well, soaked with good solvent, dissolving is including NC
Organic component；
(5) adding suitable quantity of water makes NC separate out, and small molecule organic component to be measured remains in solution, and filtrate is sample solution；
(6) preparing standard solution, detects sample solution and standard solution with liquid chromatography, calculates DIANP by external standard method
Absorb each constituent content in medicine.
Although carrying out at high temperature in calender line, because whole calendering is less than 10min, so NG, DIANP
Substantially do not decompose.The DIANP of the present invention absorbs medicine sample preparation methods, and the sample preparation time having is short, sample homogeneity is good
Advantage：
(1) DIANP absorbs medicine on plough groove type calender, is extruded by calender two Kun, at hot (85～95 DEG C) and
In the presence of external force, most of moisture is purged, calendering 2 times after, moisture is changed into 1%～3% from 20%～40%, simultaneously NC and
NG, DIANP and other solvent act on further, and physicochemical change occurs, and absorb medicine and are gradually dried, mix, plastify and closely knit,
Whole process about needs 5～10min；
(2) spice after calendering 2 times due in spice residual moisture seldom, so drying time can be greatly shortened, dry
Time is about 1hr；
(3) high temperature (85～95 DEG C) can make the movement velocity of NC macromolecular chain segment increase, molecular flexibility increases, and also can add
The dissolving of fast NG, DIANP equal solvent low molecule system, so NC macromole and solvent molecule relative diffusion rates accelerate, improves
Solubility property, mix homogeneously quickly.
In microcosmic (0.2g) aspect, the DIANP of " component is uneven " absorbs medicine, in the macroscopically (actual production of propellant powder
In) component is uniform, drives away the moisture in spice by moulding process, spice plastify under higher pressure and temperature, makes
Become there is the powder column of certain geometrical shape, certain size and compact structure.
The purpose of component detection should be the constituent content of the overall material of reaction, should not excessively be entangled with the sample of smaller scale
Constituent content.So big for uneven material sampling amount in microcosmic point, the overall material of testing result reflection will be enable
Situation, and can be greatly reduced for uniform material sampling amount.
Quantification range due to liquid chromatograph (UV-detector) makes sample must be arranged to weak solution, so sampling amount
Big just meaning needs to prepare sample solution with more multi-solvent, produces more solvent slops containing energy.If the uniformity of material can be improved,
Sampling amount just can be reduced, also just can use solvent less.
Through high temperature roll 2 times DIANP absorb medicine become uniform, therefore can the amount of down-sampling, only need accordingly
Less solvent is dissolved, and makes sample solution.After rolling process sample preparation, single sample only needs to weigh 0.2g and (is diluted to
100mL) detected, testing result can represent material by the gross.
Therefore replace sieving, drying the preparation carrying out sample by High Temperature High Pressure calendering, by mistake in former method sample preparation
Sieve, dry 4.5hr used, shorten to 1.1hr.In addition, rolling process makes sample homogeneity obtain the change of matter, therefore
The sampling amount for detection can be significantly reduced, the corresponding organic solvent amount being used for extracting dissolving is greatly reduced, containing can give up
Solvent is changed into 200mL from original 2000mL.
The present invention is described in further detail with reference to embodiments.
Specific embodiment
Embodiment 1
It is that (group is divided into NC, NG, C by the NG absorption medicine of outsourcing that certain DIANP absorbs medicine2, be transportation safety also contain 20%～
40% water) in add water dispersed with stirring in a kettle., be subsequently adding the components such as DIANP, DNT and continue stirring and evenly mixing, make absorption
The each component of medicine macroscopically mixes uniformly and in accurate measurement, and strong bonded.90% about is contained in the medicine slurry of good absorbing
Moisture, with expelling water machine, the moisture centrifuge dehydration in medicine slurry to 20%～40% is become DIANP and absorbs medicine product.
DIANP decomposes before having the characteristics that vapourizing temperature point, so current DIANP absorbs organic little point of DIANP etc. in medicine
The detection that subgroup is divided adopts liquid chromatograph external standard method, and the preparation of sample is using sieving, the methods of 55 DEG C of drying.When sieving, drying
Between more than 4.5hr, and the sample composition being prepared is still uneven in microcosmic point (0.2g level), causes sampling amount larger
(2g) testing result, just can be made to react the composition situation of material by the gross.Because the UV-detector that chromatograph of liquid is equipped with is uncomfortable
Close detection concentrated solution, need 2g sample is made into the weak solution of 1000mL, the quantity of solvent of consumption is big, the waste liquid containing energy of generation is many.
Therefore the present invention proposes DIANP and absorbs the rolling process preparation of medicine and carries out the preparation of sample.This preparation method not only takes few (pressure
Prolong less than 10min, residual moisture is dried and is less than 1hr), and make the uniformity of sample obtain the improvement of matter, therefore may be used
With the amount of down-sampling as 0.2g, correspondingly solvent slop yield decreases 10 times.
The operating procedure of the present embodiment is as follows：
(1) absorbed medicine spice from aqueous 20%～40% DIANP with quartering and take 2～3kg, roll 2 with calender
Time, 85～95 DEG C of temperature, the calendering time is about 10min, is processed into the sheet sample that thickness is not more than 2mm, makes the water in sample
Point it is changed into 1%～3%, NC and DIANP and other solvent occurs deeply to act on, plastify, 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 processed as the no more than slice of 1mm × 5mm；
(4) accurately weigh the slice 0.2g (being accurate to 0.0001g) handling well, be placed in 100mL volumetric flask, add about
80mL acetone, puts into magnetic stirring bar, organic component including NC for the stirring and dissolving；
(5) being added dropwise over 15mL water makes NC separate out (whole process is still stirred) with magnetic stirring bar, suctions out magnetic force with Magnet
Stirring rod, and rinse stirring rod with 2mL water, the water of flushing is incorporated in volumetric flask, adds water constant volume；
(6) stand more than 2hr, make most NC sedimentations；
(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 DIANP by external standard method and inhales
Receive the content of medicine small molecular organic component.
From above step it can be seen that：The sample preparation time of rolling process substantially shortens, and (sieves+dries from the 4.5hr of former method
Dry) it shorten to 1.1hr (calendering+dry)；Sample weighting amount is reduced to 0.2g from the 2g of former method, in the feelings that sample solution concentration is constant
Under condition, sample preparation solvent for use is changed into 100mL from the 1000mL of former method.
Rolling process sample preparation has the advantages that time-consuming short, solvent-oil ratio is few, but the premise that all these advantage is capable of
Must be that the accuracy of testing result cannot be below former method.Carry out following experiment for this seminar new preparation process is carried out
Checking.
1. former preparation method sample sample weighting amount determines test
Because it is substantially uneven that aqueous DIANP absorbs medicine component (0.2g level) on microcosmic, detection is uneven
Typically pass through during material to increase the methods such as sampling amount, enable testing result to reflect material overall condition.
The DIANP of certain crowd aqueous 20%～40% is absorbed medicinal multiple sample quarterlies about 1kg, then rubbing crosses 3mm
With 2mm double deck screen, take 2mm oversize about 10g, be put into drying moisture in 55 DEG C of baking ovens.Weigh respectively 0.2g, 0.5g, 1.0g,
Each 6 of 1.5g, 2.0g (being all accurate to 0.0001g) sample, is all configured to the sample solution that DIANP content is 0.2g/L, uses liquid
Phase chromatography detects DIANP content, and experiment with computing standard deviation RSD (n=6), the results are shown in Table 1 respectively.Because detection method, inspection
Survey instrument, operator are identical, if sample is uniform, with the increase of sample weighting amount, the RSD of testing result and extreme difference will not be obvious
Reduce, and as can be seen from Table 1 as sample weighting amount >=1.5g, RSD, testing result extreme difference (maximum-minima) substantially diminish
And tending to definite value, when illustrating that sampling amount at least should exceed 1.5g, testing result could represent overall material.Require in product specification
The content detection of the components such as DIANP need to make two Duplicate Samples, franchise≤0.5% of Duplicate Samples.From the point of view of the extreme difference value of table 1, when
Sample weighting amount is that during 2.0g, extreme difference value is 0.3%, the difference that the testing result of Duplicate Samples now is described below 0.3%, two
The collimation of testing result preferably, can meet product specification and require, so the sample weighting amount that former method for making sample determines is 2.0g.Table 1
Data also further demonstrate that, in 0.2g level, sample is uneven.Although the inhomogeneities in this degree are advised to big
It is footy for the production of mould, material can be made gradually really uniform by the production technology in later stage, but for detection
But it is to need to pay attention to, or even some contradictions can be brought：Sample weighting amount is very few, and testing result can not react the situation of overall physics；
Sample weighting amount is larger, and limiting it is necessary to be diluted so that solvent slop treating capacity mistake using more solvent due to detecting instrument
Greatly.Because sampling amount during such propellant powder finished product detection is 0.2g, it is desirable that absorb the preparation side of medicine by improving DIANP
Method, makes spice uniform enough, and also can reach sampling amount is 0.2g.
The former preparation method sample weighting amount of table 1 determines test
2. calendering pass determines test
The purpose sieve, dried is to obtain comparatively uniform not aqueous specimen, but the amount that can bear for instrument
For, the uniformity of sample is still not.And the absorption medicine of Microinhomogeneity is when producing propellant powder, complete by operations such as calenderings
All can reach component microcosmic point uniform, so use for reference propellant powder production technology it is desirable to microcosmic is prepared by rolling process
The upper uniform sample being used for detection.The rolling temperature producing during propellant powder is 85～95 DEG C, so seminar is also adopted by this pressure
Prolong temperature and prepare sample.Calendering pass more Multi-example is more uniform, but considers time cost, it is desirable that calendering pass is less relatively
Good.
Certain crowd of DIANP is absorbed medicine and rolls 0,1,2,3 times (after having rolled, putting into 55 DEG C of oven for drying moisture) respectively.Every kind of
The sample having rolled takes 6 points respectively at random, is respectively prepared sample solution.Operating procedure is：Weigh 0.2g (to be accurate to
0.0001g) calendering, the sample dried, with acetone solution, add water precipitation NC, and constant volume to 100mL filters and makes sample solution.
Detected with liquid chromatograph external standard method, testing result is listed in table 2.From table 2 it can be seen that after rolling 2 times, RSD, extreme difference tend to fixed
Value, meets the requirement of product specification.So finally determining that rolling temperature is 85～95 DEG C, rolls pass for 2.From practical operation feelings
Condition is seen, the whole calendering time is less than 10min, and high temperature calendering can extrude the most water absorbing in medicine, residual moisture
Drying be less than 1hr, greatly shorten than former method the total time of therefore rolling process sample preparation.
Table 2 calendering pass determines test
3. calendering preparation method sample volume determines test
During the uniform propellant powder sample of generally conventional detection, sample weighting amount is 0.2g, is diluted to 100mL.So problem
Group wishes that DIANP absorbs the sampling amount of medicine also in 0.2g.
Prepare sample with rolling process.Weigh 0.1g, 0.2g, 0.5g, 1.0g, 1.5g (being all accurate to 0.0001g) sample respectively
Each 6 of product, are all configured to the sample solution that DIANP content is 0.2g/L, detect DIANP content with liquid chromatograph external standard method, point
Other experiment with computing standard deviation RSD (n=6), the results are shown in Table 3.Because detection method, detecting instrument, operator are identical, if sample
Product are uniform, and with the increase of sample weighting amount, the RSD of testing result and extreme difference will not significantly reduce.As can be seen from Table 3 when title sample
When 0.1g increases to 1.5g, RSD is reduced to 0.9% by 1.5% to amount, and testing result extreme difference (maximum-minima) is by 0.5%
It is reduced to 0.3%, substantially belongs to the change on the same order of magnitude, that is, with the increase of sample weighting amount, detection data does not have
The change of matter.Now consider further that testing cost it is believed that when sample weighting amount is chosen as 0.2g, product specification pair can be met
The requirement of Duplicate Samples franchise, also can save time cost, and reduce solvent slop.On the other hand as can be seen that rolling preparation method
Sample weighting amount is that the representative weighing 2.0g with former method during 0.2g is on close level, and can represent overall material level.
Table 3 calendering preparation method sample weighting amount determines test
4. two kinds of sample preparation method testing results when sample weighting amount is identical
Certain DIANP medicinal two kinds of distinct methods of absorption are carried out sample preparation, and (sampling amount is 0.2g, and equal constant volume is
100mL), detect definite value with liquid chromatograph external standard method, detect 3 batches altogether, 6 Duplicate Samples of every batch of detection.It is most difficult to mix by absorbing in medicine
The testing result closing uniform DIANP and DNT is listed in table 4.As can be seen from Table 4：When sampling amount is 0.2g, prepared by the present invention
The RSD (n=6) of the testing result of method (calendering, dry water) can control 0.97%～1.33%, and extreme difference is 0.32%～
0.39%, precision is preferable；Former preparation method (sieve, dry water) is due to the uneven of sample itself so that the RSD (n of testing result
=6) it is 7.28%～12.53%, extreme difference is 1.99%～4.41%, and precision is poor.Precision is to ensure that well detection accurately
Spend high premise, therefore, when sample weighting amount is for 0.2g, sample is prepared using method of the present invention (calendering, baking water law) and carries out DIANP suction
During the detection by quantitative of receipts medicine, precision preferably, can quote testing result by way of 2 parallel results are average.From table 4
Detection data it is also seen that when being detected using multidraw (n=6), even if former preparation method (sieve, oven drying method)
The precision of testing result is bad, but 6 sample average contents are consistent with the average content of 2 samples of method of the present invention, illustrate by
When the dispersion of uneven the led to testing result of sample is larger, can be detected using multidraw method and be quoted flat
All results.
Two methods of the detection data of the absorption medicine sample of table 4 preparation
5. the expelling water effect disquisition of two kinds of preparation methoies
Moisture in spice is divided into free water, physical bond water and materialization to combine water.Free water refers to do not have and spice between
There is combination, be suspended in top layer after spice sedimentation, can be filtered with simple method.Physical bond water refers to medicine slurry hole or capillary
The moisture of infiltration in pipe, this part water just can major part be extruded under certain extruding.Materialization with reference to water refer to by hydrogen bond or its
The absorption water that its molecular separating force combines.Present invention preparation method and former preparation method are all intended to drive away the moisture in spice
Entirely, then quantitation is carried out to butt spice.From table 4 it is observed that method of the present invention prepares the testing result of sampleSubstantially all
More higher than the testing result numerical value of former preparation method, conjecture is likely due to former preparation method (sieve, dry water), can not will try
Moisture in sample is driven away completely, therefore detects the moisture in the spice after two kinds of preparation method expelling waters respectively with Karl_Fischer method.Altogether
5 batches of spices of detection, prepare expelling water, 6 Duplicate Samples of every batch of detection by two methods for every batch, sample weighting amount is 2g, and detection data is shown in Table
5.
The expelling water effect disquisition of 5 two kinds of preparation methoies of table
As can be seen from Table 5, in sample after present invention preparation method (calendering, drying) expelling water, 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%, and the present invention is described
Method is better than former preparation method expelling water effect, and the materialization that former preparation method can not be completely exhausted out in sample combines water.Due to actual medicine
Material carries out expelling water using High Temperature High Pressure, so inventive samples preparation method testing result is closer to product practical situation,
Thus can also explain listed present invention preparation method component testing result in why table 4 micro- higher than former preparation method.From table 5 number
According to it can also be seen that sample weighting amount is for, in the case of 2g, former preparation method moisture data extreme difference is significantly greater than present invention preparation method, enters one
The sample of step explanation method of the present invention preparation is more uniform than sample prepared by former method.
Conclusion：By above several test it can be seen that：The method of the invention (calendering, drying) prepares sample, relatively
In former preparation method (sieve, dry), the uniformity of sample has the improvement of matter, even if so sampling amount is 0.2g, also can protect
The preci-sion and accuracy of card testing result.And sample prepared by former preparation method (sieve, oven drying method), due to essential inequality
Even property, for ensureing that sample detection result can represent overall material, takes and increases the mode of sampling amount (single sample 2g, 2, work is flat
Row sample) so that whole preparation process not only cycle length (sieve, dry need 4.5hr), and need with substantial amounts of solvent to sample
Product are diluted.The materialization can not being completely exhausted out additionally, due to former preparation method in sample combines water so that testing result is than real
Border sample is low.It is therefore contemplated that the method for the invention (calendering, dry) prepare sample have preparation time short (calendering,
Drying needs 1.1hr), produce solvent slop few (being 1/10th of former method), more can react overall material feelings than former preparation method
Condition.
Claims (2)
1. a kind of nitrine nitramine absorbs medicine sample preparation methods it is characterised in that the method comprises the following steps：
Step one, will absorb medicine sample 2～3kg plough groove type calender with a collection of nitrine nitramine and roll 2 times, and rolling temperature 85～
95 DEG C, it is processed into the sheet sample that thickness is not more than 2mm, make nitrocellulose occur deeply to make with nitrine nitramine and other solvent
With spice plastifies and closely knit, and the moisture in sample is reduced to 1～3% by original 20%～40%；
Step 2, dries the residual moisture in sample in not higher than 55 DEG C of baking oven；
Step 3, sheet sample is processed as the no more than slice of 1mm × 5mm；
Step 4, weighs the slice that 0.2g handles well, is accurate to 0.0001g, is soaked with good solvent, and dissolving is including nitrocotton
Organic component；Described good solvent can dissolve nitrocotton and small organic molecule to be measured moreover it is possible to miscible with water, is acetone, tetrahydrochysene
Furan, dimethylformamide, dimethyl sulfoxide organic solvent；
Step 5, plus suitable quantity of water makes nitrocotton separate out, and small molecule organic component to be measured remains in solution, and filtrate is that sample is molten
Liquid, the nitrine nitramine carrying out next step with liquid chromatography absorbs the quantitative analyses of medicine small molecule organic component.
2. the method for claim 1 is it is characterised in that the described fine strip shape sample being not more than 1mm × 5mm can also be used
As soxhlet extraction method, high temperature high pressure enclosed extracting method carry out the preparation of sample solution.
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| 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 |
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