CN103235054B - Method for determining banned and restricted compounds in toys with accelerated solvent extraction and gas chromatograph-mass spectrometer - Google Patents
Method for determining banned and restricted compounds in toys with accelerated solvent extraction and gas chromatograph-mass spectrometer Download PDFInfo
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- CN103235054B CN103235054B CN201310134728.9A CN201310134728A CN103235054B CN 103235054 B CN103235054 B CN 103235054B CN 201310134728 A CN201310134728 A CN 201310134728A CN 103235054 B CN103235054 B CN 103235054B
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Abstract
The invention provides a method for determining banned and restricted compounds in toys with accelerated solvent extraction and a gas chromatograph-mass spectrometer. According to the invention, a crushed toy sample is well mixed with diatomite; the mixture is placed in an accelerated solvent extraction tank, and is extracted by using an organic solvent; and the extracted banned and restricted compounds are detected with a gas chromatography-mass spectrometry technology. According to the invention, extracted banned and restricted compounds in the toy sample are extracted with the accelerated solvent extraction method. The method is simple and fast, and has high extraction rate. The method is suitable for analysis of large-batch toy samples, and has high application value in the respects of toy production and quality inspection.
Description
Technical field
The present invention relates to a kind of method of forbidding and limit the use of compound in toy of measuring, relate in particular to a kind of accelerated solvent extraction gas chromatograph-mass spectrometer and measure the method for forbidding and limit the use of compound in toy.
Background technology
The new toy safety instruction 2009/48/EC of European Union formally announces on the official's magazine in European Union on June 30th, 2009, and formally comes into effect on July 20th, 2009, replaces historical 88/378/EC instruction in existing 20 years.The new instruction of European Union's toy safety after revision is passed through proposes higher safety requirements to toy safety.Especially aspect chemical safety, unprecedented revision has been carried out in new instruction, clearly forbids or limit poisonous and hazardous chemical substance being increased to 85 kinds from 8 kinds.Wherein ban use of 55 anaphylactoid aromatic substances (allowing to be less than 100mg/kg except cannot avoid aborning time), other 11 anaphylactoid materials must indicate title in the time that concentration exceedes 100mg/kg.For meeting the requirement of chemical project detection technique renewal aspect, chemical safety is required to give 4 year transitional period the new instruction of the chemistry that came into force in 2013.New European Union's toy safety bill is that U.S. in 2008 that continues has issued another important technology regulation for toy product since " 2008 consumer goods improvements in security bill HR4040 ", and the toy instruction of revised European Union is the harshest the strictest toy regulation in the world.The development to world's Toy Industry is produced far-reaching influence by this case.
At present, European Union does not also put into effect relevant toy product forbidding and limits the use of sensitization flavor component detection method after putting into effect new instruction, for the yet rare report of detection domestic and foreign literature of the sensitization flavor component in toy product.The people such as Ines Masuck of Germany on chromatogram A, delivered one section about toy in the detection article of sensitization perfume compound.It has simulated the situation that children under normal temperature and high temperature two states suck, adopt the enrichment of head space-solid phase micro-extraction technique in toy 23 kinds forbid or limit the use of aromatic, then measure with Gc/ms Analyser.The enrichment process of single sample needs one to two day in the method, not too suitable for laboratory routine testing.CN102565207A discloses a kind of assay method of migration quantity of harmful organisms in toy, after mechanical shaking extraction, purification, adopts Gas Chromatography-Mass Spectrometry, can detect 10 kinds of harmful organic substances in toy simultaneously.But it is not the method, adopts mechanical shaking extraction, not high for the extraction efficiency of plastic toy sample, universal in common lab.CN102628837A discloses a kind of method that multiple allergic aroma agents in toys Solid-Phase Extraction detects simultaneously, multiple allergic aroma agents in toys content is adopted to tetrahydrofuran solvent extraction, after the little column purification of neutral alumina, Gas Chromatography-Mass Spectrometry.There is equally the incomplete problem of extracting in tetrahydrofuran solvent ultrasonic extraction.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, provide a kind of accelerated solvent extraction gas chromatograph-mass spectrometer to measure the method for forbidding and limit the use of compound in toy, to measure efficiently and accurately the content of forbidding and limit the use of compound in toy.
The invention provides a kind of accelerated solvent extraction gas chromatograph-mass spectrometer and measure the method for forbidding and limit the use of compound in toy, comprise the following steps:
Step 1, after the toy sample after break process and zeyssatite are mixed, is placed in accelerated solvent extraction pond, with organic solvent extraction;
Step 2, utilizes the forbidding extracting in gas chromatography-mass spectrography technology for detection step 1 and limits the use of compound.
Preferably, in step 1, the temperature of accelerated solvent extraction is 80-120 DEG C, and pressure is 1300-1700Mpa.
Preferably, organic solvent extraction 10-30min in step 1, circulation 1-5 time.
Preferably, in step 1, toy sample and diatomaceous weight ratio are 1:(2-10).
More preferably, in step 1, the temperature of accelerated solvent extraction is 100 DEG C, and pressure is 1500Mpa.
More preferably, in step 1, use organic solvent extraction 20min, circulate 2 times.
Wherein, described organic solvent can be acetone, methylene chloride, toluene, normal hexane, ethyl acetate, toluene, tetrahydrofuran, is preferably acetone.
Wherein, toy is in advance through break process: plastic sample, grinds; Cloth suede and stationery sample, shred with scissors; Wooden sample, drilling cuttings.
Follow the example of the extract clear obtaining without purification by accelerated solvent extraction, otherwise need to purify.
Preferably, the method for forbidding and limit the use of compound in accelerated solvent extraction toy also comprises purifying step: concentrate follow the example of the extract obtaining by accelerated solvent extraction, cross silicagel column, wash-out.
Preferably, in purifying step, taking normal hexane as leacheate, the activation solvent taking the mixed solvent of normal hexane and acetone as activated silica gel post, taking acetone as eluting solvent.
The condition of work of the gas chromatograph-mass spectrometer (GCMS) that wherein, in step 2, detection is used is as follows:
Chromatographic column: 30m × 0.25mm × 0.25 μ m, DB-17MS;
Input mode: Splitless injecting samples;
Temperature programme: initial temperature is 50 DEG C, keeps 1-3min, is warming up to 100-150 DEG C with the speed of 5-30 DEG C/min, keeps being warming up to 280-320 DEG C with 5-30 DEG C/min again after 3-7min, keeps 0.5-2min;
Ionization mode: EI;
Ionizing energy: 70eV;
Injector temperature: 260-300 DEG C;
Level Four bar temperature: 120-180 DEG C;
Ion source temperature: 220-280 DEG C.
The condition of work of the gas chromatograph-mass spectrometer (GCMS) that preferably, in step 2, detection is used is as follows:
Chromatographic column: 30m × 0.25mm × 0.25 μ m, DB-17MS;
Input mode: Splitless injecting samples;
Temperature programme: initial temperature is 50 DEG C, keeps 2min, is warming up to 130 DEG C with the speed of 20 DEG C/min, keeps being warming up to 300 DEG C with 20 DEG C/min again after 6min, keeps 1min;
Ionization mode: EI;
Ionizing energy: 70eV;
Injector temperature: 280 DEG C;
Level Four bar temperature: 150 DEG C;
Ion source temperature: 250 DEG C.
Preferably, it is quantitative that the detection in step 2 adopts interior standardization.
The present invention is followed the example of and is extracted the forbidding in toy sample and limit the use of compound by accelerated solvent extraction, and method is simple, quick, extraction ratio is high, is applicable to the analysis of toy sample in enormous quantities, aspect toy production and quality testing, has very high using value.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, to understand better the present invention.
(1) preparation of positive
Select representational 15 kinds of aromatics (representing dissimilar compound containing ketone, aldehyde, ester, ether etc.) of forbidding or limit the use of in the new instruction of European Union to be mixed with solution.Wherein, aromatic is respectively Musk ambrette (2,6-dinitro-3-methoxyl-4-t-butyltoluene), jasminolene, benzyl cinnamate, 7-ethoxy-4-methyl-coumarin, to thanatol, diethyl maleate, citronellol, geraniol, linalool, benzene acetonitrile, benzalacetone, diphenylamine, MEHQ, phenmethylol, cinnamic acid.These selected materials have represented in instruction that low volatility is to high-volatile material.
Select the most difficult plastic polymer being extracted as preparing object, at PP(polypropylene), PE(tygon) and ABS(acrylonitrile-butadiene-styrene (ABS) plastics) add respectively the standard solution of above-mentioned 15 kinds of aromatics in powder, after mixing, in injection machine, dissolve injection mo(u)lding, make respectively positive.
Another preparation is containing the cloth material products of above-mentioned 15 kinds of aromatics, as positive.
(2) extraction of aromatic
Positive is shredded with scissors, after beveller grinds, obtain sample powder.
Take 0.2g sample powder and 1g zeyssatite (2-4 order) and mix in fiber sleeve, be placed in the sample cell of accelerated solvent extraction.Under the condition of temperature 80-100 DEG C and pressure 1500Mpa, use acetone extract 20min, circulate 2 times, combining extraction liquid, concentrates.
If clear after extract is concentrated, measures as sample solution without purifying directly, otherwise needs to purify.
(3) purify
In the concentrate obtaining, add 5mL normal hexane in 2, be concentrated into 2mL, upper silicagel column, wash-out; Wherein, taking normal hexane as leacheate, the activation solvent taking the mixed solvent of normal hexane and acetone as activated silica gel post, taking acetone as eluting solvent.
The sample solution obtaining is concentrated.
(4) measure
When getting 2(and obtaining sample solution and be clear) or the 3 sample solution 1mL that obtain to sample bottle, add 0.1mL inner mark solution, evenly go up gas chromatograph-mass spectrometer (GCMS) (GC-MS) instrumental analysis.Wherein, the condition of work of gas chromatograph-mass spectrometer (GCMS) is as follows:
Chromatographic column: 30m × 0.25mm × 0.25 μ m, DB-17MS;
Input mode: Splitless injecting samples;
Temperature programme: initial temperature is 50 DEG C, keeps 2min, is warming up to 130 DEG C with the speed of 20 DEG C/min, keeps being warming up to 300 DEG C with 20 DEG C/min again after 6min, keeps 1min;
Ionization mode: EI;
Ionizing energy: 70eV;
Injector temperature: 280 DEG C;
Level Four bar temperature: 150 DEG C;
Ion source temperature: 250 DEG C.
Measurement result is as shown in table 1-3.
The precision of table 115 kind of compound
The recovery unit of table 215 kind of compound: %
The detection limit of table 315 kind of compound
| Compound title | No. CAS | The μ g/mL of unit |
| Linalool | 78-70-6 | 0．01 |
| Phenmethylol | 100-51-6 | 0．03 |
| Citronellol | 106-22-9 | 0．01 |
| Diethyl maleate | 141-05-9 | 0．001 |
| Geraniol | 106-24-1 | 0．01 |
| Benzene acetonitrile | 140-29-4 | 0．01 |
| 4-metoxyphenol | 150-76-5 | 0．02 |
| 4-ethoxy-phenol | 622-62-8 | 0．03 |
| Cinnamylidene | 104-55-2 | 0．05 |
| Benzalacetone | 122-57-6 | 0．02 |
| Diphenylamine | 122-39-4 | 0.02 |
| Jasminolene | 101-86-0 | 0．001 |
| Musk ambrette | 83-66-9 | 0．02 |
| 7-ethoxy-4-methyl-coumarin | 87-5-8 | 0.03 |
| Benzyl cinnamate | 103-41-3 | 0．004 |
As can be seen from Table 1, the precision of above-mentioned 15 kinds of compounds in PP lower than or approach 10%, the precision of majority of compounds is 4% left and right, precision is good; In PE, precision lower than or approach 6%, the precision of majority of compounds is 2-4%, minimumly reaches 0.62%, precision is good; In ABS, precision lower than or approach 9%, the precision of majority of compounds is 3-4%, minimumly reaches 1.77%, precision is good.
As can be seen from Table 2, the recovery of above-mentioned 15 kinds of compounds in cloth is between 76.1-98.9, and the recovery of majority of compounds is between 80-99; The recovery in PP is between 83.3-124.5; The recovery in PE is between 93.1-118.1.
As can be seen from Table 3, the detection limit of above-mentioned 15 kinds of compounds is all less than or equal to 0.01 μ g/mL, wherein, diethyl maleate and jasminolene detection limit are low to moderate 0.001 μ g/mL, benzyl cinnamate is minimum, is 0.004 μ g/mL, illustrates that detection method of the present invention is highly sensitive.
(5) mensuration of actual toy sample
Apply method provided by the invention, buy from the market 10 kinds of ABS material toys, 10 kinds of cloth toys, 10 kinds of wooden toys are forbidden and are limited the use of the mensuration of compound, wherein, in ABS material toy, there are 9 kinds forbidding detected or limit the use of compound, in cloth toy, there are 6 kinds forbidding detected or limit the use of compound, in wooden toy, have 3 kinds forbidding detected or limit the use of compound.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the amendment done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (8)
1. an accelerated solvent extraction gas chromatograph-mass spectrometer is measured the method for forbidding and limit the use of compound in toy, it is characterized in that, wherein, described forbidding and limit the use of compound be selected from Musk ambrette (2,6-dinitro-3-methoxyl-4-t-butyltoluene), jasminolene, benzyl cinnamate, 7-ethoxy-4-methyl-coumarin, to thanatol, diethyl maleate, citronellol, geraniol, linalool, benzene acetonitrile, benzalacetone, diphenylamine, MEHQ, phenmethylol, cinnamic acid;
Comprise the following steps:
Step 1, after the toy sample after break process and zeyssatite are mixed, is placed in accelerated solvent extraction pond, with organic solvent extraction; The temperature of accelerated solvent extraction is 80-120 DEG C, and pressure is 1300-1700Mpa, organic solvent extraction 10-30min, and circulation 1-5 time, toy sample and diatomaceous weight ratio are 1:(2-10);
Step 2, utilizes the forbidding extracting in gas chromatography-mass spectrography technology for detection step 1 and limits the use of compound; The condition of work that wherein detects the gas chromatograph-mass spectrometer (GCMS) using is as follows:
Chromatographic column: 30m × 0.25mm × 0.25 μ m, DB-17MS;
Input mode: Splitless injecting samples;
Temperature programme: initial temperature is 50 DEG C, keeps 1-3min, is warming up to 100-150 DEG C with the speed of 5-30 DEG C/min, keeps being warming up to 280-320 DEG C with 5-30 DEG C/min again after 3-7min, keeps 0.5-2min;
Ionization mode: EI;
Ionizing energy: 70eV;
Injector temperature: 260-300 DEG C;
Level Four bar temperature: 120-180 DEG C;
Ion source temperature: 220-280 DEG C.
2. method according to claim 1, is characterized in that, under the condition of 100 DEG C of temperature and pressure 1500Mpa, uses organic solvent extraction 20min, circulates 2 times.
3. method according to claim 1 and 2, is characterized in that, described organic solvent is acetone, methylene chloride, toluene, normal hexane, ethyl acetate, toluene, tetrahydrofuran.
4. want the method described in 3 according to right, it is characterized in that, described organic solvent is acetone.
5. method according to claim 1, is characterized in that, described method also comprises purifying step: by following the example of by accelerated solvent extraction, the extract obtaining is concentrated, crosses silicagel column, wash-out.
6. method according to claim 5, is characterized in that, taking normal hexane as leacheate, the activation solvent taking the mixed solvent of normal hexane and acetone as activated silica gel post, taking acetone as eluting solvent.
7. method according to claim 1, is characterized in that, the condition of work that detects the gas chromatograph-mass spectrometer (GCMS) using in step 2 is as follows:
Chromatographic column: 30m × 0.25mm × 0.25 μ m, DB-17MS;
Input mode: Splitless injecting samples;
Temperature programme: initial temperature is 50 DEG C, keeps 2min, is warming up to 130 DEG C with the speed of 20 DEG C/min, keeps being warming up to 300 DEG C with 20 DEG C/min again after 6min, keeps 1min;
Ionization mode: EI;
Ionizing energy: 70eV;
Injector temperature: 280 DEG C;
Level Four bar temperature: 150 DEG C;
Ion source temperature: 250 DEG C.
8. according to the method described in claim 1 or 7, it is characterized in that, in step 2, gas chromatography-mass spectrography detects and adopts inner mark method ration.
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| CN105954381A (en) * | 2016-04-22 | 2016-09-21 | 广西壮族自治区梧州食品药品检验所 | Determination method for isoferulic acid in Rhizoma Cimicifugae |
| CN106370755A (en) * | 2016-11-14 | 2017-02-01 | 山东出入境检验检疫局检验检疫技术中心 | Method for measuring content of sensitization aromatizer in aromatic pen |
| CN106770706A (en) * | 2016-11-14 | 2017-05-31 | 山东出入境检验检疫局检验检疫技术中心 | The assay method of sensitization fragrance level in a kind of plastic material |
| CN106959344A (en) * | 2016-11-14 | 2017-07-18 | 山东出入境检验检疫局检验检疫技术中心 | The assay method of sensitization fragrance level and volatile quantity in a kind of textile material |
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