CN106383179B - A method of detection low concentration of styrene - Google Patents
A method of detection low concentration of styrene Download PDFInfo
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- CN106383179B CN106383179B CN201610697848.3A CN201610697848A CN106383179B CN 106383179 B CN106383179 B CN 106383179B CN 201610697848 A CN201610697848 A CN 201610697848A CN 106383179 B CN106383179 B CN 106383179B
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Abstract
A kind of method detecting low concentration of styrene disclosed by the invention, includes the following steps: that (1) calibration curve is drawn；Calibration curve range is reduced to 0.02 μ of μ g/mL~1.0 g/mL, MDL value to be down to 0.2 μ g/g from 5 μ g/g from 0.2 μ of μ g/mL~5.0 g/mL；(2) test liquid is prepared；Sample 1.0g is weighed into spiral cover bottle, 10mL acetone solution is added, is analyzed after 0.22 μm~0.45 μm organic phase filter membrane is crossed after 180r/min~220r/min oscillation 55min~65min by the GC-MS of carrying liqs autosampler；The same step of GC-MS analysis condition (1.4)；(3) result calculates, and calculates concentration of styrene by the styrene peak areas of sample.The present invention improves in terms of test process and test condition two, to achieve the purpose that reduce styrene detection limit.
Description
Technical field
The present invention relates to the detection method of styrene, in particular to a kind of method for detecting low concentration of styrene.
Background technique
At present in polyurethane foam raw material styrene test method there are two main ways:
1) dissolvent residual test method (referring to EPA8260C): 0.5g raw material is weighed, dissolves and extracts by 10mL acetone solvent
It takes, is tested after filtering by GC-MS, for Wastes, styrene detection limit is 0.5 μ g/g；
2) head space test method (referring to EPA5021A): weighing certain content of starting materials and enter in ml headspace bottle, gland sealing, by HS-
GC-MS test, method detection are limited to 5ug/g.
Third party detects the minimum 5ug/g of styrene detection limit that company provides at present, reports N.D. without exception lower than this value
(not detected) (remarks: equal using the minimum detectability of EPA8260C and two kinds of EPA5021A test styrene with reference to SGS
For 5ug/g).
As GB/T 27630 is updated to the standard of enforcing by proposed standard, automobile main frame maker distributes VOC in car
Measure the specific survey that limit value day is increasingly tight, and the clients such as Shanghai GM, Shanghai Volkswagen, upper vapour seat foam VOC gloomy to the river Yan Feng is proposed
Trying index and requirement, also receipts are tight, therefore applicant carries out every batch of pumping to the VOC in raw material and expects inspection monitoring.Due to styrene master
It will be from polyurethane foam raw material POP, it is ensured that styrene volatile quantity does not transfinite value in foaming, needs to guarantee benzene second in POP
Alkene content is in 3ug/g hereinafter, the test method of styrene can not be measured in current polyurethane foam raw material.
Summary of the invention
Technical problem to be solved by the present invention lies in the test methods for styrene in existing polyurethane foam raw material
Styrene-content in POP can not be detected and provide a kind of method for detecting low concentration of styrene, the party in the problem of 3ug/g or less
The styrene detection lower limit of method can achieve 3ug/g or less.
The technical problems to be solved by the invention can be achieved through the following technical solutions:
A method of detection low concentration of styrene includes the following steps:
(1) calibration curve is drawn
(1.1) 0.010 ± 0.001g of styrene is accurately weighed in a 10mL volumetric flask with assay balance, it is fixed with methanol
Hold to scale, is configured to 1000 μ g/mL stock solutions；
(1.2) stock solution of 100 μ L steps (1.1) preparation is accurately pipetted with liquid-transfering gun in 10mL volumetric flask, uses first
Alcohol is settled to scale and obtains intermediate solution, which is 10 μ g/mL；
(1.3) the calibration curve solution for drawing calibration curve is prepared
First calibration curve solution: being added the 10 μ L of intermediate solution of step (1.2) preparation, and 990 μ L of acetone volume is added,
Obtain the first calibration solution that concentration is 0.1 μ g/mL；
Second calibration curve solution: being added the 20 μ L of intermediate solution of step (1.2) preparation, and 980 μ L of acetone volume is added,
Obtain the second calibration solution that concentration is 0.2 μ g/mL；
Third calibration curve solution: the second calibration 100 μ L of solution is added, 900 μ L of acetone volume is added, obtains as 0.02 μ g/
The third of mL calibrates solution；
4th calibration curve solution: being added the 50 μ L of intermediate solution of step (1.2) preparation, and 950 μ L of acetone volume is added,
Obtain the 4th calibration solution that concentration is 0.5 μ g/mL；
5th calibration curve solution: the 4th calibration 100 μ L of solution is added, 900 μ L of acetone volume is added, obtaining concentration is 0.05
The 5th calibration solution of μ g/mL；
6th calibration curve solution: being added the 100 μ L of intermediate solution of step (1.2) preparation, and 900 μ L of acetone volume is added,
Obtain the 6th calibration solution that concentration is 1.0 μ g/mL；
(1.4) drafting of calibration curve
It analyzes step (1.3) calibration solution to obtain each calibration curve solution by the GC-MS of carrying liqs autosampler
Styrene peak areas, using concentration of styrene as abscissa, styrene peak areas is ordinate, draws calibration shown in FIG. 1 song
Line；
GC-MS analysis condition is as follows:
GC chromatographic column: TG-5MS, 60m × 0.25mm × 0.25 μm or equivalent model chromatographic column；
Injector temperature: 200~220 DEG C；
Shunt mode: it does not shunt；
Flow rate of carrier gas: 1.0mL/min；
Temperature program: 35 DEG C of holdings 5min, 10 DEG C/min are warming up to 100 DEG C, keep 1min；10 DEG C/min is warming up to 180
DEG C, keep 1min；10 DEG C/min is warming up to 240 DEG C, keeps 3min；
SCAN mode: 40.0~300.0amu of scanning range, for qualitative；
SIM mode: scanning ion 51,77,78,103,104, wherein 104 be the quantitative characteristic ion of styrene, for fixed
Amount；
Voltage gain: 1 × 105；
(2) test liquid is prepared
Sample 1.0g is weighed into spiral cover bottle, 10mL acetone solution is added, 180r/min~220r/min vibrates 55min
It is analyzed after crossing 0.22 μm of organic phase filter membrane after~65min by the GC-MS of carrying liqs autosampler；GC-MS analysis condition is synchronous
Suddenly (1.4)；
(3) result calculates
Concentration of styrene is calculated by the styrene peak areas of sample, calculation formula is as follows:
Wherein:
ConcsampleThe content (mg/kg) of styrene in sample
C-instrument analysis machine-readable number (μ g/mL)
The last constant volume (mL) of V-
W-sample mass (g)
D.F.-coefficient of dilution
In a preferred embodiment of the invention, the GC-MS of the carrying liqs autosampler analyzes used instrument
Device is Trace1300/ISQ or equivalent model Gas-phase acidity instrument.
The present invention improves in terms of test process and test condition two, to reach the mesh for reducing styrene detection limit
's.The present invention has the advantage that compared with existing dissolvent residual test method
1) sample weighting amount is increased to 1.0g from original 0.5g (sample weighting amount, which increases, excessively high has the incomplete wind of extraction by the present invention
Danger)；
2) calibration curve range is reduced to the 0.02 μ g/mL of μ g/mL~1.0 from 0.2 μ of μ g/mL~5.0 g/mL by the present invention,
MDL value is down to 0.2 μ g/g from 5 μ g/g, reduces 25 times；
3) GC shunt mode is set as not shunt mode by the present invention；
4) SIM&SCAN mode is changed to SIM mode by the present invention；
5) present invention is qualitative on the basis of SCAN mixed mark full scan, and the quantitative single mark styrene of SIM improves device sensitivity；
6) invention increases 1 × 105Voltage gain improves device sensitivity.
Detailed description of the invention
Fig. 1 is styrene calibration curve schematic diagram of the invention.
Specific embodiment
A method of detection low concentration of styrene includes the following steps:
(1) calibration curve is drawn
(1.1) 0.010 ± 0.001g of styrene is accurately weighed in a 10mL volumetric flask with assay balance, it is fixed with methanol
Hold to scale, is configured to 1000 μ g/mL stock solutions；
(1.2) stock solution of 100 μ L steps (1.1) preparation is accurately pipetted with liquid-transfering gun in 10mL volumetric flask, uses first
Alcohol is settled to scale and obtains intermediate solution, which is 10 μ g/mL；
(1.3) preparation of calibration curve solution
The calibration curve solution of each curve point is prepared according to the requirement of table 1；
Table 1
(1.4) drafting of calibration curve
It analyzes step (1.3) calibration curve solution to obtain each curve point by the GC-MS of carrying liqs autosampler
Styrene peak areas, using concentration of styrene as abscissa, styrene peak areas is ordinate, draws calibration curve shown in FIG. 1；
GC-MS analysis condition is as follows:
GC chromatographic column: TG-5MS, 60m × 0.25mm × 0.25 μm or equivalent model chromatographic column；
Injector temperature: 200~220 DEG C；
Shunt mode: it does not shunt；
Flow rate of carrier gas: 1.0mL/min；
Temperature program: 35 DEG C of holdings 5min, 10 DEG C/min are warming up to 100 DEG C, keep 1min；10 DEG C/min is warming up to 180
DEG C, keep 1min；10 DEG C/min is warming up to 240 DEG C, keeps 3min；
SCAN mode: 40.0~300.0amu of scanning range, for qualitative；
SIM mode: scanning ion 51,77,78,103,104, wherein 104 be the quantitative characteristic ion of styrene, for fixed
Amount；
Voltage gain: 1 × 105；
(2) test liquid is prepared
Polyurethane foam material sample 1.0g is weighed into spiral cover bottle, addition 10mL acetone solution, 180r/min~
By the GC- of carrying liqs autosampler after 0.22 μm~0.45 μm organic phase filter membrane excessively after 220r/min oscillation 55min~65min
MS analysis；The same step of GC-MS analysis condition (1.4)；
(3) result calculates
Concentration of styrene is calculated by the styrene peak areas of sample, calculation formula is as follows:
Wherein:
ConcsampleThe content (mg/kg) of styrene in sample
C-instrument analysis machine-readable number (μ g/mL)
The last constant volume (mL) of V-
W-sample mass (g)
D.F.-coefficient of dilution.
It is Trace1300/ISQ or equivalent model gas phase that the GC-MS of carrying liqs autosampler, which analyzes used instrument,
Mass spectrometer.
The accuracy and precision of styrene data is shown in Table 2
Table 2
The present invention and EPA8260C-2006 comparison are shown in Table 3 tables 3
| Test sample | Test method | Styrene (ug/g) | MDL(ug/g) |
| Polyethers sample 1 | Existing method | N.D. | 5 |
| Polyethers sample 2 | Existing method | N.D. | 5 |
| Polyethers sample 1 | Improved method | 2.60 | 0.2 |
| Polyethers sample 2 | Improved method | 2.36 | 0.2 |
Claims (2)
1. a kind of method of low concentration of styrene in detection polyurethane foam raw material, which comprises the steps of:
(1) calibration curve is drawn
(1.1) 0.010 ± 0.001g of styrene is accurately weighed in a 10mL volumetric flask with assay balance, extremely with methanol constant volume
Scale is configured to 1000 μ g/mL stock solutions；
(1.2) stock solution of 100 μ L steps (1.1) preparation is accurately pipetted with liquid-transfering gun in 10mL volumetric flask, it is fixed with methanol
Hold to scale and obtain intermediate solution, which is 10 μ g/mL；
(1.3) the calibration curve solution for drawing calibration curve is prepared
First calibration curve solution: being added the 10 μ L of intermediate solution of step (1.2) preparation, and 990 μ L of acetone volume is added, obtains concentration
First for 0.1 μ g/mL calibrates solution；
Second calibration curve solution: being added the 20 μ L of intermediate solution of step (1.2) preparation, and 980 μ L of acetone volume is added, obtains concentration
Second for 0.2 μ g/mL calibrates solution；
Third calibration curve solution: the second calibration 100 μ L of solution is added, 900 μ L of acetone volume is added, obtains as 0.02 μ g/mL's
Third calibrates solution；
4th calibration curve solution: being added the 50 μ L of intermediate solution of step (1.2) preparation, and 950 μ L of acetone volume is added, obtains concentration
The 4th for 0.5 μ g/mL calibrates solution；
5th calibration curve solution: the 4th calibration 100 μ L of solution is added, 900 μ L of acetone volume is added, obtaining concentration is 0.05 μ g/
The 5th calibration solution of mL；
6th calibration curve solution: being added the 100 μ L of intermediate solution of step (1.2) preparation, and 900 μ L of acetone volume is added, obtains dense
The 6th calibration solution that degree is 1.0 μ g/mL；
(1.4) drafting of calibration curve
Step (1.3) calibration curve solution is analyzed to obtain each calibration curve solution by the GC-MS of carrying liqs autosampler
Styrene peak areas, using concentration of styrene as abscissa, styrene peak areas is ordinate, draws calibration shown in FIG. 1 song
Line；
GC-MS analysis condition is as follows:
GC chromatographic column: TG-5MS, 60m × 0.25mm × 0.25 μm or equivalent model chromatographic column；
Injector temperature: 200~220 DEG C；
Shunt mode: it does not shunt；
Flow rate of carrier gas: 1.0mL/min；
Temperature program: 35 DEG C of holdings 5min, 10 DEG C/min are warming up to 100 DEG C, keep 1min；10 DEG C/min is warming up to 180 DEG C, protects
Hold 1min；10 DEG C/min is warming up to 240 DEG C, keeps 3min；
SCAN mode: 40.0~300.0amu of scanning range, for qualitative；
SIM mode: scanning ion 51,77,78,103,104, wherein 104 be the quantitative characteristic ion of styrene, for quantitative；
Voltage gain: 1 × 105；
(2) test liquid is prepared
Polyurethane foam material sample 1.0g is weighed into spiral cover bottle, 10mL acetone solution, 180r/min~220r/min is added
It is analyzed after crossing 0.22 μm~0.45 μm organic phase filter membrane after oscillation 55min~65min by the GC-MS of carrying liqs autosampler；
The same step of GC-MS analysis condition (1.4)；
(3) result calculates
Concentration of styrene is calculated by the styrene peak areas of sample, calculation formula is as follows:
Wherein:
ConcsampleThe content of styrene in sample, unit mg/kg；
The machine-readable number of C-instrument analysis, unit μ g/mL；
The last constant volume of V-, Unit/mL；
W-sample mass, unit g；
D.F.-coefficient of dilution；
Styrene detection lower limit in the polyurethane foam material sample can achieve 3ug/g or less.
2. the method for low concentration of styrene in a kind of detection polyurethane foam raw material as described in claim 1, which is characterized in that
It is Trace1300/ISQ or equivalent model gaseous mass spectrum that the GC-MS of the carrying liqs autosampler, which analyzes used instrument,
Combined instrument.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608225A (en) * | 2011-01-21 | 2012-07-25 | 中国检验检疫科学研究院 | Determination method of harmful organic substance residue in toy sample |
| CN104280500A (en) * | 2014-10-11 | 2015-01-14 | 云南中烟工业有限责任公司 | Method for detecting styrene in hot melt glue |
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2016
- 2016-08-19 CN CN201610697848.3A patent/CN106383179B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102608225A (en) * | 2011-01-21 | 2012-07-25 | 中国检验检疫科学研究院 | Determination method of harmful organic substance residue in toy sample |
| CN104280500A (en) * | 2014-10-11 | 2015-01-14 | 云南中烟工业有限责任公司 | Method for detecting styrene in hot melt glue |
Non-Patent Citations (4)
| Title |
|---|
| GC-MS Identification of Styrene and Oligomers in Polystyrene Plastic for Milk Packaging;Shirley Abrantes;《Journal of High Resolution Chromatography》;19931231;第113-115页 |
| GC–MS 法测定ABS，SAN 中残留苯乙烯和丙烯腈单体;邵秋荣等;《化学分析计量》;20150131;第24卷(第1期);第80-82页 |
| 聚苯乙烯制品中苯乙烯单体残留量检验方法及GC － MS 确证技术的建立;方从容等;《中国卫生检验杂志》;20140930;第24卷(第18期);第2589-2595页 |
| 顶空－气相色谱－质谱法测定丙烯腈－丁二烯-苯乙烯玩具中丙烯腈单体的含量;谢永萍;《理化检验-化学分册》;20151231;第51卷(第9期);第962-965页 |
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Address after: Shanghai City, Pudong New Area Kang Road 201315 Pudong Kangqiao Industrial Zone No. 669 Applicant after: Yanfeng Daotuo Ann seat Co. Address before: Kang Road, Pudong New Area Kangqiao Industrial Zone of Shanghai City, No. 669, 200120 Applicant before: Shanghai Yanfeng Johnson Controls Seating Co., Ltd. |
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Address after: 201315 No. 669 Kang'an Road, Kangqiao Industrial Zone, Pudong New District, Shanghai Patentee after: Yanfeng international Seat System Co.,Ltd. Address before: 201315 No. 669 Kangan Road, Kangqiao Industrial Zone, Pudong New District, Shanghai Patentee before: YANFENG ADIENT SEATING Co.,Ltd. |
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