CN104931638B - The detection method of TCEP and TCPP in a kind of textile, leather and plastics - Google Patents
The detection method of TCEP and TCPP in a kind of textile, leather and plastics Download PDFInfo
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Abstract
The invention discloses the detection method of TCEP and TCPP in a kind of textile, leather and plastics, adopt gas chromatography-mass spectrography to detect.Detection method is simple and efficient, highly sensitive, linear within the scope of 0.5 ~ 5mg/L, related coefficient is 0.9997, method detects and is limited to 0.5mg/L, recovery of standard addition is 94% ~ 116%, relative standard deviation RSD (n=7) is less than 6%, can be good at the detection being applied to TCEP and TCPP in textile, leather and plastics.
Description
Technical field
The present invention relates to field of chemical detection, particularly relate to the detection method of TCEP and TCPP in a kind of textile, leather and plastics.
Background technology
TCEP and tricresyl phosphate (2-chloroethyl) ester are a kind of alkylphosphonates, are used as the flame-retardant plasticizer in polyurethane, vibrin, polyacrylate and other polymkeric substance and viscosity modifier, are widely used in building, furniture and textile industry.TCEP belongs to 2 class carcinogens and 1B class genotoxicity material.By the sucking of children with chew behavior, TCEP is easy to discharge from toy.Take in TCEP and can cause kidney, liver and brain toxicity, impair one's health and bring out cancer.TCPP and tricresyl phosphate (2-chloropropyl) ester are the halo substitutes of TCEP, have the physicochemical characteristics similar with TCEP and toxicological characteristics, therefore health care and the environmental science council (SCHER) think and should be applied to TCPP to the restriction of TCEP simultaneously.
According to European Union toy safety instruction 2009/48/EC annex two appendix C, in toy, the allowable value of TCEP, TCPP is as follows:
| Material | CAS NO. | Limit value |
| TCEP: tricresyl phosphate (2-chloroethyl) ester | 115-96-8 | 5mg/kg |
| TCPP: tricresyl phosphate (2-chloropropyl) ester | 13674-84-5 | 5mg/kg |
But also there is no the special examination criteria for these two kinds of materials at present.
Summary of the invention
In order to ensure product safety, the invention provides the detection method of TCEP and TCPP in a kind of simple and efficient, highly sensitive textile, leather and plastics.
The inventive method adopts toluene to carry out ultrasonic extraction to TCEP and TCPP in textile, leather and plastic products, detect with gas chromatograph-mass spectrometer, and in conjunction with optimized parameter, establishing one pre-treatment effectively and rapidly and analysis and testing technology, providing reliable foundation for formulating corresponding standard.Key of the present invention is that the parameter optimization of gas chromatograph-mass spectrometer is arranged, and it is optimized one group of parameter that inventor has selected after having tested a lot of method parameter, and these parameters can reach short and highly sensitive effect detection time.
For realizing above-mentioned technical purpose, concrete technical scheme is as follows:
A detection method of TCEP and TCPP in textile, leather and plastic products, adopts gas chromatography-mass spectrography to detect, comprises following steps:
A, sample pre-treatments:
Accurately take pretreated sample 0.5-1.5g, be placed in 40-60mL glass reaction bottle, add containing interior target organic solvent, at 60-80 DEG C of ultrasonic extraction 60-150min, after being cooled to room temperature, the extract nylon micro porous filter membrane of 0.45 μm filters, and getting filtrate is testing sample;
B, carry out gas chromatography-mass spectrography detection to testing sample, GC conditions is: chromatographic column: HP-5MS; Column temperature condition: initial temperature 100-150 DEG C, keeps 1-2min, then rises to 120-150 DEG C with the speed of 10-15 DEG C/min, then rise to 200-300 DEG C with the speed of 20-30 DEG C/min, keeps 4-6min; Injector temperature 250-300 DEG C; Input mode: Splitless injecting samples; Sample size: 1 μ L; Carrier gas: high-pure helium, purity >99.999%, flow: 1-2ml/min;
Mass Spectrometry Conditions is: ionization mode: electron impact ionization, electron energy 70eV; Ion source temperature: 230 DEG C; Chromatography-mass spectroscopy interface temperature: 300 DEG C; Solvent delay: 3-5min; Drainage pattern: full ion scan is qualitative, Selective ion mode scanning quantitation.
Wherein in some embodiments, in described steps A, ultrasonic temperature is 70 DEG C, and ultrasonic extraction time is 120min; Described organic solvent is toluene, is inside designated as anthracene-D10, and concentration is 0.5mg/L.For ultrasonic temperature and the selection of time, can clearly find out from embodiment result, this temperature and time is optimum.
Wherein in some embodiments, in described steps A, sample pretreatment is for be cut into 1mm × 1mm size by described sample, and this sample size can increase the surface area contacted with extraction solvent, contributes to abundant extraction.
Wherein in some embodiments, accurately take pretreated sample 1.0g in described steps A, be placed in 40mL glass reaction bottle, described organic solvent is toluene, is inside designated as anthracene-D10, and concentration is 0.5mg/L, and addition is 10mL.Select 1g sample, extraction agent amount used is moderate, and the inspected object volume concentrations extracted can reach sensitivity requirement, and the interior mark response of 0.5mg/L responds ratio suitably with linear concentration, is beneficial to quantitatively.
Wherein in some embodiments, the GC conditions in described step B is: chromatographic column: HP-5MS; Column temperature condition: initial temperature 100 DEG C, keeps 2min, then rises to 150 DEG C with the speed of 15 DEG C/min, then rise to 300 DEG C with the speed of 30 DEG C/min, keeps 5min; Injector temperature 270 DEG C; Input mode: Splitless injecting samples; Sample size: 1 μ L; Carrier gas: high-pure helium, purity >99.999%, flow: 1.2ml/min.Select these parameters, be inventor rule of thumb with through test of many times, consider from aspects such as pillar serviceable life, recognizate sensitivity, analysis times and draw.
Mass Spectrometry Conditions is: ionization mode: electron impact ionization, electron energy 70eV; Ion source temperature: 230 DEG C; Chromatography-mass spectroscopy interface temperature: 300 DEG C; Solvent delay: 4.5min; Drainage pattern: full ion scan is qualitative, Selective ion mode scanning quantitation.To be the present inventor think optimized parameter, when being especially applied to Agilent equipment through test for these parameters of electron energy, ion source temperature, chromatographic mass spectrometry interface temperature; Select the solvent delay of 4.5min first detection material can be flowed out, the more polymictic material that contains before secondly stoping 4.5min enters mass spectrum, protection instrument.
Wherein in some embodiments, the specifications parameter 30m*0.25mm*0.25mm of the chromatographic column in described step B selects this pillar mainly to consider from cost angle under the prerequisite that can achieve the goal, and can effectively reduce costs.
The present invention relative to the advantage of prior art and beneficial effect is:
Detection method is using toluene as Extraction solvent, TCEP and TCPP in ultrasonic extraction textile, leather and plastic products, by selecting chromatographic column type, and extraction conditions is optimized, by the mutual close fit of these aspects, establishing gas chromatography mass spectrometry detection method of the present invention, through carrying out the confirmatory experiments such as linear, the recovery, precision, demonstrating the effect that it is accurate and practical.
Detection method is simple and efficient, highly sensitive, linear within the scope of 0.5 ~ 5mg/L, related coefficient is 0.9997, method detects and is limited to 0.5mg/L, recovery of standard addition is 94% ~ 116%, relative standard deviation RSD (n=7) is less than 6%, with industry required standard: related coefficient 0.99, method detection limit 0.5mg/L, recovery of standard addition is relevant with spiked levels with RSD, at the recovery of standard addition industry standard 80%-120% of detection limit concentration, the requirement that RSD is less than 20% is compared, the accuracy of detection method of the present invention all can meet the requirement analyzed and detect, even in related coefficient, recovery of standard addition and RSD tri-results are above standard value, prove this detection method Be very effective, can be good at being applied to textile, the detection of TCEP and TCPP in leather and plastic products.
To sum up, the range of linearity of detection method is wide, the recovery is high, precision is good, and detection limit meets the Limited Doses of EC regulation.Detection method economical and efficient and be easy to promote the use of at laboratory monitoring, can be advantageously applied to the detection of TCEP and TCPP in textile, leather and plastic products.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is the chromatogram of TCEP and TCPP in embodiment, and wherein horizontal ordinate is retention time, and ordinate is signal intensity;
Fig. 2 is the standard working curve figure of TCEP and TCPP in embodiment;
The result figure that Fig. 3 is different ultrasonic temperature in steps A in embodiment, extract under the time.
Embodiment
All features disclosed in this instructions, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this instructions (comprising any accessory claim, summary and accompanying drawing), unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
The all instrument of following embodiment, reagent comprise:
1, instrument
GCMS-7890A/5975C type gas chromatography-GC-MS (Agilent company);
CREST ultrasonic generator (Shanghai ANPEL Scientific Instrument Co., Ltd.);
HP-5MS (30m*0.25mm*0.25mm) chromatographic column (Agilent company);
0.45 μm of nylon filter head.
2, reagent
Standard items: TCEP (purity 99.0%, Dr.Ehrenstorfer company of Germany), TCPP (purity 99.0%, Dr.Ehrenstorfer company of Germany), anthracene-D10 (purity 98.0%, Dr.Ehrenstorfer company of Germany), all purchased from Shanghai ANPEL Scientific Instrument Co., Ltd..Toluene (AR level, traditional Chinese medicines Reagent Company).
Embodiment 1
A detection method of TCEP and TCPP in textile, leather and plastic products, adopts GC-MS(gas chromatography-mass spectrography) to detect, comprises following steps:
A, standard solution are prepared
The preparation of TCEP, TCPP and anthracene-D10 standard reserving solution: take a certain amount of TCEP, TCPP and anthracene-D10 standard items, with AR level toluene difference constant volume in 10mL volumetric flask, is made into the storing solution of 1000mg/L.
The preparation of TCEP and TCPP standard working solution: accurately pipette appropriate standard reserving solution, by AR level dilution with toluene, is made into the standard working solution (interior mark anthracene-D10 is 0.5mg/L) of 0.5mg/L, 1mg/L, 5mg/L.
B, sample pre-treatments
Sampling: get representational sample, be cut into about 1mm × 1mm size, accurately take 1.0g (being accurate to 0.0001g), be placed in 40mL glass reaction bottle; Add extractant: in glass reaction bottle, add toluene (containing 0.5mg/L inner mark solution) 10mL, jump a queue airtight; Ultrasonic extraction: above-mentioned reaction bulb is placed in ultrasonic generator, 70 DEG C of ultrasonic extraction 120min, as can be seen from Fig. 3 be different ultrasonic temperature in steps A in embodiment, the result figure that extracts under the time, this temperature and time is best; Filter: after being cooled to room temperature,
The extract nylon micro porous filter membrane of 0.45 μm filters, and getting filtrate is testing sample.
C, analyze testing sample gas chromatography-GC-MS (GC-MS), retention time is qualitative, typical curve inner mark method ration.
GC conditions:
Chromatographic column: HP-5MS (30m*0.25mm*0.25mm);
Column temperature condition: initial temperature 100 DEG C, keeps 2min, then rises to 150 DEG C with the speed of 15 DEG C/min, then rise to 300 DEG C with the speed of 30 DEG C/min, keeps 5min;
Injector temperature: 270 DEG C;
Input mode: Splitless injecting samples;
Sample size: 1 μ L;
Carrier gas: high-pure helium (purity >99.999%), flow: 1.2ml/min;
Mass Spectrometry Conditions:
Ionization mode: electronics bombardment (EI) ionization, electron energy 70eV;
Ion source temperature: 230 DEG C;
Chromatography-mass spectroscopy interface temperature: 300 DEG C;
Solvent delay: 4.5min;
Drainage pattern: full ion scan (SCAN) is qualitative, and Selective ion mode scanning (SIM) is quantitative.
In embodiment 2 embodiment, the retention time of object (TCEP and TCPP), fragments characteristic ion are in table 1.In embodiment, the chromatogram of TCEP and TCPP is shown in Fig. 1, and wherein horizontal ordinate is retention time, and ordinate is signal intensity;
The retention time of table 1 object, fragments characteristic ion and abundance ratio
| Material title | Retention time/min | Fragments characteristic ion/amu | Abundance ratio |
| TCEP | 8.145 | 205，143.1，63.1 | 100/78.2/134.4 |
| TCPP | 8.312 | 99，41，125 | 100/62.2/95.9 |
From table 1 and Fig. 1, under the testing conditions of embodiment 1, object (TCEP with TCPP) can be well separated.
Embodiment 3 linear relationship
Under the testing conditions that the present invention optimizes, TCEP and TCPP standard solution is detected in 0.5 ~ 5mg/L concentration range.Standard working curve is shown in Fig. 2, and as shown in Figure 2, its concentration and response have good linear relationship, linear equation: TCEP:Y=0.1758X-0.03933, TCPP:Y=0.04729X-0.02539, coefficient R
2=0.9997.
Embodiment 4 detection limit
Under the testing conditions that the present invention optimizes, carry out analysis to the standard specimen of variable concentrations and detect, the concentration limit (S/N>3) recording TCEP and TCPP is 0.5mg/L.European Union EC regulation is 5mg/kg (i.e. 0.5mg/L) to the organic Limited Doses of this two high attention rate of TCEP and TCPP.
Embodiment 5 precision
Under the testing conditions that the present invention optimizes, with the standard specimen continuous detecting 7 times of 0.5mg/L, result (see table 2) shows, its relative standard deviation RSD=5.48% and 4.30%, it can thus be appreciated that under detection method condition, precision can meet the requirement analyzed and detect.
The Precision Experiment of table 2TCEP and TCPP
Embodiment 6 recovery
To not adding the object of varying level containing in the sample of object under the testing conditions of optimization of the present invention, sample pre-treatments is carried out by the method for embodiment 1, detect the recovery of standard addition of object, each level do 3 times parallel, the results are shown in Table 3, obtain the recovery of TCEP and TCPP between 94 ~ 116%, the accuracy of visible the inventive method can meet the requirement analyzed and detect.
Table 3TCEP and TCPP recovery testu
From embodiment 1-6, the range of linearity of detection method is wide, the recovery is high, precision is good, and detection limit meets the Limited Doses of EC regulation.Detection method economical and efficient and be easy to promote the use of at laboratory monitoring, can be advantageously applied to the detection of TCEP and TCPP in textile, leather and plastic products.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (1)
1. a detection method of TCEP and TCPP in textile, leather and plastics, is characterized in that, adopts gas chromatography-mass spectrography to detect, comprises following steps:
A, sample pre-treatments:
First carry out pre-service to sample, sample pretreatment, for described sample is cut into 1mm × 1mm size, then accurately takes pretreated sample 1g, be placed in 40mL glass reaction bottle, add containing interior target organic solvent, described organic solvent is toluene, is inside designated as anthracene-D10, concentration is 0.5mg/L, addition is 10mL, and 70 DEG C of ultrasonic extraction 120min, after being cooled to room temperature, the extract nylon micro porous filter membrane of 0.45 μm filters, and getting filtrate is testing sample;
B, carry out gas chromatography-mass spectrography detection to testing sample, gas chromatography used-GC-MS meaning Agilent company produces, and GC conditions is: chromatographic column: HP-5MS, and the specifications parameter of chromatographic column is 30m*0.25mm*0.25mm; Column temperature condition: initial temperature 100 DEG C, keeps 2min, then rises to 150 DEG C with the speed of 15 DEG C/min, then rise to 300 DEG C with the speed of 30 DEG C/min, keeps 5min; Injector temperature 270 DEG C; Input mode: Splitless injecting samples; Sample size: 1 μ L; Carrier gas: high-pure helium, purity >99.999%; Flow: 1.2ml/min;
Mass Spectrometry Conditions is as follows: ionization mode: electron impact ionization, electron energy 70eV; Ion source temperature: 230 DEG C; Chromatography-mass spectroscopy interface temperature: 300 DEG C; Solvent delay: 4.5min; Drainage pattern: full ion scan is qualitative, Selective ion mode scanning quantitation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| CN104049049A (en) * | 2014-07-09 | 2014-09-17 | 南京大学 | Method for synchronously detecting plurality of organophosphorus fire retardants in bottom mud |
| CN104391069A (en) * | 2014-11-27 | 2015-03-04 | 广州广电计量检测股份有限公司 | Method for simultaneously detecting multiple phosphorus-based flame retardants in plastics |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| CN104049049A (en) * | 2014-07-09 | 2014-09-17 | 南京大学 | Method for synchronously detecting plurality of organophosphorus fire retardants in bottom mud |
| CN104391069A (en) * | 2014-11-27 | 2015-03-04 | 广州广电计量检测股份有限公司 | Method for simultaneously detecting multiple phosphorus-based flame retardants in plastics |
Non-Patent Citations (3)
| Title |
|---|
| Phosphorus flame retardants: Properties, production, environmental occurrence, toxicity and analysis;van der Veen, Ike; de Boer, Jacob;《CHEMOSPHERE》;20120425;第88卷(第10期);1119-1153 * |
| 纺织品中禁用有机磷阻燃剂测定方法的比较;王成云;《印染》;20131231(第12期);39-43、47 * |
| 超声波提取-气相色谱法测定食品包装材料中的有机磷酸酯;曾铭 等;《包装与食品机械》;20140430;第32卷(第4期);试验结果与讨论部分第2.1节 * |
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