CN102004131B - Method for detecting glyceroltriacetate in cigarette filter rods - Google Patents
Method for detecting glyceroltriacetate in cigarette filter rods Download PDFInfo
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- CN102004131B CN102004131B CN 201010512571 CN201010512571A CN102004131B CN 102004131 B CN102004131 B CN 102004131B CN 201010512571 CN201010512571 CN 201010512571 CN 201010512571 A CN201010512571 A CN 201010512571A CN 102004131 B CN102004131 B CN 102004131B
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Abstract
The invention discloses a method for detecting glyceroltriacetate in cigarette filter rods, which uses gas chromatography and uses isopropanol as a solvent. In the method provided by the invention, the isopropanol serving as the solvent can achieve the same gasification effect as ethanol, and is small in toxin and insusceptible to deliquescence and causing hydrolysis of glyceroltriacetate. In the invention, methyl laurate or propylene carbonate which is used as an internal standard substance is insusceptible to decomposition in light and can be stored easily, a chromatographic column which is a weak/medium-polarity chromatographic column, weak-polarity chromatographic column or medium-polarity chromatographic column has less impurity peaks and small baseline drift. When the method provided by the invention is used for detecting the glyceroltriacetate in the cigarette filter rods, large-batch detection can be realized and the detection result is accurate.
Description
Technical field
The present invention relates to the detection technique of cigarette filter rod, be specifically related to a kind of method that detects glyceroltriacetate in cigarette filter rods.
Background technology
The cigarette glyceryl triacetate is glycerine, the esterification products of glacial acetic acid under catalytic condition, is applied to the industries such as tobacco, cosmetics, casting, medicine, dyestuff, nontoxic, nonirritant.In tobacco business, be used for the cigarette filter tip shaping plastifier, key component glyceryl triacetate wherein plays bonding solidification to diacetate fiber, make cigarette filter rod have good elasticity, gas penetration potential and suitable hardness, directly and remote effect filter stick formation, cigarette roll even the inside and outside quality of cigarette finished product.Cigarette is very important with the quantitative detection of component in the glyceryl triacetate.
Present domestic tobacco business is measured the glyceryl triacetate in the cigarette filter rod according to YC/T 331-2010 (the mensuration vapor-phase chromatography of glyceryl triacetate in the cellulose acetate filter rod), YC/T 331-2010 is that the CRM59 by CORESTA (international tobacco scientific research Cooperation Centre) is transformed, the principle of the method is with sample inject gas chromatograph (GC), gasification separates by capillary chromatographic column, effluent detects with flame ionization ditector (FID), uses inner mark method ration.
The solvent that this method adopts is ethanol, and according to the physicochemical property of glyceryl triacetate, ethanol can be miscible with glyceryl triacetate, but finds through research, adopts ethanol as solvent, and the result is gradually changing in the continuous sample introduction testing process.Pipette glyceryl triacetate reference material 0.1g in the test, to 50mL, shake up rear upper machine testing with the ethanol constant volume, continuous sample introduction, the detected value of glyceryl triacetate is diminishing always as a result, although the RSD value is less, trend is obvious, concrete numerical value sees Table 1:
Table 1 stability experiment one adopts ethanol as solvent (sample weighting amount 0.0960g)
Analyze reason, the hydroxyl in the ethanol molecule can form hydrogen bond, so the ethanol viscosity is very large, and has hygroscopy, can absorb very soon moisture from air.In the situation that the effect of moisture and hydrogen bond is arranged, glyceryl triacetate is hydrolyzed, Partial Conversion is acetin or diacetine, the testing result of acetin in the sample+diacetine content has also confirmed this point (seeing Table 1)-in alcohol solvent, the contained glyceryl triacetate of sample go out peak area constantly descend (the RSD value is 1.87%), acetin+diacetine then continues rise (the RSD value reaches 50.45%), show that glyceryl triacetate may just be hydrolyzed, and change fairly obvious.For this reason, when CRM 59 methods of employing CORESTA or domestic filter stick tobacco rower YC/T 331-2010 detect, series standard solution and sample, all requiring is to prepare one by one, detect one by one, it is unfavorable that this detects batch samples.
Summary of the invention
The problem that the present invention solves is to provide a kind of method that detects glyceroltriacetate in cigarette filter rods, is difficult for causing the hydrolysis of glyceryl triacetate, and testing result is accurate, is suitable for the detection of batch samples.
In order to solve the problems of the technologies described above, technical scheme of the present invention is:
A kind of method that detects glyceroltriacetate in cigarette filter rods is used vapor-phase chromatography, adopts isopropyl alcohol as solvent.
As preferably, adopt methyl laurate or carbonic allyl ester as internal standard compound.
As preferably, adopt weak/middle polarity chromatographic column, low pole chromatographic column or middle polarity chromatographic column.
As preferably, when using weak/middle polarity chromatographic column or low pole chromatographic column, described internal standard compound adopts methyl laurate.
As preferably, when using the middle polarity chromatographic column, described internal standard compound adopts carbonic allyl ester.
As preferably, described chromatographic column adopting is weak/middle polarity chromatographic column or low pole chromatographic column.
As preferably, described weak/the middle polarity chromatographic column is the fixing chromatographic column of (14%-cyanogen propyl group phenyl)-methyl polysiloxane that is mutually.
As preferably, described low pole chromatographic column is the fixing chromatographic column of (5%-phenyl)-methyl polysiloxane that is mutually.
As preferably, described middle polarity chromatographic column is the fixing chromatographic column of (50%-phenyl)-methyl polysiloxane that is mutually.
The method of detection glyceroltriacetate in cigarette filter rods provided by the invention adopts isopropyl alcohol as solvent, can reach the gasification result same with ethanol, and toxicity is little, is difficult for deliquescence, is difficult for causing the hydrolysis of glyceryl triacetate.The present invention also adopts methyl laurate or carbonic allyl ester as internal standard compound, sees that light be difficult for to decompose, and easily preserves, and chromatographic column adopting is weak/middle polarity chromatographic column, low pole chromatographic column or middle polarity chromatographic column, it is less that impurity goes out the peak, and baseline wander is less.Adopt the glyceryl triacetate in the method detection cigarette filter rod provided by the invention, but mass detection, and testing result is accurate.
Description of drawings
Fig. 1 is for adopting the gas chromatogram of HP-5 chromatographic column isopropyl alcohol;
Fig. 2 is for adopting the gas chromatogram of HP-5 chromatographic column ethanol;
Fig. 3 goes out the peak spectrogram for what adopt that the HP-5 chromatographic column detects glyceryl triacetate;
Fig. 4 goes out the peak spectrogram for what adopt that the DB-1701 chromatographic column detects glyceryl triacetate;
Fig. 5 goes out the peak spectrogram for what adopt that the DB-17 chromatographic column detects glyceryl triacetate;
Fig. 6 goes out the peak spectrogram for what adopt that the DB-225MS chromatographic column detects glyceryl triacetate;
Fig. 7 goes out the peak spectrogram for what adopt that the HP-INNOWax chromatographic column detects glyceryl triacetate;
Fig. 8 be glyceryl triacetate concentration be reduced to HP-5 chromatographic column after 5 times go out the peak spectrogram;
Fig. 9 be glyceryl triacetate concentration be reduced to DB-17 chromatographic column after 5 times go out the peak spectrogram;
Figure 10 goes out the peak spectrogram for what adopt that the HP-5 chromatographic column detects impure more glyceryl triacetate;
Figure 11 goes out the peak spectrogram for what adopt that the DB-1701 chromatographic column detects impure more glyceryl triacetate;
Figure 12 goes out the peak spectrogram for what adopt that the DB-17 chromatographic column detects impure more glyceryl triacetate;
Figure 13 goes out the peak spectrogram for what adopt that the DB-225MS chromatographic column detects impure more glyceryl triacetate;
Figure 14 goes out the peak spectrogram for what adopt that the HP-INNOWax chromatographic column detects impure more glyceryl triacetate.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The method of detection glyceroltriacetate in cigarette filter rods provided by the invention, the vapor-phase chromatography principle that provides with YC/T331-2010 is identical, but by research solvent, internal standard compound and the chromatographic column of its use is replaced, and has optimized reaction conditions.
1, solvent of the present invention adopts isopropyl alcohol.
(1) carry out chromatography experiment: isopropyl alcohol and ethanol go out peak, chromatographic condition: YC 144-2008, injection port: 250 ℃ respectively on the HP-5 chromatographic column, sample size: 1 μ L, split ratio: 30: 1, carrier gas: 1.5mL/min, chromatographic column: HP-530m*0.32mm*1.0 μ m, temperature programme: 130 ℃ keep 2min, rise to 250 ℃ with 10 ℃/min, keep 5min, detecting device: 280 ℃, hydrogen: 35mL/min, air: 400mL/min, tail blows: 20mL/min; New bushing pipe 5183-4711.
Isopropyl alcohol and ethanol are all very good to the glyceryl triacetate dissolubility, can be miscible with it.
Please refer to Fig. 1 and Fig. 2, Fig. 1 is for adopting the gas chromatogram of HP-5 chromatographic column isopropyl alcohol, and Fig. 2 is for adopting the gas chromatogram of HP-5 chromatographic column ethanol.Can see employing HP-5 chromatographic column by figure, isopropyl alcohol and ethanol impurities component all went out before 4 minutes, did not have and the equitant peak of glyceryl triacetate (material retention time 8.1min).If adopt DB-1701 or DB-17 chromatographic column, the material of isopropyl alcohol and ethanol impurities goes out the peak and also can not go out the peak to the glyceryl triacetate component and cause interference (chromatogram omission).
(2) each solvent gasification result is detected, accurately takes by weighing glyceryl triacetate sample 0.1g, be settled to 50mL with isopropyl alcohol and ethanol respectively, testing result such as table 2:
The gasification result of each solvent of table 2
Can see and select isopropyl alcohol can reach the gasification result same with ethanol.
(3) to adopting isopropyl alcohol to carry out stability experiment as solvent
Table 3 stability experiment-employing isopropyl alcohol is as solvent (sample weighting amount 0.0998g)
Can obviously find out from above-mentioned experimental result, different from the situation of ethanol, prolongation along with the time, in isopropanol solvent, the peak area that goes out of the contained glyceryl triacetate of sample remains unchanged substantially, acetin+diacetine then has the trend (RSD value only 5.81%, very not obvious) of rising.Therefore, in the isopropanol solvent, glyceryl triacetate is hydrolyzed to acetin+diacetine seldom in certain storage period.
Therefore adopt isopropyl alcohol as solvent, can reach the gasification result same with ethanol, and toxicity is little, is difficult for deliquescence, be difficult for causing the hydrolysis of glyceryl triacetate.
2, chromatographic column adopting of the present invention weak/middle polarity chromatographic column, low pole chromatographic column or middle polarity chromatographic column.Weak/middle polarity chromatographic column is the fixing chromatographic column of (14%-cyanogen propyl group phenyl)-methyl polysiloxane that is mutually, such as the DB-1701 chromatographic column, the low pole chromatographic column is fixing be mutually the chromatographic column of (5%-phenyl)-methyl polysiloxane (such as HP-5 etc.), such as the HP-5 chromatographic column, the middle polarity chromatographic column is to fix to be mutually the chromatographic column of (50%-phenyl)-methyl polysiloxane, such as the DB-17 chromatographic column.And the chromatographic column that adopts among the YC/T 331-2010 is the polarity chromatographic column.The important technological parameters of each chromatographic column sees Table 4:
Each chromatographic column important technological parameters of table 4
(1) pipette glyceryl triacetate sample 0.5mL, be settled to 50mL with ethanol, shake up, adopt above each chromatographic column to detect respectively:
Please refer to Fig. 3 to Fig. 7, be respectively adopt that HP-5 chromatographic column, DB-1701 chromatographic column, DB-17 chromatographic column, DB-225MS chromatographic column, HP-INNOWax chromatographic column detect glyceryl triacetate go out the peak spectrogram.Contrast and to find out from the peak spectrogram that goes out of these five chromatographic columns, under this concentration conditions, no matter be non-polar column or in/strong polar column, leading peak has all appearred in glyceryl triacetate, along with chromatographic column polarity strengthens, the glyceryl triacetate chromatographic peak profile is variation slowly, and then peak shape is comparatively symmetrical, good on weak/middle polarity chromatographic column DB-1701.
Reduce internal standard compound concentration and test, the glyceryl triacetate sample solution concentration is reduced by 5 times (pipetting the 0.1mL constant volume to 50mL), detect.Please refer to Fig. 8 and Fig. 9, Fig. 8 be glyceryl triacetate concentration be reduced to HP-5 chromatographic column after 5 times go out the peak spectrogram, Fig. 9 be glyceryl triacetate concentration be reduced to DB-17 chromatographic column after 5 times go out the peak spectrogram.Can be seen because after reducing sample solution concentration by figure, minimizings of before HP-5 superiors, postponing a meeting or conference, the DB-17 chromatographic column also has analogue, the front ductility at peak significantly reduces, just nonpolar chromatogram master HP-5 more than a little.
Even and under low consistency conditions, the front ductility that polarity improves the peak also can increase, just as the performance when High Concentration Situation, and the strong chromatographic column of polarity can to bear working temperature lower with the middle polarity chromatographic column than nonpolar, column bleed also can be larger, and price is higher.
(2) the chromatographic resolution situation of glyceryl triacetate sample on the different chromatographic columns:
Select impure more glyceryl triacetate sample to test, please refer to Figure 10 to Figure 14, be respectively adopt that HP-5 chromatographic column, DB-1701 chromatographic column, DB-17 chromatographic column, DB-225MS chromatographic column, HP-INNOWax chromatographic column detect impure more glyceryl triacetate go out the peak spectrogram.
By seeing among the figure, 5 kinds of chromatographic columns can both realize glyceryl triacetate and impurity interfering component effective separation.Never can find out with sample chromatogram appearance time stacking diagram, on tested chromatographic column, the impurity composition that may exist in the glyceryl triacetate sample, its chromatographic retention distributed pole is wide.Adopt the stronger chromatographic column impurity of polarity to go out the peak also more, baseline drift is larger.Therefore, in, strong polarity chromatographic column INNOWax, DB-225MS will not adopt.Based on reduce impurity composition may to the thereafter selection of internal standard compound cause interferences, and these 2 of baseline stabilities of maintenance set out, HP-5 is comparatively suitable.
More than comprehensive, chromatographic column of the present invention is selected weak/middle polarity chromatographic column, low pole chromatographic column or middle polarity chromatographic column, a little less than preferred the employing/and middle polarity chromatographic column or low pole chromatographic column, and do not adopt the polarity chromatographic column.
3, the present invention adopts methyl laurate or carbonic allyl ester as internal standard compound.
The cardinal rule of Selection of internal standard has 3 points: (1) can be dissolved in the sample fully, and not with component generation chemical action to be measured; (2) peak position is close with the peak position of component to be measured as far as possible, but can separate with component to be measured the pure material of (degree of separation R 〉=1.5) fully.(3) if can not get sterling, must measure in advance its accurate content, and impurity peaks must not disturb component peaks to be measured.
The internal standard compound that adopts among the YC/T 331-2010 is trans-anethole and glyceryl tripropanoate, also there is Introduction of Literatures can use C17, but C17 is then falling far short with glyceryl triacetate in nature, does not meet 3 cardinal rules of Selection of internal standard, as the weak effect of Internal standard correction methods.
(1) component of each internal standard compound goes out the peak retention time on the different chromatographic columns
Table 5 glyceryl triacetate and the retention time of each internal standard compound on different chromatographic columns
We can see that the peak position of each internal standard compound is close with the peak position of glyceryl triacetate as far as possible from upper table, and retention time difference is less, but can separate fully with glyceryl triacetate.
(2) each internal standard compound is subjected to the situation of glyceryl triacetate impurities interference in different chromatographic columns.
Each internal standard compound of table 6 is disturbed by the glyceryl triacetate impurities in different chromatographic columns situation
Wherein the retention time of " nothing " pure retention time of expression and internal standard compound is overlapping, when trans-anethole is used for DB-17, the retention time of the two kind impurity of meeting appearance except acetin and diacetine and the retention time of internal standard compound are overlapping, therefore on DB-17, trans-anethole is not suitable as internal standard compound.When methyl laurate was used for DB-17, the retention time that the retention time of a kind of impurity except acetin and diacetine and internal standard compound can occur was overlapping, so on DB-17, methyl laurate has certain interference as internal standard compound.
Trans-anethole sees that easily light decomposes, and is unfavorable for long preservation in addition.
More than comprehensive, preferred, when using weak/middle polarity chromatographic column or low pole chromatographic column, internal standard compound adopts methyl laurate, and when using the middle polarity chromatographic column, described internal standard compound adopts carbonic allyl ester.
Above a kind of method that detects glyceroltriacetate in cigarette filter rods provided by the present invention is described in detail.Used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (1)
1. method that detects glyceroltriacetate in cigarette filter rods, it is characterized in that, use vapor-phase chromatography, adopt isopropyl alcohol as solvent, adopt methyl laurate as internal standard compound, adopt weak/middle polarity chromatographic column, described weak/the middle polarity chromatographic column is the fixing chromatographic column of (14%-cyanogen propyl group phenyl)-methyl polysiloxane that is mutually.
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| CN102608246B (en) * | 2012-03-25 | 2014-01-01 | 红云红河烟草(集团)有限责任公司 | Method for measuring moisture content in glyceryl triacetate |
| CN103926353A (en) * | 2014-05-06 | 2014-07-16 | 国家烟草质量监督检验中心 | Method for measuring content of glyceryl triacetate |
| CN108072715A (en) * | 2017-12-06 | 2018-05-25 | 湖北中烟工业有限责任公司 | The assay method of ethanol content in a kind of cigarette glyceryl triacetate |
| CN108645938B (en) * | 2018-08-20 | 2021-01-19 | 云南同创检测技术股份有限公司 | Method for determining content of glyceryl triacetate in acetate fiber filter stick based on LC-MS/MS technology |
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| CN101666785A (en) * | 2009-09-09 | 2010-03-10 | 广东中烟工业有限责任公司 | Method for quantitatively detecting components in glycerol triacetate for tobacco |
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| US8005623B2 (en) * | 2004-02-20 | 2011-08-23 | The Regents Of The University Of California | Molecular flux rates through critical pathways measured by stable isotope labeling in vivo, as biomarkers of drug action and disease activity |
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