CN105606747B - The method that one kind determines 1,3 propane sultone contents - Google Patents
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- CN105606747B CN105606747B CN201511016109.5A CN201511016109A CN105606747B CN 105606747 B CN105606747 B CN 105606747B CN 201511016109 A CN201511016109 A CN 201511016109A CN 105606747 B CN105606747 B CN 105606747B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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Abstract
This method discloses a kind of method for determining 1,3 propane sultone contents, belongs to analysis detection field, especially discloses a kind of method that gas chromatography combined with mass spectrometry determines 1,3 propane sultone contents, comprises the following steps：Take appropriate homogeneous sample in glass centrifuge tube, add n-hexane, be vortexed and mix, room temperature ultrasonic extraction, high speed centrifugation, takes supernatant liquor, repeats to extract merging supernatant liquor, it is settled to 50mL, high speed centrifugation, 2mL, membrane filtration are measured with pipette in solution mid-scale to be measured, gaschromatographic mass spectrometric analysis, quantified by external standard method.This method simple and fast, it is qualitative, quantitative accurate, sample substrate interference is effectively avoided, detection needs are disclosure satisfy that.
Description
Technical field
The invention belongs to analyze detection field, it is related to a kind of method for determining PS content, and in particular to
A kind of method that utilization gas chromatography-mass spectrography determines PS content.
Background technology
1,3- propane sultone be in important medicine intermediate and electronic chemical product, its structure containing unsaturated bond and
Hetero atom, it is irreplaceable that this unique structure makes it play the role of in synthesizing heterocyclic medicine, in recent years 1,3- propane sulphur
Acid lactone is widely used as the additive of lithium battery electrolytes, can improve battery performance, makes the repeatable charge lifetimes of battery
Greatly prolong, 1,3- propane sultones are also applied to brightener, dyestuff, double ion surfactant, sulfonating agent etc..Deposited in water
Under the conditions, the compound can slowly be hydrolyzed to corresponding corrosivity hydroxyl sulfoacid, and decomposable asymmetric choice net, which is produced, during heating has toxicity
With the sulfur dioxide smog of stench.It is colourless to weak yellow liquid under 1,3- propane sultone usual conditions, 31 DEG C of fusing point boils
Point is 276.5 DEG C, and molecular formula is C3H6O3S, and No. CAS is 1120-71-4.Structural formula is as follows：
PS has carcinogenicity, but still is used to manufacture film top layer sensitising dye, battery electrolysis by businessman
The sulfopropyl material that liquid is produced using it as intermediate.Using PS as the extensive stock of raw material, it is widely used, can be straight
Connect or indirectly contacted with people, or move in environment, its extent of injury is directly related with its content height.
At present, the correlative study on PS focuses mostly in its synthesis and application aspect, related industries production
The content detection of PS, which rarely has, in product or chemicals refers to.It is worth noting that, being related to PS
Related product mostly based on dosage form product, be aided with dyestuff and printed article.Research shows that the matrix of such product is complicated,
Detection difficulty is big.Therefore, a kind of method of accurately and reliably detection PS is set up particularly significant.Pass through accurate and effective
Detection method, can accurately know the content of PS, Related product manufacturer and manage dealer and can carry
Preceding reply, the harm that can also preferably prevent the substances on human and environment to cause.
The content of the invention
The technical problem to be solved in the present invention is how to efficiently extract out PS, and disease sets up a kind of survey
Determine the reliable method of PS content.
Technical problem of the present invention can be addressed by the following technical programs：
(1) sample preparation：To block or granular solids sample, 20-50g samples are taken, 1cm × 1cm × 1cm is first broken into
The particle of left and right, then coarse powder is carried out with high efficiency cutting pulverizer, then with high efficiency cutting pulverizer low temperature fine powder.Sample after crushing
Product powder passes through standard screen 60-80 mesh.Parallel to weigh two samples, two samples will carry out independent analysis, it is to avoid interfere.It is right
Textile or membranaceous solid sample, take representative sample 10-20g, are cut to no more than 3mm × 3mm × 3mm fragment, are used for
Sample extraction.To containing some complicated fluid chemical products of a large amount of solvent substrates, mixing to be measured；
(2) extract and determine：0.5-2g samples are weighed in 50mL glass centrifuge tubes, 20mL n-hexanes are added, are vortexed mixed
Even, room temperature ultrasonic extraction 30min, 8000r/min high speed centrifugation 10min takes supernatant liquor, and 10mL n-hexanes, which repeat to extract, to be merged
Supernatant liquor, is settled to 50mL for solution to be measured, 8000r/min high speed centrifugation 10min use pipette with n-hexane by supernatant
2mL is measured in solution mid-scale to be measured, is filtered through 0.22 μm of nylon leaching film, filtrate is analyzed through gas chromatograph-mass spectrometer (GC-MS)；
(3) instrument condition：The separation and survey of PS in sample liquid are carried out using gas chromatograph-mass spectrometer (GC-MS)
Fixed, specific instrument condition is as follows：
GC conditions, using chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μm is that column oven is initial with 60 DEG C
Temperature, 130 DEG C are warming up to 10 DEG C/min speed, keep 3min, and 180 DEG C, holding are warming up to 10 DEG C/min speed
5min, is warming up to 310 DEG C, injector temperature is 270 DEG C, sample introduction pattern is Splitless injecting samples, sample introduction with 20 DEG C/min speed
Measure as 1 μ L, column flow is 1.0mL/min, transmission line temperature is 280 DEG C.
Mass Spectrometry Conditions, using EI ion guns, ion source temperature is 230 DEG C, and the solvent delay time is 3min, using selection from
Subpattern is scanned, fragments characteristic ion qualitative, quantitative.Salbutamol Selected Ion Monitoring is shown in Table 1：
The Salbutamol Selected Ion Monitoring of table 1
| Material title | Quota ion | Qualitative ion |
| PS | 58 | 57、58、64、65、122 |
(4) calculate：Quantified by external standard method, calculates the content of object in sample as follows；
In formula：
X --- the content of determinand in sample, unit is milligrams per kilogram (mg/kg)；
C --- testing concentration in the sample solution obtained from standard substrates working curve, unit is micrograms per millilitre (μ
g/mL)；
V --- sample constant volume, unit is milliliter (mL)；
M --- sample mass is weighed, unit is gram (g)；
F --- extension rate；
Result of calculation retains three effective digitals.
Beneficial effect
The beneficial effects of the present invention are establish a kind of assay method of PS content, for main
Be related to the characteristic of sample, formulated corresponding processing mode, effectively avoid because of have water-disintegrable of PS and
The influence that pyrolysis property is caused to measure, by the way of n-hexane repeats ultrasonic extraction, it is ensured that 1 in sample, in 3- propane sulphurs
The abundant extraction of ester, is efficiently separated sample substrate with extract solution by the means of centrifugation, it is to avoid brought substrate into be measured
In sample liquid.It will repeat to extract constant volume after solution is mixed, then sample liquid in solution mid-scale to be measured is quantitatively pipetted by pipette, have
What is imitated avoids what the excessive or too small mixed layer of the density formed after sample solvent is mixed with n-hexane existed to test result
Influence, it is determined that solvent volume be conducive to it is quantitatively accurate.Optimal Mass Spectrometry Conditions and fragment ion selection ensure that stable base
Line and the accurate qualitative, quantitative of object, optimal GC conditions ensure that preferable separating effect, retention time and symmetrical
Peak shape.PS content is determined simply, fast using this method, it is qualitative, quantitative accurate, with higher recovery
Rate and precision, disclosure satisfy that the detection needs of various matrix samples.
Brief description of the drawings
Fig. 1 PS total ion chromatograms
Fig. 2 PS mass spectroscopy histograms
Embodiment
The present invention is described in further detail with reference to specific embodiment, but does not therefore limit the present invention to institute
State among scope of embodiments.
The measure of PS content in the dye sample of embodiment 1
(1) analytical procedure
50g dye samples are taken, are mixed.1.03g and 1.01g samples are weighed respectively in 50mL glass centrifuge tubes, are added
20mL n-hexanes, are vortexed and mix, and room temperature ultrasonic extraction 30min, 8000r/min high speed centrifugation 10min takes supernatant liquor, 10mL
N-hexane, which repeats to extract, merges supernatant liquor, supernatant is settled into 50mL for solution to be measured with n-hexane, 8000r/min is at a high speed
10min is centrifuged, 2mL is measured in solution mid-scale to be measured with pipette, is filtered through 0.22 μm of nylon leaching film, filtrate is through gas phase color
Spectrum-GC-MS analysis.
(2) chromatogram and mass spectrometry parameters
GC conditions, using chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μm is that column oven is initial with 60 DEG C
Temperature, 130 DEG C are warming up to 10 DEG C/min speed, keep 3min, and 180 DEG C, holding are warming up to 10 DEG C/min speed
5min, is warming up to 310 DEG C, injector temperature is 270 DEG C, sample introduction pattern is Splitless injecting samples, sample introduction with 20 DEG C/min speed
Measure as 1 μ L, column flow is 1.0mL/min, transmission line temperature is 280 DEG C.
Mass Spectrometry Conditions, using EI ion guns, ion source temperature is 230 DEG C, and the solvent delay time is 3min, using selection from
Subpattern is scanned, fragments characteristic ion qualitative, quantitative.
(3) standard working curve
Weigh purity be 99% PS standard items in 10mL volumetric flasks, dilute to obtain concentration with n-hexane
For 1000 μ g/mL PS standard reserving solution, certain volume liquid is drawn from standard reserving solution, 1 μ is configured to
G/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL series standard working solution, are determined with gas chromatography-mass spectrometry
Property quantitative analysis.
(4) qualitative, quantitative result
Do not occur in retention time window 1,3- in the peak consistent with target compound detection ion retention time, sample
The content of propane sultone is calculated as not detecting through external standard-calibration curve method.
The standard substance of the dye sample PS of embodiment 2, which is added, to be determined
(1) analytical procedure
PS negative sample in Example 1.Six parts of about 1g samples are weighed (to be accurate to three after decimal point
Position) in 50mL glass centrifuge tubes, add 1000 μ g/mL PS standard reserving solution each 0.1mL, static one section
After time, 20mL n-hexanes are added, 8000r/min high speed centrifugation 10min take supernatant liquor, and 10mL n-hexanes are repeated to extract and closed
And supernatant liquor, supernatant is settled to 50mL for solution to be measured with n-hexane, 8000r/min high speed centrifugation 10min use liquid relief
Pipe measures 2mL in solution mid-scale to be measured, is filtered through 0.22 μm of nylon leaching film, and filtrate is through gas chromatograph-mass spectrometer (GC-MS) point
Analysis.
(2) instrument condition
GC conditions, using chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μm is that column oven is initial with 60 DEG C
Temperature, 130 DEG C are warming up to 10 DEG C/min speed, keep 3min, and 180 DEG C, holding are warming up to 10 DEG C/min speed
5min, is warming up to 310 DEG C, injector temperature is 270 DEG C, sample introduction pattern is Splitless injecting samples, sample introduction with 20 DEG C/min speed
Measure as 1 μ L, column flow is 1.0mL/min, transmission line temperature is 280 DEG C.
Mass Spectrometry Conditions, using EI ion guns, ion source temperature is 230 DEG C, and the solvent delay time is 3min, using selection from
Subpattern is scanned, fragments characteristic ion qualitative, quantitative.
(3) standard working curve
Weigh purity be 99% PS standard items in 10mL volumetric flasks, dilute to obtain concentration with n-hexane
For 1000 μ g/mL PS standard reserving solution, certain volume liquid is drawn from standard reserving solution, 1 μ is configured to
G/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL series standard working solution, are determined with gas chromatography-mass spectrometry
Property quantitative analysis.
(4) qualitative, quantitative result
Occur in retention time window with the consistent peak of target compound detection ion retention time, and with standard items
Characteristic ion ratio is consistent.The retention time of object PS is 7.226min after testing, with standard items appearance
Retention time is consistent, and abundance ratio is within the scope of tolerance.The content of PS is through external standard standard in sample
Curve method is calculated.(5) precision and test result
Through 6 parallel laboratory tests determine, from standard curve read PS content be 9.01 μ g/mL, after conversion
Recovery of standard addition is 90.1%, and relative standard deviation is 2.3%.
Above-described embodiment is used for illustrative purposes only, and is not the limitation to patent of the present invention；It should be pointed out that
For one of ordinary skill in the art, in the case where not departing from present inventive concept scope, can so that various changes can be made and
Modification, these belong to protection scope of the present invention；Therefore, all equivalent changes done with scope of the invention as claimed are with repairing
Decorations, all should belong to the coverage of the claims in the present invention.
Claims (2)
1. a kind of method for determining PS content, its feature comprises the following steps：
(1) sample preparation：
To block or granular solids sample, 20-50g samples are taken, 1cm × 1cm × 1cm or so particle is first broken into, then used
High efficiency cutting pulverizer carries out coarse powder, then with high efficiency cutting pulverizer low temperature fine powder；Sample powder after crushing passes through standard
Sieve 80 or 100 mesh；Parallel to weigh two samples, two samples will carry out independent analysis, it is to avoid interfere；
To textile or membranaceous solid sample, representative sample 10-20g is taken, the broken of no more than 3mm × 3mm × 3mm is cut to
Piece, for sample extraction；
To containing some complicated fluid chemical products of a large amount of solvent substrates, mixing to be measured；
(2) extract and determine：0.5-2g samples are weighed in 50mL glass centrifuge tubes, 20mL n-hexanes are added, is vortexed and mixes, room
Warm ultrasonic extraction 30min, 8000r/min high speed centrifugation 10min, take supernatant liquor, and 20mL n-hexanes, which repeat to extract, merges upper strata
Clear liquid, 50mL is settled to for solution to be measured with n-hexane by supernatant, 8000r/min high speed centrifugation 10min, with pipette in treating
Survey solution mid-scale and measure 2mL, filtered through 0.22 μm of nylon leaching film, filtrate is analyzed through gas chromatograph-mass spectrometer (GC-MS)；
(3) instrument condition：The separation of PS and measure in sample liquid are carried out using gas chromatograph-mass spectrometer (GC-MS),
Specific instrument condition is as follows：
GC conditions, using chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μm, with 60 DEG C for column oven initial temperature,
130 DEG C are warming up to 10 DEG C/min speed, 3min is kept, 180 DEG C are warming up to 10 DEG C/min speed, 5min is kept, with
20 DEG C/min speed is warming up to 310 DEG C, and injector temperature is 270 DEG C, and sample introduction pattern is Splitless injecting samples, and sample size is 1 μ L,
Column flow is 1.0mL/min, and transmission line temperature is 280 DEG C；
Mass Spectrometry Conditions, using EI ion guns, ion source temperature is 230 DEG C, and the solvent delay time is 3min, using selection ion mould
Formula is scanned, fragments characteristic ion qualitative, quantitative；
(4) calculate：Quantified by external standard method, calculates the content of object in sample as follows；
In formula：
X --- the content of determinand in sample, unit for milligrams per kilogram；
C --- testing concentration in the sample solution obtained from standard substrates working curve, unit is micrograms per millilitre；
V --- sample constant volume, unit is milliliter；
M --- weigh sample mass, unit for gram；
F --- extension rate；
Result of calculation retains three effective digitals.
2. according to the method described in claim 1, it is characterised in that the quota ion of PS is m/z58, qualitative
Ion is m/z57,58,64,65,122.
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| CN111487346A (en) * | 2020-04-29 | 2020-08-04 | 江苏天鹏电源有限公司 | Quantitative method for detecting small amount of organic additives in electrolyte by GC-MS (gas chromatography-Mass spectrometer) combination |
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| SU1004382A1 (en) * | 1981-06-04 | 1983-03-15 | Львовский Ордена Ленина Политехнический Институт Им.Ленинского Комсомола | Process for purifying 1,3-propanesultone |
| CN101157681A (en) * | 2007-11-01 | 2008-04-09 | 姜俊 | Method for preparing 1,3 propane sultone |
| CN101456855B (en) * | 2008-11-24 | 2012-02-08 | 张家港市华盛化学有限公司 | Method for preparing 1,3-propanesultone |
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