CN102507783A - Method for detecting short-chain chlorinated paraffins (SCCPs) - Google Patents
Method for detecting short-chain chlorinated paraffins (SCCPs) Download PDFInfo
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- CN102507783A CN102507783A CN201110354021XA CN201110354021A CN102507783A CN 102507783 A CN102507783 A CN 102507783A CN 201110354021X A CN201110354021X A CN 201110354021XA CN 201110354021 A CN201110354021 A CN 201110354021A CN 102507783 A CN102507783 A CN 102507783A
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Abstract
The invention discloses a method for detecting short-chain chlorinated paraffins (SCCPs). The method comprises the following steps of: pretreating a sample by an ultrasonic extraction method; filtering extract liquor in a chromatograph bottle, and performing instrumental analysis; detecting the SCCPs by a gas chromatography-mass spectrometry technology; allowing the pretreated sample to enter a chromatographic column from a sample inlet of a gas chromatograph-mass spectrometer, and performing programmed heating; and allowing sample components which are separated by the chromatographic column to enter a mass spectrum detection part of the gas chromatograph-mass spectrometer through a port, and bombarding an ion source which is subjected to mass spectrum detection by using electrons. According to the method, an instrument is low in price and safe; an analysis method is accurate and quick and low in interference; and the SCCPs can be separated optimally.
Description
Technical field
The present invention relates to a kind of detection method of chlorinated paraffin, particularly relate to a kind of method with gas chromatography-mass spectrography technology for detection short chain chlorinated paraffin.
Background technology
Chlorinated paraffin is a kind of long-chain normal paraffin of many chloros, and chain length can change from C10 to C30, and chlorinty is between 30wt% ~ 70 wt%.According to the difference of chain length, chlorinated paraffin can be divided into short chain (C10-C13), medium chain (C14-C17) and long-chain (C18-C30) chlorinated paraffin.Chlorinated paraffin is to get through n-alkane in the petroleum fraction and chlorine molecular reaction, is the potpourri of a series of isomerss.It is owing to have better chemical stability, suitable viscosity, anti-flammability, lower performances such as vapour pressure preferably, the lubricant of therefore main adjuvant, metal processing as cutting fluid, and in plastics, paint and encapsulant, be used as fire retardant.Discover that chlorinated paraffin particularly short chain and medium chain chlorinated paraffin has toxic and bioaccumulation property to aquatic animal, even human body is had potential carcinogenicity.For this reason; Some internationalization is organized with short chain chlorinated paraffin and the material of medium chain chlorinated paraffin for preferentially forbidding; The highest limiting the quantity of in having stipulated to use; Instruction is forbidden selling and working concentration surpasses the Metalworking fluid or the leather fat of 1% short chain chlorinated paraffin like the 2002/45/EC of European Union, and the PoHS instruction of Norway has stipulated that the ceiling value of in consumer products contained medium chain chlorinated paraffin is 0.1%.So, need carry out qualitative and detection by quantitative to the chlorinated paraffin in the product, make it to meet laws and regulations requirement.Yet China does not still have the standard detecting method of chlorinated paraffin at present, and the detection method of setting up quick, accurate, highly sensitive chlorinated paraffin in China is extremely urgent.
At present; Detecting short chain chlorinated paraffin (SCCPs) mainly is to carry out the pre-treatment extraction with the method for Suo Shi extracting earlier; Use gas chromatography (GC-ECD) method of electron capture detector to detect again, perhaps use the method for high selectivity and highly sensitive electron capture negative ion mass spectrum and liquid chromatography coupling (LC-MS) to detect, the former the detectable concentration range of linearity is narrow; Measure poor reproducibility as a result, qualitative weak effect when having interference; The latter detects the cost costliness, and needs reacting gas; Defectives such as and there is complicated operation in the method for Suo Shi extracting, and time-consuming and organic reagent consumption is big.
Summary of the invention
The present invention proposes a kind of can be simply quick with the gas chromatography-mass spectrography technology, and the accurate detection method of the short chain chlorinated paraffin in the qualitative, quantitative product, and is long to solve the present pre-treatment time, complex operation, technical matterss such as poor anti jamming capability.
The present invention adopts following technical scheme to realize: a kind of detection method of short chain chlorinated paraffin, it is characterized in that, and may further comprise the steps:
The sample that takes by weighing 0.1 ~ 5g is put into container, adds 5 ~ 50ml organic reagent;
The ultrasound bath of said vesse being put into 20 ~ 100 ℃ carries out pre-treatment with 20% ~ 100% power ultrasonic extraction S hour to sample;
After treating the cooling of above-mentioned extract, be filled into 0.2 ~ 0.5 micron filter and carry out instrumental analysis in the chromatogram bottle;
Gas chromatography and mass spectrometric hyphenated technique detect the short chain chlorinated paraffin; Injector temperature to gas chromatography and GC-MS is set at 100 ~ 300 ℃; Flow rate of carrier gas is set at 0.1 ~ 2ml/min, and chromatographic column is selected polarity, low pole or non-polar column, and sampling volume is set at 10 ~ 50 μ l;
To pass through the sample said gas chromatography of process of pre-treatment and the injection port of GC-MS and get in the said chromatographic column, and carry out temperature programme, initial temperature is 40 ~ 130 ℃, keeps 0 ~ 10 minute; Be warmed up to 200 ~ 330 ℃ with 5 ~ 30 ℃/minute speed then, kept 0 ~ 10 minute;
Said each component of sample of being separated by chromatographic column is partly carried out Mass Spectrometer Method through the Mass Spectrometer Method that interface gets into said gas chromatography and GC-MS, and the ion gun of said Mass Spectrometer Method adopts electron impact ion source.
More excellent, said organic reagent is the wherein potpourri of one or more solvents of benzene class, alkyl chloride hydro carbons, ketone, ester class and alcohols solvent.
More excellent, said organic reagent is a toluene, normal hexane, and benzene, tetrahydrofuran, chloroform and acetone is the potpourri of one or more solvents wherein.
More excellent, said S hour is 0.5 ~ 24 hour.
More excellent, said S hour is 0.5 ~ 10 hour.
More excellent, the retention time of initial temperature and end temp is 2 minutes.
More excellent, said chromatographic column is selected nonpolar capillary column.
Compared with prior art, the present invention has following beneficial effect: adopt organic reagent with the mode that the ultrasonic extraction method of heating combines sample to be carried out pre-treatment, make sample extraction effect in pre-treatment efficiently quick, extract abundant simple operation; Adopt the gas chromatography-mass spectrography technology to carry out qualitative and quantitative detection, antijamming capability is strong; Select suitable chromatographic column, control suitable moving phase and set suitable flow, can carry out optimized separation short chain chlorinated paraffin (SCCPs).
Description of drawings
Fig. 1 is the chromatogram of the short chain chlorinated paraffin that detected of the embodiment of the invention 1.
Fig. 2 is the canonical plotting of the short chain chlorinated paraffin that detected of the embodiment of the invention 1.
Embodiment
Do further to detail below in conjunction with the described most preferred embodiment of accompanying drawing.
The detection method of short chain chlorinated paraffin of the present invention may further comprise the steps:
Earlier the solid sample of test being processed the length of side is 2 ~ 5 millimeters sample, and the sample that takes by weighing 0.1 ~ 5g is again put into container, adds 5 ~ 50ml organic reagent; This organic reagent is the wherein potpourri of one or more solvents of benzene class, alkyl chloride hydro carbons, ketone, ester class and alcohols solvent; Like toluene, normal hexane, benzene; Tetrahydrofuran, chloroform and acetone.
The ultrasound bath of said vesse being put into 20 ~ 100 ℃ was with 20% ~ 100% power ultrasonic extraction 0.5 ~ 24 hour, and its Best Times is 0.5 ~ 10 hour;
After treating the cooling of above-mentioned extract, be filled into 0.2 ~ 0.5 micron filter and carry out instrumental analysis in the chromatogram bottle;
Gas chromatography and mass spectrometric hyphenated technique detect the short chain chlorinated paraffin; Injector temperature to gas chromatography and GC-MS is set at 100 ~ 300 ℃; Flow rate of carrier gas is set at 0.1 ~ 2ml/min; Chromatographic column is selected polarity, low pole or non-polar column, and its best chromatographic column is nonpolar capillary column, and sampling volume is set at 10 ~ 50 μ l;
To pass through the sample said gas chromatography of process of pre-treatment and the injection port of GC-MS and get in the said chromatographic column, and carry out temperature programme, initial temperature is 40 ~ 130 ℃, keeps 0-10 minute, the best maintenance 2 minutes; Be warmed up to 200-330 ℃ with 5-30 ℃/minute speed then, kept 0-10 minute, the best maintenance 2 minutes.
Said each component of sample of being separated by chromatographic column is partly carried out Mass Spectrometer Method through the Mass Spectrometer Method that interface gets into said gas chromatography and GC-MS, and the ion gun of said Mass Spectrometer Method adopts electron impact ion source.
It is following to use the specific embodiment that above-mentioned test condition does:
Embodiment 1
With toluene is solvent, and preparation short chain chlorinated paraffin series standard solution carries out gas chromatography and GC-MS analyzing and testing by said experiment condition.Fig. 1 is the chromatogram of short chain chlorinated paraffin.With general objective peak response value concentration is mapped,, set up the typical curve of short chain chlorinated paraffin according to 3 horizontal survey results of standard solution; As shown in Figure 2; Horizontal ordinate is represented the concentration of short chain chlorinated paraffin standard solution, and ordinate is represented the gas chromatography peak area response, and the funtcional relationship of gained typical curve is Y=7373X+24232; Wherein X represents the concentration of short chain chlorinated paraffin; Y represents the response of gas chromatography peak area, and its linearly dependent coefficient is 0.9999, and this shows that this typical curve has the better linearity correlativity.
Embodiment 2
Accurately take by weighing the sample that 1.0g processes and put into container, add 20mL toluene, the ultrasound bath of putting into 23 ℃ (room temperatures) was with 100% power ultrasonic extraction 1 hour.After extraction finishes, take out container after cooling, 0.45 micron filter is filled into and carries out instrumental analysis in the chromatogram bottle excessively.Sample has been done three parallel sample, and test number is respectively a1, a2 and a3, and analysis result is seen table 1, and to first parallel sample (test number a1) replication 4 times, analysis result is seen table 2.Know that by table 1 relative standard deviation (RSD) of parallel appearance is 2.37%.Know that by table 2 relative standard deviation of reperformance test is 1.01%.
The test content of short chain chlorinated paraffin in table 1 sample
The test of short chain chlorinated paraffin repeatability in table 2 sample
| Number of times | 1 | 2 | 3 | 4 | Mean value | RSD% |
| a1 | 824 | 809 | 805 | 813 | 813 | 1.01 |
Embodiment 3
Standard solution is joined respectively in the sample, experimentize according to said sample pre-treating method and instrumental analysis detection method.Each sample is done 3 horizontal surveies and is averaged, according to actual addition and measured result, and the recovery of calculation sample, experimental result is seen table 3.Can know that by table 3 recovery of sample reaches more than 92.8%, show that the used test method is applicable to the test of short chain chlorinated paraffin.
The recovery of table 3 sample
The above is merely preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the detection method of a short chain chlorinated paraffin is characterized in that, may further comprise the steps:
The sample that takes by weighing 0.1 ~ 5g is put into container, adds 5 ~ 50ml organic reagent;
The ultrasound bath of said vesse being put into 20 ~ 100 ℃ carries out pre-treatment with 20% ~ 100% power ultrasonic extraction S hour to sample;
After treating the cooling of above-mentioned extract, be filled into 0.2 ~ 0.5 micron filter and carry out instrumental analysis in the chromatogram bottle;
Gas chromatography and mass spectrometric hyphenated technique detect the short chain chlorinated paraffin; Injector temperature to gas chromatography and GC-MS is set at 100 ~ 300 ℃; Flow rate of carrier gas is set at 0.1 ~ 2ml/min, and chromatographic column is selected polarity, low pole or non-polar column, and sampling volume is set at 10 ~ 50 μ l;
To pass through the sample said gas chromatography of process of pre-treatment and the injection port of GC-MS and get in the said chromatographic column, and carry out temperature programme, initial temperature is 40 ~ 130 ℃, keeps 0 ~ 10 minute; Be warmed up to end temp with 5 ~ 30 ℃/minute speed then, this end temp is 200 ~ 330 ℃, keeps 0 ~ 10 minute;
Said each component of sample of being separated by chromatographic column is partly carried out Mass Spectrometer Method through the Mass Spectrometer Method that interface gets into said gas chromatography and GC-MS, and the ion gun of said Mass Spectrometer Method adopts electron impact ion source.
2. the detection method of short chain chlorinated paraffin according to claim 1 is characterized in that: said organic reagent is the wherein potpourri of one or more solvents of benzene class, alkyl chloride hydro carbons, ketone, ester class and alcohols solvent.
3. the detection method of short chain chlorinated paraffin according to claim 1 and 2 is characterized in that: said organic reagent is a toluene, normal hexane, and benzene, tetrahydrofuran, chloroform and acetone is the potpourri of one or more solvents wherein.
4. the detection method of short chain chlorinated paraffin according to claim 1 is characterized in that: said S hour is 0.5 ~ 24 hour.
5. according to the detection method of claim 1 or 4 described short chain chlorinated paraffins, it is characterized in that: said S hour is 0.5 ~ 10 hour.
6. the detection method of short chain chlorinated paraffin according to claim 1 is characterized in that: the retention time of affiliated initial temperature and end temp is 2 minutes.
7. the detection method of short chain chlorinated paraffin according to claim 1 is characterized in that: said chromatographic column is selected nonpolar capillary column.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103353500A (en) * | 2013-07-12 | 2013-10-16 | 深圳信测标准技术服务股份有限公司 | Detection method for medium short-chain chlorinated paraffin in plastic and environment |
| CN103837628A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Method for detecting content of short-chain chlorinated paraffin in chlorinated paraffin product |
| CN103837623A (en) * | 2012-11-23 | 2014-06-04 | 大连方达理化环境科技有限公司 | Short-chain chlorinated paraffin online hydrogenation unit combined with gas chromatograph and application thereof |
| CN103852550A (en) * | 2014-03-26 | 2014-06-11 | 昆山洛丹伦生物科技有限公司 | Detecting method for chlorinated paraffin in plastic component of electronic element |
| CN104181266A (en) * | 2013-05-24 | 2014-12-03 | 中国科学院大连化学物理研究所 | Dechlorination deuterium-added gas chromatography-mass spectrometry method for short-chain and medium-chain chlorinated paraffin |
| CN106483239A (en) * | 2015-11-25 | 2017-03-08 | 衡阳市骏杰化工有限公司 | A kind of detection method for producing short chain chlorinated paraffin in waste liquid |
| CN106799195A (en) * | 2015-11-25 | 2017-06-06 | 衡阳市骏杰化工有限公司 | It is a kind of to determine the carbon skeleton reaction bushing pipe that chlorinated paraffin content is used |
| CN115452931A (en) * | 2022-08-04 | 2022-12-09 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Chlorinated paraffin analysis method based on adsorbent assistance-atmospheric pressure chemical ionization source-high resolution mass spectrum |
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2011
- 2011-11-10 CN CN201110354021XA patent/CN102507783A/en active Pending
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103837628A (en) * | 2012-11-23 | 2014-06-04 | 中国科学院大连化学物理研究所 | Method for detecting content of short-chain chlorinated paraffin in chlorinated paraffin product |
| CN103837623A (en) * | 2012-11-23 | 2014-06-04 | 大连方达理化环境科技有限公司 | Short-chain chlorinated paraffin online hydrogenation unit combined with gas chromatograph and application thereof |
| CN103837623B (en) * | 2012-11-23 | 2016-02-10 | 大连方达理化环境科技有限公司 | With the online hydrogenation plant of short chain chlorinated paraffin and the application of gas chromatograph coupling |
| CN104181266A (en) * | 2013-05-24 | 2014-12-03 | 中国科学院大连化学物理研究所 | Dechlorination deuterium-added gas chromatography-mass spectrometry method for short-chain and medium-chain chlorinated paraffin |
| CN104181266B (en) * | 2013-05-24 | 2016-03-16 | 中国科学院大连化学物理研究所 | The dechlorination of short chain and medium chain chlorinated paraffin adds deuterium gas chromatography-mass spectrometry analysis method |
| CN103353500A (en) * | 2013-07-12 | 2013-10-16 | 深圳信测标准技术服务股份有限公司 | Detection method for medium short-chain chlorinated paraffin in plastic and environment |
| CN103852550A (en) * | 2014-03-26 | 2014-06-11 | 昆山洛丹伦生物科技有限公司 | Detecting method for chlorinated paraffin in plastic component of electronic element |
| CN106483239A (en) * | 2015-11-25 | 2017-03-08 | 衡阳市骏杰化工有限公司 | A kind of detection method for producing short chain chlorinated paraffin in waste liquid |
| CN106799195A (en) * | 2015-11-25 | 2017-06-06 | 衡阳市骏杰化工有限公司 | It is a kind of to determine the carbon skeleton reaction bushing pipe that chlorinated paraffin content is used |
| CN115452931A (en) * | 2022-08-04 | 2022-12-09 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Chlorinated paraffin analysis method based on adsorbent assistance-atmospheric pressure chemical ionization source-high resolution mass spectrum |
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Application publication date: 20120620 |