CN104483433A - Method for measuring bisphenol-S in consumer goods - Google Patents
Method for measuring bisphenol-S in consumer goods Download PDFInfo
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- CN104483433A CN104483433A CN201410856740.5A CN201410856740A CN104483433A CN 104483433 A CN104483433 A CN 104483433A CN 201410856740 A CN201410856740 A CN 201410856740A CN 104483433 A CN104483433 A CN 104483433A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 title abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 195
- 239000000243 solution Substances 0.000 claims abstract description 66
- 150000002500 ions Chemical class 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004033 plastic Substances 0.000 claims abstract description 17
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- 238000000605 extraction Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 10
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- 239000000523 sample Substances 0.000 claims description 137
- 239000000284 extract Substances 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 25
- 238000004811 liquid chromatography Methods 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000012071 phase Substances 0.000 claims description 18
- 238000005336 cracking Methods 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002137 ultrasound extraction Methods 0.000 claims description 12
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 11
- 238000000132 electrospray ionisation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005070 sampling Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 8
- 230000000052 comparative effect Effects 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 239000012488 sample solution Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000001819 mass spectrum Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- 238000010790 dilution Methods 0.000 abstract description 7
- 239000012895 dilution Substances 0.000 abstract description 7
- 238000002390 rotary evaporation Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000123 paper Substances 0.000 description 6
- 238000004451 qualitative analysis Methods 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000010812 external standard method Methods 0.000 description 4
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- 238000005374 membrane filtration Methods 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000004753 textile Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 238000013508 migration Methods 0.000 description 2
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- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for measuring bisphenol-S in consumer goods. The measuring method includes the steps that (1) a smashed and evenly mixed sample is taken, an organic solvent is added to the sample, extraction is conducted, an extracted solution is concentrated through a rotary evaporation instrument, and dilution constant volume is conducted on the solution through methanol and water; (2) for a plastic product sample and a wooden product sample, the extracted solution generated after concentration and methanol-water constant volume are conducted is purified through a small HLB pillar; (3) the amount of bisphenol-S in the methanol-water solution obtained through the step (1) or the step (2) is measured through a liquid chromatograph-mass spectrometer; (4) Comparison between the sample and a full scan mass spectrogram of standard matter on the aspects of the retention time, the characteristic ions and the abundance ratio is conducted is conducted, whether the sample contains the bisphenol-S or not is determined, and finally the content of the bisphenol-S in the sample is calculated after conversion according to the amount of the bisphenol-S obtained in the step (3). The measuring method is rapid and simple, the content of the bisphenol-S in the consumer goods made of various materials can be accurately measured, and the detection limits each can reach 0.1 mg/kg.
Description
[technical field]
The invention belongs to technical field of analytical chemistry, specifically a kind of method measuring bis-phenol-S in daily necessities.
[background technology]
Bis-phenol-S is 4, and 4 '-dihydroxydiphenylsulisomer is obtained by phenol and sulfuric acid reaction, and its No. CAS is 80-09-1.Containing two hydroxyls and the very strong sulfuryl of an electrophilic in its molecule, so it is acid stronger than other phenols.This compound has excellent heat-resisting, fast light and antioxygenic property, main as colouring stabilizer, in addition also can with using solution additive, leather retanning agent, the spreading agent of disperse dyes high-temperature dyeing, phenolics hardening accelerator, resin fire retardants etc., it is also the intermediate of agricultural chemicals, dyestuff, auxiliary agent simultaneously.As the substitute of bisphenol-A, bisphenol S can be used as the raw material of polycarbonate, epoxy resin, polyester, the raw material of phenolics and polysulfones, polyethersulfone.In addition, bisphenol S also can be used for manufacturing color photographic materials, photograph contrast enhancement agents, thermal recording medium (developer), daily surfactant and high-efficiency deodorant etc.
The scientist in european union research centre finds in investigation, and bisphenol S is similar to the toxicity of bisphenol-A, human body is existed equally to the risk stimulating female hormone and cause liver cell poisoning.In Japan and Korea S's clear stipulaties food simulants, bisphenol S migration amount must not more than 0.05mg/L, and it is 0.05mg/kg that European Union plastics regulation (EU) No.10/2011 and China " food containers, wrappage adjuvant use hygienic standard " (GB 9685-2008) all specifys that the migration of bisphenol S in food simulants is limited the quantity.
Wei Bao inspection center of Changzhou inspection and quarantine bureau develops the detection method of bisphenol S in food simulants, but the content of bis-phenol-S how in testing product itself, thus prevent bis-phenol-S to the injury of human health from source, but there is no relevant report.
[summary of the invention]
Object of the present invention is exactly for different daily necessities, will set up the extraction of a kind of bis-phenol-S, purification and liquid chromatography mass combined instrument assay method, prevents the daily necessities containing bis-phenol-S from causing harmful effect to consumer health from source.
Design a kind of method measuring bis-phenol-S in daily necessities for achieving the above object, comprise the following steps:
1) sample pretreatment: the sample comminution except plastic products, woodwork is mixed, take appropriate, add organic solvent and ultrasonic extraction is carried out to sample, sample extraction solution Rotary Evaporators is concentrated, and carry out diluting and constant volume with first alcohol and water;
2) adopt liquid chromatography mass combined instrument determination step 1) in the solution of gained whether containing bis-phenol-S: if liquid chromatography mass Selective ion mode scanning result show sample doubtful containing bis-phenol-S time, whether the then ion full scan mass spectrogram of comparative sample and bis-phenol-S standard substance, contain bis-phenol-S in confirmatory sample;
3) if containing bis-phenol-S in confirmatory sample, then by the content of bis-phenol-S in formulae discovery sample.
Step 1) in, add that methyl alcohol is ultrasonic extracts to obtain sample solution in the sample to which, methyl alcohol is extracted solution Rotary Evaporators to concentrate, controlled pressure is 300bar therebetween, bath temperature is 70 DEG C, shifts the solution after concentrating to volumetric flask, by methanol constant volume, get this methanol solution again, dilute with water constant volume.
Step 2) in, the condition determination of liquid chromatography mass combined instrument is:
1) liquid-phase chromatographic column adopts Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, column internal diameter 2.1mm, packing material size 3.5mm;
2) mobile phase is first alcohol and water, and its blending ratio is methyl alcohol: water=35:65, and working time is 10min; Flow rate of mobile phase is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C;
3) mass spectrum ionization source adopts electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry gas temperature is 300 DEG C, and dry gas flow velocity is 10L/min, and capillary voltage is 3000V; Gathering selects full scan and Selective ion mode to scan the pattern of simultaneously carrying out, and full scan scope is m/z 50 ~ 300, and cracking voltage is 270V; Selective ion mode scanning Selective ion mode is m/z 249, and cracking voltage is 190V.
Step 2) in, in the ion full scan mass spectrogram of sample, pay close attention to the characteristic ion m/z 249, m/z 156, m/z 108, the m/z 92 that whether contain bis-phenol-S standard substance, and whether compare their abundance ratios in the sample to which identical with bis-phenol-S standard substance, when containing above-mentioned whole 4 characteristic ions in the gained chromatographic peak of sample chromatogram figure bis-phenol-S position, and abundance ratio identical with bis-phenol-S standard substance time, then in confirmatory sample containing bis-phenol-S.
The another kind of method measuring bis-phenol-S in daily necessities, comprises the following steps:
1) sample pretreatment: the sample comminution of plastic products or woodwork is mixed, take appropriate, add organic solvent and ultrasonic extraction is carried out to sample, sample extraction solution Rotary Evaporators is concentrated, and carry out diluting and constant volume with first alcohol and water;
2) Solid phase extraction: use preactivated hydrophilic-lipophilic balance solid phase extraction column to step 1) sample extracting solution of gained purifies, eluent dilute with water and constant volume;
3) adopt liquid chromatography mass combined instrument determination step 2) in the solution of gained whether containing bis-phenol-S: if liquid chromatography mass Selective ion mode scanning result show sample doubtful containing bis-phenol-S time, whether the then ion full scan mass spectrogram of comparative sample and bis-phenol-S standard substance, contain bis-phenol-S in confirmatory sample;
4) if containing bis-phenol-S in confirmatory sample, then by the content of bis-phenol-S in formulae discovery sample.
Step 1) in, when sample is plastic products, with methylene chloride, ultrasonic extraction is carried out to sample, in sample solution, dropwise add methyl alcohol after cooling, to precipitate superpolymer, concentrated by dichloro methane-methanol Rotary Evaporators, controlled pressure is 300bar therebetween again, and bath temperature is 70 DEG C, solution after transfer is concentrated is to volumetric flask, by methanol constant volume, then get this methanol solution, dilute with water constant volume.
Step 1) in, when sample is woodwork, add that methyl alcohol is ultrasonic extracts to obtain sample solution in the sample to which, methyl alcohol is extracted solution Rotary Evaporators to concentrate, controlled pressure is 300bar therebetween, and bath temperature is 70 DEG C, solution after transfer is concentrated is to volumetric flask, by methanol constant volume, then get this methanol solution, dilute with water constant volume.
Step 2) in, by by step 1) the sample extraction solution that obtains adds in advance through the hydrophilic-lipophilic balance solid phase extraction column of first alcohol and water activation, carry out drip washing with 50% methanol aqueous solution, then with methyl alcohol by bis-phenol-S by wash-out on little column packing, eluent water carries out diluting and constant volume.
Step 3) in, the condition determination of liquid chromatography mass combined instrument is:
1) liquid-phase chromatographic column adopts Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, column internal diameter 2.1mm, packing material size 3.5mm;
2) mobile phase is first alcohol and water, and its blending ratio is methyl alcohol: water=35:65, and working time is 10min; Flow rate of mobile phase is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C;
3) mass spectrum ionization source adopts electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry gas temperature is 300 DEG C, and dry gas flow velocity is 10L/min, and capillary voltage is 3000V; Gathering selects full scan and Selective ion mode to scan the pattern of simultaneously carrying out, and full scan scope is m/z 50 ~ 300, and cracking voltage is 270V; Selective ion mode scanning Selective ion mode is m/z 249, and cracking voltage is 190V.
Step 3) in, in the ion full scan mass spectrogram of sample, pay close attention to the characteristic ion m/z 249, m/z 156, m/z 108, the m/z 92 that whether contain bis-phenol-S standard substance, and whether compare their abundance ratios in the sample to which identical with bis-phenol-S standard substance, when containing above-mentioned whole 4 characteristic ions in the gained chromatographic peak of sample chromatogram figure bis-phenol-S position, and abundance ratio identical with bis-phenol-S standard substance time, then in confirmatory sample containing bis-phenol-S.
The present invention compared with the existing technology, beneficial effect is: the present invention is that a kind of sample is by Solvent Extract methods, through Solid phase extraction, liquid chromatography mass combined instrument is used to measure the method for bis-phenol-S in daily necessities, not only assay method fast, simply, and various material sample can be realized, as the Accurate Determining of bis-phenol-S content in plastic products, woodwork, paper products, textile, create the method for bis-phenol-S quantitative and qualitative analysis in unlike material, for unlike material, detectability all can reach 0.1mg/kg.
[accompanying drawing explanation]
Fig. 1 is the liquid chromatogram of bis-phenol-S in embodiment 1;
Fig. 2 is the mass spectrogram of bis-phenol-S in embodiment 2.
[embodiment]
The invention belongs to the mensuration to bis-phenol-S in daily necessities in analytical chemistry field, these daily necessities comprise plastic products, paper products, woodwork and textile etc., its principle is: by the bis-phenol-S Solvent Extract methods in sample, purify through solid phase extraction column, measure content by liquid chromatography mass combined instrument again, by the full scan mass spectrogram characteristic ion of comparative sample and standard substance and abundance ratio, testing result is confirmed.
In the present invention, the condition determination of liquid chromatography mass combined instrument is:
1) liquid-phase chromatographic column adopts Extend C18 liquid-phase chromatographic column, and specification is column length 100 millimeters, column internal diameter 2.1 millimeters, packing material size 3.5 microns;
2) mobile phase is first alcohol and water, and its blending ratio is methyl alcohol: water=35:65, and working time is 10 minutes; Flow rate of mobile phase is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C;
3) mass spectrum ionization source adopts electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry gas temperature is 300 DEG C, and dry gas flow velocity is 10L/min, and capillary voltage is 3000V.Gathering selects full scan and Selective ion mode to scan the pattern of simultaneously carrying out, and full scan scope is m/z 50 ~ 300, and cracking voltage is 270V; Selective ion mode scanning Selective ion mode is m/z 249, and cracking voltage is 190V.
The method of bis-phenol-S in mensuration daily necessities of the present invention, comprises the following steps:
1) sample pretreatment: fritter sample being ground into 2mm × 2mm × 2mm with suitable instrument.Take and pulverize and the sample mixed in right amount, add organic solvent and ultrasonic extraction is carried out to sample.For plastic products, after ultrasonic extraction, another kind of organic solvent must be added in solution, to precipitate superpolymer wherein.Sample extraction solution Rotary Evaporators concentrates, and carries out diluting and constant volume with first alcohol and water;
2) Solid phase extraction: for plastic products and woodwork, uses hydrophilic-lipophilic balance (HLB) solid phase extraction column (HLB pillar) to purify the sample extracting solution through concentrated constant volume.Will by determination step 1) the sample extraction solution that obtains, add in advance through the HLB pillar of first alcohol and water activation, with 50% methanol aqueous solution, impurity carried out drip washing, drain pillar under slightly high pressure after, with methyl alcohol by bis-phenol-S by wash-out on pillar.The eluent dilute with water collected and constant volume;
3) liquid chromatography mass combined instrument determination step 1 is adopted) or 2) content of bis-phenol-S in the solution of gained; When liquid chromatography mass Selective ion mode scanning result show sample doubtful containing bis-phenol-S time, need the ion full scan mass spectrogram of comparative sample and bis-phenol-S standard substance, to confirm that whether measured compound is for bis-phenol-S.If containing bis-phenol-S in confirmatory sample, then by the content of bis-phenol-S in formulae discovery sample.
Above-mentioned steps 1) in, when sample is plastic products, takes and pulverize and the sample mixed, add methylene chloride, 35 DEG C of water bath sonicator extract 30 minutes, are transferred in flat bottom flask after cooling.With a small amount of washed with dichloromethane sample extraction container, cleansing solution is incorporated in flat bottom flask.Jolting limit, limit dropwise adds 100mL methyl alcohol in flat bottom flask, and plastics are precipitated again.Use Rotary Evaporators to concentrate this solution to about 5mL, controlled pressure is 300bar therebetween, and bath temperature is 70 DEG C.Solution after concentrated is transferred to volumetric flask, and is settled to 10mL with methanol dilution.Pipette the solution after 2mL constant volume, dilute with water is also settled to 10mL.
Above-mentioned steps 1) in, when sample is woodwork, paper products and textile etc., takes and pulverize and the sample mixed, add methyl alcohol, ultrasonic extraction 2 times under room temperature, each 30 minutes.Merge extract, use Rotary Evaporators that extract is concentrated into about 5mL, controlled pressure is 300bar therebetween, and bath temperature is 70 DEG C.This solution is shifted, and is settled to 10mL with methanol dilution.Pipette the solution after 2mL constant volume, dilute with water is also settled to 10mL.
Above-mentioned steps 2) in, sample be plastics and woodwork time, Solid phase extraction must be carried out to sample extraction solution.With 3mL methyl alcohol and 3mL water, HLB pillar is activated successively.By by 1) the sample extraction solution of gained is added drop-wise in pillar with the flow velocity of two per second, carries out drip washing with the methanol aqueous solution 2mL of 50% to pillar, after draining pillar, uses 3mL methanol-eluted fractions under slightly high pressure.With water the eluent of collection diluted and be settled to 10mL.
Above-mentioned steps 3) in, when liquid chromatography mass Selective ion mode scanning result show sample doubtful containing bis-phenol-S time, need the ion full scan mass spectrogram of comparative sample and bis-phenol-S standard substance.In ion full scan mass spectrogram, characteristic ion m/z 249, m/z 156, m/z 108, the m/z 92 whether containing bis-phenol-S need be paid close attention to, and whether compare their abundance ratios in the sample to which identical with bis-phenol-S standard substance.When containing above-mentioned whole 4 characteristic ions in the gained chromatographic peak of sample chromatogram figure bis-phenol-S position, and when abundance ratio is identical with bis-phenol-S standard substance, then really contain bis-phenol-S in confirmatory sample.The content of bis-phenol-S in sample is calculated by quantitative equation.
Below in conjunction with specific embodiment, following further illustrating is done to the present invention:
Embodiment 1: the mensuration of bis-phenol-S in plastic cup
1. the preparation of sample:
Plastic cup is cut into the fritter of 2mm × 2mm.Take the sample 1.0g mixed, add 15mL methylene chloride, mix, 35 DEG C of water bath sonicator extract 30 minutes, are transferred in 250mL flat bottom flask by sample solution after sample cooling.With 5mL washed with dichloromethane sample extraction vessel, wash solution is incorporated to flat bottom flask.In 300bar pressure and 70 DEG C of water-baths, rotary evaporation is concentrated into about 5mL.Be transferred to by this solution in 10mL volumetric flask, divide with a small amount of methyl alcohol and wash flat bottom flask several times, wash solution is incorporated to volumetric flask, and with methanol dilution constant volume to scale.Accurately pipette this methanol solution of 2mL in another 10mL volumetric flask, dilute with water is also settled to scale.
2. extract the purification of solution:
Successively with 3mL methyl alcohol and 3mL water activation HLB pillar, by above-mentioned sample extraction solution with the flow velocity upper prop of two per second, with the methanol aqueous solution 2mL of 50%, drip washing is carried out to pillar, wash-out is carried out with 3mL methyl alcohol drain pillar under slightly high pressure after, collect eluent in 10mL volumetric flask, be settled to scale with water.After mixing with 0.22 μm of membrane filtration in sample introduction bottle, analyze with LC/MS, the amount of mensuration bis-phenol-S, by the content of bis-phenol-S in formulae discovery sample.
3. set instrument parameter:
1) liquid chromatograph condition
Liquid chromatograph: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column 2.1mm × 100mm × 3.5 μm
Mobile phase: methyl alcohol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Working time: 10min.
2) Mass Spectrometry Conditions
Ion gun: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry gas temperature: 300 DEG C
Dry gas flow velocity: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V; SIM pattern is 190V
Scan ion: m/z 249
Sweep limit: m/z 50 ~ m/z 300
4. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, sample peak mass spectrogram is compared with standard substance mass spectrogram, confirm that whether chromatographic peak retention time is consistent, in the corresponding full scan mass spectrogram of corresponding chromatographic peak, unanimously whether characteristic ion (m/z 249, m/z 156, m/z 108, m/z 92) and abundance ratio thereof, thus determine whether detect determinand in sample.
2) quantitative
Adopt typical curve quantified by external standard method
5. calculate
The content of bis-phenol-S in extract, carries out the calculating of bis-phenol-S content in sample per sample.
Embodiment 2: the mensuration of bis-phenol-S in wooden chopsticks
1. the preparation of sample:
Wooden chopsticks are cut into the fritter of 2mm × 2mm × 2mm.Take uniform sample 1.0g, add 20ml methyl alcohol, ultrasonic extraction 30 minutes under room temperature, extract solution and filter in 250mL flat bottom flask through filter paper.Sample extracts once with 20mL methyl alcohol again, merges extract.In 300bar pressure and 70 DEG C of water-baths, rotary evaporation is concentrated into about 5mL, is transferred to by solution in 10mL volumetric flask, and divides several to wash flat bottom flask with a small amount of methyl alcohol, and wash solution is incorporated in volumetric flask, and is settled to scale with methanol dilution.Accurately pipette this solution of 2mL in another 10mL volumetric flask, dilute with water is also settled to scale.
2. extract the purification of solution:
Successively with 3mL methyl alcohol and 3mL water activation HLB pillar, by above-mentioned sample extraction solution with the flow velocity upper prop of two per second, with the methanol aqueous solution 2mL of 50%, drip washing is carried out to pillar, wash-out is carried out with 3mL methyl alcohol drain pillar under slightly high pressure after, collect eluent in 10mL volumetric flask, dilute with water is settled to scale.After mixing with 0.22 μm of membrane filtration in sample introduction bottle, analyze with LC/MS, the amount of mensuration bis-phenol-S, by the content of bis-phenol-S in formulae discovery sample.
3. set instrument parameter:
1) liquid chromatograph condition
Liquid chromatograph: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column, 2.1mm × 100mm × 3.5 μm
Mobile phase: methyl alcohol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Working time: 10min.
2) Mass Spectrometry Conditions
Ion gun: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry gas temperature: 300 DEG C
Dry gas flow velocity: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V; SIM pattern is 190V
Scan ion: m/z 249
Sweep limit: m/z 50 ~ m/z 300
4. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, sample peak mass spectrogram is compared with standard substance mass spectrogram, confirm that whether chromatographic peak retention time is consistent, in the corresponding full scan mass spectrogram of corresponding chromatographic peak, unanimously whether characteristic ion (m/z 249, m/z 156, m/z 108, m/z 92) and abundance ratio thereof, thus determine whether detect determinand in sample.
2) quantitative
Adopt typical curve quantified by external standard method
5. calculate
The content of bis-phenol-S in extract, carries out the calculating of bis-phenol-S content in sample per sample.
Embodiment 3: the mensuration of bis-phenol-S in brown cardboard
1. the preparation of sample:
Brown cardboard is cut into the fritter of 2mm × 2mm × 2mm.Take uniform sample 1.0g, add 20ml methyl alcohol, ultrasonic extraction 30 minutes under room temperature, extract solution and filter in 250mL flat bottom flask through filter paper.Sample extracts once with 20mL methyl alcohol again, merges extract.In 300bar pressure and 70 DEG C of water-baths, rotary evaporation is concentrated into about 5mL, is transferred to by solution in 10mL volumetric flask, and divides several to wash flat bottom flask with a small amount of methyl alcohol, and wash solution is incorporated in volumetric flask, and is settled to scale with methanol dilution.Accurately pipette this solution of 2mL in another 10mL volumetric flask, after mixing with 0.22 μm of membrane filtration in sample introduction bottle, analyze with LC/MS, the amount of mensuration bis-phenol-S, by the content of bis-phenol-S in formulae discovery sample.
2. set instrument parameter:
1) liquid chromatograph condition
Liquid chromatograph: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column 2.1mm × 100mm × 3.5 μm
Mobile phase: methyl alcohol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Working time: 10min.
2) Mass Spectrometry Conditions
Ion gun: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry gas temperature: 300 DEG C
Dry gas flow velocity: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V; SIM pattern is 190V
Scan ion: m/z 249
Sweep limit: m/z 50 ~ m/z 300
3. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, sample peak mass spectrogram is compared with standard substance mass spectrogram, confirm that whether chromatographic peak retention time is consistent, in the corresponding full scan mass spectrogram of corresponding chromatographic peak, unanimously whether characteristic ion (m/z 249, m/z 156, m/z 108, m/z 92) and abundance ratio thereof, thus determine whether detect determinand in sample.
2) quantitative
Adopt typical curve quantified by external standard method
4. calculate
The content of bis-phenol-S in extract, carries out the calculating of bis-phenol-S content in sample per sample.
Embodiment 4: the mensuration of bis-phenol-S in red cotton
1. the preparation of sample:
Red cotton is cut into the fritter of 2mm × 2mm × 2mm.Take uniform sample 1.0g, add 20ml methyl alcohol, ultrasonic extraction 30 minutes under room temperature, extract solution and filter in 250mL flat bottom flask through filter paper.Sample extracts once with 20mL methyl alcohol again, merges extract.In 300bar pressure and 70 DEG C of water-baths, concentrated by rotary evaporation is to about 5mL, is transferred to by solution in 10mL volumetric flask, and divides several to wash flat bottom flask with a small amount of methyl alcohol, and wash solution is incorporated in volumetric flask, and is settled to scale with methanol dilution.Accurately pipette this solution of 2mL in another 10mL volumetric flask, after mixing with 0.22 μm of membrane filtration in sample introduction bottle, analyze with LC/MS, the amount of mensuration bis-phenol-S, by the content of bis-phenol-S in formulae discovery sample.
2. set instrument parameter:
1) liquid chromatograph condition
Liquid chromatograph: Agilent 1100
Chromatographic column: Extend C18 liquid-phase chromatographic column 2.1mm × 100mm × 3.5 μm
Mobile phase: methyl alcohol: water=35:65
Flow rate of mobile phase: 0.3mL/min
Chromatogram column temperature: 28 DEG C
Sampling volume: 10 μ L
Working time: 10min.
2) Mass Spectrometry Conditions
Ion gun: electrospray ionization source
Ionization pattern: negative mode
Acquisition mode: SCAN and SIM pattern
Spray needle pressure: 35psi
Dry gas temperature: 300 DEG C
Dry gas flow velocity: 10L/min
Capillary voltage: 3000V
Cracking voltage: SCAN pattern is 270V; SIM pattern is 190V
Scan ion: m/z 249
Sweep limit: m/z 50 ~ m/z 300
3. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, sample peak mass spectrogram is compared with standard substance mass spectrogram, confirm that whether chromatographic peak retention time is consistent, in the corresponding full scan mass spectrogram of corresponding chromatographic peak, unanimously whether characteristic ion (m/z 249, m/z 156, m/z 108, m/z 92) and abundance ratio thereof, thus determine whether detect determinand in sample.
2) quantitative
Adopt typical curve quantified by external standard method
4. calculate
The content of bis-phenol-S in extract, carries out the calculating of bis-phenol-S content in sample per sample.
Claims (10)
1. measure a method of bis-phenol-S in daily necessities, it is characterized in that, comprise the following steps:
1) sample pretreatment: the sample comminution except plastic products, woodwork is mixed, take appropriate, add organic solvent and ultrasonic extraction is carried out to sample, sample extraction solution Rotary Evaporators is concentrated, and carry out diluting and constant volume with first alcohol and water;
2) adopt liquid chromatography mass combined instrument determination step 1) in the solution of gained whether containing bis-phenol-S: if liquid chromatography mass Selective ion mode scanning result show sample doubtful containing bis-phenol-S time, whether the then ion full scan mass spectrogram of comparative sample and bis-phenol-S standard substance, contain bis-phenol-S in confirmatory sample;
3) if containing bis-phenol-S in confirmatory sample, then by the content of bis-phenol-S in formulae discovery sample.
2. the method for claim 1, it is characterized in that: step 1) in, add that methyl alcohol is ultrasonic extracts to obtain sample solution in the sample to which, methyl alcohol is extracted solution Rotary Evaporators to concentrate, controlled pressure is 300bar therebetween, and bath temperature is 70 DEG C, solution after transfer is concentrated is to volumetric flask, by methanol constant volume, then get this methanol solution, dilute with water constant volume.
3. the method for claim 1, is characterized in that, step 2) in, the condition determination of liquid chromatography mass combined instrument is:
1) liquid-phase chromatographic column adopts Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, column internal diameter 2.1mm, packing material size 3.5mm;
2) mobile phase is first alcohol and water, and its blending ratio is methyl alcohol: water=35:65, and working time is 10min; Flow rate of mobile phase is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C;
3) mass spectrum ionization source adopts electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry gas temperature is 300 DEG C, and dry gas flow velocity is 10L/min, and capillary voltage is 3000V; Gathering selects full scan and Selective ion mode to scan the pattern of simultaneously carrying out, and full scan scope is m/z 50 ~ 300, and cracking voltage is 270V; Selective ion mode scanning Selective ion mode is m/z 249, and cracking voltage is 190V.
4. the method for claim 1, it is characterized in that, step 2) in, in the ion full scan mass spectrogram of sample, pay close attention to characteristic ion m/z 249, m/z 156, m/z108, m/z 92 of whether containing bis-phenol-S standard substance, and whether compare their abundance ratios in the sample to which identical with bis-phenol-S standard substance, when containing above-mentioned whole 4 characteristic ions in the gained chromatographic peak of sample chromatogram figure bis-phenol-S position, and abundance ratio identical with bis-phenol-S standard substance time, then in confirmatory sample containing bis-phenol-S.
5. measure a method of bis-phenol-S in daily necessities, it is characterized in that, comprise the following steps:
1) sample pretreatment: the sample comminution of plastic products or woodwork is mixed, take appropriate, add organic solvent and ultrasonic extraction is carried out to sample, sample extraction solution Rotary Evaporators is concentrated, and carry out diluting and constant volume with first alcohol and water;
2) Solid phase extraction: use preactivated hydrophilic-lipophilic balance solid phase extraction column to step 1) sample extracting solution of gained purifies, eluent dilute with water and constant volume;
3) adopt liquid chromatography mass combined instrument determination step 2) in the solution of gained whether containing bis-phenol-S: if liquid chromatography mass Selective ion mode scanning result show sample doubtful containing bis-phenol-S time, whether the then ion full scan mass spectrogram of comparative sample and bis-phenol-S standard substance, contain bis-phenol-S in confirmatory sample;
4) if containing bis-phenol-S in confirmatory sample, then by the content of bis-phenol-S in formulae discovery sample.
6. method as claimed in claim 5, is characterized in that: step 1) in, when sample is plastic products, with methylene chloride, ultrasonic extraction is carried out to sample, in sample solution, dropwise add methyl alcohol after cooling, to precipitate superpolymer, then dichloro methane-methanol Rotary Evaporators is concentrated, controlled pressure is 300bar therebetween, bath temperature is 70 DEG C, shifts the solution after concentrating to volumetric flask, by methanol constant volume, get this methanol solution again, dilute with water constant volume.
7. method as claimed in claim 5, it is characterized in that: step 1) in, when sample is woodwork, add that methyl alcohol is ultrasonic extracts to obtain sample solution in the sample to which, methyl alcohol is extracted solution Rotary Evaporators and concentrate, controlled pressure is 300bar therebetween, bath temperature is 70 DEG C, shifts the solution after concentrating to volumetric flask, by methanol constant volume, get this methanol solution again, dilute with water constant volume.
8. method as claimed in claim 5, it is characterized in that: step 2) in, by by step 1) the sample extraction solution that obtains adds in advance through the hydrophilic-lipophilic balance solid phase extraction column of first alcohol and water activation, drip washing is carried out with 50% methanol aqueous solution, again with methyl alcohol by bis-phenol-S by wash-out on little column packing, eluent water carries out diluting and constant volume.
9. method as claimed in claim 5, is characterized in that, step 3) in, the condition determination of liquid chromatography mass combined instrument is:
1) liquid-phase chromatographic column adopts Extend C18 liquid-phase chromatographic column, and specification is column length 100mm, column internal diameter 2.1mm, packing material size 3.5mm;
2) mobile phase is first alcohol and water, and its blending ratio is methyl alcohol: water=35:65, and working time is 10min; Flow rate of mobile phase is 0.3mL/min, and sampling volume is 10 μ L, and chromatogram column temperature is 28 DEG C;
3) mass spectrum ionization source adopts electrospray ionization source, and negative mode ionizes, and spray needle pressure is 35psi, and dry gas temperature is 300 DEG C, and dry gas flow velocity is 10L/min, and capillary voltage is 3000V; Gathering selects full scan and Selective ion mode to scan the pattern of simultaneously carrying out, and full scan scope is m/z 50 ~ 300, and cracking voltage is 270V; Selective ion mode scanning Selective ion mode is m/z 249, and cracking voltage is 190V.
10. method as claimed in claim 5, it is characterized in that, step 3) in, in the ion full scan mass spectrogram of sample, pay close attention to the characteristic ion m/z 249, m/z 156, m/z 108, the m/z 92 that whether contain bis-phenol-S standard substance, and whether compare their abundance ratios in the sample to which identical with bis-phenol-S standard substance, when containing above-mentioned whole 4 characteristic ions in the gained chromatographic peak of sample chromatogram figure bis-phenol-S position, and abundance ratio identical with bis-phenol-S standard substance time, then in confirmatory sample containing bis-phenol-S.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108535370A (en) * | 2018-03-14 | 2018-09-14 | 杭州市质量技术监督检测院 | The detection method of phenolic compound in a kind of carbonic ester packaging material for food |
| CN113533609A (en) * | 2021-07-06 | 2021-10-22 | 河北大学 | Method for simply analyzing migration volume of common bisphenol substances in plastic product |
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| CN108535370A (en) * | 2018-03-14 | 2018-09-14 | 杭州市质量技术监督检测院 | The detection method of phenolic compound in a kind of carbonic ester packaging material for food |
| CN113533609A (en) * | 2021-07-06 | 2021-10-22 | 河北大学 | Method for simply analyzing migration volume of common bisphenol substances in plastic product |
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