CN101769909B - Method for quantitatively detecting perfluorooctanoic acid and salts thereof in fluororubber - Google Patents
Method for quantitatively detecting perfluorooctanoic acid and salts thereof in fluororubber Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 31
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229920001973 fluoroelastomer Polymers 0.000 title claims abstract description 19
- 150000003839 salts Chemical class 0.000 title claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000003480 eluent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000284 extract Substances 0.000 claims description 10
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 238000004458 analytical method Methods 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- 238000009795 derivation Methods 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000001212 derivatisation Methods 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000002500 ions Chemical group 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- -1 adds 200ml then Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- XOCNYZFAMHDXJK-UHFFFAOYSA-N methyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical group COC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XOCNYZFAMHDXJK-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention provides a method for quantitatively detecting perfluorooctanoic acid and salts thereof in fluororubber. The method comprises steps of dissolving, depositing, solid phase extracting and deriving a sample, and then carrying out gas phase chromatography-mass spectrography measurement on the derivative. Counted as S/N=10, the limit of quantitative detection in the method of the invention is 0.04mg/kg, and related coefficient is 0.9991. The method in the invention has the characteristics of fast sample processing, high extraction efficiency, simple derivation step, small impurity interference and high sensitivity.
Description
Technical field
The present invention relates to the method for a kind of detection by quantitative perfluoro caprylic acid and salt thereof, specifically, relate to the method for micro-perfluoro caprylic acid in a kind of detection by quantitative fluororubber and salt thereof.
Background technology
(Perfluorooctanoic Acid is a kind of surfactant of function admirable PFOA) to perfluoro caprylic acid, has good barbotage, is widely used in fields such as fluorine industry, washing agent, fire extinguishing agent.The council of the European Community-parliament of European Union and council point out in " about restrict sales and use perfluorooctane sulfonate PFOS ", and: PFOA may have with PFOS and similarly endangers, therefore, need to continue it is carried out risk assessment, seek relevant substitute and consider to formulate the measure that reduces its harm.
Because fluororubber has the characteristic that good high temperature resistant, oil resistant and the medicine of anti-the number of chemical corrode, thereby is widely used in frontiers of science and technology such as automobile, aviation, guided missile, rocket, aerospace.Along with the progressively understanding of people to PFOA harm, the fluororubber that adopts PFOA to produce by surfactant is substituted by environment-friendly type (not containing or only contain trace P FOA) fluororubber, at present, does not appear in the newspapers as yet for the detection method of the PFOA residual quantity in the fluororubber.Because fluororubber will be dissolved in the micromolecule organic solution, so conventional sample treatment and be not suitable for fluororubber.Though adopt LC/MS method testing for traces PFOA quick, sensitivity is also better, because the instrument costliness is not easy to extensive popularization; Confirm and adopt the GC/MS method to carry out component, and the quantitative sensitivity of SIM method is also higher to sample.
Summary of the invention
The purpose of this invention is to provide a kind of simply, the method for micro-perfluoro caprylic acid and salt thereof in the detection by quantitative fluororubber efficiently.
In order to realize the object of the invention, the method of perfluoro caprylic acid and salt thereof in a kind of detection by quantitative fluororubber of the present invention, it comprise with sample dissolve, the step of sedimentation, Solid-Phase Extraction and derivatization treatment, then the derivatization product is carried out gas chromatography-mass spectrum (GC/MS) and measures.Be specially: the 1) tetrahydrofuran solution of preparation sample, use the deionized water sedimentation then; 2) with the Solid-Phase Extraction column extracting of the solution after the sedimentation, use the nitrogen drying extraction column then,, collect eluent with the dried extraction column of methanol-eluted fractions; 3) in eluent, add sulfuric acid, under 70～80 ℃, derived 60～80 minutes, extract constant volume then with normal hexane; 4) extract to step 3) carries out the GC/MS analysis.
Aforesaid method, the concentration of the tetrahydrofuran solution of sample is 15～25wt% in the step 1).
Aforesaid method is carried out sedimentation with the tetrahydrofuran strong solution of sample in the step 1) with the deionized water of 10～30 times of its volumes, and fluororubber is separated out with flocculent deposit, filters and also collects filtrate; With the deionized water wash precipitation of equivalent, filter and the collection cleansing solution again, merge above-mentioned filtrate and cleansing solution.
Aforesaid method, step 2) the middle CHROMABOND EASY solid-phase extraction column that adopts.
Aforesaid method, the sulfuric acid that adds in eluent in the step 3) is for analyzing the pure concentrated sulphuric acid, and addition is 5～15% of an eluent quality.
Aforesaid method, when carrying out the GC/MS analysis in the step 4), described stratographic analysis temperature is 100 ℃.
Aforesaid method, when carrying out the GC/MS analysis in the step 4), the chromatographic column of employing is DB-1ms, thickness 0.10 μ m.
Aforesaid method, when carrying out the GC/MS analysis in the step 4), the gas chromatograph-mass spectrometer of employing is a U.S. Agilent 6890-5973N gas chromatograph-mass spectrometer, its MS source is the EI source.
Aforesaid method, when carrying out the GC/MS analysis in the step 4), the MS detecting pattern is the SIM method, selected characteristic ion fragment is m/z 59,69,131.
It is quick to adopt method of the present invention to handle sample, the extraction efficiency height, and the derivatization step is simple, and impurity disturbs little, highly sensitive, and favorable reproducibility is applicable to conventional sense as a result.
Description of drawings
Fig. 1 is the equation of linear regression of perfluoro caprylic acid standard items derivant of the present invention;
Fig. 2 is the GC/MS total ions chromatogram of PFOA derivant of the present invention;
Fig. 3 is the different acid system derivatization of the present invention efficient trend map;
Fig. 4 is derivatization efficient trend map under the different temperatures of the present invention;
Fig. 5 is derivatization efficient trend map under the different time of the present invention.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
1, instrument
U.S. Agilent 6892-5973N gas chromatograph-mass spectrometer;
Porous vacuum hydro-extraction device is joined the large volume stopple coupon.
2, chromatographic condition
Chromatographic column: DB-1ms 30m * 0.32mm * 0.10 μ m;
Column temperature: 100 ℃;
Vaporizer: 260 ℃;
Ion gun: 150 ℃;
Level Four bar: 230 ℃;
Sample size: 0.5 μ L, split ratio is 1: 10;
SIM ion: began to monitor m/z 59,69,131 in 11.8 minutes.
3, sample analysis
Quantivative approach adopts the external standard curve method, and the external standard curve adopts preparation perfluoro caprylic acid standard items to record.
The preparation mass concentration is 0,0.1,0.5,1.2,3.5, the perfluoro caprylic acid standard solution of 6mg/L, carry out GC/MS behind the derivatization and analyze, regression curve as shown in Figure 1, related coefficient is 0.9991, equation is as follows:
Y＝24756X
Wherein, Y represents the instrument response peak area; X represents perfluoro caprylic acid methyl esters concentration mg/L.
Each interpolation level is carried out 5 parallel laboratory tests respectively, accurately take by weighing 5g (being accurate to 0.1mg) fluororubber sample at every turn, be dissolved in the 20ml tetrahydrofuran, press the 0.04mg/Kg and the 1mg/Kg level of sample quality and add perfluoro caprylic acid in sample, be put in dark place dissolving 48h, the deionized water that in the tetrahydrofuran strong solution of fluororubber, adds 200ml then, fluororubber is separated out with flocculent deposit, filter and collect filtrate, use 3 washing precipitations of 200ml deionization moisture again, filter and collect cleansing solution, merge above-mentioned filtrate and cleansing solution, the solution that about 400ml is collected with the speed of 10ml/min with the enrichment of CHROMABOND EASY solid-phase extraction column, use the dry extraction column of high pure nitrogen then, with the speed wash-out dried extraction column of 5ml methyl alcohol with 1ml/min, the eluent volume is that the head space bottle of 10ml is collected, use the nitrogen purging eluent, be concentrated into 2ml.In concentrating good eluent, add 0.2g and analyze the pure concentrated sulphuric acid, seal derivatization 60min in the water-bath that is placed on 70 ℃, cooling.Extract with the 2ml normal hexane, constant volume is analyzed with GC/MS, its typical color spectrogram such as Fig. 2, and experimental data is as shown in table 1.
Table 1 adds the recovery and the RSD of level
Experimental result shows, the content that adopts method of the present invention to detect micro-perfluoro caprylic acid in the fluororubber and salt thereof is convenient, accurately and effectively, has esterification efficient preferably and concentration and separation efficient.
The perfluoro caprylic acid aqueous solution of preparation 1.00mg/L, select the CHROMABOND EASY of German MN company and HR-P SPE pillar, BESEP Carbon carbon black pillar respectively, carry out solid phase extraction concentration, with the dry extraction column of high pure nitrogen, with the speed wash-out dried extraction column of 5ml methyl alcohol with 1ml/min, the eluent volume is that the head space bottle of 10ml is collected, and uses the nitrogen purging eluent, is concentrated into 2ml.In concentrating good eluent, add 0.2g and analyze the pure concentrated sulphuric acid, seal derivatization 60min in the water-bath that is placed on 70 ℃, cooling.Extract with the 2ml normal hexane, constant volume is analyzed with GC/MS, carries out determination of recovery rates, and the result is as shown in table 2.
Table 2 Solid-Phase Extraction average recovery rate
By this implementation column as can be seen, adopt CHROMABOND EASY solid phase extraction column can obtain Solid-Phase Extraction efficient preferably.
Acetyl chloride and absolute ethyl alcohol are mixed with derivatization reagent by 1: 20 volume ratio.
Carry out 3 parallel laboratory tests, in the PFOA of 2ml 1.00mg/L methanol solution, add the pure concentrated sulphuric acid of analysis of 10%wt, seal derivatization 60min in the water-bath that is placed on 70 ℃, cooling.Extract with the 2ml normal hexane, constant volume is analyzed with GC/MS.
Carry out 3 parallel laboratory tests, in the PFOA of 2ml 1.00mg/L methanol solution, add the methyl alcohol derivatization reagent of 2ml acetyl chloride acidifying, seal derivatization 60min in the water-bath that is placed on 70 ℃, cooling.Extract with the 2ml normal hexane, constant volume is analyzed with GC/MS.
The derivatization efficient of two kinds of different acid systems sees Table 3, and its trend map as shown in Figure 3.
The derivatization efficient of the different derivatization systems of table 3
As can be seen from Table 3, the derivatization efficient of concentrated sulphuric acid acid system is a little more than the acetyl chloride acid system, but the operation of concentrated sulphuric acid acid system is easier, and reagent is cheap and easy to get, is more suitable for conventional analysis.
Embodiment 4
In the PFOA of 2ml 1.00mg/L methanol solution, add the pure concentrated sulphuric acid of analysis of 10%wt, place 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ water-bath derivatization 60min after the sealing respectively, cooling.Extract with the 2ml normal hexane, constant volume is analyzed with GC/MS.The derivatization efficient of different temperatures as shown in Figure 4.
As can be seen from Figure 4, when being 70～80 ℃, temperature all can obtain derivatization efficient preferably.
Embodiment 5
In the PFOA of 2ml 1.00mg/L methanol solution, add the pure concentrated sulphuric acid of analysis of 10%wt, place 70 ℃ water- bath derivatization 30,40,50,60,70,80min after the sealing respectively, cooling.Extract with the 2ml normal hexane, constant volume is analyzed with GC/MS.The derivatization efficient of different temperatures as shown in Figure 5.
As can be seen from Figure 5, all can obtain derivatization efficient preferably in the time of in 60～80min scope.
Though above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (5)
1. the method for perfluoro caprylic acid and salt thereof in the detection by quantitative fluororubber is characterized in that it comprises the steps:
1) tetrahydrofuran solution of preparation sample, the concentration of the tetrahydrofuran solution of described sample is 15～25wt%, use the deionized water sedimentation of 10～30 times of its volumes then, fluororubber is separated out with flocculent deposit, filter and collect filtrate, with the deionized water wash precipitation of equivalent, filter and the collection cleansing solution again, merge above-mentioned filtrate and cleansing solution;
2) solution after the sedimentation is used CHROMABOND EASY Solid-Phase Extraction column extracting, used the nitrogen drying extraction column then,, collect eluent with the dried extraction column of methanol-eluted fractions;
3) add the pure concentrated sulphuric acid of analysis in eluent, addition is 5～15% of an eluent quality, derives under 70～80 ℃ 60～80 minutes, extracts constant volume then with normal hexane;
4) extract to step 3) carries out the GC/MS analysis.
2. the method for claim 1 is characterized in that, when carrying out the GC/MS analysis in the step 4), described chromatogram column analysis temperature is 100 ℃.
3. method as claimed in claim 1 or 2 is characterized in that, when carrying out the GC/MS analysis in the step 4), the chromatographic column of employing is DB-1ms, thickness 0.10 μ m.
4. method as claimed in claim 1 or 2 is characterized in that, when carrying out the GC/MS analysis in the step 4), the gas chromatograph-mass spectrometer of employing is a U.S. Agilent 6890-5973N gas chromatograph-mass spectrometer, and its MS source is the EI source.
5. the method for claim 1 is characterized in that, when carrying out the GC/MS analysis in the step 4), the MS detecting pattern is the SIM method, and selected characteristic ion fragment is m/z 59,69 and 131.
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| CN104820001B (en) * | 2015-01-08 | 2017-09-26 | 西藏神州瑞霖环保科技股份有限公司 | A kind of method for determining perfluoro caprylic acid content |
| CN104849373A (en) * | 2015-05-27 | 2015-08-19 | 四川大学 | Method for testing residual amount of perfluoro caprylic acid in leather based on precolumn derivatization-high performance liquid chromatography-fluorescence detector |
| CN106290670B (en) * | 2016-09-29 | 2017-12-22 | 浙江万里学院 | A kind of method of column front derivation chromatogram ration analysis perfluorocarboxylic acid compound |
| CN108005641B (en) * | 2017-12-13 | 2023-08-15 | 捷贝通石油技术集团股份有限公司 | Oil-based trace chemical tracer and method for evaluating contribution rate of oil production of each section of horizontal well |
| CN108169380A (en) * | 2018-01-19 | 2018-06-15 | 浙江工业大学 | A kind of deriving method for high performance liquid chromatography detection perfluoro caprylic acid |
| CN109342588A (en) * | 2018-10-19 | 2019-02-15 | 重庆大学 | An optimized method for solid-phase extraction of PFOA from landfill leachate |
| CN109682895A (en) * | 2018-12-18 | 2019-04-26 | 福建省产品质量检验研究院 | A kind of quantitative detecting method of additive |
| CN114577921B (en) * | 2020-12-02 | 2023-12-26 | 中昊晨光化工研究院有限公司 | Method for detecting perfluorooctyl sulfonic acid residues in polytetrafluoroethylene emulsion |
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Owner name: ZHONGHAO CHENGUANG RESEARCH INSTITUTE OF CHEMICAL Free format text: FORMER NAME: ZHONGHAO CHENGUANG CHEMICAL RESEARCH INST. |
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Address after: 643201 Zigong County, Sichuan Province, Chenguang Road, No. 135, Fushun Patentee after: Zhonghao Chenguang Chemical Institute Co., Ltd. Address before: 643201 Zigong County, Sichuan Province, Chenguang Road, No. 135, Fushun Patentee before: Zhonghao Chenguang Chemical Research Inst. |
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Granted publication date: 20111207 Termination date: 20180120 |