CN105866089B - A kind of method of Fluorometric assay phthalic ester plasticizer - Google Patents
A kind of method of Fluorometric assay phthalic ester plasticizer Download PDFInfo
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Abstract
The present invention provides a kind of methods of Fluorometric assay phthalic ester plasticizer in technical field of chemical detection, first use the phthalic acid ester in tetrahydrofuran dissolving test sample；Dioxane and strong base solution is added, phthalic acid ester is hydrolyzed into phthalate, the solution after purification hydrolysis；Take purified upper layer aqueous solution, sequentially add hydrochloric acid solution, PBS solution, copper nitrate solution and hydrogenperoxide steam generator, phthalate is converted to the hydroxyl phthalic salt that can be fluoresced, manganese dioxide and strong base solution are added after reaction, it stands or is centrifuged, retain supernatant aqueous solution as solution to be measured, finally solution to be measured is measured with fluorescence method；The present invention can quickly analysis obtains the content of phthalic ester plasticizer under conditions of not needing large-scale detection device, easy to operate and at low cost, this method can be used for the phthalic acid ester content detection of plastics, toy, painting layer, packaging material for food etc..
Description
Technical field
The present invention relates to a kind of detection method, in particular to a kind of side of Fluorometric assay phthalic ester plasticizer
Method.
Background technique
Phthalate compound, which is mainly used for being added in high molecular polymer as plasticizer, increases material
Flexibility, be widely used in toy, packaging material for food, medical blood bag and sebific duct, vinyl flooring and wallpaper, detergent,
In hundreds of products such as lubricating oil, personal-care supplies.Phthalic acid ester has estrogenic effect, may interfere with organism endocrine
System influences the normal secretions of biological hormone in vivo, can produce teratogenesis, carcinogenic, mutagenesis.Therefore, to phthalic acid
The detection of ester is more and more important.Currently, detection phthalate compound national standard and document mostly use greatly GC,
GC-MS, HPLC, LC-MS method.Although these instrumental methods have the advantages that rigorous, accurate, sensitive, require to use big
The disadvantages of type instrument, generally existing method time long, cumbersome, professional degree are high.
Summary of the invention
For the defects in the prior art, it is an object of the invention to overcome the deficiencies in the prior art described above place, mentions
For a kind of method of Fluorometric assay phthalic ester plasticizer, detection sensitivity is high, easy to operate and at low cost, is not required to
Want large-scale detection device.
The purpose of the present invention is what is be achieved through the following technical solutions：A kind of Fluorometric assay phthalate plasticising
The method of agent, described detection method includes the following steps：
（A1）Solution is produced：It quantitatively weighs and shreds or broken test sample, the four of 10~400 times of example weight are added
Hydrogen furans, is fully dissolved in phthalic ester plasticizer in tetrahydrofuran, and dissolved solution is as sample solution；Using
The tetrahydrofuran solution of phthalic acid ester content distribution gradient is as standard solution；
（A2）Hydrolysis：It is separately added into dioxane in above-mentioned sample solution and solution to be measured and strong base solution carries out water
Solution, phthalic acid ester is hydrolyzed into phthalate after reacting in a water bath；
（A3）Purification：The salting liquid of high concentration is added, upper layer aqueous solution is removed after layering, then extracted with methylene chloride
It takes, upper layer aqueous solution is retained after layering；
（A4）Fluorescent derivatization：Go bail for the upper layer aqueous solution stayed, sequentially add hydrochloric acid solution, PBS solution, copper nitrate solution and
Phthalate is converted to the hydroxyl phthalic salt that can be fluoresced, titanium dioxide is added after reaction by hydrogenperoxide steam generator
Manganese and strong base solution, stand or centrifugation is layered, and retain supernatant solution as solution to be measured；
（A5）Detection：Fluorescent strength determining is carried out to each solution to be measured with fluorescence method, it will measurement corresponding with sample solution
As a result measurement result corresponding with standard solution is compared, and obtains the content of phthalic acid ester.
The present invention dissolves the phthalic ester plasticizer in test sample using tetrahydrofuran, then uses dioxane
It is hydrolyzed, strong base solution is added after hydrolysis and is extracted by phthalic acid ester hydrolysis salifying, then with organic solvent, retains after layering
Upper layer aqueous solution reduces the interference to then detecting to remove organic matter, takes out upper layer aqueous solution, successively into upper layer aqueous solution
Hydrochloric acid solution, PBS solution, copper nitrate solution and hydrogenperoxide steam generator is added, manganese dioxide sufficiently is added after reaction in a water bath
And strong base solution, it stands or centrifugation, reservation supernatant solution is finally measured as solution to be measured with fluorescence method；With existing skill
Art is compared, the beneficial effects of the present invention are：This method can quickly be analyzed under conditions of not needing large-scale detection device
It is easy to operate and at low cost to the content of phthalic ester plasticizer, this method can be used for plastics, toy, painting layer,
The phthalic acid ester content of packaging material for food etc. detects.
As a further improvement of the present invention, when measuring fluorescence intensity, using sepectrophotofluorometer, ultraviolet lamp box or
Microplate reader is measured.
As a further improvement of the present invention, the step of being detected using fluorescence method is specific as follows：
（1）The fluorescence intensity of the solution to be measured is detected using sepectrophotofluorometer；
（2）The content of phthalic acid ester in the corresponding absorbance value of standard solution and standard solution is subjected to Linear Quasi
It closes, obtains the standard curve of absorbance value Yu phthalic acid ester content corresponding relationship；
（3）The corresponding absorbance value of sample solution is measured, then phthalic acid in sample solution is determined by standard curve
The content of ester, then the content of phthalic acid ester in sample is obtained through converting.
As a further improvement of the present invention, the step of being detected using fluorescence method is specific as follows：
1）It takes solution to be measured to add in microwell plate, microwell plate is put into ultraviolet lamp box, ultraviolet lamp is opened, measures each solution
Blue-fluorescence brightness；
2）It is compareed by the blue-fluorescence brightness of standard solution and sample solution, obtains the phthalic acid in test sample
The content interval of ester.
As a further improvement of the present invention, the salting liquid of the high concentration is 20% or more mass content under room temperature
One of NaCl, KCl, LiCl solution.
As a further improvement of the present invention, the strong base solution is one of NaOH, KOH, LiOH solution.
Detailed description of the invention
Fig. 1 is the absorbance value of Plays solution of the present invention and the corresponding relationship of phthalic ester concentration.
Specific embodiment
Embodiment 1
A kind of method of Fluorometric assay phthalic ester plasticizer, for phthalic acid ester in detection PVC plastic
The method of class plasticizer loading carries out as follows：
（A1）Solution is produced：PVC plastic is shredded, the test sample after 20mg is shredded is weighed, test sample weight is added
10 times of tetrahydrofuran, is fully dissolved in phthalic ester plasticizer in tetrahydrofuran；Phthalic acid ester is quantitatively weighed,
Phthalic acid ester is dissolved in tetrahydrofuran, compound concentration is the phthalic acid ester of 0,1,5,20,100 mg/L respectively
Standard solution；
（A2）Hydrolysis：The LiOH solution of 2mL dioxane and 0.5 mol/L of 3mL is added, is stood in 55 DEG C of water-baths anti-
Phthalic acid ester after 2h is answered to be hydrolyzed into phthalate；
（A3）Purification：After phthalic acid ester is hydrolyzed into phthalate, 1 mL mass content is added into solution
For 30% KCl solution, layering is centrifuged after oscillation, the aqueous solution after layering removes upper layer；It is extracted, is shaken with 4mL methylene chloride
It is centrifuged layering after swinging 30s, retains supernatant aqueous solution；
（A4）Fluorescent derivatization：Take 2mL retain supernatant aqueous solution, sequentially add 0.75mL 1mol/L hydrochloric acid solution,
1.4 mL by 0.25mol/L KH2PO4With the K of 0.25 mol/L2HPO4PBS solution that solution mixes, 20 μ L 1mol/L
Copper nitrate solution and 80 μ L mass contents be 30% hydrogenperoxide steam generator, in 55 DEG C of water-bath stand reaction 1h after be added
The KOH solution that 1mg manganese dioxide and 800 μ L mass contents are 30%, is centrifuged after oscillation, retains supernatant solution as to be measured molten
Liquid；
（A5）Detection：Emission spectrum is scanned using sepectrophotofluorometer, the wavelength of excitation spectrum is 312nm, detects 5
Standard solution is in the fluorescence intensity that emission spectrum wavelength is at 425nm, 5 standard solution（0,1,5,20,100 mg/L）Suction
Luminosity is respectively 4.2,10.3,31.0,132.4,404.3, by the dense of the absorbance value of the standard solution measured and standard solution
Degree carries out linear fit, obtains the standard curve of absorbance value Yu phthalic acid ester content corresponding relationship（As shown in Figure 1）；Sample
The absorbance value of product solution is 26.2, the content of phthalic acid ester in sample solution is determined by standard curve, through converting
The content of phthalic acid ester is about 0.035% in sample out.
Embodiment 2
A kind of method of Fluorometric assay phthalic ester plasticizer, for phthalic acid ester in detection PVC plastic
The method of class plasticizer loading carries out as follows：
（A1）Solution is produced：PVC plastic is shredded, the test sample after 20mg is shredded is weighed, test sample weight is added
400 times of tetrahydrofuran, is fully dissolved in phthalic ester plasticizer in tetrahydrofuran；Quantitatively weigh phthalic acid
Phthalic acid ester is dissolved in tetrahydrofuran by ester, and compound concentration is the phthalic acid of 0,1,5,20,100 mg/L respectively
The standard solution of ester；
（A2）Hydrolysis：The LiOH solution of 2mL dioxane and 0.5 mol/L of 3mL is added, is stood in 55 DEG C of water-baths anti-
Phthalic acid ester after 2h is answered to be hydrolyzed into phthalate；
（A3）Purification：After phthalic acid ester is hydrolyzed into phthalate, 1 mL mass content is added into solution
For 20% NaCl solution, stratification, the aqueous solution after layering removes upper layer；It is extracted with 4mL methylene chloride, vibrates 30s
Centrifugation layering afterwards retains supernatant aqueous solution；
（A4）Fluorescent derivatization：Take 2mL retain upper layer aqueous solution, sequentially add 0.75mL 1mol/L hydrochloric acid solution,
1.4 mL by 0.25mol/L KH2PO4With the K of 0.25 mol/L2HPO4PBS solution that solution mixes, 20 μ L 1mol/L
Copper nitrate solution and 80 μ L mass contents be 30% hydrogenperoxide steam generator, in 55 DEG C of water-bath stand reaction 1h after be added
The NaOH solution that 1mg manganese dioxide and 800 μ L mass contents are 30%, is centrifuged after oscillation, retains supernatant solution as to be measured molten
Liquid；
（A5）Detection：Emission spectrum is scanned using sepectrophotofluorometer, the wavelength of excitation spectrum is 312nm, detects 5
The corresponding solution to be measured of standard solution is in the fluorescence intensity that emission spectrum wavelength is at 425nm, 5 standard solution（0,1,5,20,
100 mg/L）Corresponding absorbance is respectively 4.2,10.3,31.0,132.4,404.3, by the corresponding suction of the standard solution measured
Shading value and the concentration of phthalic acid ester carry out linear fit, obtain absorbance value and phthalic acid ester content corresponding relationship
Standard curve（As shown in Figure 1）；The corresponding absorbance value of sample solution is 26.5, is determined in sample solution by standard curve
The content of phthalic acid ester show that the content of phthalic acid ester in sample is about 0.04% through conversion.
Embodiment 3
A kind of method of Fluorometric assay phthalic ester plasticizer, for O-phthalic in detection plastic toys sample
The method of acid ester type plasticizer carries out as follows：
（A1）Solution is produced：Taking phthalic acid ester content is respectively the standard plastic sample of 0,300,3000 mg/kg, will
Plastic sample shreds, and weighs the test sample after 10mg is shredded, and is separately added into sample into test sample and standard plastic sample
The tetrahydrofuran that 100 times of weight, is fully dissolved in phthalic ester plasticizer in tetrahydrofuran；
（A2）Hydrolysis：The LiOH solution of 1mL dioxane and 0.5 mol/L of 1.5mL is added, is stood in 55 DEG C of water-baths
Phthalic acid ester is hydrolyzed into phthalate after reaction 2h, and the phthalic acid salting liquid after hydrolysis is as sample solution；
（A3）Purification：After phthalic acid ester is hydrolyzed into phthalate, 0.5 mL mass is added into solution and contains
The LiCl solution that amount is 40%, is centrifuged layering after oscillation, the aqueous solution after layering removes upper layer；2mL methylene chloride is added to be extracted
It takes, is centrifuged after vibrating 30s, retain supernatant aqueous solution；
（A4）Fluorescent derivatization：Take 1mL retain supernatant aqueous solution, sequentially add 0.375mL 1mol/L hydrochloric acid solution,
0.7 mL by 0.25mol/L 0.25 mol/L KH2PO4With the K of 0.25 mol/L2HPO4The PBS that solution mixes is molten
The hydrogenperoxide steam generator that liquid, the copper nitrate solution of 10 μ L 1mol/L and 40 μ L mass contents are 30%, stands in 55 DEG C of water-baths
0.5mg manganese dioxide and 400 μ L mass contents are added as 30% LiOH solution after reacting 1h, layering is centrifuged after oscillation, is retained
Supernatant solution is as solution to be measured；
（A5）Detection：It takes solution to be measured to add in microwell plate, microwell plate is put into ultraviolet lamp box, ultraviolet lamp is opened, will examine
The blue-fluorescence brightness of solution corresponding to the standard sample and test sample measured is compareed, and obtains adjacent benzene two in test sample
The content interval of formic acid esters, the brighter display of the more blue-fluorescence of phthalic acid ester content.
Above-mentioned steps（A5）In, fluorescent brightness measurement can also be carried out to solution to be measured using microplate reader, can equally obtained
Obtain the content of phthalic acid ester in test sample.In addition, 20% or more mass content under room temperature can be used in the salting liquid of high concentration
One of NaCl, KCl, LiCl solution；Strong base solution can be one of NaOH, KOH, LiOH solution.
The present invention is not limited to the above embodiments, on the basis of technical solution disclosed by the invention, the skill of this field
For art personnel according to disclosed technology contents, one can be made to some of which technical characteristic by not needing creative labor
A little replacements and deformation, these replacements and deformation all fall in the scope of protection of the present invention.
Claims (6)
1. a kind of method of Fluorometric assay phthalic ester plasticizer, which is characterized in that the detection method include with
Lower step：
（A1）Solution is produced：It quantitatively weighs and shreds or broken test sample, 10~400 times of example weight of tetrahydro furan is added
It mutters, is fully dissolved in phthalic ester plasticizer in tetrahydrofuran, dissolved solution is as sample solution；Using adjacent benzene
The tetrahydrofuran solution of dicarboxylic acid esters content distribution gradient is as standard solution；
（A2）Hydrolysis：Dioxane is separately added into above-mentioned sample solution and solution to be measured and strong base solution is hydrolyzed,
Phthalic acid ester is hydrolyzed into phthalate after reacting in water-bath；
（A3）Purification：The salting liquid of high concentration is added, upper layer aqueous solution is removed after layering, then extracted with methylene chloride, point
Retain upper layer aqueous solution after layer；
（A4）Fluorescent derivatization：It goes bail for the upper layer aqueous solution stayed, sequentially adds hydrochloric acid solution, PBS solution, copper nitrate solution and peroxide
Change hydrogen solution, phthalate is converted to the hydroxyl phthalic salt that can be fluoresced, after reaction be added manganese dioxide and
Strong base solution, stands or centrifugation is layered, and retains supernatant solution as solution to be measured；
（A5）Detection：Fluorescent strength determining is carried out to each solution to be measured with fluorescence method, it will measurement result corresponding with sample solution
Measurement result corresponding with standard solution is compared, and obtains the content of phthalic acid ester.
2. the method for Fluorometric assay phthalic ester plasticizer according to claim 1, it is characterised in that step
（A5）In, when measuring fluorescence intensity, it is measured using sepectrophotofluorometer, ultraviolet lamp box or microplate reader.
3. the method for Fluorometric assay phthalic ester plasticizer according to claim 2, it is characterised in that（A5）
In step, the step of being detected using fluorescence method, is as follows：
（1）The fluorescence intensity of the solution to be measured is detected using sepectrophotofluorometer；
（2）The content of phthalic acid ester in the corresponding absorbance value of standard solution and standard solution is subjected to linear fit,
Obtain the standard curve of absorbance value Yu phthalic acid ester content corresponding relationship；
（3）The corresponding absorbance value of sample solution is measured, then phthalic acid ester in sample solution is determined by standard curve
Content, then the content of phthalic acid ester in sample is obtained through converting.
4. the method for Fluorometric assay phthalic ester plasticizer according to claim 2, it is characterised in that（A5）
In step, the step of being detected using fluorescence method, is as follows：
1）It takes solution to be measured to add in microwell plate, microwell plate is put into ultraviolet lamp box, ultraviolet lamp is opened, measures the blue of each solution
Fluorescent brightness；
2）It is compareed by the blue-fluorescence brightness of standard solution and sample solution, obtains the phthalic acid ester in test sample
Content interval.
5. the method for Fluorometric assay phthalic ester plasticizer according to claim 1, it is characterised in that step
（A3）In, the salting liquid of the high concentration is one of NaCl, KCl, LiCl solution of 20% or more mass content under room temperature.
6. the method for Fluorometric assay phthalic ester plasticizer described in any one according to claim 1~5, special
Sign is that the strong base solution is one of NaOH, KOH, LiOH solution.
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| CN109932348A (en) * | 2019-03-28 | 2019-06-25 | 南京源恒环境研究所有限公司 | A kind of PAEs molecule sensitivity detection screening technique based on disubstituted modification |
| CN110530835B (en) * | 2019-09-27 | 2022-03-04 | 山西省农业科学院农产品加工研究所 | Fluorescence method detection method for phthalate plasticizer in oil substances |
| CN110514636B (en) * | 2019-09-27 | 2022-04-19 | 山西省农业科学院农产品加工研究所 | Fluorescence method for detecting phthalate plasticizer in water-soluble material |
| CN110514635B (en) * | 2019-09-27 | 2022-04-19 | 山西省农业科学院果树研究所 | Fluorescence method for detecting phthalate plasticizer in water-soluble material |
| CN113484261A (en) * | 2021-06-18 | 2021-10-08 | 北京市农林科学院 | Ultraviolet detection method for polyethylene terephthalate micro-plastic |
| CN116359190B (en) * | 2023-04-03 | 2023-11-07 | 中山永恒检测科技有限公司 | Method for detecting phthalate plasticizer in plastic toy by fluorescence method |
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