CN102175785B - Method for detecting VOC (Volatile Organic Compound) matters in toy paint - Google Patents
Method for detecting VOC (Volatile Organic Compound) matters in toy paint Download PDFInfo
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Abstract
The invention discloses a method for detecting VOC (Volatile Organic Compound) matters in toy paint. The method comprises the following steps of: carrying out qualitative detection on the VOC matters in the toy paint by utilizing an automatic static headspace-capillary column gas chromatography method and combining condition parameters optimized by a taguchi methodology, and carrying out quantitative detection on the VOC matters in the toy paint according to the qualitative detection result, wherein the condition parameters optimized by the taguchi methodology are as follows: the volume of a reference liquid in a headspace bottle is 50 microliters, the weight of a sample in the headspace bottle is 0.05g, a balance temperature of the reference liquid and the sample in an automatic headspace sample injector is 90 DEG C, and the balance time of the reference liquid and the sample in the automatic headspace sample injector is 1 hour. When the method disclosed by the invention is used for detecting the VOC matters in the toy paint with complex ingredients, the toy paint does not need to be diluted, and the sample does not need to be injected manually, thus the full-automatic sample injection can be realized; the detection on the VOC matters including benzene, toluene, ethyl benzene or xylene and the like is finished by one experiment, the method is simple, convenient and fast, and the accuracy of results is high.
Description
Technical field
The present invention relates to the coating detection field, be specifically related to the detection method of VOC material in a kind of toy paint.
Background technology
Along with people's going deep into gradually the environmental protection concept, the environmental protection index of toy for children improves again, especially the GB 24613-2009 (GB) that played implementation on October 1st, 2010 makes outside the requirement with regard to the solvable amount of objectionable impurities removing heavy metals and the phthalic acid salt content to human body and environment in the toy for children coating, also stipulate: boiling point is less than or equal to volatile compound (VOC) content≤720g/L of 250 ℃, benzene content≤0.3%, the content summation of toluene, ethylbenzene and dimethylbenzene≤30%.
The VOC material refers to that fusing point is lower than room temperature and the general name of the volatile organic compounds of boiling point between 50～250 ℃, such as common VOC material benzene class material, the acetone etc. such as benzene, toluene, ethylbenzene and dimethylbenzene are arranged, wherein, benzene class material is because toxicity is larger, so receive more many concerns.
Also stipulated toluene among the GB 24613-2009, the corresponding test method of this three classes objectionable impurities of ethylbenzene and dimethylbenzene, need use two kinds of instrument (GC-FID in this test method, GC-MS, FI-IR), and minute five experiments are finished, whole test procedure is comparatively complicated, and this test method all uses solvent suitably to dilute rear sample introduction test, but because the popularity of toy coating kind, some coating does not have good intermiscibility and causes using the direct injecting chromatograph of automatic sample handling system with solvent, causes owing to extension rate is excessive perhaps that the low content material can't detect in the sample.
Headspace injection method is the distinctive a kind of sample injection method of gas chromatography, be applicable to the large component analysis of volatility, wherein, the Static Headspace analytical technology is the earliest form that occurs in the headspace analysis development, and obtain widely promotion and application, the Static Headspace analytical technology is mainly used in measuring those at 200 ℃ of lower volatilizable analytes, and the sample that relatively is difficult to carry out pre-treatment.Static headspace analysis can be divided three classes on the instrument pattern: head space gas direct injected pattern, balance pressurization sampling sample introduction pattern and pressurization constant-volume sampling sample introduction pattern.
Headspace analysis is to measure the content of these components in raw sample by the gas componant of sample substrate top, its main theoretical basis of the reform of Chinese economic structure is to exist partition equilibrium between gas phase and the condensed phase (liquid phase and solid phase) under certain condition, so the composition of gas phase can reflect the composition of condensed phase.Can regard headspace analysis as a kind of gaseous extraction method, namely do " solvent " with gas and extract volatile ingredient in the sample, thereby headspace analysis be exactly a kind of desirable sample purification method.
As a kind of analytical approach, headspace analysis has the lot of advantages of self, at first is exactly simple, it is only got gas and partly analyzes, having greatly reduced sample itself may be to interference or the pollution of analyzing, and as the sample treatment that GC analyzes, head space is the easiest; Secondly, be to make the rear sample introduction of gasification, headspace analysis has different mode, can be suitable for various samples by the Optimum Operation parameter; The 3rd, the requirement that the sensitivity of headspace analysis can satisfy regulatory; The 4th, the minimizing that headspace sampling can be relative is shortened analysis time for the sample size of the higher solvent of the boiling point of dissolution sample.
At present, there is not yet the relevant report that detects VOC material in the analysis toy paint with the headspace sampling analytical approach.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide that a kind of method is simple and efficient, result's detection method of VOC material in the toy paint accurately.
Above-mentioned purpose of the present invention is achieved by following scheme:
The inventor holds volatile characteristics at normal temperatures for the VOC material, attempts capillary column-Capillary Column GC is introduced in the detection of VOC material in the toy paint:
Toy is painted through the heating balance first, VOC material in the toy paint evaporates into gaseous state, then the head space automatic sampler is with in the volatilization gas part inject gas chromatograph, carry out qualitative and quantitative analysis, found that the method can realize the detection of VOC material in the toy paint, and simple and quick.
But the inventor also finds in process of the test, when adopting capillary column-Capillary Column GC to detect, the conditional parameters such as quantitative result is marked, and liquid is long-pending, sample size, equilibrium temperature and equilibration time affect larger, distinct analysis result will appear in the different parameters condition, therefore be difficult to obtain the exact value of sample, and composition is very complicated in the toy paint, and the Stability and veracity that detects is also had certain influence.
For the problems referred to above, the inventor considers and must study the various conditional parameters of capillary column-Capillary Column GC in toy inspection.At present, experimental design method commonly used has a variety of, and the inventor determines to adopt field mouth method to come experiment condition is optimized by after various experimental design methods commonly used being carried out conceptual design and screening.
The present invention adopts capillary column-Capillary Column GC that the VOC class material in the toy paint is detected, this experiment is divided into two parts, one is the Static Headspace sample introduction, also be equivalent to pretreatment process, one is exactly analysis of capillary column Gc, and concerning whole test, what testing result was had the greatest impact is exactly the pre-treatment part, and the inventor finds by research is rear, in pretreatment process, four conditional parameters that affect most the experimental result accuracy are: the mark liquid that adds in the head space bottle is long-pending, add the example weight in the head space bottle, mark liquid and equilibrium temperature and the equilibration time of sample in the head space automatic sampler, wherein, mark liquid amasss and has influence on quantitative accuracy, the size of example weight means whether heated volatile is complete, and the selection of equilibrium temperature and equilibration time can affect liquid gas balance, thereby the result is exerted an influence.
The inventor by the field oral examination test analyze with statistical method after, above-mentioned four conditional parameters that affect the experiment accuracy most are optimized, the top condition that obtains is: add the long-pending 50 μ L of selection of head space bottle acceptance of the bid liquid, add in the head space bottle example weight and select 0.05g, mark liquid and the equilibrium temperature of sample in the head space automatic sampler to select 90 ℃, mark liquid and the equilibration time of sample in the head space automatic sampler to select 1 hour, find that after testing the optimization of these four conditional parameters can be so that headspace sampling experimental result value be more accurate.
In sum, the inventor obtains a kind of simple and quick, and Detection accuracy is high, and can once test just can paint toy in the method that detects of VOC material:
The method is to adopt capillary column-Capillary Column GC, and in conjunction with by the conditional parameter after the mouth method optimization of field VOC material in the toy paint being carried out first qualitative detection, again VOC material in the toy paint is quantitatively detected according to the qualitative detection result, specifically comprise the steps:
1, qualitative detection
Step 1.
The preparation of mark liquid:
With methyl alcohol as solvent, be dissolved in after the pure material mixing with all VOC materials commonly used or that may use in the toy paint and be made into the hybrid standard working solution in the methyl alcohol, and add in this hybrid standard working solution in the 20ml head space bottle of packing into behind the label diethylene adipate, compress with the sealing of silicon rubber dottle pin at once;
The sample preparation:
Pack into after taking by weighing a certain amount of toy paint to be measured and adding the label diethylene adipate in the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once;
Step 2. capillary column-Capillary Column GC detects
The above-mentioned head space bottle that the hybrid standard working solution is housed and head space bottle that toy paint to be measured is housed are placed in the automatic headspace sample injector, carry out balance after, sample introduction separates in gas chromatograph, data acquisition;
In the above-mentioned automatic headspace sample injector, equilibrium temperature is 90 ℃, and equilibration time is 1 hour;
In gas chromatograph, the sample introduction temperature is 100 ℃ with the composition sample introduction in the automatic headspace sample injector, and the transfer tube temperature is 120 ℃;
In the gas chromatograph, injector temperature is 230 ℃, and input mode is shunting, and split ratio is 50;
The chromatographic column that gas chromatography adopts is polysiloxane polymer capillary column DB624, and its chromatographic column specification is 60m * 0.32mm * 1.80um;
Adopt temperature programme to be in the gas chromatographic analysis: initial temperature is 40 ℃, keeps 2min, and the speed with 4 ℃/min rises to 130 ℃ afterwards, keeps 2min, and the speed with 50 ℃/min rises to 240 ℃ again, keeps 2min;
The carrier gas of gas chromatographic analysis is nitrogen, and constant current mode is 2.0ml/min;
The temperature that gas chromatography flame ionization ditector (FID) is analyzed is 250 ℃, and hydrogen is empty than being 30:300;
The qualitative VOC species analysis of step 3.
After the detection by step 2, obtain respectively hybrid standard working solution chromatogram and toy to be measured paint chromatogram, then two chromatograms are analyzed: at first analyze toy paint chromatogram to be measured, material in this chromatogram before the label diethylene adipate chromatographic peak all is defined as the VOC material, then contrast this two chromatograms, thereby can determine concrete VOC material in the toy paint to be measured according to the retention time identical with the standard VOC material of hybrid standard working solution chromatogram in the toy paint chromatogram to be measured.
In the above-mentioned steps 1, because qualitative detection just to whether containing the VOC material or contain which VOC material in the toy paint to be measured detects, therefore it is very inaccurate to carry out the concentration requirement of the various samples that capillary column-Capillary Column GC detects for need, as when preparing the hybrid standard working solution, as long as the concentration of this hybrid standard working solution is higher than chromatographic detection limit; Add the label diethylene adipate in the hybrid standard working solution, as long as the concentration of this diethylene adipate is higher than chromatographic detection limit; Add the label diethylene adipate in the toy paint to be measured, as long as the concentration of this diethylene adipate is higher than chromatographic detection limit.
After above-mentioned qualitative detection, can understand in the toy paint to be measured and whether contain the VOC material and specifically contain which VOC material, next will carry out quantitative test to the VOC material that contains in the toy paint to be measured.
2, quantitative test
Step 1.
The preparation of mark liquid:
Know concrete VOC material in the toy to be measured paint by above-mentioned qualitative detection, so its solute of preparation of hybrid standard working solution only need to adopt the pure material of the concrete VOC material that comprises in the toy paint to get final product when quantitative test; Take methyl alcohol as solvent, after mixing, the pure material of all VOC materials that will contain in the fixed toy paint is dissolved into the hybrid standard working solution that is made into a series of concentration in the methyl alcohol after qualitative detection, then described a series of concentration hybrid standard working solutions are pipetted respectively in 50 μ l to the 20ml head space bottles, compress with the sealing of silicon rubber dottle pin at once;
The sample preparation:
Take by weighing in toy paint 0.05g to the 20ml head space bottle to be measured, compress with the sealing of silicon rubber dottle pin at once;
Blank preparation: get 50 μ l methyl alcohol to 20ml head space bottle, compress with the sealing of silicon rubber dottle pin, as blank;
Step 2. capillary column-Capillary Column GC detects
With the above-mentioned head space bottle that the hybrid standard working solution is housed, the head space bottle of toy paint to be measured is housed and blank head space bottle is housed and place in the automatic headspace sample injector, carry out balance after, sample introduction separates in gas chromatograph, data acquisition;
In the above-mentioned automatic headspace sample injector, equilibrium temperature is 90 ℃, and equilibration time is 1 hour;
In gas chromatograph, the sample introduction temperature is 100 ℃ with the composition sample introduction in the automatic headspace sample injector, and the transfer tube temperature is 120 ℃;
In the gas chromatograph, injector temperature is 230 ℃, and input mode is shunting, and split ratio is 50;
The chromatographic column that gas chromatography adopts is polysiloxane polymer capillary column DB624, and its chromatographic column specification is 60m * 0.32mm * 1.80um;
Adopt temperature programme to be in the gas chromatographic analysis: initial temperature is 40 ℃, keeps 2min, and the speed with 4 ℃/min rises to 130 ℃ afterwards, keeps 2min, and the speed with 50 ℃/min rises to 240 ℃ again, keeps 2min;
The carrier gas of gas chromatographic analysis is nitrogen, and constant current mode is 2.0ml/min;
The temperature that gas chromatography flame ionization ditector (FID) is analyzed is 250 ℃, the empty ratio of hydrogen: 30: 300;
Step 3. interpretation of result
External standard method by gas chromatography is carried out quantitative test to capillary column-capillary column gas chromatography testing result.
Compared with prior art, the present invention has following beneficial effect:
1. the present invention adopts capillary column-Capillary Column GC that VOC material in the toy paint of complicated component is detected, need not to dilute, need not hand sampling and reach the full automation sample introduction, once benzene is finished in experiment, toluene, the detection of the VOC such as ethylbenzene or dimethylbenzene material, the method simple and fast, the result is satisfied;
2. the present invention is in order to improve the accuracy of detection method, selecting field mouth method from numerous experimental data optimization methods comes the important parameter that affects testing result is optimized, field mouth method is the quality engineering method of a kind of low cost, high benefit, it emphasizes that the raising of product quality is not by check, but by design and optimal conditions; From the field oral examination test, can obtain the statistical method that best mark liquid is long-pending, sample size, equilibrium temperature and equilibration time make headspace sampling experimental result value more accurate;
3. the inventor finds by research, and mark liquid is long-pending to have influence on quantitative accuracy, and the size of example weight means whether heated volatile is complete, and equilibrium temperature and equilibration time then can affect liquid gas balance, thereby the result is exerted an influence; Therefore, the inventor is optimized the conditional parameter of these four keys, after the parameter after employing is optimized is carried out test experience, has greatly guaranteed the accuracy of testing result;
4. detection method of the present invention is first VOC material in the toy paint have been carried out carrying out after the qualitative detection quantitative test again, the collocation of qualitative and quantitative is so that detection method of the present invention is more accurate, in addition, adopting diethylene adipate during qualitative detection is label, the boiling point of diethylene adipate is 251 ℃, and the selection of label has also improved the qualitative detection accuracy.
Description of drawings
Fig. 1 is that the S/N of PPS-100 toy paint sample compares response diagram;
Fig. 2 is that the S/N of AG-100 toy paint sample compares response diagram;
Fig. 3 is that the S/N of SSA-100 toy paint sample compares response diagram.
Embodiment
Below in conjunction with specific embodiment the present invention is done further description, but specific embodiment is not done any restriction to the present invention.
Embodiment 1 test parameters optimization
The inventor finds in research process, when adopting the head space auto injection, the parameter that quantitative result is had the greatest impact is A (it is long-pending to add head space bottle acceptance of the bid liquid), B (adding example weight in the head space bottle), C (mark liquid and the equilibrium temperature of sample in the head space automatic sampler) and D (mark liquid and the equilibration time of sample in the head space automatic sampler). adopts the field cause for gossip to test above-mentioned each parameter verified, four each corresponding three levels of controlling elements, as shown in table 1:
Table 1 controlling elements and three corresponding levels thereof
| Controlling elements | Explanation | Lever 1 | Lever2 | Lever 3 |
| A | Mark liquid is long-pending | 20μL | 50μL | 2mL |
| B | Example weight | 0.05g | 0.1g | 2g |
| C | Equilibrium temperature | 80℃ | 90℃ | 100℃ |
| D | Equilibration time | 30min | 45min | 1h |
In the above-mentioned table 1, each controlling elements adopts three levels, and three levels that adopt are and can realize data of the present invention.
Present embodiment for detection of toy paint adopt PPS-100, AG-100 and SSA-100, adopt orthogonal table L9 (34) experimental program of three levels to test to these three kinds of toy paint, totally 9 groups of tests, these 9 groups experiments all adopt capillary column-Capillary Column GC to detect, mark liquid preparation in each experiment, sample preparation, blank preparation and the parameter of head-space sampler, the parameter of stratographic analysis etc., four conditions in changing table 1, other conditions all are consistent.
Each sample carries out 5 Duplicate Samples tests simultaneously. and obtain following test findings and see Table 2.
Table 2 field mouth orthogonal table L9 (3
4) mean value and the S/N ratio of experimental program and test findings
In the above-mentioned table 2, Ave. is the mean value of 5 Duplicate Samples tests.
In the above-mentioned table 2, S/N is than computing formula:
M-hopes the order value;
The standard deviation of 5 measurement results of every group of experiment of S-single sample.
With above-mentioned test findings and result of calculation adopt the field mouth mapping software of mintab obtain S/N than response diagram respectively shown in Fig. 1,2 and 3.
Among Fig. 1,2 and 3, A1, A2 and A3 refer to Lever 1, Lever 2 and the Lever3 of controlling elements A; B1, B2 and B3 refer to Lever 1, Lever 2 and the Lever3 of controlling elements B; C1, C2 and C3 refer to Lever 1, Lever 2 and the Lever3 of controlling elements C; D1, D2 and D3 refer to Lever 1, Lever 2 and the Lever3 of controlling elements D.
Among Fig. 1,2 and 3, according to Definite purpose, be the S/N field mouth principle better than larger quality, the optimal selection of controlled factors A, B, C and D is: A 2, B 1, C 2 and D 3, i.e. A adding head space bottle acceptance of the bid liquid is long-pending to be that example weight is that 0.05g, C mark liquid and the equilibrium temperature of sample in the head space automatic sampler are 90 ℃, D marks liquid and the equilibration time of sample in the head space automatic sampler is 1 hour in 50 μ L, the B adding head space bottle.
Embodiment 2
Present embodiment adopts capillary column-Capillary Column GC, and 1 obtains four Optimal Parameters in conjunction with the embodiments, and the VOC material in the toy paint is detected.
The toy paint that present embodiment is used for detecting adopts toy paint PPS-100, toy paint AG-100 and toy paint SSA-100.
Instrument adopts: the Japanese SHIMADZU GC-2010Plus of company gas chromatograph (being with liquid automatic sampler and fid detector), Italian DANI HSS86.50 head space automatic sampler.
1, qualitative detection
Step 1.
The preparation of mark liquid:
With methyl alcohol as solvent, be dissolved in after the pure material mixing with all VOC materials commonly used or that may use in the toy paint and be made into the hybrid standard working solution in the methyl alcohol, and add in this hybrid standard working solution in the 20ml head space bottle of packing into behind the label diethylene adipate, compress with the sealing of silicon rubber dottle pin at once.
The sample preparation:
Pack into after taking by weighing a certain amount of toy paint PPS-100 and adding the label diethylene adipate in the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once;
Pack into after taking by weighing a certain amount of toy paint AG-100 and adding the label diethylene adipate in the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once;
Pack into after taking by weighing a certain amount of toy paint SSA-100 and adding the label diethylene adipate in the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once.
Step 2. capillary column-Capillary Column GC detects
The above-mentioned head space bottle that the hybrid standard working solution is housed, the head space bottle that toy paint PPS-100 is housed, the head space bottle that the head space bottle of toy paint AG-100 is housed and toy paint SSA-100 is housed are placed in the automatic headspace sample injector, after carrying out balance, sample introduction separates in gas chromatograph, data acquisition;
In the above-mentioned automatic headspace sample injector, equilibrium temperature is 90 ℃, and equilibration time is 1 hour;
In gas chromatograph, the sample introduction temperature is 100 ℃ with the composition sample introduction in the automatic headspace sample injector, and the transfer tube temperature is 120 ℃;
In the gas chromatograph, injector temperature is 230 ℃, and input mode is shunting, and split ratio is 50;
The chromatographic column that gas chromatography adopts is polysiloxane polymer capillary column DB624, and its chromatographic column specification is 60m * 0.32mm * 1.80um;
Adopt temperature programme to be in the gas chromatographic analysis: initial temperature is 40 ℃, keeps 2min, and the speed with 4 ℃/min rises to 130 ℃ afterwards, keeps 2min, and the speed with 50 ℃/min rises to 240 ℃ again, keeps 2min;
The carrier gas of gas chromatographic analysis is nitrogen, and constant current mode is 2.0ml/min;
The temperature that gas chromatography flame ionization ditector (FID) is analyzed is 250 ℃, the empty ratio of hydrogen: 30: 300;
The qualitative VOC species analysis of step 3.
After the detection by step 2, obtain respectively hybrid standard working solution chromatogram, toy paint PPS-100 chromatogram, toy paint AG-100 chromatogram and toy paint SSA-100 chromatogram, then four chromatograms are analyzed: at first analyze three toy paint chromatograms to be measured, material in these three chromatograms before the label diethylene adipate chromatographic peak all is defined as the VOC material, then three chromatograms are compared with hybrid standard working solution chromatogram respectively, thereby determine concrete VOC material in the toy paint to be measured according to the retention time identical with the standard VOC material of hybrid standard working solution chromatogram in the toy paint chromatogram to be measured.
By analyzing rear discovery, all contain toluene, ethylbenzene, o-xylene, m-xylene and P-xylene among toy paint PPS-100, toy paint AG-100 and the toy paint SSA-100, then these five kinds of benzene class materials are carried out following quantitative test.
In addition, for most of toy paint, generally can contain these five kinds of benzene class materials of toluene, ethylbenzene, o-xylene, m-xylene and P-xylene, therefore, if just these the five kinds of benzene class materials in the toy paint are detected, can save above-mentioned qualitative detection so, directly carry out following quantitative test.
2, quantitative test
After carrying out qualitative detection by PPS-100, toy paint AG-100 and toy paint SSA-100, next the clear and definite concrete VOC material that comprises in these three kinds of toys paint carries out quantitative test to VOC material in these three kinds of toys paint.
Step 1.
The preparation of mark liquid:
Be dissolved into the hybrid standard working solution that is mixed with a series of concentration in the methyl alcohol after the pure standard substance mixing with these five kinds of benzene classes of toluene, ethylbenzene, o-xylene, m-xylene and P-xylene; The concentration of toluene in the mixed standard solution of described a series of concentration is respectively 2,10,25,50 and 75g/L, the concentration of ethylbenzene in the mixed standard solution of described a series of concentration is respectively 5,10,25,50 and 75g/L, the concentration of o-xylene in the mixed standard solution of described a series of concentration is respectively 2.5,5,10,20 and 40g/L, the concentration of m-xylene in the mixed standard solution of described a series of concentration is respectively 5,10,20,30 and 40g/L, the concentration of P-xylene in the mixed standard solution of described a series of concentration is respectively 5,10,20,30 and 40g/L;
The hybrid standard working solution of above-mentioned a series of concentration is pipetted respectively in 50 μ l to the 20ml head space bottles, compress with the sealing of silicon rubber dottle pin at once.
The sample preparation:
Take by weighing in 0.05g toy paint PPS-100 to the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once;
Take by weighing in 0.05g toy paint AG-100 to the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once;
Take by weighing in 0.05g toy paint SSA-100 to the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once.
Blank preparation: get 50 μ l methyl alcohol to 20ml head space bottle, compress with the sealing of silicon rubber dottle pin, as blank.
Step 2. capillary column-Capillary Column GC detects
With the above-mentioned head space bottle that the hybrid standard working solution is housed, the head space bottle of toy paint to be measured is housed and blank head space bottle is housed and place in the automatic headspace sample injector, carry out balance after, sample introduction separates in gas chromatograph, data acquisition;
In the above-mentioned automatic headspace sample injector, equilibrium temperature is 90 ℃, and equilibration time is 1 hour;
In gas chromatograph, the sample introduction temperature is 100 ℃ with the composition sample introduction in the automatic headspace sample injector, and the transfer tube temperature is 120 ℃;
In the gas chromatograph, injector temperature is 230 ℃, and input mode is shunting, and split ratio is 50;
The chromatographic column that gas chromatography adopts is polysiloxane polymer capillary column DB624, and its chromatographic column specification is 60m * 0.32mm * 1.80um;
Adopt temperature programme to be in the gas chromatographic analysis: initial temperature is 40 ℃, keeps 2min, and the speed with 4 ℃/min rises to 130 ℃ afterwards, keeps 2min, and the speed with 50 ℃/min rises to 240 ℃ again, keeps 2min;
The carrier gas of gas chromatographic analysis is nitrogen, and constant current mode is 2.0ml/min;
The temperature that gas chromatography flame ionization ditector (FID) is analyzed is 250 ℃, the empty ratio of hydrogen: 30: 300;
Step 3. interpretation of result
External standard method by gas chromatography is carried out quantitative test to capillary column-capillary column gas chromatography testing result, and the result is as shown in table 3.
The test result of table 3 toluene, ethylbenzene and dimethylbenzene
In the above-mentioned table 3, summation refers to the content summation of toluene, ethylbenzene, o-xylene, m-xylene and P-xylene in the toy paint.
In the above-mentioned table 3, the impact of negligible density, 1% is equal to 10g/l.
In order to verify the detection method of present embodiment, whether its testing result is accurate, present embodiment also detects liquid auto injection mode among these three kinds of toy paint employing GB 24613-2009 (GB), send simultaneously Guangdong inspection and quarantine bureau to adopt GB 24613-2009 method to detect, the test result of its toluene, ethylbenzene and xylene content summation relatively sees Table 4.
The as a result deck watch of toluene, ethylbenzene and xylene content summation in the toy paint that three kinds of detection methods of table 4 obtain
In the above-mentioned table 4, the impact of negligible density, 1% is equal to 10g/l.
As can be seen from Table 4, three kinds of methods detect the results that obtain, and its mean relative deviation all＜5% illustrates that thus detection method of the present invention can accomplish accurately to detect the content of VOC material in the toy paint really.And two kinds of methods of detection method of the present invention and other compare, and are simple and quick, and with low cost.
Claims (3)
1. the detection method of VOC material during a toy paints, it is characterized in that this detection method is to adopt capillary column-Capillary Column GC, and in conjunction with by the conditional parameter after the mouth method optimization of field VOC material in the toy paint being detected, the conditional parameter after the mouth method optimization of described field refer to add head space bottle acceptance of the bid liquid long-pending be 50 μ L, to add in the head space bottle example weight be that 0.05g, mark liquid and the equilibrium temperature of sample in the head space automatic sampler are that 90 ℃, mark liquid and the equilibration time of sample in the head space automatic sampler are 1 hour;
This detection method be first take diethylene adipate as label, methyl alcohol is solvent, after adopting capillary column-Capillary Column GC that the VOC material in the toy paint is carried out qualitative detection, adopt again capillary column-Capillary Column GC that the VOC material in the toy paint is carried out quantitative test;
Described VOC material is toluene, ethylbenzene, o-xylene, m-xylene or P-xylene.
2. the detection method of VOC material in the described a kind of toy paint according to claim 1 is characterized in that described that VOC material in the toy paint is carried out the concrete operation step of qualitative detection is as follows:
Step 1.
Mark liquid prepares: the pure material of all VOC materials commonly used was dissolved into and is made into the hybrid standard working solution in the methyl alcohol during toy was painted, and add in this hybrid standard working solution in the 20ml head space bottle of packing into behind the label diethylene adipate, compress with the sealing of silicon rubber dottle pin at once;
Sample preparation: pack into after taking by weighing toy paint to be measured and adding the label diethylene adipate in the 20ml head space bottle, compress with the sealing of silicon rubber dottle pin at once;
Step 2. capillary column-Capillary Column GC detects
The above-mentioned head space bottle that the hybrid standard working solution is housed and head space bottle that toy paint to be measured is housed are placed in the automatic headspace sample injector, carry out balance after, sample introduction separates in gas chromatograph, data acquisition;
In gas chromatograph, the sample introduction temperature is 100 ℃ with the composition sample introduction in the automatic headspace sample injector, and the transfer tube temperature is 120 ℃;
In the gas chromatograph, injector temperature is 230 ℃, and input mode is shunting, and split ratio is 50;
The chromatographic column that gas chromatography adopts is polysiloxane polymer capillary column DB624, and its chromatographic column specification is 60m * 0.32mm * 1.80um;
Adopt temperature programme to be in the gas chromatographic analysis: initial temperature is 40 ℃, keeps 2min, and the speed with 4 ℃/min rises to 130 ℃ afterwards, keeps 2min, and the speed with 50 ℃/min rises to 240 ℃ again, keeps 2min;
The carrier gas of gas chromatographic analysis is nitrogen, and constant current mode is 2.0ml/min;
The temperature of gas chromatography flame ionization ditector analysis is 250 ℃, and hydrogen is empty than being 30: 300;
The qualitative VOC species analysis of step 3.
After the detection by step 2, obtain respectively hybrid standard working solution chromatogram and toy to be measured paint chromatogram, material in the toy to be measured paint chromatogram before the label diethylene adipate chromatographic peak all is defined as the VOC material, thereby the retention time again by contrast toy paint to be measured chromatogram and hybrid standard working solution chromatogram realizes toy to be measured is painted the qualitative of VOC material in the chromatogram.
3. the detection method of VOC material in the described a kind of toy paint according to claim 1 is characterized in that described that VOC material in the toy paint is carried out the concrete operation step of quantitative test is as follows:
Step 1.
Mark liquid preparation: the pure material that will determine all VOC materials that toy contains in painting is dissolved into the hybrid standard working solution that is made into a series of concentration in the methyl alcohol, then described a series of hybrid standard working solutions are pipetted respectively in 50 μ l to the 20ml head space bottles, compress with the sealing of silicon rubber dottle pin at once;
Sample preparation: take by weighing in toy paint 0.05g to the 20ml head space bottle to be measured, compress with the sealing of silicon rubber dottle pin at once;
Blank preparation: get 50 μ l methyl alcohol to 20ml head space bottle, compress with the sealing of silicon rubber dottle pin, as blank;
Step 2. capillary column-Capillary Column GC detects
With the above-mentioned head space bottle that the hybrid standard working solution is housed, the head space bottle of toy paint to be measured is housed and blank head space bottle is housed and place in the automatic headspace sample injector, carry out balance after, sample introduction separates in gas chromatograph, data acquisition;
In gas chromatograph, the sample introduction temperature is 100 ℃ with the composition sample introduction in the automatic headspace sample injector, and the transfer tube temperature is 120 ℃;
In the gas chromatograph, injector temperature is 230 ℃, and input mode is shunting, and split ratio is 50;
The chromatographic column that gas chromatography adopts is polysiloxane polymer capillary column DB624, and its chromatographic column specification is 60m * 0.32mm * 1.80um;
Adopt temperature programme to be in the gas chromatographic analysis: initial temperature is 40 ℃, keeps 2min, and the speed with 4 ℃/min rises to 130 ℃ afterwards, keeps 2min, and the speed with 50 ℃/min rises to 240 ℃ again, keeps 2min;
The carrier gas of gas chromatographic analysis is nitrogen, and constant current mode is 2.0ml/min;
The temperature of gas chromatography flame ionization ditector analysis is 250 ℃, and hydrogen is empty than being 30: 300;
Step 3. interpretation of result
External standard method by gas chromatography is carried out quantitative test to capillary column-capillary column gas chromatography testing result.
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| CN102520082B (en) * | 2011-12-01 | 2013-09-18 | 湖南省湘维有限公司 | Method for determining volatile components in polyvinyl alcohol in full-evaporation headspace gas chromatography |
| CN104330513B (en) * | 2014-11-04 | 2016-03-02 | 广西中烟工业有限责任公司 | A kind of method detecting halogenated hydrocarbons content in essence and flavoring agent |
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| CN106990190B (en) * | 2016-11-15 | 2019-03-05 | 惠州市长润发涂料有限公司 | A method of volatile organic content in measurement coating paint film |
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| CN107703247A (en) * | 2017-10-23 | 2018-02-16 | 广东省东莞市质量监督检测中心 | Method that is a kind of while detecting volatile organic matter in coating |
| CN113109203A (en) * | 2021-03-26 | 2021-07-13 | 深圳海关玩具检测技术中心 | Detection apparatus for VOC material in toy paint |
| CN113960229A (en) * | 2021-10-22 | 2022-01-21 | 云南中烟工业有限责任公司 | Method for measuring content of methanol in bead blasting essential oil for cigarettes |
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