CN102680624B - Method for detecting methyl acetate in adhesive for smoke - Google Patents
Method for detecting methyl acetate in adhesive for smoke Download PDFInfo
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- CN102680624B CN102680624B CN201210137821.0A CN201210137821A CN102680624B CN 102680624 B CN102680624 B CN 102680624B CN 201210137821 A CN201210137821 A CN 201210137821A CN 102680624 B CN102680624 B CN 102680624B
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Abstract
The invention discloses a method for detecting methyl acetate in adhesive for smoke. A headspace gas chromatography specifically comprises the following steps of: weighing a sampled to be detected in a headspace sampling bottle, sealing the headspace bottle, balancing the headspace bottle for 30-40 minutes at the temperature of 100-120 DEG C, and exacting gas in the bottle to carry out gas chromatography, wherein the gas chromatograph has the column temperature condition that the initial temperature is 50 DEG C, preserving the temperature for 2 minutes, the raising the temperature to 60 DEG C at the speed of 1DEG C/min, preserving the temperature for 5 minutes, raising the temperature is to 120 DEG C at the speed of 3DEG C/min, and preserving the temperature for 5 minutes. The method provided by the invention is used for analyzing the methyl acetate in the adhesive for smoke, wherein the method is simple, quick, and good in reproducibility.
Description
Technical field
The present invention relates to organism detection field, particularly a kind of headspace gas chromatography detecting for organism.
Background technology
Volatile organic content in adhesive for cigarette, that is organic residue (methyl alcohol, acetone, methyl acetate, the tert-butyl alcohol, vinyl acetate, ethyl acetate etc.) is to be introduced by raw material itself, is mainly residual monomer and organic solvent.Methyl acetate can make cigarette produce bad smell with adhesive, also has certain anesthesia and spread effect simultaneously, and human body is existed to certain harm.Standard of USSR requirement, in water body, methyl acetate maximum permissible concentration is 0.1mg/L, in the atmosphere of residential block, maximum acceptable concentration (MPC) is 0.07mg/m3(maximal value, round the clock average).
Society, people, to healthy growing interest, cause smoking material to be tending towards " greenization " and " innoxious ", therefore, research and development to organic residue carry out effectively, analysis test method fast and accurately, to guaranteeing that cigarette product quality has positive effect.The machine residue analysis method of common are has headspace gas chromatography, gas-liquid balance method, extraction with carbon disulfide method etc.Owing to finding, do not affect the solvent of detected intensity and dissolve cigarette adhesive, so cannot adopt gas-liquid balance method and extraction with carbon disulfide method to detect the organic residue in adhesive for cigarette; And headspace gas chromatography can directly be put into sample head space bottle and analyzes, exempt the pre-treatment step of sample, be applicable to the analysis of the trace low-boiling compound of liquid and solid sample.At present, headspace gas chromatography is used for the mensuration of dissolvent residual in wrappage for cigarette, but yet there are no so far with headspace gas chromatography, detects the report of the organic residue in adhesive for cigarette, does not also put into effect relevant industry standard.Although the employing headspace gas chromatography-mass spectrometries such as Zhu Bin have carried out the analysis of quantitative and qualitative analysis with adhesive to cigarette, the adhesive system of analyzing is different, and contained organic residue is different; Mass spectrometer is expensive in addition, complicated operation, can not meet the testing requirement of medium-sized and small enterprises.
The present invention studies the condition of GC conditions, head-space sampler and sample addition, explore headspace gas chromatography for detection of the feasibility of methyl acetate particularly of the volatile organic content in adhesive for cigarette, for setting up relevant industry standard, provide reference and foundation.
Summary of the invention
The detection method that the object of this invention is to provide methyl acetate in the cigarette use adhesive that a kind of precision is high, the recovery is good.
The present invention achieves the above object by following scheme.
A detection method for methyl acetate in adhesive for cigarette, adopts headspace gas chromatography, and take testing sample and be placed in headspace sampling bottle, sealing top empty bottle, head space bottle after balance 30-40min, extracts gas in bottle and carries out gas chromatographic analysis at 100-120 ℃; The column temperature condition of gas chromatograph is: initial temperature is 50 ℃, keeps 2min, with 1 ℃/min, is warming up to 60 ℃, keeps 5min, then is warming up to 120 ℃ with 3 ℃/min, keeps 5min.
Preferably, the equilibrium temperature of head space bottle is 100 ℃, and equilibration time is 30min.
Preferably, head space bottle condition setting is: head space bottle injection annulus temperature is 120 ℃, and transmission line temperature is 140 ℃.
Preferably, analytical conditions for gas chromatography is set to: carrier gas is nitrogen, and post is pressed as 0.05MPa; Injector temperature: 260 ℃; Fid detector temperature: 270 ℃; Split ratio: 10:1.
The chromatographic column that the present invention uses is preferably used DB-624 chromatographic column, more preferably the DB-624 chromatographic column of 60m * 0.32mm * 1.8 μ m.
Above-mentioned detection method is specially adapted to the detection of methyl acetate.
While using method provided by the invention to measure, specifically comprise the following steps:
(1) preparation standard solution I: get 5mL methyl acetate, in 25mL volumetric flask, obtain standard solution I with ethanol constant volume;
(2) preparation standard solution II: get 1.25mL standard solution I, be surely dissolved in (wherein the concentration of methyl acetate is 92.00 g/L) in 25mL volumetric flask with ethanol;
(3) get respectively standard solution II 1 μ L, 3 μ L, 5 μ L, 8 μ L, 10 μ L in head space bottle, by described condition, measure, according to response signal, densimeter is calculated the regression equation of typical curve;
(4) take cigarette and be placed in headspace sampling bottle with adhesive sample 1.0-1.2g, by described condition, measure, according to response signal and regression equation calculation, go out concentration.
Wherein, preferably to take cigarette be 1.0g by the quality of adhesive sample to step (4).
The present invention has following beneficial effect: with residual methyl acetate in adhesive for Headspace Gas Chromatography cigarette, exempt the pre-treatment step of complex sample, and disturb less, spectrogram is simple, and result accurately and reliably.Adopt pervaporation headspace gas chromatography to make working curve, efficiency is high, good linearity.The features such as detecting of the method is limited to 1.49 μ g, and relative standard deviation is 1.2%, and the recovery is 91%, shows that the method is highly sensitive, and accuracy is good, and method is easy, quick, accurate.
Accompanying drawing explanation
Fig. 1: non-temperature programme collection of illustrative plates (a) and temperature programme collection of illustrative plates (b);
Fig. 2: equilibration time when 30min, the graph of a relation of equilibrium temperature and gas chromatography response signal;
Fig. 3: equilibrium temperature in the time of 100 ℃, the graph of a relation of equilibration time and gas chromatography response signal;
Fig. 4: equilibrium temperature is 100 ℃, when equilibration time is 30min, the graph of a relation of sample addition and gas chromatography response signal.
Embodiment
The reagent that the present embodiment is used is: adhesive, analytically pure methyl acetate for cigarette.
The instrument that the present embodiment is used is: GC9800 gas chromatograph (Shanghai Kechuang Chromatograph Instruments Co., Ltd.); DK-3001A type head-space sampler and head space bottle and Manual cap pressing device (Beijing Zhong Xing analytical instrument Institute for New Technologies).
Head space condition setting is: head space bottle heating-up temperature is 100 ℃, and injection annulus temperature is 120 ℃, and transmission line temperature is 140 ℃, and sample equilibration time is 30min.
Gas chromatograph is set to: chromatographic column is the DB-624 chromatographic column of 60m * 0.32mm * 1.8 μ m; Carrier gas is high pure nitrogen (purity is greater than 99%), and post is pressed as 0.05MPa; Injector temperature: 260 ℃; Fid detector temperature: 270 ℃; Split ratio: 10:1; Column temperature condition is: initial temperature is 50 ℃, keeps 2min, with 1 ℃/min, is warming up to 60 ℃, keeps 5min, then is warming up to 120 ℃ with 3 ℃/min, keeps 5min.
The present embodiment detects with methyl acetate in adhesive cigarette by following steps:
(1) preparation standard solution I: get 5mL methyl acetate, in 25mL volumetric flask, obtain standard solution I with ethanol constant volume;
(2) preparation standard solution II: get 1.25mL standard solution I, be surely dissolved in (wherein the concentration of methyl acetate is 92.00 g/L) in 25mL volumetric flask with ethanol;
(3) get respectively standard solution II 1 μ L, 3 μ L, 5 μ L, 8 μ L, 10 μ L are placed in 20mL head space bottle, use immediately sealing gasket sealing top empty bottle, head space bottle is at 100 ℃ after balance 30min, extract gas 1mL in bottle and under imposing a condition, carry out gas chromatographic analysis, according to response signal, densimeter is calculated the regression equation of typical curve;
(4) take cigarette and be placed in 20mL headspace sampling bottle with adhesive sample 1.00g, use immediately sealing gasket sealing top empty bottle, head space bottle is at 100 ℃ after balance 30min, extract gas 1mL in bottle and under imposing a condition, carry out gas chromatographic analysis, according to response signal and regression equation calculation, go out concentration, result is that the content of methyl acetate is 17.91 μ g/g.
working curve and detection limit
In step (3), get respectively standard solution II 1 μ L, 3 μ L, 5 μ L, 8 μ L, 10 μ L in head space bottle, by selected condition sample introduction, analyze, according to response signal, densimeter is calculated to regression equation, according to signal to noise ratio (S/N ratio) (S/ N=3), calculate detection limit, the results are shown in Table 1.
Table 1 working curve and detection limit
| Component | Regression equation (μ g) | The range of linearity (μ g) | Related coefficient | Detection limit (μ g) |
| Methyl acetate | A=33.73C-8.97 | 0～92 | 0.9995 | 1.49 |
recovery experiment and precision
Accurately take two parts of same sample, a copy of it adds known quantity solvent standard specimen to be measured, and another part do not add, and measures under the same conditions 5 times, by adding the amount of the measuring calculate recovery rate of solvent to be measured, and calculates replicate determination relative standard deviation 5 times, the results are shown in Table 2.
Table 2 method precision and the recovery
Analysis result shows, the method is 0～92 μ g to the range of linearity of methyl acetate organic residue; The relative standard deviation of measurement result is 1.2%; The recovery of sample is 91%.
comparative example 1
The impact of gas chromatography column temperature
This comparative example has compared non-temperature programme and the impact of two kinds of column temperature modes of temperature programme on separating effect, non-temperature programme maintains 120 ℃ by column temperature, and temperature programme as described in Example 1, other condition determinations are also identical with the condition determination of embodiment 1, obtain spectrogram (a is non-temperature programme, and b is temperature programme) as shown in Figure 1.
As shown in Figure 1, the gas chromatography peak obtaining under the condition of non-temperature programme is intensive inseparable, and effect is bad, and the gas chromatography peak obtaining under temperature programme condition can be good at separation, effective.For the wider sample of boiling spread, temperature programme can make more lower boiling component obtain good separation in low initial temperature, along with the rising of column temperature, the component of higher also can flow out faster, and with compared with low boiling component is the same, can access separated good spike.So, the column temperature condition of the gas chromatograph of use embodiment 1, that is: initial temperature is 50 ℃, keep 2min, with 1 ℃/min, be warming up to 60 ℃, keep 5min, with 3 ℃/min, be warming up to 120 ℃ again, keep 5min, when cigarette is detected with methyl acetate in adhesive, can obtain more excellent effect.
comparative example 2
The impact of equilibrium temperature
Get 1.00g sample respectively at 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ temperature balance 30min measure, other condition determinations, with the condition determination of embodiment 1, obtain the response signal of gas chromatography and the Changing Pattern of equilibrium temperature as shown in Figure 2.
As shown in Figure 2, when temperature is less than 100 ℃, response increases along with the rising of equilibrium temperature, and when equilibrium temperature is 100 ℃, response is maximum, and when equilibrium temperature is greater than 100 ℃, response reduces along with the rising of equilibrium temperature.According to Henry law, the rising of equilibrium temperature is conducive to methyl acetate in adhesive and evaporate in gas phase, but equilibrium temperature is too high, can make the pressure in head space bottle excessive, causes sealing variation.Therefore, 100 ℃ of embodiment 1 selection is more excellent equilibrium temperature.
comparative example 3
The impact of equilibration time
Get sample difference balance 10min, 20min, 30min, 40min, 50min, the 60min at 100 ℃ of 1.00g, measure, other condition determinations, with the condition determination of embodiment 1, obtain the response signal of gas chromatography and the Changing Pattern of equilibration time as shown in Figure 3.
As shown in Figure 3, the response signal of gas chromatography increases along with the prolongation of equilibration time, and when equilibration time is 30min, response signal reaches a maximal value, and when equilibration time continues to increase, response signal can remain unchanged and even slightly decline.Illustrate when equilibration time is 30min, in head space bottle, reached vapor liquid equilibrium.Therefore the 30min that, embodiment 1 selects is equilibration time preferably.
comparative example 4
The impact of sample addition
Getting respectively 0.25g, 0.50g, 0.75g, 1.00g, 1.25g, 1.50g sample balance 30min at 100 ℃ measures, other condition determinations, with the condition determination of embodiment 1, obtain the Changing Pattern of gas chromatography response signal and sample addition as shown in Figure 4.
As shown in Figure 4, along with the increase of sample quality, gas chromatography response signal increases, when the quality of adhesive is 1.00g, obtain peak response signal, when the quality of adhesive is greater than 1.00g, response signal, along with the increase variation of adhesive quality tends towards stability, even has the trend reducing.When the quality of the adhesive in head space bottle is less than 1.00g, increase along with adhesive quality, the amount of volatile matter in head space bottle in gas phase also can increase, so response signal has corresponding increase, when the quality of adhesive is greater than 1.00g, in head space bottle, pressure is excessive, the sealing variation that causes head space bottle, make in gas phase volatile matter overflow, cause recruitment in gas phase to reach mobile equilibrium with escaped quantity, so response signal variation tends towards stability.Therefore the 1.00g adhesive that, embodiment 1 selects is more excellent addition.
Claims (6)
1. the detection method of methyl acetate in adhesive for a cigarette, adopt headspace gas chromatography, it is characterized in that: take testing sample and be placed in headspace sampling bottle, sealing top empty bottle, head space bottle after balance 30min, extracts gas in bottle and carries out gas chromatographic analysis at 100-120 ℃; The column temperature condition of gas chromatograph is: initial temperature is 50 ℃, keeps 2min, with 1 ℃/min, is warming up to 60 ℃, keeps 5min, then is warming up to 120 ℃ with 3 ℃/min, keeps 5min;
Chromatographic column is the DB-624 chromatographic column of 60m * 0.32mm * 1.8 μ m.
2. detection method as claimed in claim 1, is characterized in that: the equilibrium temperature of head space bottle is 100 ℃.
3. detection method as claimed in claim 1, is characterized in that head space bottle condition setting is: head space bottle injection annulus temperature is 120 ℃, and transmission line temperature is 140 ℃.
4. detection method as claimed in claim 1, is characterized in that analytical conditions for gas chromatography is set to: carrier gas is nitrogen, and post is pressed as 0.05MPa; Injector temperature: 260 ℃; Fid detector temperature: 270 ℃; Split ratio: 10:1.
5. detection method as claimed in claim 1, is characterized in that comprising the following steps:
(1) preparation standard solution I: get 5mL methyl acetate, in 25mL volumetric flask, obtain standard solution I with ethanol constant volume;
(2) preparation standard solution II: get 1.25mL standard solution I, be surely dissolved in 25mL volumetric flask with ethanol;
(3) get respectively standard solution II 1 μ L, 3 μ L, 5 μ L, 8 μ L, 10 μ L in head space bottle, by described condition, measure, according to response signal, densimeter is calculated the regression equation of typical curve;
(4) take cigarette and be placed in headspace sampling bottle with adhesive sample 1.0-1.2g, by described condition, measure, according to response signal and regression equation calculation, go out concentration.
6. detection method as claimed in claim 5, it is characterized in that taking cigarette is 1.0g by the quality of adhesive sample.
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| CN106526006A (en) * | 2016-11-01 | 2017-03-22 | 湖北中烟工业有限责任公司 | Method for detecting volatiles residue in hot-melt adhesive for cigarettes |
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| CN102879511B (en) * | 2012-09-27 | 2014-10-15 | 甘肃烟草工业有限责任公司 | Method for determining volatile organic compounds in polyvinyl acetate type water-based adhesive |
| CN112326858A (en) * | 2020-10-22 | 2021-02-05 | 扬州联博药业有限公司 | Method for detecting residual amount of methyl acetate in oxytetracycline hydrochloride |
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| US4159894A (en) * | 1978-02-13 | 1979-07-03 | The Boeing Company | Method for determining formulation and chemical structure of materials by improved pyrolysis gas chromatography |
| JP2008281340A (en) * | 2007-05-08 | 2008-11-20 | Mitsubishi Electric Corp | Analysis method of formaldehyde |
| CN101650280A (en) * | 2009-09-09 | 2010-02-17 | 广东中烟工业有限责任公司 | Quantitive detection method of volatile organic compounds in additive of cigarette filter stick |
| CN101701949B (en) * | 2009-11-05 | 2012-08-01 | 中国烟草总公司郑州烟草研究院 | Measurement method of volatile organic compound in tobacco lining paper |
| CN102353734A (en) * | 2011-07-12 | 2012-02-15 | 湖南中烟工业有限责任公司 | Process for determining residual monomers in adhesive |
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| CN106526006A (en) * | 2016-11-01 | 2017-03-22 | 湖北中烟工业有限责任公司 | Method for detecting volatiles residue in hot-melt adhesive for cigarettes |
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