CN109603779A - A kind of pH response type cigarette discoloration adsorbent material and preparation method thereof, cigarette filter - Google Patents
A kind of pH response type cigarette discoloration adsorbent material and preparation method thereof, cigarette filter Download PDFInfo
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- CN109603779A CN109603779A CN201811644085.1A CN201811644085A CN109603779A CN 109603779 A CN109603779 A CN 109603779A CN 201811644085 A CN201811644085 A CN 201811644085A CN 109603779 A CN109603779 A CN 109603779A
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- resin
- discoloration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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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
- A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
- A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
Abstract
The present invention relates to a kind of pH response type cigarette discoloration adsorbent materials and preparation method thereof, cigarette filter, belong to cigarette filter technical field.Preparation method of the invention includes: that polyalcohol stephanoporate absorption resin is carried out ammoxidation, and amination polyalcohol stephanoporate is made and adsorbs resin；Amination polyalcohol stephanoporate absorption resin is subjected to zinc ion chelating reaction, zinc ion complexing resin is made；By zinc ion complexing resin and pH indicator type colour-changing agent be uniformly mixed in water to get.The harmful components such as main flume volatile carbonyl compound and hydrogen cyanide can selectively be reduced using material made from preparation method of the invention, wherein hydrogen cyanide selectively reduces by 30~80%, and volatile carbonyl compound total amount selectively reduces by 20~50%；It can be effectively reduced cigarette smoke stimulation, promote cigarette sensory quality, consumer can be allowed to be observed during smoking cigarette because of the process that grain color changes after selective absorption harmful ingredients in flue gas.
Description
Technical field
The present invention relates to a kind of pH response type cigarette discoloration adsorbent materials and preparation method thereof, cigarette filter, belong to cigarette
Filter tip technical field.
Background technique
With the growing interest to smoking and health problem, exploitation of the countries in the world to cigarette filter tip material and filter structures
Increasingly pay attention to, occurs adding some functional materials in filter stick to achieve the purpose that reducing tar and reducing harm, as application publication number is
The Chinese invention patent application of CN101396170A discloses cigarette composite filter tip made of a kind of modified absorbing material granules, can
Remove part harmful components.Authorization Notice No. is that the Chinese utility model patent of CN201108028Y will be made by surfactant
Amine based material be added in vinegar fibre and obtain binary combined filter tip, alternative reduces harmful volatile carbonyl in cigarette smoke
Close object.Trimethyl ammonium chloride base acethydrazide is modified porous by the Chinese utility model patent that Authorization Notice No. is CN201491709U
Strong base material made from hydroxyapatite, which is added in vinegar fibre, obtains binary combined filter tip, and alternative reduces in cigarette mainstream flue gas
Hydrocyanic acid release amount.The above-mentioned prior art does not disclose while to the technical solution of hydrogen cyanide and volatile carbonyl compound.
Summary of the invention
The object of the present invention is to provide a kind of pH response type cigarette preparation methods of discoloration adsorbent material, made from this method
PH response type cigarette with discoloration adsorbent material can simultaneously in main flume hydrogen cyanide and volatile carbonyl compound inhale
It is attached.
The present invention also provides it is a kind of can simultaneously in main flume hydrogen cyanide and volatile carbonyl compound carry out
The pH response type cigarette of absorption discoloration adsorbent material.
The present invention also provides a kind of using the above-mentioned pH response type cigarette cigarette filter of discoloration adsorbent material, can be simultaneously
To in main flume hydrogen cyanide and volatile carbonyl compound adsorb.
In order to achieve the goal above, skill used by the preparation method of pH response type cigarette of the invention with discoloration adsorbent material
Art scheme is:
A kind of pH response type cigarette preparation method of discoloration adsorbent material, includes the following steps:
1) polyalcohol stephanoporate absorption resin is subjected to ammoxidation, amination polyalcohol stephanoporate is made and adsorbs resin；
2) amination polyalcohol stephanoporate absorption resin is subjected to zinc ion chelating reaction, zinc ion complexing resin is made；
3) by zinc ion complexing resin and pH indicator type colour-changing agent be uniformly mixed in water to get；The pH indicator type becomes
Toner is bromocresol green, bromocresol green sodium, Bromothymol blue, Congo red, methyl red, any one in bromocresol purple.
The preparation method of pH response type cigarette of the invention discoloration adsorbent material, pH response type cigarette obtained discoloration absorption
1) material, which has the advantage that, can selectively reduce the harmful components such as main flume volatile carbonyl compound and hydrogen cyanide,
Wherein hydrogen cyanide selectively reduces by 30~80%, and volatile carbonyl compound total amount selectively reduces by 20~50%；2) can have
Effect reduces cigarette smoke stimulation, promotes cigarette sensory quality；3) after being applied to cigarette product, consumer can be allowed straight in suction
It connects and observes because of the process that grain color changes after selective absorption harmful ingredients in flue gas, both enhanced the novelty of product appearance
Property, and enhance perception of the consumer to the technological element of a product.
Preferably, the zinc ion chelating reaction include by amination polyalcohol stephanoporate absorption resin with containing the molten of zinc ion
Liquid is mixed；The mixing is that amination polyalcohol stephanoporate absorption resin is added in solution containing zinc ion to stir 3~8h.It is logical
Crossing stirring can make reaction more abundant.
Preferably, the zinc ion chelating reaction further includes by amination polyalcohol stephanoporate absorption resin and containing zinc ion
After solution mixing, it is separated by solid-liquid separation, obtained solid is dried at 40~60 DEG C.Energy is dried at a lower temperature
Enough guarantee that the porous structure of the amination modified product of resin is not destroyed.
Preferably, the solution containing zinc ion is the solution of soluble zinc salt；The mass fraction of the soluble zinc salt
It is 1.0~6.6%.By control soluble zinc salt mass fraction above range can make zinc ion with polymer complex
It is more uniform in porous polymer dispersion when reaction, thus adsorption effect of the reinforcing material to object noxious ingredient in flue gas.
In order to keep reaction more abundant, described be uniformly mixed is that pH indicator type colour-changing agent water is added in zinc ion complexing resin
2~8h is stirred in solution.
In order to control adsorbance of the pH indicator type colour-changing agent on zinc ion complexing resin, to reach higher discoloration effect
Fruit, it is preferred that the mass fraction of the pH indicator type colour-changing agent aqueous solution is 0.02~0.5%.
For the color uniformity after making zinc ion complexing resin support pH indicator type colour-changing agent, combine material at
This, it is preferred that the mass ratio of the zinc ion complexing resin and pH indicator type colour-changing agent aqueous solution is 1:(2~5).
Preferably, polyalcohol stephanoporate absorption resin is made by the method included the following steps: by acrylate monomer,
Crosslinking agent, pore-foaming agent, initiator, which are dispersed in water phase, carries out suspension polymerization, removes pore-foaming agent and polyalcohol stephanoporate tree is made
Rouge.Using polyalcohol stephanoporate made from this method absorption resin material pore distribution it is more uniform, aperture is smaller, specific surface area more
Greatly, and the stability of the modified complex compound of zinc ion can be enhanced.
The pH response type cigarette of the invention technical solution used by discoloration adsorbent material are as follows:
It is a kind of to be become using the above-mentioned pH response type cigarette pH response type cigarette made from the preparation method of adsorbent material that changes colour
Color adsorbent material.
PH response type cigarette of the invention discoloration adsorbent material, can not only selectively reduce main flume volatile carbonyl
The harmful components such as compound and hydrogen cyanide reduce flue gas stimulation, promote product sensory quality, and consumer is in aspiration procedure
The scientific and technological content that product is contained can be perceived by the variation of material color.
Technical solution used by cigarette filter of the invention are as follows:
A kind of cigarette filter, including above-mentioned pH response type cigarette discoloration adsorbent material；The pH response type cigarette discoloration
Additive amount of the adsorbent material in cigarette filter is 20~80mg.
Cigarette filter of the invention can not only selectively reduce main flume volatile carbonyl compound and hydrogen cyanide etc.
Harmful components reduce flue gas stimulation, promote product sensory quality, and consumer can pass through material color in aspiration procedure
Variation, the scientific and technological content that is contained of perception product.
Specific embodiment
The present invention provides a kind of pH response type cigarette preparation methods of discoloration adsorbent material, include the following steps:
1) polyalcohol stephanoporate absorption resin is subjected to ammoxidation, amination polyalcohol stephanoporate is made and adsorbs resin；
2) amination polyalcohol stephanoporate absorption resin is subjected to zinc ion chelating reaction, zinc ion complexing resin is made；
3) by zinc ion complexing resin and pH indicator type colour-changing agent be uniformly mixed in water to get；The pH indicator type becomes
Toner is bromocresol green, bromocresol green sodium, Bromothymol blue, Congo red, methyl red, any one in bromocresol purple.
Preferably, the zinc ion chelating reaction include by amination polyalcohol stephanoporate absorption resin with containing the molten of zinc ion
Liquid is mixed.The mixing is that amination polyalcohol stephanoporate absorption resin is added in solution containing zinc ion to stir 3~8h.
Preferably, there is no significant changes for partial size, aperture and the specific surface area of zinc ion chelating reaction front and back resin.
Preferably, the zinc ion chelating reaction further includes by amination polyalcohol stephanoporate absorption resin and containing zinc ion
After solution mixing, it is separated by solid-liquid separation, obtained solid is dried at 40~60 DEG C.The processing time of the drying be 3~
6h。
Preferably, the solution containing zinc ion is the solution of soluble zinc salt；The mass fraction of the soluble zinc salt
It is 1.0~6.6%.The soluble zinc salt is at least one of zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, preferably chlorine
Change zinc.
Preferably, the mass ratio of the amination polyalcohol stephanoporate resin and the solution containing zinc ion is 1:2.5~30.
Preferably, the pH color change interval of the pH indicator type colour-changing agent is 3.0~7.6.
Preferably, described be uniformly mixed is that zinc ion complexing resin is added in pH indicator type colour-changing agent aqueous solution to stir 2
~8h.
Preferably, the mass fraction of the pH indicator type colour-changing agent aqueous solution is 0.02~0.5%.
Preferably, the mass ratio of the zinc ion complexing resin and pH indicator type colour-changing agent aqueous solution is 1:(2~5).
Preferably, step 3) further include after mixing, be separated by solid-liquid separation, will be separated by solid-liquid separation resulting solid washed,
It is dry.The temperature of the drying is 40~60 DEG C, and the time is 4~6h.
Preferably, step 3) further include first by pH indicator type colour-changing agent adjust in water pH be 2.7~3.6, add zinc
Ion complexation resin is uniformly mixed.
Preferably, the polyalcohol stephanoporate absorption resin is spherical shape.
Preferably, polyalcohol stephanoporate absorption resin is made by the method included the following steps: by acrylate monomer,
Crosslinking agent, pore-foaming agent, initiator, which are dispersed in water phase, carries out suspension polymerization, removes pore-foaming agent and polyalcohol stephanoporate tree is made
Rouge.
Preferably, the water phase is the mixed solution that polyvinyl alcohol and sodium chloride take water as a solvent.It is further preferred that institute
The mass fraction for stating polyvinyl alcohol in mixed solution is 0.5~2%.In the mixed solution mass fraction of sodium chloride be 5~
12%.
Preferably, acrylate monomer, crosslinking agent, pore-foaming agent, initiator are dispersed in water phase is first by acrylate
After monomer, crosslinking agent, pore-foaming agent and initiator mixing, then dispersed in water phase.
It is further preferred that the quality of the mixed solution and acrylate monomer, crosslinking agent, pore-foaming agent and initiator are total
Mass ratio is 1:(3~5).
Preferably, reaction system being stirred during suspension polymerization, the revolving speed of the stirring is 150~
200rpm.The volume for the reactor that the suspension polymerization uses is 200~300mL.
Preferably, pore-foaming agent is removed by washing.The solvent used that washs is methanol and/or ethyl alcohol.Using solvent
The content of the pore-foaming agent into efflux is washed when being washed lower than limitation requirement.The preparation method of polyalcohol stephanoporate absorption resin
It further include that can also remove unreacted acrylate monomer while removing pore-foaming agent.
Preferably, the preparation method of polyalcohol stephanoporate absorption resin further includes passing through washing removal pore-foaming agent using solvent
Afterwards, it adopts and is washed with water to noresidue in efflux, be then dried.
Preferably, the acrylate monomer has the following structure:
Wherein, R1Selected from H or-CH3, R2Selected from-OCH3、-OCH2CH3、-OCH2CH2CH3、-OCH(CH2CH3)2In one
Kind.
Preferably, the mass ratio of the pore-foaming agent and acrylate monomer is (1~2.5): 1.It is further preferred that described
The mass ratio of pore-foaming agent and acrylate monomer is (1.5~2.2): 1.The pore-foaming agent is organic solvent.The pore-foaming agent is
At least one of atoleine, gasoline, petroleum ether, n-hexane, toluene.
Preferably, the temperature of the suspension polymerization is 55~75 DEG C, and the time is 10~14h.
Preferably, the crosslinking agent is at least one of divinylbenzene, bisacrylamide.
Preferably, the mass ratio of the crosslinking agent and acrylate monomer is 1:(1~4).It is further preferred that the friendship
The mass ratio for joining agent and acrylate monomer is 1:(1.5~4).
There is no particular limitation for the initiator used to suspension polymerization, is used for the initiation of polymerization reaction in the prior art
Agent is used equally for suspension polymerization of the invention.Preferably, the initiator is azodiisobutyronitrile.It is further preferred that
The dosage of the initiator is the 0.5~2% of acrylate monomer and crosslinking agent gross mass.
Preferably, the partial size of the polyalcohol stephanoporate absorption resin is 0.8~1.7mm.
Preferably, the average pore size of the polyalcohol stephanoporate absorption resin is 15~25nm.Polyalcohol stephanoporate is adsorbed and is set
On the one hand the average pore size of rouge, which is controlled, can guarantee that the load capacity of material surface functional group is high in 15~25nm, on the other hand
Flue gas can be made to come into full contact with when flowing through porous resin with material, to guarantee have to hydrogen cyanide and volatile carbonyl compound etc.
Evil substance has stronger absorption property.
Preferably, the BET specific surface area of the polyalcohol stephanoporate absorption resin is 40~100m2/g。
Preferably, the ammoxidation is that polyalcohol stephanoporate absorption resin is amination modified using ethylenediamine progress.
Preferably, the amination modified method, comprising the following steps: by polyalcohol stephanoporate absorption resin in ethylenediamine
After middle swelling, 6~12h is reacted in 80~140 DEG C.
The ethylenediamine used in swelling process is excessive compared to polyalcohol stephanoporate absorption resin.Preferably, described molten
The swollen time is 8~12h.
Preferably, the amination modified method further includes that will react post-consumer polymer porous adsorption resin to wash into
Property, then it is dried.
Amination polyalcohol stephanoporate adsorbs resin and adsorbs resin compared to amination modified preceding polyalcohol stephanoporate, partial size,
There is no significant changes for aperture and specific surface area.
The present invention also provides made from a kind of preparation method using above-mentioned pH response type cigarette with discoloration adsorbent material
PH response type cigarette discoloration adsorbent material.
The present invention also provides a kind of cigarette filters, including above-mentioned pH response type cigarette discoloration adsorbent material；It is described
Additive amount of the cigarette pH response type cigarette discoloration adsorbent material in cigarette filter is 20~80mg.
It, can be in single cigarette filter tip when preparing cigarette filter with discoloration adsorbent material using pH response type cigarette of the invention
A kind of independent pH response type cigarette of the color discoloration adsorbent material of addition, is also possible to two kinds or more of color mix pH response
Type cigarette discoloration adsorbent material.
Preferably, the cigarette filter includes filter core and the transparent formed paper that is wrapped in outside filter core；The filter core includes institute
State cigarette filter adsorbent material.Filter core is wrapped up using transparent formed paper, consumer can be made directly to observe in suction
The colourshifting process of functional material to after because of selective absorption harmful ingredients in flue gas.
It is further preferred that the cigarette filter is ternary cavity type composite filter tip, the filter core includes setting gradually
First cylindrical filter material segment, the cavity segment filled with the cigarette filter adsorbent material, the second cylindrical filter material segment；It is described
Cavity segment crosses column filter material segment, the second cylindrical filter material segment two end faces close to each other and described transparent by described first
Forming paper surrounds.The first cylindrical filter material segment, the second cylindrical filter material segment can be independently from convention filter filter materials
Middle selection, such as acetate fiber, acid fiber by polylactic, paper filter material.The first cylindrical filter material segment, the second cylindrical filter material
Material section can the structures such as independent choice setting groove, concentric circles or middle line corresponding section of filter material is supported.
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
In following embodiment, Examples 1 to 4 is the embodiment of the preparation method of pH response type cigarette discoloration adsorbent material,
Embodiment 5 is the embodiment of pH response type cigarette discoloration adsorbent material, and embodiment 6~9 is the embodiment of cigarette filter.
Embodiment 1
The preparation method of the pH response type cigarette of the present embodiment discoloration adsorbent material, comprising the following steps:
1) a certain amount of polyethylene of dispersing agent alcohol 1788 is weighed, after being added to the water sufficiently swelling, makes it in a heated condition
Sufficiently dissolution, is configured to polyvinyl alcohol water solution, and sodium chloride is then added, and stirring dissolves sodium chloride sufficiently, is configured to containing poly-
The mixed solution that vinyl alcohol mass fraction is 0.6%, sodium chloride mass fraction is 7% is to get water phase；
There-necked flask is added according to the ratio that mass ratio is 30:70:150 in divinylbenzene, ethyl acrylate, atoleine
It is stirred mixing, initiator azodiisobutyronitrile is then added, and (quality of the initiator of addition is divinylbenzene and propylene
The 2% of acetoacetic ester gross mass) dissolution after, obtain oily phase；
Water phase obtained is added in the there-necked flask (250mL) equipped with blender, reflux condensing tube and thermometer and is warming up to
40 DEG C, oily phase mutually then is taken for the ratio of 1:4 with the mass ratio of water phase according to oily, is added in there-necked flask, then adjusts under stiring
Turn over speed is 200rpm (oil bead diameter size is suitable) and is stirred continuously down the suspension polymerisation 12h at (60 ± 2) DEG C with the revolving speed.
After polymerization reaction, pore-foaming agent atoleine is removed using ethanol washing, is washed with water and washs into efflux without ethyl alcohol residual,
Sphere polymers porous adsorption resin is obtained after drying, screening.The partial size of the sphere polymers porous adsorption resin be 0.8~
1.4mm, average pore size 20nm, BET specific surface area 80m2/g。
2) excessive ethylenediamine is added into the resulting sphere polymers porous adsorption resin of step 1), 8h is swollen, 120
10h is reacted at DEG C, is washed to neutrality after reaction, is drying to obtain the spherical amination polyalcohol stephanoporate absorption resin of white.Ammonia
Partial size, average pore size and the BET specific surface area of base fluidized polymer porous adsorption resin resin have no significant change.
3) zinc sulfate that mass fraction is 1.65% is added in the resulting amination polyalcohol stephanoporate absorption resin of step 2)
In aqueous solution, the mass ratio of control amination polyalcohol stephanoporate absorption resin and zinc salt solution is 1:30, is stirred at room temperature
Then 8h is washed to non-metallic ion outflow, then the dry 6h in 40 DEG C of baking oven, obtains spherical zinc ion complexing resin.Zinc
Partial size, average pore size and the BET specific surface area of ion complexation resin are also without significant change.
4) pH indicator type colour-changing agent bromocresol green sodium is configured to the aqueous solution that mass fraction is 0.3%, utilizes citric acid
Adjusting pH value of solution is 2.8.The spherical zinc ion complexing resin of the resulting white of step 3) is added in solution, control zinc ion complexing
The mass ratio of resin and aqueous solution is 1:3, and filtering, washing after mechanical stirring 6h, dry 6h, obtains deep orange in 40 DEG C of baking oven
The pH response type electrochromic particles of color to get.The partial size of spherical zinc ion complexing resin is 0.8~1.4mm, average pore size after dyeing
For 20nm, BET specific surface area 80m2/g。
Embodiment 2
The preparation method of the pH response type cigarette of the present embodiment discoloration adsorbent material, comprising the following steps:
1) a certain amount of polyethylene of dispersing agent alcohol 1788 is weighed, after being added to the water sufficiently swelling, makes it in a heated condition
Sufficiently dissolution, is configured to polyvinyl alcohol water solution, and sodium chloride is then added, and stirring dissolves sodium chloride sufficiently, is configured to containing poly-
The mixed solution that vinyl alcohol mass fraction is 1.2%, sodium chloride mass fraction is 10% is to get water phase；
The ratio for being 20:80:40:80 according to mass ratio by divinylbenzene, ethyl methacrylate, atoleine, toluene
Example is added there-necked flask and is stirred mixing, and initiator azodiisobutyronitrile is then added, and (quality of the initiator of addition is diethyl
The 1% of alkenyl benzene and ethyl methacrylate gross mass) dissolution after, obtain oily phase；
Water phase obtained is added in the there-necked flask (250mL) equipped with blender, reflux condensing tube and thermometer and is warming up to
40 DEG C, oily phase mutually then is taken for the ratio of 1:5 with the mass ratio of water phase according to oily, is added in there-necked flask, then adjusts under stiring
Turn over speed is 160rpm (oil bead diameter size is suitable) and is stirred continuously down the suspension polymerisation 12h at (60 ± 2) DEG C with the revolving speed.
After polymerization reaction, pore-foaming agent atoleine and toluene are removed using ethanol washing, is washed with water and washs into efflux without second
Alcohol residual, obtains sphere polymers porous adsorption resin after drying, screening.The partial size of the sphere polymers porous adsorption resin
For 1.4~1.7mm, average pore size 22nm, BET specific surface area 72m2/g。
2) excessive ethylenediamine is added into the resulting sphere polymers porous adsorption resin of step 1), is swollen 10h,
12h is reacted at 120 DEG C, is washed to neutrality after reaction, is drying to obtain the spherical amination polyalcohol stephanoporate absorption resin of white.
Partial size, average pore size and the BET specific surface area of amination polyalcohol stephanoporate absorption resin have no significant change.
3) the zinc sulfate water that mass fraction is 6.6% is added in the resulting amination polyalcohol stephanoporate absorption resin of step 2)
In solution, the mass ratio of control amination polyalcohol stephanoporate absorption resin and zinc salt solution is 1:2.5, is stirred at room temperature
Then 8h is washed to non-metallic ion outflow, then the dry 6h in 40 DEG C of baking oven, obtains spherical zinc ion complexing resin.Zinc
Partial size, average pore size and the BET specific surface area of ion complexation resin are also without significant change.
4) it by the Congo red aqueous solution for being configured to mass fraction and being 0.1% of pH indicator type colour-changing agent, is adjusted using citric acid
PH value of solution is 2.7.The spherical zinc ion complexing resin of the resulting white of step 3) is added in solution, zinc ion complexing resin is controlled
Mass ratio with aqueous solution is 1:5, and filtering, washing after mechanical stirring 6h, dry 4h, obtains azury in 60 DEG C of baking oven
PH response type electrochromic particles to get.The partial size of spherical zinc ion complexing resin is 1.4~1.7mm after dyeing, average pore size is
22nm, BET specific surface area 72m2/g。
Embodiment 3
The preparation method of the pH response type cigarette of the present embodiment discoloration adsorbent material, comprising the following steps:
1) a certain amount of polyethylene of dispersing agent alcohol 1788 is weighed, after being added to the water sufficiently swelling, makes it in a heated condition
Sufficiently dissolution, is configured to polyvinyl alcohol water solution, and sodium chloride is then added, and stirring dissolves sodium chloride sufficiently, is configured to containing poly-
The mixed solution that vinyl alcohol mass fraction is 1.5%, sodium chloride mass fraction is 10% is to get water phase；
There-necked flask is added according to the ratio that mass ratio is 40:60:100 in divinylbenzene, methyl methacrylate, gasoline
It is stirred mixing, initiator azodiisobutyronitrile is then added, and (quality of the initiator of addition is divinylbenzene and methyl
The 1.5% of methyl acrylate gross mass) dissolution after, obtain oily phase；
Water phase obtained is added in the there-necked flask (250mL) equipped with blender, reflux condensing tube and thermometer and is warming up to
40 DEG C, oily phase mutually then is taken for the ratio of 1:4.5 with the mass ratio of water phase according to oily, is added in there-necked flask under stiring, then
Adjustment revolving speed is 180rpm (oil bead diameter size is suitable) and is stirred continuously down the suspension polymerisation at (60 ± 2) DEG C with the revolving speed
12h.After polymerization reaction, pore-foaming agent gasoline is removed using ethanol washing, is washed with water and washs into efflux without ethyl alcohol residual,
Sphere polymers porous adsorption resin is obtained after drying, screening.The partial size of the sphere polymers porous adsorption resin be 1.0~
1.4mm, average pore size 16nm, BET specific surface area 75m2/g。
2) excessive ethylenediamine is added into the resulting sphere polymers porous adsorption resin of step 1), 8h is swollen, 140
6h is reacted at DEG C, is washed to neutrality after reaction, is drying to obtain the spherical amination polyalcohol stephanoporate absorption resin of white.Amino
Significant change does not occur for partial size, average pore size and the BET specific surface area of fluidized polymer porous adsorption resin.
3) the zinc sulfate water that mass fraction is 3.3% is added in the resulting amination polyalcohol stephanoporate absorption resin of step 3)
In solution, the mass ratio of control amination polyalcohol stephanoporate absorption resin and zinc salt solution is 1:20, and 8h is stirred at room temperature,
Then it is washed to non-metallic ion outflow, then the dry 6h in 40 DEG C of baking oven, obtains spherical zinc ion complexing resin.Zinc ion
Partial size, average pore size and the BET specific surface area of complexing resin are also without significant change.
4) pH indicator type colour-changing agent Bromothymol blue is configured to the aqueous solution that mass fraction is 0.5%, utilizes lemon
Acid-conditioning solution pH is 3.0.The spherical zinc ion complexing resin of white is added in solution, porous adsorption resin and aqueous solution are controlled
Mass ratio be 1:2, filtering, washing after mechanical stirring 6h, the dry 6h in 40 DEG C of baking oven obtain the pH that color is lemon yellow
Response type electrochromic particles to get.The partial size of spherical zinc ion complexing resin is 1.0~1.4mm after dyeing, average pore size is
16nm, BET specific surface area 75m2/g。
Embodiment 4
The preparation method of the pH response type cigarette of the present embodiment discoloration adsorbent material, comprising the following steps:
1) a certain amount of polyethylene of dispersing agent alcohol 1788 is weighed, after being added to the water sufficiently swelling, makes it in a heated condition
Sufficiently dissolution, is configured to polyvinyl alcohol water solution, and sodium chloride is then added, and stirring dissolves sodium chloride sufficiently, is configured to containing poly-
The mixed solution that vinyl alcohol mass fraction is 2%, sodium chloride mass fraction is 12% is to get water phase；
By divinylbenzene, methyl methacrylate, gasoline according to mass ratio be 33:67:100 ratio be stirred it is mixed
It closes, initiator azodiisobutyronitrile is then added, and (quality of the initiator of addition is divinylbenzene and methyl methacrylate
The 0.5% of gross mass) dissolution after, obtain oily phase；
Water phase obtained is added in the there-necked flask (250mL) equipped with blender, reflux condensing tube and thermometer and is warming up to
45 DEG C, oily phase mutually then is taken for the ratio of 1:3 with the mass ratio of water phase according to oily, is added in there-necked flask, then adjusts under stiring
Turn over speed is 200rpm (oil bead diameter size is suitable) and is stirred continuously down the suspension polymerisation 10h at (65 ± 2) DEG C with the revolving speed.
After polymerization reaction, pore-foaming agent gasoline is removed using ethanol washing, is washed with water and washs into efflux without ethyl alcohol residual, through dry
Sphere polymers porous adsorption resin is obtained after dry, screening.The partial size of the sphere polymers porous adsorption resin be 1.4~
1.7mm, average pore size 21nm, BET specific surface area 65m2/g。
2) excessive ethylenediamine is added into the resulting sphere polymers porous adsorption resin of step 1), 12h is swollen, 80
8h is reacted at DEG C, is washed to neutrality after reaction, is drying to obtain the spherical amination polyalcohol stephanoporate absorption resin of white.Amino
Significant change does not occur for partial size, average pore size and the BET specific surface area of fluidized polymer porous adsorption resin.
3) the zinc sulfate water that mass fraction is 1.0% is added in the resulting amination polyalcohol stephanoporate absorption resin of step 3)
In solution, the mass ratio of control amination polyalcohol stephanoporate absorption resin and zinc salt solution is 1:10, and 3h is stirred at room temperature,
Then it is washed to non-metallic ion outflow, then the dry 6h in 40 DEG C of baking oven, obtains spherical zinc ion complexing resin.Zinc ion
Partial size, average pore size and the BET specific surface area of complexing resin are also without significant change.
4) pH indicator type colour-changing agent methyl red is configured to the aqueous solution that mass fraction is 0.02%, is adjusted using citric acid
PH value of solution is 3.6.The spherical zinc ion complexing resin of white is added in solution, the quality of porous adsorption resin and aqueous solution is controlled
Than for 1:4, filtering, washing after mechanical stirring 2h, the dry 6h in 40 DEG C of baking oven obtain the pH response type that color is lemon yellow
Electrochromic particles to get.After dyeing the partial size of spherical zinc ion complexing resin be 1.4~1.7mm, average pore size 21nm, BET ratio
Surface area is 63m2/g。
Embodiment 5
Above-mentioned pH response type cigarette discoloration absorption is respectively adopted with discoloration adsorbent material for the pH response type cigarette of the present embodiment
Preparation method in the Examples 1 to 4 of material is made, and details are not described herein again.
Embodiment 6
The cigarette filter of the present embodiment be ternary cavity type composite filter tip, including filter core and be wrapped in outside filter core it is transparent at
Shape paper, filter core include the first column acetate fiber section set gradually, cavity segment and the second column acetate fiber section；Cavity segment by
First acetate fiber section, the second acetate fiber section two end faces close to each other and the transparent formed paper being wrapped in outside filter core enclose
At；PH response type cigarette discoloration adsorbent material obtained, the pH response type cigarette in full embodiment 1 is filled in cavity segment to be inhaled with discoloration
The loading of enclosure material is 40mg.
The cigarette filter of the present embodiment can make cigarette mainstream flue gas hydrogen cyanide selectively reduce by 55.3%, volatile carbonyl
Total amount of compound selectively reduces by 35.3%；The irritation of cigarette smoke is obviously reduced；The pH of filter tip transparent section in aspiration procedure
Response type electrochromic particles gradually become yellow green by darkorange, have good visual effect.
Embodiment 7
The cigarette filter of the present embodiment be ternary cavity type composite filter tip, including filter core and be wrapped in outside filter core it is transparent at
Shape paper, filter core include the first column acetate fiber section set gradually, cavity segment and the second column acetate fiber section；Cavity segment by
First acetate fiber section, the second acetate fiber section two end faces close to each other and the transparent formed paper being wrapped in outside filter core enclose
At；PH response type cigarette discoloration adsorbent material obtained, the pH response type cigarette in full embodiment 2 is filled in cavity segment to be inhaled with discoloration
The loading of enclosure material is 60mg.
The cigarette filter of the present embodiment can make cigarette mainstream flue gas hydrogen cyanide selectively reduce by 69.8%, volatile carbonyl
Total amount of compound selectively reduces by 42.3%；The irritation of cigarette smoke is obviously reduced；The pH of filter tip transparent section in aspiration procedure
Response type electrochromic particles gradually become honey color by light blue, have good visual effect.
Embodiment 8
The cigarette filter of the present embodiment be ternary cavity type composite filter tip, including filter core and be wrapped in outside filter core it is transparent at
Shape paper, filter core include the first column acetate fiber section set gradually, cavity segment and the second column acetate fiber section；Cavity segment by
First acetate fiber section, the second acetate fiber section two end faces close to each other and the transparent formed paper being wrapped in outside filter core enclose
At；PH response type cigarette discoloration adsorbent material obtained, the pH response type cigarette in full embodiment 3 is filled in cavity segment to be inhaled with discoloration
The loading of enclosure material is 20mg.
The cigarette filter of the present embodiment can make cigarette mainstream flue gas hydrogen cyanide selectively reduce by 40.2%, volatile carbonyl
Total amount of compound selectively reduces by 20.3%；The irritation of cigarette smoke reduces；The pH response of filter tip transparent section in aspiration procedure
Type electrochromic particles gradually become buff by lemon yellow, have good visual effect.
Embodiment 9
The cigarette filter of the present embodiment be ternary cavity type composite filter tip, including filter core and be wrapped in outside filter core it is transparent at
Shape paper, filter core include the first column acetate fiber section set gradually, cavity segment and the second column acetate fiber section；Cavity segment by
First acetate fiber section, the second acetate fiber section two end faces close to each other and the transparent formed paper being wrapped in outside filter core enclose
At；PH response type cigarette discoloration adsorbent material obtained, the pH response type cigarette in full embodiment 4 is filled in cavity segment to be inhaled with discoloration
The loading of enclosure material is 80mg.
The cigarette filter of the present embodiment can make cigarette mainstream flue gas hydrogen cyanide selectively reduce by 77.9%, volatile carbonyl
Total amount of compound selectively reduces by 46.8%；The irritation of cigarette smoke reduces；The pH response of filter tip transparent section in aspiration procedure
Type electrochromic particles gradually become aubergine by red, have good visual effect.
Comparative example
The cigarette of this comparative example is common unitary acetate fiber filter tip, is not added with functional material.
Experimental example
The cigarette filter in embodiment 6~9 and comparative example is hinged with respectively with cigarette using transparent tipping paper, circumference is made
23.4mm, the Virginian-type cigarette that length is 84mm, are then respectively adopted YC/T 253-2008 (determination of hydrogen cyanide in mainstream cigarette smoke
Measurement continuous flow method) and YC/T 254-2008 (the measurement high-efficient liquid phase color of main carbonyl compounds in main stream cigarette smoke
Spectrometry) in standard method measure the burst size of hydrogen cyanide and volatile carbonyl compound in each cigarette mainstream flue gas, measurement
It the results are shown in Table 1.
The content and reduced rate of hydrogen cyanide and volatile carbonyl compound in 1 cigarette mainstream flue gas of table
From data in table 1: cigarette filter of the invention can be such that volatile carbonyl compound in main flume selects
Property reduce by 20%~50%, hydrogen cyanide selectively reduce by 30%~80%, to reduce the stimulation of cigarette smoke, promote cigarette
Quality.
Claims (10)
1. a kind of pH response type cigarette preparation method of discoloration adsorbent material, characterized by the following steps:
1) polyalcohol stephanoporate absorption resin is subjected to ammoxidation, amination polyalcohol stephanoporate is made and adsorbs resin；
2) amination polyalcohol stephanoporate absorption resin is subjected to zinc ion chelating reaction, zinc ion complexing resin is made；
3) by zinc ion complexing resin and pH indicator type colour-changing agent be uniformly mixed in water to get；The pH indicator type colour-changing agent
For any one in bromocresol green, bromocresol green sodium, Bromothymol blue, Congo red, methyl red, bromocresol purple.
2. the pH response type cigarette according to claim 1 preparation method of discoloration adsorbent material, it is characterised in that: the zinc
Ion complexation modification includes mixing amination polyalcohol stephanoporate absorption resin with the solution containing zinc ion；The mixing is
Amination polyalcohol stephanoporate absorption resin is added in solution containing zinc ion and stirs 3~8h.
3. the pH response type cigarette according to claim 2 preparation method of discoloration adsorbent material, it is characterised in that: the zinc
Ion complexation modification further includes after mixing amination polyalcohol stephanoporate absorption resin with the solution containing zinc ion, being separated by solid-liquid separation,
Obtained solid is dried at 40~60 DEG C.
4. the pH response type cigarette according to claim 2 preparation method of discoloration adsorbent material, it is characterised in that: described to contain
The solution of zinc ion is the solution of soluble zinc salt；The mass fraction of the soluble zinc salt is 1.0~6.6%.
5. the pH response type cigarette according to claim 1 preparation method of discoloration adsorbent material, it is characterised in that: described mixed
Conjunction is uniformly that zinc ion complexing resin is added in pH indicator type colour-changing agent aqueous solution to stir 2~8h.
6. the pH response type cigarette according to claim 5 preparation method of discoloration adsorbent material, it is characterised in that: the pH
The mass fraction of indicator type colour-changing agent aqueous solution is 0.02~0.5%.
7. the pH response type cigarette according to claim 5 or 6 preparation method of discoloration adsorbent material, it is characterised in that: institute
The mass ratio for stating zinc ion complexing resin and pH indicator type colour-changing agent aqueous solution is 1:(2~5).
8. the pH response type cigarette according to claim 1 preparation method of discoloration adsorbent material, it is characterised in that: described poly-
It closes object porous adsorption resin to be made by the method included the following steps: by acrylate monomer, crosslinking agent, pore-foaming agent, initiator
It is dispersed in water phase and carries out suspension polymerization, remove pore-foaming agent and polyalcohol stephanoporate resin is made.
9. pH made from a kind of preparation method using pH response type cigarette as described in claim 1 with discoloration adsorbent material is responded
Type cigarette discoloration adsorbent material.
10. a kind of cigarette filter, it is characterised in that: including pH response type cigarette as claimed in claim 9 discoloration adsorbent material；
Additive amount of the pH response type cigarette discoloration adsorbent material in cigarette filter is 20~80mg.
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