CN102617782B - Preparation method and application of polymethyl methacrylate (polyMMA) intercommunicated porous material - Google Patents

Preparation method and application of polymethyl methacrylate (polyMMA) intercommunicated porous material Download PDF

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CN102617782B
CN102617782B CN2012100865981A CN201210086598A CN102617782B CN 102617782 B CN102617782 B CN 102617782B CN 2012100865981 A CN2012100865981 A CN 2012100865981A CN 201210086598 A CN201210086598 A CN 201210086598A CN 102617782 B CN102617782 B CN 102617782B
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polymethylmethacrylate
cigarette
water
porous
intercommunication porous
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CN102617782A (en
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杨松
张晓兵
孙学辉
王宜鹏
赵乐
颜权平
聂聪
谢复炜
刘惠民
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Zhengzhou Tobacco Research Institute of CNTC
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Zhengzhou Tobacco Research Institute of CNTC
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Abstract

The invention relates to a preparation method of a polymethyl methacrylate (polyMMA) intercommunicated porous material, which is characterized in that high inner phase emulsion polymerization of methyl methacrylate (MMA) is utilized to obtain the polyMMA intercommunicated porous material with ester functional group. The polymethyl methacrylate intercommunicated porous material is prepared from methyl methacrylate, a crosslinking agent, a pore-forming agent, an emulsifier, water, inorganic salt and an initiator. The material can effectively adsorb the harmful substance phenol in smoke. 10-30mg of the material is added to one cigarette filter stick, so the phenol release amount in the cigarette main-stream smoke can be selectively lowered by more than 25%, and the tar release amount is basically unchanged or slightly lowered; and the quality of the cigarette is not negatively influenced, thereby achieving the goal of selectively lowering the phenol release amount in the cigarette smoke.

Description

A kind of preparation method and application thereof of polymethylmethacrylate intercommunication porous material
Technical field
The invention belongs to Harm reduction techniques and add Material Field, specifically ester group intercommunication porous material of phenol burst size and its preparation method and application in a kind of selectivity reducing cigarette main flume.This material is applied to cigarette filter rod, can effectively reduces phenol burst size in main flume, the sucking quality of cigarette do not had a negative impact simultaneously.
Background technology
Phenol is one of main objectionable constituent of cigarette mainstream flue gas, Volatile phenolics in cigarette smoke mainly produces in the cigarette burning process, " cigarette hazardness Research on Index System " project is by the relation of research objectionable constituent burst size and flue gas biologic activity, find that phenol is to affect one of topmost objectionable constituent of cigarette mainstream flue gas hazardness, therefore, the phenol content reduced in cigarette smoke is significant for reducing cigarette hazardness.
For the phenol how reduced in cigarette smoke, many correlative studys have also been carried out both at home and abroad.Wang Hongwei etc. (Wang Hongwei, Fang Ding, Xu Zhiqiang, etc. Agriculture of Anhui science, 2009 (10) 4371-4372.) studied chitosan-Fe 2+the adsorption of complex compound to harmful ingredients in flue gas, show that it all has stronger adsorption to flue gas moisture, phenol and HCN.Study a kind of macropore microporous hybrid starch granule in the CN101531779 patent, it has been made an addition in the filter core of cigarette filter, made binary or ternary composite filter tip, can effectively reduce tar, phenol, prussic acid and the carbon monoxide amount of sending in flue gas.The common activated carbon fiber of reaming of take in the CN101015394A patent is carrier, by reaming, pickling process by the aluminum nitrate of difference amount or iron nitrate or both blending dispersion on carrier, then prepare different loads amount Al through roasting 2o 3, Fe 2o 3, Al 2o 3-Fe 2o 3modified active carbon fiber, it is prepared into to composite filter tip, can reduce tar, phenol, pyrocatechol, Resorcinol, Resorcinol, p-meta-cresol and ortho-cresol etc. in flue gas.In CN 101664228A, select dark chamber calixarene compound as adding material, utilize Molecular Recognization and the cavity size selection effect of calixarene compound, simultaneously benzo [a] pyrene and the phenol burst size in selectivity reducing cigarette fume.Invented in CN 101433818A patent that a kind of cigarette mainstream flue gas is coal-tar middle oil for adsorbing, the novel mesoporous material of phenol, tobacco-specific nitrosamine etc.Mesoporous material is to have the mesopore molecular sieve of 3 dimension reticulated microstructure, only stone pattern as SBA-15, or plating is decorated with " liquid film " or passes through metal oxide as the three-dimensional netted microtexture of zirconium white modification, the SBA-15 meso-porous molecular sieve material of only stone pattern.CN101919589A, CN101974124A, CN101919591A, CN101961646A etc. have invented the polymeric additive of a series of reduction phenol substances in cigarette smoke gas.Such additive is the phenol objectionable impurities in the moisture selectivity reducing cigarette fume utilized in material.United States Patent (USP) (US6779529) has been announced a kind of by fibrous filter segment, selected adsorbent section and a general sorbent segment cigarette filter that coaxial serial connection forms mutually, its selected adsorbent section is that phenolic resin as matrix resin forms after primary amine and secondary amine functionalization, and this filter tip can be removed some specific compositions as phenol etc. from flue gas.
In sum, some explorations and research have been carried out aspect the phenol burst size both at home and abroad in reducing cigarette smoke, but these technology are poor to the selective adsorption capacity of phenol in cigarette smoke, the material preparation process is complicated simultaneously, cost is higher, all is not used widely.
Polymkeric substance intercommunication porous material is a kind of material with special pore structure obtained by the High Internal Phase Emulsion method.Wherein the disperse phase template can form " abscess " of several microns to tens microns, form micron-sized fenestra between two abscesses, can on cell wall, form nano level " pore " if add pore-creating agent in the external phase monomer, the existence of pore increases considerably the specific surface area of material.
The ester group contained in methyl methacrylate can and the phenolic hydroxyl group of phenol between stronger hydrogen bond action occurs, therefore, with the alternative phenol burst size reduced in flue gas of the PolyMMA intercommunication porous material of ester function base, also there is no at present research report and the patent documentation about this respect.
Summary of the invention
Purpose of the present invention just is being based on above-mentioned prior art situation and preparation method and the application thereof of a kind of polymethylmethacrylate intercommunication porous material of developing, the present invention, by the High Internal Phase Emulsion polymerization of methyl methacrylate, obtains a kind of polymethylmethacrylate intercommunication porous material PolyMMA with ester group functional group.This material is applied to cigarette filter rod, the objectionable impurities phenol in can the active adsorption flue gas, and releasing content of coke tar slightly reduces, and the sucking quality of cigarette is not had a negative impact simultaneously, thus reach the purpose of phenol burst size in selectivity reducing cigarette fume.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of polymethylmethacrylate intercommunication porous material of the present invention, High Internal Phase Emulsion polymerization by methyl methacrylate, obtain a kind of intercommunication porous material (PolyMMA) with polymethylmethacrylate of ester function group, its concrete steps are as follows:
(1) first configure oil phase, consist of methyl methacrylate (MMA), linking agent, pore-creating agent, emulsifying agent, its concrete proportioning: the concrete proportioning of oil phase: methyl methacrylate 2-3ml, linking agent 2-3ml, pore-creating agent 3-5ml, emulsifying agent 1-2g.
(2) then configure water, consist of water, inorganic salt and initiator, its concrete proportioning: the concrete proportioning of water: water 50-70ml, inorganic salt 0.5-2g, initiator 0.1-0.2g.
(3) under 500-700rpm, water is slowly added in oil phase and forms High Internal Phase Emulsion, put it into subsequently in 50-60 ℃ of baking oven reaction 24-48 hour.By the solid product of gained, water and the extracting of ethanol difference are 24 hours respectively, obtain the intercommunication porous material of polymethylmethacrylate in vacuum drying oven after drying.
In the present invention, linking agent used is ethyleneglycol dimethyacrylate, trihydroxy methyl propane trimethyl acrylate or glycerol three (α-methacrylic acid) ester.Pore-creating agent used is toluene or dimethylbenzene.Emulsifying agent used is Arlacel-60 Soxylat A 25-7 (TWEEN 60), Glycerin, mixed triester with caprylic acid capric acid or mono succinate glyceryl ester.Inorganic salt are calcium chloride or sodium-chlor.Initiator is Potassium Persulphate or ammonium persulphate.
The methyl methacrylate intercommunication porous material application that utilizes aforesaid method to prepare is added on cigarette filter, in can the selectivity reducing cigarette main flume, the phenol burst size be more than 25%, and releasing content of coke tar is substantially constant or slightly reduction, the sucking quality of cigarette do not had a negative impact, the addition of methyl methacrylate intercommunication porous material is every filter tip 10-30mg simultaneously.
Filter tip provided by the invention adds material and has following advantage:
1. this patent contrivance is the intercommunication porous material that contains ester group, contains micron-sized hole in material, and these holes communicate, and is beneficial to the fast transport of flue gas in material; And material possesses higher specific surface area, be beneficial to flue gas and fully contact with material.
2. material contains special ester function base, can with flue gas in objectionable impurities phenol stronger hydrogen bond action occurs, be conducive to improve Pyrogentisinic Acid's adsorption rate.
This patent contrivance can the selectivity reducing cigarette main flume in the phenol burst size, effectively reduce and reach more than 25%.
This patent contrivance to the sucking quality of cigarette without negative impact.
Embodiment
Below with example, further illustrate flesh and blood of the present invention, but content of the present invention is not limited to this.
Embodiment 1
First configure oil phase, consist of 2ml MMA, the 3ml ethyleneglycol dimethyacrylate, 5ml toluene, 1g TWEEN 60, then configure water, consists of 56ml water, 0.5g calcium chloride and 0.15g Potassium Persulphate.Under high-speed stirring, water is slowly added in oil phase and forms High Internal Phase Emulsion, put it into subsequently in 50-60 ℃ of baking oven, react 24 hours.By the solid product of gained, water and the extracting of ethanol difference are 24 hours respectively, and in vacuum drying oven, drying obtains PolyMMA material 1.
Using PolyMMA material 1 as composite filter tip addition material, use, addition is 15mg/cig, take that not add the material modified cigarette of any filter tip be control sample, carry out the cigarette smoking test according to the standard aspiration condition on smoking machine, and carry out the detection of phenol burst size according to standard YC/T255-2008.Three of each sample Duplicate Samples, result as shown in Table 1.
Table one PolyMMA material 1 reduces the result of phenol burst size
The above results shows, material of the present invention can be for the production of composite filter tip cigarette, material can the selectivity reducing cigarette main flume in phenol burst size 29.5%.In addition, Analyses Methods for Sensory Evaluation Results shows, this filter tip adds material the smoking property of cigarette quality is had no adverse effects.
Embodiment 2
First configure oil phase, consist of 2ml MMA, 3ml trihydroxy methyl propane trimethyl acrylate, 5ml toluene, 1g Glycerin, mixed triester with caprylic acid capric acid, then configure water, consists of 56ml water, 0.5g calcium chloride and 0.15g Potassium Persulphate.Under high-speed stirring, water is slowly added in oil phase and forms High Internal Phase Emulsion, put it into subsequently in 50-60 ℃ of baking oven, react 24 hours.By the solid product of gained, water and the extracting of ethanol difference are 24 hours respectively, and in vacuum drying oven, drying obtains PolyMMA material 2.
Using PolyMMA material 2 as composite filter tip addition material, use, addition is 15mg/cig, take that not add the material modified cigarette of any filter tip be control sample, carry out the cigarette smoking test according to the standard aspiration condition on smoking machine, and carry out the detection of phenol burst size according to standard YC/T255-2008.Three of each sample Duplicate Samples, result as shown in Table 2.
Table two PolyMMA material 2 reduces the result of phenol burst size
The above results shows, material of the present invention can be for the production of composite filter tip cigarette, material can the selectivity reducing cigarette main flume in phenol burst size 29.1%.In addition, Analyses Methods for Sensory Evaluation Results shows, this filter tip adds material the smoking property of cigarette quality is had no adverse effects.
Embodiment 3
First configure oil phase, consist of 3ml MMA, 2ml glycerol three (α-methacrylic acid) ester, 5ml dimethylbenzene, 1g mono succinate glyceryl ester, then configure water, consists of 56ml water, 0.5g sodium-chlor, 0.15g Potassium Persulphate.Under high-speed stirring, water is slowly added in oil phase and forms High Internal Phase Emulsion, put it into subsequently in 50-60 ℃ of baking oven, react 24 hours.By the solid product of gained, water and the extracting of ethanol difference are 24 hours respectively, and in vacuum drying oven, drying obtains PolyMMA material 3.
Using PolyMMA material 3 as composite filter tip addition material, use, addition is 15mg/cig, take that not add the material modified cigarette of any filter tip be control sample, carry out the cigarette smoking test according to the standard aspiration condition on smoking machine, and carry out the detection of phenol burst size according to standard YC/T255-2008.Three of each sample Duplicate Samples, result as shown in Table 3.
Table three PolyMMA material 3 reduces the result of phenol burst size
The above results shows, material of the present invention can be for the production of composite filter tip cigarette, material can the selectivity reducing cigarette main flume in phenol burst size 28.6%.In addition, Analyses Methods for Sensory Evaluation Results shows, this filter tip adds material the smoking property of cigarette quality is had no adverse effects.

Claims (7)

1. the preparation method of a polymethylmethacrylate intercommunication porous material, it is characterized in that: by the High Internal Phase Emulsion polymerization of methyl methacrylate, obtain a kind of intercommunication porous material with polymethylmethacrylate of ester function group, its concrete steps are as follows:
First configure oil phase, consist of methyl methacrylate, linking agent, pore-creating agent, emulsifying agent; The concrete proportioning of oil phase: methyl methacrylate 2-3ml, linking agent 2-3ml, pore-creating agent 3-5ml, emulsifying agent 1-2g;
Then configure water, consist of water, inorganic salt and initiator; The concrete proportioning of water: water 50-70ml, inorganic salt 0.5-2g, initiator 0.1-0.2g;
Under 500-700rpm, water is slowly added in oil phase and forms High Internal Phase Emulsion, put it into subsequently in 50-60 ℃ of baking oven reaction 24-48 hour;
By the solid product of gained, water and the extracting of ethanol difference are 24 hours respectively, obtain the intercommunication porous material of polymethylmethacrylate in vacuum drying oven in drying.
2. the preparation method of polymethylmethacrylate intercommunication porous material according to claim 1, it is characterized in that: linking agent used is ethyleneglycol dimethyacrylate, trihydroxy methyl propane trimethyl acrylate or glycerol three (α-methacrylic acid) ester.
3. the preparation method of polymethylmethacrylate intercommunication porous material according to claim 1, it is characterized in that: pore-creating agent used is toluene or dimethylbenzene.
4. the preparation method of polymethylmethacrylate intercommunication porous material according to claim 1, it is characterized in that: emulsifying agent is Arlacel-60 Soxylat A 25-7 (TWEEN 60), Glycerin, mixed triester with caprylic acid capric acid or mono succinate glyceryl ester.
5. the preparation method of polymethylmethacrylate intercommunication porous material according to claim 1, it is characterized in that: inorganic salt used are calcium chloride or sodium-chlor.
6. the preparation method of polymethylmethacrylate intercommunication porous material according to claim 1, it is characterized in that: initiator used is Potassium Persulphate or ammonium persulphate.
7. the application of polymethylmethacrylate intercommunication porous material on cigarette that utilizes the described method of claim 1 to prepare, it is characterized in that: polymethylmethacrylate intercommunication porous material is added in cigarette filter, in can the selectivity reducing cigarette main flume, the phenol burst size be more than 25%, and its addition is every filter tip 10-30mg.
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CN102974323A (en) * 2012-11-20 2013-03-20 红云红河烟草(集团)有限责任公司 Preparation method of absorbent for selectively reducing phenol content in smoke of cigarette
CN103506092B (en) * 2013-09-27 2016-03-16 湖南中烟工业有限责任公司 A kind of support type polyamide-amine dendritic macromolecule cigarette smoke heavy metal ion adsorbent and its preparation method and application
CN104558438B (en) * 2014-12-24 2017-01-18 中科院广州化学有限公司 Methacrylate polymer-inorganic compound through hole material as well as preparation method and application thereof
CN104558998B (en) * 2015-01-28 2016-08-17 云南中烟工业有限责任公司 A kind of filter tip efficient absorption rod of graphene-polymer composite aerogel and preparation method thereof
CN105037672B (en) * 2015-08-27 2017-08-25 厦门大学 A kind of isocyanates capillary copolymer material and preparation method and application
CN107096399A (en) * 2016-02-22 2017-08-29 深圳市启德环保科技有限公司 A kind of high pressure resistant porous polymer PMMA filter membrane materials
CN109438606A (en) * 2018-11-09 2019-03-08 北京化工大学 A kind of construction method of fluid injection porous material smooth surface
CN111387544A (en) * 2020-05-11 2020-07-10 河南中烟工业有限责任公司 Preparation method of novel filter stick with fragrance holding function

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GB1137742A (en) * 1966-03-11 1968-12-27 Union Carbide Corp Tobacco smoke filters
US6897247B2 (en) * 2001-08-14 2005-05-24 Polye Inc. High internal phase polymeric emulsion composition

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