CN106872620B - The measuring method of glycol ether substance in a kind of cigarette packaging paper - Google Patents
The measuring method of glycol ether substance in a kind of cigarette packaging paper Download PDFInfo
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- CN106872620B CN106872620B CN201710287474.2A CN201710287474A CN106872620B CN 106872620 B CN106872620 B CN 106872620B CN 201710287474 A CN201710287474 A CN 201710287474A CN 106872620 B CN106872620 B CN 106872620B
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- G—PHYSICS
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- 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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- 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
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Abstract
The present invention provides a kind of measuring method of glycol ether substance in cigarette packaging paper, specifically comprises the following steps: the preparation of 1) sample；2) preparation of standard specimen；3) sample detection: carrying out HS GC/mass spectroscopy for sample and standard specimen respectively, obtains the total ion current figure and selection ion figure of sample and standard specimen；4) qualitative analysis: it is control with the retention time of glycol ether substance in the total ion current figure of standard specimen and fragment ion peak, determines glycol ether substance present in sample；5) quantitative analysis: standard working curve is established by the content and its selection ion figure of glycol ether in standard specimen, quantified by external standard method obtains the content of glycol ether substance in sample.The measuring method of glycol ether substance in a kind of cigarette packaging paper provided by the invention, high sensitivity, repeatability and the rate of recovery are good, provide effective technological means for the qualitative and quantitative analysis of glycol ether substance in cigarette packaging paper.
Description
Technical field
The invention belongs to tobacco detection technique field, it is related to a kind of measurement side of glycol ether substance in cigarette packaging paper
Method.
Background technique
Glycol ether is the important derivatives of ethylene oxide, and application is relatively broad, is commonly used for the hydrotropy of ink, adhesive
Agent also acts as stabilizer, diluent, paint stripper, detergent, anti-icing fluid etc..Glycol ether have certain toxicity, water solubility and
Volatility can lead to environmental pollution, be listed in highest attention substance.Cigarette packaging paper includes that cigarette box packaging paper is (hard box, soft
Box) and wrapping paper, generally using ink, diluent, stabilizer etc. in production printing process, if there is gylcol ether
The residual of substance will cause adverse effect to Product quality and safety.
Currently, there is not been reported for the analysis of glycol ether substance in cigarette item and box packaging paper, it is necessary to establish cigarette item
With the accurately and reliably detection method of glycol ether substance in box packaging paper.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide ethylene glycol in a kind of cigarette packaging paper
The measuring method of ether material uses cigarette using HS GC/mass spectrometric hyphenated technique for solving to lack in the prior art
Glycol ether substance 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 glycol ether substance in a kind of cigarette packaging paper
Measuring method, specifically comprise the following steps:
1) preparation of sample: after taking cigarette packaging paper sample to be cut, being put into ml headspace bottle, and matrix correction agent is added,
As sample, seal to be measured；
2) preparation of standard specimen: taking the corresponding body paper of cigarette packaging paper sample, is cut into the area one with sample in step 1)
It causes, is put into ml headspace bottle, standard working solution is added, as standard specimen, seal to be measured；
3) sample detection: the standard specimen progress HS GC for respectively preparing the sample of step 1) preparation and step 2)/
Mass spectrum (HS-GC/MS) measurement obtains the total ion current figure (TIC) and selection ion figure (SIM) of sample and standard specimen；
4) qualitative analysis: with the retention time of glycol ether substance in the total ion current figure (TIC) of step 3) standard specimen and
Fragment ion peak is control, determines glycol ether substance present in sample；
5) quantitative analysis: pass through the content of glycol ether substance in step 2) standard specimen and the selection ion of step 3) standard specimen
The quota ion peak for scheming the glycol ether substance that (SIM) is determined, establishes the standard working curve of glycol ether substance, then root
According to the quota ion peak for the glycol ether substance that the selection ion figure (SIM) of step 3) sample determines, quantified by external standard method is carried out,
Obtain the content of glycol ether substance in sample.
Preferably, glycol ether substance is selected from 2-methyl cellosolve (C in the cigarette packaging paper3H8O2), 2- ethyoxyl
Ethyl alcohol (C4H10O2), butoxy ethanol (C6H14O2), 2- methoxyethyl acetate (C5H10O3), 2- ethoxyethyl group acetic acid
Ester (C6H12O3), 2- butoxy ethyl acetate (C8H16O3), diethylene glycol dimethyl ether (C6H14O3), diethylene glycol diethyl ether
(C8H18O3) one of or a variety of combinations.
Preferably, in step 1), the cigarette packaging paper sample is selected from rigid pack paper, soft box packaging paper or wrapping paper
One of.
The rigid pack paper refers to that the dedicated paper by a certain number of cigarette packages at hard box, the hard box are hard box volume
The outer packing box body of cigarette.The soft box packaging paper refers to the dedicated paper by a certain number of cigarette packages at soft box, the soft box
For the outer packing box body of soft box cigarette.Described wrapping paper refer to by a certain number of box-packed (hard box or soft box) cigarette packages at
The dedicated paper of item, the item are the outer packing box body of a certain 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 include 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 described 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, in step 1), the test sample is put into ml headspace bottle, is that the printing surface of sample is rolled into tubular inwardly to put
Enter in ml headspace bottle.Avoid pollution sample.
Preferably, in step 1), the matrix correction agent is glyceryl triacetate (C9H14O6)。
Preferably, in step 1), it is 100-2000 μ L that volume, which is added, in the matrix correction agent.
It is highly preferred that it is 1000 μ L that volume, which is added, in the matrix correction agent.
Preferably, in step 2), the corresponding body paper of the cigarette packaging paper sample is selected from rigid pack paper body paper, soft box packet
Fill one of paper body paper or wrapping paper body paper.
The corresponding body paper of the cigarette packaging paper sample refers to the base paper for item or box packaging paper, it is specific as art post paperboard,
Art paper, coated duplex board with grey back, composite card paper etc..
Preferably, in step 2), the preparation of the standard working solution, comprising the following steps:
A suitable 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2- methoxy ethyl second) are weighed respectively
Acid esters, 2- ethoxyethyl acetate, 2- butoxy ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether mark
Quasi- substance is configured to Standard Stock solutions with the dissolution of matrix correction agent and constant volume；
B) pipette different amounts of step A respectively) in Standard Stock solutions, with matrix correct dilution agent constant volume, preparation one
The standard working solution of serial various concentration.
It is highly preferred that step A) in, the concentration of every kind of glycol ether substance is 5mg/mL in the Standard Stock solutions.
It is highly preferred that step B) in, the concentration range of every kind of glycol ether substance should be covered in the standard working solution
The content of corresponding glycol ether substance in lid sample.
It is further preferred that the concentration range of every kind of glycol ether substance 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, in step 2), it is 100-2000 μ L that volume, which is added, in the standard working solution.
It is highly preferred that it is 1000 μ L that volume, which is added, in the standard working solution.
Preferably, in step 3), the total ion current figure refer to obtained under full scan (SCAN) mode to selected
The spectrogram that all ions within the scope of ion monitoring change over time.The selection ion figure refers in Salbutamol Selected Ion Monitoring
(SIM) spectrogram changed over time that selected specific ion is monitored obtained under mode.
Preferably, in step 3), the analysis condition of the head space (HS) are as follows:
Sample loop: 3.0mL；Sample equilibration temperature: 80 DEG C；Sample loop temperature: 180 DEG C；Transmission line temperature: 200 DEG C；Sample
Equilibration time: 45min；Sample bottle moulding pressure: 138kPa；Pressing time: 0.2min；Inflationtime: 0.2min；Sample loop is flat
It weighs the time: 0.05min；Sample injection time: 1.0min.
Preferably, in step 3), the analysis condition of the gas chromatography/mass spectrometry (GC/MS) are as follows:
Gas-chromatography (GC) condition are as follows: carrier gas: high-purity helium (He), purity >=99.999%；Injector temperature: 200 DEG C；
DB-624 capillary chromatographic column (60m × 0.32mm × 1.8 μm)；Column flow rate: 1.5mL/min (constant current mode)；Split ratio:
30:1；Temperature program: 40 DEG C of holding 2min of initial temperature rise to 200 DEG C with the speed of 4 DEG C/min, keep 10min.
Mass spectrum (MS) condition are as follows: satellite interface temperature: 280 DEG C；Ion source temperature: 230 DEG C；Quadrupole rod temperature: 150 DEG C；
Ionization mode: electron bombardment ionization source (EI)；Ionizing energy: 70eV；Scanning mode: full scan (SCAN) and Salbutamol Selected Ion Monitoring
(SIM) simultaneously detection pattern；Full scan monitoring range: 35-350amu；Selection (quantitative) ion monitoring parameter is shown in Table 1.
Selection (quantitative) ion monitoring parameter of 1 glycol ether substance of table
| Time (min) | Substance title | Quota ion (m/z) |
| 5.00 | 2-methyl cellosolve | 45 |
| 15.00 | Cellosolvo | 59 |
| 20.00 | 2- methoxyethyl acetate | 58 |
| 24.00 | 2- ethoxyethyl acetate | 59 |
| 24.00 | Butoxy ethanol | 57 |
| 24.00 | Diethylene glycol dimethyl ether, diethylene glycol diethyl ether | 59 |
| 24.00 | 2- butoxy ethyl acetate | 57 |
Preferably, in step 4), the retention time of glycol ether substance in the total ion current figure (TIC) with standard specimen
Refer to for control, the chromatographic peak of glycol ether substance in the total ion current figure (TIC) of chromatographic peak and standard specimen in sample spectrogram
Whether occur at identical retention time.Identical retention time referred herein is within the scope of ± the 0.2min of retention time.
Preferably, in step 4), the fragment ion of glycol ether substance in the total ion current figure (TIC) with standard specimen
Peak is that control refers to, the fragment of total ion current figure (TIC) glycol ether substance of chromatographic peak and standard specimen in sample spectrogram from
Whether whether consistent and abundance than is consistent the mass-to-charge ratio of son.The abundance ratio specifically, as relative abundance > 50%, is permitted
Perhaps ± 10% deviation；When relative abundance 20%~50%, allow ± 15% deviation；When relative abundance 10%~20%, permit
Perhaps ± 20% deviation；When relative abundance≤10%, allow to have ± 50% deviation；Qualitative can confirm at this time is target compound.
Preferably, in step 5), the external standard method refers to: the standard specimen of step 2) preparation is carried out head space-by step 3)
Gas chromatography/mass spectrometry (HS-GC/MS) measurement, to the content of glycol ether substance in standard specimen and its quota ion peak area into
Row linear fit corresponds to its corresponding content respectively with the quota ion peak area of various glycol ether substances, draws corresponding
Standard working curve, obtain the regression equation of above-mentioned each standard working curve；Sample prepared by step 1) is passed through into step again
3) HS GC/mass spectrum (HS-GC/MS) measurement, various glycol ether substances present in the sample by acquisition are carried out
Quota ion peak area, respectively substitute into respective substance standard working curve regression equation in, sample can be calculated
In corresponding glycol ether substance content.
Preferably, in step 5), the content of the glycol ether substance 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 glycol ether substance is with contained glycol ether in the wrapping paper of every square metre of area
The milligram number meter of substance, mg/m2。
As described above, the present invention provides second in a kind of cigarette packaging paper using HS GC/mass spectrometric hyphenated technique
The qualitativing quantitative measuring method of glycol ethers substance.Sample pre-treatments are easy in the measuring method, and operating automation degree is high, mark
The linear relationship of quasi- working curve is good, and the sensitivity of method, repeatability and the rate of recovery are satisfactory, has preferable accuracy
And precision, effective technological means is provided for the qualitative and quantitative analysis of glycol ether substance in cigarette packaging paper.
Detailed description of the invention
Fig. 1 is shown as HS GC/mass spectrogram of glycol ether substance in standard specimen of the invention, wherein 1 is
2-methyl cellosolve；2 be cellosolvo；3 be 2- methoxyethyl acetate；4 be 2- ethoxyethyl acetate；5 are
Butoxy ethanol；6 be diethylene glycol dimethyl ether；7 be diethylene glycol diethyl ether；8 be 2- butoxy ethyl acetate.
Fig. 2 is shown as 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 soft box packaging paper sample of cigarette of the invention, contains in the sample
There is 2- ethoxyethyl acetate.
Fig. 4 is shown as HS GC/mass spectrogram of cigarette wrapping paper sample of the invention, contains in the sample
Butoxy ethanol.
Specific embodiment
The present invention is further explained combined with specific embodiments below, it should be appreciated that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that in the following example not specifically dated process equipment or device be all made of conventional equipment in the art or
Device；All pressure values and range all refer to relative pressure.
In addition, it should also be understood that, one or more method and step mentioned in the present invention does not repel before and after the combination step
It can also be inserted into other methods step there may also be other methods step or between these explicitly mentioned steps, unless separately
It is described；It should also be understood that the combination connection relationship between one or more equipment/device mentioned in the present invention is not repelled
The two equipment/devices specifically mentioned before and after the unit equipment/device there may also be other equipment/device or at these it
Between can also be inserted into other equipment/device, unless otherwise indicated.Moreover, unless otherwise indicated, the number of various method steps is only
Identify the convenient tool of various method steps, rather than for the arrangement order of limitation various method steps or limits the enforceable model of the present invention
It encloses, relativeness is altered or modified, and without material changes in technical content, when being also considered as, the present invention is enforceable
Scope.
The reagent and instrument that following embodiment uses are as follows:
1. reagent and material
2-methyl cellosolve, 99.9%；Cellosolvo, 99%；Butoxy ethanol, 99%；2- methoxy ethyl
Acetic acid esters, 99%；2- ethoxyethyl acetate, 98%；2- butoxy ethyl acetate, 99%, the above reagent is purchased from the U.S.
Sigma-Aldrich company.Diethylene glycol dimethyl ether, 99%, Chinese lark prestige scientific & technical corporation.Diethylene glycol diethyl ether, 99%,
AlfaAesar company, the U.S..Glyceryl triacetate, 99%, Shanghai longitude and latitude chemical company.Rigid pack paper, soft box packaging paper, item
Wrapping paper sample and its body paper are both from Shanghai Tobacco group company.
2. instrument
G1888 head space -7890B gas-chromatography/5977A mass spectrometer (HS-GC/MS, Agilent company, the U.S.)；
20mL ml headspace bottle (Agilent company, the U.S.)；Assay balance (sensibility reciprocal 0.1mg, Mettler-Toledo company, the U.S.)；Piston
Formula liquid-transfering gun (1000 μ L, German Brand company)；Paper knife (German TATA).
Embodiment 1
1, the preparation of sample
Cigarette packaging paper sample is taken to 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 cigarette packaging paper sample after cutting is rolled into cylinder inwardly
Shape is put into ml headspace bottle, and glyceryl triacetate 100-2000 μ L, preferably 1000 μ L are added, and as test sample, is sealed to be measured.
2, the preparation of standard specimen
The corresponding body paper of cigarette packaging paper sample is taken to be cut into certain area, rigid pack paper body paper or 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 is added,
Preferably 1000 μ L are sealed to be measured as standard specimen.
The preparation of standard working solution: suitable 2-methyl cellosolve, cellosolvo, 2- butoxy second are weighed respectively
Alcohol, 2- methoxyethyl acetate, 2- ethoxyethyl acetate, 2- butoxy ethyl acetate, diethylene glycol dimethyl ether, two
Ethylene glycol diethyl ether standard substance is configured to Standard Stock solutions, then pipette respectively not with glyceryl triacetate dilution and constant volume
The Standard Stock solutions of same volume, with glyceryl triacetate dilution and constant volume, a series of standard work for obtaining various concentrations is molten
Liquid.The concentration of every kind of glycol ether substance is 5mg/mL in Standard Stock solutions.Every kind of glycol ether in standard working solution
The concentration range of substance should cover the content of corresponding glycol ether substance in sample, every kind of second in preferred standard working solution
The concentration range of glycol ethers substance is 5-2000 μ g/mL.
3, sample detection
Respectively by the sample that above-mentioned steps 1 are handled and the standard specimen that step 2 is handled by HS GC/mass spectrum of setting
Analysis condition carries out HS-GC/MS measurement, obtains the total ion current figure (TIC) and selection ion figure (SIM) of sample and standard specimen.With
The retention time of glycol ether substance and fragment ion peak are control in the total ion current figure (TIC) of standard specimen, are determined in sample
Existing glycol ether substance.It is true by the selection ion figure (SIM) of the content of glycol ether substance in standard specimen and standard specimen
The quota ion peak of fixed glycol ether substance, establishes the standard working curve of glycol ether substance, further according to sample
The quota ion peak for the glycol ether substance for selecting ion figure (SIM) to determine carries out quantified by external standard method, obtains second two in sample
The content of alcohol ethers material composition.When quantitative analysis, the content of glycol ether substance is with contained mesh in unit area wrapping paper
Mark the mass number meter of compound.Specifically, the content of glycol ether substance is with contained in the wrapping paper of every square metre of area
The milligram number meter of glycol ether substance, mg/m2。
Wherein, the analysis condition of the head space (HS) are as follows:
Sample loop: 3.0mL；Sample equilibration temperature: 80 DEG C；Sample loop temperature: 180 DEG C；Transmission line temperature: 200 DEG C；Sample
Equilibration time: 45min；Sample bottle moulding pressure: 138kPa；Pressing time: 0.2min；Inflationtime: 0.2min；Sample loop is flat
It weighs the time: 0.05min；Sample injection time: 1.0min.
The analysis condition of the gas chromatography/mass spectrometry (GC/MS) are as follows:
GC conditions are as follows: carrier gas: high-purity helium (He), purity >=99.999%；Injector temperature: 200 DEG C；DB-
624 capillary chromatographic columns (60m × 0.32mm × 1.8 μm)；Column flow rate: 1.5mL/min (constant current mode)；Split ratio: 30:
1；Temperature program: 40 DEG C of holding 2min of initial temperature rise to 200 DEG C with the speed of 4 DEG C/min, keep 10min.
Mass Spectrometry Conditions are as follows: satellite interface temperature: 280 DEG C；Ion source temperature: 230 DEG C；Quadrupole rod temperature: 150 DEG C；Ionization
Mode: electron bombardment ionization source (EI)；Ionizing energy: 70eV；Scanning 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 as shown in the step 2 of embodiment 1, carries out head space-by the step 3 of embodiment 1
Gas chromatography/mass spectrometry (HS-GC/MS) detects, HS GC/mass spectrogram such as Fig. 1 institute of glycol ether substance in standard specimen
Show.Using the quota ion peak area of glycol ether substance as ordinate (Y-axis), corresponding content is (with the hard box packet of unit area
Fill the mass number meter of contained target compound in paper, mg/m2) it is abscissa (X-axis), linear fit is carried out, standard work is established
Curve, standard working curve did not forced origin.The retention time of glycol ether substance, standard work on rigid pack paper body paper
Make curvilinear equation and its coefficient (R2), linear concentration range 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 glycol ether substance on 2 rigid pack paper body paper of table
| Substance title | Retention time/min | Standard working curve equation | R2 | Linear concentration range (mg/m2) |
| 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 acetate | 22.168 | Y=43636X-4826 | 0.9995 | 0.4277-171.07 |
| 2- ethoxyethyl acetate | 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 acetate | 33.204 | Y=19293X-4262 | 0.9978 | 0.3854-154.15 |
Embodiment 3
Certain brand rigid pack pattern product is taken to 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 inwardly and is put into ml headspace bottle, is separately added into the triacetic acid glycerol of same volume
Ester seals to be measured.The sample of above-mentioned preparation is subjected to HS GC/mass spectroscopy by step 3 in embodiment 1, is taken twice
The average value of parallel determination as glycol ether substance in the brand rigid pack pattern product analysis as a result, retain decimal point after
Two, specific test result is shown in Fig. 2.As shown in Figure 2, which contains cellosolvo and 2- butoxy second
Alcohol.
Embodiment 4
Certain brand rigid pack pattern product is taken to produce more 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 inwardly and is put into ml headspace bottle, is separately added into the glyceryl triacetate of same volume
With the standard working solution of known concentration, seal to be measured.Take the corresponding body paper of rigid pack pattern product by step in embodiment 1
2 cut and are added the standard working solution of minimum concentration, prepare 10 parallel standard specimens 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 method is calculated separately 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), it is specific to tie
Fruit is shown in Table 3.As shown in table 3, the precision of this method, accuracy and sensitivity are satisfactory.
Repeatability, the rate of recovery and the detection limit test result of 3 rigid pack pattern product of table
Embodiment 5
The soft box packaging paper sample of certain brand is taken to 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 inwardly and is put into ml headspace bottle, is separately added into the triacetic acid glycerol of same volume
Ester seals to be measured.The sample of above-mentioned preparation is subjected to HS GC/mass spectroscopy by step 3 in embodiment 1, is taken twice
The average value of parallel determination as glycol ether substance in the soft box packaging paper sample of the brand analysis as a result, retain decimal point after
Two, specific test result is shown in Fig. 3.As shown in Figure 3, which contains 2- ethoxyethyl acetate.
Embodiment 6
Certain brand bar wrapping paper sample is taken to produce two parts of parallel samples by step 1 cutting in embodiment 1, by the item after cutting
The printing surface of wrapping paper sample is rolled into tubular inwardly and is put into ml headspace bottle, is separately added into the glyceryl triacetate of same volume, close
It seals to be measured.The sample of above-mentioned preparation is subjected to HS GC/mass spectroscopy by step 3 in embodiment 1, is taken parallel twice
The average value of measurement as glycol ether substance in the brand bar wrapping paper sample analysis as a result, retain 2 significant digits,
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 in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (8)
1. the measuring method of glycol ether substance, specifically comprises the following steps: in a kind of cigarette packaging paper
1) preparation of sample: after taking cigarette packaging paper sample to be cut, being put into ml headspace bottle, and matrix correction agent is added, as
Sample seals to be measured；
2) preparation of standard specimen: taking the corresponding body paper of cigarette packaging paper sample, is cut into consistent with the area of sample in step 1), puts
Enter in ml headspace bottle, standard working solution is added, as standard specimen, seals to be measured；
3) standard specimen of the sample of step 1) preparation and step 2) preparation sample detection: is subjected to HS GC/mass spectrum respectively
Measurement obtains the total ion current figure and selection ion figure of sample and standard specimen；
4) qualitative analysis: with the retention time and fragment ion peak of glycol ether substance in the total ion current figure of step 3) standard specimen
For control, glycol ether substance present in sample is determined；
5) quantitative analysis: true by the content of glycol ether substance in step 2) standard specimen and the selection ion figure of step 3) standard specimen
The quota ion peak of fixed glycol ether substance, establishes the standard working curve of glycol ether substance, further according to step 3)
The quota ion peak for the glycol ether substance that the selection ion figure of sample determines, carries out quantified by external standard method, obtains second in sample
The content of glycol ethers substance；
Glycol ether substance is by 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2- in the cigarette packaging paper
Methoxyethyl acetate, 2- ethoxyethyl acetate, 2- butoxy ethyl acetate, diethylene glycol dimethyl ether, diethyl two
Diethylene glycol diethyl ether composition；
In step 3), the analysis condition of the head space are as follows:
Sample loop: 3.0mL；Sample equilibration temperature: 80 DEG C；Sample loop temperature: 180 DEG C；Transmission line temperature: 200 DEG C；Sample equilibration
Time: 45min；Sample bottle moulding pressure: 138kPa；Pressing time: 0.2min；Inflationtime: 0.2min；
Sample loop equilibration time: 0.05min；Sample injection time: 1.0min；
In step 3), the analysis condition of the gas chromatography/mass spectrometry are as follows:
GC conditions are as follows: carrier gas: high-purity helium, purity >=99.999%；Injector temperature: 200 DEG C；DB-624 capillary
Chromatographic column, 60m × 0.32mm × 1.8 μm；Column flow rate: 1.5mL/min, constant current mode；Split ratio: 30:1；Temperature program:
40 DEG C of holding 2min of initial temperature rise to 200 DEG C with the speed of 4 DEG C/min, keep 10min；
Mass Spectrometry Conditions are as follows: satellite interface temperature: 280 DEG C；Ion source temperature: 230 DEG C；Quadrupole rod temperature: 150 DEG C；Ionization mode:
Electron bombardment ionization source；Ionizing energy: 70eV；Scanning mode: full scan and Salbutamol Selected Ion Monitoring while detection pattern；
Full scan monitoring range: 35-350amu；Salbutamol Selected Ion Monitoring parameter is as follows；
Substance title: 2-methyl cellosolve, time: 5min, quota ion: 45m/z；
Substance title: cellosolvo, time: 15min, quota ion: 59m/z；
Substance title: 2- methoxyethyl acetate, time: 20min, quota ion: 58m/z；
Substance title: 2- ethoxyethyl acetate, time: 24min, quota ion: 59m/z；
Substance title: butoxy ethanol, time: 24min, quota ion: 57m/z；
Substance title: diethylene glycol dimethyl ether, diethylene glycol diethyl ether, time: 24min, quota ion: 59m/z；
Substance title: 2- butoxy ethyl acetate, time: 24min, quota ion: 57m/z；
The retention time of the 2-methyl cellosolve: 13.031min；
The retention time of the cellosolvo: 16.530min；
The retention time of the 2- methoxyethyl acetate: 22.168min；
The retention time of the 2- ethoxyethyl acetate: 25.219min；
The retention time of the butoxy ethanol: 25.877min；
The retention time of the diethylene glycol dimethyl ether: 27.242min；
The retention time of the diethylene glycol diethyl ether: 32.538min；
The retention time of the 2- butoxy ethyl acetate: 33.204min.
2. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 1, which is characterized in that
In step 1), the cigarette packaging paper sample is selected from one of rigid pack paper, soft box packaging paper or wrapping paper.
3. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 2, which is characterized in that
The rigid pack paper is length × wide=22cm × 5.5cm as the cutting area of sample；The soft box packaging paper is as sample
Cutting area be length × wide=15.5cm × 10cm；Described wrapping paper is length × wide=22cm as the cutting area of sample
×5.5cm。
4. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 1, which is characterized in that
In step 1), the matrix correction agent is glyceryl triacetate, and it is 100-2000 μ L that volume, which is added, in the matrix correction agent.
5. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 1, which is characterized in that
In step 2), 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 item packet
Fill one of paper body paper.
6. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 1, which is characterized in that
In step 2), it is 100-2000 μ L that volume, which is added, in the standard working solution.
7. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 1, which is characterized in that
In step 2), the preparation of the standard working solution, comprising the following steps:
A suitable 2-methyl cellosolve, cellosolvo, butoxy ethanol, 2- methoxy ethyl acetic acid) are weighed respectively
The standard of ester, 2- ethoxyethyl acetate, 2- butoxy ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether
Substance is configured to Standard Stock solutions with the dissolution of matrix correction agent and constant volume；
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 concentration.
8. the measuring method of glycol ether substance in a kind of cigarette packaging paper according to claim 1, which is characterized in that
In step 5), the content of the glycol ether substance is with the mass number of glycol ether substance contained in unit area wrapping paper
Meter.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226792A (en) * | 2011-04-01 | 2011-10-26 | 广州市谱尼测试技术有限公司 | Detection method for 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethanol acetate and 2-ethoxyethanol acetate |
| CN102998387A (en) * | 2012-11-23 | 2013-03-27 | 江苏中烟工业有限责任公司 | Method for determining ethylene glycol monomethyl ether, glycol ether, ethylene glycol ether acetate, glycol and diglycol in food wrap paper |
| CN103399111A (en) * | 2013-07-10 | 2013-11-20 | 江苏中烟工业有限责任公司 | Method for selectively measuring ethylene glycol monoethyl ether acetate in dry food packaging paper based on headspace-gas chromatography/mass spectrometry |
-
2017
- 2017-04-27 CN CN201710287474.2A patent/CN106872620B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226792A (en) * | 2011-04-01 | 2011-10-26 | 广州市谱尼测试技术有限公司 | Detection method for 2-methoxyethanol, 2-ethoxyethanol, 2-methoxyethanol acetate and 2-ethoxyethanol acetate |
| CN102998387A (en) * | 2012-11-23 | 2013-03-27 | 江苏中烟工业有限责任公司 | Method for determining ethylene glycol monomethyl ether, glycol ether, ethylene glycol ether acetate, glycol and diglycol in food wrap paper |
| CN103399111A (en) * | 2013-07-10 | 2013-11-20 | 江苏中烟工业有限责任公司 | Method for selectively measuring ethylene glycol monoethyl ether acetate in dry food packaging paper based on headspace-gas chromatography/mass spectrometry |
Non-Patent Citations (2)
| Title |
|---|
| 微波辅助萃取-气相色谱/质谱-选择离子检测法同时测定纺织品中15种乙二醇醚类有机溶剂残留量;王成云 等;《产业用纺织品》;20151231(第7期);第38-44页 * |
| 顶空-气相色谱质谱联用法分析烟用纸张中26种溶剂残留物;杜显生 等;《中华纸业》;20160731;第37卷(第14期);第27-30页 * |
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