CN109239120A - A kind of method of nuclear magnetic resonance hydrogen spectruming determining 1,2- Propylene Glycol Dinitrate moisture content - Google Patents
A kind of method of nuclear magnetic resonance hydrogen spectruming determining 1,2- Propylene Glycol Dinitrate moisture content Download PDFInfo
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Abstract
The invention discloses a kind of nuclear magnetic resonance hydrogen spectruming determinings 1, the method of 2- Propylene Glycol Dinitrate (PGDN) moisture content, realize that the quantitative detection to micro-moisture, specific steps include: the configuration and nuclear magnetic resonance spectroscopy detection of (1) internal standard compound sample solution based on nucleus magnetic hydrogen spectrum internal standard method；(2) addition of 1,2- Propylene Glycol Dinitrate sample to be measured and nuclear magnetic resonance spectroscopy detection；(3) characteristic peak each in nuclear magnetic resonance spectroscopy is belonged to, determines the characteristic peak and internal standard compound characteristic peak of water, and integrated respectively, substitute into the content that correlation formula calculates corresponding moisture.This method has many advantages, such as that easy to operate, sample size is few, reproducible, can quickly to 1,2-propanediol dinitrate contained humidity content carry out quantitative detection, can specific aim solve explosive wastewater application in correlated quality product control critical issue.
Description
Technical field
The invention belongs to energetic material gauge check fields, and in particular to a kind of nuclear magnetic resonance hydrogen spectruming determining 1,2-PD two
The method of nitrate (PGDN) moisture content belongs to explosive wastewater product analysis detection field.
Background technique
Nitrate is as excellent plasticizer, and since its oxygen balance is preferable, burning and explosion property are good, answers extensively at present
For composite propellant and double base propellant field.Especially 1,2- Propylene Glycol Dinitrate (PGDN) is as in propellant composition
Main energetic and plasticizer component, to semi-rigid nitrocellulose become can extrude molding material and reduce glass transition temperature have
Important function, due to the excellent performances such as its is cheap, basic components burn rate is low and cryogenic mechanics performance is good, as of new generation high
Energetic plasticiser in energy propellant is widely applied
Due to atmosphere moisture diffusion and raw material are not dry etc., the 1,2-propanediol dinitrate that produces
In usually in contain a certain amount of moisture, moisture content for the nitrate of high-energy, be influence its stability, compatibility
An important factor for etc. important physicochemical characteristic.Some researches show that under same period of storage, using nitrate as the energetic binder of matrix
Agent water content is bigger, and stability is lower.It is required in the operating specification of certain class composite explosives, moisture content must not be higher than
0.5%, therefore in actual production and storage process, strict control wherein moisture content is needed, is realized to moisture in nitrate
The accurate detection of content.Common trace water content has oven drying method, condensed steam water, Karl_Fischer method, near infrared spectrum
Method etc., but due to 1,2-propanediol dinitrate as nitrate explosive high-energy, high sensitivity, high risk characteristic, for
Moisture detecting method has specific demand: (1) the sample amount of taking should be lacked as far as possible, to reduce security risk in detection process.It passes
The oven drying method and drier of system, although being once applied to the detection of nitrate esters product moisture as standard method, as constant
Analysis method (test is with sample amount generally in 5~10g), it is clear that since sample size is excessive, so that taking, there are larger for test process
Security risk；(2) external forces such as friction, electrostatic, shock should be avoided in test process, as far as possible to avoid high sensitivity nitric acid
Under outside energy effect combustion explosion occurs for ester.Common karl Fischer moisture measurement method in test process due to needing to generate
Iodine is ionized into iodide ion by electric current, and is monitored by electricity to reaction process, and inevitable electric current and charge were being tested
Generation in journey, it is clear that exist using limitation；(3) test method should be simple, convenient and rapid as far as possible, and has higher sensitivity.Near-infrared
For spectroscopic methodology as relative measurement method, measurement sensitivity is higher, but its calibration needs one-to-one standard substance, and draws corresponding
Working curve, also higher cost, method are cumbersome for corresponding quantitative analysis work, for simple, convenient and rapid testing requirement there is also
Limitation.(4) moisture in other additives and reagent and environmental condition should be avoided or exclude as far as possible in test process to tie measurement
The influence of fruit.Quantitative nuclear magnetic resonance (Quantitative nuclear magnetic resonance, qNMR) technology does not need
Determinand reference substance, sample pre-treatments step is easy, quick, detection efficiency can be significantly improved, in recent years by United States Pharmacopeia, English
State's pharmacopeia, European Pharmacopoeia, Chinese Pharmacopoeia (2010 editions) are included in succession.In recent years, since nuclear magnetic resonance spectroscopy quantitative technique is sensitive
Degree is high, qNMR technology using more and more extensive, in bulk pharmaceutical chemicals, pharmaceutical preparation, residual solvent measurement, sample component ratio measuring
Etc. be widely used.
Summary of the invention
For the demand at this stage to explosive wastewater content accurate quantitative analysis, the present invention provides a kind of nuclear magnetic resonance spectroscopies
The method for measuring the moisture content of 1,2-propanediol dinitrate (PGDN), this method use nuclear magnetic resonance spectroscopy internal standard method pair
Moisture content carries out accurate quantitative analysis, has many advantages, such as that easy to operate, sampling quantity is few, reproducible.Technical solution is specific as follows:
(1) internal standard compound 5-15mg is accurately weighed, deuterated solvent 0.5-0.8ml dissolution is added, is transferred in nuclear magnetic tube, seals up
Membrana oralis sealing.Prepared sample solution is placed in ultrasonic oscillation instrument after concussion mixing, it is total to carry out nuclear-magnetism to sample later
Hydrogen spectrum of shaking is tested.The quantitative nuclear-magnetism test condition are as follows: nmr spectrometer resonant frequency is 400~800MHz, temperature 25-35
DEG C, delay time 30s-60s, pulse angle is 30~90 °, and sampling number is 32-128 times.
(2) the nuclear-magnetism sample cell that test is completed is removed, 1,2-propanediol dinitrate 10-30mg is added, then seal up mouth
Film sealing, and shaken with ultrasonic oscillation instrument to uniformly mixed.To be added 1,2- Propylene Glycol Dinitrate after sample again into
The test of row nuclear magnetic resonance spectroscopy, the quantitative nuclear-magnetism test condition are consistent with previous step.
(3) after testing, the characteristic peak tested in the nuclear magnetic resonance spectroscopy obtained respectively twice is belonged to, is determined
The characteristic peak and internal standard compound characteristic peak of water, and integrate respectively, integration method is to remove after the leveling of spectrogram baseline to characteristic peak13C
It is integrated after satellites, calculates 3 times and be averaged.Water characteristic peak integral area and internal standard compound characteristic peak integral area are respectively obtained,
Data substitution formula (a) is obtained into corresponding impurity content.
In formula:
PxBiodiversity percentage composition, is indicated in-sample to be tested with %；
PSThe Reinheitszahl of-internal standard compound, is indicated with %；
msThe quality of-the internal standard compound being added, unit mg；
Quality, unit mg is added in m -1,2-propanediol dinitrate sample；
MsThe relative molecular mass of-internal standard compound；
MxThe relative molecular mass of-water；
HsThe number of resonant nucleus in the functional group of -1 mole of internal standard compound characteristic signal；
Hx- 1 mole of water generates the number of resonant nucleus in the functional group of signal；
AsThe peak area at-internal standard compound characteristic signal peak；
A1- be not added 1,2- Propylene Glycol Dinitrate sample water characteristic signal peak peak area；
A2The peak area at the water characteristic signal peak of the sample of-addition 1,2- Propylene Glycol Dinitrate；
Preferably, moisture content detection method in above-mentioned test 1,2-propanediol dinitrate sample, in the step (1)
Internal standard compound is hexamethyldisiloxane, paracide, benzene high sterling or standard substance, and deuterated solvent is deuterated dimethyl sulfoxide
(DMSO).Benzene and paracide not with 1,2-propanediol dinitrate component reaction, favorable solubility, and are easier to obtain high
Sterling or purity rubric substance, all hydrogen is in identical chemical environment in substance, i.e., in nuclear magnetic resonance spectroscopy spectrogram all only
There is one group of characteristic peak, the internal standard compound requirement of nucleus magnetic hydrogen spectrum is quantified suitable for this system.The selection of deuterated solvent is mainly according to internal standard
The solvent borne of object and sample, the solvent borne of comprehensive 1,2-propanediol dinitrate, can be selected deuterated acetone or deuterated dimethyl is sub-
Sulfone is solvent, but in an experiment discovery sample size is close and water content it is similar under the conditions of, water peak in deuterated DMSO solvent samples
For peak shape is sharp and symmetrical single absorption peak, water characteristic peak is asymmetric bimodal in deuterated acetone solvent samples, analysis be by
Hydrogen atom can generate fast exchange, the i.e. hydrone that a hydrogen atom is replaced by D-atom in D-atom and water in deuterated acetone
Content increases, and eventually leads to water peak in nuclear magnetic spectrogram and has occurred and splits point.It is symmetrical single when carrying out nuclear-magnetism characteristic peak integral calculation
Peak can generate smaller integral calculation error in contrast.Consider that the effumability of acetone may be to sample nuclear magnetic spectrogram simultaneously
Stability has an impact, and comprehensive analysis consideration selects deuterated dimethyl sulfoxide to quantify core as 1,2-propanediol dinitrate system
The dicyandiamide solution of Magnetic testi
Preferably, 1,2-propanediol dinitrate sample weighting amount should be 2-3 times of internal standard compound in experiment.The control of this condition
It is since in the test of quantitative nuclear-magnetism, one important condition is that the ratio between the two characteristic peak integrated area values contrasted are not answered
It is excessive to differ multiple, in 1:10 between 10:1, quantitative integration brings final result for discovery control in specific practical operation
Error it is smaller.Therefore comprehensively consider the factors such as moisture content in 1,2-propanediol dinitrate sample, internal standard compound molecular weight, really
Determining 1,2-propanediol dinitrate sample weighting amount should be 2-3 times of internal standard compound this condition, may make internal standard compound characteristic peak and water peak
Area ratio controls in the above range, detects basis as suitable quantitative nuclear-magnetism.
Since determination of moisture compares with the measurement of other impurities with particularity, i.e. either deuterated solvent, interior
There is the presence of micro-moisture in mark object or air, it is therefore necessary to exclude water contained in these parts during the test
It measures, the content of micro-moisture in Accurate Determining 1,2-propanediol dinitrate sample.Integral residual quantity is taken with regard to the design of this problem
Method carry out sample in moisture content accurate calculating, i.e., first to do not add 1,2-propanediol dinitrate only in deuterated solvent
Addition internal standard compound sample carries out quantitative nuclear-magnetism detection, obtains integral area of the water peak relative to internal standard compound characteristic peak in this system
Value, then precisely weighed into nuclear-magnetism sample and 1,2-propanediol dinitrate sample is added, then with the progress of same experiment condition
Quantitative nuclear-magnetism detection, further obtains integrated area value of the water peak relative to internal standard compound in this system.It is tested by quantitative nuclear-magnetism
Mechanism do not have in not cospectral graph theoretically comparable although the integral area of characteristic peak simultaneously not absolute terms in nuclear magnetic spectrogram
Property, but the internal standard compound magnitude as contained in testing twice is constant, and test condition is identical, therefore in stable condition in instrument test
Under conditions of internal standard peak peak height, peak shape and peak position remain unchanged, integrated area value of the water peak relative to internal standard compound characteristic peak
Moisture magnitude contained in value added and 1,2-propanediol dinitrate is directly proportional, can be calculated by quantitative nuclear-magnetism formula.
Simultaneously because the resonant frequency of nuclear magnetic resonance spectrometer is higher, i.e., power is higher, correspondingly resolution ratio, sensitivity and sampling stability
It will significantly improve.Therefore for the analysis calibrating of micro-moisture in 1,2-propanediol dinitrate system, global alignment is different
The Stability and veracity of the nmr spectrometer testing result of power, optimal selection 800M nmr spectrometer carry out quantitative detection, can obtain
Obtain signal-to-noise ratio more preferably nucleus magnetic hydrogen spectrum spectrogram.
Important parameter of the delay time as quantitative nuclear-magnetism, has direct influence for the result of final quantitative integration,
Since there are multiple compounds, chemical structure is different in nuclear-magnetism sample to be measured, so that the relaxation of the proton of different protons is not
Together, it eventually leads in proton same time after the excitation of nmr spectrometer magnetic fields, it is real required for recovery Boltzmann balance
Border is different, therefore delay time is too short that may cause collected signal be not reply equilibrium state proton, and characteristic peak is caused to go out
Peak is incomplete, and quantitative result is inaccurate.Pointedly the nuclear-magnetism behavior of 1,2- Propylene Glycol Dinitrate system is ground by a series of
Study carefully, test of many times finally considers the fast and easy of the accuracy of experimental result, reproducibility and detection method simultaneously, it is final really
Surely the delay time of 30s-60s is selected, this parameter area can guarantee that internal standard compound and water all reach complete relaxation and restores flat
Weighing apparatus state, to guarantee on the basis of internal standard compound content to the accuracy of water and basis weight.
In the present invention 1,2-propanediol dinitrate sample weighting amount be 10-30mg, although this is because improve dosing accuracy,
The demand for reducing error, configure highly concentrated solution as far as possible to reach the better signal-to-noise ratio of spectrogram, but sample solution concentration simultaneously
It is excessively high to may cause that solute Distribution in solution is uneven, and viscosity is excessive, cause spectral line broadening, while as far as possible for safety issue
Reduce 1,2- Propylene Glycol Dinitrate dosage.Therefore sample weighting amount is limited in 10-30mg, has not only reached preferable signal-to-noise ratio but also has protected
Hold the uniformity and free-running property of solution.
Compared to the prior art, above-mentioned 1,2-propanediol dinitrate moisture content detection method established by the present invention
It is few mainly to have the beneficial effect that sample size dosage is taken in (1) test, effectively prevents conventional aqueous detection method since sample is taken
Security risk caused by amount is big；(2) test method solves height as non-destructive testing without external forces such as friction, electrostatic substantially
Sensitivity nitrate is under outside energy effect the problem of sensitive explosive；(3) test is simple, convenient and rapid, can be completed with rapid batch,
Precision height, favorable reproducibility are tested, there is higher sensitivity, and without standard reference material or draw working curve；(4) method knot
Internal standard method and integral difference assay are closed, having effectively removed other than sample residual moisture in reagent influences test bring.It is comprehensive with
On, the method for the moisture content of quantitative nuclear magnetic resonance spectroscopy is suitable for this kind of high-energy of 1,2-propanediol dinitrate, high sensitivity
With the analysis detection of the nitrate sample of high risk, one is provided for the trace moisture analysis detection of same type explosive wastewater product
The method and thinking of fast quantification.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum spectrogram of 1,2- Propylene Glycol Dinitrate
Specific embodiment
To make those skilled in the art carry out more preferably technical solution to technical solution of the present invention, below with reference to some tools
Technical solution of the present invention is further elaborated in body embodiment.
Embodiment 1
1,2- Propylene Glycol Dinitrate1The foundation of H NMR spectra
1.1 instruments and sample
800 type NMR spectrometer with superconducting magnet of Bruker Ascend (German BRUKER company)；Mettler Toledo
Ten a ten thousandth balance of XP6 type (METTLER company of Switzerland)；(deuterated degree > 99.8%, U.S. CIL are public for deuterated dimethyl sulfoxide
Department)；5mm standard nuclear-magnetism sample cell (NORELL company of the U.S.)；Hexamethyldisiloxane high sterling (pacifies resistance to Jilin Chemical, purity
99%)；1,2- Propylene Glycol Dinitrate (Xi'an Inst. of Modern Chemistry).
The preparation and measurement of 1.2 samples to be tested
Internal standard compound hexamethyldisiloxane 15mg is accurately weighed in 5mm nuclear magnetic tube, it is sub- that the deuterated dimethyl of 0.5ml is then added
Sulfone is sealed with sealed membrane after mixing, and prepared nuclear-magnetism sample is directly used in1H NMR test.After test, then
It is removed to the nuclear-magnetism sample cell for completing test, after addition 1,2-propanediol dinitrate 30mg is sufficiently mixed, it is close to seal up membrana oralis
Envelope, then by sample with the progress of same test condition1H NMR is tested, wherein test parameter and condition are as follows: observing frequency
800.3MHz, measuring temperature 300K, 90 ° of pulses, 3 μ s of spectrum width, sampled data points 65536, scanning times 128 times, delay time
40s。
1.3 sample1H H NMR spectroscopy map analysis
According to1H NMR spectra data in literature, comprehensive 1,2-propanediol dinitrate chemical property, using Topspin 3.5
To detection gained1H NMR spectra calibrated, baseline correction and phase adjustment, divides feelings according to the coupling at proton signal peak column
Condition and chemical displacement value are belonged to accordingly, as shown in table 1 below.The water proton signals peak of chemical shift δ 3.32, and chemistry
It is displaced the hexamethyldisiloxane signal peak of δ 0.02, is separated with other signal peaks well and symmetrically and evenly, meets the base of quantitative nuclear-magnetism
This condition.
1 1,2- Propylene Glycol Dinitrate nucleus magnetic hydrogen spectrum Spectra peak recognition table of table
1.4 methodological study
Stability: taking with a 1,2-propanediol dinitrate sample, according to above-mentioned experiment condition and method, respectively 0,
2,4,6,8,12h carry out1H NMR experiment, records the relative integral area of water peak to calculate the moisture relative amount of sample,
Calculate RSD value；
Repeatability: taking 6 parts of same batch 1,2-propanediol dinitrate, carries out according to above-mentioned experiment condition and method1H
NMR experiment records the relative integral area of water peak to calculate the moisture relative amount of sample, calculates RSD value；
Precision: it takes with a 1,2-propanediol dinitrate sample, according to above-mentioned experiment condition and method METHOD FOR CONTINUOUS DETERMINATION 6
It is secondary, the relative integral area of water peak is recorded to calculate the moisture relative amount of sample, calculates RSD value；
Recovery of standard addition: taking same batch 1,2-propanediol dinitrate sample, according to above-mentioned experiment condition and method into
Row1After H NMR experiment, then accurate that 3mg is added, 5mg pure water is carried out according to above method after pure water is added every time1H NMR
Experiment records the relative integral area of water peak to calculate moisture relative amount, calculates the rate of recovery.
Linear verification: taking same batch 1,2-propanediol dinitrate sample, and precision weighs sample about 10mg, 12mg,
15mg, 20mg carry out 1H NMR experiment according to above-mentioned experiment condition and method respectively, record the relative integral area of water peak from
And calculate moisture relative amount, statistical test result it is linear.
Experimental result is shown in the following table 2, statistics indicate that method has good linear relationship, precision, stability and repetition
Property, while recovery of standard addition value shows method equally and has preferable accuracy.
2 nuclear magnetic resonance hydrogen spectruming determining 1,2- Propylene Glycol Dinitrate moisture methodological study result of table
Embodiment 2
Moisture content in nuclear magnetic resonance hydrogen spectruming determining different batches 1,2- Propylene Glycol Dinitrate
Internal standard compound hexamethyldisiloxane 5.9mg is accurately weighed in 5mm nuclear magnetic tube, the deuterated dimethyl of 0.6ml is then added
Sulfoxide is sealed with sealed membrane after mixing, and prepared nuclear-magnetism sample is directly used in1H NMR test, test parameter and item
Part are as follows: observing frequency 800.3MHz, measuring temperature 300K, 90 ° of pulses, 3 μ s of spectrum width, sampled data points 65536, scanning times
64 times, delay time 40s.The nuclear-magnetism sample cell that test is completed is removed again, it is abundant that 1,2-propanediol dinitrate 13mg is added
After mixing, membrana oralis sealing is sealed up, then by sample with the progress of same test condition1H NMR test.By the same way not to three batches
1,2-propanediol dinitrate sample with lot number is detected, and nmr spectrum is recorded, and calculates moisture content, as a result as follows
Table 3.
3 different batches 1,2- Propylene Glycol Dinitrate determination of moisture of table
| Lot number | Water content/% |
| 180531 | 0.756 |
| 180320 | 0.923 |
| 180309 | 0.556 |
You need to add is that above-mentioned specific embodiment carried out the moisture detecting method of 1,2-propanediol dinitrate
It is described as illustrative and non-limiting, above embodiments 1-2 is not the implementable whole embodiments of this patent, can be according to limited model
It encloses and specifically enumerates more examples again, therefore the modifications and variations in the case where not departing from present general inventive concept, belong to present invention protection model
Within enclosing.
The present invention establishes the nuclear magnetic resonance spectroscopy trace water content of 1,2-propanediol dinitrate, solves biography
The big safety problem of detection method amount of samples of uniting is prominent, needs one-to-one standard substance, the problems such as method is cumbersome, surveys
Examination takes that sample size dosage is few, and test method is lossless and substantially without external forces such as friction, electrostatic, effectively prevents conventional aqueous
Detection method is since macro-analysis dosage is big and high sensitivity nitrate the problem of sensitive explosive, is surveyed under outside energy effect
It tries simple, convenient and rapid, can be completed with rapid batch, experiment precision is high, favorable reproducibility, in combination with internal standard method and integral difference assay,
Having effectively removed other than sample residual moisture in reagent influences test bring.Especially suitable for high-energy, high sensitivity, high-risk
Dangerous 1,2-propanediol dinitrate sample detection provides effective point for the control of the quality of explosive wastewater raw material and product
Analyse ways and means.
Claims (4)
1. a kind of method of nuclear magnetic resonance hydrogen spectruming determining 1,2-propanediol dinitrate (PGDN) moisture content, it is characterised in that packet
Containing step in detail below:
(1) 5~15mg of internal standard compound is weighed, 0.5~0.8ml of deuterated reagent dissolution is added, is transferred in nuclear magnetic tube, it is close to seal up membrana oralis
Envelope.Prepared sample solution is placed in ultrasonic oscillation instrument after shaking 10~20s and nuclear magnetic resonance spectroscopy survey is carried out to sample
Examination, nuclear magnetic resonance spectroscopy test condition are as follows: nmr spectrometer resonant frequency be 400~800MHz, 25~35 DEG C of temperature, delay time
For 30s~60s, pulse angle is 30~90 °, and sampling number is 32~128 times；
(2) the nuclear-magnetism sample cell that test is completed is removed, 10~30mg of 1,2-propanediol dinitrate is added, then to seal up membrana oralis close
Envelope, and shaken with ultrasonic oscillation instrument, nuclear magnetic resonance spectroscopy is carried out again to the sample after addition 1,2-propanediol dinitrate
Test, the quantitative nuclear-magnetism test condition are consistent with previous step；
(3) after testing, the characteristic peak in nuclear magnetic resonance spectroscopy obtained respectively to step 1 and step 2 belongs to, really
Determine the characteristic peak and internal standard compound characteristic peak of water, and integrate respectively, integration method is to go after the leveling of spectrogram baseline to characteristic peak
It removes13It is integrated after C satellites, calculates 3 times and be averaged, respectively obtain water characteristic peak integral area and internal standard compound characteristic peak integral face
Data substitution following formula is obtained corresponding moisture content by product:
Wherein PxFor moisture content in sample to be tested, PSFor the Reinheitszahl of internal standard compound, msFor the quality of the internal standard compound of addition, m
Quality, M is added for 1,2-propanediol dinitrate samplesFor the relative molecular mass of internal standard compound, MxFor the average molecular matter of water
Amount, HsFor the number of resonant nucleus in the functional group of 1 mole of internal standard compound characteristic signal, HxIn the functional group for generating signal for 1 mole of water
The number of resonant nucleus, AsFor the peak area at internal standard compound characteristic signal peak, A1For the sample that 1,2- Propylene Glycol Dinitrate is not added
The peak area at water characteristic signal peak, A2For the peak area at the water characteristic signal peak of the sample of addition 1,2- Propylene Glycol Dinitrate.
2. the method for nuclear magnetic resonance hydrogen spectruming determining 1,2-propanediol dinitrate moisture content, feature exist according to claim 1
Attach most importance to hydrogen dimethylamino base sulfoxide in, deuterated solvent used.
3. the method for nuclear magnetic resonance hydrogen spectruming determining 1,2-propanediol dinitrate moisture content according to claim 1, internal standard used
Object requires benzene, paracide or hexamethyldisiloxane for high sterling or standard items.
4. according to the method for claim 3 nuclear magnetic resonance hydrogen spectruming determining 1,2-propanediol dinitrate moisture content, feature exists
In 1,2-propanediol dinitrate sample-adding quality should be 2-3 times of internal standard compound.
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| CN110031497A (en) * | 2019-04-29 | 2019-07-19 | 北京市食品安全监控和风险评估中心（北京市食品检验所） | The method for detecting 1,2- propylene glycol in fluid milk |
| CN110031497B (en) * | 2019-04-29 | 2022-03-08 | 北京市食品安全监控和风险评估中心（北京市食品检验所） | Method for detecting 1, 2-propylene glycol in liquid milk |
| CN112557432A (en) * | 2020-11-20 | 2021-03-26 | 江苏中旗科技股份有限公司 | Content determination method of bis- (N-bis (dimethylamino) methylene) -chloridized imine salt catalyst |
| CN116559216A (en) * | 2023-04-28 | 2023-08-08 | 齐鲁制药有限公司 | Method for determining esterification degree of primary alcohol in sucrose laurate |
| CN116559216B (en) * | 2023-04-28 | 2024-01-05 | 齐鲁制药有限公司 | Method for determining esterification degree of primary alcohol in sucrose laurate |
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