CN105181868B - Measure 13 kinds of benzene homologues and the methods and applications of phthalate compound in water base adhesive simultaneously - Google Patents
Measure 13 kinds of benzene homologues and the methods and applications of phthalate compound in water base adhesive simultaneously Download PDFInfo
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Abstract
The invention discloses a kind of 13 kinds of benzene homologues and the method for phthalate compound in water base adhesive of mensuration simultaneously.The present invention filters i.e. obtain sample liquid through hexamethylene extraction after using ultra-pure water vibrating dispersion sample, utilize gas chromatograph-mass spectrometer, in single injected sampling, 13 kinds of compounds in smoke aqueous gel are measured simultaneously, chromatographic peak separates preferably, result shows, the regression equation correlation coefficient of each component all reaches more than 0.997, the detection by quantitative of 6 kinds of benzene homologues is limited to 0.04～0.07 μ g/g, the detection by quantitative of 7 kinds of phthalate compounds is limited to 0.5～4.2 μ g/g, have accurately, quickly, highly sensitive, favorable reproducibility, response rate advantages of higher, meet quantitative requirement.
Description
Technical field
The present invention relates to the detection technique field of smoke aqueous gel, measure in water base adhesive more particularly, to one simultaneously
13 kinds of benzene homologues and the method for phthalate compound and in the cigarette application of hydrosol context of detection.
Background technology
Water base adhesive is the water solublity with water as disperse medium or emulsion adhesive, is mainly used in production of cigarettes industry
Cigarette mouth building, Medicated cigarette are spigot joint, filter stick center line and cigarette package etc..During producing water base adhesive, because raw material or operation
Technological problems, may introduce some materials such as benzene homologues, phthalate.The countries tobacco industry quality to water base adhesive
Monitor particularly severe, the benzene homologues that wherein may remain and phthalate material have been done respectively corresponding limitation rule
Fixed, and formulated the standard detecting method of correspondence.
In existing achievement in research, Yang Bin etc. proposes to use gas chromatography/mass spectrometry cigarette with in aqua type latex
Phthalic acid ester, carry out latex sample carrying out after ultrasonic extraction obtains sample with the hexane solution added with internal standard material
Detection；Zhang Pingquan etc. propose to use the method for phthalic acid ester content in gas chromatography/mass spectrometry water base adhesive to change
Enter, in order to improve detection efficiency, avoid again the damage of instrument simultaneously, use the capillary tube color of benzene homologues content in test water base adhesive
Spectrum post establishes and measures the improved method of phthalic acid ester content in water base adhesive.
But actually detected research finds, when high-volume monitoring sample, uses 2 set methods to detect in same substrate respectively
Different material, pre-treatment is time-consuming, solvent-oil ratio is big, and for large batch of pattern detection, detection efficiency is the highest.
Summary acquisition single injected sampling just can detect benzene homologues and phthalate compound in smoke aqueous gel simultaneously and have important
Actual application value.
Cao Mei and the Zhu Zhong " benzene in vortex mixed assisting ultrasonic extraction-hplc simultaneous determination water base adhesive
It is thing and phthalic ester plasticizer ", in the way of vortex mixed assisting ultrasonic extraction process sample, use whirlpool mixing
Device biased sample, makes sample be dispersed in extractant, and the mode re-using ultrasonic extraction extracts object, establishes and makes
By the benzene homologues in hplc simultaneous determination water base adhesive and the method for 5 kinds of phthalate materials, have studied
Different extractants, extracting mode and the condition impact on object testing result thereof, it is determined that use ethyl acetate as extraction
Take agent, the condition such as the phase that specifically flows, detection wavelength, flow and sample size, its extracting method proposed and specific efficiently
Under liquid chromatography testing conditions, the peak area of 5 kinds of benzene homologues and 5 kinds of phthalic ester plasticizers and its matter in water base adhesive
Amount concentration is linear.And point out, extractant kind is the key factor affecting ultrasonic extraction efficiency, between solvent and substrate
Interaction and object dissolubility in a solvent, all ultrasonic extraction efficiency is had an impact, the ultrasonic extraction of different solvents
Take efficiency difference greatly.For water base adhesive, its system is high molecular polymer, and viscosity is stronger.If using polarity stronger
The moderate dichloromethane of methanol, ethanol and polarity make solvent, although whole sample substrate system can be scatter, but wherein
Macromole impurity also can enter in sample introduction liquid, be unfavorable for follow-up chromatographic isolation.If using the normal hexane of low pole, sample
Substrate can not be completely dispersed, and can affect the extraction efficiency of object.Consider extraction efficiency and the sample base of object
The analyzing influence of confrontation instrument, selection ethyl acetate is extractant.
Lai Ying proposes a kind of GC-MS and measures benzene homologues and phthalate in adhesive for building simultaneously
The method of plasticizer, using n-tetradecane as internal standard substance, is studied extracting method and chromatographic condition, with Cao Mei after comparing
Draw identical research conclusion with Zhu Zhong, determined that ethyl acetate is the highest to dissolubility and the extraction efficiency of sample, and determine
Chromatographic condition targetedly, gained detection limit is between 0.5～4.2mg/L.
For the water base adhesive of cigarette, sample treatment and chromatographic condition that existing research summary obtains do not have rationally
Specific aim, lack of smoke aqueous gel, single injected sampling at present and just can detect many of benzene homologues and adjacent benzene two simultaneously
The relation technological researching of formic ether compounds and technology report.
Summary of the invention
The technical problem to be solved in the present invention is to detect wherein benzene homologues and adjacent benzene two for detecting water base adhesive simultaneously simultaneously
The technical deficiency of formic ether compounds content, it is provided that a kind of single injected sampling just can measure in water base adhesive simultaneously multiple benzene homologues with
The method of phthalate compound.
Another technical problem that the invention solves the problems that is to provide the application in terms of the detection cigarette hydrosol of the described method.
The purpose of the present invention is achieved by the following technical programs:
There is provided a kind of and measure the benzene homologues in water base adhesive and the method for phthalate compound simultaneously, utilize gas phase
Chromatograph-mas spectrometer, to 6 kinds of benzene homologues in smoke aqueous gel and 7 kinds of phthalate chemical combination in single injected sampling
Thing totally 13 kinds of compounds realize measuring simultaneously, set up and measure the benzene homologues in water base adhesive and phthalate compound simultaneously
Accurate, quick, highly sensitive, the analyzing detecting method of favorable reproducibility.
The inventive method is quantitative with two kinds of internal standard substances, and the detection method after optimization includes preparation and the standard work of sample solution
Making the configuration of solution, sample, after pre-treatment, imports gaschromatographic mass spectrometry and is analyzed step.Detection method behaviour after optimized
It is simple accurate to make, single injected sampling 13 kinds of compounds of detection, and the chromatographic condition used makes the chromatographic peak of 13 kinds of compounds separate relatively
Good, and have preferable linear dependence, there is highly sensitive, reproducible, response rate advantages of higher, practicality is good.
Described benzene homologues is 6 kinds, is respectively as follows: benzene, toluene, ethylbenzene, o-Dimethylbenzene, meta-xylene and xylol；Described
Phthalate compound is 7 kinds, be respectively as follows: dimethyl phthalate (DMP), diethyl phthalate (DEP),
Diisobutyl phthalate (DIBP), the positive dibutyl ester of phthalic acid (DBP), butyl benzyl phthalate (BBP), neighbour
Phthalic acid two (2-ethyl) own ester (DEHP), dioctyl phthalate (DNOP).
The two internal standard substance is respectively as follows: methyl-n-butyl ketone and benzyl benzoate.
Specifically, described detection method comprises the following steps:
S1. the preparation of standard working solution；
The standard substance of benzene homologues are benzene, toluene, ethylbenzene, o-Dimethylbenzene, meta-xylene and xylol, phthalic acid ester
Compounds standard substance are dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic acid two isobutyl
Ester (DIBP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), phthalic acid two (2-ethyl)
Own ester (DEHP), dioctyl phthalate (DNOP), be configured to mixed standard solution through stepwise dilution；
S2. the preparation of sample solution: take smoke aqueous gel sample, adds ultra-pure water vibrating dispersion, adds cyclohexane give and is
Extractant, takes the supernatant through being filtrated to get sample solution after extraction；
The addition of described ultra-pure water is 2mL:0.3g with the ratio of the quality of smoke aqueous gel sample；Described hexamethylene
Addition is 10mL:0.3g with the ratio of the quality of smoke aqueous gel sample；
S3. gas chromatography-mass spectrometry analysis: standard working solution and sample solution are examined with gas chromatograph-mass spectrometer
Cls analysis, described detection analysis is to use selective ion to carry out qualitative analysis, uses internal mark working curve method quantitatively to divide
Analysis.
Wherein, the preparation process of standard working solution described in step S1 is:
By the benzene homologues of 5000mg/L mixed mark solution with hexamethylene stepwise dilution, obtain the standard work that concentration is 20 μ g/mL
Make solution A；The most accurately weighing various phthalic acid ester standard substance, the standard work being configured to 250ug/mL with hexamethylene is molten
Liquid B；Accurately pipette standard working solution A and each 10,20,50,100, the 200 μ L of standard working solution B, with containing 0.4 μ g/mL
The cyclohexane solution of methyl-n-butyl ketone (benzene homologues internal standard) and 0.15 μ g/mL benzyl benzoate (phthalic acid ester internal standard) is settled to
10mL, mix homogeneously；Standard solution to these 5 variable concentrations carries out GC-MS analysis respectively, and with component color spectral peak face to be measured
Long-pending is that vertical coordinate, mass concentration X (μ g/mL) corresponding with component to be measured are for horizontal with the ratio Y of corresponding internal standard chromatographic peak area
Coordinate, carries out regression analysis, obtains regression equation and the correlation coefficient of each component.
Inner mark solution preparation process: internal standard storing solution: the most accurately weigh 0.01g (being accurate to 0.001g) methyl-n-butyl ketone and
0.015g (being accurate to 0.001g) benzyl benzoate, in 10mL volumetric flask, is diluted to scale with hexamethylene, prepares respectively
The internal standard storing solution becoming concentration to be 1.0mg/ml and 1.5mg/ml.
Mixing internal standard working solution: be that 0.4 μ g/mL methyl-n-butyl ketone is (in benzene homologues by two kinds of internal standard storing solution stepwise dilutions
Mark) and the cyclohexane solution of 0.15 μ g/mL benzyl benzoate (phthalic acid ester internal standard).
Preferably, in the preparation of sample solution described in step S2, on shaker, shake 30min after adding hexamethylene carry out
Extraction, takes the supernatant and obtains sample solution for gas chromatography-mass spectrometry analysis through 0.45um organic facies membrane filtration after standing.
The running parameter of gas chromatography-mass spectrum described in S3 is:
Heating schedule: 40 DEG C keep 3min, 10 DEG C/min to rise to 110 DEG C, and 20 DEG C/min rises to 180 DEG C, 10 DEG C/min liter
To 250 DEG C, keep 30min.Carrier gas is He, flow velocity 1.0mL/min；
Chromatographic column uses HP-INNOWAX capillary column (30m × 0.25mm × 0.25 μm), injection port 240 DEG C, sample size 1
μ L, split ratio 10:1；
Ionization mode is EI, solvent delay 3min.Detection mode is for selecting ion detection (SIM), and ion source temperature is 230
DEG C, level Four bar temperature is 150 DEG C.
The characteristic ion that employing selective ion described in S3 carries out qualitative analysis is as shown in table 1:
Table 1 characteristic ion
| Compound | Quota ion (m/z) | Assisted quantitative ion (m/z) |
| Benzene | 78 | 51 |
| Toluene | 91 | 51 |
| Methyl-n-butyl ketone | 58 | 100 |
| Ethylbenzene | 91 | 106 |
| P-xylene | 91 | 106 |
| Meta-xylene | 91 | 106 |
| Ortho-xylene | 91 | 106 |
| Dimethyl phthalate | 163 | 77 |
| Diethyl phthalate | 149 | 177 |
| Diisobutyl phthalate | 149 | 223 |
| Benzyl benzoate | 105 | 212 |
| The positive dibutyl ester of phthalic acid | 149 | 223 |
| Butyl benzyl phthalate | 149 | 91 |
| Phthalic acid two (2-ethyl) ester | 149 | 167 |
| The positive dioctyl ester of phthalic acid | 149 | 279 |
Use internal mark working curve method to carry out the Specification Curve of Increasing of quantitative analysis described in S3 and result computational methods are: move
Take standard working solution sample introduction, every grade standard solution parallel assay 2 times, average.With each determinand material chromatographic peak
Area and internal standard peak area ratio Y be vertical coordinate, its respective quality concentration X (μ g/mL) be that abscissa carries out regression analysis, draw
Standard curve.Determinand chromatographic peak area in the sample solution that will record under the same terms and the ratio of internal standard peak area, generation
Enter standard curve, try to achieve the mass concentration (μ g/mL) of determinand in sample solution.
The inventive method has in terms of contained benzene homologues and phthalate compound in the detection cigarette hydrosol
Good application.While single injected sampling of the present invention can realize 13 kinds of compounds, detection is analyzed, preferably, therefore, and the present invention
Method especially can be advantageously applied to high-volume and/or quickly detect the hydrosol context of detection analyzing volume smoking material.Institute
State the hydrosol and include but not limited to the water solublity with water as disperse medium or emulsion adhesive.Described volume smoking material include but
Be not limited to be used in that cigarette mouth building, Medicated cigarette be spigot joint, material in the material such as filter stick center line and cigarette package or operation.
Beneficial effects of the present invention:
The present invention is first for the water base adhesive of cigarette, it is provided that the qualitative and quantitative detecting analysis side of a kind of efficiently and accurately
Method.Through single injected sampling, so that it may detect 6 kinds of benzene homologues contained therein and 7 kinds of phthalate compounds simultaneously.
In terms of the process of sample liquid, existing document report and achievement in research all use ethyl acetate to do in hydrosol detection
The extractant used, in conjunction with ultrasonic extraction.The present invention breaks through the technology prejudice in existing research, uses cyclohexane give for extraction
Solvent, is combined in the ultra-pure water of addition reasonable amount when sample carries out pre-treatment and, as dispersant, adds after sample dispersion again
Enter extractant hexamethylene, it is achieved that fully extract.The present invention need not take ultrasonic extraction, and direct sample dissolution is simple to operate, greatly
Simplify greatly pre-treatment step, liberated manpower, decrease loaded down with trivial details operation, thus decrease error, and need not use
The special equipments such as ultrasonic instrument, overcome simultaneously and use ethyl acetate to make the extractant that smoke aqueous gel detection is analyzed, the chief
The solution that phase exists is muddy, cannot be centrifuged or technological deficiency that membrane filtration, subsequent step are difficult to.
Further, the present invention, after the science pre-treatment completing sample solution, optimizes whole detection chromatographic condition, uses
Gas chromatograph-mass spectrometer carries out detection and analyzes standard working solution and sample solution, uses selective ion to carry out qualitative point
Analysis, uses internal mark working curve method to carry out quantitative analysis.Have only to single injected sampling, to the 6 kinds of benzene homologues and 7 in smoke aqueous gel
Kind of phthalate compound totally 13 kinds of compounds realize measuring simultaneously, set up measure simultaneously the benzene homologues in water base adhesive and
Accurate, quick, highly sensitive, the analyzing detecting method of favorable reproducibility of phthalate compound.Experimental result shows, respectively
The regression equation correlation coefficient of component all reaches more than 0.997, and the detection by quantitative of 6 kinds of benzene homologues is limited to 0.04～0.07 μ g/g, and 7
The detection by quantitative planting phthalate compound is limited to 0.5～4.2 μ g/g, complies fully with quantitative requirement.
Accompanying drawing explanation
The standard curve of Fig. 1 benzene.
The standard curve of Fig. 2 toluene.
The standard curve of Fig. 3 ethylbenzene.
The standard curve of Fig. 4 xylol.
The standard curve of Fig. 5 meta-xylene.
The standard curve of Fig. 6 o-Dimethylbenzene.
The standard curve of Fig. 7 dimethyl phthalate (DMP).
The standard curve of Fig. 8 diethyl phthalate (DEP).
The standard curve of Fig. 9 diisobutyl phthalate (DIBP).
The standard curve of Figure 10 dibutyl phthalate (DBP).
The standard curve of Figure 11 butyl benzyl phthalate (BBP).
The standard curve of Figure 12 phthalic acid two (2-ethyl) own ester (DEHP).
The standard curve of Figure 13 dioctyl phthalate (DNOP).
Detailed description of the invention
The inventive method is further illustrated below in conjunction with the accompanying drawings with specific embodiment.Following embodiment and accompanying drawing are only used for showing
Example explanation, it is impossible to be interpreted as limitation of the present invention.Unless stated otherwise, the reagent raw material used in following embodiment is normal
Advising reagent raw material that is commercial or that be either commercially available, unless stated otherwise, the method and apparatus used in following embodiment is this
The conventional use of method and apparatus in field
Embodiment 1
S1. the preparation of standard working solution:
The standard substance of benzene homologues are benzene, toluene, ethylbenzene, o-Dimethylbenzene, meta-xylene and xylol, phthalic acid ester
Compounds standard substance are dimethyl phthalate (DMP), diethyl phthalate (DEP), phthalic acid two isobutyl
Ester (DIBP), dibutyl phthalate (DBP), butyl benzyl phthalate (BBP), phthalic acid two (2-ethyl)
Own ester (DEHP), dioctyl phthalate (DNOP), be configured to mixed standard solution through stepwise dilution；
S2. the preparation of sample solution: weigh and accurately weigh 0.3g (being accurate to 0.0001g) the cigarette hydrosol and (test every time
All randomly select in commercial cigarette hydrosol sample, the most therefore limit the scope of the invention) sample in 25mL tool plug triangle
In Ping, add 2mL ultra-pure water, after sample dispersion, add 10mL contain 0.4 μ g/mL methyl-n-butyl ketone (benzene homologues internal standard) and 0.15 μ
The cyclohexane solution of g/mL benzyl benzoate (phthalic acid ester internal standard), after concussion extraction 30min, takes upper layer of extraction liquid and adds
Centrifuge tube is centrifuged 5min, takes the supernatant GC/MS analysis for next step.
S3. gas chromatography-mass spectrometry analysis: standard working solution and sample solution are examined with gas chromatograph-mass spectrometer
Cls analysis, described detection analysis is to use selective ion to carry out qualitative analysis, uses internal mark working curve method quantitatively to divide
Analysis.
The preparation process of standard working solution is:
By the benzene homologues of 5000mg/L mixed mark solution with hexamethylene stepwise dilution, obtain the standard work that concentration is 20 μ g/mL
Make solution A；The most accurately weighing various phthalic acid ester standard substance, the standard work being configured to 250ug/mL with hexamethylene is molten
Liquid B；Accurately pipette standard working solution A and each 10,20,50,100, the 200 μ L of standard working solution B, with containing 0.4 μ g/mL
The cyclohexane solution of methyl-n-butyl ketone (benzene homologues internal standard) and 0.15 μ g/mL benzyl benzoate (phthalic acid ester internal standard) is settled to
10mL, mix homogeneously；Standard solution to these 5 variable concentrations carries out GC-MS analysis respectively, and with component color spectral peak face to be measured
Long-pending is that vertical coordinate, mass concentration X (μ g/mL) corresponding with component to be measured are for horizontal with the ratio Y of corresponding internal standard chromatographic peak area
Coordinate, carries out regression analysis, obtains regression equation and the correlation coefficient of each component.
Inner mark solution preparation process: internal standard storing solution: the most accurately weigh 0.01g (being accurate to 0.001g) methyl-n-butyl ketone and
0.015g (being accurate to 0.001g) benzyl benzoate, in 10mL volumetric flask, is diluted to scale with hexamethylene, prepares respectively
The internal standard storing solution becoming concentration to be 1.0mg/ml and 1.5mg/ml.
Mixing internal standard working solution: be that 0.4 μ g/mL methyl-n-butyl ketone is (in benzene homologues by two kinds of internal standard storing solution stepwise dilutions
Mark) and the cyclohexane solution of 0.15 μ g/mL benzyl benzoate (phthalic acid ester internal standard).
The running parameter of gas chromatography-mass spectrum described in S3 is:
Heating schedule: 40 DEG C keep 3min, 10 DEG C/min to rise to 110 DEG C, and 20 DEG C/min rises to 180 DEG C, 10 DEG C/min liter
To 250 DEG C, keep 30min.Carrier gas is He, flow velocity 1.0mL/min；
Chromatographic column uses HP-INNOWAX capillary column (30m × 0.25mm × 0.25 μm), injection port 240 DEG C, sample size 1
μ L, split ratio 10:1；
Ionization mode is EI, solvent delay 3min.Detection mode is for selecting ion detection (SIM), and ion source temperature is 230
DEG C, level Four bar temperature is 150 DEG C.
The characteristic ion that employing selective ion described in S3 carries out qualitative analysis is as shown in table 1:
Table 1 characteristic ion
Use internal mark working curve method to carry out the Specification Curve of Increasing of quantitative analysis described in S3 and result computational methods are: move
Take standard working solution sample introduction, select the characteristic ion of determinand to carry out Gc-ms.Every grade standard solution parallel assay 2
Secondary, average.With each determinand material chromatographic peak area and internal standard peak area ratio Y as vertical coordinate, its respective quality
Concentration X (μ g/mL) is that abscissa carries out regression analysis, draws standard curve, as shown in accompanying drawing 1 to accompanying drawing 13.By the same terms
Under determinand chromatographic peak area in the sample solution that records and the ratio of internal standard peak area, substitute into standard curve, try to achieve sample
The mass concentration (μ g/mL) of determinand in solution, by being calculated the content (ug/g) of determinand in sample.Testing result is such as
Shown in table 2:
The testing result of table 2 single injected sampling 13 kinds of compounds of detection
Meanwhile, the standard solution of least concentration grade is carried out 10 mensuration, calculates its standard deviation, with 3 times of standard deviation
Difference, as the qualitative detection limit of this component, using 10 times of standard deviations as the detection by quantitative limit of this component, is shown in Table 3.Result
Display, the regression equation correlation coefficient of each component all reaches more than 0.997, the detection by quantitative of 6 kinds of benzene homologues be limited to 0.04～
0.07 μ g/g, the detection by quantitative of 7 kinds of phthalate compounds is limited to 0.5～4.2 μ g/g, meets quantitative requirement.
The detection limit of 3 13 kinds of compounds of table, response rate result
| Compound | Detection limit (ug/g) | The response rate (%) | RSD (%, n=6) |
| Benzene | 0.06 | 96.55% | 1.92% |
| Toluene | 0.04 | 99.03% | 2.60% |
| Ethylbenzene | 0.06 | 97.34% | 1.65% |
| Xylol | 0.07 | 93.70% | 1.44% |
| Meta-xylene | 0.05 | 96.02% | 0.68% |
| O-Dimethylbenzene | 0.05 | 94.02% | 0.54% |
| Dimethyl phthalate | 0.50 | 89.87% | 0.52% |
| Diethyl phthalate | 0.58 | 92.86% | 0.69% |
| Diisobutyl phthalate | 1.43 | 98.81% | 0.97% |
| Dibutyl phthalate | 0.97 | 101.14% | 0.78% |
| Butyl benzyl phthalate | 2.34 | 98.12% | 2.57% |
| Phthalic acid two (2-ethyl) own ester | 4.20 | 100.14% | 2.08% |
| Dioctyl phthalate | 1.32 | 99.38% | 2.70% |
Claims (9)
1. one kind measures the benzene homologues in water base adhesive and the method for phthalate compound simultaneously, it is characterised in that institute
Stating benzene homologues is 6 kinds, is respectively as follows: benzene, toluene, ethylbenzene, o-Dimethylbenzene, meta-xylene and xylol；Described phthalic acid
Ester type compound is 7 kinds, be respectively as follows: dimethyl phthalate, diethyl phthalate, diisobutyl phthalate,
N-butyl phthalate, butyl benzyl phthalate, phthalic acid two (2-ethyl) own ester, phthalic acid are just
Dioctyl ester；
Said method comprising the steps of:
S1. the preparation of standard working solution；
S2. the preparation of sample solution: take smoke aqueous gel sample, adds ultra-pure water vibrating dispersion, adds cyclohexane give for extraction
Solvent, takes the supernatant through being filtrated to get sample solution after extraction；The addition of described ultra-pure water and smoke aqueous gel sample
The ratio of quality is 2mL:0.3g；The addition of described hexamethylene is 10mL with the ratio of the quality of smoke aqueous gel sample:
0.3g；
S3. gas chromatography-mass spectrometry analysis: with gas chromatograph-mass spectrometer, standard working solution and sample solution are carried out detection and divide
Analysis, described detection analysis is to use selective ion to carry out qualitative analysis, uses internal mark working curve method to carry out quantitative analysis；
The running parameter of gas chromatography-mass spectrum described in S3 is:
Heating schedule: 40 DEG C keep 3min, 10 DEG C/min to rise to 110 DEG C, and 20 DEG C/min rises to 180 DEG C, and 10 DEG C/min is raised to 250
DEG C, keep 30min；Carrier gas is He, flow velocity 1.0mL/min；
The capillary column of chromatographic column employing HP-INNOWAX, 30m × 0.25mm × 0.25 μm, injection port 240 DEG C, sample size 1 μ L,
Split ratio 10:1；
Ionization mode is EI, solvent delay 3min；Detection mode is for selecting ion detection (SIM), and ion source temperature is 230 DEG C,
Level Four bar temperature is 150 DEG C.
Measure the benzene homologues in water base adhesive and the method for phthalate compound the most simultaneously,
It is characterized in that, the preparation process of standard working solution described in step S1 is:
By the benzene homologues of 5000mg/L mixed mark solution with hexamethylene stepwise dilution, obtain the standard work that concentration is 20 μ g/mL molten
Liquid A；The most accurately weigh various phthalic acid ester standard substance, be configured to the standard working solution B of 250 μ g/mL with hexamethylene；
Accurately pipette standard working solution A and each 10,20,50,100, the 200 μ L of standard working solution B, with containing benzene homologues internal standard 0.4 μ
The cyclohexane solution of g/mL methyl-n-butyl ketone and phthalic acid ester internal standard 0.15 μ g/mL benzyl benzoate is settled to 10mL, and mixing is all
Even；Standard solution to these 5 variable concentrations carries out GC-MS analysis respectively, and interior with corresponding with component chromatographic peak area to be measured
The ratio Y of mark chromatographic peak area is vertical coordinate, with corresponding mass concentration X of component to be measured as abscissa, carry out regression analysis,
Obtain regression equation and the correlation coefficient of each component；
The preparation method of internal standard storing solution is: the most accurately weigh 0.01g methyl-n-butyl ketone and 0.015g benzyl benzoate, respectively at
In 10mL volumetric flask, it is diluted to scale with hexamethylene, is configured to the internal standard deposit that concentration is 1.0mg/ml and 1.5mg/ml respectively
Liquid；
The preparation method of mixing internal standard working solution is: by two kinds of internal standard storing solution stepwise dilutions be 0.4 μ g/mL2-hexanone and
The cyclohexane solution of 0.15 μ g/mL benzyl benzoate.
Measure the benzene homologues in water base adhesive and the method for phthalate compound the most simultaneously,
It is characterized in that, in the preparation of sample solution described in step S2, on shaker, shake 30min after adding hexamethylene extract
Take, take the supernatant after standing and obtain sample solution for gas chromatography-mass spectrometry analysis through 0.45 μm organic facies membrane filtration.
Measure the benzene homologues in water base adhesive and the method for phthalate compound the most simultaneously,
It is characterized in that, the characteristic ion that employing selective ion described in step S3 carries out qualitative analysis is as follows:
Measure the benzene homologues in water base adhesive and the method for phthalate compound the most simultaneously,
It is characterized in that, described in step S3, use internal mark working curve method to carry out Specification Curve of Increasing and the result calculating side of quantitative analysis
Method is: pipettes standard working solution sample introduction, every grade standard solution parallel assay 2 times, averages；With each determinand material
Chromatographic peak area and internal standard peak area ratio Y be vertical coordinate, its respective quality concentration X be that abscissa carries out regression analysis, draw
Standard curve；Determinand chromatographic peak area in the sample solution that will record under the same terms and the ratio of internal standard peak area, generation
Enter standard curve, obtain the mass concentration of determinand in sample solution, by being calculated the content of determinand in primary sample.
6. the application of method described in any one of claim 1 to 5, it is characterised in that be applied to detection and analyze in the cigarette hydrosol
Contained benzene homologues and phthalate compound aspect.
Application the most according to claim 6, it is characterised in that be applied to high-volume and/or quickly detect analysis cigarette water
Contained benzene homologues and phthalate compound aspect in colloidal sol.
Application the most according to claim 6, it is characterised in that it is water-soluble that the described hydrosol includes for water as disperse medium
Property or emulsion adhesive.
Application the most according to claim 6, it is characterised in that the described cigarette hydrosol is for being used in cigarette mouth building, Medicated cigarette
The cigarette hydrosol in spigot joint, filter stick center line and cigarette package.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510587417.7A CN105181868B (en) | 2015-09-15 | 2015-09-15 | Measure 13 kinds of benzene homologues and the methods and applications of phthalate compound in water base adhesive simultaneously |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510587417.7A CN105181868B (en) | 2015-09-15 | 2015-09-15 | Measure 13 kinds of benzene homologues and the methods and applications of phthalate compound in water base adhesive simultaneously |
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| Publication Number | Publication Date |
|---|---|
| CN105181868A CN105181868A (en) | 2015-12-23 |
| CN105181868B true CN105181868B (en) | 2016-10-26 |
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| CN106841442B (en) * | 2017-01-25 | 2020-05-05 | 江苏中烟工业有限责任公司 | Method for simultaneously determining vinyl acetate and six benzene series in water-based adhesive |
| CN112881559B (en) * | 2021-01-20 | 2023-08-18 | 广东产品质量监督检验研究院（国家质量技术监督局广州电气安全检验所、广东省试验认证研究院、华安实验室） | Method for rapidly detecting phthalate content |
| CN113533585A (en) * | 2021-08-26 | 2021-10-22 | 中国疾病预防控制中心环境与健康相关产品安全所 | Method for rapidly and simultaneously measuring 18 polycyclic aromatic hydrocarbons and 15 phthalic acid esters in indoor dust deposit by high-flux low-solvent |
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| CN101614709B (en) * | 2009-07-16 | 2012-04-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring phthalic acid ester (PAE) in water-based adhesive for tobacco |
| CN102253140A (en) * | 2011-06-22 | 2011-11-23 | 红云红河烟草(集团)有限责任公司 | Method for testing content of benzene and benzene series in water base adhesive for tobaccos |
| CN103115979A (en) * | 2013-01-29 | 2013-05-22 | 河北中烟工业有限责任公司 | Method for simultaneous determination of phthalic acid ester and adipate in cigarette auxiliary material |
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