CN102002888A - Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof - Google Patents
Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof Download PDFInfo
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- CN102002888A CN102002888A CN 201010283643 CN201010283643A CN102002888A CN 102002888 A CN102002888 A CN 102002888A CN 201010283643 CN201010283643 CN 201010283643 CN 201010283643 A CN201010283643 A CN 201010283643A CN 102002888 A CN102002888 A CN 102002888A
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Abstract
The invention provides cellulose paper capable of reducing the benzo(a)pyrene content of the smoke of cigarettes, which carries deionized liquid and, when used in acetate fiber filter tips, can reduce the benzo(a)pyrene content of the smoke of the cigarettes considerably, thereby reducing the harm caused to smokers without influencing the mouthfeel of the cigarettes. The additive of the cellulose paper can be prepared by a simple technique and added conveniently. The paper meets the requirement on industrial production.
Description
Technical field
The invention belongs to technical field of cigarette preparation, be specifically related to cellulose paper, preparation method and the application thereof of benzo [a] pyrene content in a kind of reduction cigarette smoke.
Background technology
Be subjected to the influence of the World Health Organization and anti-smoking campaign, the contradiction between smoking and the health becomes increasingly conspicuous.Cigarette burning is the reaction of a complexity, and 1987, people such as Hoffmann reported the content of 5 kinds of snuffs of U.S. benzo [a] pyrenes on dry basis.It is considered to the high activity carcinogen, and ultimate carcinogen has four kinds of isomers, and it and DNA form covalent bonds, cause dna damage, and not multiple if DNA can not repair or repair, cell just canceration may take place.Other three kinds of isomers also have carcinogenesis.Animal experiment comprises per os, through skin, suction, through the peritonaeum hypodermic injection, all occur carcinogenic.Many countries experimentize with 9 kinds of animals in succession, adopt multiple method of administration, and the result obtains bringing out the positive report of cancer.In polycyclic aromatic hydrocarbon, the BaP pollution is the widest, carcinogenic is the strongest.And may influence the mouthfeel of cigarette, cause that astringent taste, pungent and pleasant impression are clean or the like.Therefore, adopt effective harm reduction means, optionally reducing the loss that at utmost reduces flavor component in the cigarette smoke in the cigarette smoke in the harmful components, significantly improve the security of sucking of cigarette, be to be related to the future of tobacco business and the important topic of development, have crucial meaning.
At present, reduce both at home and abroad that the research method of harmful components mainly comprises in the cigarette: dilution method, adsorption filtration method and catalytic oxidation.Filter tip ventilation dilution method is the at present external a kind of reducing tar and reducing harm technology that extensively adopts, but it is bigger to the influence of cigarette flavor amount, and acceptance level is lower at home, has certain difficulty in the development of Chinese style cigarette with in using.
The adsorption filtration method is studied more extensive at home and abroad, and adsorbent commonly used mainly contains active carbon, carbon molecular sieve, carbonized polymers, polymer absorbant, silica gel, activated alumina, clay and zeolite and hemoglobin etc.People such as Zhou Jun write articles and point out at " Chinese tobacco association academic nd Annual Meeting collection in 2006 ": the composite filter of modified Nano material is produced nanometer 3mg Zhongnanhai cigarette, the total amount selectivity reduction rate of harmful peculiar N-nitrosamine of tobacco is 53.5% in its flue gas, the total amount selectivity reduction rate of harmful condensed-nuclei aromatics is 67.20%, aromatic amine total amount selectivity reduction rate is 52.5%, carbonyls selectivity reduction rate is 39.2%, and phenolic compound selectivity reduction rate is 34.6%.Applying nano Fe in the United States Patent (USP) 20040025895
2O
3Deng harmful components such as oxynitrides, carbon monoxide, hydrogen cyanide, a-BaP, nitrosamine, phenols, acetaldehyde and benzene in the reduction cigarette smoke.People such as Li Shaoming point out in the specialist paper of " tobacco production in 2003 and health and environmental protection coordinated development seminar and China and foreign countries' tobacco environmental protection science and technology exhibition rules, specialist paper and collection of thesis ": add in the cigarette filter after Y zeolite is carried out modification; make benzo [a] pyrene that the reduction of certain amplitude be arranged, can also reduce other harmful substances in the cigarette simultaneously.
Above technology can reduce tar and other harmful substance simultaneously by stopping and adsorbing of solid matter, its effect is not so obvious as report on the low-coke tar cigarette but be applied in, the reduction amplitude of tar will be higher than harmful substance and reduce amplitude, and can not reach the requirement that high selectivity reduces the cigarette smoke harmful components.
Summary of the invention
Purpose of the present invention aims to provide the cellulose paper of benzo [a] pyrene content in a kind of reduction cigarette smoke, and this cellulose paper can high selectivity reduce benzo [a] pyrene content in the cigarette smoke, does not influence the cigarette mouthfeel when minimizing works the mischief to the smoker.
The present invention is ion liquid cellulose paper for load has, wherein:
Described ionic liquid is made up of organic cation and inorganic anion, and organic cation is a kind of in the imidazol ion that replaces of alkyl, the quaternary ammonium alkyl ion, and inorganic anion is Cl
-, Br
-, SO
4 2-, PO
4 3-, NO
3 -, AlCl
4 -, [PF
6]
-, [BF
4]
-, FeClx
-In a kind of.
Imidazol ion, the alkyl substituent in the quaternary ammonium alkyl ion or the alkyl that described alkyl replaces is a kind of in 1,2,3,4,5, the 6 carbon alkyl.
Ionic liquid accounts for 0.2%～5% of cellulose paper quality.
Another object of the present invention aims to provide the preparation method who reduces the additive of benzo [a] pyrene in the cigarette smoke.
Because the present invention is ion liquid cellulose paper for load has, its ion liquid carrying method has following a kind of: prepared ion liquid dissolving in water or ethanol, is coated on ionic liquid solution cellulose paper surface, online drying then.
Preferably dry down at 70 ℃-105 ℃.
The mass percent concentration of the ionic liquid solution that is made into is 5% to 20%.
The present invention can also modify ion liquid CATION, adds coupling group, and the plain paper surface group of coupling group and carrier fibre reacts and ionic liquid is fixed in carrier surface.Like this, coupling group can be short and rapid with the carrier surface radical reaction time, connects stable.Described coupling group is preferably triethoxysilane or trimethoxy silane.
The 3rd purpose of the present invention aims to provide the application mode of described cellulose paper.
Described application mode is: load is had the shaping paper of ion liquid cellulose paper as cigarette filter tip.This cellulose paper can high selectivity reduce benzo [a] pyrene content in the cigarette smoke, does not influence the cigarette mouthfeel when minimizing works the mischief to the smoker.
Compared with prior art, the present invention has following advantage:
1) the present invention is immobilized to cellulose paper with ionic liquid dexterously, make benzo [a] pyrene and ionic liquid anion or cationoid reaction in the flue gas, thereby the selectivity that realizes component-benzo [a] pyrene reduces, and content of material such as tar, CO, nitrosamines are not had influence basically, in minimizing the harm that the smoker causes is not influenced the cigarette mouthfeel simultaneously.
2) compare with traditional solid adsorption material, the present invention has widened the sorbing material scope.
3) carrier required for the present invention is cellulose paper, does not need other processing, can directly be used as the shaping paper in the cigarette.
4) additive technology of preparing of the present invention is simple, adds convenience and is suitable for industrial production requirement.
The specific embodiment
Following examples are intended to more specifically describe the present invention rather than limitation of the invention further.
Embodiment 1:
N-methylimidazole, chloro-normal butane and toluene are added in the there-necked flask successively, add thermal agitation and react.After reaction finished, washing, recrystallization, products therefrom were dry in vacuum drying chamber.Obtain chloro 1-butyl-3-methylimidazole (BMIC).With AlCl
3Slowly add in proportion among the BMIC, in dried case, stirred 20 hours.In order to prevent AlCl
3Decompose, be reflected in the inert atmosphere and carry out.Synthesize 1-butyl 3-methylimidazole chloro-aluminate ([BMIM]-AlCl
4), with ethanol is solvent, be made into mass fraction and be 12% solution, utilize existing coating process, the load capacity by 5% is applied on the cellulose paper, 85 ℃ of online dryings, this cellulose paper is prepared into the mouth rod as shaping paper and tow, and cigarette becomes cigarette, and this mouth rod is respectively 0,0.5%, 38.2% to tar, CO, benzo [a] pyrene clearance.The sample cigarette does not change the suction mouthfeel basically through smokeing panel test.
Embodiment 2:
With the hydrochloride of 1-ethyl (triethoxy is silica-based)-3-ethyl imidazol(e) of preparation is solvent with water, be made into mass fraction and be 20% mixed solution, utilize existing coating process, load capacity by 5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 0,2%, 20.2% to tar, CO, benzo [a] pyrene clearance.
Embodiment 3:
Get the salt compounded of iodine of 1-ethyl (triethoxy is silica-based)-3-ethyl imidazol(e), add FeCl
3Stir, in dried case, stir 24h.With ethanol is solvent, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 0.07%, 7.2%, 41.9% to tar, CO, benzo [a] pyrene clearance.
Embodiment 4:
Get the salt compounded of iodine of 1-ethyl (triethoxy is silica-based)-3-methylimidazole, add FeCl
3Stir, in dried case, stir 24h.With ethanol is solvent, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 0,1.8%, 40.6% to tar, CO, benzo [a] pyrene clearance.
Embodiment 5:
Get the salt compounded of iodine of 1-ethyl (triethoxy is silica-based)-3-methylimidazole, add FeCl
3Stir, in dried case, stir 24h.With ethanol is solvent, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 2%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 0.5%, 2%, 21.4% to tar, CO, benzo [a] pyrene clearance.
Embodiment 6:
Get the salt compounded of iodine of 1-ethyl (triethoxy is silica-based)-3-methylimidazole, add FeCl
3Stir, in dried case, stir 24h.Load capacity by 0.5% slowly is added drop-wise to it on cellulose paper, and excessive ionic liquid carries out extracting with carrene in apparatus,Soxhlet's, and vacuumize is 24 hours under the catalyst normal temperature after the extracting, preserves in inert atmosphere.Utilize existing coating process, the load capacity by 0.2% is applied on the cellulose paper, 85 ℃ of online dryings, this cellulose paper is prepared into the mouth rod as shaping paper and tow, and cigarette becomes cigarette, and this mouth rod is respectively 0.5%, 2%, 11.0% to tar, CO, benzo [a] pyrene clearance.
Embodiment 7:
It is solvent that 1-ethyl (trimethoxy the is silica-based)-3-methylimidazole for preparing is added to ethanol, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 7.5%, 0,38.2% to tar, CO, benzo [a] pyrene clearance.
Embodiment 8:
With the 1-butyl-3-methyl imidazolium tetrafluoroborate of preparation is solvent with ethanol, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this compound bar is respectively 8.5%, 0,41.7% to tar, CO, benzo [a] pyrene clearance.
Embodiment 9:
With the 1-butyl-3-methylimidazole hexafluorophosphate of preparation is solvent with water, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 0.5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 0,0,11.9% to tar, CO, benzo [a] pyrene clearance.
Embodiment 10:
Triethylamine chloride/FeCl with preparation
3Add to ethanol is solvent, be made into mass fraction and be 20% solution, utilize existing coating process, load capacity by 5%, be applied on the cellulose paper,, this cellulose paper be prepared into the mouth rod as shaping paper and tow 85 ℃ of online dryings, cigarette becomes cigarette, and this mouth rod is respectively 4.5%, 0,43.1% to tar, CO, benzo [a] pyrene clearance.
Claims (12)
1. cellulose paper that reduces benzo [a] pyrene content in the cigarette smoke, it is characterized in that, load has ionic liquid on the described cellulose paper, and wherein ionic liquid is made up of organic cation and inorganic anion: organic cation is a kind of in the imidazol ion that replaces of alkyl, the quaternary ammonium alkyl ion; Inorganic anion is Cl
-, Br
-, SO
4 2-, PO
4 3-, NO
3 -, AlCl
4 -, [PF
6]
-, [BF
4]
-, FeCl
x -In one or several.
2. cellulose paper according to claim 1 is characterized in that: imidazol ion, the alkyl substituent in the quaternary ammonium alkyl ion or the alkyl that described alkyl replaces is a kind of in 1,2,3,4,5, the 6 carbon alkyl.
3. according to the described cellulose paper of claim 1, it is characterized in that: add coupling group ion liquid CATION is modified.
4. according to the cellulose paper of claim 3, it is characterized in that: described coupling group is the silica-based or trimethoxy silane of triethoxy.
5. according to each described cellulose paper of claim 1-4, it is characterized in that: ionic liquid accounts for 0.2%～5% of cellulose paper quality.
6. the preparation method of the cellulose paper of benzo [a] pyrene content in the described reduction cigarette smoke of claim 1, it is characterized in that: with ethanol or water is solvent, add the ionic liquid wiring solution-forming, at normal temperatures ionic liquid solution is coated on cellulose paper surface, drying.
7. method according to claim 6 is characterized in that, the mass percent concentration of ionic liquid solution is 5% to 20%.
8. method according to claim 6 is characterized in that, and is dry down at 70 ℃-105 ℃.
9. method according to claim 6 is characterized in that: ion liquid CATION is modified, add coupling group, coupling group and cellulose paper surface group react and ionic liquid are fixed in the cellulose paper surface.
10. method according to claim 9 is characterized in that: described coupling group is triethoxysilane or trimethoxy silane.
11. the application of each described cellulose paper of claim 1-4 is characterized in that, described cellulose paper is used as the shaping paper that reduces the cigarette filter tip of benzo [a] pyrene content in the cigarette smoke.
12. the application of the described cellulose paper of claim 5 is characterized in that, described cellulose paper is used as the shaping paper that reduces the cigarette filter tip of benzo [a] pyrene content in the cigarette smoke.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102836433A CN102002888B (en) | 2010-09-16 | 2010-09-16 | Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof |
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|---|---|---|---|
| CN2010102836433A CN102002888B (en) | 2010-09-16 | 2010-09-16 | Cellulose paper capable of reducing benzo(a)pyrene content of smoke of cigarettes, preparation method thereof and use thereof |
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| CN102002888B CN102002888B (en) | 2012-05-30 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104939317A (en) * | 2015-07-10 | 2015-09-30 | 湖北中烟工业有限责任公司 | Application of halogenated alkylimidazolium ionic liquid as cigarette filter additive |
| CN105167186A (en) * | 2015-07-10 | 2015-12-23 | 湖北中烟工业有限责任公司 | Cigarette filter tip additive for reducing aromatic phenol content in smoke |
| CN108903055A (en) * | 2018-08-17 | 2018-11-30 | 佛山市森昂生物科技有限公司 | A kind of preparation method of papery cigarette filter tip |
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| CN1101241A (en) * | 1994-03-11 | 1995-04-12 | 郑其岚 | Filter bar for cigarette and its production |
| US5409021A (en) * | 1992-04-22 | 1995-04-25 | Safaev; Radzhab D. | Cigarette filter |
| CN1849949A (en) * | 2006-06-09 | 2006-10-25 | 张家口卷烟厂 | Cigarette filter-tip of reducing harm component in smoke and retaining fragrance component |
| CN101297715A (en) * | 2008-06-26 | 2008-11-05 | 湖南中烟工业有限责任公司 | Additive agent for reducing aldehydes matter content in cigarette flue gas, production method and application thereof |
| 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 |
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2010
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Patent Citations (5)
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| US5409021A (en) * | 1992-04-22 | 1995-04-25 | Safaev; Radzhab D. | Cigarette filter |
| CN1101241A (en) * | 1994-03-11 | 1995-04-12 | 郑其岚 | Filter bar for cigarette and its production |
| CN1849949A (en) * | 2006-06-09 | 2006-10-25 | 张家口卷烟厂 | Cigarette filter-tip of reducing harm component in smoke and retaining fragrance component |
| CN101297715A (en) * | 2008-06-26 | 2008-11-05 | 湖南中烟工业有限责任公司 | Additive agent for reducing aldehydes matter content in cigarette flue gas, production method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104939317A (en) * | 2015-07-10 | 2015-09-30 | 湖北中烟工业有限责任公司 | Application of halogenated alkylimidazolium ionic liquid as cigarette filter additive |
| CN105167186A (en) * | 2015-07-10 | 2015-12-23 | 湖北中烟工业有限责任公司 | Cigarette filter tip additive for reducing aromatic phenol content in smoke |
| CN104939317B (en) * | 2015-07-10 | 2019-06-11 | 湖北中烟工业有限责任公司 | Purposes of the halogenated alkyl glyoxaline ion liquid as cigarette filter-tip additive agent |
| CN108903055A (en) * | 2018-08-17 | 2018-11-30 | 佛山市森昂生物科技有限公司 | A kind of preparation method of papery cigarette filter tip |
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| Publication number | Publication date |
|---|---|
| CN102002888B (en) | 2012-05-30 |
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