CN110806442A - Selection method for optimal extraction reagent for detecting phthalate in plastic - Google Patents

Selection method for optimal extraction reagent for detecting phthalate in plastic Download PDF

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CN110806442A
CN110806442A CN201911200529.7A CN201911200529A CN110806442A CN 110806442 A CN110806442 A CN 110806442A CN 201911200529 A CN201911200529 A CN 201911200529A CN 110806442 A CN110806442 A CN 110806442A
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detected
detecting
phthalate
reagent
plastic
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梁茜茜
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Dalian University
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Dalian University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622Ion mobility spectrometry
    • G01N27/624Differential mobility spectrometry [DMS]; Field asymmetric-waveform ion mobility spectrometry [FAIMS]
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00Sampling; Preparing specimens for investigation
    • G01N1/28Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/44Sample treatment involving radiation, e.g. heat

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Abstract

The invention relates to the technical field of chemical detection, in particular to a selection method of an optimal extraction reagent for detecting phthalate esters in plastics. The main technical scheme is as follows: (1) dissolving equivalent substances to be detected in different solvents respectively to obtain a solution to be detected with the concentration of 0.1 g/mL; (2) detecting the liquid to be detected by an ion mobility spectrometry method; analyzing the difference between the detection result values of all groups and the actually given quantification, and taking the solvent used by the group with the minimum difference as the optimal reagent; the solvent is ethanol, n-hexane, methanol and acetone. The method adopts nontoxic, low-cost and good-solubility ethanol as an organic solvent to detect the phthalate compounds in the plastics, and has accurate, rapid and efficient detection result.

Description

Selection method for optimal extraction reagent for detecting phthalate in plastic
Technical Field
The invention relates to the technical field of chemical detection, in particular to a selection method of an optimal extraction reagent for detecting phthalate esters in plastics.
Background
In recent years, with the mass production and use of plastic products, phthalates have become the most common class of contaminants worldwide. In view of the many hazards of phthalates, the united states, european union, etc. have continued to set forth several environmental regulations restricting their use, and the united states Environmental Protection Agency (EPA) has placed 6 PAEs on a list of heavily regulated pollutants. Recently, the U.S. environmental protection agency has placed phthalates on the list of specialty materials with "serious health or environmental concerns" in the first chemical action program, in accordance with the existing toxic materials control act (TSCA). China is one of the main countries for producing and using PAEs, and the annual output of the PAEs exceeds 200 ten thousand tons. With the increasing use of PAEs, the pollution caused by PAEs is not negligible. The 'perfume toxic' event reminds people that PAEs threaten our life health at any moment. In the aspect of packaging food and daily chemical products, the PAEs are particularly applied as plasticizers of flexible plastics, and various plastic boxes and plastic bags contain the PAEs. The PAEs and the plastic matrix do not form chemical covalent bonds, so that the PAEs can be dissolved out when contacting water, grease and the like contained in the packaged food, and the food is polluted. Therefore, the development of a new phthalate detection technology which is rapid and highly sensitive and is suitable for rapid screening of a large number of samples has important significance for researching the pollution current situation of phthalate substances in China, planning the use and management of phthalate and protecting the life health of people.
Disclosure of Invention
In order to make up the defects of the prior art, the most suitable extracting agent is screened by comparing the types and the contents of the dissolved PAEs of the plastic packaging materials (No. 1 PTE) by the several extracting solvents. The technical scheme of the invention is as follows: a selection method for detecting an optimal extraction reagent of phthalate in plastic comprises the following steps:
(1) dissolving equivalent substances to be detected in different solvents respectively to obtain a solution to be detected with the concentration of 0.1 g/mL;
(2) detecting the liquid to be detected by an ion mobility spectrometry method; analyzing the difference between the detection result values of all groups and the actually given quantification, and taking the solvent used by the group with the minimum difference as the optimal reagent;
the solvent is ethanol, n-hexane, methanol and acetone.
Further, the parameters adopted in the ion mobility spectrometry method are as follows: the temperature of the thermal analysis sample injector is 180 ℃, the temperature of the ion migration tube is 130 ℃, and the electric field intensity of the migration zone is 220V/cm.
The invention has the following beneficial effects: the method takes ammonia as a reagent molecule to detect the phthalate ester compounds in trace amount in food, can simultaneously detect various phthalate ester compounds, and has the characteristics of high efficiency, accuracy and rapidness. The ethanol is used as a solvent, and has the characteristics of no toxicity, low irritation, low cost and good solubility.
Drawings
FIG. 1 is an ion mobility spectrum of a phthalate detection dissolved out from a plastic with ethanol as an extractant;
FIG. 2 is an ion migration spectrum of phthalate in plastic dissolved out by n-hexane as an extractant;
FIG. 3 is an ion migration spectrum of phthalate in plastic dissolved out by methanol as extractant;
FIG. 4 is an ion migration spectrum of phthalate dissolved out of plastic by acetone as extractant;
FIG. 5 is a graph showing the migration time with the temperature of the migration tube;
FIG. 6 is a graph of response intensity versus temperature of a migration tube;
FIG. 7 is a graph showing the migration time along with the variation of the electric field intensity of the migration tube;
FIG. 8 is a graph showing the response intensity along with the variation of the electric field intensity of the migration tube;
FIG. 9 is a graph of response intensity versus injector temperature;
FIG. 10 is a graph showing the results of detection in example 2.
Detailed Description
The invention is further described with reference to specific embodiments, and unless otherwise indicated, the materials and equipment used in the invention are conventional in the art.
Example 1
The detection method comprises the following steps:
(1) dispersing Plastic (PVC) to be detected in a solvent, performing ultrasonic treatment for 15min, and uniformly dispersing to obtain a sample solution;
(2) reagent molecules are obtained through a dynamic configuration and dilution device of gas, the reagent molecules are carried by carrier gas to enter an ion migration tube, the reagent molecules are ionized in a 63Ni ionization source to generate reagent molecular ions, and the reagent molecular ions enter a reaction zone;
(3) dripping the sample prepared in the step (1) on a polytetrafluoroethylene sampling sheet, inserting a thermal desorption sample injector after the solvent is volatilized, and entering a reaction area of an ion migration tube after thermal desorption and gasification to react with reagent molecular ions to form product ions;
(4) the product ions enter a migration area of the ion migration tube under the action of ion gate pulse to carry out separation detection; the reagent molecule is ammonia, the temperature of the thermal desorption sample injector is 200 ℃, the temperature of the ion migration tube is 100 ℃, and the electric field intensity of the migration zone is 220V/cm.
The types and contents of dissolved PAEs in the plastic packaging material are respectively researched by taking ethanol, normal hexane, methanol and acetone as extracting agents, and the results are 1-4. The results show that, as in fig. 1, for the purpose of comparing the extraction effect, an ion mobility spectrum of ethanol itself is also presented in fig. 1. It can be seen from the figure that ethanol as an extractant extracted a weak DMP signal from the plastic bottle with a peak intensity of about 20 mV. As can be seen from FIG. 2, when n-hexane was used as the plastic extraction solvent, substantially no product ion peak corresponding to phthalate was observed in the ion mobility spectrum. From fig. 3, by comparing the ion mobility spectra of the blanks of phthalate and methanol dissolved out from the plastic, we can clearly observe the product ion peak of DBP with peak intensity as high as 100 mV. From FIG. 4, it can be seen that NH is excluded from ammonia4+(H2O)nThe peak is a characteristic peak having a migration time of 16.22ms in addition to the reagent ion peak, and it is preliminarily presumed that this peak is a cluster ion formed by the addition reaction of acetone molecules and ammonia reagent ions. Acetone, however, fails to extract the phthalate from the plastic packaging because no relevant product ion peaks are observed on the ion mobility spectrum.
By comparison, when ethanol and methanol are used as extraction solvents, DMP and DBP can be respectively dissolved out, and other two solvents basically have no dissolved substances, and the ethanol has the characteristics of no toxicity, low cost and good solubility, so the ethanol is selected as the extraction solvent.
Example 2
(1) Respectively dispersing 0.5g of plastic packaging material (1# -7#) in 5mL of ethanol solvent, performing ultrasonic treatment for 15min, and uniformly dispersing to obtain sample liquid; 1# PET-mineral water bottle, 2# HDPE-chewing gum bottle, 3# PVC-wire skin, 4# polyethylene-preservative film, 5# polypropylene-disposable spoon and 6# polystyrene-snack box;
(2) reagent molecules are obtained through a dynamic configuration and dilution device of gas, the reagent molecules are carried by carrier gas to enter an ion migration tube, the reagent molecules are ionized in a 63Ni ionization source to generate reagent molecular ions, and the reagent molecular ions enter a reaction zone;
(3) dripping 5 mu L of the sample liquid prepared in the step (1) on a polytetrafluoroethylene sampling sheet, inserting a thermal desorption sample injector after an ethanol solvent is volatilized, entering a reaction area of an ion migration tube after thermal desorption and gasification, and reacting with reagent molecular ions to form product ions;
(4) the product ions enter a migration area of the ion migration tube under the action of ion gate pulse to carry out separation detection; the reagent molecule is ammonia, the temperature of the thermal desorption sample injector is 180 ℃, the temperature of the ion migration tube is 130 ℃, and the electric field intensity of the migration zone is 220V/cm.
TABLE 1 statistical Table of quantitative results for phthalate ester standards
Figure BDA0002295773410000041
The results of the quantitative analysis of five typical phthalates (DMP, DEP, DBP, BBP and DEHP) are summarized in Table 1. The accuracy of the labeling recovery test method is adopted, and the labeling recovery rates of DMP, DEP, DBP, BBP and DEHP are 101.32%, 87.53%, 125.56%, 91.54% and 97.32% respectively. The result shows that the method has better accuracy and can be used for rapid screening of phthalate.
The results are shown in FIG. 10. The result of combining the quantitative standard curve in the table 1 shows that the concentration of DMP dissolved out from the No. 1 PET-mineral water bottle is calculated to be about 4 mg/kg; the concentration of DBP dissolved out of the No. 2 HDPE-chewing gum bottle is about 0.4 mg/kg; the concentration of dissolved DEP of the No. 3 PVC-wire sheath is about 2.4mg/kg, the concentration of dissolved DBP is about 35mg/kg, and the concentration of dissolved DEHP is about 40 mg/kg; the concentration of dissolved DBP in the 7# PC-bottle was about 1 mg/kg. The PAEs content in the plastic packaging materials is lower than the national specified 0.1 percent standard, and the plastic packaging materials are preliminarily determined to be qualified commodities.
Example 4 Effect of migration tube temperature on phthalate detection
The detection method of this example was the same as that of example 1 except for the temperature of the transfer tube.
In conjunction with fig. 5 and 6, it can be observed that as the temperature of the migration tube increases from 60 ℃ to 100 ℃, the migration time of the characteristic ion peak of the DMP shows a decreasing trend, i.e. the mobility gradually increases, and the sensitivity correspondingly increases, which is indicated by the increase in PIP peak intensity. This phenomenon may occur because the complex product ions undergo de-clustering with increasing temperature, i.e., stripping of water molecules from the shell of the hydrated ions results in a decrease in the effective mass of the ions, while a decrease in the reduced mass results in an increase in their mobility. At the same time, at high temperatures, the product ions are also fragmented into small fragment ions with high mobility. In addition, the increase of the temperature can also lead to depolymerization of dimer product ions, the species is more single, and the peak intensity of the monomer is increased.
Example 5 Effect of electric field intensity in transition zone on phthalate detection
The detection method of this embodiment is the same as that of embodiment 1 except for the electric field intensity in the transition region.
As shown in fig. 7-8, the migration times of RIP and six PAEs were reduced with increasing electric field intensity, and the reduction degree was consistent, indicating that there was no significant reduction in the peak-to-peak separation of RIP and PIP. The peak height of the characteristic ion peak of PAEs increases with increasing electric field strength. The effect of measurement under the condition of the electric field intensity of 220V/cm is best because the influence of both the signal intensity and the separation degree is comprehensively considered.
Example 6 Effect of injector temperature on phthalate detection
The detection method of this example was the same as that of example 1 except for the injector temperature.
FIG. 9 shows that with increasing injector temperature (140-180 ℃), the DMP increases first, then plateaus at 140-180 ℃ and then decreases. The reason for this was analyzed and this could be related to the boiling point of the phthalate ester and the thermal desorption rate of the vaporization in the injector. For example, DMP has a low boiling point and thus is sufficiently thermally resolved at a relatively low temperature.
The foregoing examples are provided for illustration and description of the invention only and are not intended to limit the invention to the scope of the described examples. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications are within the scope of the present invention as claimed.

Claims (2)

1. A selection method for detecting an optimal extraction reagent of phthalate in plastic is characterized by comprising the following steps:
(1) dissolving equivalent substances to be detected in different solvents respectively to obtain a solution to be detected with the concentration of 0.1 g/mL;
(2) detecting the liquid to be detected by an ion mobility spectrometry method; analyzing the difference between the detection result values of all groups and the actually given quantification, and taking the solvent used by the group with the minimum difference as the optimal reagent;
the solvent is ethanol, n-hexane, methanol and acetone.
2. The method for selecting the optimal extraction reagent for detecting the phthalates in the plastic according to claim 1, wherein the parameters adopted in the ion mobility spectrometry method are as follows: the temperature of the thermal analysis sample injector is 180 ℃, the temperature of the ion migration tube is 130 ℃, and the electric field intensity of the migration zone is 220V/cm.
CN201911200529.7A 2019-11-29 2019-11-29 Selection method for optimal extraction reagent for detecting phthalate in plastic Pending CN110806442A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030096422A1 (en) * 2001-11-16 2003-05-22 Ong Eng Shi Pressurized liquid extraction method and apparatus
CN101852766A (en) * 2009-04-01 2010-10-06 中国科学院大连化学物理研究所 Method for detecting phthalate ester plasticizer in plastic
CN104251789A (en) * 2014-09-25 2014-12-31 中华人民共和国台州出入境检验检疫局 Extraction method of phthalate compound in leather toy material
CN105974007A (en) * 2016-04-27 2016-09-28 华中科技大学 Method for detecting phthalic acid ester in soil
CN110412181A (en) * 2019-07-12 2019-11-05 山东师范大学 The detection method of PAEs and BHT in a kind of krill

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030096422A1 (en) * 2001-11-16 2003-05-22 Ong Eng Shi Pressurized liquid extraction method and apparatus
CN101852766A (en) * 2009-04-01 2010-10-06 中国科学院大连化学物理研究所 Method for detecting phthalate ester plasticizer in plastic
CN104251789A (en) * 2014-09-25 2014-12-31 中华人民共和国台州出入境检验检疫局 Extraction method of phthalate compound in leather toy material
CN105974007A (en) * 2016-04-27 2016-09-28 华中科技大学 Method for detecting phthalic acid ester in soil
CN110412181A (en) * 2019-07-12 2019-11-05 山东师范大学 The detection method of PAEs and BHT in a kind of krill

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
边照阳: "《QuEChERS技术及应用》", 31 December 2017, 边照阳 *

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