CN108872429A - The detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather - Google Patents
The detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather Download PDFInfo
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Abstract
The present invention provides a kind of detection methods of 2- ethylhexyl diphenyl phosphate in leather.The detection method of 2- ethylhexyl diphenyl phosphate, includes the following steps in leather of the invention：1) solvent extraction：Sample treatment is less than to the particle of 10mm at any dimension, is placed in organic solvent and extracts；2) extract liquor thickening filtration, constant volume：Thickening filtration, solvent constant volume will be carried out through step 1) extract liquor extracted；3) it is detected using gas chromatography-mass spectrometry, solution after step 2) constant volume carries out gaschromatographic mass spectrometric analysis, qualitative analysis is carried out by chromatographic retention and mass spectrum, the intensity of quota ion is compared with standard solution, obtains the content of 2- ethylhexyl diphenyl phosphate in sample.The detection method of 2- ethylhexyl diphenyl phosphate in leather of the invention, method is simple, accuracy rate is high, repeated and reproducibility is excellent.
Description
Technical field
The invention belongs to leather detection technique field, it is related to a kind of detection of 2- ethylhexyl diphenyl phosphate in leather
Method.
Background technique
As constantly expanding for leather application field is increasing with demand, the fire as caused by leather also constantly increases
Add.According to statistics, the fire as caused by leather accounts for about more than half of fire sum, especially building home fire, leather kindling
The main reason for sprawling causes ratio shared by fire bigger, and bedding and indoor decoration leather are on fire.Therefore, flourishing
Country just proposes flame-retardancy requirements to leather early in the 60-70 age in 20th century, and has formulated each leather-like flame-retardant standard and method
Rule.
Main substitute of the organophosphorus ester (organophosphate esters, OPEs) as brominated flame-retardant,
It is widely used in plastics, textile, electronic equipment and household items, and yield and dosage are significantly increased.Due to OPEs
Mainly it is added in product with simple physics mode, therefore inevitably via each in its production, use, disposal process
Kind approach enters in environment, has detection in agricultural land soil at present.Compared with PBDEs (polybrominated diphenyl ethers), the overall parent of OPEs
Lipid is weaker, and bioconcentration is relatively weak, but environmental risk is small unlike PBDEs.Biological toxicology is studies have shown that OPEs has
There are neurotoxicity, carcinogenicity, endocrine disrupting, potential threat is caused to human health.Therefore, OPEs is as a kind of novel
Pollutant, problem of environmental pollution have caused the concern of global scholar.Currently, the detection method of OPEs mainly has gas-chromatography
Method (GC), gas chromatography-mass spectrometry (GC-MS), the other joint technology of gas-chromatography-(GC-NPD, GC-EI-MS etc., liquid
Phase chromatography (HPLC), Liquid Chromatography-Mass Spectrometry (HPLC-MS/MS) etc..
CN106908549A is disclosed a kind of while being measured 12 kinds of remaining methods of OPEs in pedotheque, which utilizes
High performance liquid chromatography-mass spectrometry technology combination liquid-liquid extraction and Solid Phase Extraction detect 12 kinds of phosphoric acid esters in pedotheque simultaneously
The remaining method of compound, pedotheque are supervised through liquid-liquid extraction and Solid Phase Extraction with high performance liquid chromatography-mass spectrometry instrument MRM
Measured ion pattern analysis, quantified by external standard method, for this method for most of OPEs, detection limit is low, and stability is good, detects sensitive
Degree is high, for the rapid screening of OPEs in pedotheque, can satisfy 12 kinds of remaining detections of OPEs in pedotheque substantially and wants
It asks；But repeatability and reproducibility when detection method detection is to be improved.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide 2- ethylhexyl diphenylphosphoric acids in a kind of leather
The detection method of ester, method is simple, accuracy rate is high, repeated and reproducibility is excellent.
For this purpose, the present invention uses following technical scheme：
The detection method of 2- ethylhexyl diphenyl phosphate, the detection method include the following steps in a kind of leather：
1) solvent extraction：Sample treatment is less than to the particle of 10mm at any dimension, is placed in organic solvent and extracts,
Wherein, the dosage of the organic solvent and the sample is 1:(10~50) g/mL；
2) extract liquor thickening filtration, constant volume：It will carry out thickening filtration through step 1) extract liquor extracted, solvent constant volume,
Wherein, the mass ratio of the volume after constant volume and sample is (5~20):1mL/g；
3) it is detected using gas chromatography-mass spectrometry, the solution after step 2) constant volume carries out gaschromatographic mass spectrometry
Analysis, obtains the content of 2- ethylhexyl diphenyl phosphate in sample；
Wherein, the chromatographic condition of gas chromatographic analysis is：Temperature programmed control is set as：145~155 DEG C of initial temperature holdings
0.5~1min rises to 305~315 DEG C with 20~30 DEG C/min, keeps 2min or more；Injector temperature is 295~305 DEG C；
Ionization mode in mass spectral analysis is electron impact ionization, 225~235 DEG C of ion source temperature, solvent delay 5~
6min, 280~285 DEG C of makings interface temperature, mode determination is selection ion scan mode qualitative and quantitative analysis, scanning range 50
To 365amu.
In step 1), need targetedly to adjust organic solvent used according to object 2- ethylhexyl diphenyl phosphate
Type, come guarantee extraction validity and completeness, further increase the accuracy rate of detection.Further, described organic molten
Agent is the mixture of one of n-hexane, tetrahydrofuran and methanol or at least two.The mixture is typical but unrestricted
Combination be n-hexane, tetrahydrofuran mixture, the mixture of n-hexane, methanol, the mixture of tetrahydrofuran and methanol, just oneself
The mixture of alkane, tetrahydrofuran and methanol.
In step 1), the time of the extraction is 1~3h, such as extraction time is 1h, 2h, 3h.
In step 2), the detailed process of the thickening filtration is：Extracted by filtration liquid, rotary evaporation, being settled to 10mL must be to
Survey liquid；Blank assay is done simultaneously.
In step 2), the solvent of the constant volume is the organic solvent in step 1), that is, the solvent held is n-hexane, tetrahydro
One of furans and methanol or at least two mixture.
It is selected in present invention, it is desirable to targetedly being adjusted in mass spectral analysis according to object 2- ethylhexyl diphenyl phosphate
Ion and relative abundance ratio are selected, the validity of the accuracy rate and detection that improve detection could be corresponded to, it is preferable that in step 3), matter
Selected described in spectrum analysis the design parameter of ion for：
It selects ion (SIM)：M/z=94,170,250,251,362；Wherein, 362 be quota ion；
Select ion relative abundance ratio：With m/z=94 relative abundance for 100%, then：M/z=170 relative abundance is 12.0
~16.3%；M/z=250 relative abundance is 10.2~13.8%：M/z=251 relative abundance is 9.9~13.3%；M/z=
362 relative abundances are 4.2~12.7%.
In step 3), the chromatographic column of the gas chromatography-mass spectrometry is DB-5MS.
In step 3), carrier gas when analysis is high-purity helium.
As a preferred solution of the present invention, the detection method of 2- ethylhexyl diphenyl phosphate includes following step in leather
Suddenly：
1) solvent extraction：Sample treatment is less than to the particle of 10mm at any dimension, is placed in organic solvent and extracts 1
~3h, wherein the dosage of the organic solvent and the sample is 1:(10~50) g/mL, the organic solvent be n-hexane,
One of tetrahydrofuran and methanol or at least two mixture；
2) extract liquor thickening filtration, constant volume：Thickening filtration will be carried out through step 1) extract liquor extracted, using step 1)
In organic solvent constant volume, wherein the mass ratio of volume and sample after constant volume be (5~20):1mL/g；
3) it is detected using gas chromatography-mass spectrometry, chromatographic column DB-5MS, the solution after step 2) constant volume
Gaschromatographic mass spectrometric analysis is carried out, obtains the content of 2- ethylhexyl diphenyl phosphate in sample；
Wherein, the chromatographic condition of gas chromatographic analysis is：Temperature programmed control is set as：145~155 DEG C of initial temperature holdings
0.5~1min rises to 305~315 DEG C with 20~30 DEG C/min, keeps 2min or more；Injector temperature is 295~305 DEG C；
Ionization mode in mass spectral analysis is electron impact ionization, 225~235 DEG C of ion source temperature, solvent delay 5~
6min, 280~285 DEG C of makings interface temperature, mode determination is selection ion scan mode qualitative and quantitative analysis, scanning range 50
To 365amu.
Further, selected described in mass spectral analysis the design parameter of ion for：
It selects ion (SIM)：M/z=94,170,250,251,362；Wherein, 362 be quota ion；
Select ion relative abundance ratio：With m/z=94 relative abundance for 100%, then：M/z=170 relative abundance is 12.0
~16.3%；M/z=250 relative abundance is 10.2~13.8%：M/z=251 relative abundance is 9.9~13.3%；M/z=
362 relative abundances are 4.2~12.7%.
Compared with prior art, beneficial effects of the present invention are：
The present invention uses gas chromatography-mass spectrometry, by optimizing gas-chromatography, mass spectrographic operating parameter, can accurately examine
The content of 2- ethylhexyl diphenyl phosphate in sample, the retention time of object 2- ethylhexyl diphenyl phosphate
It is short, suitable fragment ion is selected, anti-jamming effectiveness is obvious.Detection method of the invention is simple, accuracy rate is high, it is repeated and
Reproducibility is excellent；It takes 10 parts of same sample to be shredded respectively, extract post analysis, the relative standard deviation of ten test results is maximum
It is 1.36%；Reproducibility test result relative standard deviation is carried out by 5 laboratories respectively for same sample to be up to
1.89%.
Detailed description of the invention
Fig. 1 is after the embodiment sample of the detection method of 2- ethylhexyl diphenyl phosphate in leather of the invention is handled
Solution in 2- ethylhexyl diphenyl phosphate total ion chromatogram；
Fig. 2 is the 2- ethylhexyl diphenyl phosphate mass spectrogram under the corresponding SIM mode of Fig. 1；
Fig. 3 is the peak intensity of the 2- ethylhexyl diphenyl phosphate of the embodiment 1 of invention and the regression curve of concentration.
Specific embodiment
1-3 with reference to the accompanying drawing, and pass through specific embodiment to further illustrate the technical scheme of the present invention.
Instrument and equipment in embodiment：
Gas chromatography mass spectrometry instrument GC/MS：Japanese Shimadzu SHIMADZU GCMS-QP2010Plus, chromatographic column：U.S.'s peace is prompt
Human relations company DB-5MS, length 30m, internal diameter 0.25mm, 0.25 μm of thickness, resistance to extreme temperature：350℃.
The content of 2- ethylhexyl diphenyl phosphate is calculated as follows：
In formula：
XiThe i content of 2- ethylhexyl diphenyl phosphate, unit mg/kg in-sample；
cisThe concentration of 2- ethylhexyl diphenyl phosphate i, unit mg/L in-standard working solution；
The peak intensity of the i of 2- ethylhexyl diphenyl phosphate in A-test solution；
AibThe peak intensity of the i of 2- ethylhexyl diphenyl phosphate in-blank；
V-test solution constant volume, unit mL；
AisThe peak intensity of 2- ethylhexyl diphenyl phosphate i in-standard working solution；
M-sample mass, unit g.
Embodiment 1
1, detecting step：
1) sample preparation：By leather be cut into 5 × 5 × 5mm of size to test sample；
2) organic solvent extracts：It weighs sample 1.0013g and waits for test sample, be placed in ultrasonic extraction bottle, n-hexane is added
30mL, sealing are placed in ultrasound 1 hour in ultrasonic extraction instrument, obtain extract liquor；
3) it is concentrated：Extracted by filtration liquid, rotary evaporation are settled to 10mL and obtain prepare liquid, while doing blank assay；
4) it measures：Sample and blank solution are drawn respectively, and the peak intensity for obtaining 2- ethylhexyl diphenyl phosphate substitutes into
Made regression equation acquires the concentration of 2- ethylhexyl diphenyl phosphate in sample blank solution and test liquid, in turn
Calculate the content of 2- ethylhexyl diphenyl phosphate in leather.
2, instrument condition and parameter：
GC conditions：Carrier gas：High-purity helium, injector temperature：300 DEG C, column flow：2.0mL/min, program liter
Temperature：150 DEG C of reservation 1min are warming up to 310 DEG C with 20 DEG C/min, 310 DEG C of reservation 3min.
Mass Spectrometry Conditions：Ionization mode：Electron impact ionization, ion source temperature：230 DEG C, solvent delay 5.5min, makings connects
Mouth temperature：280 DEG C, mode determination：Select ion scan mode qualitative and quantitative analysis.
3, the qualitative and quantitative analysis of 2- ethylhexyl diphenyl phosphate：
The reservation of 2- ethylhexyl diphenyl phosphate total ion chromatogram under above-mentioned instrument condition and Parameter Conditions
Time is Rt=9.45min, is selected ion (SIM)：M/z=94,170,250,251,362, wherein 362 be quota ion.
Fig. 1 is the total ion chromatography of 2- ethylhexyl diphenyl phosphate in the solution after the embodiment of the present invention sample treatment
Figure.
Fig. 2 is the 2- ethylhexyl diphenyl phosphate mass spectrogram under SIM mode.
Fig. 3 is the peak intensity of 2- ethylhexyl diphenyl phosphate and the regression curve of concentration, calibration curve y=
17483x+120。
Specification Curve of Increasing
The 2- ethylhexyl diphenyl phosphate standard items of 100mg/L are named as A, organic solvent is done with n-hexane, are used
100mL and 10mL volumetric flask is prepared, as shown in table 1：
Table 1
The working curve of 2- ethylhexyl diphenyl phosphate is done with A1, A2, A3, A4, A5 and six concentration points of blank, it is right
The standard sample concentration and peak intensity answered such as table 2, for the linear requirements of working curve 0.98 or more, target production is not added in blank spot
Object 2- ethylhexyl diphenyl phosphate.
Table 2
| Solution numbers after dilution | Concentration mg/L | Peak intensity |
| A1 | 0 | 150 |
| A2 | 0.5 | 9532 |
| A3 | 1 | 17714 |
| A4 | 2 | 34020 |
| A5 | 5 | 83578 |
| Blank | 10 | 177093 |
The concentration that the calibration curve being used as measures 2- ethylhexyl diphenyl phosphate in solution is 7.361mg/L, sample
Middle 2- ethylhexyl diphenyl phosphate content is 73.83mg/kg.10 parts of same sample are taken to be shredded respectively, extract post analysis,
The content obtained in final sample is respectively：73.09,73.91,75.02,73.17,73.89,74.22,74.01,74.55,
72.35,73.97mg/kg, the relative standard deviation of ten test results are 1.04%, it is seen that the weight of detection method of the invention
Renaturation is fine.It is as follows that reproducibility test result difference has been carried out by 5 laboratories respectively for same sample：72.21,73.84,
74.02,73.17,75.73mg/kg, relative standard deviation 1.75%, it is seen that detection method of the invention is in different experiments
Also good reproducibility is achieved between room.
Embodiment 2
The present embodiment is the difference from embodiment 1 is that organic solvent is tetrahydrofuran；
The concentration that the calibration curve being used as measures 2- ethylhexyl diphenyl phosphate in solution is 7.315mg/L, sample
Middle 2- ethylhexyl diphenyl phosphate content is 73.30mg/kg.10 parts of same sample are taken to be shredded respectively, extract post analysis,
The content obtained in final sample is respectively：72.92,73.84,74.02,73.17,75.13,74.02,73.17,75.43,
72.98,74.21mg/kg, the relative standard deviation of ten test results are 1.18%, it is seen that the weight of detection method of the invention
Renaturation is fine.It is as follows that reproducibility test result difference has been carried out by 5 laboratories respectively for same sample：71.63,73.88,
74.11,73.17,75.43mg/kg, relative standard deviation 1.89%, it is seen that detection method of the invention is in different experiments
Also good reproducibility is achieved between room.
Embodiment 3
The present embodiment is the difference from embodiment 1 is that organic solvent is methanol；
The concentration that the calibration curve being used as measures 2- ethylhexyl diphenyl phosphate in solution is 7.301mg/L, sample
Middle 2- ethylhexyl diphenyl phosphate content is 72.94mg/kg.10 parts of same sample are taken to be shredded respectively, extract post analysis,
The content obtained in final sample is respectively：76.07,73.89,74.26,73.32,75.28,74.1773.32,75.58,
73.13,74.36mg/kg, the relative standard deviation of ten test results are 1.36%, it is seen that the weight of detection method of the invention
Renaturation is fine.It is as follows that reproducibility test result difference has been carried out by 5 laboratories respectively for same sample：71.66,73.21,
74.04,73.10,75.35mg/kg, relative standard deviation 1.85%, it is seen that detection method of the invention is in different experiments
Also good reproducibility is achieved between room.
Comparative example 1
This comparative example is the difference from embodiment 1 is that organic solvent is acetone；
Measuring 2- ethylhexyl diphenyl phosphate in solution is to measure 2- ethylhexyl diphenyl phosphate in solution
Concentration is 7.324mg/L, and 2- ethylhexyl diphenyl phosphate content is 73.17mg/kg in sample.Take 10 parts points of same sample
It does not shredded, extract post analysis, the content obtained in final sample is respectively：75.70,73.91,74.46,73.72,75.98,
74.47,73.40,75.63,73.53,74.41mg/kg, the relative standard deviation of ten test results are 1.27%, it is seen that this
Repeatability is good for the detection method of invention.Reproducibility test result point has been carried out by 5 laboratories respectively for same sample
It is not as follows：72.11,73.15,74.14,73.37,75.51mg/kg, relative standard deviation 1.72%.
Comparative example 2
This comparative example is the difference from embodiment 1 is that organic solvent is methylene chloride；
The concentration for measuring 2- ethylhexyl diphenyl phosphate in solution is 7.305mg/L, 2- ethylhexyl two in sample
Phosphenylic acid ester content is 73.27mg/kg.It takes 10 parts of same sample shredded respectively, extract post analysis, obtains in final sample
Content be respectively：75.66,74.08,74.53,73.79,76.06,74.54,73.47,75.71,73.60,74.48mg/
Kg, the relative standard deviation of ten test results are 1.24%, it is seen that repeatability is good for detection method of the invention.For same
It is as follows that a sample has carried out reproducibility test result difference by 5 laboratories respectively：74.67,76.88,77.92,76.60,
79.37mg/kg, relative standard deviation 1.74%.
Comparative example 3
This comparative example is the difference from embodiment 1 is that organic solvent is chloroform；
The concentration for measuring 2- ethylhexyl diphenyl phosphate in solution is 7.322mg/L, 2- ethylhexyl two in sample
Phosphenylic acid ester content is 73.98mg/kg.It takes 10 parts of same sample shredded respectively, extract post analysis, obtains in final sample
Content be respectively：75.74,74.16,74.61,73.66,76.13,74.62,73.40,75.78,73.68,74.56mg/
Kg, the relative standard deviation of ten test results are 1.29%, it is seen that repeatability is good for detection method of the invention.For same
It is as follows that a sample has carried out reproducibility test result difference by 5 laboratories respectively：74.99,76.15,77.18,75.87,
78.61mg/kg, relative standard deviation 1.81%.
Above embodiments are only used to illustrate method detailed of the invention, and the invention is not limited to above-mentioned method detaileds, i.e.,
Do not mean that the invention must rely on the above detailed methods to implement.It should be clear to those skilled in the art, right
Any improvement of the invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection of concrete mode
Deng all of which fall within the scope of protection and disclosure of the present invention.
Claims (9)
1. the detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather, which is characterized in that the detection method includes
Following steps：
1) solvent extraction：Sample treatment is less than to the particle of 10mm at any dimension, is placed in organic solvent and extracts,
In, the dosage of the organic solvent and the sample is 1:(10~50) g/mL；
2) extract liquor thickening filtration, constant volume：Thickening filtration, solvent constant volume will be carried out through step 1) extract liquor extracted, wherein
The mass ratio of volume and sample after constant volume is (5~20):1mL/g；
3) it is detected using gas chromatography-mass spectrometry, the solution after step 2) constant volume carries out gaschromatographic mass spectrometry point
Analysis, obtains the content of 2- ethylhexyl diphenyl phosphate in sample；
Wherein, the chromatographic condition of gas chromatographic analysis is：Temperature programmed control is set as：145~155 DEG C of initial temperature holdings 0.5~
1min rises to 305~315 DEG C with 20~30 DEG C/min, keeps 2min or more；Injector temperature is 295~305 DEG C；
Ionization mode in mass spectral analysis is electron impact ionization, 225~235 DEG C of ion source temperature, 5~6min of solvent delay,
280~285 DEG C of makings interface temperature, mode determination be selection ion scan mode qualitative and quantitative analysis, scanning range 50 to
365amu。
2. detection method according to claim 1, which is characterized in that in step 1), the organic solvent is n-hexane, four
One of hydrogen furans and methanol or at least two mixture.
3. detection method according to claim 1 or 2, which is characterized in that in step 1), time of the extraction is 1~
3h。
4. detection method described in one of -3 according to claim 1, which is characterized in that in step 2), the tool of the thickening filtration
Body process is：Extracted by filtration liquid, rotary evaporation are settled to the prepare liquid of 10mL.
5. detection method described in one of -4 according to claim 1, which is characterized in that in step 2), the solvent of the constant volume is
Organic solvent in step 1).
6. detection method described in one of -5 according to claim 1, which is characterized in that select the tool of ion described in mass spectral analysis
Body parameter is：
It selects ion (SIM)：M/z=94,170,250,251,362；Wherein, 362 be quota ion；
Select ion relative abundance ratio：With m/z=94 relative abundance for 100%, then：M/z=170 relative abundance be 12.0~
16.3%；M/z=250 relative abundance is 10.2~13.8%：M/z=251 relative abundance is 9.9~13.3%；M/z=362
Relative abundance is 4.2~12.7%.
7. detection method described in one of -6 according to claim 1, which is characterized in that in step 3), the gaschromatographic mass spectrometry
The chromatographic column of combined instrument is DB-5MS.
8. detection method described in one of -7 according to claim 1, which is characterized in that in step 3), carrier gas when analysis is height
Pure helium.
9. detection method described in one of -8 according to claim 1, which is characterized in that the detection method includes the following steps：
1) solvent extraction：Sample treatment is less than to the particle of 10mm at any dimension, be placed in organic solvent extraction 1~
3h, wherein the dosage of the organic solvent and the sample is 1:(10~50) g/mL, the organic solvent are n-hexane, four
One of hydrogen furans and methanol or at least two mixture；
2) extract liquor thickening filtration, constant volume：Thickening filtration will be carried out through step 1) extract liquor extracted, using in step 1)
Organic solvent constant volume, wherein the mass ratio of volume and sample after constant volume is (5~20):1mL/g；
3) it is detected using gas chromatography-mass spectrometry, chromatographic column DB-5MS, the solution after step 2) constant volume carries out
Gaschromatographic mass spectrometric analysis obtains the content of 2- ethylhexyl diphenyl phosphate in sample；
Wherein, the chromatographic condition of gas chromatographic analysis is：Temperature programmed control is set as：145~155 DEG C of initial temperature holdings 0.5~
1min rises to 305~315 DEG C with 20~30 DEG C/min, keeps 2min or more；Injector temperature is 295~305 DEG C；
Ionization mode in mass spectral analysis is electron impact ionization, 225~235 DEG C of ion source temperature, 5~6min of solvent delay,
280~285 DEG C of makings interface temperature, mode determination be selection ion scan mode qualitative and quantitative analysis, scanning range 50 to
365amu；
Selected described in mass spectral analysis the design parameter of ion for：
It selects ion (SIM)：M/z=94,170,250,251,362；Wherein, 362 be quota ion；
Select ion relative abundance ratio：With m/z=94 relative abundance for 100%, then：M/z=170 relative abundance be 12.0~
16.3%；M/z=250 relative abundance is 10.2~13.8%：M/z=251 relative abundance is 9.9~13.3%；M/z=362
Relative abundance is 4.2~12.7%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810699321.3A CN108872429A (en) | 2018-06-29 | 2018-06-29 | The detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| SU1525557A1 (en) * | 1987-12-28 | 1989-11-30 | Челябинский государственный университет | Method of determining di-2-ethylhexylphosphate |
| CN102628843A (en) * | 2012-03-14 | 2012-08-08 | 浙江出入境检验检疫局检验检疫技术中心 | Gas chromatography for detection of phosphate fire-retardant plasticizer in textile |
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