CN102175791B - Method for detecting multiple allergic aroma agents in toys - Google Patents
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- CN102175791B CN102175791B CN 201110005509 CN201110005509A CN102175791B CN 102175791 B CN102175791 B CN 102175791B CN 201110005509 CN201110005509 CN 201110005509 CN 201110005509 A CN201110005509 A CN 201110005509A CN 102175791 B CN102175791 B CN 102175791B
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Abstract
The invention relates to the fields of analytical chemistry and toy safety, in particular to a method for detecting multiple allergic aroma agents in toys, and is mainly the sample preparations and gas chromatography/mass spectrometry for the contents of 45 allergic aroma agents in various toys. The number and type of the allergic aroma agents are various; the boiling point range of the aroma agents is wide, and the requirements for quantity limit are high, so that how to perform simple, fast, efficient and green detection is a great challenge; the method in the invention overcomes the shortages of the existing method by thermal desorption preparation technology and gas chromatography/mass spectrometry technology; a detection method of multiple allergic aroma agents in toys is built; and the method can synchronously detect the contents of 45 allergic aroma agents in toys conveniently, fast, accurately and efficiently.
Description
Technical field
The present invention relates to analytical chemistry, toy safety field, specifically, relating to the detection method of multiple allergic aroma agents in toys content, is mainly sample preparation and the Gas Chromatography-Mass Spectrometry of 45 kinds of anaphylaxis flavouring agent content in various toys (comprising that children use perfumed soap, down toy, plastic toy, plasticine, rubber etc.).
Background technology
The safe direct relation of toy quality children's physical and mental health, and therefore along with people rise to the attention rate of articles for children, toy safety has become a hot topic.In recent years, the quality safety of toy for children and potential safety hazard problem more and more obtain the extensive concern of countries in the world, external many countries particularly more developed country are very strict to the management of children toys ' quality safety case, require more and more stricter to toy safety, content is variation also, and the anaphylaxis flavouring agent that European Union proposes is forbidden and limited the use of material is exactly a best example.The anaphylaxis flavouring agent is irritant to eyes and respiratory tract, contact skin can cause allergic reaction, large to children's health harmfulness, on Dec 18th, 2008, European Parliament has passed through the new instruction of European Union's toy (2009/48/EC), in formal enforcement on July 20th, 2009, propose first to forbid using in toy the anaphylaxis flavouring agent, the chemical part of this instruction will be in formal enforcement on July 20th, 2013.According to the 2009/48/EC of European Union instruction, the anaphylaxis flavouring agent can be divided into two groups, and one group comprises the multiple scents such as benzylalcohol, and European Union stipulates that it forbids in toy, if but irreplaceable on technique, can use, but concentration must not surpass 100mg/kg; And another group comprises 4-methoxyl benzylalcohol, Ergol, cinnamic acid acid benzyl ester, citronellol, fanesol, jasminolene, butylbenzene ylmethyl propionic aldehyde, limonene, linalool, methyl 2-octynoate and α-daphnone totally 11 kinds of flavouring agents, need clearly identify higher than 100mg/kg if its content in toy is stipulated in European Union's 2009/48/EC instruction.
at present, adopt the pre-treatment mode of organic solvent extraction for the detection of fragrance matter more, disposal route and step are complicated, the anaphylaxis flavouring agent that the new instruction of European Union's toy limits has volatility or half volatile, need simultaneously to use poisonous to human body and environment in a large number, harmful organic solvent, therefore need development can satisfy minimizing and even do not use poisonous organic solvent, can adapt to and process complex dielectrics, trace constituent, the requirement of special nature constituent analysis, centralized procurement sample as far as possible, extraction, purify, concentrated, pre-separation, sample introduction, reduce the Sample Pretreatment Technique of operation steps.Along with the development of thermal desorption technology, bringing into play more and more important effect at volatility, semi-volatile organic compounds analysis field.At the detection field of flavouring agent material, the thermal desorption pre-treating method also more and more is used at present, but the detection of the anaphylaxis flavouring agent in not yet relating to toy both at home and abroad in the exploitation of method at present.
Anaphylaxis flavouring agent number is various, and kind is various, and these flavouring agent boiling spreads distribute large, limits the quantity of that it is high to require, and how to carry out easy, quick, efficient, green check, is a very large challenge.Usually, in the fragrance of the matrix such as food and cigarette detects, the method that adopts for ester class, alcohols, aldoketones, little molecule acids, aldehydes matter mostly is GC or GC-MS, and the method that coumarin substances is adopted mostly is GC, GC-MS or HPLC, HPLC-MS/MS.But the fragrance matter that detects in these matrix is independent individuality, and the formation system, do not contain the anaphylaxis flavouring agent that the new instruction of European Union's toy limits yet.Simultaneously, the present detection method that does not also have both at home and abroad for anaphylaxis flavouring agent in toy.
Summary of the invention
The object of the invention is to overcome now methodical deficiency, set up a kind of detection method of multiple allergic aroma agents in toys, with content convenient, fast, that detect simultaneously accurately and efficiently 45 kinds of anaphylaxis flavouring agents in toy.
The present invention is achieved by the following technical solutions:
The absorption of the residual employing of multiple allergic aroma agents in toys Tenax TA (2,6-diphenyl p-phenylene) adsorbent, rear Gas Chromatography-Mass Spectrometry is analysed in pyrolysis.
The sample preparation of 45 kinds of anaphylaxis flavouring agent content and the method for gas chromatography-mass spectrum Fast Measurement in toy described in the present invention (comprising that children use perfumed soap, down toy, plastic toy, plasticine, rubber etc.) comprise the following steps:
1. extract:
Accurately take 20～30mg (being accurate to 0.01mg) sample, put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, opens carrier gas, flow velocity is 300～350mL/min, set temperature is 55 ℃, processes sample 5～7min, and temperature is risen to rapidly 70 ℃, keep again 5～7min, at last temperature is risen to rapidly 85 ℃, keep 10～15min, subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured.The method parameter that adopts is respectively as shown in table 1, table 2:
Table 1 thermal desorption device condition
| Shunt mode | Without shunting |
| Initial temperature | 30～45℃ |
| Time delay | 0.3～1 minute |
| Programming rate | 60℃/min |
| Finishing temperature | 300～310℃ |
| Retention time | 5～7min |
| The transmission line temperature | 300～310℃ |
| Carrier gas | Nitrogen |
Table 2 cold-trap device condition
| Shunt mode | Without shunting |
| Initial temperature | -150～-120℃ |
| Equilibration time | 0.5～1.5 minutes |
| Programming rate | 10℃/min |
| Finishing temperature | 300～310℃ |
| The final time | 3～5min |
2. measure:
The Gas Chromatography-Mass Spectrometry condition sees Table 3
Determining of table 3 gas chromatograph-mass spectrometer (GCMS) device condition of work
Table 4 flavouring agent standard items information
The assay method of 45 kinds of anaphylaxis flavouring agent content in toy of the present invention, be used for sample preparation and the Gas Chromatography-Mass Spectrometry of 45 kinds of anaphylaxis flavouring agent content of various toys (comprising that children use perfumed soap, down toy, plastic toy, plasticine, rubber etc.), simple, quick, accurate, efficient.Analysis result according to information such as the structure of matter of anaphylaxis flavouring agent, physicochemical property, toxicity, solvent-free sample preparation technology---the thermal desorption technology is carried out pre-treatment to sample in final selection, without any need for solvent, with direct solid sample introduction, then directly carrying out supper-fast GC-MS analyzes, anaphylaxis flavouring agent in the utmost point quick and precisely detects toy in the short time has been realized the sample preparation robotization, in linearize.Also in formulation, the part forbidding flavouring agent standard items in its instruction yet do not have commercialization due to the concrete rules of European Union, so this time in research, the kind of flavouring agent has comprised the part forbidding in the european union directive and all limited the use of material.The required sample size of the detection method of quick solvent-free extraction is few, and is simple to operate, highly sensitive, can greatly shorten the flow process of detection, greatly improves analysis efficiency.In addition, the database that the application adopts is the NIST spectrum storehouse that the American National Institute Of Science And Technology is set up, and in the anaphylaxis flavouring agent of studying, have and severally do not include in this spectrum storehouse, respectively anti--2-hexenoic aldehyde dimethyl-acetal (CAS:18318-83-7), 1-(4-methoxyphenyl)-1-penten-3-one (CAS:104-27-8), 5-methyl-2,3-acetyl butyryl (CAS:13706-86-0).Simple and convenientization for later qualitative process, we compose the storehouse to NIST and are optimized, with this several do not include material be added to the spectrum storehouse, enrich NIST and composed the storehouse, realized the optimization of mass spectrum searching database, for providing convenience in later research work, thereby measure across class when realizing plurality of classes flavouring agent material.
Embodiment
The method of multiple allergic aroma agents in toys of the present invention, it is characterized in that the 45 kinds of residual employing of the anaphylaxis flavouring agent Tenax TA (2 in toy (comprising that children use perfumed soap, down toy, plastic toy, plasticine, rubber etc.), 6-diphenyl p-phenylene) adsorbent absorption, rear Gas Chromatography-Mass Spectrometry is analysed in pyrolysis.
Embodiment 1
Children use sample preparation and the assay method of 45 kinds of anaphylaxis flavouring agents in perfumed soap:
(1) extract:
Accurately take 22.15mg (being accurate to 0.01mg) sample, put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, opens carrier gas, and flow velocity is 300mL/min.Set temperature is 55 ℃, processes sample 5min, temperature is risen to rapidly 70 ℃, then keep 5min, at last temperature is risen to rapidly 85 ℃, keeps 10min.Subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured.The method parameter that adopts is respectively as shown in table 1, table 2:
Table 1 thermal desorption device condition
| Shunt mode | Without shunting |
| Initial temperature | 30℃ |
| Time delay | 0.3 minute |
| Programming rate | 60℃/min |
| Finishing temperature | 300℃ |
| Retention time | 5min |
| The transmission line temperature | 300℃ |
| Carrier gas | Nitrogen |
Table 2 cold-trap device condition
| Shunt mode | Without shunting |
| Initial temperature | -150℃ |
| Equilibration time | 0.5 minute |
| Programming rate | 10℃/min |
| Finishing temperature | 300℃ |
| The final time | 3min |
(2) measure: the Gas Chromatography-Mass Spectrometry condition sees Table 3
Determining of table 3 gas chromatograph-mass spectrometer (GCMS) device condition of work
GC-MS ion acquisition condition: table 4 and table 5 have provided respectively ion acquisition condition and quantitative, the qualitative ion of these two groups of flavouring agent standard items.
The ion acquisition condition of first group of flavouring agent standard items of table 4
The ion acquisition condition of second group of flavouring agent standard items of table 5
the method has selective enrichment to children with 45 kinds of anaphylaxis flavouring agents in perfumed soap, purifying and mensuration are added standard items and are carried out recovery experiment in sample, take the 22.15mg sample, add respectively 5, 10, the standard items of three levels of 20ng, compare with anaphylaxis flavouring agent ratio of response on gas chromatograph-mass spectrometer (GCMS) in matrix zero standard working fluid and liquid to be measured, the relative recovery of above-mentioned 45 kinds of anaphylaxis flavouring agents is between 71.02～109.86%, relative standard deviation is between 4.94～16.37%, and wherein the recovery of ethyl crotonate is respectively 73.08～79.61%, 74.31～76.57%, 71.02～80.37%, the recovery of benzylalcohol is 85.23～89.01%, 86.12～90.37%, 88.33～92.91%, the recovery of butylbenzene ylmethyl propionic aldehyde is 80.12～87.36%, 86.72～92.31%, 87.28～92.54%, the recovery of benzyl salicylate is 75.71～81.79%, 83.45～87.82%, 84.11～90.32%.
Embodiment 2
The sample preparation of 45 kinds of anaphylaxis flavouring agents and assay method in down toy:
(1) extract:
Accurately take 20.32mg (being accurate to 0.01mg) powder lint, put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, opens carrier gas, and flow velocity is 330mL/min.Set temperature is 55 ℃, processes sample 7min, temperature is risen to rapidly 70 ℃, then keep 7min, at last temperature is risen to rapidly 85 ℃, keeps 15min.Subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured.The method parameter that adopts is respectively as shown in table 1, table 2:
Table 1 thermal desorption device condition
| Shunt mode | Without shunting |
| Initial temperature | 35℃ |
| Time delay | 0.5 minute |
| Programming rate | 60℃/min |
| Finishing temperature | 300℃ |
| Retention time | 5min |
| The transmission line temperature | 305℃ |
| Carrier gas | Nitrogen |
Table 2 cold-trap device condition
| Shunt mode | Without shunting |
| Initial temperature | -140℃ |
| Equilibration time | 1.0 minute |
| Programming rate | 10℃/min |
| Finishing temperature | 305℃ |
| The final time | 4min |
(2) measure: the Gas Chromatography-Mass Spectrometry condition sees Table 3
Determining of table 3 gas chromatograph-mass spectrometer (GCMS) device condition of work
GC-MS ion acquisition condition is with embodiment 1.
the method has selective enrichment to 45 kinds of anaphylaxis flavouring agents in down toy, purifying and mensuration, add standard items and carry out recovery experiment in sample, take the 20.32mg sample, add respectively 5, 10, the standard items of three levels of 20ng, compare with anaphylaxis flavouring agent ratio of response on gas chromatograph-mass spectrometer (GCMS) in matrix zero standard working fluid and liquid to be measured, the relative recovery of above-mentioned 45 kinds of anaphylaxis flavouring agents is between 69.25～103.47%, relative standard deviation is between 5.78～12.45%, wherein the recovery of ethyl crotonate is respectively 69.25～75.34%, 73.03～79.28%, 71.33～79.87%, the recovery of benzylalcohol is 84.37～89.01%, 85.22～95.37%, 86.09～92.15, the recovery of butylbenzene ylmethyl propionic aldehyde is 87.33～93.47%, 96.91～103.47%, 92.39～102.88%, the recovery of benzyl salicylate is 87.22～93.45%, 81.38～90.59%, 85.60～92.31%.
Embodiment 3
The sample preparation of 45 kinds of anaphylaxis flavouring agents and assay method in plastic toy:
(1) extract:
Accurately take the blue plastics of 22.89mg (being accurate to 0.01mg), put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, opens carrier gas, and flow velocity is 320mL/min.Set temperature is 55 ℃, processes sample 6min, temperature is risen to rapidly 70 ℃, then keep 6min, at last temperature is risen to rapidly 85 ℃, keeps 12min.Subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured.The method parameter that adopts is respectively as shown in table 1, table 2:
Table 1 thermal desorption device condition
| Shunt mode | Without shunting |
| Initial temperature | 32℃ |
| Time delay | 0.4 minute |
| Programming rate | 60℃/min |
| Finishing temperature | 302℃ |
| Retention time | 6min |
| The transmission line temperature | 302℃ |
| Carrier gas | Nitrogen |
Table 2 cold-trap device condition
| Shunt mode | Without shunting |
| Initial temperature | -130℃ |
| Equilibration time | 0.8 minute |
| Programming rate | 10℃/min |
| Finishing temperature | 302℃ |
| The final time | 5min |
(2) measure: the Gas Chromatography-Mass Spectrometry condition sees Table 3
Determining of table 3 gas chromatograph-mass spectrometer (GCMS) device condition of work
GC-MS ion acquisition condition is with embodiment 1.
the method has selective enrichment to 45 kinds of anaphylaxis flavouring agents in plastic toy, purifying and mensuration, add standard items and carry out recovery experiment in sample, take the 22.89mg sample, add respectively 5, 10, the standard items of three levels of 20ng, compare with anaphylaxis flavouring agent ratio of response on gas chromatograph-mass spectrometer (GCMS) in matrix zero standard working fluid and liquid to be measured, the relative recovery of above-mentioned 45 kinds of anaphylaxis flavouring agents is between 65.34～98.73%, relative standard deviation is between 6.02～18.33%, wherein the recovery of ethyl crotonate is respectively 67.83～73.66%, 65.34～72.81%, 69.77～75.89%, the recovery of benzylalcohol is 77.38～80.94%, 80.12～87.68%, 79.53～88.16%, the recovery of butylbenzene ylmethyl propionic aldehyde is 84.39～91.57%, 85.27～93.22%, 90.11～98.73%, the recovery of benzyl salicylate is 73.88～85.21%, 79.45～85.37%, 82.17～89.98%.
Embodiment 4
The sample preparation of 45 kinds of anaphylaxis flavouring agents and assay method in plasticine:
(1) extract:
Accurately take 25.09mg (being accurate to 0.01mg) pink colour plasticine, put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, opens carrier gas, and flow velocity is 350mL/min.Set temperature is 55 ℃, processes sample 5min, temperature is risen to rapidly 70 ℃, then keep 5min, at last temperature is risen to rapidly 85 ℃, keeps 10min.Subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured.The method parameter that adopts is respectively as shown in table 1, table 2:
Table 1 thermal desorption device condition
| Shunt mode | Without shunting |
| Initial temperature | 40℃ |
| Time delay | 0.8 minute |
| Programming rate | 60℃/min |
| Finishing temperature | 308℃ |
| Retention time | 7min |
| The transmission line temperature | 310℃ |
| Carrier gas | Nitrogen |
Table 2 cold-trap device condition
| Shunt mode | Without shunting |
| Initial temperature | -150℃ |
| Equilibration time | 0.5 minute |
| Programming rate | 10℃/min |
| Finishing temperature | 310℃ |
| The final time | 3min |
(2) measure: the Gas Chromatography-Mass Spectrometry condition sees Table 3
Determining of table 3 gas chromatograph-mass spectrometer (GCMS) device condition of work
GC-MS ion acquisition condition is with embodiment 1.
the method has selective enrichment to 45 kinds of anaphylaxis flavouring agents in plasticine, purifying and mensuration are added standard items and are carried out recovery experiment in sample, take the 25.09mg sample, add respectively 5, 10, the standard items of three levels of 20ng, compare with anaphylaxis flavouring agent ratio of response on gas chromatograph-mass spectrometer (GCMS) in matrix zero standard working fluid and liquid to be measured, the relative recovery of above-mentioned 45 kinds of anaphylaxis flavouring agents is between 72.06～123.33%, relative standard deviation is between 6.02～18.33%, and wherein the recovery of ethyl crotonate is respectively 73.16～79.88%, 74.39～78.17%, 72.06～81.38%, the recovery of benzylalcohol is 72.06～81.59%, 76.97～83.28%, 85.66～92.35%, the recovery of butylbenzene ylmethyl propionic aldehyde is 98.77～110.46%, 108.24～123.33%, 89.73～102.10%, the recovery of benzyl salicylate is 93.80～105.36%, 97.58～110.39%, 90.64～100.71%.
Embodiment 5
The sample preparation of 45 kinds of anaphylaxis flavouring agents and assay method in rubber:
(1) extract:
Accurately take the white rubber of 29.15mg (being accurate to 0.01mg), put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, opens carrier gas, and flow velocity is 330mL/min.Set temperature is 55 ℃, processes sample 7min, temperature is risen to rapidly 70 ℃, then keep 7min, at last temperature is risen to rapidly 85 ℃, keeps 15min.Subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured.The method parameter that adopts is respectively as shown in table 1, table 2:
Table 1 thermal desorption device condition
| Shunt mode | Without shunting |
| Initial temperature | 45℃ |
| Time delay | 1.0 minute |
| Programming rate | 60℃/min |
| Finishing temperature | 310℃ |
| Retention time | 7min |
| The transmission line temperature | 310℃ |
| Carrier gas | Nitrogen |
Table 2 cold-trap device condition
| Shunt mode | Without shunting |
| Initial temperature | -120℃ |
| Equilibration time | 1.5 minute |
| Programming rate | 10℃/min |
| Finishing temperature | 300℃ |
| The final time | 5min |
(2) measure: the Gas Chromatography-Mass Spectrometry condition sees Table 3
Determining of table 3 gas chromatograph-mass spectrometer (GCMS) device condition of work
GC-MS ion acquisition condition is with embodiment 1.
the method has selective enrichment to 45 kinds of anaphylaxis flavouring agents in rubber, purifying and mensuration, add standard items and carry out recovery experiment in sample, take the 29.15mg sample, add respectively 5, 10, the standard items of three levels of 20ng, compare with anaphylaxis flavouring agent ratio of response on gas chromatograph-mass spectrometer (GCMS) in matrix zero standard working fluid and liquid to be measured, the relative recovery of above-mentioned 45 kinds of anaphylaxis flavouring agents is between 62.25～110.74%, relative standard deviation is between 4.79～15.18%, wherein the recovery of ethyl crotonate is respectively 62.58～74.39%, 62.25～77.13%, 73.69～80.17%, the recovery of benzylalcohol is 65.84～72.17%, 80.79～86.52%, 73.56～83.11%, the recovery of butylbenzene ylmethyl propionic aldehyde is 78.36～86.14%, 93.55～110.74%, 85.32～94.79%, the recovery of benzyl salicylate is 77.21～83.69%, 88.32～95.47%, 99.59～109.22%.
Claims (4)
1. the detection method of a multiple allergic aroma agents in toys, is characterized in that: after by the thermal desorption technology, testing sample being carried out pre-treatment, utilize the multiple anaphylaxis flavouring agent of gas chromatography-mass spectrography technology for detection;
describedly by the thermal desorption technology, testing sample is carried out pre-treatment and comprise the following steps: accurately take 20～30mg testing sample, put into the quartz ampoule of sample thermal treatment instrument with clean antimagnetic type tweezer, the adsorption tube that will be loaded with subsequently adsorbent inserts in sample thermal treatment instrument, open carrier gas, flow velocity is 300～350mL/min, set temperature is 55 ℃, process sample 5～7min, then temperature is risen to rapidly 70 ℃, keep again 5～7min, at last temperature is risen to rapidly 85 ℃, keep 10～15min, subsequently adsorption tube is put on the thermal desorption automatic sampler to be measured, wherein:
The condition of thermal desorption device is: shunt mode is the nothing shunting, 30～45 ℃ of initial temperatures, and 0.3～1 minute time delay, 60 ℃/min of programming rate, 300～310 ℃ of finishing temperatures, retention time 5～7min, 300～310 ℃ of transmission line temperature, carrier gas is nitrogen;
The condition of cold-trap device is: shunt mode is for without shunting, initial temperature-150～-120 ℃, equilibration time 0.5～1.5 minute, 10 ℃/min of programming rate, 300～310 ℃ of finishing temperatures, final time 3～5min;
Gas chromatograph-mass spectrometer (GCMS) device condition of work: chromatographic column: J﹠amp; W DB-5MS, 30m * 0.25mm i.d., 0.25 μ m; Carrier gas: He, purity＞99.999%, flow velocity 1.2mL/min; Injector temperature: 275 ℃～290 ℃; Input mode: Splitless injecting samples; Temperature programme: keep 2min at 50 ℃, then be warming up to 275 ℃ with the speed of 10 ℃/min, keep 2min in this temperature; Drainage pattern: SCAN/SIM gathers simultaneously; Quantitative manner: the SIM ion is quantitative; Sweep limit: 30m/z to 300m/z; EI electron energy: 70eV; GC-MS interface temperature: 280 ℃～290 ℃; The solvent delay time: 2.0～3.0min;
Wherein multiple anaphylaxis flavouring agent is flavouring agent as shown in the table:
2. detection method according to claim 1, wherein toy is selected from children with perfumed soap, down toy, plastic toy, plasticine, rubber.
3. detection method according to claim 1, wherein when accurately taking testing sample, be accurate to 0.01mg.
4. detection method according to claim 1, wherein said adsorbent is TenaxTA, namely 2,6-diphenyl p-phenylene.
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| CN102393438B (en) * | 2011-11-10 | 2014-01-08 | 中国检验检疫科学研究院 | Method for simultaneously determining residual quantities of sixteen sensitized aldehyde and ketone perfumes in toy |
| CN103235054B (en) * | 2013-04-17 | 2014-09-10 | 宁波检验检疫科学技术研究院 | Method for determining banned and restricted compounds in toys with accelerated solvent extraction and gas chromatograph-mass spectrometer |
| CN106018645B (en) * | 2016-06-30 | 2018-04-27 | 聚光科技(杭州)股份有限公司 | The automatic method that the solvent delay time is set |
| RU2640507C1 (en) * | 2016-11-02 | 2018-01-09 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Воронежский государственный университет инженерных технологий" (ФГБОУ ВО "ВГУИТ") | Method of organoleptic evaluation of children's toys based on plastisol from polyvinylchloride |
| CN113999719A (en) * | 2021-10-21 | 2022-02-01 | 上海应用技术大学 | Method for comprehensively utilizing kettle bottoms after beta-ionone rectification |
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