CN110850007B - Method for measuring phthalate component migration in filter stick by simulating real smoking of cigarette - Google Patents
Method for measuring phthalate component migration in filter stick by simulating real smoking of cigarette Download PDFInfo
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- CN110850007B CN110850007B CN201911108457.3A CN201911108457A CN110850007B CN 110850007 B CN110850007 B CN 110850007B CN 201911108457 A CN201911108457 A CN 201911108457A CN 110850007 B CN110850007 B CN 110850007B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
Abstract
The invention relates to a method for measuring the transfer of phthalate components in a filter stick by simulating real smoking of a cigarette, belonging to the technical field of chemical analysis and testing. The method comprises three steps of measuring the amount of phthalate ester components actually sucked by a simulated cigarette, measuring the total amount of phthalate ester volatile components in a cigarette filter stick and calculating the mobility. During detection, an HS-TD-GC/MS method is adopted for detection. The method can meet the requirement of accurately measuring the transfer volume of the phthalate component in the cigarette filter stick, and provides a scientific, simple and convenient new method for objectively evaluating the residual safety of the phthalate component in the cigarette filter stick.
Description
Technical Field
The invention belongs to the technical field of chemical analysis and testing, and particularly relates to a method for determining the migration of phthalate components in a filter stick by simulating real smoking of a cigarette.
Background
The cigarette filter stick is a tool specially designed for smokers, and can reduce smoke, tar and suspended particles generated during combustion when the cigarette is smoked. And (3) the interception function on particulate matters and harmful components of cigarette smoke. In recent years, in order to reduce harm and tar and highlight the personalized style of cigarette products, the application of a new material capable of realizing specific effects in a filter tip to highlight the characteristics of the cigarette products becomes a new technological innovation hotspot. The cigarette product researchers aim at expanding consumer groups, and the developed cigarette products achieve the effects of reducing harm and tar, enhancing pleasure, comfort and satisfaction of consumers and the like by adding novel materials such as blasting beads, particles and aromatic threads into the filter tips. New filter tip materials such as blasting beads, particles, incense threads and the like are increasingly applied to more cigarette brands at home and abroad, and the trend of development and application to the mastery brands of various enterprises is shown in recent two years.
The cigarette filter is formed by bonding the filter stick and the tipping paper through water-based glue. A certain amount of plasticizer is added into the tows in the process of forming the filter stick, a certain amount of phthalate ester components are contained in some plasticizers, and the phthalate esters may also be contained in the water-based adhesive used in the process of forming the filter stick and the printing ink used in the process of producing the tipping paper for the cigarette. On the other hand, various novel filter sticks are increasingly applied to cigarettes, and fillers, functional additives, coloring agents, core essences and coating materials used by various households in the filter sticks are different; the use of a large number of new materials also has the possibility of introducing phthalate components, which brings new safety risks to cigarettes.
At present, phthalate esters are items for frequently detecting tobacco materials (paper, filter sticks) and tobacco additives (essence) in the tobacco industry in China. The phthalate plasticizer can cause functional changes of central nerves and peripheral nervous systems, shows strong endocrine interference, is an environmental hormone, can seriously affect normal physiological functions of human bodies after being accumulated in vivo for a long time, and has the hazards of teratogenesis, carcinogenesis, mutagenesis and the like.
In the currently reported filter stick phthalate detection method, the content in the filter stick is mainly measured, and the mobility of the filter stick in the cigarette smoke is not considered. For cigarette products, only the part migrating to the smoke of the cigarettes can act with human bodies, so that the evaluation on the safety of the phthalate component residue in the filter stick on the basis of considering the migration rate is more in line with the reality of the cigarette products.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provide the method for simulating real smoking of the cigarette to determine the transfer amount of the phthalate component in the filter stick, the method can meet the requirement of accurately determining the transfer amount of the phthalate component in the filter stick, and a scientific, simple and convenient new method is provided for safety evaluation of the phthalate component residue in the filter stick.
All percentages used herein are by weight unless otherwise indicated.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: the device comprises an airflow preheating cavity, a numerical control three-way valve, a purging pipe and a dynamic headspace gas chromatography-mass spectrometry instrument;
the numerical control three-way valve is arranged between the airflow preheating cavity and the purging pipe;
the gas outlet of the purging pipe is connected with a dynamic headspace gas chromatography-mass spectrometry instrument;
the airflow preheating cavity is connected with an air inlet of the numerical control three-way valve;
the air flow preheating cavity is a quartz glass tube, and the gas in the tube is preheated by adopting infrared radiation;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature rise program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating an ISO standard smoking mode or a Canada deep smoking mode sucks and purges the filter stick, when smoking is simulated, air flow enters a purging pipe and is communicated with the filter stick, and when static combustion is simulated, the air flow directly enters the atmosphere; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) HS-TD-GC/MS detection: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, phthalate components adsorbed in the trap are desorbed through high-temperature analysis and then enter the gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging tube, starting a heating program of the airflow preheating cavity to heat, and continuously purging the filter stick for 8-15min by using gas at 180-240 ℃;
(2.2) performing measurement by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate component detected in the step (1.2) by the sum of the amount of each phthalate component detected in the step (1.2), and multiplying by 100% to obtain the phthalate component;
the phthalate-based component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
Further, it is preferable that the purge pipe includes a pipe body and a pipe cap; the pipe body is connected with the pipe cap; two sealing rings which are used for fixing the filter stick and only allow airflow to pass through from the filter tip are arranged in the tube body, and the two sealing rings are respectively arranged at two ends of the filter stick. The sealing ring can realize the sealing between the filter stick and the blowing pipe wall, avoid the side of blowing air flow to pass through and ensure the air flow to pass through the filter stick. By adjusting the size and the position of the sealing ring up and down, the requirements of filter tip tests of all specifications of cigarettes can be met, such as conventional cigarettes, medium cigarettes, thin cigarettes, long filter cigarettes, short filter cigarettes and the like, as shown in figure 3.
The arrangement of the airflow preheating cavity can realize the programmed temperature rise of the gas in the cavity, so that the temperature of the airflow passing through the filter stick is consistent with the actual sweeping temperature of the cigarette smoke.
The numerical control three-way valve can realize automatic switching, can simulate the standard smoking condition of the smoking machine, the airflow does not pass through the filter rod when the cigarette is in a static combustion state and is directly discharged to the outside, and the airflow passes through the filter rod to purge the bead blasting filter rod when the cigarette is in a smoking state.
Further, in the step (1), preferably, the filter stick is purged by simulating an ISO standard suction mode, the purging is continued for 2 seconds every 1 minute, and the flow rate of the purging air flow is 17.5mL/min; the Canadian deep suction mode is simulated to purge the filter stick, the purging lasts for 2 seconds every 30 minutes, and the flow rate of the purging airflow is 22.5mL/min; purging for 8-10 times.
Namely, the method simulates an ISO standard suction mode to purge the filter stick, and simulates 2s cigarette suction time, and the process is as follows: switching by a numerical control three-way valve, wherein airflow enters from an air inlet of the numerical control three-way valve, and then enters a purging pipe from one air outlet to purge and elute the exploded beads in the filter stick, and the purging time is 2s; then, simulating the static burning time of the 58s cigarette, and the process is as follows: through the switching of the numerical control three-way valve, air flow enters from an air inlet of the numerical control three-way valve and then enters atmosphere from another air outlet without passing through the filter rod.
Purging 8-10 times, namely simulating 8-10 mouths of suction.
Further, in the step (2), the temperature of the trap is preferably-10 ℃, the high-temperature desorption temperature is preferably 220-250 ℃, the desorption time is preferably 2-5min, the temperature of the transmission line is preferably 250-280 ℃, and the temperature of the valve box is preferably 250-280 ℃.
Further, it is preferable that, in the step (2), the gas chromatography conditions are as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the sample inlet temperature is 280 ℃; the split ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C/min at a rate of 20 deg.C/min, and is maintained for 1min, and then increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
Further, it is preferable that, in the step (2), the mass spectrometry conditions are as follows: auxiliary interface temperature: 250-280 ℃; an ionization mode: an electron impact source (EI); ion source temperature: 220 to 250 ℃; ionization energy: 60-70eV; quadrupole rod temperature: 180-200 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
Further, it is preferable that the amount of phthalate ester components actually sucked by a simulated cigarette is measured and the total amount of phthalate ester volatile components in a cigarette filter stick is measured after not less than 10 filter sticks are collected, and then the measurement is performed.
Further, it is preferable that the adsorbent material of the trap is ring-shaped silica-coated zirconia particles.
The preparation method of the zirconium oxide particles coated by the annular silicon resin comprises the following steps:
A. 200.0g of phenyltrimethoxysilane was added to a mixed solution of 200mL of anhydrous methanol and 1400mL of benzene, then 8.2g of water and 65.9g of potassium hydroxide were added and stirred to a uniform solution, and after stirring for 1 hour, the mixed solution was subjected to rotary evaporation to remove the solvent. After a period of time, colorless transparent needle crystals (potassium phenylsiliconate) were formed, filtered, and the resulting crystals were washed with n-hexane and dried in a vacuum oven at 40 ℃ for 24h to give a white solid with a yield of 78%.
151.8g of white solid is added into 500mL of n-hexane solution at a time, 243g of dimethyl hydrogen chlorosilane is added, stirring is carried out, and reflux reaction is carried out for 12 hours. After cooling to room temperature, the mixture was filtered, and the filtrate was washed with deionized water to neutrality, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation to give 178g of a colorless transparent oil (triphenyltrisilacylotrisiloxane) in a yield of more than 98.8%.
B. 200g of vinyltrimethoxysilane was added to 1300mL of an anhydrous methanol solution, 89g of potassium hydroxide was then added thereto, and after the solution became uniform by vigorous stirring, the mixture was refluxed for 30 minutes, and then 200mL of an anhydrous methanol solution containing 76.7g of copper chloride was added thereto and refluxed for 30 minutes. Cooling, filtering, freezing the filtrate at-10 deg.C, generating blue crystal (potassium vinyl silanolate/copper salt) after a period of time, washing the filtered crystal with methanol solution, and drying in vacuum oven at 40 deg.C for 24 hr to obtain blue powder with yield of 76.2%.
60g of blue powder is added into 350mL of n-hexane solution at one time, 77.2g of trimethyl-chlorosilane is added, stirring is carried out, and reflux reaction is carried out for 12 hours. After cooling to the greenhouse, filtering, washing the filtrate to be neutral by water, drying by anhydrous sodium sulfate, filtering, and then removing the solvent by rotary evaporation to obtain colorless transparent oily substance (hexavinylcyclohexasiloxane) with the yield of more than 74.1%.
C. Taking triphenyl trisilico hydrogen cyclotrisiloxane and hexavinyl cyclohexasiloxane according to the mass ratio of 1.2:1, adding zirconia particles (the particle diameter is 100-150 meshes) which are 6-10 times of the total amount of the siloxane, fully stirring to coat the siloxane on the surfaces of the zirconia particles, then adding a Karstedt catalyst with the mass of 0.002 percent of the siloxane, fully stirring, defoaming in vacuum, granulating at 100 ℃, curing for 1h, and curing at 200 ℃ for 8h to obtain the zirconia particles coated by the annular silicon resin.
The particulate material is loaded into a trap of a commercial dynamic headspace analyzer as an adsorbent for the trap. The granular material has good heat resistance, obvious thermal decomposition can occur only at 500 ℃, and the mass retention rate reaches 80% at 1000 ℃. Actual test results surface: the material has large adsorption capacity on phthalate components, good stability at high temperature, reversible adsorption and desorption, can be repeatedly used, and can completely meet the requirement of dynamic headspace analysis on the phthalate components.
The retention time, quantitative and qualitative ion of each target analyte of the present invention are shown in table 1, and a typical chromatogram is shown in fig. 4.
TABLE 1 phthalic acid ester compositions and internal standards Retention time, quantitative and qualitative ion selection
In the invention, because the phthalate ester component only migrates a small part, at least 10 filter rods are blown in an accumulated way in order to reach the quantitative limit of an instrument.
When the heating program is set, cigarettes of different specifications are actually smoked on a smoking machine, the actual temperature of smoke passing through the filter stick is measured by a thermocouple, and then the setting is carried out according to the measurement result.
Further, preferably, in order to realize quantitative analysis of phthalate components, in the invention, 7 concentration gradients (0.1, 0.5, 2.5, 7.5, 15, 30, 50) with a concentration in the range of 0.1 to 50 mg/L are prepared, 1.0 μ L of standard working solution sample injection is made to make a working curve (the amount of each phthalate component is 0.1 to 50 μ g, linear regression is performed by taking the quantitative ion peak area of each analyte as a vertical coordinate and the concentration of each analyte as a horizontal coordinate), and thus, a linear relation of each target compound in the concentration level range of 0.1 to 50 μ g is obtained (R is a good linear relation (R) in the concentration level range of 0.1 to 50 μ g 2 >0.999). Adding a standard solution into an actual sample, wherein the concentration is the lowest standard solution concentration (0.1 mug/mL), carrying out parallel determination for 10 times, taking the relative average standard deviation SD of 10 times of determination, taking the SD which is 3 times as the detection limit of the determination method, taking the SD which is 10 times as the quantification limit of the determination method, and adding the internal standard solution in an amount of 5 mug/mL. The results are shown in Table 2.
TABLE 2 Linear relationship, detection limits and quantitation limits for 19 phthalates
Compared with the prior art, the invention has the beneficial effects that:
(1) The method comprehensively considers the transfer of the phthalate compounds in the cigarette filter stick to the cigarette smoke, and overcomes the problems that the total content in the filter stick is mainly determined and the transfer of the phthalate compounds to the cigarette smoke is not considered in the traditional filter stick phthalate detection method. The migration amount is comprehensively considered, and the evaluation on the safety of the phthalate ester component residue can better accord with the reality of cigarette products.
(2) The device adopted by the invention has simple structure and easy operation. Compared with the direct analysis of cigarette smoke, the method can deduct the complex background generated by cigarette combustion. The whole analysis process is on-line operation, so that errors caused by multiple sample transfer in other methods are avoided, and the measurement result of the phthalate ester component is more accurate and reliable; compared with other simulation migration devices, the device provided by the invention simulates the actual situation closer to cigarette smoking, and the obtained result is more objective and reliable.
(3) The precise purging pipe is adopted in the invention, the purging pipe is of a clamping sleeve type structure with a sealing ring, the sealing ring can realize sealing between the filter rod and the purging pipe wall, and the side edge of purging airflow is prevented from passing (the airflow can be ensured to pass through the filter rod). The requirements of testing filter sticks (conventional cigarettes, medium cigarettes, fine cigarettes, long filter cigarettes, short filter cigarettes and the like) with all specifications of cigarettes can be met by adjusting the sizes and the positions (up and down) of the sealing rings.
(4) The invention also adopts the zirconia particles wrapped by the annular silicon resin as the adsorption material of the trap for the first time. The material has large adsorption capacity, good stability at high temperature, good adsorption and desorption reversibility to phthalate compounds, high adsorption and desorption completeness of components to be detected, and can obviously improve the accuracy and precision of analysis results.
Drawings
FIG. 1 is a schematic diagram of the structure of an apparatus used in the present invention;
FIG. 2 is an exploded view of the purge tube;
wherein, 1, an air flow preheating cavity is formed; 2. a numerical control three-way valve; 3. a purge tube; 3-1, a pipe body; 3-2, a pipe body; 3-3, sealing rings; 4. a dynamic headspace gas chromatography-mass spectrometry instrument; 5. filtering the filter stick; 5-1, an upper filter rod core; 5-2, lower filter stick core; 5-3, tipping paper; 6. bead blasting;
FIG. 3 is a schematic view of different types of cigarette filter rods installed in the purge tube; wherein a is a filter stick of a conventional cigarette, b is a filter stick of a fine cigarette, and c is a filter stick of a short filter cigarette;
FIG. 4 is a chromatogram for the detection of 16 phthalate components;
wherein, 1-DMP, 2-DEP, 3-DAP, 4-DIBP, 5-DBP, 6-DMEP, 7-BMPP, 8-DEEP, 9-DPP, 10-DHXP, 11-BBP, 12-DBEP, 13-DCHP, 14-DEHP, 15-DPPA, 16-DNOP, 17-DINP, 18-DNP, 19-TBP and IS-internal standard.
Detailed Description
The present invention will be described in further detail with reference to examples.
It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The materials or equipment used are not indicated by manufacturers, and all are conventional products available by purchase.
Example 1
A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: as shown in fig. 1 to 3, the device comprises an airflow preheating chamber 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature rise program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating an ISO standard smoking mode sucks and purges the filter stick, air flow enters a purging pipe to be communicated with the filter stick during simulation of smoking, and air flow directly enters atmosphere during simulation of static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) detecting by using an HS-TD-GC/MS method: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, phthalate components adsorbed in the trap are desorbed through high-temperature analysis and then enter the gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and continuously purging the filter stick for 8min by using 180 ℃ gas;
(2.2) performing measurement by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate ester component detected in the step (1.2) by the sum of the amount of each phthalate ester component detected in the step (1.2), and multiplying by 100% to obtain the finished product;
the phthalate ester component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butyl benzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds in every 1 minute, and the flow rate of purge air flow is 17.5mL/min; purging 8 times.
In the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 220 ℃, the desorption time is 2min, the temperature of the transmission line is 250 ℃, and the temperature of the valve box is 250 ℃.
The gas chromatography conditions were as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the temperature of a sample inlet is 280 ℃; the split ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C/min at a rate of 20 deg.C/min, and is maintained for 1min, and then increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
The mass spectrometry conditions were as follows: auxiliary interface temperature: 250 ℃; an ionization mode: an electron bombardment source; ion source temperature: 220 ℃; ionization energy: 60eV; temperature of the quadrupole rods: 180 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
When the amount of the phthalate ester component actually sucked by the simulated cigarette is measured and the total amount of the phthalate ester volatile component in the cigarette filter stick is measured, 10 filter sticks are required to be collected and then detected.
The test cigarette filter stick is a conventional cigarette flavoring filter stick with the specification of 30mm. And taking the filter stick from the cigarette, and placing the filter stick into a purging pipe for determination.
The measurement result shows that: DMP and DAP are detected in the sample, and the total content is 1.22 and 1.48 respectivelyµg/branch, the transport amount is 62.7 ng/branch and 71.4 ng/branch respectively, and the mobility is 5.14 percent and 4.82 percent respectively. Compared with the concentration (4 to 8 percent) of the rat with slight influence on growth by mouth or the maximum allowable residual quantity (0.3 to 1.5 mg/kg) of the food additive, the drug brings about an ampereThe whole risk is negligible, and the safety risk caused by the introduction of phthalate residues does not exist in the filter stick.
Example 2
A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: as shown in fig. 1 to 3, the device comprises an airflow preheating chamber 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature rise program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating an ISO standard smoking mode sucks and purges the filter stick, air flow enters a purging pipe to be communicated with the filter stick during simulation of smoking, and air flow directly enters atmosphere during simulation of static combustion; meanwhile, the actual number of the suction openings of the cigarettes is simulated;
(1.2) detecting by using an HS-TD-GC/MS method: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, phthalate components adsorbed in the trap are desorbed through high-temperature analysis and then enter the gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and continuously purging the filter stick for 15min by using gas at 240 ℃;
(2.2) measuring by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate component detected in the step (1.2) by the sum of the amount of each phthalate component detected in the step (1.2), and multiplying by 100% to obtain the phthalate component;
the phthalate ester component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butyl benzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5mL/min; purging was performed 9 times.
In the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 250 ℃, the desorption time is 5min, the temperature of the transmission line is 280 ℃, and the temperature of the valve box is 280 ℃.
The gas chromatography conditions were as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the sample inlet temperature is 280 ℃; the split ratio is 16; temperature rising procedure:the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C at a rate of 20 deg.C/min, and is maintained for 1min, and then the temperature is increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
The mass spectrometry conditions were as follows: auxiliary interface temperature: 280 ℃; an ionization mode: an electron bombardment source; ion source temperature: 250 ℃; ionization energy: 70eV; quadrupole rod temperature: 200 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
When the amount of the phthalate ester component actually sucked by the simulated cigarette is measured and the total amount of the phthalate ester volatile component in the cigarette filter stick is measured, 10 filter sticks are required to be collected and then detected.
The test cigarette filter stick is a conventional cigarette bead blasting filter stick with the specification of 25mm. And taking the filter stick from the cigarette, pinching the blasting beads, and filling the blasting beads into a purging tube for measurement.
The determination result shows that no phthalate component is detected in the filter stick, and the safety risk caused by the introduction of the phthalate component does not exist.
Example 3
A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the air flow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature-rising program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating an ISO standard smoking mode sucks and purges the filter stick, air flow enters a purging pipe to pass through the filter stick during smoking simulation, and air flow directly enters atmosphere during static combustion simulation; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) detecting by using an HS-TD-GC/MS method: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, the phthalate ester component adsorbed in the trap is desorbed through high-temperature analysis and then enters a gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging tube, starting a heating program of the airflow preheating cavity to heat, and continuously purging the filter stick for 10min by using 120 ℃ gas;
(2.2) performing measurement by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate component detected in the step (1.2) by the sum of the amount of each phthalate component detected in the step (1.2), and multiplying by 100% to obtain the phthalate component;
the phthalate ester component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butyl benzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5mL/min; purging 10 times.
In the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 240 ℃, the desorption time is 3.5min, the temperature of the transmission line is 260 ℃, and the temperature of the valve box is 260 ℃.
The gas chromatography conditions were as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the temperature of a sample inlet is 280 ℃; the flow splitting ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C/min at a rate of 20 deg.C/min, and is maintained for 1min, and then increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
The mass spectrometry conditions were as follows: auxiliary interface temperature: 260 ℃; an ionization mode: an electron bombardment source; ion source temperature: 240 ℃; ionization energy: 65eV; temperature of the quadrupole rods: 190 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
When the amount of the phthalate ester component actually sucked by the simulated cigarette is measured and the total amount of the phthalate ester volatile component in the cigarette filter stick is measured, 10 filter sticks are required to be collected and then detected.
The test cigarette filter stick is a filter stick with particles added into a conventional cigarette, and the specification is 25mm. And taking the filter stick from the cigarette, and placing the filter stick into a purging pipe for determination.
The determination result shows that no phthalate component is detected in the filter stick, and the safety risk caused by the introduction of the phthalate component does not exist.
Example 4
A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: as shown in fig. 1 to 3, the device comprises an airflow preheating chamber 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The air flow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature rise program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating an ISO standard smoking mode sucks and purges the filter stick, air flow enters a purging pipe to be communicated with the filter stick during simulation of smoking, and air flow directly enters atmosphere during simulation of static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) HS-TD-GC/MS detection: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, phthalate components adsorbed in the trap are desorbed through high-temperature analysis and then enter the gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging tube, starting a heating program of the airflow preheating cavity to heat, and continuously purging the filter stick for 10min by using 220 ℃ gas;
(2.2) measuring by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate ester component detected in the step (1.2) by the sum of the amount of each phthalate ester component detected in the step (1.2), and multiplying by 100% to obtain the finished product;
the phthalate-based component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
In the step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purge air flow is 17.5mL/min; purging was performed 9 times.
In the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 230 ℃, the desorption time is 3.2min, the temperature of the transmission line is 270 ℃, and the temperature of the valve box is 260 ℃.
The gas chromatography conditions were as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the temperature of a sample inlet is 280 ℃; the split ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C at a rate of 20 deg.C/min, and is maintained for 1min, and then the temperature is increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
Mass spectrometry conditions were as follows: auxiliary interface temperature: 270 ℃; an ionization mode: an electron bombardment source; ion source temperature: 235 ℃; ionization energy: 64eV; temperature of the quadrupole rods: 195 ℃; scanning range: 45amu to 350amu; a selective ion acquisition mode is employed.
When the amount of the phthalate ester component actually sucked by the simulated cigarette is measured and the total amount of the phthalate ester volatile component in the cigarette filter stick is measured, 20 filter sticks are required to be collected and then detected.
The test cigarette filter stick is a conventional cigarette filter stick added with flavor threads, and the specification is 30mm. And (4) taking the filter stick from the cigarette, and filling the filter stick into a purging pipe for measurement.
The determination result shows that no phthalate component is detected in the filter stick, and the safety risk caused by the introduction of the phthalate component does not exist.
Example 5
A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the airflow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The airflow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the airflow preheating cavity to heat, and enabling the temperature of the purging airflow at each opening to be consistent with the temperature of the filter stick which is actually sucked and circulated by the cigarette on the smoking machine; after the temperature-rising program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating a Canada deep smoking mode sucks and purges the filter stick, air flow enters a purging pipe to pass through the filter stick during suction simulation, and air flow directly enters atmosphere during static combustion simulation; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) HS-TD-GC/MS detection: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, phthalate components adsorbed in the trap are desorbed through high-temperature analysis and then enter the gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging tube, starting a heating program of the airflow preheating cavity to heat, and continuously purging the filter stick for 12min by using gas at 230 ℃;
(2.2) measuring by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate component detected in the step (1.2) by the sum of the amount of each phthalate component detected in the step (1.2), and multiplying by 100% to obtain the phthalate component;
the phthalate-based component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
In the step (1), a Canada deep suction mode is simulated to purge the filter stick, the purging is continued for 2 seconds every 30 seconds, and the flow rate of the purging airflow is 22.5mL/min; purging was performed 9 times.
In the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 235 ℃, the desorption time is 3.5min, the temperature of the transmission line is 250 ℃, and the temperature of the valve box is 250 ℃.
The gas chromatography conditions were as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the sample inlet temperature is 280 ℃; the split ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C/min at a rate of 20 deg.C/min, and is maintained for 1min, and then increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
The mass spectrometry conditions were as follows: auxiliary interface temperature: 250 ℃; an ionization mode: an electron bombardment source; ion source temperature: 220 ℃; ionization energy: 60eV; temperature of the quadrupole rods: 180 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
When the amount of the phthalate ester component actually sucked by the simulated cigarette is measured and the total amount of the phthalate ester volatile component in the cigarette filter stick is measured, 20 filter sticks are required to be collected and then detected.
The test cigarette filter stick is a fine cigarette bead blasting filter stick with the specification of 35mm. And taking the filter stick from the cigarette, breaking the blasting beads by pinching, and filling the filter stick into a purging tube for determination.
The determination result shows that no phthalate component is detected in the filter stick, and the safety risk caused by the introduction of the phthalate component does not exist.
Example 6
A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks adopts the following devices: as shown in fig. 1 to 3, the device comprises an airflow preheating cavity 1, a numerical control three-way valve 2, a purging pipe 3 and a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the numerical control three-way valve 2 is arranged between the airflow preheating cavity 1 and the purging pipe 3;
the gas outlet of the purging pipe 3 is connected with a dynamic headspace gas chromatography-mass spectrometry instrument 4;
the air flow preheating cavity 1 is connected with an air inlet of a numerical control three-way valve 2.
The air flow preheating cavity 1 is a quartz glass tube, and gas in the tube is preheated by adopting infrared radiation.
The purging pipe 3 comprises a pipe body 3-1 and a pipe cap 3-2; the pipe body 3-1 is connected with the pipe cap 3-2; two sealing rings 3-3 which are used for fixing the filter stick 5 and only allow air flow to pass through from the filter tip are arranged in the tube body 3-1, and the two sealing rings 3-3 are respectively arranged at two ends of the filter stick 5;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components actually sucked by the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature-rising program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating a Canada deep smoking mode sucks and purges the filter stick, air flow enters a purging pipe to pass through the filter stick during suction simulation, and air flow directly enters atmosphere during static combustion simulation; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) detecting by using an HS-TD-GC/MS method: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, the phthalate ester component adsorbed in the trap is desorbed through high-temperature analysis and then enters a gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and continuously purging the filter stick for 14min by using gas at 200 ℃;
(2.2) performing measurement by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate component detected in the step (1.2) by the sum of the amount of each phthalate component detected in the step (1.2), and multiplying by 100% to obtain the phthalate component;
the phthalate-based component includes dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate.
In the step (1), a Canada deep suction mode is simulated to purge the filter stick, the purging is continued for 2 seconds every 30 seconds, and the flow rate of the purging airflow is 22.5mL/min; purging was performed 9 times.
In the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 240 ℃, the desorption time is 2.8min, the temperature of the transmission line is 265 ℃, and the temperature of the valve box is 265 ℃.
The gas chromatography conditions were as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the temperature of a sample inlet is 280 ℃; the flow splitting ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C at a rate of 20 deg.C/min, and is maintained for 1min, and then the temperature is increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
The mass spectrometry conditions were as follows: auxiliary interface temperature: 280 ℃; an ionization mode: an electron bombardment source; ion source temperature: 250 ℃; ionization energy: 70eV; temperature of the quadrupole rods: 200 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
When the amount of the phthalate ester component actually sucked by the simulated cigarette is measured and the total amount of the phthalate ester volatile component in the cigarette filter stick is measured, 20 filter sticks are required to be collected and then detected.
The test cigarette filter stick is a medium cigarette bead blasting filter stick with the specification of 25mm. And taking the filter stick from the cigarette, breaking the blasting beads by pinching, and filling the filter stick into a purging tube for determination.
The determination result shows that no phthalate component is detected in the filter stick, and the safety risk caused by the introduction of the phthalate component does not exist.
In addition, in order to accurately measure the total amount of the phthalate components in the filter stick, the filter stick with 19 artificially added phthalates is prepared, and the adding amount of the 19 components in each cigarette filter stick is respectively 2.0µg. After the filter stick is placed in the purging tube, purging is carried out for 10min at 220 ℃ continuously, so that the phthalate ester component in the filter stick can be completely purged out, and the total amount of the phthalate ester component is measured by the method of example 2, and the result is shown in table 3. As can be seen from the results in Table 3, the recovery rates of the 19 phthalate esters are all greater than 86.9%, which indicates that the determination results of the method are reliable. Meanwhile, a filter stick containing the 19 phthalic acid esters is artificially prepared to simulate real smoking and blowing of cigarettes, the blowing mode is as in example 2, the phthalic acid ester components are determined by the method of example 2, and the detection results are shown in table 3.
TABLE 3
As can be seen from the results in Table 3, the mobility of the 19 phthalate ester components was between 3.50 and 5.16%. This type of component does migrate, but the proportion that migrates is small.
Because the transferable phthalate ester component in the cigarette filter stick is likely to react with the human body, the transfer amount of the phthalate ester component needs to be objectively considered when the safety of the residual phthalate ester component in the cigarette filter stick is evaluated.
The migration volume of the same filter stick is measured in parallel for 5 times, the Relative Standard Deviation (RSD) is between 3.0 and 4.4 percent, and the method has good reproducibility and can meet the requirement of accurately measuring the migration volume of the phthalate ester component.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A method for simulating real smoking of cigarettes to determine the transfer of phthalate components in filter sticks is characterized by adopting the following devices: the device comprises an airflow preheating cavity, a numerical control three-way valve, a purging pipe and a dynamic headspace gas chromatography-mass spectrometry instrument;
the numerical control three-way valve is arranged between the airflow preheating cavity and the purging pipe;
the gas outlet of the purging pipe is connected with a dynamic headspace gas chromatography-mass spectrometry instrument;
the airflow preheating cavity is connected with an air inlet of the numerical control three-way valve;
the airflow preheating cavity is a quartz glass tube, and the gas in the tube is preheated by adopting infrared radiation;
the method comprises the following steps:
step (1), measuring the amount of phthalate ester components in the actual smoking of the simulated cigarette:
(1.1) gas flow purging: putting the filter stick into a purging pipe, starting a heating program of the air flow preheating cavity to heat, and enabling the temperature of every interval purging air flow to be consistent with the temperature of the filter stick when the cigarette is actually sucked on a smoking machine and smoke flows through the cigarette; after the temperature rise program is adjusted, switching is carried out through a three-way valve, a smoking machine simulating an ISO standard smoking mode or a Canada deep smoking mode sucks and purges the filter stick, when smoking is simulated, air flow enters a purging pipe and is communicated with the filter stick, and when static combustion is simulated, the air flow directly enters the atmosphere; meanwhile, the actual number of suction openings of the cigarette is simulated;
(1.2) HS-TD-GC/MS detection: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, and after trapping is finished, the phthalate ester component adsorbed in the trap is desorbed through high-temperature analysis and then enters a gas chromatography-mass spectrometry instrument for detection;
step (2), measuring the total amount of phthalate ester volatile components in the cigarette filter stick:
(2.1) gas flow purging: putting the filter stick into a purging tube, starting a heating program of the airflow preheating cavity to heat, and continuously purging the filter stick for 8-15min by using gas at 180-240 ℃;
(2.2) performing measurement by the same method as the step (1.2);
and (3) calculating the mobility:
dividing the sum of the amount of each phthalate component detected in the step (1.2) by the sum of the amount of each phthalate component detected in the step (1.2), and multiplying by 100% to obtain the phthalate component;
the phthalate ester component comprises dimethyl phthalate, diethyl phthalate, diallyl phthalate, diisobutyl phthalate, dibutyl phthalate, di (2-methoxy) ethyl phthalate, di (4-methyl-2-pentyl) phthalate, di (2-ethoxy) ethyl phthalate, dipentyl phthalate, dihexyl phthalate, butylbenzyl phthalate, di (2-butoxy) ethyl phthalate, dicyclohexyl phthalate, di (2-ethyl) hexyl phthalate, diphenyl phthalate, di-n-octyl phthalate, diisononyl phthalate, dinonyl phthalate and tributyl phosphate; the adsorption material of the trap is zirconia particles wrapped by annular silicon resin.
2. The method for simulating real smoking of a cigarette to determine the migration of the phthalate ester component in the filter stick according to claim 1, wherein the purging tube comprises a tube body and a tube cap; the pipe body is connected with the pipe cap; two sealing rings which are used for fixing the filter stick and only allow airflow to pass through from the filter tip are arranged in the tube body, and the two sealing rings are respectively arranged at two ends of the filter stick.
3. The method for simulating real smoking of cigarettes to determine the transfer of the phthalate ester components in the filter sticks according to claim 1, wherein in the step (1), the filter sticks are purged by simulating an ISO standard smoking mode, purging is continuously carried out for 2 seconds every 1 minute, and the flow rate of purging airflow is 17.5mL/min; purging the filter stick by simulating a Canadian deep suction mode, wherein purging is continuously carried out for 2 seconds every 30 days, and the flow speed of the purging airflow is 22.5mL/min; purging for 8-10 times.
4. The method for simulating the transfer of the phthalate ester components in the filter stick for the real smoking determination of the cigarette according to claim 1, wherein in the step (2), the temperature of the trap is-10 ℃, the high-temperature desorption temperature for desorption is 220-250 ℃, the desorption time is 2-5min, the temperature of the transmission line is 250-280 ℃, and the temperature of the valve box is 250-280 ℃.
5. The method for simulating the real smoking of the cigarette to measure the transfer of the phthalate ester component in the filter stick according to the claim 1, wherein in the step (2), the gas chromatography conditions are as follows: the chromatographic column is DB-5MS capillary column with specification of 30m × 0.25mm × 0.25μm; the sample inlet temperature is 280 ℃; the split ratio is 16; temperature rising procedure: the initial temperature is 60 deg.C, and is maintained for 1min, and the temperature is increased to 220 deg.C at a rate of 20 deg.C/min, and is maintained for 1min, and then the temperature is increased to 280 deg.C at a rate of 5 deg.C/min, and is maintained for 15min.
6. The method for simulating the transfer of the phthalate ester components in the cigarette filter stick for the real smoking determination according to claim 1, wherein in the step (2), the mass spectrum conditions are as follows: auxiliary interface temperature: 250-280 ℃; an ionization mode: an electron bombardment source; ion source temperature: 220 to 250 ℃; ionization energy: 60-70eV; quadrupole rod temperature: 180-200 ℃; scanning range: 45amu to 350amu; a selective ion collection mode is employed.
7. The method for simulating real smoking of cigarettes to determine the transfer of the phthalate ester components in the filter sticks according to claim 1, wherein when the amount of the phthalate ester components actually smoked by the simulated cigarettes is determined and the total amount of the phthalate ester volatile components in the filter sticks of the cigarettes is determined, no less than 10 filter sticks need to be trapped and then detected.
8. The method for simulating real smoking of a cigarette to determine the transfer of the phthalate ester component in the filter stick according to claim 1, wherein the preparation method of the annular silicon resin coated zirconia particles is as follows:
A. adding 200.0g of phenyltrimethoxysilane into a mixed solution of 200mL of anhydrous methanol and 1400mL of benzene, then adding 8.2g of water and 65.9g of potassium hydroxide, stirring until a uniform solution is obtained, stirring for 1h, and then performing rotary evaporation on the mixed solution to remove the solvent; generating colorless transparent needle-shaped crystals after a period of time, filtering, washing the obtained crystals with n-hexane, and drying in a vacuum oven at 40 ℃ for 24h to obtain white solids;
151.8g of white solid is taken and added into 500mL of n-hexane solution at one time, 243g of dimethyl hydrogen chlorosilane is added, stirring is carried out, and reflux reaction is carried out for 12 hours; cooling to room temperature, filtering, washing the filtrate with deionized water to neutrality, drying with anhydrous sodium sulfate, filtering, and removing the solvent by rotary evaporation to obtain triphenyltrisilacylotrisiloxane;
B. adding 200g of vinyltrimethoxysilane into 1300mL of anhydrous methanol solution, then adding 89g of potassium hydroxide, stirring, refluxing for 30min after the solution becomes uniform, adding 200mL of anhydrous methanol solution containing 76.7g of copper chloride, and refluxing for 30min; cooling, filtering, placing the filtrate in a freezing environment at-10 deg.C, generating blue crystal after a period of time, washing the filtered crystal with methanol solution, and drying in a vacuum oven at 40 deg.C for 24 hr to obtain blue powder;
adding 60g of blue powder into 350mL of n-hexane solution at one time, adding 77.2g of trimethyl-chlorosilane, stirring, and carrying out reflux reaction for 12 hours; cooling to a greenhouse, filtering, washing the filtrate with water to be neutral, drying with anhydrous sodium sulfate, filtering, and removing the solvent by rotary evaporation to obtain hexavinylcyclohexasiloxane;
C. taking triphenyl trisilico hydrogen cyclotrisiloxane and hexavinyl cyclohexasiloxane according to the mass ratio of 1.2:1, adding zirconium oxide particles which are 6-10 times of the total mass of the triphenyltrisilahydrosyclotrisiloxane and the hexavinylcyclohexane hexasiloxane, stirring to coat the siloxane on the surfaces of the zirconium oxide particles, then adding Karstedt catalyst which is 0.002% of the total mass of the triphenyltrisilahydrosyclotrisiloxane and the hexavinylcyclohexane hexasiloxane, stirring, defoaming in vacuum, granulating at 100 ℃, curing for 1h, and curing for 8h at 200 ℃ to obtain the zirconium oxide particles coated by the cyclic silicon resin.
9. The method for measuring the migration of the phthalate ester component in the filter stick through real smoking of the simulated cigarette according to claim 8, wherein the particle size of the zirconia particles is 100 to 150 meshes.
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