CN105606747A - Method for determining content of 1,3-propanesultone - Google Patents

Abstract

The invention discloses a method for determining the content of 1,3-propanesultone, belongs to the field of analysis and detection and in particular discloses a method for determining the content of the 1,3-propanesultone by using gas chromatography-mass spectrometry. The method comprises the following steps: putting a proper amount of uniform sample into a glass centrifugal pipe; adding n-hexane and uniformly mixing by vortex; carrying out ultrasonic extraction at a room temperature and centrifuging at a high speed; taking supernatant liquid and repeatedly extracting and combining the supernatant liquid; making the volume constant until the volume is 50mL; centrifuging at a high speed; metering 2mL at a middle scale of a solution to be detected by using a pipette; filtering with a filtering membrane, and carrying out gas chromatography-mass spectrometry analysis; quantifying with an external standard method. The method disclosed by the invention is simple and rapid, and accurate in qualitative and quantitative properties; the interference of sample matrix is effectively avoided and detection requirements can be met.

Description

A kind of method of measuring PS content

Technical field

The invention belongs to analyzing and testing field, relate to a kind of method of measuring PS content, be specifically related to a kind of profitMeasure the method for PS content with gas chromatography-mass spectrography.

Background technology

1,3-propane sultone is important medicine intermediate and electronic chemical product, contains unsaturated bond and hetero atom in its structure,The structure of this uniqueness makes it in synthesizing heterocyclic medicine, have irreplaceable effect, and in recent years 1,3-propane sultone is by largeAmount, as the additive of lithium battery electrolytes, can be improved battery performance, makes can greatly the extending in the recharge life-span of battery, 1,3-propane sultone is also applied to brightener, dyestuff, double ion surfactant, sulfonating agent etc. Under the condition existing at water,This compound can slowly be hydrolyzed to corresponding corrosivity hydroxyl sulfoacid, can decompose and produce the titanium dioxide with toxicity and stench when heatingSulphur smog. Under 1,3-propane sultone usual conditions, be colourless to weak yellow liquid, 31 DEG C of fusing points, boiling point is 276.5 DEG C,Molecular formula is C3H6O3S, is for No. CAS 1120-71-4. Structural formula is as follows:

PS chemical structural formula

PS tool carcinogenicity, but still by businessman for the manufacture of film top layer light sensitivity dyestuff, battery electrolyte taking its asThe sulfopropyl material that intermediate is produced. Extensive stock taking PS as raw material, is widely used, can be direct or indirectContact with people, or move in environment, its extent of injury is directly related with its content height.

At present, focus mostly on and synthesize and application aspect at it about the correlative study of PS, related industries product or changeIn product, the content detection of PS rarely has and mentions. It should be noted that the relevant product that relates to PSProduct are main mainly with formulation product greatly, are aided with dye well printed article. Research shows, the matrix complexity of this series products, detection difficultyGreatly. Therefore, set up a kind of method that detects accurately and reliably PS very important. By detection side accurately and effectivelyMethod, can know the content of PS accurately, Related product manufacturer and manage dealer and can tackle in advance, alsoThe harm that can better prevent this material to cause the mankind and environment.

Summary of the invention

The technical problem to be solved in the present invention is how effectively to extract PS, sick a kind of mensuration 1,3-that sets upThe reliable method of propane sultone content.

Technical problem of the present invention can be solved by the following technical programs:

(1) sample preparation: to solid sample, get 20-50g sample, be first broken into the particle of 1cm × 1cm × 1cm left and right,Carry out meal with high efficiency cutting pulverizer again, then use high efficiency cutting pulverizer low temperature fine powder. Sample is pulverized at twice, for the first timeSample discards, and gets sample for the second time. Sample powder after pulverizing is by standard screen 60-80 order. Parallelly take two samples, twoSample will carry out independent analysis, avoids phase mutual interference. To textile or membranaceous solid sample, get representative sample 10-20g, cut outCut the fragment for being not more than 3mm × 3mm × 3mm, for sample extraction. To some liquid that contain a large amount of solvent substrate complexityHeavy chemicals, mixes to be measured;

(2) abstraction and quantification: take 0.5-2g sample in 50mL glass is centrifugal, add 20mL n-hexane, vortex mixes,The ultrasonic extraction of room temperature 30min, 8000r/min high speed centrifugation 10min, gets supernatant liquor, and 10mL n-hexane repeats to extract and mergesSupernatant liquor, with n-hexane, supernatant being settled to 50mL is solution to be measured, 8000r/min high speed centrifugation 10min, with moving liquidPipe scale in the middle of solution to be measured measures 2mL, filters through 0.22 μ m nylon leaching film, and filtrate is divided through gas chromatograph-mass spectrometer (GC-MS)Analyse;

(3) instrument condition: the present invention adopts gas chromatograph-mass spectrometer (GC-MS) to carry out separation and the survey of PS in sample liquidFixed, concrete instrument condition is as follows:

GC conditions, adopts chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μ m, and taking 60 DEG C as column oven initial temperature,Be warmed up to 130 DEG C with the speed of 10 DEG C/min, keep 3min, be warmed up to 180 DEG C with the speed of 10 DEG C/min, keep 5min,Be warmed up to 310 DEG C with the speed of 20 DEG C/min, injector temperature is 270 DEG C, and sample introduction pattern is Splitless injecting samples, and sample size is 1 μ L,Post flow is 1.0mL/min, and transmission line temperature is 280 DEG C.

Mass spectrum condition, adopts EI ion gun, and ion source temperature is 230 DEG C, and the solvent delay time is 3min, adopts and selects ionPattern scans, feature fragment ion qualitative, quantitative. Select ion monitoring in table 1:

Table 1 is selected ion monitoring

Material title	Quota ion	Qualitative ion
			PS	58	57、58、64、65、122

(4) calculate: external standard method is quantitative, calculates as follows the content of object in sample;

$X=\frac{c\×V\×1000}{m\×1000}\×f$

In formula:

X---the content of determinand in sample, unit is milligrams per kilogram (mg/kg);

Testing concentration c---the sample solution that obtains from standard matrix working curve, unit is every milliliter of microgram (μ g/mL);

V---sample constant volume, unit is milliliter (mL);

M---take sample mass, unit is gram (g);

F---extension rate;

Result of calculation retains three position effective digitals.

Beneficial effect

Beneficial effect of the present invention is, has set up a kind of assay method of PS content, for relating generally to sampleThe characteristic of product, has formulated corresponding processing mode, effectively avoids the water-disintegrable and pyrolysis pair having because of PSThe impact that mensuration causes, adopt n-hexane to repeat the mode of ultrasonic extraction, ensured fully carrying of PS in sampleGet, separate effective to sample substrate and extract by centrifugal means, avoid substrate to bring into and treat in sample measuring liquid. To weighExtract again solution and mix rear constant volume, more quantitatively pipette sample liquid by pipette scale in the middle of solution to be measured, effectively avoided sampleThe impact that the excessive or too small mixed layer of density forming after product solvent mixes with n-hexane exists test result, definite solventVolume is conducive to quantitatively accurately. Optimum mass spectrum condition and fragment ion select to have ensured that baseline and object are fixed accurately stablyProperty quantitative, optimum GC conditions has ensured better separating effect, retention time and symmetrical peak shape. Employing this method is surveyedDetermine PS content simple, quick, qualitative, quantitatively accurate, there is the higher rate of recovery and precision, Neng GoumanThe detection of the various matrix samples of foot needs.

Brief description of the drawings

Fig. 1 .1,3-propane sultone TIC

Fig. 2 .1,3-propane sultone mass spectrum block diagram

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention is described in further detail, but does not therefore limit the present invention to described enforcementAmong example scope.

The mensuration of PS content in embodiment 1 dye sample

(1) analytical procedure

Get 50g dye sample, mix. Take respectively 1.03g and 1.01g sample in 50mL glass centrifuge tube, add 20mLN-hexane, vortex mixes, the ultrasonic extraction of room temperature 30min, 8000r/min high speed centrifugation 10min, gets supernatant liquor, 10mLN-hexane repeats to extract and merges supernatant liquor, and with n-hexane, supernatant being settled to 50mL is solution to be measured, and 8000r/min at a high speedCentrifugal 10min, measures 2mL with pipette scale in the middle of solution to be measured, filters through 0.22 μ m nylon leaching film, and filtrate is through gasPhase chromatograph-mas spectrometer is analyzed.

(2) chromatogram and mass spectrum parameter

GC conditions, adopts chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μ m, and taking 60 DEG C as column oven initial temperature,Be warmed up to 130 DEG C with the speed of 10 DEG C/min, keep 3min, be warmed up to 180 DEG C with the speed of 10 DEG C/min, keep 5min,Be warmed up to 310 DEG C with the speed of 20 DEG C/min, injector temperature is 270 DEG C, and sample introduction pattern is Splitless injecting samples, and sample size is 1 μ L,Post flow is 1.0mL/min, and transmission line temperature is 280 DEG C.

Mass spectrum condition, adopts EI ion gun, and ion source temperature is 230 DEG C, and the solvent delay time is 3min, adopts and selects ionPattern scans, feature fragment ion qualitative, quantitative.

(3) standard working curve

Take purity and be 99% PS standard items in 10mL volumetric flask, dilute to such an extent that concentration is with n-hexaneThe PS standard reserving solution of 1000 μ g/mL is drawn certain volume liquid from standard reserving solution, is mixed with 1The series standard working solution of μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, uses GC-MSCarry out qualitative and quantitative analysis.

(4) qualitative, quantitative result

In retention time window, there is not the peak consistent with target compound detection ion retention time, in sample 1,3-propane sulphurThe content of lactone is calculated as and does not detect through external standard-calibration curve method.

The standard substance of embodiment 2 dye sample PSs adds mensuration

(1) analytical procedure

Get the PS negative sample in embodiment 1. Take six parts of about 1g samples (be accurate to decimal point after three)In 50mL glass is centrifugal, add the each 0.1mL of PS standard reserving solution of 1000 μ g/mL, static one section timeBetween after, add 20mL n-hexane, 8000r/min high speed centrifugation 10min, gets supernatant liquor, 10mL n-hexane repeat extractMerge supernatant liquor, with n-hexane, supernatant being settled to 50mL is solution to be measured, and 8000r/min high speed centrifugation 10min usesPipette scale in the middle of solution to be measured measures 2mL, filters through 0.22 μ m nylon leaching film, and filtrate is through gas chromatography-mass spectrographyInstrument is analyzed.

(2) instrument condition

GC conditions, adopts chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μ m, and taking 60 DEG C as column oven initial temperature,Be warmed up to 130 DEG C with the speed of 10 DEG C/min, keep 3min, be warmed up to 180 DEG C with the speed of 10 DEG C/min, keep 5min,Be warmed up to 310 DEG C with the speed of 20 DEG C/min, injector temperature is 270 DEG C, and sample introduction pattern is Splitless injecting samples, and sample size is 1 μ L,Post flow is 1.0mL/min, and transmission line temperature is 280 DEG C.

Mass spectrum condition, adopts EI ion gun, and ion source temperature is 230 DEG C, and the solvent delay time is 3min, adopts and selects ionPattern scans, feature fragment ion qualitative, quantitative.

(3) standard working curve

Take purity and be 99% PS standard items in 10mL volumetric flask, dilute to such an extent that concentration is with n-hexaneThe PS standard reserving solution of 1000 μ g/mL is drawn certain volume liquid from standard reserving solution, is mixed with 1The series standard working solution of μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 20 μ g/mL, uses GC-MSCarry out qualitative and quantitative analysis.

(4) qualitative, quantitative result

In retention time window, there is the peak consistent with target compound detection ion retention time, and with the feature of standard items fromSub-ratio is consistent. The retention time of object PS is 7.226min after testing, goes out peak retention time with standard itemsUnanimously, and abundance ratio within tolerance scope. In sample, the content of PS calculates through external standard calibration curve method.

(5) precision and test result

Measure through 6 parallel laboratory tests, read to such an extent that PS content is 9.01 μ g/mL from calibration curve, mark-on after convertingThe rate of recovery is 90.1%, and relative standard deviation is 2.3%.

Above-described embodiment is used for illustrative purposes only, and is not the restriction to patent of the present invention; It should be pointed out that forThose of ordinary skill in the art, in the situation that not departing from the present invention and conceiving scope, can also make various variations and modification,These all belong to protection scope of the present invention; Therefore, all equalizations of doing with the claims in the present invention scope change and modify, allShould belong to the coverage of the claims in the present invention.

Claims (2)

1. measure a method for PS content, its feature comprises the steps:

(1) sample preparation:

To solid sample, get 20-50g sample, be first broken into the particle of 1cm × 1cm × 1cm left and right, then carry out meal with high efficiency cutting pulverizer, then use high efficiency cutting pulverizer low temperature fine powder. Sample is pulverized at twice, and sample discards for the first time, gets sample for the second time; Sample powder after pulverizing is by standard screen 80 or 100 orders. Parallelly take two samples, two samples will carry out independent analysis, avoid phase mutual interference;

To textile or membranaceous solid sample, get representative sample 10-20g, be cut to the fragment that is not more than 3mm × 3mm × 3mm, for sample extraction;

To some fluid chemical goods that contain a large amount of solvent substrate complexity, mix to be measured;

(2) abstraction and quantification: take 0.5-2g sample in 50mL glass is centrifugal, add 20mL n-hexane, vortex mixes, the ultrasonic extraction of room temperature 30min, 8000r/min high speed centrifugation 10min, get supernatant liquor, 20mL n-hexane repeats to extract merging supernatant liquor, with n-hexane, supernatant being settled to 50mL is solution to be measured, 8000r/min high speed centrifugation 10min, measure 2mL with pipette scale in the middle of solution to be measured, filter through 0.22 μ m nylon leaching film, filtrate is through gas chromatograph-mass spectrometer (GC-MS) analysis;

(3) instrument condition: the present invention adopts gas chromatograph-mass spectrometer (GC-MS) to carry out separation and the mensuration of PS in sample liquid, and concrete instrument condition is as follows:

GC conditions, adopts chromatographic column DB-5MS, 30m × 0.25mm × 0.25 μ m, taking 60 DEG C as column oven initial temperature, be warmed up to 130 DEG C with the speed of 10 DEG C/min, keep 3min, be warmed up to 180 DEG C with the speed of 10 DEG C/min, keep 5min, be warmed up to 310 DEG C with the speed of 20 DEG C/min, injector temperature is 270 DEG C, sample introduction pattern is Splitless injecting samples, sample size is 1 μ L, and post flow is 1.0mL/min, and transmission line temperature is 280 DEG C;

Mass spectrum condition, adopts EI ion gun, and ion source temperature is 230 DEG C, and the solvent delay time is 3min, adopts choice ion pattern to scan, feature fragment ion qualitative, quantitative;

(4) calculate: external standard method is quantitative, calculates as follows the content of object in sample;

In formula:

X---the content of determinand in sample, unit is milligrams per kilogram;

Testing concentration c---the sample solution that obtains from standard matrix working curve, unit is every milliliter of microgram;

V---sample constant volume, unit is for rising;

M---take sample mass, unit is gram;

F---extension rate;

Result of calculation retains three position effective digitals.

2. method according to claim 1, is characterized in that, the quota ion of PS is m/z58, and qualitative ion is m/z57,58,64,65,122.