CN101921364B - Polycationic additive capable of reducing benzo [a] pyrene in cigarette smoke and preparation method thereof - Google Patents
Polycationic additive capable of reducing benzo [a] pyrene in cigarette smoke and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polycationic additive capable of reducing benzo[a]pyrene in cigarette smoke and a preparation method thereof; and the filter tip additive uses porous material as carrier and loads functionalized polycation on the surface of the porous material. The preparation method of the filter tip additive comprises the following steps: completely and uniformly mixing the porous material with water solution of the functionalized polycation; standing by and filtering; and drying the solid material obtained from filter in vacuum environment to obtain the filter tip additive. Compared with the cigarette in same standard on the market, the cigarette composite filter tip can reduce the content of benzo[a]pyrene in cigarette smoke by 19-35%.
Description
Technical field
The present invention relates to reducing cigarette tar and reducing harm reduction technical field, be specifically related to the polycationic additive capable and the preparation method of benzo [a] pyrene in a kind of reduction cigarette smoke.
Background technology
Along with the continuous enhancing of society to smoking and health problem concern, the reducing tar and reducing harm technical study of cigarette product has caused the great attention of tobacco industry.And polycyclic aromatic hydrocarbons is one type of main in the cigarette smoke, that quantity is maximum carcinogens, and wherein the carcinogenic activity with benzo [a] pyrene is the strongest again.Therefore, the content that reduces polycyclic aromatic hydrocarbons such as benzo [a] pyrene in the cigarette smoke has become the important subject in the reducing cigarette tar and reducing harm reduction technical study.Tobacco general bureau of country also will reduce the research target of the content conduct Chinese style reducing cigarette tar and reducing harm reduction at present of 7 kinds of objectionable constituent such as benzo in the cigarette smoke [a] pyrene.
Research shows; Tobacco itself only contains a spot of polycyclic aromatic hydrocarbons, and the polycyclic aromatic hydrocarbons overwhelming majority in the cigarette smoke is in smoking process, to be produced by the free radical reaction of components such as terpenes, plant sterol (like Stigmasterol), wax, sugar, amino acid, Mierocrystalline cellulose through thermo-cracking, elevated temperature heat building-up reactions and various elementary hydrocarbon.Therefore, present many methods all are through in pipe tobacco, adding various additives, and the production process of intervening polycyclic aromatic hydrocarbons reduces the content of polycyclic aromatic hydrocarbons such as benzo in the flue gas [a] pyrene.But these class methods often make the mouthfeel of flue gas be affected, and also can increase the content of other objectionable constituent sometimes.Filter tip has become indispensable part in the low harm cigarette as the bridge of contact smoker and main flume.At present, also there are many reports to disclose in cigarette filter to add various additives to reduce the content of polycyclic aromatic hydrocarbons such as benzo in the flue gas [a] pyrene; The mesoporous molecular sieve of in one Chinese patent application CN200610083014.X, the surface being modified through organo silane coupling agent like the people such as Meng Zhaoyu of Hongta tobacco group is applied to reduce in the cigarette filter content of multiple objectionable constituent such as Polycyclic Aromatic Hydrocarbons in Cigarette Smoke.People such as the Tan Ying of Changsha Cigarette Factory disclose the lauric modified silica-gel of covalent bonding behind a kind of silica gel surface silicon alkanisation in Chinese patent ZL 02114041.3; And with it as cigarette filter-tip additive agent, can effectively reduce the content of benzo in the cigarette smoke [a] pyrene.But in these additives of filter tip of reporting, the author often can only realize the simplification modification of porous material, and can not introduce multiple modification group simultaneously on the surface of porous material.
Summary of the invention
The invention provides a kind of novel functional poly positively charged ion.
The present invention also provide a kind of surface through the cation modified porous material of functional poly as the cigarette filter-tip additive agent that reduces benzo [a] pyrene content in the cigarette smoke.
The present invention also provides the preparation method of the cigarette filter-tip additive agent of benzo [a] pyrene content in a kind of reduction cigarette smoke.
The additives of filter tip of benzo [a] pyrene content in a kind of reduction cigarette smoke, be with the porous material be carrier and in the porous material surface load the cationic material of functional poly.
Described porous material can select for use this area to have the material of vesicular structure; These porous materials itself have certain absorption property or have a certain amount of negative charge; Can be used as the carrier of cationic polyelectrolyte, a kind of as in gac, sepiolite, zeolite, molecular sieve, macroporous adsorbent resin, the silica gel etc.
The functional poly positively charged ion of described functional poly cation chosen covalent bonding flavonoid compound, preferably with the multipolymer shown in the following formula I structural formula:
Formula I
Wherein, x/y=1/50～10/1, x/y is a constitutive molar ratio, x and y are positive integer;
N is 1～4 integer;
R
2A kind of in benzyl, ethyl, butyl, the hexadecyl;
R
1A kind of in four kinds of groups shown in following formula VI, formula VII, formula VIII, the formula IX:
Formula VI formula VII
Formula VII formula IX
The R that is selected for use
1Group is respectively that the primary hydroxyl position (shown in VI, formula VII, formula VIII, formula IX) on the sugar ring is located to lack a Wasserstoffatoms and the group that forms in puerarin, peoniflorin, naringin, icarin.
Described functional poly positively charged ion generally is by covalent bonding R
1Methacrylic polymerisable monomer and covalent bonding R
2The quaternary ammonium salt polymerisable monomer through copolyreaction preparation.Wherein, described covalent bonding R
1The structural formula of methacrylic polymerisable monomer be generally as shown in the formula shown in the II; This type monomer is prepared by existing enzymatic interesterification procedure; The general lypase that adopts is as catalyzer, with in corresponding methacryloxy vinyl fatty ester (shown in the following formula III of structure) and the flavonoid compounds such as commercially available puerarin, icarin, peoniflorin, naringin a kind of 45～55 ℃ down reaction prepared in 12 hours～3 days and got.And wherein said methacryloxy vinyl fatty ester generally be by corresponding hydroxy fatty acid (structure is as shown in the formula shown in the IV) earlier with vinyl acetate at mercuric acetate and sulphuric acid catalysis, neutralized verdigris as reacting under the stopper, obtain product and obtain with the methacrylic chloride prepared in reaction again.
Formula II; Formula III; Formula IV;
Among formula II, formula III and the formula IV, n is 1～4 integer, and has identical implication, the R among the formula II with n among the formula I
1With the R among the formula I
1Has identical implication.
Described covalent bonding R
2The quaternary ammonium salt polymerisable monomer generally be through dimethylaminoethyl methacrylate respectively with benzyl bromine, monobromethane, NBB, bromine n-Hexadecane etc. in a kind of prepared in reaction get, its structural formula is generally shown in the formula V:
Formula V;
Covalent bonding R
2Quaternary ammonium salt polymerisable monomer formula V in R
2With the R among the cationic structural formula formula of the described functional poly I
2Has identical implication.
Described functional poly positively charged ion is according to the preparation of the method for existing radical polymerization, generally adopts Diisopropyl azodicarboxylate as initiator, and initiator joined contains covalent bonding R
1Methacrylic polymerisable monomer and covalent bonding R
2The polymerizing pipe of quaternary ammonium salt polymerisable monomer in, in nitrogen protection in 65～75 ℃ of reaction preparations in 20～24 hours and getting down.
The cationic weight-average molecular weight of described functional poly is preferably 8 * 10
3～2 * 10
5, can reach better effect.
The cationic quality percentage composition of functional poly is preferably 0.01%～5% in the described additives of filter tip, can reach better effect.
The preparation method of the additives of filter tip of benzo [a] pyrene content in the described reduction cigarette smoke comprises:
Porous material and the cationic aqueous solution thorough mixing of functional poly is even, leave standstill after-filtration, the solid matter vacuum-drying with filtration obtains obtains additives of filter tip.
In order to reach better effect, preferably:
The concentration of the cationic aqueous solution of described functional poly is 0.1g/L～10g/L.
Described dwell temperature is 20 ℃～50 ℃, and the time is 30min～1h.
Described vacuum-drying condition is 80 ℃～160 ℃ following vacuum-drying 1h～12h.
The additives of filter tip of benzo [a] pyrene content can be used for preparing cigarette filter in the described reduction cigarette smoke.
Consider that from practicing thrift cost and reaching preferable effect in the cigarette filter of a cigarette, the addition of additives of filter tip is 20mg～80mg in the described cigarette filter.
The specification of cigarette filter of the present invention can be according to the filter tip specification of commercial cigarettes, and the preparation method adopts the conventional preparation method of this area cigarette composite filter tip.
Compared with prior art, the present invention has following advantage:
In the cationic side chain of functional poly of the present invention covalent bonding hydrophobic chain segment such as flavonoid compound such as puerarin and n-hexadecyl.Through at these functional poly positively charged ions of porous material surface load, just can be implemented in porous material surface and introduce flavonoid compound and hydrophobic segment simultaneously.And, through changing required two kinds of monomer (the covalent bonding R of complex functionality polycation
1Methacrylic polymerisable monomer and covalent bonding R
2The quaternary ammonium salt polymerisable monomer) feed ratio, the content of content of flavonoids and hydrophobic chain segment in the functional poly positively charged ion that the present invention can convenient control obtains, thus further regulate and control the composition structure and the character on porous material additive surface.
Compare with the commercial cigarettes of same specification, adopt the cigarette composite filter tip of additives of filter tip preparation of the present invention can make the content of benzo in the cigarette smoke [a] pyrene reduce by 19%～35%, can guarantee that cigarette possesses mouthfeel preferably simultaneously.
Embodiment
Following examples are intended to explain the present invention rather than the present invention are limited.
Embodiment 1
8.0 gram dimethylaminoethyl methacrylates are joined in the round-bottomed flask that contains 10.0 milliliters of benzyl bromines (or a kind of in the monobromethane, NBB, bromine n-Hexadecane) and 20.0 milliliters of acetone, reacted 12 hours down, prepare four kinds of covalent bonding R respectively at 30 ℃
2The quaternary ammonium salt polymerisable monomer.With four kinds of covalent bonding R that make
2The structure of quaternary ammonium salt polymerisable monomer respectively through the infrared spectrum characterization analytical proof.Wherein, the diffuse reflectance infrared spectroscopy fignal center of dimethyl benzyl methylacryoyloxyethyl brometo de amonio is: 3004,1722,1634, and 959cm
-1The diffuse reflectance infrared spectroscopy fignal center of dimethyl ethyl methylacryoyloxyethyl brometo de amonio is: 1720,1634, and 959cm
-1The diffuse reflectance infrared spectroscopy fignal center of dimethylbutyl methylacryoyloxyethyl brometo de amonio is: 1717,1634, and 959cm
-1The diffuse reflectance infrared spectroscopy fignal center of dimethyl-hexadecyl methylacryoyloxyethyl brometo de amonio is: 2918,1721,1634, and 959cm
-1
Through the infrared spectrum characterization analysis, above-mentioned characteristic signal peak appears respectively in prepared quaternary polymerisable monomer, shows that success makes the covalent bonding R of desired structure
2The quaternary ammonium salt polymerisable monomer, its structure is following:
Wherein, R in the dimethyl benzyl methylacryoyloxyethyl brometo de amonio
2Be benzyl; R in the dimethyl ethyl methylacryoyloxyethyl brometo de amonio
2Be ethyl; R in the dimethylbutyl methylacryoyloxyethyl brometo de amonio
2Be butyl; R in the dimethyl-hexadecyl methylacryoyloxyethyl brometo de amonio
2Be hexadecyl.
Embodiment 2
10.0 milliliters of substituted lipid acid of terminal hydroxyl (structural formula is:
n value is respectively 1,2,3 or 4), 120.0 milliliters of vinyl acetates, 2.1 gram mercuric acetates, acetate in minute copper and 0.2 milliliter of vitriol oil are joined in the three-necked flask; Stir down at 50 ℃; Reacted 3 hours, and prepared four kinds of substituted vinyl fatty esters of terminal hydroxyl (structural formula is:
n value is respectively 1,2,3 or 4) respectively.With the product that obtains behind column chromatography purification; Join in the round-bottomed flask that contains 15.0 milliliters of methylene dichloride and 5.0 milliliters of triethylamines; And, stir reaction down 2 hours to wherein dripping 4.9 milliliters of methacrylic chlorides, prepare four kinds of methacryloxy vinyl fatty esters respectively.
The structure of four kinds of methacryloxy vinyl fatty esters that make is confirmed by phenetic analysis such as ir spectras, all had following diffuse reflectance infrared spectroscopy peak: 1755,1730,1645cm
-1Show that success makes four kinds of methacryloxy vinyl fatty esters of following structural formula; The n value is respectively 1,2,3 or 4, and the compound of corresponding n value is respectively methacryloxypropioniacid acid vinyl acetate (n=1), methacryloxy vinyl butyrate (n=2), methacryloxy valeric acid vinyl acetate (n=3) or methacryloxy vinyl caproate (n=4):
Embodiment 3
(structural formula is:
n=1) and available from the 4.2 gram puerarins of Nanjing Zelang Pharmaceutical Technology Inc. join in the Erlenmeyer flask that contains 0.5 gram lypase CAL-B, at 50 ℃ of reaction preparation in 12 hours methacryloxypropioniacid acid puerarin esters down with 7.4 gram methacryloxypropioniacid acid vinyl acetate of preparation among the embodiment 2.The structure of preparation product is confirmed through the infrared spectrum characterization analysis.
Through the infrared spectrum characterization analysis, the diffuse reflectance infrared spectroscopy peak of methacryloxypropioniacid acid puerarin ester appears in prepared product: 3381,1725,1632,1591,1178, and 1011cm
-1Show that success makes methacryloxypropioniacid acid puerarin ester, its structure is:
R wherein
1Structure following:
0.132 gram initiator Diisopropyl azodicarboxylate being joined 12.4 of preparation among the 0.6 gram methacryloxypropioniacid acid puerarin ester that contains above-mentioned preparation and the embodiment 1 restrains in the polymerizing pipe of dimethyl benzyl methylacryoyloxyethyl brometo de amonios (structural formula is:
); In nitrogen protection, 70 ℃ are reacted 24 hours preparation functional poly positively charged ions down.
The structure of the above-mentioned polycation that obtains confirms that through phenetic analysis such as ir spectras its diffuse reflectance infrared spectroscopy peak is: 3382,1728, and 1149cm
-1Show and have following structure:
Wherein, n=1, x/y=1/50, x/y are corresponding methacryloxypropioniacid acid puerarin ester structure unit and the constitutive molar ratio of corresponding dimethyl benzyl methylacryoyloxyethyl brometo de amonio structural unit, R
1Be in the present embodiment R in the methacryloxypropioniacid acid puerarin ester structure formula
1Structure, R
2Be benzyl; The cationic weight-average molecular weight of functional poly of preparation is 2 * 10
5
With the porous material gac is carrier; Under agitation thorough mixing is even with the cationic aqueous solution of functional poly of gac and the above-mentioned preparation of 10mg/mL; And under 50 ℃, leave standstill the 45min after-filtration; The solid matter that filtration is obtained obtains required additives of filter tip at 80 ℃ of following vacuum-drying 12h.Wherein, the cationic quality percentage composition of the functional poly of load is 5% in the additive.Current potential through Zeta potential analysis-e/or determining matrix material is+25mv to confirm that thus additives of filter tip is the material that functionalization polycation layer is arranged in the activated carbon surface load.
This additive is applied in the cigarette filter, makes the cigarette sample that contains above-mentioned additives of filter tip in the cigarette filter by the conventional preparation method of cigarette, as the sample cigarette, the addition of above-mentioned additives of filter tip is 40mg in the cigarette filter of every cigarette.As the contrast cigarette, the material of its cigarette filter is a cellulose acetate with the sharp crowd of the commercial cigarettes new edition of same specification.Adopt the orthoscopic smoking machine to carry out the cigarette smoking experiment, the suction capacity is 35.0 milliliters, and suction time is 2 seconds, and suction is spaced apart 58 seconds.Through the content of benzo [a] pyrene in the gas chromatography mass spectrometry detection by quantitative cigarette smoke, the reduced rate of benzo [a] pyrene is D (%)=(S by formula
Contrast-S
Sample)/S
Contrast* 100% calculates, and wherein D is a reduced rate, S
SampleFor the cigarette sample that contains additive is the content of benzo [a] pyrene of sample cigarette, S
ContrastThe content of benzo [a] pyrene for the contrast cigarette sample.The result is as shown in table 1, and the content that records benzo [a] pyrene in the sample cigarette flue gas that contains this additive according to present method reduces knows clearly 24%, and mouthfeel is better.
Table 1 additives of filter tip is to the reduction effect of benzo in the cigarette smoke [a] pyrene content
| The contrast cigarette | The sample cigarette | Reduced rate | |
| Benzo [a] pyrene content | 7.73ng/ | 5.87ng/ | 24％ |
Embodiment 4
(structural formula is:
n=2) and available from the 6.8 gram icarin of Nanjing Zelang Pharmaceutical Technology Inc. join in the Erlenmeyer flask that contains 0.5 gram lypase CAL-B, at 50 ℃ of reaction preparation in 3 days methacryloxy butyric acid icarin esters down with 7.9 gram methacryloxy vinyl butyrates of preparation among the embodiment 2.The structure of preparation product is confirmed through the infrared spectrum characterization analysis.
Through the infrared spectrum characterization analysis, the diffuse reflectance infrared spectroscopy peak of methacryloxy butyric acid icarin ester appears in prepared product: 3358,1725,1640, and 1184cm
-1Show that success makes methacryloxy butyric acid icarin ester, its structure is:
R wherein
1Structure following:
0.089 gram initiator Diisopropyl azodicarboxylate being joined 0.186 of preparation among the 8.4 gram methacryloxy butyric acid icarin esters that contain above-mentioned preparation and the embodiment 1 restrains in the polymerizing pipe of dimethyl ethyl methylacryoyloxyethyl brometo de amonio (structural formula is:
); In nitrogen protection, 70 ℃ are reacted 24 hours preparation functional poly positively charged ions down.
The structure of the above-mentioned polycation that obtains confirms that through phenetic analysis such as ir spectras its diffuse reflectance infrared spectroscopy peak is: 3413,1731, and 1184cm
-1Show and have following structure:
Wherein, n=2, x/y=10/1, x/y are corresponding methacryloxy butyric acid icarin ester structure unit and the constitutive molar ratio of corresponding dimethyl ethyl methylacryoyloxyethyl brometo de amonio structural unit, R
1Be in the present embodiment R in the methacryloxy butyric acid icarin ester structure formula
1Structure, R
2Be ethyl; The cationic weight-average molecular weight of functional poly of preparation is 8 * 10
3
With the porous material sepiolite is carrier; Under agitation thorough mixing is even with the cationic aqueous solution of functional poly of sepiolite and the above-mentioned preparation of 0.1mg/mL; And under 20 ℃, leaving standstill the 1h after-filtration, the solid matter that filtration is obtained obtains required additive at 100 ℃ of following vacuum-drying 8h.Wherein, the cationic content of the functional poly of additive area load is about 0.01%.Current potential through Zeta potential analysis-e/or determining matrix material is+5mv to confirm that thus additives of filter tip is the material that functionalization polycation layer is arranged in the sepiolite surface-assembled.
This additive is applied in the cigarette filter, makes the cigarette sample that contains above-mentioned additives of filter tip in the cigarette filter by the conventional preparation method of cigarette, as the sample cigarette, the addition of above-mentioned additives of filter tip is 20mg in the cigarette filter of every cigarette.As the contrast cigarette, the material of its cigarette filter is a cellulose acetate with the sharp crowd of the commercial cigarettes new edition of same specification.
The detection method of content of benzo in the cigarette smoke [a] pyrene is with embodiment 3.The result is as shown in table 2, and the content that records benzo [a] pyrene in the sample cigarette flue gas that contains this additive according to present method has reduced by 19%, and mouthfeel is better.
Table 2 additives of filter tip is to the reduction effect of benzo in the cigarette smoke [a] pyrene content
| The contrast cigarette | The sample cigarette | Reduced rate | |
| Benzo [a] pyrene content | 7.72ng/ | 6.25ng/ | 19％ |
Embodiment 5
(structural formula is:
n=3) and available from the 4.7 gram peoniflorins of Nanjing Zelang Pharmaceutical Technology Inc. join in the Erlenmeyer flask that contains 0.5 gram lypase CAL-B, at 50 ℃ of reaction preparation in 3 days methacryloxy valeric acid peoniflorin esters down with 8.5 gram methacryloxy valeric acid vinyl acetate of preparation among the embodiment 2.The infrared spectrum characterization analysis of passing through of preparation product is confirmed.
Through the infrared spectrum characterization analysis, the diffuse reflectance infrared spectroscopy peak of methacryloxy valeric acid peoniflorin ester appears in prepared product: 3358,1725,1640, and 1184cm
-1Show that success makes methacryloxy valeric acid peoniflorin ester, its structure is:
R wherein
1Structure following:
0.049 gram initiator Diisopropyl azodicarboxylate being joined 4.2 of preparation among the 0.6 gram methacryloxy valeric acid peoniflorin ester that contains above-mentioned preparation and the embodiment 1 restrains in the polymerizing pipe of dimethylbutyl methylacryoyloxyethyl brometo de amonios (structural formula is:
); In nitrogen protection, 70 ℃ are reacted 24 hours preparation functional poly positively charged ions down.
The structure of the above-mentioned polycation that obtains confirms that through phenetic analysis such as ir spectras its diffuse reflectance infrared spectroscopy peak is: 3378,1729, and 1456cm
-1Show and have following structure:
Wherein, n=3, x/y=1/20, x/y are corresponding methacryloxy valeric acid peoniflorin ester structure unit and the constitutive molar ratio of corresponding dimethylbutyl methylacryoyloxyethyl brometo de amonio structural unit; R
1Be in the present embodiment R in the methacryloxy valeric acid peoniflorin ester structure formula
1Structure, R
2Be butyl; The cationic weight-average molecular weight of functional poly of preparation is 1.1 * 10
5
With the porous material zeolite is carrier; Under agitation thorough mixing is even with the cationic aqueous solution of functional poly of zeolite and the above-mentioned preparation of 5mg/mL; And under 30 ℃, leaving standstill the 30min after-filtration, the solid matter that filtration is obtained obtains required additive at 160 ℃ of following vacuum-drying 1h.Wherein, the cationic content of the functional poly of additive area load is about 1%.Current potential through Zeta potential analysis-e/or determining matrix material is+17mv to confirm that thus additives of filter tip is the material that is assembled with the functional poly cationic layer at zeolite surface.
This additive is applied in the cigarette filter, makes the cigarette sample that contains above-mentioned additives of filter tip in the cigarette filter by the conventional preparation method of cigarette, as the sample cigarette, the addition of above-mentioned additives of filter tip is 60mg in the cigarette filter of every cigarette.As the contrast cigarette, the material of its cigarette filter is a cellulose acetate with the sharp crowd of the commercial cigarettes new edition of same specification.
The detection method of content of benzo in the cigarette smoke [a] pyrene is with embodiment 3.The result is as shown in table 3, and the content that records benzo [a] pyrene in the sample cigarette flue gas that contains this additive according to present method has reduced by 27%, and mouthfeel is better.
Table 3 additives of filter tip is to the reduction effect of benzo in the cigarette smoke [a] pyrene content
| The contrast cigarette | The sample cigarette | Reduced rate | |
| Benzo [a] pyrene content | 7.72ng/ | 5.31ng/ | 27％ |
Embodiment 6
(structural formula is:
n=4) and available from the 5.8 gram naringins of Nanjing Zelang Pharmaceutical Technology Inc. join in the Erlenmeyer flask that contains 0.5 gram lypase CAL-B, at 50 ℃ of reaction preparation in 2 days methacryloxy caproic acid naringin esters down with 9.1 gram methacryloxy vinyl caproates of preparation among the embodiment 2.The product structure of preparation is confirmed through the infrared spectrum characterization analysis.
Through the infrared spectrum characterization analysis, the diffuse reflectance infrared spectroscopy peak of methacryloxy caproic acid naringin ester appears in prepared product: 3342,1641,1179, and 1014cm
-1Show that success makes methacryloxy caproic acid naringin ester, its structure is:
R wherein
1Structure following:
0.046 gram initiator Diisopropyl azodicarboxylate being joined 3.8 of preparation among the 0.8 gram methacryloxy caproic acid naringin ester that contains above-mentioned preparation and the embodiment 1 restrains in the polymerizing pipe of dimethyl-hexadecyl methylacryoyloxyethyl brometo de amonios
; In nitrogen protection, 70 ℃ are reacted 24 hours preparation functional poly positively charged ions down.
The structure of the above-mentioned polycation that obtains confirms that through phenetic analysis such as ir spectras its diffuse reflectance infrared spectroscopy peak is: 3381,2923,1730, and 1180cm
-1Show and have following structure:
Wherein, n=4, x/y=1/10, x/y are corresponding methacryloxy caproic acid naringin ester structure unit and the constitutive molar ratio of corresponding dimethyl-hexadecyl methylacryoyloxyethyl brometo de amonio structural unit; R
1Be in the present embodiment R in the methacryloxy caproic acid naringin ester structure formula
1Structure, R
2Be hexadecyl; The cationic weight-average molecular weight of functional poly of preparation is 3 * 10
4
With the porous material molecular sieve is carrier; Under agitation thorough mixing is even with the cationic aqueous solution of functional poly of molecular sieve and the above-mentioned preparation of 1mg/mL; And under 25 ℃, leaving standstill the 50min after-filtration, the solid matter that filtration is obtained obtains required additive at 150 ℃ of following vacuum-drying 4h.Wherein, the cationic content of the functional poly of additive area load is about 0.5%.Current potential through Zeta potential analysis-e/or determining matrix material is+15mv to confirm that thus additives of filter tip is the material that functionalization polycation layer is arranged in the molecular sieve surface-assembled.
This additive is applied in the cigarette filter, makes the cigarette sample that contains above-mentioned additives of filter tip in the cigarette filter by the conventional preparation method of cigarette, as the sample cigarette, the addition of above-mentioned additives of filter tip is 80mg in the cigarette filter of every cigarette.As the contrast cigarette, the material of its cigarette filter is a cellulose acetate with the sharp crowd of the commercial cigarettes new edition of same specification.
The detection method of content of benzo in the cigarette smoke [a] pyrene is with embodiment 3.The result is as shown in table 4, and the content that records benzo [a] pyrene in the sample cigarette flue gas that contains this additive according to present method has reduced by 35%, and mouthfeel is better.
Table 4 additives of filter tip is to the reduction effect of benzo in the cigarette smoke [a] pyrene content
| The contrast cigarette | The sample cigarette | Reduced rate | |
| Benzo [a] pyrene content | 7.72ng/ | 5.02ng/ | 35％ |
Embodiment 7
0.094 gram initiator Diisopropyl azodicarboxylate being joined 3.8 of preparation among the 5.6 gram methacryloxypropioniacid acid puerarin esters that contain preparation among the embodiment 3 and the embodiment 1 restrains in the polymerizing pipe of dimethyl-hexadecyl methylacryoyloxyethyl brometo de amonios (structural formula is:
); In nitrogen protection, 70 ℃ are reacted 24 hours preparation functional poly positively charged ions down.
The structure of the above-mentioned polycation that obtains confirms that through phenetic analysis such as ir spectras its diffuse reflectance infrared spectroscopy peak is: 3385,2923,1730, and 1178cm
-1Show and have following structure:
Wherein, n=1, x/y=1/1, x/y are corresponding methacryloxypropioniacid acid puerarin ester structure unit and the constitutive molar ratio of corresponding dimethyl-hexadecyl methylacryoyloxyethyl brometo de amonio structural unit; R
1Be in the present embodiment R in the methacryloxypropioniacid acid puerarin ester structure formula
1Structure, R
2Be hexadecyl; The cationic weight-average molecular weight of functional poly of preparation is 2 * 10
4
With the porous material macroporous adsorbent resin is carrier; Under agitation thorough mixing is even with the cationic aqueous solution of functional poly of macroporous adsorbent resin and the above-mentioned preparation of 0.5mg/mL; And under 40 ℃, leave standstill the 40min after-filtration; The solid matter that filtration is obtained obtains required additive at 110 ℃ of following vacuum-drying 6h.Wherein, the cationic content of the functional poly of additive area load is about 0.1%.Current potential through Zeta potential analysis-e/or determining matrix material is+11mv to confirm that thus additives of filter tip is the material that functionalization polycation layer is arranged in the macroporous adsorbent resin surface-assembled.
This additive is applied in the cigarette filter, makes the cigarette sample that contains above-mentioned additives of filter tip in the cigarette filter by the conventional preparation method of cigarette, as the sample cigarette, the addition of above-mentioned additives of filter tip is 50mg in the cigarette filter of every cigarette.As the contrast cigarette, the material of its cigarette filter is a cellulose acetate with the sharp crowd of the commercial cigarettes new edition of same specification.
The detection method of content of benzo in the cigarette smoke [a] pyrene is with embodiment 3.The result is as shown in table 5, and the content that records benzo [a] pyrene in the sample cigarette flue gas that contains this additive according to present method has reduced by 32%, and mouthfeel is better.
Table 5 additives of filter tip is to the reduction effect of benzo in the cigarette smoke [a] pyrene content
| The contrast cigarette | The sample cigarette | Reduced rate | |
| Benzo [a] pyrene content | 7.72ng/ | 5.25ng/ | 32％ |
Embodiment 8
0.041 gram initiator Diisopropyl azodicarboxylate being joined 2.4 of preparation among the 1.7 gram methacryloxy butyric acid icarin esters that contain preparation among the embodiment 4 and the embodiment 1 restrains in the polymerizing pipe of dimethyl benzyl methylacryoyloxyethyl brometo de amonios (structural formula is:
); In nitrogen protection, 70 ℃ are reacted 24 hours preparation functional poly positively charged ions down.
The structure of the above-mentioned polycation that obtains confirms that through phenetic analysis such as ir spectras its diffuse reflectance infrared spectroscopy peak is: 3412,1728, and 1180cm
-1Show and have following structure:
Wherein, n=2, x/y=1/5, x/y are corresponding methacryloxy butyric acid icarin ester structure unit and the constitutive molar ratio of corresponding dimethyl benzyl methylacryoyloxyethyl brometo de amonio structural unit; R
1Be in the present embodiment R in the methacryloxy butyric acid icarin ester structure formula
1Structure, R
2Be benzyl; The cationic weight-average molecular weight of functional poly of preparation is 1 * 10
4
With porous material silica gel is carrier; Under agitation thorough mixing is even with the cationic aqueous solution of functional poly of silica gel and the above-mentioned preparation of 0.2mg/mL; And under 35 ℃, leaving standstill the 45min after-filtration, the solid matter that filtration is obtained obtains required additive at 120 ℃ of following vacuum-drying 2h.Wherein, the cationic content of the functional poly of additive area load is about 0.05%.Current potential through Zeta potential analysis-e/or determining matrix material is+10mv to confirm that thus additives of filter tip is the material that functionalization polycation layer is arranged in the silica gel surface-assembled.
This additive is applied in the cigarette filter, makes the cigarette sample that contains above-mentioned additives of filter tip in the cigarette filter by the conventional preparation method of cigarette, as the sample cigarette, the addition of above-mentioned additives of filter tip is 30mg in the cigarette filter of every cigarette.As the contrast cigarette, the material of its cigarette filter is a cellulose acetate with the sharp crowd of the commercial cigarettes new edition of same specification.
The detection method of content of benzo in the cigarette smoke [a] pyrene is with embodiment 3.The result is as shown in table 6, and the content that records benzo [a] pyrene in the sample cigarette flue gas that contains this additive according to present method has reduced by 22%, and mouthfeel is better.
Table 6 additives of filter tip is to the reduction effect of benzo in the cigarette smoke [a] pyrene content
| The contrast cigarette | The sample cigarette | Reduced rate | |
| Benzo [a] pyrene content | 7.72ng/ | 6.02ng/ | 22％ |
Claims (9)
1. functional poly positively charged ion, for the multipolymer shown in the following formula I structural formula:
Formula I
Wherein, x/y=1/50～10/1, x/y is a constitutive molar ratio, x and y are positive integer;
N is 1～4 integer;
R
2A kind of in benzyl, ethyl, butyl, the hexadecyl;
R
1A kind of in four kinds of groups shown in following formula VI, formula VII, formula VIII, the formula IX:
Formula VI formula VII
Formula VIII formula IX.
2. an additives of filter tip that reduces benzo [a] pyrene content in the cigarette smoke is characterized in that, described additives of filter tip be with the porous material be carrier and in the porous material surface load the cationic material of functional poly;
Described functional poly positively charged ion is with the multipolymer shown in the following formula I structural formula:
Formula I
Wherein, x/y=1/50～10/1, x/y is a constitutive molar ratio, x and y are positive integer;
N is 1～4 integer;
R
2A kind of in benzyl, ethyl, butyl, the hexadecyl;
R
1A kind of in four kinds of groups shown in following formula VI, formula VII, formula VIII, the formula IX:
Formula VI formula VII
Formula VIII formula IX;
Described porous material is a kind of in gac, sepiolite, zeolite, molecular sieve, macroporous adsorbent resin, the silica gel.
3. the additives of filter tip of benzo [a] pyrene content is characterized in that the cationic weight-average molecular weight of described functional poly is 8 * 10 in the reduction cigarette smoke according to claim 2
3～2 * 10
5
4. the additives of filter tip of benzo [a] pyrene content is characterized in that in the reduction cigarette smoke according to claim 2, and the cationic quality percentage composition of functional poly is 0.01%～5% in the described additives of filter tip.
5. according to the preparation method of the additives of filter tip of benzo [a] pyrene content in each described reduction cigarette smoke of claim 2～4, comprising:
Porous material and the cationic aqueous solution thorough mixing of functional poly is even, leave standstill after-filtration, the solid matter vacuum-drying with filtration obtains obtains additives of filter tip.
6. the preparation method of the additives of filter tip of benzo [a] pyrene content is characterized in that the concentration of the cationic aqueous solution of described functional poly is 0.1g/L～10g/L in the reduction cigarette smoke according to claim 5.
7. the preparation method of the additives of filter tip of benzo [a] pyrene content in the reduction cigarette smoke according to claim 5, it is characterized in that: described dwell temperature is 20 ℃～50 ℃, and the time is 30min～1h;
Described vacuum-drying condition is 80 ℃～160 ℃ following vacuum-drying 1h～12h.
8. according to the application in the preparation cigarette filter of the additives of filter tip of benzo [a] pyrene content in each described reduction cigarette smoke of claim 2～4.
9. application according to claim 8 is characterized in that, in the cigarette filter of a cigarette, the addition of additives of filter tip is 20mg～80mg in the described cigarette filter.
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| CN2010102788340A CN101921364B (en) | 2010-09-10 | 2010-09-10 | Polycationic additive capable of reducing benzo [a] pyrene in cigarette smoke and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674961A (en) * | 1996-04-12 | 1997-10-07 | E. I. Du Pont De Nemours And Company | Oil water and solvent resistant paper by treatment with fluorochemical copolymers |
| CN101664228A (en) * | 2009-09-24 | 2010-03-10 | 湖南中烟工业有限责任公司 | Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof |
| CN101692934A (en) * | 2009-10-22 | 2010-04-14 | 湖南中烟工业有限责任公司 | Additive for lowering harmful constituents in cigarette flue gas and cigarette thereof |
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2010
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5674961A (en) * | 1996-04-12 | 1997-10-07 | E. I. Du Pont De Nemours And Company | Oil water and solvent resistant paper by treatment with fluorochemical copolymers |
| CN101664228A (en) * | 2009-09-24 | 2010-03-10 | 湖南中烟工业有限责任公司 | Calixarene additive capable of simultaneously and optionally reducing benzo (alpha) pyrene and phenol contents in cigarette smoke and application method thereof |
| CN101692934A (en) * | 2009-10-22 | 2010-04-14 | 湖南中烟工业有限责任公司 | Additive for lowering harmful constituents in cigarette flue gas and cigarette thereof |
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