CN106872620A - The assay method of gylcol ether material in a kind of cigarette packaging paper - Google Patents
The assay method of gylcol ether material in a kind of cigarette packaging paper Download PDFInfo
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- CN106872620A CN106872620A CN201710287474.2A CN201710287474A CN106872620A CN 106872620 A CN106872620 A CN 106872620A CN 201710287474 A CN201710287474 A CN 201710287474A CN 106872620 A CN106872620 A CN 106872620A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The present invention provides a kind of assay method of gylcol ether material in cigarette packaging paper, specifically includes following steps：1）The preparation of sample；2）The preparation of standard specimen；3）Sample detection：Sample and standard specimen are carried out into headspace gas chromatography/mass spectroscopy respectively, the total ion current figure and selection ion figure of sample and standard specimen is obtained；4）Qualitative analysis：The retention time and fragment ion peak of gylcol ether material are control with the total ion current figure of standard specimen, determine gylcol ether material present in sample；5）Quantitative analysis：Standard working curve is set up by the content and its selection ion figure of glycol ether in standard specimen, quantified by external standard method obtains the content of gylcol ether material in sample.The assay method of gylcol ether material in a kind of cigarette packaging paper that the present invention is provided, sensitivity is high, repeated and the rate of recovery is good, for the qualitative and quantitative analysis of gylcol ether material in cigarette packaging paper provide effective technological means.
Description
Technical field
The invention belongs to tobacco detection technique field, it is related to a kind of measure side of gylcol ether material in cigarette packaging paper
Method.
Background technology
Glycol ether is the important derivatives of oxirane, using relatively broad, is commonly used for the hydrotropy of ink, adhesive
Agent, also acts as stabilizer, diluent, paint stripper, cleaning agent, anti-icing fluid etc..Glycol ether have certain toxicity, it is water-soluble and
Volatility, can cause environmental pollution, be listed in highest attention material.Cigarette packaging paper includes that cigarette box packaging paper is (hard box, soft
Box) and bar wrapping paper, ink, diluent, stabilizer etc. are commonly used in printing process is produced, if there is gylcol ether
The residual of material, will have undesirable effect to Product quality and safety.
At present, in cigarette bar and box packaging paper the analysis of glycol ether material there is not been reported, it is necessary to set up cigarette bar
With the accurately and reliably detection method of glycol ether material in box packaging paper.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide ethylene glycol in a kind of cigarette packaging paper
The assay method of ether material, is used cigarette for solving to lack in the prior art using HS GC/mass spectrometric hyphenated technique
Gylcol ether material carries out the problem of qualitative and quantitative detection in wrapping paper.
In order to achieve the above objects and other related objects, the present invention provides gylcol ether material in a kind of cigarette packaging paper
Assay method, specifically include following steps：
1) preparation of sample：Take after cigarette packaging paper sample cut, be put into ml headspace bottle, add matrix correction agent,
As sample, seal to be measured；
2) preparation of standard specimen：Take the corresponding body paper of cigarette packaging paper sample, be cut into and step 1) in sample area one
Cause, be put into ml headspace bottle, add standard working solution, as standard specimen, seal to be measured；
3) sample detection：Respectively by step 1) prepare sample and step 2) prepare standard specimen carry out HS GC/
Mass spectrum (HS-GC/MS) is determined, and obtains total ion current figure (TIC) and selection ion figure (SIM) of sample and standard specimen；
4) qualitative analysis：With step 3) in the total ion current figure (TIC) of standard specimen the retention time of gylcol ether material and
Fragment ion peak is control, determines gylcol ether material present in sample；
5) quantitative analysis：By step 2) content and step 3 of gylcol ether material in standard specimen) standard specimen selection ion
The quota ion peak of the gylcol ether material that figure (SIM) determines, sets up the standard working curve of gylcol ether material, then root
According to step 3) the quota ion peak of gylcol ether material that selection ion figure (SIM) of sample determines, quantified by external standard method is carried out,
Obtain the content of gylcol ether material in sample.
Preferably, gylcol ether material is selected from 2-methyl cellosolve (C in the cigarette packaging paper3H8O2), 2- ethyoxyls
Ethanol (C4H10O2), butoxy ethanol (C6H14O2), 2- methoxyethyl acetates (C5H10O3), 2- ethoxyethyl group acetic acid
Ester (C6H12O3), 2- butoxy ethyl acetates (C8H16O3), diethylene glycol dimethyl ether (C6H14O3), diethylene glycol diethyl ether
(C8H18O3) in one or more of combination.
Preferably, step 1) in, the cigarette packaging paper sample is selected from rigid pack paper, soft box packaging paper or bar wrapping paper
In one kind.
The rigid pack paper refer to by a number of cigarette package into hard box dedicated paper, the hard box be hard box volume
The external packing box body of cigarette.The soft box packaging paper refer to by a number of cigarette package into soft box dedicated paper, the soft box
It is the external packing box body of soft box cigarette.The bar wrapping paper refer to by a number of box-packed (hard box or soft box) cigarette package into
The dedicated paper of bar, the bar is the external packing box body of a number of box-packed (hard box or soft box) cigarette, in general 10 boxes volume
Cigarette is packaged into 1.Above-mentioned wrapping paper includes master package face, and the master package bread contains printing surface.
It is highly preferred that the rigid pack paper is length × wide=22cm × 5.5cm as the cutting area of sample.The sanction
The region for cutting area should be comprising master package face.
It is highly preferred that the soft box packaging paper is length × wide=15.5cm × 10cm as the cutting area of sample.It is described
The region for cutting area should include master package face.
It is highly preferred that the bar wrapping paper is length × wide=22cm × 5.5cm as the cutting area of sample.The cutting
The region of area should include master package face.
Preferably, step 1) in, the test sample is put into ml headspace bottle, is that the printing surface of sample is rolled into tubular inwardly to put
In entering ml headspace bottle.Avoid polluting sample.
Preferably, step 1) in, the matrix correction agent is glyceryl triacetate (C9H14O6)。
Preferably, step 1) in, it is 100-2000 μ L that the matrix correction agent adds volume.
It is highly preferred that it is 1000 μ L that the matrix correction agent adds volume.
Preferably, step 2) in, the corresponding body paper of the cigarette packaging paper sample is selected from rigid pack paper body paper, soft box bag
One kind in dress paper body paper or bar wrapping paper body paper.
The corresponding body paper of the cigarette packaging paper sample refers to the base paper for bar or box packaging paper, it is specific as art post paperboard,
Art paper, coated duplex board with grey back, composite card paper etc..
Preferably, step 2) in, the preparation of the standard working solution is comprised the following steps：
A appropriate 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2- methoxy ethyl second) are weighed respectively
Acid esters, 2- ethoxyethyl acetates, 2- butoxy ethyl acetates, diethylene glycol dimethyl ether, the mark of diethylene glycol diethyl ether
Quasi- material, is dissolved and constant volume with matrix correction agent, is configured to Standard Stock solutions；
B) pipette different amounts of step A respectively) in Standard Stock solutions, with matrix correct dilution agent constant volume, prepare one
The standard working solution of serial various concentrations.
It is highly preferred that step A) in, the concentration of every kind of gylcol ether material is 5mg/mL in the Standard Stock solutions.
It is highly preferred that step B) in, the concentration range of every kind of gylcol ether material should be covered in the standard working solution
The content of corresponding gylcol ether material in lid sample.
It is further preferred that the concentration range of every kind of gylcol ether material is 5-2000 μ in the standard working solution
g/mL。
The standard working solution at least prepares 5 grades.
It is highly preferred that step A) or B) in, the matrix correction agent be glyceryl triacetate (C9H14O6)。
Preferably, step 2) in, it is 100-2000 μ L that the standard working solution adds volume.
It is highly preferred that it is 1000 μ L that the standard working solution adds volume.
Preferably, step 3) in, the total ion current figure refers to be obtained under full scan (SCAN) pattern to selecting
The spectrogram that all ions in the range of ion monitoring are changed over time.The selection ion figure refers in Salbutamol Selected Ion Monitoring
(SIM) spectrogram for changing over time being monitored to the specific ion selected for being obtained under pattern.
Preferably, step 3) in, the analysis condition of the head space (HS) is：
Sample loop：3.0mL；Sample equilibration temperature：80℃；Sample loop temperature：180℃；Transmission line temperature：200℃；Sample
Equilibration time：45min；Sample bottle moulding pressure：138kPa；Pressing time：0.2min；Inflationtime：0.2min；Sample loop is put down
The weighing apparatus time：0.05min；Sample injection time：1.0min.
Preferably, step 3) in, the analysis condition of the gas chromatography/mass spectrometry (GC/MS) is：
Gas-chromatography (GC) condition is：Carrier gas：High-purity helium (He), purity >=99.999%；Injector temperature：200℃；
DB-624 capillary chromatographic columns (60m × 0.32mm × 1.8 μm)；Column flow rate：1.5mL/min (constant current mode)；Split ratio：
30:1；Heating schedule：40 DEG C of holding 2min of initial temperature, 200 DEG C are risen to the speed of 4 DEG C/min, keep 10min.
Mass spectrum (MS) condition is：Satellite interface temperature：280℃；Ion source temperature：230℃；Quadrupole rod temperature：150℃；
Ionization mode：Electron bombardment ionization source (EI)；Ionizing energy：70eV；Scan mode：Full scan (SCAN) and Salbutamol Selected Ion Monitoring
(SIM) while detection pattern；Full scan monitoring range：35-350amu；Selection (quantitative) ion monitoring parameter is shown in Table 1.
Selection (quantitative) ion monitoring parameter of the gylcol ether material of table 1
| Time (min) | Material title | Quota ion (m/z) |
| 5.00 | 2-methyl cellosolve | 45 |
| 15.00 | Cellosolvo | 59 |
| 20.00 | 2- methoxyethyl acetates | 58 |
| 24.00 | 2- ethoxyethyl acetates | 59 |
| 24.00 | Butoxy ethanol | 57 |
| 24.00 | Diethylene glycol dimethyl ether, diethylene glycol diethyl ether | 59 |
| 24.00 | 2- butoxy ethyl acetates | 57 |
Preferably, step 4) in, the retention time of gylcol ether material in the total ion current figure (TIC) with standard specimen
For control refers to, the chromatographic peak of gylcol ether material in the total ion current figure (TIC) of the chromatographic peak in sample spectrogram and standard specimen
Whether occur at identical retention time.Identical retention time referred herein is in the range of ± the 0.2min of retention time.
Preferably, step 4) in, the fragment ion of gylcol ether material in the total ion current figure (TIC) with standard specimen
Peak refers to for control, the fragment of the chromatographic peak in sample spectrogram and total ion current figure (TIC) gylcol ether material of standard specimen from
Whether whether consistent and abundance ratio is consistent the mass-to-charge ratio of son.The abundance ratio specifically, as relative abundance ＞ 50%, permits
Perhaps ± 10% deviation；When relative abundance 20%~50%, it is allowed to ± 15% deviation；When relative abundance 10%~20%, permit
Perhaps ± 20% deviation；When relative abundance≤10%, it is allowed to have ± 50% deviation；It is target compound that qualitative can now confirm.
Preferably, step 5) in, the external standard method refers to：By step 2) prepare standard specimen pass through step 3) carry out head space-
Gas chromatography/mass spectrometry (HS-GC/MS) is determined, and the content of gylcol ether material in standard specimen and its quota ion peak area are entered
Row linear fit, respectively with its corresponding content of the quota ion peak area correspondence of various gylcol ether materials, draws corresponding
Standard working curve, obtain the regression equation of above-mentioned each standard working curve；Again by step 1) prepare sample pass through step
3) carry out HS GC/mass spectrum (HS-GC/MS) to determine, various gylcol ether materials present in the sample that will be obtained
Quota ion peak area, respectively substitute into respective substance standard working curve regression equation in, you can be calculated sample
In corresponding gylcol ether material content.
Preferably, step 5) in, the content of the gylcol ether material is with contained ethylene glycol in unit area wrapping paper
The mass number meter of ether material.
It is highly preferred that the content of the gylcol ether material is with contained glycol ether in every square metre of wrapping paper of area
The milligram number meter of class material, mg/m2。
As described above, the present invention uses HS GC/mass spectrometric hyphenated technique to provide second in a kind of cigarette packaging paper
The qualitativing quantitative measuring method of glycol ethers material.Sample pre-treatments are easy in the assay method, and operating automation degree is high, mark
The linear relationship of quasi- working curve is good, and the sensitivity of method, the repeated and rate of recovery are satisfactory, with preferable accuracy
And precision, for the qualitative and quantitative analysis of gylcol ether material in cigarette packaging paper provide effective technological means.
Brief description of the drawings
Fig. 1 is shown as the HS GC/mass spectrogram of gylcol ether material in standard specimen of the invention, wherein, 1 is
2-methyl cellosolve；2 is cellosolvo；3 is 2- methoxyethyl acetates；4 is 2- ethoxyethyl acetates；5 are
Butoxy ethanol；6 is diethylene glycol dimethyl ether；7 is diethylene glycol diethyl ether；8 is 2- butoxy ethyl acetates.
Fig. 2 is shown as the HS GC/mass spectrogram of cigarette rigid pack paper sample of the invention, contains in the sample
There are cellosolvo and butoxy ethanol.
Fig. 3 is shown as HS GC/mass spectrogram of the cigarette of the invention with soft box packaging paper sample, contains in the sample
There are 2- ethoxyethyl acetates.
Fig. 4 is shown as the HS GC/mass spectrogram of cigarette bar wrapping paper sample of the invention, contains in the sample
Butoxy ethanol.
Specific embodiment
The present invention is expanded on further with reference to specific embodiment, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than limit the scope of the invention.
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages of the invention and effect easily.The present invention can also be by specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that process equipment not specific dated in the following example or device using conventional equipment in the art or
Device；All pressure values and scope are all referring to relative pressure.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
Can also there is other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described；It should also be understood that the combination annexation between one or more the equipment/devices mentioned in the present invention is not repelled
Can also exist before and after the unit equipment/device other equipment/device or two equipment/devices specifically mentioning at these it
Between can also insert other equipment/device, unless otherwise indicated.And, unless otherwise indicated, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting enforceable model of the invention
Enclose, being altered or modified for its relativeness is of the invention enforceable when being also considered as in the case of without essence change technology contents
Category.
The reagent and instrument that following examples are used are as follows：
1. reagent and material
2-methyl cellosolve, 99.9%；Cellosolvo, 99%；Butoxy ethanol, 99%；2- methoxy ethyls
Acetic acid esters, 99%；2- ethoxyethyl acetates, 98%；2- butoxy ethyl acetates, 99%, above reagent is purchased from the U.S.
Sigma-Aldrich companies.Diethylene glycol dimethyl ether, 99%, Chinese lark prestige scientific ＆ technical corporation.Diethylene glycol diethyl ether, 99%,
AlfaAesar companies of the U.S..Glyceryl triacetate, 99%, Shanghai longitude and latitude chemical company.Rigid pack paper, soft box packaging paper, bar
Wrapping paper sample and its body paper are both from Shanghai Tobacco group company.
2. instrument
G1888 head spaces -7890B gas-chromatographies/5977A GC-MSs (HS-GC/MS, Agilent companies of the U.S.)；
20mL ml headspace bottles (Agilent companies of the U.S.)；Assay balance (sensibility reciprocal is 0.1mg, Mettler-Toledo companies of the U.S.)；Piston
Formula liquid-transfering gun (1000 μ L, German Brand companies)；Paper knife (German TATA).
Embodiment 1
1st, the preparation of sample
Take cigarette packaging paper sample and be cut into certain area, clipping region should include master package face.When cigarette packaging paper is
When rigid pack paper or bar wrapping paper, cutting area is length × wide=22cm × 5.5cm；When cigarette packaging paper is soft box packaging paper
When, cutting area is length × wide=15.5cm × 10cm.The printing surface of the cigarette packaging paper sample after cutting is rolled into cylinder inwardly
Shape is put into ml headspace bottle, adds glyceryl triacetate 100-2000 μ L, preferably 1000 μ L, as test sample, is sealed to be measured.
2nd, the preparation of standard specimen
Take the corresponding body paper of cigarette packaging paper sample and be cut into certain area, rigid pack paper body paper or bar wrapping paper body paper
Cutting area be length × wide=22cm × 5.5cm；The cutting area of soft box packaging paper body paper be length × wide=15.5cm ×
10cm.Cigarette packaging paper body paper after cutting is rolled into tubular to be put into ml headspace bottle, standard working solution 100-2000 μ L are added,
Preferably 1000 μ L, as standard specimen, seal to be measured.
The preparation of standard working solution：Appropriate 2-methyl cellosolve, cellosolvo, 2- butoxy second are weighed respectively
Alcohol, 2- methoxyethyl acetates, 2- ethoxyethyl acetates, 2- butoxy ethyl acetates, diethylene glycol dimethyl ether, two
Ethylene glycol diethyl ether standard substance, is diluted and constant volume with glyceryl triacetate, is configured to Standard Stock solutions, then pipette respectively not
The Standard Stock solutions of same volume, are diluted and constant volume with glyceryl triacetate, and a series of standard work for obtaining various concentrations is molten
Liquid.The concentration of every kind of gylcol ether material is 5mg/mL in Standard Stock solutions.Every kind of glycol ether in standard working solution
The concentration range of class material should cover the content of corresponding gylcol ether material in sample, every kind of second in preferred standard working solution
The concentration range of glycol ethers material is 5-2000 μ g/mL.
3rd, sample detection
The standard specimen that above-mentioned steps 1 are processed sample and step 2 respectively is processed is by the HS GC/mass spectrum for setting
Analysis condition carries out HS-GC/MS measure, obtains total ion current figure (TIC) and selection ion figure (SIM) of sample and standard specimen.With
The retention time and fragment ion peak of gylcol ether material are control in the total ion current figure (TIC) of standard specimen, in determining sample
The gylcol ether material of presence.Selection ion figure (SIM) by the content of gylcol ether material in standard specimen and standard specimen is true
The quota ion peak of fixed gylcol ether material, sets up the standard working curve of gylcol ether material, further according to sample
The quota ion peak of the gylcol ether material that selection ion figure (SIM) determines, carries out quantified by external standard method, obtains second two in sample
The content of alcohol ethers material composition.During quantitative analysis, the content of gylcol ether material is with contained mesh in unit area wrapping paper
Mark the mass number meter of compound.Specifically, the content of gylcol ether material is with contained in every square metre of wrapping paper of area
The milligram number meter of gylcol ether material, mg/m2。
Wherein, the analysis condition of the head space (HS) is：
Sample loop：3.0mL；Sample equilibration temperature：80℃；Sample loop temperature：180℃；Transmission line temperature：200℃；Sample
Equilibration time：45min；Sample bottle moulding pressure：138kPa；Pressing time：0.2min；Inflationtime：0.2min；Sample loop is put down
The weighing apparatus time：0.05min；Sample injection time：1.0min.
The analysis condition of the gas chromatography/mass spectrometry (GC/MS) is：
GC conditions are：Carrier gas：High-purity helium (He), purity >=99.999%；Injector temperature：200℃；DB-
624 capillary chromatographic columns (60m × 0.32mm × 1.8 μm)；Column flow rate：1.5mL/min (constant current mode)；Split ratio：30:
1；Heating schedule：40 DEG C of holding 2min of initial temperature, 200 DEG C are risen to the speed of 4 DEG C/min, keep 10min.
Mass Spectrometry Conditions are：Satellite interface temperature：280℃；Ion source temperature：230℃；Quadrupole rod temperature：150℃；Ionization
Mode：Electron bombardment ionization source (EI)；Ionizing energy：70eV；Scan mode：Full scan (SCAN) and Salbutamol Selected Ion Monitoring (SIM) are same
When detection pattern；Full scan monitoring range：35-350amu；Selection (quantitative) ion monitoring parameter is shown in Table 1.
Embodiment 2
Rigid pack paper body paper standard specimen is prepared shown in such as the step of embodiment 12, the step of by embodiment 13 carry out head space-
Gas chromatography/mass spectrometry (HS-GC/MS) detection, HS GC/mass spectrogram such as Fig. 1 institutes of gylcol ether material in standard specimen
Show.With the quota ion peak area of gylcol ether material as ordinate (Y-axis), its corresponding content is (with the hard box bag of unit area
The mass number meter of contained target compound, mg/m in dress paper2) it is abscissa (X-axis), linear fit is carried out, set up standard work
Curve, standard working curve did not forced origin.The retention time of gylcol ether material, standard work on rigid pack paper body paper
Make curvilinear equation and its coefficient (R2), linear concentration scope it is as shown in table 2.As shown in Table 2, the coefficients R of standard working curve2≥
0.995, it is linear good.
The standard working curve of gylcol ether material on the rigid pack paper body paper of table 2
| Material title | Retention time/min | Standard working curve equation | ||
| 2-methyl cellosolve | 13.031 | Y=106411X-41933 | 0.9989 | 0.4065-162.61 |
| Cellosolvo | 16.530 | Y=54036X-18175 | 0.9990 | 0.3822-152.89 |
| 2- methoxyethyl acetates | 22.168 | Y=43636X-4826 | 0.9995 | 0.4277-171.07 |
| 2- ethoxyethyl acetates | 25.219 | Y=22875X-3257 | 0.9995 | 0.4012-160.50 |
| Butoxy ethanol | 25.877 | Y=45422X-14350 | 0.9977 | 0.3593-143.70 |
| Diethylene glycol dimethyl ether | 27.242 | Y=51866X-14040 | 0.9992 | 0.3920-156.79 |
| Diethylene glycol diethyl ether | 32.538 | Y=15062X-4268 | 0.9993 | 0.3750-150.02 |
| 2- butoxy ethyl acetates | 33.204 | Y=19293X-4262 | 0.9978 | 0.3854-154.15 |
Embodiment 3
Take certain brand rigid pack pattern product and produce two parts of parallel samples by step 1 cutting in embodiment 1, after cutting
The printing surface of rigid pack pattern product is rolled into tubular and is put into ml headspace bottle inwardly, is separately added into the triacetic acid glycerine of same volume
Ester, seals to be measured.The sample of above-mentioned preparation is carried out into HS GC/mass spectroscopy by step 3 in embodiment 1, is taken twice
The average value of parallel determination as glycol ether material in the brand rigid pack pattern product analysis result, retain decimal point after
Two, specific test result is shown in Fig. 2.As shown in Figure 2, the rigid pack pattern product contain cellosolvo and 2- butoxy second
Alcohol.
Embodiment 4
Take certain brand rigid pack pattern product and produce many parts of parallel samples by step 1 cutting in embodiment 1, after cutting
The printing surface of rigid pack pattern product is rolled into tubular and is put into ml headspace bottle inwardly, is separately added into the glyceryl triacetate of same volume
With the standard working solution of concentration known, seal to be measured.The corresponding body paper of rigid pack pattern product is taken by step in embodiment 1
2 are cut and add the standard working solution of least concentration, and 10 parallel standard specimens are prepared respectively.By the sample and standard specimen of above-mentioned preparation
HS GC/mass spectroscopy is carried out by step 3 in embodiment 1 respectively, the repetition of computational methods is distinguished according to measurement result
Property (relative standard deviation), the rate of recovery, detection limit (=3 times of standard deviations) and quantitative limit (=10 times of standard deviations), specific knot
Fruit is shown in Table 3.As shown in table 3, the precision of this method, accuracy and sensitivity are satisfactory.
The repeatability of the rigid pack pattern product of table 3, the rate of recovery and test limit result of the test
Embodiment 5
Take the soft box packaging paper sample of certain brand and produce two parts of parallel samples by step 1 cutting in embodiment 1, after cutting
The printing surface of soft box packaging paper sample is rolled into tubular and is put into ml headspace bottle inwardly, is separately added into the triacetic acid glycerine of same volume
Ester, seals to be measured.The sample of above-mentioned preparation is carried out into HS GC/mass spectroscopy by step 3 in embodiment 1, is taken twice
The average value of parallel determination as glycol ether material in the soft box packaging paper sample of the brand analysis result, retain decimal point after
Two, specific test result is shown in Fig. 3.As shown in Figure 3, the soft box packaging paper sample contains 2- ethoxyethyl acetates.
Embodiment 6
Take certain brand bar wrapping paper sample and produce two parts of parallel samples by step 1 cutting in embodiment 1, by the bar after cutting
The printing surface of wrapping paper sample is rolled into tubular and is put into ml headspace bottle inwardly, is separately added into the glyceryl triacetate of same volume, close
Envelope is to be measured.The sample of above-mentioned preparation is carried out into HS GC/mass spectroscopy by step 3 in embodiment 1, is taken parallel twice
The average value of measure retains 2 significant digits as the analysis result of glycol ether material in the brand bar wrapping paper sample,
Specific test result is shown in Fig. 4.As shown in Figure 4, this bar wrapping paper sample contains butoxy ethanol.
So, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under without prejudice to spirit and scope of the invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
Into all equivalent modifications or change, should be covered by claim of the invention.
Claims (11)
1. in a kind of cigarette packaging paper gylcol ether material assay method, specifically include following steps：
1) preparation of sample：Take after cigarette packaging paper sample cut, be put into ml headspace bottle, add matrix correction agent, as
Sample, seals to be measured；
2) preparation of standard specimen：Take the corresponding body paper of cigarette packaging paper sample, be cut into and step 1) in sample area it is consistent, put
Enter in ml headspace bottle, add standard working solution, as standard specimen, seal to be measured；
3) sample detection：Respectively by step 1) prepare sample and step 2) prepare standard specimen carry out HS GC/mass spectrum
Determine, obtain the total ion current figure and selection ion figure of sample and standard specimen；
4) qualitative analysis：With step 3) retention time and fragment ion peak of gylcol ether material in the total ion current figure of standard specimen
It is control, determines gylcol ether material present in sample；
5) quantitative analysis：By step 2) content and step 3 of gylcol ether material in standard specimen) standard specimen selection ion figure it is true
The quota ion peak of fixed gylcol ether material, sets up the standard working curve of gylcol ether material, further according to step 3)
The quota ion peak of the gylcol ether material that the selection ion figure of sample determines, carries out quantified by external standard method, obtains second in sample
The content of glycol ethers material.
2. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Gylcol ether material is selected from 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2- first in the cigarette packaging paper
Epoxide ethylhexoate, 2- ethoxyethyl acetates, 2- butoxy ethyl acetates, diethylene glycol dimethyl ether, diethylene glycol
One or more in diethyl ether of combination.
3. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Step 1) in, the cigarette packaging paper sample is selected from the one kind in rigid pack paper, soft box packaging paper or bar wrapping paper.
4. in a kind of cigarette packaging paper according to claim 3 gylcol ether material assay method, it is characterised in that
The rigid pack paper is length × wide=22cm × 5.5cm as the cutting area of sample；The soft box packaging paper is used as sample
Cutting area be length × wide=15.5cm × 10cm；The bar wrapping paper is length × wide=22cm as the cutting area of sample
×5.5cm。
5. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Step 1) in, the matrix correction agent is glyceryl triacetate, and it is 100-2000 μ L that the matrix correction agent adds volume.
6. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Step 2) in, the corresponding body paper of the cigarette packaging paper sample is selected from rigid pack paper body paper, soft box packaging paper body paper or bar bag
One kind in dress paper body paper.
7. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Step 2) in, it is 100-2000 μ L that the standard working solution adds volume.
8. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Step 2) in, the preparation of the standard working solution is comprised the following steps：
A appropriate 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2- methoxy ethyl acetic acid) are weighed respectively
Ester, 2- ethoxyethyl acetates, 2- butoxy ethyl acetates, diethylene glycol dimethyl ether, the standard of diethylene glycol diethyl ether
Material, is dissolved and constant volume with matrix correction agent, is configured to Standard Stock solutions；
B) pipette different amounts of step A respectively) in Standard Stock solutions, with matrix correct dilution agent constant volume, prepare a series of
The standard working solution of various concentrations.
9. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, it is characterised in that
Step 3) in, the analysis condition of the head space is：
Sample loop：3.0mL；Sample equilibration temperature：80℃；Sample loop temperature：180℃；Transmission line temperature：200℃；Sample equilibration
Time：45min；Sample bottle moulding pressure：138kPa；Pressing time：0.2min；Inflationtime：0.2min；When sample loop is balanced
Between：0.05min；Sample injection time：1.0min.
10. in a kind of cigarette packaging paper according to claim 1 gylcol ether material assay method, its feature exists
In step 3) in, the analysis condition of the gas chromatography/mass spectrometry is：
GC conditions are：Carrier gas：High-purity helium, purity >=99.999%；Injector temperature：200℃；DB-624 capillaries
Chromatographic column, 60m × 0.32mm × 1.8 μm；Column flow rate：1.5mL/min, constant current mode；Split ratio：30:1；Heating schedule：
40 DEG C of holding 2min of initial temperature, 200 DEG C are risen to the speed of 4 DEG C/min, keep 10min；
Mass Spectrometry Conditions are：Satellite interface temperature：280℃；Ion source temperature：230℃；Quadrupole rod temperature：150℃；Ionization mode：
Electron bombardment ionization source；Ionizing energy：70eV；Scan mode：Full scan and Salbutamol Selected Ion Monitoring are while detection pattern；Full scan is monitored
Scope：35-350amu；Salbutamol Selected Ion Monitoring parameter is as follows；
Material title：2-methyl cellosolve, time：5min, quota ion：45m/z；
Material title：Cellosolvo, time：15min, quota ion：59m/z；
Material title：2- methoxyethyl acetates, time：20min, quota ion：58m/z；
Material title：2- ethoxyethyl acetates, time：24min, quota ion：59m/z；
Material title：Butoxy ethanol, time：24min, quota ion：57m/z；
Material title：Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, time：24min, quota ion：59m/z；
Material title：2- butoxy ethyl acetates, time：24min, quota ion：57m/z.
The assay method of gylcol ether material in a kind of 11. cigarette packaging papers according to claim 1, its feature exists
In step 5) in, the content of the gylcol ether material is with the matter of contained gylcol ether material in unit area wrapping paper
Amount number meter.
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