CN110152625A - A kind of adsorbent, preparation method and application reducing ammonia of main stream smoke of cigarette burst size - Google Patents
A kind of adsorbent, preparation method and application reducing ammonia of main stream smoke of cigarette burst size Download PDFInfo
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- CN110152625A CN110152625A CN201810149191.6A CN201810149191A CN110152625A CN 110152625 A CN110152625 A CN 110152625A CN 201810149191 A CN201810149191 A CN 201810149191A CN 110152625 A CN110152625 A CN 110152625A
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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
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
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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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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Abstract
The invention belongs to cigarette additive technical fields, and in particular to one kind can reduce the adsorbent of ammonia of main stream smoke of cigarette burst size, be the copolymer of beta-cyclodextrin and itaconic acid.The present invention also provides the preparation method of the adsorbent, the adsorbent is connect with itaconic acid using beta-cyclodextrin as raw material, and polymerization obtains the polymer for having high adsorption to ammonia.The invention also discloses the applications of the adsorbent, are added a certain amount of polymer in cigarette filter, 40% or more ammonia in cigarette mainstream flue gas are optionally greatly reduced, while maintaining the mouthfeel of flue gas again.The sorbent preparation method that the present invention synthesizes is simple, is convenient for industrialized production, and safe and stable property is high.
Description
Technical field
The invention belongs to field of harm and tar reduction of cigarettes, and in particular to one kind can reduce ammonia of main stream smoke of cigarette burst size
Sorbent preparation method and application.
Background technique
The nitrogenous compound that ammonia in cigarette smoke is mainly derived from tobacco and other auxiliary materials includes protein, ammonia
Base acid, nitrate, ammonium, amide, alkaloid and nitrogen-containing heterocycle compound.Suitable nitrogenous compound content can keep flue gas appropriate
Sense organ degree, but excessively high nitrogenous compound content not only makes flue gas coarse food grain, and generation is charred taste, stimulates vision and the breathing system of human body
System, but also a large amount of harmful components can be generated.Therefore the ammonia content reduced in cigarette mainstream flue gas is significant.
The burst size that ammonia of main stream smoke of cigarette is reduced using absorption method is a kind of effective method.G, Li et al. with
Ferrous oxalate and alcohols are prepared for a series of nano cages, which has certain assimilation effect to ammonia.Deng
Etc. being prepared for titanate nanotube and ferrite nanometer sheet, and its is investigated and removing of hazardous compound in cigarette smoke has been imitated
Fruit.The result shows that ferrite nanotube has good removal effect to ammonia, hydroquinone, catechol and phenol.But
These adsorbent preparation process are cumbersome, and the price of raw material is higher, are not particularly suited for large-scale industrial production.
In the prior art, some methods or structure for being intended to reduce ammonia in main flume are also reported.For example, Publication No.
The Chinese patent literature of CN101946978A discloses a kind of cigarette processing method for reducing ammonia content, mainly using micro-
Wave changes cigarette primary processing technique to realize.
The Chinese patent literature of Publication No. CN102697182A discloses the addition active component protoporphyrin in filter stick
The method for closing object.
The prior art is related to the problems such as technique is more complex or active component safety, at high cost, thus application prospect exists
Certain difficulty.
Summary of the invention
The first object of the present invention is to provide a kind of adsorbent for reducing ammonia of main stream smoke of cigarette；Selectively
The burst size of ammonia of main stream smoke of cigarette is significantly reduced, the injury to human body is reduced.
The second object of the present invention is to provide the preparation method of adsorbent described in one kind.
The third object of the present invention is to provide the application of adsorbent described in one kind.
A kind of adsorbent reducing ammonia of main stream smoke of cigarette burst size is the copolymer of beta-cyclodextrin and itaconic acid.
Adsorbent of the present invention, can be with mainstream smoke for the polymer containing a large amount of carboxyls using beta-cyclodextrin as carrier
Ammonia in gas reacts, to reduce the content of ammonia in main flume.
There are 7 saccharide ring structures ,-CH on 5 of each saccharide ring in beta-cyclodextrin molecule2- the OH (- OH in non-saccharide ring) is most
It is active, it that is to say the site of 7 He polymerization of itaconic acid, in product of the present invention ,-the CH in 7 saccharide rings2In-OH, until
Few one and polymerization of itaconic acid.
Preferably, at least one of the copolymer of 1 schematic construction of adsorbent isof formula:
Limit R1~R7It is alone H or the itaconic acid segment of formula 2, wherein R1~R7In, at least one substituent group is 2 chain of formula
Section；
In formula 2, x is the degree of polymerization；X is 1~1000.
It is obtained preferably, the adsorbent issues raw free radical polymerization in initiator initiation by beta-cyclodextrin and itaconic acid
It arrives.
Further preferably, in the copolymer of the beta-cyclodextrin and itaconic acid, the mass percent of beta-cyclodextrin is
61.3-70.2%
Preferably, the particle size range of the adsorbent is 50-200 mesh.Absorption under the preferred particle size range
Effect is more excellent.
The present invention also provides described in one kind reduction ammonia of main stream smoke of cigarette burst size adsorbent preparation method,
Under initiator effect polymerization reaction occurs for beta-cyclodextrin and itaconic acid；After polymerization, polymerization inhibitor is added and terminates reaction；Polymerization
Product is washed, precipitating, is dried to get the adsorbent.
In preparation method of the present invention, first beta-cyclodextrin and itaconic acid are mixed, then again under initiator, beta-cyclodextrin table
The hydroxyl in face generates free radical monomer under initiator effect, and free radical monomer with itaconic acid hair tonic polymerization reaction, generates in turn
The copolymer is made in the cross-linked graft polymer of beta-cyclodextrin and itaconic acid.Beta-cyclodextrin and itaconic acid carry out instead in advance
It answers, is the surrounding molecules that the itaconic acid of easy autohemagglutination is dispersed in beta-cyclodextrin, so that the probability of this autohemagglutination reduces, beta-cyclodextrin
Probability as carrier increases；And then the graft polymerization of beta-cyclodextrin and itaconic acid is increased, there is rush to the absorption property of material
Into effect.
Preparation method of the present invention prepares equation square formula 1:
It is that the pi-conjugated double bond of π-is formed with carboxyl on itaconic acid of the present invention, it is high in the radical polymerization composition and division in a proportion that initiator causes
Temperature causes more violent；So facilitate to promote grafting rate, and then promotes adsorption effect.
Preferably, the molar ratio of beta-cyclodextrin and itaconic acid is 1: 6-1: 31.It is more conducively poly- under the preferred ratio
Splice grafting branch, and then help that the excellent adsorbent of absorption property is made；Excessively high amount of substance than and too low amount of substance ratio not
Conducive to the generation of graft reaction.
In the present invention, preferably in water by beta-cyclodextrin and itaconic acid difference solvent, respective solution is obtained, then will dissolution
There is the solution Hybrid Heating of raw material to react.
Preferably, beta-cyclodextrin and itaconic acid react at 40-80 DEG C.Under the preferred range temperature, preferably
Reaction time is 20-40min；Further preferably 30min.
After beta-cyclodextrin and itaconic acid reaction, initiator is added into reaction system.
Preferably, the initiator is potassium peroxydisulfate and/or ammonium persulfate.
In the present invention, by the monomer (beta-cyclodextrin and itaconic acid), raw radical polymerization is issued in initiator initiation
Reaction is closed, processes, the ammonium persulfates such as the chain initiation of graft polymerization reaction experience, chain transmitting, chain termination are produced in a heated condition
The hydroxyl on raw surface free radical attack beta-cyclodextrin (β-CD-OH) generates free radical monomer, and chain occurs and causes；Free radical monomer
And then reacted with itaconic acid, chain transmitting and chain termination occurs, ultimately produces the cross-linked graft polymer of beta-cyclodextrin and itaconic acid.
Itaconic acid carboxyl and C=C formation π-are pi-conjugated, cause in initiator and generate free radical on beta-cyclodextrin, beta-cyclodextrin
Upper free radical goes to be easier to attack C=C polymerization；It polymerize obtained product compared to ester chain, helps to improve grafting rate；And then it mentions
Rise adsorption effect.
Preferably, the dosage of the initiator is the 1wt%-7wt% of monomer beta-cyclodextrin.
Preferably, the temperature of polymerization process is 40-80 DEG C.Polymerization reaction is carried out under the preferable temperature, is helped
In further promotion graft effect, and then further promote the effect of adsorbent.Excessively high reaction temperature or too low reaction temperature
Degree is all unfavorable for graft reaction.
Under the preferred polymerization temperature, preferred polymerization reaction time is 1-5h；Further preferably 3h.
After the completion of polymerization reaction, polymerization inhibitor is added into polymerization reaction system, terminates polymerization reaction.Preferably, described
Polymerization inhibitor be hydroquinone aqueous solution, wherein hydroquinone molar concentration be 0.05-0.10mol/L.
Preferably, the cleaning solution is the aqueous solution of methanol, wherein the percentage by volume of methanol is 20~40%；
Further preferably 30%.
Preferably, the precipitating reagent that precipitation process uses is acetone.
In the present invention, drying process preferably carries out under vacuum conditions.
Beta-cyclodextrin and itaconic acid are dissolved in deionized water respectively, add by the preparation method of adsorbent of the present invention
Initiator polymerization is added in thermal response 30min；After the reaction was completed, polymerization inhibitor is added and terminates reaction；After washing precipitating, vacuum drying,
To obtain the final product.
The present invention also provides the applications of the adsorbent described in one kind, as additive addition in cigarette filter rod.
In the present invention, the adsorbent is added directly in cigarette filter rod, without being loaded on carrier in advance.The present invention
The copolymer be can be used as into adsorbent addition in cigarette filter, alternative reduces the content of ammonia in main flume.
Preferably, the application, the cigarette filter rod is binary compound filter candle or Three-element composite filter core.
In the present invention, according to the difference of cigarette filter rod type, the addition position of adsorbent of the present invention is carried out preferably,
Adsorption effect can further be promoted.
Preferably, the adsorbent adds at the close pipe tobacco end of binary compound filter candle.
Preferably, interlude of the adsorbent addition in Three-element composite filter core.
In the present invention, particle size range when as adsorbent is 50-200 mesh.
Preferably, the additive amount in cigarette filter rod is 5mg/ branch -20mg/ branch.
The present invention at graft polymers in addition to can reduce the ammonia in cigarette mainstream flue gas, moreover it is possible to reduce cigarette mainstream
Phenol compound in flue gas.This is because the hydroxyl on phenol contacts instead with carboxyl a large amount of on graft polymers reaction
It answers.
Mechanism of the invention are as follows:
It is synthesized with the Raolical polymerizable of initiator, graft polymerization reaction undergoes chain to cause, chain transmits, chain termination
Etc. processes, initiator in a heated condition caused by the surface free radical attack beta-cyclodextrin (β-CD-OH) hydroxyl generate from
By base monomer, chain occurs and causes；Free radical monomer is reacted with itaconic acid in turn, and chain transmitting (transmitting of C-C chain) and chain termination occurs,
Ultimately produce the cross-linked graft polymer of beta-cyclodextrin and itaconic acid；Compared to the polymer of ester bond transmitting, absorption of the invention
The carboxyl amount of one molecular cell of agent load is more, and absorption property is more excellent.
Advantages of the present invention essentially consists in:
Itaconic acid is carried on beta-cyclodextrin by the present invention for the first time, and obtains the cyclodextrin containing more carboxyls by polymerization reaction
Quasi polymer.Absorption when the additive amount of adsorbent of the invention in cigarette filter rod is 10mg/ branch, to ammonia in main flume
Efficiency is up to 46%, and does not make significant difference to cigarette odor-absorbing, has good selectivity.In addition, the absorption that the present invention synthesizes
Agent preparation method is simple, is convenient for industrialized production, and safe and stable property is high.
Detailed description of the invention
Fig. 1 is itaconic acid, beta-cyclodextrin and adsorbent1H NMR spectra；
Wherein, Fig. 1 (I) (II) (III) is successively IA (itaconic acid), β-CD and β-CD-g-IA (adsorbent)1H NMR
Spectrogram.As shown in Fig. 1 (I), the displacement characteristic absorption peak of IA is located at 13.0ppm-2.0ppm, and wherein 12.4ppm (H-a) is carboxyl
Hydrogen peak；6.1ppm (H-c) and 5.7ppm (H-d) is the hydrogen peak on carbon-carbon double bond, and 2.5ppm (H-b) is to be connected to methylene in double bond
The hydrogen peak of base；3.2ppm and 3.4ppm is the deuterated DMSO of solvent and water peak.The characteristic absorption peak of the β-CD as shown in Fig. 1 (II),
7.6ppm (H-e) is 6 hydroxyl hydrogen peaks, and 6.5ppm (H-g) is 3 hydroxyl hydrogen peaks, and 5.8ppm (H-h) is 2 hydroxyl hydrogen peaks,
4.8ppm(H-i1,2) it is hydrogen peak on 6 methylene, 6.2ppm (H-f), 3.8ppm (H-j), 3.7ppm (H-k), 3.2ppm
(H-n), 2.5ppm (H-m) is the upper corresponding hydrogen peak β-CD.The β-CD-g-IA as shown in Fig. 1 (III)1H NMR spectra is kept
The characteristic peak of IA and β-CD.It is associated in grafting process, is connected after the carbon-carbon double bond fracture of IA with ehter bond, by ether with β-CD in IA
The supplied for electronic conjugation of key influences, and the H-c and H-d of IA is moved to 4.4ppm (H-p to low field1,2)；Simultaneously as IA exists
Self-polymeric reaction is influenced by carboxyl blind zone, and the methylene hydrogen peak (H-b) at the upper 2.5ppm of IA is moved to 1.0ppm to low field[21].More than1H NMR characterization result shows that IA successfully grafts on β-CD.More than1H NMR characterization result demonstrate beta-cyclodextrin with
The graft polymers reaction of itaconic acid follows the reaction mechanism mechanism of reaction shown in picture.
Specific embodiment
Following embodiment is intended to illustrate invention, rather than further limits to the scope of the present invention.
The detection of ammonia of main stream smoke of cigarette is referring to professional standard YC/T 377-2010.
Embodiment 1
In the deionized water for taking the beta-cyclodextrin of 6.17mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 60 DEG C, and 223.00mg initiator ammonium persulfate is then added, the reaction was continued 3h.It is eventually adding 5ml concentration
Reaction is terminated for the hydroquinone aqueous solution of 0.075mol/L.Mixture system is cooled to room temperature, with methanol aqueous solution (30:
70) it washs, is poured into acetone and precipitates, filter, and be washed with deionized, be dried in vacuo at 40 DEG C for 24 hours, obtain white powder
Solid is adsorbent.Adsorbent is placed in cigarette filter, dosage is 10mg/ branch, to cigarette main flue under ISO suction mode
The adsorption efficiency of ammonia is 44% in gas.
Embodiment 2
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 223.00mg initiator ammonium persulfate is then added, the reaction was continued 3h.It is eventually adding 5ml concentration
Reaction is terminated for the hydroquinone aqueous solution of 0.08mol/L.Mixture system is cooled to room temperature, with methanol aqueous solution (30:
70) it washs, is poured into acetone and precipitates, filter, and be washed with deionized, be dried in vacuo at 40 DEG C for 24 hours, obtain white powder
Solid is adsorbent.Adsorbent is placed in cigarette filter, dosage is 10mg/ branch, to cigarette main flue under ISO suction mode
The adsorption efficiency of ammonia is 46% in gas.
Embodiment 3
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 223.00mg initiator ammonium persulfate is then added, the reaction was continued 3h.It is eventually adding 5ml concentration
Reaction is terminated for the hydroquinone aqueous solution of 0.08mol/L.Mixture system is cooled to room temperature, with methanol aqueous solution (30:
70) it washs, is poured into acetone and precipitates, filter, and be washed with deionized, be dried in vacuo at 40 DEG C for 24 hours, obtain white powder
Solid is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, unreacted monomer is removed, after dry
Adsorbent is placed in cigarette filter, dosage is 10mg/ branch, is imitated under ISO suction mode to the absorption of ammonia of main stream smoke of cigarette
Rate is 46%.
Embodiment 4
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 223.00mg initiator ammonium persulfate is then added, the reaction was continued 3h.It is eventually adding 5ml concentration
Reaction is terminated for the hydroquinone aqueous solution of 0.08mol/L.Mixture system is cooled to room temperature, with methanol aqueous solution (30:
70) it washs, is poured into acetone and precipitates, filter, and be washed with deionized, be dried in vacuo at 40 DEG C for 24 hours, obtain white powder
Solid is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, unreacted monomer is removed, after dry
Adsorbent is placed in cigarette filter, dosage is 25mg/ branch,
It is excessive to be measured cigarette resistance to suction, measurement result inaccuracy influences mouthfeel of smoking.
Embodiment 5
Polymeric reaction temperature is 40 DEG C, initiator amount 1%: specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 40 DEG C, and 74.00mg initiator ammonium persulfate is then added, the reaction was continued 3h.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 39%.
Embodiment 6
Polymerization reaction range is 0.5h, initiator amount 1%, specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 70mg initiator ammonium persulfate is then added, the reaction was continued 0.5h.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 32%.
Embodiment 7
Change the dosage of initiator:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 223mg initiator ammonium persulfate is then added, the reaction was continued 3h.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
Embodiment 8
Change the dosage of initiator:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 372mg initiator ammonium persulfate is then added, the reaction was continued 3h.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
Embodiment 9
Change the dosage of initiator:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 521mg initiator ammonium persulfate is then added, the reaction was continued 3h.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
The dosage of initiator is exactly the 1%-7% referring to monomer mass, and selection is exactly 1%, 3%, 5%, the four of 7%
The dosage of a point, adsorption rate in dosage 3% be it is highest, grafting rate is also the largest.
Embodiment 10
Change the mass ratio of the material example of beta-cyclodextrin and itaconic acid:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, addition 40mmol itaconic acid, 80
30min is reacted at DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
Embodiment 11
Change the mass ratio of the material example of beta-cyclodextrin and itaconic acid:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, addition 81mmol itaconic acid, 80
30min is reacted at DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
Embodiment 12
Change the mass ratio of the material example of beta-cyclodextrin and itaconic acid:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 162mmol itaconic acid is added,
30min is reacted at 80 DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
Embodiment 13
Change the mass ratio of the material example of beta-cyclodextrin and itaconic acid:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 208mmol itaconic acid is added,
30min is reacted at 80 DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 43%.
The mass ratio of the material of beta-cyclodextrin and itaconic acid is 1: 6；1:12；1:18；1:24；1: 30, there are 7 on beta-cyclodextrin
Reaction site is almost not involved in reaction wherein there is a site activity excessively poor, so the mass ratio of the material is 1: 6, is lower than this
A value Raolical polymerizable is insufficient.
Comparative example 1:
It is compared with embodiment 1, difference is, polymeric reaction temperature is 30 DEG C:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 208mmol itaconic acid is added,
30min is reacted at 30 DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 31%.
Comparative example 2:
It is compared with embodiment 1, difference is, polymeric reaction temperature is 90 DEG C:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 208mmol itaconic acid is added,
30min is reacted at 90 DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 23%.
Polymerization temperature is higher than 80 degrees Celsius, and initiator is easy to cause to inactivate, and the polymerization temperature lower than 40 DEG C cannot make to draw
The activity of hair agent reaches maximum, is easy to cause the reduction of grafting rate, reaction process slows down.
Comparative example 3
This comparison case inquires into the dosage (0.5wt%) of initiator, specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 208mmol itaconic acid is added,
30min is reacted at 80 DEG C, and 37.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 26%.
Comparative example 4
This comparison case inquires into the dosage (8wt%) of initiator, specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 208mmol itaconic acid is added,
30min is reacted at 80 DEG C, and 600.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mo1/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 28%.
Comparative example 5
This comparison case inquires into the amount (1: 7.7) of the substance of beta-cyclodextrin and itaconic acid, specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 50.4mmol itaconic acid is added,
30min is reacted at 80 DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 29%.
Comparative example 6
This comparison case inquires into the amount (1: 107) of the substance of beta-cyclodextrin and itaconic acid, specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 701mmol itaconic acid is added,
30min is reacted at 80 DEG C, and 372.00mg initiator ammonium persulfate, the reaction was continued 3h is then added.Being eventually adding 5ml concentration is
The hydroquinone aqueous solution of 0.08mol/L terminates reaction.Mixture system is cooled to room temperature, with methanol aqueous solution (30: 70)
Washing, is poured into acetone and precipitates, and filters, and be washed with deionized, is dried in vacuo at 40 DEG C for 24 hours, and it is solid to obtain white powder
Body is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, remove unreacted monomer, will after dry
Adsorbent is placed in cigarette filter, and dosage is 10mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is 33.4%.
From each embodiment, comparative example 5 and 6 it is found that the amount of the substance of beta-cyclodextrin and itaconic acid of the presently claimed invention
In range, it is more advantageous to the promotion of grafting rate.
Comparative example 7
This comparison case inquires into additive amount, specific as follows:
In the deionized water for taking the beta-cyclodextrin of 6.57mmol to be dissolved in 100ml at 60 DEG C, 122.22mmol clothing health is added
Acid reacts 30min at 80 DEG C, and 223.00mg initiator ammonium persulfate is then added, the reaction was continued 3h.It is eventually adding 5ml concentration
Reaction is terminated for the hydroquinone aqueous solution of 0.08mol/L.Mixture system is cooled to room temperature, with methanol aqueous solution (30:
70) it washs, is poured into acetone and precipitates, filter, and be washed with deionized, be dried in vacuo at 40 DEG C for 24 hours, obtain white powder
Solid is adsorbent.By this adsorbent in the aqueous solution of methanol Soxhlet extraction 48h, unreacted monomer is removed, after dry
Adsorbent is placed in cigarette filter, dosage is 1mg/ branch, to the adsorption efficiency of ammonia of main stream smoke of cigarette under ISO suction mode
It is very low, almost without adsorptivity.
Claims (18)
1. a kind of adsorbent for reducing ammonia of main stream smoke of cigarette burst size, which is characterized in that be beta-cyclodextrin and itaconic acid
Graft copolymer.
2. reducing the adsorbent of ammonia of main stream smoke of cigarette burst size as described in claim 1, which is characterized in that beta-cyclodextrin
Mass percent be 61.3%-70.2%.
3. reducing the adsorbent of ammonia of main stream smoke of cigarette burst size as described in claim 1, which is characterized in that the suction
Attached dose of partial size is 50-200 mesh.
4. a kind of preparation side of the described in any item adsorbents for reducing ammonia of main stream smoke of cigarette burst size of claims 1 to 3
Method, which is characterized in that under initiator effect polymerization reaction occurs for beta-cyclodextrin and itaconic acid；After polymerization, polymerization inhibitor is added
Agent terminates reaction；Polymerizate is washed, precipitating, is dried to get the adsorbent.
5. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In the molar ratio of beta-cyclodextrin and itaconic acid is 1: 6~1: 31.
6. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In beta-cyclodextrin and itaconic acid react at 40-80 DEG C.
7. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 6, feature exists
In the reaction time is 20~40min.
8. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In the initiator is potassium peroxydisulfate and/or ammonium persulfate.
9. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In the dosage of the initiator is the 1wt%-7wt% of the quality of monomer beta-cyclodextrin.
10. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In the temperature of polymerization process is 40-80 DEG C.
11. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size, feature as claimed in claim 10
It is, polymerization reaction time 1-5h.
12. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In the polymerization inhibitor is the aqueous solution of hydroquinone, wherein hydroquinone molar concentration is 0.05-0.10mol/L.
13. reducing the preparation method of the adsorbent of ammonia of main stream smoke of cigarette burst size as claimed in claim 4, feature exists
In the cleaning solution is the aqueous solution of methanol, wherein the percentage by volume of methanol is 20~40%；
The precipitating reagent that precipitation process uses is acetone.
14. a kind of any one of adsorbent as claimed in any one of claims 1 to 3 or claim 5~14 preparation method system
The application of the adsorbent obtained, which is characterized in that as additive addition in cigarette filter rod.
15. the application of adsorbent as claimed in claim 14, which is characterized in that the additive amount in cigarette filter rod is 5mg/
Branch -20mg/ branch.
16. the application of adsorbent as claimed in claim 15, which is characterized in that the cigarette filter rod is binary compound filter candle
Or Three-element composite filter core.
17. the application of adsorbent as claimed in claim 16, which is characterized in that the adsorbent is added in binary composite filter
The close pipe tobacco end of stick.
18. the application of adsorbent as claimed in claim 16, which is characterized in that the adsorbent addition is filtered in tri compound
The interlude of stick.
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| CN112841718A (en) * | 2019-11-28 | 2021-05-28 | 湖南中烟工业有限责任公司 | Cigarette filter stick additive with function of reducing ammonia release amount in main stream smoke of cigarette, and preparation method and application thereof |
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