CN113466396A - Method for detecting migration amount of plasticizer in skin contact material - Google Patents
Method for detecting migration amount of plasticizer in skin contact material Download PDFInfo
- Publication number
- CN113466396A CN113466396A CN202110695373.5A CN202110695373A CN113466396A CN 113466396 A CN113466396 A CN 113466396A CN 202110695373 A CN202110695373 A CN 202110695373A CN 113466396 A CN113466396 A CN 113466396A
- Authority
- CN
- China
- Prior art keywords
- sample
- sebum
- plasticizer
- temperature
- absorbent cotton
- 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.)
- Granted
Links
- 239000004014 plasticizer Substances 0.000 title claims abstract description 41
- 238000013508 migration Methods 0.000 title claims abstract description 26
- 230000005012 migration Effects 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 210000002374 sebum Anatomy 0.000 claims abstract description 29
- 238000001514 detection method Methods 0.000 claims abstract description 22
- -1 phthalate ester Chemical class 0.000 claims abstract description 7
- 238000000605 extraction Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 229920000742 Cotton Polymers 0.000 claims description 22
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 20
- 239000012086 standard solution Substances 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 10
- BKUSIKGSPSFQAC-RRKCRQDMSA-N 2'-deoxyinosine-5'-diphosphate Chemical compound O1[C@H](CO[P@@](O)(=O)OP(O)(O)=O)[C@@H](O)C[C@@H]1N1C(NC=NC2=O)=C2N=C1 BKUSIKGSPSFQAC-RRKCRQDMSA-N 0.000 claims description 9
- 102100035474 DNA polymerase kappa Human genes 0.000 claims description 9
- 101710108091 DNA polymerase kappa Proteins 0.000 claims description 9
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 claims description 9
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 9
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 5
- 239000012224 working solution Substances 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004445 quantitative analysis Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002137 ultrasound extraction Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 238000004451 qualitative analysis Methods 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 2
- 235000020778 linoleic acid Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 abstract description 2
- 210000004243 sweat Anatomy 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000008029 phthalate plasticizer Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000005556 hormone Substances 0.000 description 3
- 229940088597 hormone Drugs 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011097 chromatography purification Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 230000001850 reproductive effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004995 male reproductive system Anatomy 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
-
- 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
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
- G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
- G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
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)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
本发明属于化合物检测技术领域，具体涉及一种皮肤接触材料中增塑剂迁移量的检测方法。该方法通过以下步骤实现：（1）样品中增塑剂迁移（2）增塑剂提取（3）迁移量测定。本发明提供的检测方法中，利用皮脂模拟物作为增塑剂迁移介质，能够更加准确的评估材料中邻苯二甲酸酯类塑化剂在接触人体过程中向皮肤的迁移情况，为后续评估人体对增塑剂的吸收量，进而制定皮肤接触材料中增塑剂的安全限值提供科学检测基础，且操作简单、重复性好。
The invention belongs to the technical field of compound detection, and in particular relates to a method for detecting the migration amount of plasticizers in skin contact materials. The method is achieved by the following steps: (1) plasticizer migration in the sample (2) plasticizer extraction (3) migration measurement. In the detection method provided by the present invention, the sebum simulant is used as a plasticizer migration medium, which can more accurately evaluate the migration of phthalate ester plasticizers in the material to the skin during the process of contacting the human body, which is for the subsequent evaluation of the human body. The absorption of plasticizers and the establishment of safety limits for plasticizers in skin-contact materials provide a scientific basis for testing, and the operation is simple and repeatable.
Description
Technical Field
The invention belongs to the technical field of compound detection, and particularly relates to a method for detecting migration quantity of a plasticizer in a skin contact material.
Background
The phthalate plasticizer is widely used in plastic products to improve the plasticity and strength of the plastic products, is an important endocrine disrupter existing in the environment, has the toxicity of carcinogenicity, mutagenicity, teratogenicity, reproductive function destruction and the like, can be enriched through a food chain, and attracts wide attention of all countries in the world. Researches show that the phthalate can enter human bodies through skin contact, drinking water, respiratory systems and other modes, can be gradually accumulated in the human bodies and can be decomposed into corresponding metabolites to further harm human health, and the phthalate also has the functions of interfering the development of male reproductive systems and deteriorating reproductive capacity, and is an environmental hormone pollutant.
At present, the detection method of the phthalate plasticizer mainly focuses on the total content of the substances in the material or the migration amount of the substances in media such as wine, food and the like, and further considers the intake condition of the substances in human bodies. However, with the popularization of skin contact products such as intelligent wearable products and the like, the direct migration of the phthalate plasticizer from the material to the skin of the human body becomes a new risk point causing harm to the human body. Bovine glycogen and the like provide a method for detecting the migration amount of phthalate ester environmental hormone in textile in artificial sweat, but because phthalate ester is a fat-soluble substance and has low solubility in sweat with water as a main component, the method cannot effectively evaluate the real migration condition of the phthalate ester substance. In the prior art, the detection of the migration amount of the plasticizer in the skin contact material is relatively less documented.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for detecting the migration quantity of a plasticizer in a skin contact material.
In order to achieve the purpose, the specific technical scheme of the invention is as follows:
the invention provides a method for detecting the migration quantity of a plasticizer in a skin contact material, which comprises the following steps:
(1) accurately weighing a part with uniform material and smooth surface in a sample, wiping the surface, heating a sebum simulant in a constant-temperature drying box, treating the sample to be detected with the heated sebum simulant, and drying at constant temperature;
(2) wiping the sample and the surface of the tin foil paper by absorbent cotton, transferring the absorbent cotton adsorbed with sebum into a centrifuge tube, soaking the absorbent cotton by an extracting agent, performing ultrasonic extraction after vortex, removing the absorbent cotton, centrifuging, and collecting supernatant;
(3) preparing a standard working solution: diluting the plasticizer standard solution by using normal hexane, and respectively preparing series standard solutions of BBP, DBP, DEHP, DNOP, DINP and DIDP;
(4) and (3) blowing and concentrating the supernatant at 35 ℃ by nitrogen until the supernatant is nearly dry, accurately fixing the volume by using normal hexane, and carrying out qualitative and quantitative analysis by GC/MS (gas chromatography/mass spectrometry) on the same standard solution.
Further, in the step (1), the mass ratio of the sample to the sebum simulant is 2: 5; the constant-temperature drying is carried out for 8 hours at the constant temperature of 37 +/-1 ℃ in a constant-temperature drying box; the method for processing the sample to be detected comprises the following steps: smearing on the surface of the sample or soaking the sample in the sebum simulant.
The sebum-mimicking agent used in the present invention is oleic acid or linoleic acid.
Further, in the step (2), the specific operation process is as follows: transferring the absorbent cotton adsorbed with 5g of sebum into a centrifuge tube, soaking the absorbent cotton in 10.0mL of an extracting agent, performing vortex extraction for 2.0min, performing ultrasonic extraction for 12.0min, removing the absorbent cotton, centrifuging the extract at 5000r/min for 5min, and collecting the supernatant; the extracting agent is n-hexane saturated acetonitrile.
Further, in the step (3), the concentrations of the BBP, DBP, DEHP and DNOP standard solutions are 0.5, 2.0, 5.0, 8.0 and 10.0 mg/L; the concentrations of the DINP and DIDP standard solutions are 0, 2, 5, 10, 20 and 50 mg/L.
In the detection process, the GC-MS working conditions are as follows:
a chromatographic column: DB-5MS quartz capillary chromatographic column, 30m × 250 μm × 0.25 μm;
temperature programming: maintaining at 180 deg.C for 0.5min, raising temperature to 280 deg.C at 20 deg.C/min, and maintaining for 7 min;
carrier gas: helium with purity more than or equal to 99.999 percent in a constant pressure mode;
sample inlet temperature: the split ratio is 25:1 at 300 ℃;
interface temperature of chromatography-mass spectrometry: 280 ℃;
an ion source: the temperature of the electron ionization source EI is 230 ℃;
electron energy: 70 eV;
a mass analyzer: a quadrupole mass analyser;
scanning mode: qualitative in full SCAN (SCAN) mode, quantitative in selective ion SCAN (SIM) mode;
solvent retardation: 4 min;
gain factor: 1.00.
further, the retention time and characteristic ions of BBP, DBP, DEHP, DNOP, DINP and DIDP are specifically:
the invention has the beneficial effects that:
(1) in the detection method provided by the invention, the sebum simulacrum is used for extracting the plasticizer, so that the absorption of a human body to the plasticizer can be simulated more truly, the extraction is thorough, the operation is simple, and the repeatability is good.
(2) According to the detection method provided by the invention, the sebum simulacrum is used as a plasticizer migration medium, so that the migration condition of the phthalate plasticizer in the material to the skin in the process of contacting the human body can be more accurately evaluated, and a scientific detection basis is provided for the subsequent evaluation of the absorption amount of the plasticizer by the human body and further the formulation of the safety limit value of the plasticizer in the skin contact material.
Drawings
FIG. 1 is a mass spectrum of plasticizer measured in example 1.
FIG. 2 is a chromatogram for comparing the effect of measuring the transfer amount of sebum and the transfer amount of artificial sweat;
wherein A is a sebum migration amount chromatogram; and B is an artificial sweat migration amount chromatogram.
Detailed Description
The technical solution of the present invention is further explained and illustrated by the following specific examples.
Materials and apparatus
1. Reagent: plasticizer standard solution: commercial standards (BBP, DBP, DEHP, DNOP: 500mg/L, DINP and DIDP: 5000 mg/L); n-hexane: carrying out chromatographic purification; acetonitrile: and (4) carrying out chromatographic purification.
2. Instruments and devices: gas chromatography/mass spectrometry (GC/MS): electron Impact (EI) ionization source with 70eV, NIST mass spectra gallery; an electronic balance: the precision is 0.1 mg; a vortex mixer; an ultrasonic extractor; a high speed centrifuge; tin foil paper; constant temperature drying cabinet.
Example 1
(1) Plasticizer migration in samples
Selecting a part which is made of a PVC material and has uniform material and smooth surface in the glasses nose pad, accurately weighing 2.0g of sample, and wiping the surface; heating 5.0g of sebum simulacrum (oleic acid) to 37 +/-1 ℃ in a constant-temperature drying box, keeping for 10min, uniformly coating the heated sebum simulacrum on the surface of a sample to enable sebum to completely immerse the sample, covering with tin foil, and placing in the constant-temperature drying box for constant temperature of 8h at the temperature of 37 +/-1 ℃;
(2) plasticizer extraction
Wiping a sample and the surface of a tin foil paper by using sufficient absorbent cotton which is cleaned and dried by methanol to adsorb a sebum simulant, transferring the absorbent cotton adsorbed with the sebum simulant into a 50mL centrifuge tube, soaking the absorbent cotton in 10.0mL acetonitrile saturated by normal hexane, whirling for 2.0min, ultrasonically extracting for 12.0min, removing the absorbent cotton, centrifuging extract for 5min at 5000r/min, collecting supernatant, if layering is not obvious, freezing to promote sebum solidification, blowing nitrogen at 35 ℃ to concentrate the supernatant to be nearly dry, accurately fixing the volume to 1.0mL by using the normal hexane, and analyzing by GC/MS.
(3) Measurement of migration amount
GC-MS working conditions
A chromatographic column: DB-5MS quartz capillary chromatographic column, 30m × 250 μm × 0.25 μm;
temperature programming: maintaining at 180 deg.C for 0.5min, raising temperature to 280 deg.C at 20 deg.C/min, and maintaining for 7 min;
carrier gas: helium with purity more than or equal to 99.999 percent in a constant pressure mode;
sample inlet temperature: the split ratio is 25:1 at 300 ℃;
interface temperature of chromatography-mass spectrometry: 280 ℃;
an ion source: the temperature of the electron ionization source EI is 230 ℃;
electron energy: 70 eV;
a mass analyzer: a quadrupole mass analyser;
scanning mode: qualitative in full SCAN (SCAN) mode, quantitative in selective ion SCAN (SIM) mode;
solvent retardation: 4 min;
gain factor: 1.00.
preparing a standard working solution: diluting the plasticizer standard solution with n-hexane to prepare series standard solutions with BBP, DBP, DEHP and DNOP concentrations of 0.5, 2.0, 5.0, 8.0 and 10.0mg/L and DINP and DIDP concentrations of 0, 2, 5, 10, 20 and 50mg/L respectively. And testing the standard solution on a machine according to the sequence of the concentration from low to high. The test method of the sample extracting solution to be tested is the same as that of the standard solution. The mass spectra of the 6 plasticizers are shown in FIG. 1. The retention times and characteristic ions of the 6 plasticizers are shown in table 1.
TABLE 16 Retention time and characteristic ions of the plasticizers (liquid film method)
(I) qualitative analysis
When the sample is measured, if the retention time of the detected chromatographic peak is consistent with that of the standard substance, all selected ions appear in the sample mass spectrogram after the background is subtracted, and the abundance ratio is consistent with that of the standard substance, the existence of the corresponding phthalate in the sample can be judged.
(II) quantitative analysis
According to the migration volume of the object to be tested in the test solution, selecting standard working solutions with similar concentrations, and testing the standard working solutions and the test solution respectively under the same conditions. The response values of the phthalate to be measured in the standard solution and the test solution are both in the linear range of the detection of the instrument, and if the detection response value of the test solution is beyond the linear range of the detection of the instrument, the phthalate can be measured after being diluted properly.
The standard adopts an external standard method to carry out quantitative analysis on the plasticizer. In the chromatogram, proper quantitative ions are selected for peak area integration, DINP and DIDP are respectively integrated after base lines of chromatographic peak groups of all isomers are leveled, and the sum of the areas is calculated.
1. Calculation of results
The migration of each phthalate in the sample was calculated according to formula (1):
in the formula: xi-the migration of a phthalate i in the sample, in μ g/g;
cithe concentration of a certain phthalate i in the extracting solution is obtained by a calibration curve, and the unit is mug/mL;
v is volume of extract in mL;
m is the weight of the sample in g.
2. Detection limit and quantitation lower limit
The detection limit and the lower limit of quantification of the plasticizer in 6 by the detection method provided by the present invention are shown in table 2.
TABLE 26 detection and lower quantification limits for plasticizers
3. Recovery rate
The recovery analysis was performed by quantitatively adding a standard solution of an appropriate known concentration to the sample. The recovery rate of the 6 plasticizers is 75-116%.
4. Precision degree
The absolute difference between the results of two independent tests obtained under repetitive conditions is not more than 20% of the arithmetic mean of the two measurements, subject to a 95% confidence level.
Comparative example 1
Step (1) same as example 1;
(2) plasticizer extraction
Wiping a sample and the surface of a tin foil paper by using sufficient absorbent cotton which is cleaned and dried by methanol to adsorb a sebum simulant, transferring the absorbent cotton adsorbed with the sebum simulant into a 50mL centrifuge tube, soaking the absorbent cotton in 10.0mL of normal hexane, vortexing for 2.0min, ultrasonically extracting for 12.0min, removing the absorbent cotton, centrifuging extract for 5min at 5000r/min, collecting supernatant, and if the supernatant is still obviously layered, freezing to promote sebum solidification, blowing nitrogen at 35 ℃ to concentrate the supernatant to be nearly dry, accurately fixing the volume to 1.0mL by using the normal hexane, and analyzing by GC/MS.
When the soaking was performed with a single n-hexane, the plasticizer could not be extracted from the sebum simulant, and at the same time, when the solvent was changed to a single acetonitrile, the plasticizer could not be extracted from the sebum simulant.
Comparative example 2
Selecting a part with uniform material and smooth surface in the sample, accurately weighing 2.0g of the sample, and wiping the surface; soaking a sample by using 5.0g of artificial sweat to enable the sweat to completely immerse the sample, and placing the sample in a constant-temperature drying oven to be kept at the constant temperature of 37 +/-1 ℃ for 8 hours; the method provided by the migration of phthalate ester environmental hormone in textile in artificial sweat is adopted for detection.
Through comparison, three plasticizers, namely DBP, DNOP and DEHP, are detected in the sebum simulant in the detection method provided by the invention, the content of DNOP is far higher than that of the other two plasticizers, and when the material is used by contacting the skin for a long time, the migrated plasticizer directly acts on the skin, so that potential threats are caused to the health and safety of human bodies. However, the artificial sweat mainly comprises inorganic salt and water, and has no obvious dissolution effect on the plasticizer, so the plasticizer is not detected in the extracting solution of the artificial sweat, and the actual use risk of a certain material cannot be comprehensively investigated only by using the artificial sweat. The specific comparison graph is shown in fig. 2.
Claims (7)
1. A method for detecting the migration amount of a plasticizer in a skin contact material is characterized by comprising the following steps:
(1) accurately weighing a part with uniform material and smooth surface in a sample, wiping the surface, heating a sebum simulant in a constant-temperature drying box, treating the sample to be detected with the heated sebum simulant, and drying at constant temperature;
(2) wiping the sample and the surface of the tin foil paper by absorbent cotton, transferring the absorbent cotton adsorbed with sebum into a centrifuge tube, soaking the absorbent cotton by an extracting agent, performing ultrasonic extraction after vortex, removing the absorbent cotton, centrifuging, and collecting supernatant;
(3) preparing a standard working solution: diluting the plasticizer standard solution by using normal hexane, and respectively preparing series standard solutions of BBP, DBP, DEHP, DNOP, DINP and DIDP;
(4) and (3) blowing and concentrating the supernatant at 35 ℃ by nitrogen until the supernatant is nearly dry, accurately fixing the volume by using normal hexane, and carrying out qualitative and quantitative analysis by GC/MS (gas chromatography/mass spectrometry) on the same standard solution.
2. The method according to claim 1, wherein in the step (1), the mass ratio of the sample to the sebum-mimicking agent is 2: 5; the constant-temperature drying is carried out for 8 hours at the constant temperature of 37 +/-1 ℃ in a constant-temperature drying box; the method for processing the sample to be detected comprises the following steps: smearing on the surface of the sample or soaking the sample in the sebum simulant.
3. The assay of claim 2, wherein the sebum mimetic is oleic acid or linoleic acid.
4. The detection method according to claim 1 or 2, wherein in the step (2), the specific operation process is as follows: transferring the absorbent cotton adsorbed with 5g of sebum into a centrifuge tube, soaking the absorbent cotton in 10.0mL of an extracting agent, performing vortex extraction for 2.0min, performing ultrasonic extraction for 12.0min, removing the absorbent cotton, centrifuging the extract at 5000r/min for 5min, and collecting the supernatant; the extracting agent is n-hexane saturated acetonitrile.
5. The detection method according to claim 1, wherein in the step (3), the concentrations of the BBP, DBP, DEHP and DNOP standard solutions are 0.5, 2.0, 5.0, 8.0 and 10.0 mg/L; the concentrations of the DINP and DIDP standard solutions are 0, 2, 5, 10, 20 and 50 mg/L.
6. The detection method according to any one of claims 1 to 5, wherein in the step (4), the GC-MS working conditions are as follows:
a chromatographic column: DB-5MS quartz capillary chromatographic column, 30m × 250 μm × 0.25 μm;
temperature programming: maintaining at 180 deg.C for 0.5min, raising temperature to 280 deg.C at 20 deg.C/min, and maintaining for 7 min;
carrier gas: helium with purity more than or equal to 99.999 percent in a constant pressure mode;
sample inlet temperature: the split ratio is 25:1 at 300 ℃;
interface temperature of chromatography-mass spectrometry: 280 ℃;
an ion source: the temperature of the electron ionization source EI is 230 ℃;
electron energy: 70 eV;
a mass analyzer: a quadrupole mass analyser;
scanning mode: qualitative in full SCAN (SCAN) mode, quantitative in selective ion SCAN (SIM) mode;
solvent retardation: 4 min;
gain factor: 1.00.
7. the detection method according to claim 6, wherein the retention times and characteristic ions of BBP, DBP, DEHP, DNOP, DINP and DIDP are specifically:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110695373.5A CN113466396B (en) | 2021-06-23 | 2021-06-23 | Method for detecting migration quantity of plasticizer in skin contact material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110695373.5A CN113466396B (en) | 2021-06-23 | 2021-06-23 | Method for detecting migration quantity of plasticizer in skin contact material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113466396A true CN113466396A (en) | 2021-10-01 |
| CN113466396B CN113466396B (en) | 2024-09-17 |
Family
ID=77869371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110695373.5A Active CN113466396B (en) | 2021-06-23 | 2021-06-23 | Method for detecting migration quantity of plasticizer in skin contact material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113466396B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114878762A (en) * | 2022-05-05 | 2022-08-09 | 宁夏回族自治区食品检测研究院 | Detection method, detection system and detection device for accumulation amount of plasticizer in linseed oil |
| CN119125390A (en) * | 2024-11-13 | 2024-12-13 | 浙江省质量科学研究院 | Skin migration amount measuring method and application of 20 organophosphorus flame retardants in cosmetic sponge |
| CN119125390B (en) * | 2024-11-13 | 2025-02-18 | 浙江省质量科学研究院 | Test method and application of skin migration of 20 organophosphorus flame retardants in cosmetic sponges |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE702623A (en) * | 1966-08-12 | 1968-02-12 | ||
| US20060165739A1 (en) * | 2005-01-06 | 2006-07-27 | Mary Kay Inc. | Alcohol-free microemulsion composition |
| CN104076104A (en) * | 2014-07-15 | 2014-10-01 | 浙江出入境检验检疫局检验检疫技术中心 | Method for detecting transfer volume of phosphate ester plasticisers in acid sweat in textile |
| CN104535666A (en) * | 2015-02-11 | 2015-04-22 | 浙江中烟工业有限责任公司 | A method of measuring migration amounts of eighteen phthalic acid esters in a conveyor belt by adopting a gas chromatography-mass spectrometry instrument |
| CN106770801A (en) * | 2017-02-21 | 2017-05-31 | 福建出入境检验检疫局检验检疫技术中心 | Gas chromatography determines 5 kinds of methods of antioxidant migration amount in packaging material |
| CN108709947A (en) * | 2018-07-10 | 2018-10-26 | 中国检验检疫科学研究院 | The assay method of phthalic ester plasticizer the amount of migration in food contact material |
| CN108918739A (en) * | 2018-08-28 | 2018-11-30 | 华南协同创新研究院 | A kind of pre-treating method and efficient liquid-phase chromatography method measuring alkannin in O/W type Asian puccoon skin care milk |
-
2021
- 2021-06-23 CN CN202110695373.5A patent/CN113466396B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE702623A (en) * | 1966-08-12 | 1968-02-12 | ||
| US20060165739A1 (en) * | 2005-01-06 | 2006-07-27 | Mary Kay Inc. | Alcohol-free microemulsion composition |
| CN104076104A (en) * | 2014-07-15 | 2014-10-01 | 浙江出入境检验检疫局检验检疫技术中心 | Method for detecting transfer volume of phosphate ester plasticisers in acid sweat in textile |
| CN104535666A (en) * | 2015-02-11 | 2015-04-22 | 浙江中烟工业有限责任公司 | A method of measuring migration amounts of eighteen phthalic acid esters in a conveyor belt by adopting a gas chromatography-mass spectrometry instrument |
| CN106770801A (en) * | 2017-02-21 | 2017-05-31 | 福建出入境检验检疫局检验检疫技术中心 | Gas chromatography determines 5 kinds of methods of antioxidant migration amount in packaging material |
| CN108709947A (en) * | 2018-07-10 | 2018-10-26 | 中国检验检疫科学研究院 | The assay method of phthalic ester plasticizer the amount of migration in food contact material |
| CN108918739A (en) * | 2018-08-28 | 2018-11-30 | 华南协同创新研究院 | A kind of pre-treating method and efficient liquid-phase chromatography method measuring alkannin in O/W type Asian puccoon skin care milk |
Non-Patent Citations (6)
| Title |
|---|
| BAJAGAIN, R ET AL: "Enhanced migration of plasticizers from polyvinyl chloride consumer products through artificial sebum", 《SCIENCE OF THE TOTAL ENVIRONMENT》, 31 May 2023 (2023-05-31), pages 1 - 10 * |
| BAJAGAIN, R ET AL: "Enhanced migration of plasticizers from polyvinyl chloride consumer products through artificial sebum", 《SCIENCE OF THE TOTAL ENVIRONMENT》, vol. 874, 20 May 2023 (2023-05-20), pages 1 - 10 * |
| HUANG, YM ET AL: "Nanosilver Migrated into Food-Simulating Solutions from Commercially Available Food Fresh Containers", 《PACKAGING TECHNOLOGY AND SCIENCE》, vol. 24, no. 5, 1 August 2011 (2011-08-01), pages 291 - 297 * |
| SHI, W ET AL: "Phthalate Esters on Hands of Office Workers: Estimating the Influence of Touching Surfaces", 《ENVIRONMENTAL SCIENCE & TECHNOLOGY LETTERS》, vol. 4, no. 1, 8 February 2017 (2017-02-08), pages 1 - 5 * |
| XIE, MJ ET AL: "Phthalates and alternative plasticizers and potential for contact exposure from children\'s backpacks and toys", 《JOURNAL OF EXPOSURE SCIENCE AND ENVIRONMENTAL EPIDEMIOLOGY》, vol. 26, no. 1, 13 January 2016 (2016-01-13), pages 119 - 124 * |
| 中华人民共和国国家质量监督检验检疫总局、中国国家标准化管理委员会: "气相色谱-质谱法(GC-MS)与配有热裂解/热脱附的气相色谱-质谱法(Py/TD-GC-MS)测定聚合物中的邻苯二甲酸酯", 《GB/T 39560.8, 电子电气产品中某些物质的测定》, 1 May 2021 (2021-05-01), pages 1 - 10 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114878762A (en) * | 2022-05-05 | 2022-08-09 | 宁夏回族自治区食品检测研究院 | Detection method, detection system and detection device for accumulation amount of plasticizer in linseed oil |
| CN114878762B (en) * | 2022-05-05 | 2024-04-19 | 宁夏回族自治区食品检测研究院 | Method, system and device for detecting plasticizer accumulation amount in sesame oil |
| CN119125390A (en) * | 2024-11-13 | 2024-12-13 | 浙江省质量科学研究院 | Skin migration amount measuring method and application of 20 organophosphorus flame retardants in cosmetic sponge |
| CN119125390B (en) * | 2024-11-13 | 2025-02-18 | 浙江省质量科学研究院 | Test method and application of skin migration of 20 organophosphorus flame retardants in cosmetic sponges |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113466396B (en) | 2024-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Habila et al. | Activated carbon from waste as an efficient adsorbent for malathion for detection and removal purposes | |
| Yu et al. | Sol–gel polydimethylsiloxane/poly (vinylalcohol)‐coated stir bar sorptive extraction of organophosphorus pesticides in honey and their determination by large volume injection GC | |
| Kataoka et al. | Determination of the oxidative stress biomarker urinary 8-hydroxy-2⿲-deoxyguanosine by automated on-line in-tube solid-phase microextraction coupled with liquid chromatography⿿ tandem mass spectrometry | |
| Feng et al. | Determination of volatile nitrosamines in latex products by HS-SPME–GC–MS | |
| Ruan et al. | A simplified fabric phase sorptive extraction method for the determination of amphetamine drugs in water samples using liquid chromatography-mass spectrometry | |
| CN113466396A (en) | Method for detecting migration amount of plasticizer in skin contact material | |
| CN108169383A (en) | The method and kit of total thyroid hormone in a kind of measure serum | |
| CN114166974B (en) | Method for detecting triethylamine in soil and sediment by gas chromatography-mass spectrometry | |
| CN112198249B (en) | Detection method of ethanolamine compound in soil | |
| Zachariadis et al. | Effect of sample matrix on sensitivity of mercury and methylmercury quantitation in human urine, saliva, and serum using GC‐MS | |
| CN111474259A (en) | Method for synchronously extracting and analyzing multiple flame retardants in hair | |
| Zhang et al. | Determination of aromatic amines from azo dyes reduction by liquid‐phase sorbent trapping and thermal desorption‐gas chromatography‐mass spectrometry | |
| Koc et al. | Application of gas chromatography to determination of Total Organic Fluorine after defluorination of perfluorooctanoic acid as a model compound | |
| Liu et al. | Quantification of selected monohydroxy metabolites of polycyclic aromatic hydrocarbons in human urine | |
| CN105486741A (en) | Preparation method and detection method of nano-immunosensor used for rapidly detecting benzo(a)pyrene | |
| CN112129873B (en) | Method for detecting cyanophos pesticide residue in soil | |
| Jin-Xiang et al. | Solid phase microextraction-ion mobility spectrometry for rapid determination of trace dichlorovos in tea drinks | |
| Shen et al. | Determination of pyrethroid residues in tobacco by means of solid phase microextraction and GC/MS with the aid of ultrasonic assisted extraction using water as extracting solvent | |
| CN111060630B (en) | Method for measuring moisture content in water-based paint based on GC-MS | |
| CN114624325A (en) | Quantitative analysis method for ion mobility spectrometry spectrogram identification | |
| CN113418994A (en) | Method for measuring content of syphilis and ecstasy in human hair by combining flash evaporation-gas chromatography/mass spectrometry method with micro-reaction device | |
| CN108387656B (en) | Method for detecting bis(hydroxymethyl)imidazolidinyl urea in cosmetics by liquid chromatography-mass spectrometry | |
| CN112379025A (en) | Gas chromatography-mass spectrometry detection method of hydrofluoroether solvent | |
| CN112697898B (en) | Method for rapidly determining content of ustilagin A in urine or cell culture medium by liquid chromatography-mass spectrometry | |
| Prieto et al. | Comparison of solid-phase extraction and solid-phase microextraction using octadecylsilane phase for the determination of pesticides in water samples |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |