CN104738814A - Micro-nano structure filter tip additive reducing phenol in cigarette smoke and preparation method and application thereof - Google Patents

Micro-nano structure filter tip additive reducing phenol in cigarette smoke and preparation method and application thereof Download PDF

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Publication number
CN104738814A
CN104738814A CN201510071043.3A CN201510071043A CN104738814A CN 104738814 A CN104738814 A CN 104738814A CN 201510071043 A CN201510071043 A CN 201510071043A CN 104738814 A CN104738814 A CN 104738814A
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Prior art keywords
filter tip
additives
cigarette
filter
phenol
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CN201510071043.3A
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CN104738814B (en
Inventor
周国俊
周建华
李霞
刘金莉
徐建
卢昕博
蒋健
夏骏
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China Tobacco Zhejiang Industrial Co Ltd
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China Tobacco Zhejiang Industrial Co Ltd
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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/061—Use of materials for tobacco smoke filters containing additives entrapped within capsules, sponge-like material or the like, for further release upon smoking
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/062—Use of materials for tobacco smoke filters characterised by structural features
    • A24D3/063—Use of materials for tobacco smoke filters characterised by structural features of the fibers
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)

Abstract

The invention relates to a micro-nano structure filter tip additive reducing phenol in cigarette smoke. According to the micro-nano structure filter tip additive, coconut shell charcoal for cigarettes serves as a carrier, and the surface of the carrier is loaded with polyelectrolyte nano particles. The polyelectrolyte nano particles are self-assembly bodies of amphoteric ionic polymers containing hydroxyl groups, and the mass percentage of the polyelectrolyte nano particles in the filter tip additive is 0.1%-5.0%. Compared with a contrast cigarette of the same specification, a cigarette filter tip containing the additive can reduce the release amount of the phenol in the cigarette main stream smoke by 10%-20%. A preparation process of the filter tip additive is simple and has good industrial applicability.

Description

A kind of micro-nano structure additives of filter tip reducing phenol in cigarette smoke and its preparation method and application
Technical field
The present invention relates to Harm reduction techniques technical field, be specifically related to a kind of micro-nano structure additives of filter tip reducing phenol in cigarette smoke and its preparation method and application.
Background technology
Along with the continuous enhancing that society pays close attention to smoking and health problem, the harm reduction technical research of cigarette product has caused the great attention of tobacco business.For harmful components various in cigarette smoke, researcher has developed multiple harm reduction technology, if any composite filter tip, application filter tip ventilation dilution technology, uses high-air-permeability and the fast cigarette paper of Burning velocity, mixes the method such as expanded cut tobacco and expanded cut stem.Being wherein one of conventional harm reduction means to the modification of cigarette filter, by adding or composite biological material, macromolecular material and nano material etc. in cigarette filter, reaching the effect effectively reducing harmful constituents in cigarette flue gas.
Phenolic compounds in cigarette smoke has kind more than 40, wherein topmostly comprises phenol, benzenediol and methylphenol etc.Flue gas phenolic compound is mainly derived from the cracking of polyphenol compound in tobacco leaf (chlorogenic acid and rutin sophorin), plays a very important role to the flavouring essence quality of cigarette.But some aldehydes matter has tumor promotion, phenol, m-cresol, p-cresol, o-cresol, resorcinol etc. have been included by Hoffman list, list the recommendatory control composition reducing cigarette harmfulness in.Disclose in Chinese patent CN 101664228 B and p-[1-(4-hydroxy phenyl)-1-Methylethyl] cup [8] aromatic hydrocarbons is directly added in cigarette filter as cigarette additive, reduce the content of phenol in flue gas.It is carrier that Chinese patent ZL201010278343.6 discloses with porous material, with the mode alternate load polyanion of LBL self-assembly and polycationic material, reaches phenol decomposition effect.But these materials in actual production process or preparation cost higher, or complex process, be not suitable for large-scale industrial production.Therefore, be necessary to develop a kind of novel additives of filter tip.
Summary of the invention
For the above deficiency of prior art, first object of the present invention is to provide a kind of micro-nano structure additives of filter tip reducing phenol in cigarette smoke, and this additives of filter tip effectively can reduce the burst size of phenol in flue gas.Second object of the present invention is to provide the preparation method of above-mentioned additives of filter tip, and the method is simply controlled, is suitable for suitability for industrialized production.3rd object of the present invention is to provide the application of above-mentioned additives of filter tip.
In order to realize first above-mentioned object, present invention employs following technical scheme:
Reduce a micro-nano structure additives of filter tip for phenol in cigarette smoke, described additives of filter tip with cigarette coconut husk charcoal for carrier, and at carrier surface load polyelectrolyte nanoparticle; Described polyelectrolyte nanoparticle is the self-assembly of amphoteric ion polymer, and described amphoteric ion polymer is the amphoteric ion copolymer containing hydroxyl; The mass percentage of described polyelectrolyte nanoparticle in additives of filter tip is 0.1 ~ 5.0%.
The polyelectrolyte nanoparticle of cigarette coconut husk carbon surface of the present invention load both can increase the contact of flue gas and material, can not block again the hole of coconut husk charcoal; Hydroxy functional group wherein, quaternary ammonium salt group etc. are conducive to adsorbing phenol, increase the effect reducing phenol.
The mass percentage of described polyelectrolyte nanoparticle in additives of filter tip is 0.1 ~ 5.0%.The burst size of phenol in flue gas effectively can be reduced under cost-saving prerequisite.As preferably, the mass percentage of described polyelectrolyte nanoparticle in additives of filter tip is 0.2 ~ 2.0%.
As preferably, described amphoteric ion copolymer comprises the copolymer of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylate and N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(3-sulfopropyl) ammonium salt.As preferred again, described acrylate is the one in acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate and glycidyl acrylate.
In order to realize second above-mentioned object, present invention employs following technical scheme:
Prepare a method for the micro-nano structure additives of filter tip of phenol in above-mentioned reduction cigarette smoke, the method comprises the following steps:
1) monomer containing quaternary ammonium salt group, acrylate monomer and zwitterionic monomer are added to the water, pass into nitrogen, add the oxidation-reduction initiator that mass percent concentration is 1 ~ 3%, solution/emulsion polymerisation is carried out at 35 ~ 50 DEG C, polymerization time is 8 ~ 24 hours, obtains the dispersion liquid of polyelectrolyte nanoparticle;
2) with cigarette coconut husk charcoal for carrier, be impregnated in the dispersion liquid of above-mentioned polyelectrolyte nanoparticle, drive the mode of growth in situ by electrostatic, at a certain amount of polyelectrolyte nanoparticle of its area load, after filtration, obtain the additives of filter tip of micro-nano structure after washing and drying.
As preferably, the monomer containing quaternary ammonium salt group, acrylate monomer and the mass concentration of zwitterionic monomer in water described in step 1) are respectively 0.1 ~ 5%, 0.1 ~ 5% and 1 ~ 15%.
As preferably, step 2) described in electrostatic drive the condition of growth in situ be at 25 ~ 35 DEG C, standing 0.5 ~ 3.5 hour.
In order to realize the 3rd above-mentioned object, present invention employs following technical scheme:
Above-mentioned additives of filter tip reduces the application in the cigarette filter of phenol in cigarette smoke in preparation.
Reduce a cigarette filter for phenol in cigarette smoke, with the addition of above-mentioned additives of filter tip in this cigarette filter, described additives of filter tip is 10 ~ 60 mg often propping up the addition in filter tip.
As preferably, described cigarette filter is binary combined filter tip, the common filter stick comprising nearly mouth end and the charge bar of nearly pipe tobacco end superposed vertically; Described charge bar is made up of described additives of filter tip and common filter stick material; Or described cigarette filter is ternary composite filter tip, the charge bar comprising two sections of common filter sticks and superpose vertically, described charge bar is between two sections of common filter sticks; Described charge bar forms by described additives of filter tip or by described additives of filter tip and common filter stick material.
Common filter stick of the present invention preferably uses the fine rod of the vinegar of this area and papery mouth rod.
Compared with prior art, tool of the present invention has the following advantages: micro-nano structure additives of filter tip of the present invention, achieves the burst size effectively reducing phenol in cigarette smoke with the functional group of the polyelectrolyte nanoparticle of the special construction of cigarette coconut husk carbon surface load nano particle and load.Compared with the contrast cigarette of same specification, the cigarette filter containing additive of the present invention can make the burst size of phenol in cigarette mainstream flue gas reduce by 10 ~ 20%.Additives of filter tip preparation technology of the present invention is simple, has good industrial applicibility.
Detailed description of the invention
Embodiment 1:
By the acrylic acid-2-hydroxyl ethyl ester of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 1 mass parts, 1 mass parts and the N of 25 mass parts, N-dimethyl N-(2-methylacryoyloxyethyl) N-(3-sulfopropyl) ammonium salt is added to the water, be made into the mixed liquor that concentration is 10wt%, pass into nitrogen, add the oxidation-reduction initiator K that concentration is 3wt% 2s 2o 8and NaHSO 3(1:1), at 35 DEG C, carry out solution/emulsion polymerisation, polymerization time is 24 hours, obtains the dispersion liquid of polyelectrolyte nanoparticle.Cigarette coconut husk charcoal is impregnated in the dispersion liquid of polyelectrolyte nanoparticle, 0.5 h is left standstill at 25 DEG C, drive growth in situ mode by electrostatic, at its area load polyelectrolyte nanoparticle, after filtration, wash and obtain micro-nano structure additives of filter tip after drying.Wherein, the mass percentage of polyelectrolyte nanoparticle in additive is about 0.1%.
By above-mentioned additive application in cigarette filter, the addition often propped up in cigarette filter is about 20 mg, measures the burst size of phenol in cigarette mainstream flue gas, not use the same specification cigarette of additive for control sample.Shown in result table 1.
Table 1. additives of filter tip of the present invention is on the impact of phenol release amount in main flume
Embodiment 2:
By the 2-hydroxypropyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 5 mass parts, 5 mass parts and the N of 10 mass parts, N-dimethyl N-(2-methylacryoyloxyethyl) N-(3-sulfopropyl) ammonium salt is added to the water, be made into the mixed liquor that concentration is 10wt%, pass into nitrogen, add the oxidation-reduction initiator K that concentration is 1wt% 2s 2o 8and NaHSO 3(1:1), at 35 DEG C, carry out solution/emulsion polymerisation, polymerization time is 24 hours, obtains the dispersion liquid of polyelectrolyte nanoparticle.Cigarette coconut husk charcoal is impregnated in the dispersion liquid of polyelectrolyte nanoparticle, 3.5 h are left standstill at 35 DEG C, drive growth in situ mode by electrostatic, at its area load polyelectrolyte nanoparticle, after filtration, wash and obtain micro-nano structure additives of filter tip after drying.Wherein, the mass percentage of polyelectrolyte nanoparticle in additive is about 5%.
By above-mentioned additive application in cigarette filter, the addition often propped up in cigarette filter is about 30 mg.Measure the burst size of phenol in cigarette mainstream flue gas, not use the same specification cigarette of additive for control sample.Shown in result table 2.
Table 2. additives of filter tip of the present invention is on the impact of phenol release amount in main flume
Embodiment 3:
By the glycidyl acrylate of the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of 2 mass parts, 1 mass parts and the N of 20 mass parts, N-dimethyl N-(2-methylacryoyloxyethyl) N-(3-sulfopropyl) ammonium salt is added to the water, be made into the mixed liquor that mass percent concentration is 10wt%, pass into nitrogen, add the oxidation-reduction initiator K that mass percent concentration is 1.5wt% 2s 2o 8and NaHSO 3(1:1), at 35 DEG C, carry out solution/emulsion polymerisation, polymerization time is 24 hours, obtains the dispersion liquid of polyelectrolyte nanoparticle.Cigarette coconut husk charcoal is impregnated in the dispersion liquid of polyelectrolyte nanoparticle, 1.5 h are left standstill at 25 DEG C, drive growth in situ mode by electrostatic, at its area load polyelectrolyte nanoparticle, after filtration, wash and obtain micro-nano structure additives of filter tip after drying.Wherein, the mass percentage of polyelectrolyte nanoparticle in additive is about 1.5%.
By above-mentioned additive application in cigarette filter, the addition often propped up in cigarette filter is about 45 mg.Measure the burst size of phenol in cigarette mainstream flue gas, not use the same specification cigarette of additive for control sample.Shown in result table 3.
Table 3. additives of filter tip of the present invention is on the impact of phenol release amount in main flume
。

Claims (10)

1. reduce a micro-nano structure additives of filter tip for phenol in cigarette smoke, it is characterized in that: described additives of filter tip with cigarette coconut husk charcoal for carrier, and at carrier surface load polyelectrolyte nanoparticle; Described polyelectrolyte nanoparticle is the self-assembly of amphoteric ion polymer, and described amphoteric ion polymer is the amphoteric ion copolymer containing hydroxyl; The mass percentage of described polyelectrolyte nanoparticle in additives of filter tip is 0.1 ~ 5.0%.
2. the micro-nano structure additives of filter tip of phenol in reduction cigarette smoke according to claim 1, is characterized in that: the mass percentage of described polyelectrolyte nanoparticle in additives of filter tip is 0.2 ~ 2.0%.
3. the micro-nano structure additives of filter tip of phenol in reduction cigarette smoke according to claim 1 and 2, it is characterized in that: described amphoteric ion copolymer comprises the copolymer of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylate and N, N-dimethyl N-(2-methylacryoyloxyethyl) N-(3-sulfopropyl) ammonium salt.
4. the micro-nano structure additives of filter tip of phenol in reduction cigarette smoke according to claim 3, is characterized in that: described acrylate is the one in acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate and glycidyl acrylate.
5. prepare a method for the micro-nano structure additives of filter tip of phenol in the reduction cigarette smoke described in claim 1 ~ 4 any one claim, it is characterized in that the method comprises the following steps:
1) monomer containing quaternary ammonium salt group, acrylate monomer and zwitterionic monomer are added to the water, pass into nitrogen, add the oxidation-reduction initiator that mass percent concentration is 1 ~ 3%, solution/emulsion polymerisation is carried out at 35 ~ 50 DEG C, polymerization time is 8 ~ 24 hours, obtains the dispersion liquid of polyelectrolyte nanoparticle;
2) with cigarette coconut husk charcoal for carrier, be impregnated in the dispersion liquid of above-mentioned polyelectrolyte nanoparticle, drive the mode of growth in situ by electrostatic, at a certain amount of polyelectrolyte nanoparticle of its area load, after filtration, obtain the additives of filter tip of micro-nano structure after washing and drying.
6. the preparation method of additives of filter tip according to claim 5, is characterized in that: the monomer containing quaternary ammonium salt group, acrylate monomer and the mass concentration of zwitterionic monomer in water described in step 1) are respectively 0.1 ~ 5%, 0.1 ~ 5% and 1 ~ 15%.
7. the preparation method of additives of filter tip according to claim 5, is characterized in that: step 2) described in electrostatic drive the condition of growth in situ at 25 ~ 35 DEG C, leave standstill 0.5 ~ 3.5 hour.
8. the additives of filter tip according to any one of claim 1 ~ 4 reduces the application in the cigarette filter of phenol in cigarette smoke in preparation.
9. reduce a cigarette filter for phenol in cigarette smoke, it is characterized in that: containing the additives of filter tip described in any one of claim 1 ~ 4 in this filter tip, described additives of filter tip is 10 ~ 60 mg often propping up the addition in filter tip.
10. a kind of cigarette filter reducing phenol in cigarette smoke according to claim 9, is characterized in that: described cigarette filter is binary combined filter tip, the common filter stick comprising nearly mouth end and the charge bar of nearly pipe tobacco end superposed vertically; Described charge bar is made up of described additives of filter tip and common filter stick; Or described cigarette filter is ternary composite filter tip, the charge bar comprising two sections of common filter sticks and superpose vertically, described charge bar is between two sections of common filter sticks; Described charge bar forms by described additives of filter tip or by described additives of filter tip and common filter stick.
CN201510071043.3A 2015-02-11 2015-02-11 Micro-nano structure additives of filter tip of phenol and its preparation method and application in a kind of reduction cigarette smoke Active CN104738814B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108077994A (en) * 2017-12-21 2018-05-29 中国烟草总公司郑州烟草研究院 The coating fluid of phenol release amount in a kind of filter stick type cigarette mainstream flue gas for reducing paper
CN110959908A (en) * 2019-11-18 2020-04-07 湖北中烟工业有限责任公司 Adsorbing material for cigarette filter stick
WO2021129607A1 (en) * 2019-12-24 2021-07-01 齐鲁工业大学 Zwitterionic gel polymer electrolyte, and preparation therefor and application thereof
CN113115980A (en) * 2021-04-01 2021-07-16 中国烟草总公司郑州烟草研究院 Method for reducing phenol content in waste gas

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CN101919591A (en) * 2010-09-10 2010-12-22 浙江中烟工业有限责任公司 Poly glucosamine hexanedioic acid vinyl ester material for reducing content of phenol type substances
CN101919589A (en) * 2010-09-10 2010-12-22 浙江中烟工业有限责任公司 Chitosan polycation composite material reducing phenols materials in cigarette smoke
CN102443093A (en) * 2010-09-30 2012-05-09 北京市光明化工科技开发中心 Absorbent polymer, composite fiber and composite fiber cigarette filter tip
EP2792410A1 (en) * 2013-04-15 2014-10-22 Goldemar Solutions, S.L. Method of manufacturing a catalyst comprising gold nanoparticles, the catalyst and its use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101919591A (en) * 2010-09-10 2010-12-22 浙江中烟工业有限责任公司 Poly glucosamine hexanedioic acid vinyl ester material for reducing content of phenol type substances
CN101919589A (en) * 2010-09-10 2010-12-22 浙江中烟工业有限责任公司 Chitosan polycation composite material reducing phenols materials in cigarette smoke
CN102443093A (en) * 2010-09-30 2012-05-09 北京市光明化工科技开发中心 Absorbent polymer, composite fiber and composite fiber cigarette filter tip
EP2792410A1 (en) * 2013-04-15 2014-10-22 Goldemar Solutions, S.L. Method of manufacturing a catalyst comprising gold nanoparticles, the catalyst and its use

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108077994A (en) * 2017-12-21 2018-05-29 中国烟草总公司郑州烟草研究院 The coating fluid of phenol release amount in a kind of filter stick type cigarette mainstream flue gas for reducing paper
CN108077994B (en) * 2017-12-21 2021-02-26 中国烟草总公司郑州烟草研究院 Coating liquid for reducing phenol release amount in mainstream smoke of paper filter stick type cigarette
CN110959908A (en) * 2019-11-18 2020-04-07 湖北中烟工业有限责任公司 Adsorbing material for cigarette filter stick
WO2021129607A1 (en) * 2019-12-24 2021-07-01 齐鲁工业大学 Zwitterionic gel polymer electrolyte, and preparation therefor and application thereof
CN113115980A (en) * 2021-04-01 2021-07-16 中国烟草总公司郑州烟草研究院 Method for reducing phenol content in waste gas

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