CN114755339A - Method for detecting 4, 4' -difluorobenzophenone in plastic product - Google Patents
Method for detecting 4, 4' -difluorobenzophenone in plastic product Download PDFInfo
- Publication number
- CN114755339A CN114755339A CN202210421335.5A CN202210421335A CN114755339A CN 114755339 A CN114755339 A CN 114755339A CN 202210421335 A CN202210421335 A CN 202210421335A CN 114755339 A CN114755339 A CN 114755339A
- Authority
- CN
- China
- Prior art keywords
- difluorobenzophenone
- mppo
- plastic product
- mobile phase
- standard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000004033 plastic Substances 0.000 title claims abstract description 91
- 229920003023 plastic Polymers 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000013508 migration Methods 0.000 claims abstract description 56
- 230000005012 migration Effects 0.000 claims abstract description 56
- 238000001514 detection method Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- 239000000047 product Substances 0.000 claims description 78
- 238000000605 extraction Methods 0.000 claims description 39
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 33
- 230000005284 excitation Effects 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000012086 standard solution Substances 0.000 claims description 21
- 230000010355 oscillation Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 12
- 239000011550 stock solution Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000005526 G1 to G0 transition Effects 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 238000011088 calibration curve Methods 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 238000005202 decontamination Methods 0.000 claims 1
- 230000003588 decontaminative effect Effects 0.000 claims 1
- 229920013638 modified polyphenyl ether Polymers 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 33
- 238000004458 analytical method Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920006380 polyphenylene oxide Polymers 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012156 elution solvent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 and for this reason Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/62—Detectors specially adapted therefor
- G01N30/74—Optical detectors
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a method for detecting 4, 4' -difluorobenzophenone in a plastic product. The invention adopts a simulant-modified polyphenyl ether to analyze 4, 4' -difluorobenzophenone in the plastic product migration, accurately reflects the migration characteristic of the plastic product and food in a dry contact state, can truly reflect the migration process of the plastic product and food in the dry contact state, and is a set of complete detection processes established from the absence to the existence. The detection method for migration of the transferee 4,4 '-difluorobenzophenone in the plastic product, provided by the invention, can simulate the migration behavior of the plastic product and food in a dry contact state, can quickly and accurately realize the determination of the content of the transferee 4, 4' -difluorobenzophenone in the plastic product, is simple and easy to implement, is green and environment-friendly, has strong controllability and good repeatability, and is more suitable for popularization and application.
Description
Technical Field
The invention belongs to the technical field of 4,4 '-difluorobenzophenone analysis and detection, and relates to a method for detecting 4, 4' -difluorobenzophenone in a plastic product.
Background
4, 4' -Difluorobenzophenone (DFBP) belongs to a harmful substance in plastic products listed in the national standard, and the migration limit of the harmful substance in plastic products in the national standard is defined to be 0.05 mg/kg. Specifically, when the plastic product is in dry contact with substances such as food and the like in a high-temperature environment, the Specific Migration Limit (SML) of 4, 4' -difluorobenzophenone is 0.05mg/kg according to the requirements of GB 4806.6-2016 (national food safety standard plastic resin for food contact) and GB 9685 one 2016 (national food safety standard material for food contact and additive for products) for use.
However, after the research of documents and related standards, no related test method exists in the prior art, no corresponding measurement method exists in the national standard, and no measurement method capable of truly reflecting the migration of plastic products in a state of contacting with food exists.
Therefore, how to find a more suitable way to solve the above technical problems in the prior art has become one of the problems to be solved by many front-line researchers and research and development enterprises in the field.
The invention provides an analysis method for analyzing 4, 4' -difluorobenzophenone in a plastic product migration substance by adopting a simulant (modified polyphenylene oxide), and accurately reflects the migration characteristic of the plastic product and the food in a dry contact state.
Disclosure of Invention
The invention aims to provide a method for detecting 4,4 '-difluorobenzophenone in a plastic product, which is a migration detection method capable of truly reflecting the dry contact state of the plastic product and food and can quickly and accurately detect the content of the 4, 4' -difluorobenzophenone.
The invention provides a method for detecting 4, 4' -difluorobenzophenone in a plastic product, which comprises the following steps:
1) directly contacting a plastic product to be detected with the purified MPPO, and then carrying out a contact migration process under a sealed condition to obtain the MPPO contacted with the plastic product;
2) placing the MPPO which is obtained in the step and is contacted with the plastic product into an extraction solvent, and performing vortex oscillation extraction to obtain a solution to be detected;
3) and (3) carrying out HPLC analysis on the solution to be detected obtained in the step to obtain the peak area of the substance to be detected, namely 4,4 ' -difluorobenzophenone, and calculating according to the HPLC concentration-peak area curve of the 4,4 ' -difluorobenzophenone to obtain the concentration of the 4,4 ' -difluorobenzophenone in the plastic product to be detected.
Preferably, the MPPO is modified polyphenylene oxide;
the shape of the plastic product comprises one or more of a sheet shape, a block shape and a granular shape;
the shape of the MPPO comprises one or more of a sheet shape, a block shape and a particle shape;
the particle size of the MPPO particles is 60-80 meshes.
Preferably, the step of purifying treatment comprises one or more of leaching, filtering, washing and drying;
the ratio of the plastic product to be detected to the MPPO is 0.1-0.5 dm2：1g；
The direct contact includes placing the plastic article to be tested on top of the MPPO.
Preferably, the direct contact is a dry contact;
the temperature in the contact migration process is 100-250 ℃;
the time of the contact migration process is 12-48 h.
Preferably, the extraction solvent comprises methanol;
the rotation speed of the vortex oscillation is 1500-4000 r/min;
and the vortex oscillation time is 5-15 min.
Preferably, the vortex oscillation step further comprises the steps of centrifugation and supernatant filtration;
the supernatant taking and filtering mode comprises water phase filter membrane filtration;
the aperture of the water-phase filter membrane is 0.35-0.5 μm.
Preferably, the HPLC concentration-peak area curve of 4,4 ' -difluorobenzophenone is a calibration curve of the compound to be detected, in which an integrated peak area of a 4,4 ' -difluorobenzophenone standard solution measured by high performance liquid chromatography is an ordinate, and a concentration of the 4,4 ' -difluorobenzophenone standard solution is an abscissa.
Preferably, the plotting of the HPLC concentration-peak area curve of 4, 4' -difluorobenzophenone comprises the following steps:
weighing a quantitative 4,4 '-difluorobenzophenone standard, performing constant volume with a methanol solution to obtain a standard stock solution, and diluting with methanol to obtain a 4, 4' -difluorobenzophenone standard diluent;
diluting a plurality of 4,4 '-difluorobenzophenone standard diluents with different concentrations by using methanol to obtain a series of 4, 4' -difluorobenzophenone standard solutions;
the concentration of the series of 4, 4' -difluorobenzophenone standard solutions is 0.1-5.5 mu g/mL;
after measuring the series of 4,4 '-difluorobenzophenone standard solutions obtained in the above steps by high performance liquid chromatography, the HPLC concentration-peak area curve of 4, 4' -difluorobenzophenone was plotted using the integrated peak area of the obtained 4,4 '-difluorobenzophenone as the ordinate and the concentration of 4, 4' -difluorobenzophenone as the abscissa.
Preferably, the conditions of said HPLC comprise:
a chromatographic column: column length 150mm, inner diameter 4.6mm, filler particle size 5 μm, stationary phase C18 (LUNA); mobile phase A: 1% aqueous acetic acid, mobile phase B: acetonitrile; column temperature: 30 ℃; column flow rate: 1 mL/min; sample introduction volume: 10 mu L of the solution;
elution gradient: 0min, mobile phase A80% and mobile phase B20%; for 12min, mobile phase A50% and mobile phase B50%; 18 min: 20% of mobile phase A and 80% of mobile phase B; 19 min: mobile phase a 80%, mobile phase B20%.
Preferably, the detector of the HPLC comprises a fluorescence detector and an ultraviolet detector in series;
the conditions of the fluorescence detector comprising:
0min: the excitation wavelength is 284nm, and the emission wavelength is 332 nm; 5 min: the excitation wavelength is 275nm, and the emission wavelength is 315 nm; 7.5 min: the excitation wavelength is 277nm, and the emission wavelength is 319 nm; 11 min: the excitation wavelength is 272nm, and the emission wavelength is 309 nm; 20 min: the excitation wavelength is 273nm, and the emission wavelength is 323 nm;
the conditions of the ultraviolet detector include:
0-20 min: the absorption wavelength is 254nm and the reference wavelength is 360 nm.
The invention provides a method for detecting 4, 4' -difluorobenzophenone in a plastic product, which comprises the following steps of firstly, directly contacting the plastic product to be detected with MPPO subjected to purification treatment, and then carrying out a contact migration process under a sealing condition to obtain the MPPO contacted with the plastic product; then placing the MPPO obtained in the step and contacted with the plastic product into an extraction solvent, and performing vortex oscillation extraction to obtain a solution to be detected; and finally, carrying out HPLC analysis on the solution to be detected obtained in the step to obtain the peak area of the substance to be detected, namely 4,4 ' -difluorobenzophenone, and calculating according to an HPLC concentration-peak area curve of the 4,4 ' -difluorobenzophenone to obtain the concentration of the 4,4 ' -difluorobenzophenone in the plastic product to be detected. Compared with the prior art, the invention creatively adopts a simulant, namely modified polyphenylene oxide (MPPO), to analyze the 4, 4' -difluorobenzophenone in the plastic product migration object, accurately reflects the migration characteristic of the plastic product and food in a dry contact state, can truly reflect the migration process of the plastic product and food in the dry contact state, and is a set of complete detection process from scratch. The method for detecting migration of the transferee 4,4 '-difluorobenzophenone in the plastic product can simulate the migration behavior of the plastic product and food in a dry contact state, and can quickly and accurately realize the determination of the content of the transferee 4, 4' -difluorobenzophenone in the plastic product.
The invention is a set of detection method established based on specific MPPO purification treatment method, migration experiment method for plastic products, MPPO extraction method, instrumental determination method, especially the specific steps of chromatographic use type, analysis condition, elution solvent composition, gradient and the like, can simulate the migration behavior of the plastic products and food in a dry contact state, truly reflect the actual contact state of the plastic products and the food, quickly and accurately realize the detection of the migration amount of 4,4 '-difluorobenzophenone in the plastic products, effectively solves the problem that no method for detecting the migration amount of 4, 4' -difluorobenzophenone in the plastic products exists in the prior art, and has the advantages of simplicity, easy implementation, environmental protection, strong controllability and good repeatability, thus being more suitable for popularization and application.
Drawings
FIG. 1 is a schematic diagram of a migration test apparatus according to the present invention.
Detailed Description
In order to further understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity of analytical purity or the purity conventionally employed in the field of 4, 4' -difluorobenzophenone assay.
The invention provides a method for detecting 4, 4' -difluorobenzophenone in a plastic product, which comprises the following steps:
1) directly contacting a plastic product to be detected with the purified MPPO, and then carrying out a contact migration process under a sealed condition to obtain the MPPO contacted with the plastic product;
2) placing the MPPO which is obtained in the step and is contacted with the plastic product into an extraction solvent, and performing vortex oscillation extraction to obtain a solution to be detected;
3) and (3) carrying out HPLC analysis on the solution to be detected obtained in the step to obtain the peak area of the substance to be detected, namely 4,4 ' -difluorobenzophenone, and calculating according to the HPLC concentration-peak area curve of the 4,4 ' -difluorobenzophenone to obtain the concentration of the 4,4 ' -difluorobenzophenone in the plastic product to be detected.
According to the invention, firstly, a plastic product to be detected is directly contacted with the purified MPPO, and then a contact migration process is carried out under a sealing condition, so as to obtain the MPPO contacted with the plastic product.
In the present invention, the MPPO is a modified polyphenylene ether. Specifically, the modified polyphenylene ether is preferably modified polyphenylene ether (MPPO) manufactured or sold by Buchembv, the Netherlands.
In the present invention, the shape of the plastic product preferably includes one or more of a sheet shape, a block shape and a granular shape, and more preferably a sheet shape, a block shape or a granular shape.
In the present invention, the shape of the MPPO preferably includes one or more of a sheet shape, a block shape, and a granular shape, and more preferably a sheet shape, a block shape, or a granular shape.
In the invention, the particle size of the MPPO particles, namely the granular MPPO, is preferably 60-80 meshes, more preferably 64-76 meshes, and more preferably 68-72 meshes.
In the present invention, the step of the purification treatment preferably includes one or more steps of leaching, filtering, washing and drying, more preferably, a plurality of steps of leaching, filtering, washing and drying.
In the invention, the ratio of the plastic product to be measured to the MPPO is preferably 0.1-0.5 dm2: 1g, more preferably 0.15 to 0.45dm2: 1g, more preferably 0.2 to 0.4dm2: 1g, more preferably 0.25 to 0.35dm2：1g。
In the present invention, said direct contact preferably comprises placing the plastic article to be tested on top of the MPPO.
In the present invention, the direct contact is preferably dry contact.
In the invention, the temperature in the contact migration process is preferably 100-250 ℃, more preferably 130-220 ℃, and more preferably 160-190 ℃.
In the invention, the time of the contact migration process is preferably 12-48 h, more preferably 17-43 h, more preferably 27-38 h, and more preferably 32-33 h.
The MPPO obtained in the step and contacted with the plastic product is placed in an extraction solvent, and vortex oscillation extraction is carried out to obtain a solution to be detected.
In the present invention, the extraction solvent preferably includes methanol.
In the invention, the rotation speed of the vortex oscillation is preferably 1500-4000 r/min, more preferably 2000-3500 r/min, and more preferably 2500-3000 r/min.
In the invention, the time of the vortex oscillation is preferably 5-15 min, more preferably 7-13 min, and more preferably 9-11 min.
In the present invention, the vortexing preferably includes centrifugation and filtration of the supernatant.
In the present invention, the filtration of the supernatant preferably comprises filtration with an aqueous membrane.
In the invention, the pore diameter of the water phase filter membrane is preferably 0.35-0.5 μm, more preferably 0.38-0.47 μm, and more preferably 0.41-0.44 μm.
According to the invention, the peak area of the 4,4 ' -difluorobenzophenone to be detected is obtained after the HPLC analysis is carried out on the to-be-detected liquid obtained in the step, and the concentration of the 4,4 ' -difluorobenzophenone in the plastic product to be detected is obtained by calculating according to the HPLC concentration-peak area curve of the 4,4 ' -difluorobenzophenone.
In the present invention, the HPLC concentration-peak area curve of 4,4 ' -difluorobenzophenone is preferably a calibration curve of the compound to be measured in which the integrated peak area of the 4,4 ' -difluorobenzophenone standard solution measured by high performance liquid chromatography is the ordinate and the concentration of the 4,4 ' -difluorobenzophenone standard solution is the abscissa.
In the present invention, the plotting of the HPLC concentration-peak area curve of 4, 4' -difluorobenzophenone preferably comprises the following steps:
weighing a quantitative 4,4 '-difluorobenzophenone standard, performing constant volume by using a methanol solution to obtain a standard stock solution, and diluting by using methanol to obtain a 4, 4' -difluorobenzophenone standard diluent;
diluting a plurality of 4,4 '-difluorobenzophenone standard diluents with different concentrations by using methanol to obtain a series of 4, 4' -difluorobenzophenone standard solutions;
the concentration of the series of 4, 4' -difluorobenzophenone standard solutions is 0.1-5.5 mu g/mL;
after measuring the series of 4,4 '-difluorobenzophenone standard solutions obtained in the above steps by high performance liquid chromatography, the HPLC concentration-peak area curve of 4, 4' -difluorobenzophenone was plotted using the integrated peak area of the obtained 4,4 '-difluorobenzophenone as the ordinate and the concentration of 4, 4' -difluorobenzophenone as the abscissa.
In the invention, the concentration of the series of 4, 4' -difluorobenzophenone standard solutions is preferably 0.1-5.5 mu g/mL, more preferably 0.5-5 mu g/mL, more preferably 1.5-4 mu g/mL, and more preferably 2.5-3 mu g/mL.
In the present invention, the conditions of the HPLC preferably include:
a chromatographic column: column length 150mm, inner diameter 4.6mm, filler particle size 5 μm, stationary phase C18 (LUNA); mobile phase A: 1% aqueous acetic acid, mobile phase B: acetonitrile; column temperature: 30 ℃; column flow rate: 1 mL/min; sample injection volume: 10 mu L of the solution;
elution gradient: 0min, mobile phase A80% and mobile phase B20%; 12min, mobile phase A50% and mobile phase B50%; and (4) 18 min: mobile phase A20%, mobile phase B80%; 19 min: 80% of mobile phase A and 20% of mobile phase B.
In the present invention, the detector of the HPLC preferably comprises a fluorescence detector in series with an ultraviolet detector.
In the present invention, the conditions of the fluorescence detector preferably include:
0min: the excitation wavelength is 284nm, and the emission wavelength is 332 nm; 5 min: the excitation wavelength is 275nm, and the emission wavelength is 315 nm; 7.5 min: the excitation wavelength is 277nm, and the emission wavelength is 319 nm; 11 min: the excitation wavelength is 272nm, and the emission wavelength is 309 nm; and (20 min): the excitation wavelength was 273nm and the emission wavelength was 323 nm.
In the present invention, the conditions of the ultraviolet detector preferably include:
0-20 min: the absorption wavelength is 254nm, the reference wavelength is 360 nm.
The invention is a complete and detailed integral detection process, better reflects the migration characteristic of 4,4 ' -difluorobenzophenone in plastic products, improves the migration detection accuracy and higher repeatability of the 4,4 ' -difluorobenzophenone in the plastic products, and the detection method of the 4,4 ' -difluorobenzophenone in the plastic products can specifically comprise the following steps:
(1) MPPO purification treatment: placing the MPPO in a round-bottom flask, heating and refluxing the MPPO by acetone for leaching, performing suction filtration by quantitative filter paper after leaching, washing the MPPO by acetone, airing the purified MPPO in a fume hood, placing the MPPO in an oven for drying, taking out the MPPO and sealing the MPPO for later use.
(2) Migration of plastic products: splitting a certain area of plastic product test sample, and preparing a plurality of parallel test samples for each test sample. Weighing MPPO according to a certain proportion of plastic products/MPPO, uniformly paving the MPPO to the bottom of a glass weighing vessel, placing the plastic products above the MPPO, sealing the glass weighing vessel and placing the glass weighing vessel into a thermostat, setting a certain test temperature, and starting timing after the test temperature is reached; after the contact time is reached, the plastic article is removed from the oven.
(3) Extraction: transferring the MPPO in the culture dish into a centrifuge tube with a plug, adding a mixed solution of methanol, an acetic acid aqueous solution and methanol, acetonitrile or acetone solvent as an extraction solvent, performing vortex oscillation on a vortex oscillator for a certain time, and centrifuging; filtering the supernatant with water phase filter membrane, and detecting.
(4) Preparation of standard solution: weighing a certain amount of 4, 4' -difluorobenzophenone standard substance, and preparing a standard stock solution by constant volume with a methanol solution; accurately transferring a certain amount of 4,4 '-difluorobenzophenone standard stock solution, metering the volume to a scale by using methanol, and fully and uniformly mixing to obtain a 4, 4' -difluorobenzophenone standard diluent; taking 5 gradient 4,4 '-difluorobenzophenone standard stock solutions, respectively placing the stock solutions in 25mL volumetric flasks, diluting the stock solutions to a scale with methanol, and fully and uniformly mixing the stock solutions to obtain a series of 4, 4' -difluorobenzophenone standard solutions.
(5) Drawing a standard curve: and (3) measuring 4,4 '-difluorobenzophenone in the standard solution prepared in the step (4) by using HPLC (high performance liquid chromatography), obtaining an integrated peak area of the compound, and establishing a calibration curve of the compound to be measured by using the peak area as an ordinate and using the concentration of 4, 4' -difluorobenzophenone in milligrams per liter (mg/L) as an abscissa.
(6) And (3) measuring the migration quantity: and (4) carrying out HPLC analysis on the filtered supernatant in the step (3) to obtain the peak area of the substance to be detected 4, 4' -difluorobenzophenone, and calculating according to a correction curve to obtain the concentration of the substance to be detected.
Specifically, the liquid chromatography conditions are as follows:
a chromatographic column: column length 150mm, inner diameter 4.6mm, filler particle size 5 μm, stationary phase C18 (LUNA); mobile phase A: 1% aqueous acetic acid, mobile phase B: acetonitrile; column temperature: 30 ℃; column flow rate: 1 mL/min; sample introduction volume: 10 μ L.
Elution gradient: 0min, mobile phase A80% and mobile phase B20%; 12min, mobile phase A50% and mobile phase B50%; 18 min: 20% of mobile phase A and 80% of mobile phase B; 19 min: 80% of mobile phase A and 20% of mobile phase B. The analysis time was 20 min.
Specifically, the liquid chromatography detector is a fluorescence detector connected with an ultraviolet detector in series;
specifically, the conditions of the fluorescence detector are as follows: 0min: the excitation wavelength is 284nm, and the emission wavelength is 332 nm; 5 min: the excitation wavelength is 275nm, and the emission wavelength is 315 nm; 7.5 min: the excitation wavelength is 277nm, and the emission wavelength is 319 nm; 11 min: the excitation wavelength is 272nm, and the emission wavelength is 309 nm; 20 min: the excitation wavelength is 273nm, and the emission wavelength is 323 nm;
specifically, the ultraviolet detector conditions are as follows: 0-20 min: the absorption wavelength is 254nm and the reference wavelength is 360 nm.
In order to obtain better extraction effect, the MPPO extraction solvent is selected. In the european union EN 14338-2003 standard, acetone is recommended for direct extraction of the migrated species in MPPO. However, 4' -difluorobenzophenone is easily soluble in methanol aqueous solution, and for this reason, matrix effect after MPPO extraction by solvents such as methanol, a mixed solution of 1% acetic acid aqueous solution and methanol (volume ratio of 1: 1), acetonitrile and acetone was examined by a matrix addition method in an experiment. The content result shows that the peak is not detected in the mixed solution of 1% acetic acid water solution and methanol, and the extraction content of acetonitrile and acetone is lower than that of methanol water solution; finally, the present invention employs methanol as the extraction solvent for MPPO.
The MPPO extraction conditions are optimized, a vortex extraction mode is adopted in an experiment, and the influence of different vortex extraction time and extraction times on the extraction of the substance to be detected adsorbed in the MPPO is inspected. The detection response of an instrument obtained by vortex for 2min is 100%, and experimental results show that the extraction effect difference of different vortex time is not large (+/-10%), and the extraction purpose can be achieved by vortex extraction for 10min once. Finally, the invention preferably adopts the extraction condition of one vortex extraction for 10 min.
The invention optimizes the migration volume of 4,4 '-difluorobenzophenone at different temperatures, selects the simulated temperatures of 150 ℃, 175 ℃ and 200 ℃, and compares the influence of different simulated temperatures on the migration volume of 4, 4' -difluorobenzophenone. The results show that: the migration amount of 4, 4' -difluorobenzophenone increases when the temperature of the simulant increases from 150 ℃ to 175 ℃; at an increase to 200 c, the migration rate is essentially unchanged, probably because at 175 c, the free target has been completely adsorbed as MPPO with high adsorptivity, so the migration experiment temperature is preferably chosen to be 175 c.
The invention also evaluates the sensitivity, the recovery rate and the repeatability of the analysis method, adopts a method of adding standard in 0.5g blank MPPO to carry out experiments on the recovery rate and the precision of the analysis method, the adding standard level is respectively 2 mug, 4 mug and 8 mug, each adding standard level is measured for 5 times in parallel, and the detection Limit (LOD) of the analysis method is obtained by calculating according to the S/N ratio which is more than or equal to 3. The result shows that the substance has good linear relation (R2 is 1), the LOD is 0.005-0.021 mg/kg, the recovery rate of 3 standard addition levels is 91.4-119.5%, and the precision is lower than 5%.
Referring to fig. 1, fig. 1 is a schematic diagram of a migration test apparatus according to the present invention. Wherein, 1-plastic product material; 2-glass weighing vessel; 3-MPPO.
The invention has the advantages that no method for detecting the migration quantity of the 4,4 '-difluorobenzophenone in the plastic product exists at present, a set of complete detection method is established from the beginning, and the detection of the migration substance of the 4, 4' -difluorobenzophenone in the plastic product can be rapidly realized.
The steps of the invention provide a method for detecting 4, 4' -difluorobenzophenone in a plastic product. The invention adopts a simulant, namely modified polyphenylene oxide (MPPO), to analyze 4, 4' -difluorobenzophenone in the plastic product migration, accurately reflects the migration characteristic of the plastic product and food in a dry contact state, can truly reflect the migration process of the plastic product and food in the dry contact state, and is a set of complete detection processes from the absence to the existence. The method for detecting migration of the transferee 4,4 '-difluorobenzophenone in the plastic product can simulate the migration behavior of the plastic product and food in a dry contact state, and can quickly and accurately realize the determination of the content of the transferee 4, 4' -difluorobenzophenone in the plastic product.
The invention is a set of detection method established based on specific MPPO purification treatment method, migration experiment method for plastic products, MPPO extraction method, instrumental determination method, especially the specific steps of chromatographic use type, analysis condition, elution solvent composition, gradient and the like, can simulate the migration behavior of the plastic products and food in a dry contact state, truly reflect the actual contact state of the plastic products and the food, quickly and accurately realize the detection of the migration amount of 4,4 '-difluorobenzophenone in the plastic products, effectively solves the problem that no method for detecting the migration amount of 4, 4' -difluorobenzophenone in the plastic products exists in the prior art, and has the advantages of simplicity, easy implementation, environmental protection, strong controllability and good repeatability, thus being more suitable for popularization and application.
For further illustration of the present invention, the following will describe the method for detecting 4, 4' -difluorobenzophenone in a plastic product in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, but not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
The reagents used in the following examples of the present invention are all commercially available.
Example 1
The migration test apparatus in FIG. 1 was used.
(1) MPPO purification treatment: placing the MPPO in a round-bottom flask, heating and refluxing the MPPO by acetone for leaching for 6 hours, leaching the MPPO by quantitative filter paper after leaching, washing the MPPO for 2-3 times by the acetone, airing the purified MPPO in a fume hood, placing the MPPO in a 160 ℃ drying oven for drying for 6 hours, taking out the MPPO and sealing the MPPO for later use.
(2) Migration of plastic products: split a certain area (0.25 dm)2) 3 parallel specimens per sample were prepared. According to a plastic product/MPPO of 0.25dm2Weighing MPPO according to the proportion of 1g, uniformly paving the MPPO to the bottom of a glass weighing vessel, placing a plastic product above the MPPO, sealing the glass weighing vessel and placing the glass weighing vessel into a thermostat, setting the testing temperature to be 175 ℃, and starting timing after the testing temperature is reached; after a contact time of 24h had been reached, the plastic article was removed from the oven.
(3) And (3) extraction: transferring the MPPO in the culture dish into a 15mL centrifuge tube with a plug, adding 10mL methanol, performing vortex oscillation on a vortex oscillator at a speed of 2000r/min for 10min, and centrifuging at 4000r/min for 5 min; 5mL of the supernatant was filtered through a 0.45 μm aqueous membrane and was then assayed.
(4) Preparation of a standard solution: weighing 20mg of 4, 4' -difluorobenzophenone, diluting to 20mL with methanol, and fully and uniformly mixing; accurately transferring 1mL of 4,4 '-difluorobenzophenone standard stock solution into a 10mL volumetric flask, metering the volume to a scale with methanol, and fully and uniformly mixing to obtain a standard diluent with the concentration of 4, 4' -difluorobenzophenone of 100 mu g/mL. Accurately transferring 0.02mL, 0.05mL, 0.1mL, 0.2mL and 0.5mL of the standard dilution, respectively placing the standard dilutions in 10mL volumetric flasks, diluting to the scale with methanol, and mixing well to obtain 4, 4' -difluorobenzophenone concentrations of 0.2. mu.g/mL, 0.5. mu.g/mL, 1.0. mu.g/mL, 2.0. mu.g/mL and 5.0. mu.g/mL, respectively.
(5) Drawing a standard curve: and (5) measuring 4,4 '-difluorobenzophenone in the standard solution prepared in the step (4) by using HPLC (high performance liquid chromatography), obtaining an integrated peak area of the compound, and establishing a calibration curve of the compound to be measured by using the peak area as a vertical coordinate and using the concentration of 4, 4' -difluorobenzophenone in milligrams per liter (mg/L) as a horizontal coordinate.
(6) And (3) measuring the migration quantity: and (4) carrying out HPLC analysis on the filtered supernatant in the step (3) to obtain the peak area of the substance to be detected 4, 4' -difluorobenzophenone, and calculating according to a correction curve to obtain the concentration of the substance to be detected.
Further, the liquid chromatography conditions are as follows:
a chromatographic column: column length 150mm, inner diameter 4.6mm, filler particle size 5 μm, stationary phase C18 (LUNA); mobile phase A: 1% aqueous acetic acid, mobile phase B: acetonitrile; column temperature: 30 ℃; column flow rate: 1 mL/min; sample introduction volume: 10 μ L.
Elution gradient: 0min, mobile phase A80% and mobile phase B20%; 12min, mobile phase A50% and mobile phase B50%; 18 min: 20% of mobile phase A and 80% of mobile phase B; and (3) 19 min: 80% of mobile phase A and 20% of mobile phase B. The analysis time was 20 min.
Further, the liquid chromatogram detector is a fluorescence detector connected with an ultraviolet detector in series;
further, the fluorescence detector conditions are: 0min: the excitation wavelength is 284nm, and the emission wavelength is 332 nm; 5 min: the excitation wavelength is 275nm, and the emission wavelength is 315 nm; 7.5 min: the excitation wavelength is 277nm, and the emission wavelength is 319 nm; 11 min: the excitation wavelength is 272nm, and the emission wavelength is 309 nm; 20 min: the excitation wavelength is 273nm, and the emission wavelength is 323 nm;
further, the ultraviolet detector conditions are as follows: 0-20 min: the absorption wavelength is 254nm and the reference wavelength is 360 nm.
Example 2
The difference from example 1 is that: the extraction solvent in the step (3) is acetone or acetonitrile solution, and the vortex oscillation time is 5 min;
example 3
The difference from example 1 is that: the extraction solvent in the step (3) is a mixed solution of 1% acetic acid water solution and methanol, and the vortex oscillation time is 10 min.
Example 4
The difference from example 1 is that: the test temperature in step (2) was 200 ℃.
Referring to table 1, table 1 shows the detection results in examples 1 to 4 of the present invention.
TABLE 1
| Name (R) | Content (microgram/ml) |
| Example 1 | 0.16 |
| Example 2 | 0.13 |
| Example 3 | Not detected out |
| Example 4 | 0.16 |
The results show the matrix effect after MPPO extraction by solvents such as methanol, a mixed solution of 1% acetic acid water solution and methanol (volume ratio is 1: 1), acetonitrile, acetone and the like. The content results show that no peak is detected in the mixed solution of 1% acetic acid water solution and methanol, and the extraction content of acetonitrile and acetone is lower than that of methanol water solution. Methanol is used as the optimal extraction solvent for MPPO.
The foregoing detailed description of the method for detecting 4, 4' -difluorobenzophenone in a plastic article provided by the present invention has been presented and the principles and embodiments of the present invention are described herein using specific examples, which are intended to facilitate an understanding of the method and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for detecting 4, 4' -difluorobenzophenone in a plastic product is characterized by comprising the following steps:
1) directly contacting a plastic product to be detected with the purified MPPO, and then carrying out a contact migration process under a sealed condition to obtain the MPPO contacted with the plastic product;
2) placing the MPPO which is obtained in the step and is contacted with the plastic product into an extraction solvent, and performing vortex oscillation extraction to obtain a solution to be detected;
3) and (3) carrying out HPLC analysis on the solution to be detected obtained in the step to obtain the peak area of the substance to be detected, namely 4,4 ' -difluorobenzophenone, and calculating according to the HPLC concentration-peak area curve of the 4,4 ' -difluorobenzophenone to obtain the concentration of the 4,4 ' -difluorobenzophenone in the plastic product to be detected.
2. The method as set forth in claim 1, wherein the MPPO is a modified polyphenylene ether;
the shape of the plastic product comprises one or more of sheet, block and particle;
the shape of the MPPO comprises one or more of a sheet shape, a block shape and a particle shape;
the particle size of the MPPO particles is 60-80 meshes.
3. The assay of claim 1, wherein the step of decontamination processing comprises one or more of leaching, filtering, washing and drying;
the ratio of the plastic product to be detected to the MPPO is 0.1-0.5 dm2：1g；
The direct contacting includes placing the plastic article to be tested on the MPPO.
4. The detection method according to claim 1, wherein the direct contact is a dry contact;
the temperature in the contact migration process is 100-250 ℃;
the time of the contact migration process is 12-48 h.
5. The detection method according to claim 1, wherein the extraction solvent comprises methanol;
the rotational speed of the vortex oscillation is 1500-4000 r/min;
and the vortex oscillation time is 5-15 min.
6. The detection method according to claim 1, wherein the vortex oscillation further comprises the steps of centrifugation and supernatant filtration;
the supernatant taking and filtering mode comprises water phase filter membrane filtration;
the aperture of the water-phase filter membrane is 0.35-0.5 μm.
7. The detection method according to claim 1, wherein the HPLC concentration-peak area curve of 4,4 ' -difluorobenzophenone is a calibration curve of the test compound in which the integrated peak area of a 4,4 ' -difluorobenzophenone standard solution measured by high performance liquid chromatography is plotted on the ordinate and the concentration of the 4,4 ' -difluorobenzophenone standard solution is plotted on the abscissa.
8. The detection method according to claim 1, wherein the step of plotting the HPLC concentration-peak area curve of 4, 4' -difluorobenzophenone comprises the following steps:
weighing a quantitative 4,4 '-difluorobenzophenone standard, performing constant volume with a methanol solution to obtain a standard stock solution, and diluting with methanol to obtain a 4, 4' -difluorobenzophenone standard diluent;
diluting a plurality of 4,4 '-difluorobenzophenone standard diluents with different concentrations by using methanol to obtain a series of 4, 4' -difluorobenzophenone standard solutions;
the concentration of the series of 4, 4' -difluorobenzophenone standard solutions is 0.1-5.5 mu g/mL;
measuring the series of 4,4 '-difluorobenzophenone standard solutions obtained in the steps by using a high performance liquid chromatography, and drawing an HPLC concentration-peak area curve of 4, 4' -difluorobenzophenone by taking the integrated peak area of the obtained 4,4 '-difluorobenzophenone as an ordinate and the concentration of 4, 4' -difluorobenzophenone as an abscissa.
9. The detection method according to claim 1, wherein the conditions of HPLC comprise:
and (3) chromatographic column: column length 150mm, inner diameter 4.6mm, filler particle size 5 μm, stationary phase C18 (LUNA); mobile phase A: 1% aqueous acetic acid, mobile phase B: acetonitrile; column temperature: 30 ℃; column flow rate: 1 mL/min; sample introduction volume: 10 mu L of the solution;
elution gradient: 0min, the mobile phase A accounts for 80 percent, and the mobile phase B accounts for 20 percent; for 12min, mobile phase A50% and mobile phase B50%; 18 min: 20% of mobile phase A and 80% of mobile phase B; 19 min: mobile phase a 80%, mobile phase B20%.
10. The detection method according to claim 1, wherein the detector of the HPLC comprises a fluorescence detector in series with an ultraviolet detector;
the conditions of the fluorescence detector, comprising:
0min: the excitation wavelength is 284nm, and the emission wavelength is 332 nm; 5 min: the excitation wavelength is 275nm, and the emission wavelength is 315 nm; 7.5 min: the excitation wavelength is 277nm, and the emission wavelength is 319 nm; 11 min: the excitation wavelength is 272nm, and the emission wavelength is 309 nm; 20 min: the excitation wavelength is 273nm, and the emission wavelength is 323 nm;
the conditions of the ultraviolet detector include:
0-20 min: the absorption wavelength is 254nm and the reference wavelength is 360 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210421335.5A CN114755339A (en) | 2022-04-21 | 2022-04-21 | Method for detecting 4, 4' -difluorobenzophenone in plastic product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210421335.5A CN114755339A (en) | 2022-04-21 | 2022-04-21 | Method for detecting 4, 4' -difluorobenzophenone in plastic product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114755339A true CN114755339A (en) | 2022-07-15 |
Family
ID=82330721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210421335.5A Pending CN114755339A (en) | 2022-04-21 | 2022-04-21 | Method for detecting 4, 4' -difluorobenzophenone in plastic product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114755339A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012001131A1 (en) * | 2010-07-02 | 2012-01-05 | Solvay Specialty Polymers Usa, L.L.C. | Method of making poly(aryl ether ketones) from 4,4' difluorobenzophenone comprising oxidizing species and/or nitro compounds |
| CN104198621A (en) * | 2014-09-26 | 2014-12-10 | 云南中烟工业有限责任公司 | Method for simultaneous determination of special migration volume of multiple preservatives in paper and paperboard |
| CN104237438A (en) * | 2014-09-26 | 2014-12-24 | 云南中烟工业有限责任公司 | Method of utilizing Tenax as simulant with GCMS (Gas Chromatography Mass Spectrometry) to determine transfer volume of aromatic amine in paper and paperboard |
| CN109061026A (en) * | 2018-09-05 | 2018-12-21 | 九江天赐高新材料有限公司 | The method that the PEEK sample of a kind of pair of synthesis carries out analysis detection |
| CN109298090A (en) * | 2018-10-24 | 2019-02-01 | 通标标准技术服务(上海)有限公司 | A method of 1,3- butadiene and acrylonitrile specific transfer amount in measurement dry food contact plastics |
| CN110967421A (en) * | 2019-11-15 | 2020-04-07 | 正大青春宝药业有限公司 | Method for detecting related substances of flunarizine hydrochloride preparation |
| CN113341018A (en) * | 2021-06-08 | 2021-09-03 | 上海烟草集团有限责任公司 | Method for measuring migration amount of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO (maximum power point tracking) |
-
2022
- 2022-04-21 CN CN202210421335.5A patent/CN114755339A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012001131A1 (en) * | 2010-07-02 | 2012-01-05 | Solvay Specialty Polymers Usa, L.L.C. | Method of making poly(aryl ether ketones) from 4,4' difluorobenzophenone comprising oxidizing species and/or nitro compounds |
| CN104198621A (en) * | 2014-09-26 | 2014-12-10 | 云南中烟工业有限责任公司 | Method for simultaneous determination of special migration volume of multiple preservatives in paper and paperboard |
| CN104237438A (en) * | 2014-09-26 | 2014-12-24 | 云南中烟工业有限责任公司 | Method of utilizing Tenax as simulant with GCMS (Gas Chromatography Mass Spectrometry) to determine transfer volume of aromatic amine in paper and paperboard |
| CN109061026A (en) * | 2018-09-05 | 2018-12-21 | 九江天赐高新材料有限公司 | The method that the PEEK sample of a kind of pair of synthesis carries out analysis detection |
| CN109298090A (en) * | 2018-10-24 | 2019-02-01 | 通标标准技术服务(上海)有限公司 | A method of 1,3- butadiene and acrylonitrile specific transfer amount in measurement dry food contact plastics |
| CN110967421A (en) * | 2019-11-15 | 2020-04-07 | 正大青春宝药业有限公司 | Method for detecting related substances of flunarizine hydrochloride preparation |
| CN113341018A (en) * | 2021-06-08 | 2021-09-03 | 上海烟草集团有限责任公司 | Method for measuring migration amount of 10 volatile and semi-volatile compounds in packaging printing paper to MPPO (maximum power point tracking) |
Non-Patent Citations (2)
| Title |
|---|
| 周晓东 等: "4,4′-二氟二苯甲酮的合成研究", vol. 5, no. 5, pages 38 - 41 * |
| 王国军 等: "HPLC测定聚丙烯餐具中12种抗氧化剂迁移量", vol. 38, no. 23, pages 55 - 59 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108663471B (en) | Method for determining contents of multiple endocrine disruptors in estuary sediments | |
| CN114002338B (en) | Method for measuring migration quantity of additive in food contact material | |
| CN113391015A (en) | Method for detecting 14 phenolic compounds in soil | |
| CN111337596A (en) | Detection method of perfluorocarboxylic acid compound | |
| CN114778732A (en) | Method for detecting hydroquinone in plastic product | |
| CN113777210A (en) | Method for simultaneously detecting water-soluble anion and cation contents in atmosphere-particles by using rapid solvent extraction-ion chromatography | |
| CN107703222B (en) | Method for determining trace organic amine in atmospheric particulates | |
| CN114755339A (en) | Method for detecting 4, 4' -difluorobenzophenone in plastic product | |
| CN108802243B (en) | Method for simultaneously detecting bentazone, 2,4-D, 2, 4-dichlorophen, 2,4, 6-trichlorophenol and pentachlorophenol in water | |
| CN108828123B (en) | Method for measuring content of butyraldehyde and paraldehyde in polyvinyl butyral resin | |
| CN113607852B (en) | Method for measuring turpentine in soil | |
| CN115112807A (en) | Method for rapidly determining volatile fatty acid in sludge | |
| CN114609295A (en) | High performance liquid chromatography analysis method for quinic acid content in tala enzymolysis waste liquid | |
| CN111077255A (en) | Method for detecting migration volume of 4, 4'-biphenol and 4,4' -dichlorodiphenyl sulfone in PPSU (polypropylene sulfone) milk bottle | |
| CN112630348A (en) | Detection method for detecting selenate selenite in water by using HPLC-ICP-MS | |
| CN105319301B (en) | A kind of assay method of the indigo middle non-pigmented organic matter of food additives | |
| CN114152690A (en) | Method for detecting acetaldehyde content in solid material | |
| CN109507336B (en) | Method for detecting organic solvent residue in glutamine dipeptide | |
| CN109507306A (en) | The measuring method of tributyl 2-acetylcitrate in a kind of water base adhesive | |
| CN115236221B (en) | Method for detecting dihydric alcohol compound in environmental medium | |
| CN115453022B (en) | Method for rapidly judging formaldehyde content in white spirit | |
| CN104198626B (en) | Trace enrofloxacin extracting and enriching and quantitative method on suspended particulate substance in water | |
| CN113984871B (en) | Method for determining shale soluble organic carbon isotope by using EA-IRMS | |
| CN111044666B (en) | Analysis method for trace carbon powder and salt residue in dibasic acid | |
| CN115616120B (en) | Method for simultaneously measuring contents of 11 feeding organic acids in organic acidifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |