CN110850009A - Simulation determination method for migration of cooling agent component in cigarette filter stick to cigarette smoke - Google Patents
Simulation determination method for migration of cooling agent component in cigarette filter stick to cigarette smoke Download PDFInfo
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Abstract
The invention relates to a simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke, and belongs to the technical field of analytical chemistry. The method comprises the following steps: the cigarette filter stick added with the cooling agent is placed into a purging pipe, the device provided by the invention is adopted to simulate real smoking of a cigarette to purge the filter stick, the adsorption cold trap is used for trapping the components of the purged cooling agent, the content of the components of the cooling agent is measured through a gas chromatography-mass spectrometry connected with a dynamic headspace after trapping is finished, and then the mobility is calculated. The method can meet the requirement of accurately measuring the migration quantity of the cooling agent component in the cigarette filter stick to the cigarette smoke, and provides a scientific, simple and convenient new method for objectively evaluating the release and effect of the cooling agent component in the cigarette filter stick.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, and particularly relates to a simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke.
Background
Cooling agents are chemical substances that produce a cooling effect on the mouth and smell of a person. Such as L-menthol, which has the advantages of fresh cool taste, low price, easy acquisition and the like, and is widely applied to a plurality of fields of daily chemicals, foods, tobaccos, medical and sanitary products and the like. With the increasing demand of consumers for cooling flavor, technologists develop various novel cooling agents to meet the consumption demands of different fields. The cool type is common abroad, and the domestic market demand is on the increasing trend in recent years. Currently, common cooling agents in the tobacco industry comprise L-menthol, isopulegol, menthone, menthyl lactate, menthone glycerol ketal, N-ethyl-p-menthyl-3-formamide, 2-isopropyl-N, 2, 3-trimethylbutanamide and other components, and multiple components are usually compounded to meet the requirements of the taste and the durability of cigarettes.
At present, various cigarette manufacturers at home and abroad develop a plurality of cigarette cooling agent adding technologies, such as tobacco shred adding, cigarette paper adding, filter tip adding and the like. The filter tip added with the cooling agent is an important cooling cigarette making mode because the filter tip has the advantages of avoiding loss and pyrolysis in the cigarette storage and combustion smoking processes, avoiding loss of the cigarette during the static combustion period, increasing the transfer efficiency of functional components and the like. In order to improve the retention effect of adding cooling ingredients and highlight the personalized style of cigarette products, cigarette product developers also develop new ways of adding cooling agents to filters such as blasting beads, granules, aromatic threads and the like by aiming at expanding consumer groups. At present, new filter tip materials such as exploded beads, particles, aromatic threads and the like are increasingly applied to more cigarette brands at home and abroad and show a rapid growth trend.
At present, the method for analyzing and detecting the components of the cooling agent added to the filter tip generally adopts the method of directly measuring the content of the added components in the filter tip or adopting a smoking machine to capture cigarette smoke for analysis. The direct measurement is simple to operate, but the release amount of the added components to the smoke of the cigarette during smoking of the cigarette cannot be objectively reflected. If the cigarette smoke is analyzed, the sample analysis process is not complicated, and the chemical components generated by cigarette combustion are thousands of, and the complicated background will bring great influence on the analysis of the added cool components. Therefore, how to overcome the defects of the prior art is a problem which needs to be solved in the technical field of analytical chemistry at present.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method for simulating and measuring the migration of cooling agent components in a cigarette filter stick to cigarette smoke, which can meet the requirement of accurately measuring the migration amount of cooling agent components added in the filter stick and provides a scientific, simple and convenient new method for evaluating the release amount of the cooling agent added in the filter stick.
All percentages used herein are by weight unless otherwise indicated.
The purpose of the invention is realized by the following technical scheme.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke 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 method comprises the following steps:
step (1), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
The numerical control three-way valve can realize automatic switching, can simulate the standard smoking condition of a smoking machine, the air flow is not communicated with the filter rod when the cigarette is in a static combustion state and is directly discharged to the outside, and the air flow is communicated with the filter rod to purge the bead blasting filter rod when the cigarette is in a smoking state.
Further, preferably, the gas flow preheating chamber is a quartz glass tube, and the gas in the tube is preheated by using infrared radiation. The arrangement can realize the programmed temperature rise of the gas in the cavity, so that the temperature of the air flow passing through the filter stick is consistent with the actual sweeping temperature of the cigarette smoke.
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.
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 17.5 mL/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 22.5 mL/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 2 s; and then, simulating the static burning time of the 58s cigarette, wherein the process comprises the following steps: 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 adsorption material of the trap is preferably polybutadiene-coated silica gel particles, which have a large adsorption capacity for cooling agent components, good stability at high temperature, reversible adsorption and desorption, and can be reused many times. The temperature of the trap is-10 ℃, the high-temperature desorption temperature is 180-.
Further, it is preferable that the preparation method of the polybutadiene-coated silica gel particle is as follows:
adding polybutadiene, a sensitizer and toluene into a beaker, uniformly mixing, adding silica gel particles modified by triethoxyvinylsilane, carrying out ultrasonic oscillation reaction, carrying out rotary evaporation to remove toluene after the reaction is finished, introducing argon into a container filled with a product, carrying out radiation crosslinking after sealing, washing with benzene and acetone in sequence, and drying to obtain the modified silica gel particles;
the mass ratio of polybutadiene to the sensitizer to the triethoxy vinyl silane modified silica gel particles is 12-15: 1.0-1.5: 120 to 150 parts;
the mass ratio of polybutadiene to the volume of toluene is 12-15 g: 0.8-1.2L.
Further, the particle size of the silica gel particles is preferably 100-150 meshes; the drying temperature is 200 ℃, and the drying time is 6 h; the ultrasonic oscillation time is 35-45 min; the mass of benzene and acetone used for washing is 2-3 times that of the triethoxyvinylsilane modified silica gel particles; the sensitizer is ethylene glycol dimethacrylate or triethylene glycol dimethacrylate.
Further, it is preferable that, in the step (2), the gas chromatography conditions are as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
Further, it is preferable that, in the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
Further, it is preferable that, in the step (2), the method of calculating the mobility is: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility; mobility = (peak area simulating actual pumping measurement/peak area of total amount) × 100%.
When the measurement of the components of the actually sucked cooling agent is simulated, each filter stick is replaced by a new filter stick after being blown, the filter sticks are blown again, and not less than 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and (3) replacing a new filter stick by adopting the same device, continuously purging the filter stick for 8-15 min by using 180-plus-240 ℃ gas, continuously purging by replacing the new filter stick again after purging is finished, purging not less than 5 filter sticks in total (the purging number of the filter sticks is consistent with the purging number of the simulated actually sucked cooling agent component measurement timing), and measuring the total amount of the cooling agent component. The total measurement trapping, desorption, GC and MS conditions are completely the same as the measurement conditions for simulating the actual amount of the cooling agent component sucked.
This is due to the fact that the cooling agent component migrates only to a small extent, and at least 5 filter rods are swept cumulatively in order to reach the limit of quantitation of the instrument.
When the heating program is set, cigarettes of different specifications are actually smoked on the smoking machine, the actual temperature of smoke passing through the filter stick is measured by the thermocouple, and then the setting is carried out according to the measurement result.
The ion selection parameter principle of the invention is as follows: selecting ions with higher specificity and response from mass spectrum ion fragments of each solvent residue as quantitative ions; and selecting other 1-2 fragment ions as auxiliary qualitative ions. The ion selection parameters are shown in table 1. Typical chromatogram 4.
TABLE 1 quantitative and qualitative selection of ions for Cooling agent Components
Further, in order to realize quantitative analysis of cooling agent components, in the invention, 7 cooling agent control samples are adopted, mixed standard working solution preparation solutions with six concentration levels of 250, 100, 50, 25, 10 and 1.0 mg/mL are prepared, a 1.0 μ L sample injection is carried out under the preferable chromatographic condition to prepare a working curve, and the cooling agent components entering a chromatographic system are respectively 250, 100, 50, 25, 10 and 1.0 μ g. The response value (chromatographic peak) of the quantitative ions of the cooling agent is taken as the Y value of the ordinate, the concentration of the cooling agent is taken as the X value of the abscissa, and the working curve is shown in Table 2. And the quantitative analysis of the components of the transferable cooling agent can be realized according to the comparison between the chromatographic peak signal of the sample to be detected and the working curve.
TABLE 2 working curves of seven cooling agent components
Compared with the prior art, the invention has the beneficial effects that:
(1) the method comprehensively considers the transfer of cooling agent component compounds in the cigarette filter stick to the cigarette smoke, and overcomes the problems that the total content in the filter stick is mainly measured and the transfer of the cooling agent component compounds to the cigarette smoke is not considered in the traditional filter stick cooling agent component detection method. The method can accurately measure the mobility of the cool component added in the cigarette filter stick to the cigarette smoke, thereby determining the release amount and the release rule of the added cool component.
(2) The device adopted by the invention has simple structure and easy operation. Compared with the direct analysis of cigarette smoke, the interference of the complex background generated by cigarette combustion on the determination of the cooling agent component can be deducted; the whole analysis process is operated on line, so that errors caused by multiple sample transfer in other methods are avoided, and the measurement result of the cooling agent 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) According to the invention, the precise purging tube is adopted, the purging tube is of a ferrule type structure with a sealing ring, the sealing ring can realize sealing between the filter rod and the purging tube wall, and the side edge of purging airflow is prevented from passing (the airflow is 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 polybutadiene coated silica gel 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 cooling agent component compounds, high completeness of adsorption and desorption of components to be detected, and can remarkably 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 detecting 7 cooling agent standards;
wherein 1 is menthone, 2 is isopulegol, 3 is L-menthol, 4 is 2-isopropyl-N, 2, 3-trimethylbutanamide (WS-23), 5 is menthyl lactate, 6 is N-ethyl-p-menthyl-3-carboxamide (WS-3), and 7 is menthone glycerol ketal.
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.
The triethoxyvinylsilane modified silica gel particles adopted by the invention are purchased from Nanjing England New Material technology Limited and are spherical silica gels with the particle size of 100-150 meshes.
Example 1
A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke 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 method comprises the following steps:
step (1), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
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, the flow rate of purge air flow is 17.5 mL/min, and purging is carried out for 8 times.
In the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 200 ℃, the desorption time is 3min, the temperature of a transmission line is 220 ℃, and the temperature of a valve box is 220 ℃.
In the step (2), the gas chromatography conditions were as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
In the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
In the step (2), the method for calculating the mobility in the step (2) is as follows: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, every time a filter stick is swept, a new filter stick is replaced, the filter stick is swept again, and 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 10min by using gas at the temperature of 200 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 5 filter sticks in total, and measuring the total amount of the components of the cooling agent.
The test cigarette filter stick is a conventional cigarette (the cooling agent is added along with the glyceryl triacetate in the process of forming the filter stick), and the specification is 30 mm.
The measurement result shows that: the filter stick contains isopulegol, L-menthol and WS-23, and has total content of 34.2, 221.8 and 155.2µg/cigarette, the simulated release amount to the smoke migration of the cigarette is 5.47, 29.1 and 18.4 respectivelyµg/cigarette, and the simulation measurement results of the migration rate from the filter stick to the cigarette smoke are respectively 16.0 percent, 13.1 percent and 11.9 percent.
Example 2
A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke 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), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
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 17.5 mL/min; purging 8 times.
In the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 240 ℃, the desorption time is 5min, the temperature of a transmission line is 260 ℃, and the temperature of a valve box is 260 ℃.
In the step (2), the gas chromatography conditions were as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
In the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
In the step (2), the method for calculating the mobility in the step (2) is as follows: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, every time a filter stick is swept, a new filter stick is replaced, the filter stick is swept again, and 6 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 15 min by using gas at 180 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 6 filter sticks in total, and measuring the total amount of the components of the cooling agent.
The test cigarette filter stick is a conventional cigarette gel flavor-carrying filter stick with the specification of 30 mm.
The measurement result shows that: the filter stick contains four cool components including menthone, isopulegol, L-menthol and menthyl lactate, and the total content is 55.6, 112.8, 187.4, and 76.3µg/cigarette, the simulated release amount to the smoke migration of the cigarette is respectively 9.62, 17.8, 23.9 and 6.92µg/cigarette, and the results of the simulation determination of the migration rate from the filter stick to the cigarette smoke are respectively 17.3%, 15.8%, 12.8% and 9.1%.
Example 3
A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke is characterized by comprising the following steps:
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), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
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 17.5 mL/min; purging was performed 9 times.
In the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 180 ℃, the desorption time is 2min, the temperature of a transmission line is 240 ℃, and the temperature of a valve box is 250 ℃.
In the step (2), the gas chromatography conditions were as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
In the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
In the step (2), the method for calculating the mobility in the step (2) is as follows: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, every time a filter stick is swept, a new filter stick is replaced, the filter stick is swept again, and 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 8min by using gas at 240 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 5 filter sticks in total, and measuring the total amount of the components of the cooling agent.
The test cigarette filter stick is a conventional cigarette bead blasting filter stick with the specification of 25 mm. And taking the filter stick from the cigarette, pinching the blasting beads, and filling the blasting beads into a purging pipe.
The measurement result shows that: the samples have four cool components of menthone, isopulegol, L-menthol and WS-23 detected, and the total contents are respectively 118.2, 122.6, 202.7 and 63.4µg/cigarette, the simulated release amount to the smoke migration of the cigarette is respectively 16.78, 15.22, 22.35 and 6.27µg/cigarette, the migration rate from the filter stick to the cigarette smoke is respectively 14.2%, 12.4%, 11.0% and 9.9%.
Example 4
A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke 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), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
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, the flow rate of purge air flow is 17.5 mL/min, and purging is carried out for 9 times.
In the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 200 ℃, the desorption time is 3min, the temperature of a transmission line is 240 ℃, and the temperature of a valve box is 240 ℃.
The preparation method of the polybutadiene coated silica gel particles comprises the following steps: adding polybutadiene, a sensitizer and toluene into a beaker, uniformly mixing, adding silica gel particles modified by triethoxyvinylsilane, carrying out ultrasonic oscillation reaction, carrying out rotary evaporation to remove toluene after the reaction is finished, introducing argon into a container filled with a product, carrying out radiation crosslinking after sealing, washing with benzene and acetone in sequence, and drying to obtain the modified silica gel particles;
the mass ratio of polybutadiene, sensitizer and silica gel particles modified by triethoxyvinylsilane is 12: 1.0: 120 of a solvent;
the ratio of the mass of polybutadiene to the volume of toluene was 12 g: 0.8L.
The particle size of the silica gel particles is 100-150 meshes; the ultrasonic oscillation time is 35 min; the mass of benzene and acetone used for washing is 2 times of that of the silica gel particles modified by the triethoxyvinylsilane; the sensitizer is ethylene glycol dimethacrylate.
In the step (2), the gas chromatography conditions were as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
In the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
In the step (2), the method for calculating the mobility in the step (2) is as follows: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, every time a filter stick is swept, a new filter stick is replaced, the filter stick is swept again, and 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 5min by using gas at the temperature of 200 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 5 filter sticks in total, and measuring the total amount of the components of the cooling agent.
The test cigarette filter stick is a conventional cigarette filter stick added with flavor threads, and the specification is 30 mm.
The measurement result shows that: the samples have four cool components of L-menthol, menthyl lactate, WS-3 and menthone glycerol ketal detected, and the total content is 194.6, 208.7, 155.2 and 88.4 respectivelyµg/cigarette, the simulated release amount to the smoke migration of the cigarette is respectively 21.62, 18.92, 15.37 and 7.24µg/cigarette, and the simulation measurement results of the migration rate from the filter stick to the cigarette smoke are respectively 11.1%, 9.1%, 9.9% and 8.2%.
Example 5
A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke is characterized by comprising the following steps:
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), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
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 22.5 mL/min; purging 9 ports.
In the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 190 ℃, the desorption time is 3.2min, the temperature of a transmission line is 250 ℃, and the temperature of a valve box is 250 ℃.
The preparation method of the polybutadiene coated silica gel particles comprises the following steps: adding polybutadiene, a sensitizer and toluene into a beaker, uniformly mixing, adding silica gel particles modified by triethoxyvinylsilane, carrying out ultrasonic oscillation reaction, carrying out rotary evaporation to remove toluene after the reaction is finished, introducing argon into a container filled with a product, carrying out radiation crosslinking after sealing, washing with benzene and acetone in sequence, and drying to obtain the modified silica gel particles;
the mass ratio of polybutadiene, sensitizer and silica gel particles modified by triethoxyvinylsilane is 15: 1.5: 150;
the ratio of the mass of polybutadiene to the volume of toluene was 15 g: 1.2L.
The particle size of the silica gel particles is 100-150 meshes; the drying temperature is 200 ℃, and the drying time is 6 h; the ultrasonic oscillation time is 45 min; the mass of benzene and acetone used for washing is 3 times of that of the silica gel particles modified by the triethoxyvinylsilane; the sensitizer is ethylene glycol dimethacrylate.
In the step (2), the gas chromatography conditions were as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
In the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
In the step (2), the method for calculating the mobility in the step (2) is as follows: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, every time a filter stick is swept, a new filter stick is replaced, the filter stick is swept again, and 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 10min by using gas at 180 ℃, continuously purging by replacing the new filter stick again after purging is finished, purging 5 filter sticks in total, and measuring the total amount of the components of the cooling agent.
The test cigarette filter stick is a fine cigarette bead blasting filter stick with the specification of 35 mm. And taking the filter stick from the cigarette, pinching the blasting beads, and filling the blasting beads into a purging pipe.
The measurement result shows that: the samples were tested for three cool components, namely menthone, isopulegol and L-menthol, and the total contents were 208.4, 155.7 and 122.6 respectivelyµg/cigarette, the simulated release amount to the smoke migration of the cigarette is respectively 28.32, 18.67 and 15.79µg/cigarette, and the simulation measurement results of the migration rate from the filter stick to the cigarette smoke are respectively 13.6 percent, 12.0 percent and 12.9 percent.
Example 6
A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke is characterized by comprising the following steps:
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), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
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 22.5 mL/min; purging was performed 9 times.
In the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 200 ℃, the desorption time is 2.8min, the transmission line temperature is 230 ℃, and the valve box temperature is 230 ℃.
Adding polybutadiene, a sensitizer and toluene into a beaker, uniformly mixing, adding silica gel particles modified by triethoxyvinylsilane, carrying out ultrasonic oscillation reaction, carrying out rotary evaporation to remove toluene after the reaction is finished, introducing argon into a container filled with a product, carrying out radiation crosslinking after sealing, washing with benzene and acetone in sequence, and drying to obtain the modified silica gel particles;
the preparation method of the polybutadiene coated silica gel particles comprises the following steps: adding polybutadiene, a sensitizer and toluene into a beaker, uniformly mixing, adding silica gel particles modified by triethoxyvinylsilane, carrying out ultrasonic oscillation reaction, carrying out rotary evaporation to remove toluene after the reaction is finished, introducing argon into a container filled with a product, carrying out radiation crosslinking after sealing, washing with benzene and acetone in sequence, and drying to obtain the modified silica gel particles;
the mass ratio of polybutadiene, sensitizer and silica gel particles modified by triethoxyvinylsilane is 13: 1.2: 145;
the ratio of the mass of polybutadiene to the volume of toluene was 13 g: 1L of the compound.
The particle size of the silica gel particles is 100-150 meshes; the drying temperature is 200 ℃, and the drying time is 6 h; the ultrasonic oscillation time is 40 min; the mass of benzene and acetone used for washing is 2.3 times and 2.7 times of that of the triethoxyvinylsilane modified silica gel particles respectively; the sensitizer is triethylene glycol dimethacrylate;
in the step (2), the gas chromatography conditions were as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; split ratio20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
In the step (2), the mass spectrum conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
In the step (2), the method for calculating the mobility in the step (2) is as follows: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, every time a filter stick is swept, a new filter stick is replaced, the filter stick is swept again, and 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and replacing a new filter stick by adopting the same device, continuously purging the filter stick for 10min by using 185 ℃ gas, continuously purging by replacing the new filter stick again after purging is finished, purging 5 filter sticks in total, and measuring the total amount of the components of the cooling agent.
The test cigarette filter stick is a medium cigarette bead blasting filter stick with the specification of 25 mm. And taking the filter stick from the cigarette, pinching the blasting beads, and filling the blasting beads into a purging pipe.
The measurement result shows that: the samples were tested for three cool components, namely menthone, isopulegol and L-menthol, and the total contents were 188.4, 257.8 and 208.9 respectivelyµg/cigarette, the simulated release amount to the smoke migration of the cigarette is respectively 26.77, 33.20 and 25.18µg/cigarette, the migration rate from the filter stick to the cigarette smoke is respectively 14.2 percent, 12.9 percent and 12.1 percent.
In addition, in order to accurately measure the total amount of the cooling agent components in the filter stick, the filter stick with 7 artificially added cooling agent components is prepared in the invention, and the adding amount of the 7 components in each cigarette filter stick is 100µg. After the filter stick is placed in the purging tube, purging is carried out for 10min at 180 ℃ continuously, so that the cooling agent component in the filter stick can be completely purged out, and the cooling is measured by the method of example 3The total amount of flavor components, and the results are shown in Table 3. As can be seen from the results in Table 3, the recovery rates of the measurement results of the 7 cooling agent components are all more than 87.2%, which shows that the recovery rate of the total measurement result of the method is high and the result is reliable. Meanwhile, the filter stick containing the 7 cooling agents is artificially prepared to simulate the real smoking and blowing of the cigarette, the blowing mode is as in example 3, the components of the cooling agents are measured by the method of example 1, and the detection results are shown in table 3.
TABLE 3
As can be seen from the results in Table 3, the 7 cooling agent components indeed have migration, and the migration rate is between 7.62 and 15.6 percent; and the mobility has direct correlation with the boiling point of the compound, and the higher the boiling point is, the lower the mobility is, which indicates that the addition of components with low boiling points such as menthone, isopulegol and L-menthol in the filter stick is beneficial to the release to smoke.
The migration amount of the same filter stick is subjected to parallel measurement for 5 times, the Relative Standard Deviation (RSD) is 3.6-4.3%, and the method has good reproducibility and can meet the requirement of accurate measurement of the migration amount of the cooling agent added to the filter stick. The method can accurately measure the mobility of the cooling ingredient added in the cigarette filter stick to the cigarette smoke, thereby determining the release amount and the release rule of the added cooling ingredient, effectively guiding the adding amount and the adding proportion of the cooling in different types of cigarette filter sticks and objectively evaluating the actual effect of the cooling type cigarette filter stick.
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 (10)
1. A simulation determination method for migration of cooling agent components in a cigarette filter stick to cigarette smoke is characterized by comprising the following steps:
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 method comprises the following steps:
step (1), purging with gas flow: 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, the smoking machine is simulated to suck and blow the filter rods, air flow enters a blowing pipe to pass through the filter rods during simulated sucking, and the air flow directly enters the atmosphere during simulated static combustion; meanwhile, the actual number of suction openings of the cigarette is simulated;
step (2), trapping by an adsorption trap, thermal desorption sample injection and gas chromatography-mass spectrometry analysis: the gas passing through the filter stick enters a trap of a dynamic headspace gas chromatography-mass spectrometry instrument for trapping, after trapping is finished, the cooling agent components adsorbed in the trap are desorbed through high-temperature analysis, then the gas enters the gas chromatography-mass spectrometry instrument for detection, and the mobility is calculated;
the cooling agent comprises menthone, isopulegol, L-menthol, 2-isopropyl-N, 2, 3-trimethylbutanamide, menthyl lactate, N-ethyl-p-menthyl-3-carboxamide and menthone glycerol ketal.
2. The method for simulated measurement of the migration of cooling agent components in a cigarette filter stick to cigarette smoke according to claim 1, wherein the airflow preheating chamber is a quartz glass tube, and infrared radiation is used for preheating gas in the tube.
3. The method for the simulated determination of the migration of cooling agent components in a cigarette filter stick to cigarette smoke 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.
4. The method for simulated determination of migration of cooling agent components in a cigarette filter stick to cigarette smoke according to claim 1, wherein in step (1), the filter stick is purged by simulating an ISO standard suction mode, purging is continued for 2 seconds every 1 minute, and the flow rate of purge gas flow is 17.5 mL/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 22.5 mL/min; purging for 8-10 times.
5. The method for simulated measurement of the migration of cooling agent components in the cigarette filter stick to the cigarette smoke according to claim 1, wherein in the step (2), the adsorption material of the trap is polybutadiene coated silica gel particles, the temperature of the trap is-10 ℃, the high-temperature desorption temperature is 180 ℃ minus 240 ℃, the desorption time is 2-5min, the transmission line temperature is 220 ℃ minus 260 ℃, and the valve box temperature is 220 ℃ minus 260 ℃.
6. The method for simulated measurement of migration of cooling agent components in the cigarette filter stick to cigarette smoke according to claim 5, wherein the preparation method of the polybutadiene coated silica gel particles is as follows:
adding polybutadiene, a sensitizer and toluene into a beaker, uniformly mixing, adding silica gel particles modified by triethoxyvinylsilane, carrying out ultrasonic oscillation reaction, carrying out rotary evaporation to remove toluene after the reaction is finished, introducing argon into a container filled with a product, carrying out radiation crosslinking after sealing, washing with benzene and acetone in sequence, and drying to obtain the modified silica gel particles;
the mass ratio of polybutadiene to the sensitizer to the triethoxy vinyl silane modified silica gel particles is 12-15: 1.0-1.5: 120 to 150 parts;
the mass ratio of polybutadiene to the volume of toluene is 12-15 g: 0.8-1.2L.
7. The simulated measurement method for migration of cooling agent components in the cigarette filter stick to cigarette smoke according to claim 6, wherein the particle size of silica gel particles is 100-150 meshes; the drying temperature is 200 ℃, and the drying time is 6 h; the ultrasonic oscillation time is 35-45 min; the mass of benzene and acetone used for washing is 2-3 times that of the triethoxyvinylsilane modified silica gel particles; the sensitizer is ethylene glycol dimethacrylate or triethylene glycol dimethacrylate.
8. The method for simulated measurement of the migration of cooling agent components in a cigarette filter stick to cigarette smoke according to claim 1, wherein in the step (2), the gas chromatography conditions are as follows: the chromatographic column is HP-Innowax elastic quartz capillary column with specification of 30 m × 0.25mm × 0.25μm; the temperature of a sample inlet is 250 ℃; the split ratio is 20: 1; keeping the initial temperature of the column box at 50 ℃ for 1 min, then increasing the temperature to 100 ℃ at 10 ℃/min, then increasing the temperature to 210 ℃ at 5 ℃/min, then increasing the temperature to 240 ℃ at 30 ℃/min, and keeping the temperature for 5 min; the carrier gas was helium with a constant flow of 1.0 mL/min.
9. The method for simulated determination of migration of cooling agent components in a cigarette filter stick to cigarette smoke according to claim 1, wherein in step (2), mass spectrometry conditions are as follows: the temperature of the auxiliary interface is 220 ℃; the ionization mode is an electron bombardment source, the ionization energy is 70eV, the ion source temperature is 230 ℃, the quadrupole rod temperature is 150 ℃, the solvent delay time is 4.0 min, and a selective ion monitoring mode is adopted.
10. The method for simulated measurement of the migration of cooling agent components in a cigarette filter stick to cigarette smoke according to claim 1, wherein in the step (2), the method for calculating the migration rate comprises the following steps: the amount of the simulated actual sucked cooling agent component measured by a gas chromatography-mass spectrometer is divided by the total amount of the cooling agent component to obtain the mobility;
when the measurement of the components of the actually sucked cooling agent is simulated, each filter stick is replaced by a new filter stick after being blown, the filter sticks are blown again, and not less than 5 filter sticks are used in total;
the method for detecting the total amount of the cooling agent components comprises the following steps: and (3) replacing a new filter stick by adopting the same device, continuously purging the filter stick for 8-15 min by using 180-plus-240 ℃ gas, continuously purging by replacing the new filter stick again after purging is finished, purging not less than 5 filter sticks totally, and measuring the total amount of the components of the cooling agent.
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