CN102331475A - Method for measuring phthalate ester content of tipping paper for tobaccos - Google Patents
Method for measuring phthalate ester content of tipping paper for tobaccos Download PDFInfo
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Abstract
The invention discloses a method for measuring the phthalate ester content of tipping paper for tobaccos. The method comprises the steps of: preparation of internal standard extract liquor, standard working solution and sample solution, gas chromatography-mass spectrography, calculation of measurement results and the like. The improved and optimized measurement method has the advantages of operation simplicity and accuracy, high sensitivity, high recovery rate, high repeatability and the like. Errors caused by pretreatment or apparatus precision and the like are effectively reduced by utilizing an internal standard quantity. Under adopted chromatographic conditions, seven target compounds and internal standard chromatographic peaks have relatively higher degrees of separation, relatively higher linear correlation and the detection limit of 0.01 to 0.03 mu g per centimeter spare. By the method, a standard recovery rate is 94 to 106 percent and an average relative standard deviation is 3.4 to 4.8.
Description
Technical field
The invention belongs to cigarette material physical and chemical inspection technical field, be specifically related to a kind of method of measuring phthalate compound content in the cigarette tipping paper.
Background technology
Cigarette tipping paper is a material important in the production of cigarettes process, is the dedicated paper that filter tip and Cigarette are hinged with, and is commonly called as yew paper.A large amount of ink printing materials that use add the processing characteristics that phthalate compound can improve printing ink in the printing ink in the production of cigarettes process.
Phthalic ester is the general name of a compounds, is phthalic anhydride and the product of alcohol reaction gained, and is tasteless or have a little smell, and main application is to make plastifier.The phthalate material is one type of environmental hormone.Can cause endocrine disturbance, reproduction malfunction etc.There are 7 kinds to be classified as " preferentially monitoring the pollutant list " by Environmental Protection Agency in the phthalate; Be respectively repefral (DMP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP); N-butyl phthalate (DBP); Phthalic acid two (2 one ethyls are own) ester (DEHP), dioctyl phthalate (DOP), phthalic acid dibutyl benzyl ester (BBP).
US Consumer Product Safety Commission's issue directive document; Requirement was from February 10th, 2009, and the content of 6 types of phthalic esters must not surpass 0.1%, the product of every content overproof in toy for children or the child care products; Make whenever, all must not import, distribution and sale.
The new guidance standard (2005/84/EC) about phthalic acid salt of European Union's promulgation began to carry out on January 16th, 2007.According to the requirement of European Union's new standard, DEHP (DHP), DBP (dibutyl phthalate) and BBP (phthalic acid butyloxy phenyl) will be limited in employed PVC material, paint, coating; Printing ink, plastic cement, printing; Weaving, chemical products, packing.Corresponding D INP (diisononyl phthalate); DIDP (diisooctyl phthalate) and DNOP (dioctyl phthalate) also be limited in toy for children and clothes and might be placed in the article in the mouth and use, the content of above-mentioned 6 kinds of compositions must not surpass 0.1%.Its related product not only comprises toy, clothes and the nursing product that baby below 36 months is virgin, and what also comprised other age brackets children uses may be put into all article in the mouth.
At present to the mensuration of phthalate material mainly at food, plastic package material, textile, atmosphere, soil, water and medical field; Mensuration to phthalic ester; Early stage reported method has: colourimetry, titrimetry and AAS etc., low, the poor selectivity of the sensitivity of these methods.National successively issue in recent years the mensuration of GB/T 20388-2006 textile phthalic ester; The mensuration of GB/T 21911-2008 Phthalic Acid Esters in Food; Three standards such as mensuration of phthalic ester in the GB/T 21928-2008 food plastic wrappage, external examination criteria has " articles for children-tableware and feeding utensil " EN14372:2004.The method that adopts is the gas chromatography-mass spectrum logotype.
Isopropyl alcohol extraction-the vapor-phase chromatography of reports such as Liu Zechun is measured phthalate compound in cigarette tipping paper and the wrapping paper simultaneously; Adopt FID to detect; We find through experiment; Adopt and select ion scan sensitivity higher, detectability is lower, and adopts and select the ion pair experimental result quantitatively more accurate.Phthalate compound does not appear in the newspapers in the cigarette tipping paper and relevant combined gas chromatography mass spectrometry detects; Cigarette tipping paper has significant effects as a kind of important cigarette product material to the quality and the security of cigarette product; Therefore; From the security of cigarette material and aesthetic quality's angle, analyze the content of phthalate compound in the cigarette tipping paper, aspects such as correct evaluation and strict control safety of products have great importance.
Summary of the invention
The objective of the invention is to deficiency, a kind of method of measuring phthalate compound content in the cigarette tipping paper is provided to prior art.
The object of the invention is realized through following technical scheme.
Except as otherwise noted, the percentage that the present invention adopted is percent by weight.
A kind of method of measuring phthalate compound content in the cigarette tipping paper may further comprise the steps:
1, the preparation of interior mark extract: with Ergol is interior mark standard items, is extractant with ethanol, and being prepared into concentration is the interior mark extract of 0.2～0.5 μ g/mL;
2, the preparation of standard operation solution: choose repefral DMP, diethyl phthalate DEP, diisobutyl phthalate DIBP, n-butyl phthalate DBP, butyl benzyl phthalate BBP, the own ester DEHP of phthalic acid two (2-ethyl), the positive dioctyl ester DNOP of phthalic acid, as the standard items of phthalate compound; Become the hybrid standard storing solution with the ethanolic solution stepwise dilution, mark matrix correcting fluid is prepared into standard operation solution in adding respectively then;
3, the preparation of sample solution: with interior mark extract extraction cigarette tipping paper sample, the gained clear liquid is sample solution;
4, gaschromatographic mass spectrometric analysis: utilize gas chromatography mass spectrometer that standard operation solution and sample solution are carried out check and analysis;
5, typical curve is drawn and result's calculating: its respective concentration of chromatographic peak area comparison with 7 kinds of phthalate compounds and interior mark Ergol is carried out regretional analysis, obtains typical curve; With the chromatographic peak area ratio of 7 kinds of phthalate compounds in the sample solution that records under the same terms and interior mark Ergol, the substitution typical curve is tried to achieve the content of phthalate compound in the cigarette tipping paper sample.
The preparation method of mark extract specifically may further comprise the steps in described:
(1) preparation of mark storing solution I in: accurately take by weighing 100 mg～250 mg Ergols in 100 mL volumetric flasks, be settled to scale and mixing with ethanol, obtaining concentration is the interior mark storing solution I of 1.0～2.5 mg/mL;
(2) preparation of mark storing solution II in: accurately pipette in 1 mL mark storing solution I in 50 mL volumetric flasks, be settled to scale and shake up with ethanol, obtaining concentration is the inner mark solution II of 20～50 μ g/mL;
(3) preparation of mark extract in: accurately pipette and mark the storing solution II in 10 mL in 1000 mL volumetric flasks, appearance ethanol is settled to scale and shakes up, and obtaining concentration is the interior mark extract of 0.2～0.5 μ g/mL.
The preparation method of described standard operation solution specifically may further comprise the steps:
(1) hybrid standard storing solution: the phthalate compound that accurately takes by weighing 50～100 mg respectively is in 100 mL volumetric flasks, and with dissolve with ethanol and be settled to scale, mixing obtains the hybrid standard storing solution I that concentration is 0.5～1.0 mg/mL;
(2) standard operation solution: the hybrid standard storing solution pipettes 50 μ L, 100 μ L, 250 μ L, 500 μ L, 1000 μ L and 2500 μ L respectively and places 100 mL volumetric flasks; The interior mark liquid that adds 20～50 μ g respectively; Be settled to scale and shake up with ethanol, obtain other standard operation solution of 6 concentration levels.
Described cigarette tipping paper sample is cut to the fragment that is not more than 1 cm * 1 cm earlier before extraction.
Described gaschromatographic mass spectrometric analysis, its chromatographic condition is: elasticity capillary column, 5% phenyl/95% methyl polysiloxane
,30m length * 0.25mm internal diameter * 0.25 μ m thickness, injector temperature: 280 ℃, sample size: 1 μ L, carrier gas is: helium, purity>=99.999%, split ratio: 50:1, constant current flow velocity: 1.2mL/min; Heating schedule is: 100 ℃ of initial temperatures, keep 1min, and with the speed to 180 of 20 ℃/min ℃, ℃ keep 10min with the speed to 280 of 10 ℃/min again; Its mass spectrophotometry condition for the transmission line temperature is: 280 ℃; Ionization EI energy is 70 eV; Ion source temperature is: 300 ℃; Solvent delay times 3 min selects ion scan Mode S IM fractional scanning, carries out quantitative test with characteristic ion.
With respect to prior art, the present invention has the following advantages:
1, the disposal route of sample and chromatographic condition are improved and optimize; Accurately cut 20 cm * 4 cm cigarette paper material; Be cut to the fragment extraction that is not more than 1 cm * 1 cm again; Solvent is chosen ethanol, can effectively extract the phthalate compound in the sample, the sensitivity that has improved detection method greatly.
2, utilize inner mark method ration,, utilize the relative peak area value of component to carry out the calculating of quantized data through the adding of internal standard compound, can be without constant volume, and can reduce the error that pre-treating method reappearance and instrument precision problem are brought.
3, the chromatographic condition that the inventive method adopted makes 7 kinds of target compounds and interior mark chromatographic peak, and all degree of separation is better, and all has the better linearity correlativity, and detection limit is at 0.01～0.03 μ g/cm
2Between.
4, the recovery of standard addition of the inventive method is between 94%～106%, and average relative standard deviation (RSD) explains that the recovery of the inventive method is high, good reproducibility between 3.4～4.8.
Description of drawings
Fig. 1 is the process flow diagram of assay method of the present invention;
Fig. 2 is the chromatograph mass spectrum analysis figure of standard operation solution;
Fig. 3 is the chromatograph mass spectrum analysis figure of sample solution;
Fig. 4 is the canonical plotting of repefral (DMP);
Fig. 5 is the canonical plotting of diethyl phthalate (DEP);
Fig. 6 is the canonical plotting of diisobutyl phthalate (DIBP);
Fig. 7 is the canonical plotting of n-butyl phthalate (DBP);
Fig. 8 is the canonical plotting of butyl benzyl phthalate (BBP);
Fig. 9 is the canonical plotting of phthalic acid two (2-ethyl) own ester (DEHP);
Figure 10 is the canonical plotting of the positive dioctyl ester of phthalic acid (DNOP).
Embodiment
Below in conjunction with accompanying drawing and embodiment technical scheme of the present invention is done further to specify, but accompanying drawing and embodiment are not to qualification of the present invention.
Measure the content (it is as shown in Figure 1 to measure flow process) 1 of phthalate compound in the cigarette tipping paper, the preparation of interior mark extract:
(1) preparation of mark storing solution I in: accurately take by weighing 250 mg Ergols in 100 mL volumetric flasks, be settled to scale and mixing with ethanol, obtaining concentration is the interior mark storing solution I of 2.5 mg/mL; Interior mark storing solution I seals in 4 ℃ of refrigerators to be deposited, and is valid for three months;
(2) preparation of mark storing solution II in: accurately pipette in 1 mL mark storing solution I in 50 mL volumetric flasks, be settled to scale and shake up with ethanol, obtaining concentration is the inner mark solution II of 50 μ g/mL; Interior mark storing solution II need be at present with join at present;
(3) preparation of mark extract in: accurately pipette and mark the storing solution II in the 10mL in 1000 mL volumetric flasks, appearance ethanol is settled to scale and shakes up, and obtaining concentration is the interior mark extract of 0.5 μ g/mL; Interior mark extract need be at present with join at present;
2, the preparation of standard operation solution:
(1) hybrid standard storing solution I: the phthalate compound that accurately takes by weighing 100 mg respectively is in 100 mL volumetric flasks, and with dissolve with ethanol and be settled to scale, mixing obtains hybrid standard storing solution I, and wherein each concentration of component is respectively 1.0 mg/mL; Hybrid standard storing solution I seals in 4 ℃ of refrigerators and deposits, and is valid for three months;
(2) standard operation solution: the hybrid standard storing solution I that pipettes 50 μ L, 100 μ L, 250 μ L, 500 μ L, 1000 μ L and 2500 μ L respectively is in 100 mL volumetric flasks; The interior mark that adds 50 μ g respectively; Be settled to scale and shake up with ethanol, obtain other standard operation solution of 6 concentration levels.Standard operation solution need be at present with join at present;
3, the preparation of sample solution:
Accurately cut 20 cm * 4 cm cigarette tipping paper samples; Be cut to the fragment that is not more than 1 cm * 1 cm again, put into 50 mL conical flasks then, add 30 mL and contain interior target extract; Ultrasonic extraction 30 min; Static, to get supernatant liquor and cross the organic filter membrane of 0.45 μ m, the sample solution that obtains is used for gaschromatographic mass spectrometric analysis; If sample solution concentration is higher than standard operation solution maximum concentration, sample introduction again after should diluting.The sample solution chromatogram is analyzed as shown in Figure 3.
4, chromatograph mass spectrum analysis: get standard operation solution and sample solution respectively and carry out chromatograph mass spectrum analysis; Its chromatographiccondition is: elasticity capillary column, 5% phenyl/95% methyl polysiloxane [30m (length) * 0.25mm (internal diameter) * 0.25 μ m (thickness)], injector temperature: 280 ℃; Sample size: 1 μ L; Carrier gas is: helium (purity >=99.999%), split ratio: 50:1, constant current flow velocity: 1.2 mL/min; Heating schedule is: 100 ℃ of initial temperatures, keep 1min, and with the speed to 180 of 20 ℃/min ℃, ℃ keep 10min with the speed to 280 of 10 ℃/min again.
The mass spectrophotometry condition is: the transmission line temperature is: 280 ℃; Ionization (EI) energy is 70 eV; Ion source temperature is: 300 ℃; Solvent delay times 3 min selects ion scan pattern (SIM) fractional scanning, carries out quantitative test with characteristic ion.Each component characteristics ion is selected as shown in table 1, and the chromatograph mass spectrum analysis result of standard operation solution is as shown in Figure 2;
Table 1 phthalate compound characteristic ion is selected
| Sequence number | The compound title | Qualitative ion and abundance | Quota ion | |
| 1 | Repefral (DMP) | 163:77（100:18） | 163 | 77 |
| 2 | Diethyl phthalate (DEP) | 149:177（100:28） | 149 | 77 |
| 3 | Ergol (interior mark) | 105:91（100:46） | 105 | 91 |
| 4 | Diisobutyl phthalate (DIBP) | 149:223（100:10） | 149 | 223 |
| 5 | N-butyl phthalate (DBP) | 149:223（100:5） | 149 | 223 |
| 6 | Butyl benzyl phthalate (BBP) | 149:91（100:72） | 149 | 91 |
| 7 | Phthalic acid two (2-ethyl) own ester (DEHP) | 149:167（100:29） | 149 | 167 |
| 8 | The positive dioctyl ester of phthalic acid (DNOP) | 149:279（100:7） | 149 | 279 |
5, typical curve is drawn and result's calculating:
At first the chromatographic peak area with 7 kinds of phthalate compounds and interior mark Ergol carries out regretional analysis to its respective concentration, obtains typical curve (typical curve of 7 kinds of phthalate compounds is shown in Fig. 4-10) and regression equation and related coefficient; Get least concentration standard operation solution, do 10 parallel experiments, basis of calculation deviation, 3 times of standard deviations are detection limit, and 10 times of standard deviations are the detection by quantitative limit, and the result is as shown in table 2:
The typical curve of phthalate compound, related coefficient and detectability in table 2 cigarette tipping paper
| Title | Regression equation | Related coefficient | Detection limit μ g/cm 2 | Quantitative limit μ g/cm 2 |
| Repefral (DMP) | y=0.0145x | 0.9997 | 0.03 | 0.09 |
| Diethyl phthalate (DEP) | y=0.0146x | 0.9995 | 0.03 | 0.09 |
| Diisobutyl phthalate (DIBP) | y=0.0169x | 0.9999 | 0.03 | 0.08 |
| N-butyl phthalate (DBP) | y=0.0197x | 0.9998 | 0.03 | 0.09 |
| Butyl benzyl phthalate (BBP) | y=0.0805x | 0.9991 | 0.02 | 0.08 |
| Phthalic acid two (2-ethyl) own ester (DEHP) | y=0.0110x | 0.9995 | 0.01 | 0.04 |
| The positive dioctyl ester of phthalic acid (DNOP) | y=0.0167x | 0.9991 | 0.01 | 0.03 |
To record the chromatographic peak area ratio of 7 kinds of phthalate compounds and interior mark Ergol then, the typical curve that substitution is drawn is tried to achieve the content of phthalate compound in the sample, and computing formula is following:
In the formula:
X i The content of phthalate compound in the – sample, unit are every square centimeter of microgram
(μg/cm
2)；
C i Phthalate compound concentration in the sample that – is drawn by typical curve, unit is every milliliter of microgram (μ g/mL);
C 0 Phthalate compound concentration in the blank that – is drawn by typical curve, unit is every milliliter of microgram (μ g/mL);
V– extract volume, unit are milliliter (mL);
m– cuts the area of sample, and unit is square centimeter (cm
2);
Concrete outcome is as shown in table 3:
The testing result of phthalate compound content in table 3 cigarette tipping paper
| Title | Content (μ g/cm 2) |
| Repefral (DMP) | N.D. |
| Diethyl phthalate (DEP) | N.D. |
| Diisobutyl phthalate (DIBP) | 0.13 |
| N-butyl phthalate (DBP) | 1.53 |
| Butyl benzyl phthalate (BBP) | N.D. |
| Phthalic acid two (2-ethyl) own ester (DEHP) | 0.67 |
| The positive dioctyl ester of phthalic acid (DNOP) | N.D. |
Annotate: N.D. representes not detect
Can know by table 2, the chromatographic condition that is adopted make that 7 kinds of target compounds and interior mark chromatographic peak all separate better, and have the better linearity correlativity, detection limit is at 0.01～0.03 μ g/cm
2Between.
1, the preparation of sample solution: the cigarette tipping paper that accurately cuts 20 cm * 4 cm; Be cut to the fragment extraction that is not more than 1 cm * 1 cm again, put into 50 mL conical flasks then, add 30 mL and contain interior target extract; Ultrasonic extraction 30 min; Static, to get supernatant liquor and cross the organic filter membrane of 0.45 μ m, the sample solution that obtains is used for gaschromatographic mass spectrometric analysis;
2, adopt the chromatogram mass spectrum condition analysis sample solution of embodiment 1;
3, will record 7 kinds of phthalate compounds and interior target chromatographic peak area ratio; The typical curve that substitution embodiment 1 is drawn; Try to achieve the content of phthalate compound in the sample, computing method are with the computing method of embodiment 1, and concrete result of calculation is as shown in table 4.
The testing result of phthalate compound content in table 4 cigarette tipping paper
| Title | Content (μ g/cm 2) |
| Repefral (DMP) | N.D. |
| Diethyl phthalate (DEP) | N.D. |
| Diisobutyl phthalate (DIBP) | 0.41 |
| N-butyl phthalate (DBP) | 3.14 |
| Butyl benzyl phthalate (BBP) | N.D. |
| Phthalic acid two (2-ethyl) own ester (DEHP) | 1.57 |
| The positive dioctyl ester of phthalic acid (DNOP) | N.D. |
Annotate: N.D. representes not detect
Embodiment 3
Present embodiment is following to the detection method of the repeatability of the inventive method and recovery of standard addition:
Each the phthalic ester standard specimen that in sample, adds high, normal, basic 3 variable concentrations respectively; Each sample is measured respectively 5 times; The chromatograph mass spectrum analysis condition is with the chromatograph mass spectrum analysis condition of embodiment 1; Calculate the relative standard deviation of the value of measuring behind recovery of standard addition and the mark-on of phthalate compound in this method cigarette tipping paper according to analysis result, the result is as shown in table 5:
Phthalate compound recovery of standard addition and standard deviation result in table 5 cigarette tipping paper
| Title | The recovery (%) | RSD(%) |
| Repefral (DMP) | 95.2 | 3.4 |
| Diethyl phthalate (DEP) | 97.3 | 4.1 |
| Diisobutyl phthalate (DIBP) | 103.2 | 4.8 |
| N-butyl phthalate (DBP) | 105.1 | 4.3 |
| Butyl benzyl phthalate (BBP) | 102.4 | 3.8 |
| Phthalic acid two (2-ethyl) own ester (DEHP) | 94.7 | 4.6 |
| The positive dioctyl ester of phthalic acid (DNOP) | 96.8 | 4.1 |
Can be known that by table 5 recovery of 7 kinds of target compounds is between 94%～106%, average relative standard deviation (RSD) explains that the recovery of the inventive method is high, good reproducibility between 3.4～4.8.
Mark liquid and standard solution were that example describes with one of them concentration value only in present embodiment was resulting; Typical curve and regression equation that interior mark liquid that other concentration values are prepared and standard solution chromatograph mass spectrum analysis are obtained are same as the previously described embodiments; Only the position in the scatter diagram is different; And do not influence the mensuration result of sample yet, enumerate no longer one by one at this.The embodiment that lifts method for a better understanding of the present invention just, do not have any restriction, promptly said method or the method that is equal to above-mentioned situation all comprise in the protection domain of technical scheme of the present invention.
Claims (4)
1. method of measuring phthalate compound content in the cigarette tipping paper may further comprise the steps:
(1) preparation of mark extract in: with Ergol is interior mark standard items, is extractant with ethanol, and being prepared into concentration is the interior mark extract of 0.2～0.5 μ g/mL;
(2) preparation of standard operation solution: choose repefral DMP, diethyl phthalate DEP, diisobutyl phthalate DIBP, n-butyl phthalate DBP, butyl benzyl phthalate BBP, the own ester DEHP of phthalic acid two (2-ethyl), the positive dioctyl ester DNOP of phthalic acid, as the standard items of phthalate compound; Become the hybrid standard storing solution with the ethanolic solution stepwise dilution, mark matrix correcting fluid is prepared into standard operation solution in adding respectively then;
(3) preparation of sample solution: with interior mark extract extraction cigarette tipping paper sample, the gained clear liquid is sample solution;
(4) gaschromatographic mass spectrometric analysis: utilize gas chromatography mass spectrometer that standard operation solution and sample solution are carried out check and analysis;
(5) typical curve is drawn and result's calculating: its respective concentration of chromatographic peak area comparison with 7 kinds of phthalate compounds and interior mark Ergol is carried out regretional analysis, obtains typical curve; With the chromatographic peak area ratio of 7 kinds of phthalate compounds in the sample solution that records under the same terms and interior mark Ergol, the substitution typical curve is tried to achieve the content of phthalate compound in the cigarette tipping paper sample.
2. assay method according to claim 1 is characterized in that: the preparation method of mark extract specifically may further comprise the steps in described:
(1) preparation of mark storing solution I in: accurately take by weighing 100 mg～250 mg Ergols in 100 mL volumetric flasks, be settled to scale and mixing with ethanol, obtaining concentration is the interior mark storing solution I of 1.0～2.5 mg/mL;
(2) preparation of mark storing solution II in: accurately pipette in 1 mL mark storing solution I in 50 mL volumetric flasks, be settled to scale and shake up with ethanol, obtaining concentration is the inner mark solution II of 20～50 μ g/mL;
(3) preparation of mark extract in: accurately pipette and mark the storing solution II in 10 mL in 1000 mL volumetric flasks, appearance ethanol is settled to scale and shakes up, and obtaining concentration is the interior mark extract of 0.2～0.5 μ g/mL.
3. assay method according to claim 1 is characterized in that: the preparation method of described standard operation solution specifically may further comprise the steps:
(1) hybrid standard storing solution: the phthalate compound that accurately takes by weighing 50～100 mg respectively is in 100 mL volumetric flasks, and with dissolve with ethanol and be settled to scale, mixing obtains the hybrid standard storing solution I that concentration is 0.5～1.0 mg/mL;
(2) standard operation solution: the hybrid standard storing solution pipettes 50 μ L, 100 μ L, 250 μ L, 500 μ L, 1000 μ L and 2500 μ L respectively and places 100 mL volumetric flasks; The interior mark liquid that adds 20～50 μ g respectively; Be settled to scale and shake up with ethanol, obtain other standard operation solution of 6 concentration levels.
4. assay method according to claim 1 is characterized in that: described gaschromatographic mass spectrometric analysis, its chromatographic condition is: elasticity capillary column, 5% phenyl/95% methyl polysiloxane
,30m length * 0.25mm internal diameter * 0.25 μ m thickness, injector temperature: 280 ℃, sample size: 1 μ L, carrier gas is: helium, purity>=99.999%, split ratio: 50:1, constant current flow velocity: 1.2mL/min; Heating schedule is: 100 ℃ of initial temperatures, keep 1min, and with the speed to 180 of 20 ℃/min ℃, ℃ keep 10min with the speed to 280 of 10 ℃/min again; Its mass spectrophotometry condition for the transmission line temperature is: 280 ℃; Ionization EI energy is 70 eV; Ion source temperature is: 300 ℃; Solvent delay times 3 min selects ion scan Mode S IM fractional scanning, carries out quantitative test with characteristic ion.
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| CN102590382A (en) * | 2012-02-10 | 2012-07-18 | 河北中烟工业有限责任公司 | Determination method of phthalic acid ester in printing ink for cigarette |
| CN103091410A (en) * | 2013-01-25 | 2013-05-08 | 广西中烟工业有限责任公司 | Method for measuring phthalate type compound content in reconstituted tobacco |
| CN103091410B (en) * | 2013-01-25 | 2014-07-16 | 广西中烟工业有限责任公司 | Method for measuring phthalate type compound content in reconstituted tobacco |
| CN103630624A (en) * | 2013-11-22 | 2014-03-12 | 中国烟草总公司湖北省公司 | Method for determining 18 phthalic acid ester compounds in cigarette paper materials |
| CN103630624B (en) * | 2013-11-22 | 2016-01-06 | 中国烟草总公司湖北省公司 | The assay method of 18 kinds of phthalate compounds in cigarette paper material |
| CN106501398A (en) * | 2016-10-20 | 2017-03-15 | 福建中烟工业有限责任公司 | The method for separating and detecting phthalate material |
| CN107422054A (en) * | 2017-07-24 | 2017-12-01 | 云南省烟草农业科学研究院 | One detection method for growing tobacco middle nitre benzene bacterium ester residual quantity |
| CN107422054B (en) * | 2017-07-24 | 2019-12-10 | 云南省烟草农业科学研究院 | method for detecting residual quantity of meptyldinocap in tobacco |
| CN108318463A (en) * | 2018-01-09 | 2018-07-24 | 上海烟草集团有限责任公司 | A kind of fluorescence spectrum rapid assay methods for phthalate substance in paper wrapper |
| CN108362787A (en) * | 2018-01-16 | 2018-08-03 | 国家烟草质量监督检验中心 | The assay method of harmful components in a kind of processing method of Cigarette paper sample, Cigarette paper |
| CN108152424A (en) * | 2018-02-08 | 2018-06-12 | 河南中烟工业有限责任公司 | The detection method of citric acid ester plasticizer content in a kind of cigarette paper wrapper |
| CN108562659A (en) * | 2018-02-08 | 2018-09-21 | 河南中烟工业有限责任公司 | The detection method of benzoates plasticizer content in a kind of cigarette paper wrapper |
| CN109374540A (en) * | 2018-09-27 | 2019-02-22 | 阜阳师范学院 | A method of measuring the content of chromium in solution (VI) and manganese (VII) simultaneously |
| CN110470767A (en) * | 2019-08-27 | 2019-11-19 | 甘肃烟草工业有限责任公司 | Phthalic acid ester and measuring method while Polychlorinated biphenyls in food wrapper |
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