CN101974124B - Sugar-containing bipolymer additive for reducing phenol substance contained in cigarette smoke - Google Patents
Sugar-containing bipolymer additive for reducing phenol substance contained in cigarette smoke Download PDFInfo
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Abstract
The invention discloses a sugar-containing bipolymer additive for reducing phenol substances contained in cigarette smoke. The additive takes a granular porous material as a carrier and granular porous material is loaded with hydrophilic polycations; and the hydrophilic polycations are sugar-containing bipolymers. If the sugar-containing bipolymer additive can be used for preparing a cigarette filter, the harmful phenol substances contained in the cigarette smoke can be reduced selectively by utilizing moisture contained in the sugar-containing bipolymer additive; in addition, because multiple fragrant organic compounds are water-insoluble, the invention reduces the harmful phenol components contained in the cigarette smoke and can also possibly prevent fragrant components from being lost, thereby maintaining the internal quality of cigarettes.
Description
Technical field
The present invention relates to reducing cigarette tar and reducing harm reduction technical field, be specifically related to the sugared copolymer additive that contains of content of phenol type substances in a kind of selectivity reducing cigarette fume.
Background technology
For a long time, the World tobacco industry is paid much attention to the work of cigarette lowering harm and decreasing coking always.WHO has especially clearly regulation to the control of harmful ingredients in flue gas in recent years, has obtained the active response of countries in the world.To various objectionable constituent in the cigarette smoke, the investigator has been developed the multiple evil technology of falling, and wherein the modification to cigarette filter is the most effectively to fall one of harmful means; Through interpolation in cigarette filter or composite nano materials, macromolecular material and biomaterial etc., reach the effect of some objectionable constituent of effective reduction cigarette smoke.
The cigarette smoke composition is very many, mainly is divided into two types of hydrophilic composition and hydrophobicity compositions.Result of study shows: with some metal catalysts, porous or mesoporous adsorption material, nano material; Also have of the modification of material such as biomacromolecule DNA, lowly played good effect for what hydrophobicity polycyclic aromatic hydrocarbons such as objectionable constituent such as benzopyrene and CO were fallen to cigarette filter; The low CO type cigarette of metallic catalyst has appearred on the market in cigarette filter, adding.The investigator finds with materials such as oxyphorase, tea matter composite modified to cigarette filter, perhaps uses NaA type zeolite composite modified to cigarette filter, for the reduction of unwanted components such as nitroso compound, aldehyde ketone compound certain effect arranged also.
Phenolic cpd is a kind of main objectionable impurities in the cigarette smoke, can through mucocutaneous, respiratory tract and digestive tube get in the body with cell magma in protein generation chemical reaction, cause that the stupor of the property accumulated chronic poisoning or acute poisoning is dead.Wherein maximum with the toxicity of phenol again, so phenol classified as one of index property compound of cigarette smoke objectionable impurities, needs monitor and control it.At present, some researchs have begun to pay close attention to the reduction of phenols objectionable impurities in the cigarette smoke.The extract mixture that discloses among the Chinese patent ZL200710162960.8 some herbal medicine is incorporated in the pipe tobacco as the method that reduces phenols objectionable impurities in the cigarette smoke; But this method might influence the trouble-free burning of pipe tobacco; The mouthfeel of flue gas is affected, even can increases other objectionable constituent.The calixarene that discloses among the one Chinese patent application CN200910307638.9 solid powdery directly is added in the cigarette filter as additive, can reduce about 40% phenol, but the toxicity of calixarene self is still waiting to consider.In addition, disclose ionic liquid, MOX additive among one Chinese patent application CN200810031589.6 and the one Chinese patent application CN200710034453.6 respectively, and had certain phenol effect of falling as filter stick; But these two kinds of material preparation technology more complicated, and the filter-tip hygienic safety problem that is added with ionic liquid or MOX also needs further to investigate.Therefore, be necessary to develop a kind of novel cigarette filter-tip additive agent.
Summary of the invention
The present invention is based on phenol type substances principle soluble in water, design and developed a kind of wetting ability polycation, promptly contain sugared copolymer, be used to reduce the content of phenol type substances.
The present invention also provides the additive of phenols harmful substance contents in a kind of selectivity reducing cigarette fume.
A kind ofly contain sugared copolymer, for the multipolymer shown in the following formula I structural formula:
Formula I;
Wherein, R
1Be glycosyl, select in glucone, fructosyl, sucrose base, malt-base, lactose base, the cotton seed glycosyl one or more for use;
Contain R
2The polymerizable cationic monomer of group is allylamine hydrochloride, N; A kind of in N-DMAA hydrochloride, N-methacrylic amine hydrochlorate, methylacryoyloxyethyl trimethyl ammonium chloride, the dimethyl diallyl ammonium chloride is used for containing sugared copolymer and introducing and contain R to described
2The structural unit of group;
N is 1～10 integer;
X: y=10: 1～1: 10, and x: y representes constitutive molar ratio.
The described existing building-up reactions in sugared copolymer employing this area that contains prepares, through containing R
2The polymerizable cationic monomer of group according to the conventional polymerization method in this area with contain R
1The glycosyl two vinyl acetate polymerizations of group and getting, and the compound method of putting down in writing in the general RR with reference to people such as Wuqi County (Macromol.Biosci.2006,6,78-83) synthesize.General method is: at first synthetic diacid divinyl ester: diacid and vinyl acetate are mixed, and reaction makes diacid divinyl ester under the effect of catalyzer; Then, mixes with sugar with gained diacid divinyl ester, under the katalysis of bacillus alkaline protease, react, crude product obtains light yellow product glycosyl two vinyl acetates after column chromatography for separation is extracted, again with glycosyl two vinyl acetates and contain R
2The polymerizable cationic monomer of group mixes, and adds persulfate aqueous solution, under nitrogen protection, carries out radical polymerization, and thick polymerisate is after the water dialysis, and lyophilize promptly gets the sugared binary copolymerization product that contains finally.
Described sugar can be selected one or more in glucose, fructose, sucrose, SANMALT-S, lactose, the raffinose etc. for use.
The described R that contains
2The polymerizable cationic monomer of group can be selected the commercially available prod for use.
The additive of phenol harmful substance contents in a kind of selectivity reducing cigarette fume, be with the porous material be carrier and on porous material load the material of wetting ability polycation.
The present invention finds that the wetting ability polycation has the ability of moisture water conservation, and the ability of its moisture water conservation has guaranteed the moisture content in the additive, makes moisture play the effect that phenol objectionable impurities selectivity in the cigarette smoke is reduced.
Described wetting ability polycation is selected the sugared copolymer that contains shown in the described formula I structural formula for use.Contain a large amount of hydroxyl structures described containing in the sugared copolymer, promoted and phenolic cpd between reactive force.
Described porous material is the carrier of additive, and its porous adsorptive power provides guarantee for the load of wetting ability polycation; The porous material of preferred particulates shape, granular profile can better meet the production demand of cigarette filter, and described granular porous material can be selected this area granular porous material commonly used for use; In the preferred zeyssatite of described porous material, silica gel, gac, macroporous adsorbent resin, molecular sieve, zeolite, the sepiolite etc. one or more.
The quality percentage composition of the wetting ability polycation of load in the described additive is preferably 0.05%～5%, can under the prerequisite of practicing thrift cost, more effectively remove the phenols objectionable impurities.
The particle diameter of described additive is preferably 0.05mm～3mm, and specific surface area is preferably 20m
2/ g～1500m
2/ g, quality water ratio are preferably 10%～40% (testing method of quality water ratio is generally: 100 ℃ of dry 2h, according to the calculated mass water ratio of poor quality before and after dry).
The preparation method of described additive comprises: the mode of wetting ability polycation through common dipping absorption loaded on the porous material, make additive; Concrete steps comprise: the aqueous solution thorough mixing of porous material and wetting ability polycation is even, leave standstill after-filtration, and the solid matter vacuum-drying with filtration obtains obtains additive.
The concentration of the aqueous solution of described wetting ability polycation is preferably 0.2g/L～10g/L.
To be water-keeping material through an effect of carrying of porous material construct described additive forms with hydrophilic polycation; Described additive is applied to prepare in the cigarette filter, just can utilizes the phenol objectionable impurities in the moisture selectivity reducing cigarette fume in the additive.
In the filter stick total mass in the cigarette filter of a cigarette, the quality percentage composition of described additive is preferably 5%～50%.
Described cigarette filter can be the binary compound cigarette filter, comprises common filter stick and the axial and synergetic composite filter of common filter stick along common filter stick; Described composite filter is perhaps processed by described additive and common filter stick material by described additive; Composite filter contacts with the pipe tobacco section when being used to prepare cigarette.Wherein, described composite filter is preferably 1～2: 1～2 with the length ratio of common filter stick.
Described cigarette filter can also be the three-stage compound cigarette filter, comprises the axial and synergetic composite filter of common filter stick of the common filter stick of two sections common filter sticks and edge, and described composite filter is between two sections common filter sticks; Described composite filter is perhaps processed by described additive and common filter stick material by described additive; Common filter stick contacts with the pipe tobacco section when being used to prepare cigarette.Wherein, described composite filter is preferably 0.5～2: 1 with the length ratio of the common filter stick of each section.
Material selection this area of described common filter stick is applicable to the material of doing filter stick, as selecting in cellulose acetate commonly used, polypropylene fibre, paper fiber, viscose fiber, the Lyocell fiber (being disappearing fibre) etc. one or more for use.
Composite filter of the present invention and common filter stick all adopt the conventional preparation method of this area filter stick to prepare.
The specification of cigarette filter of the present invention can be according to the filter tip specification of commercial cigarettes.
Described phenol type substances comprise phenol ,-in the phenol compound such as cresols, p-Cresol, neighbour-cresols one or more.
Compared with prior art, the present invention has following advantage:
The cigarette filter of additive preparation of the present invention can effectively reduce the phenol objectionable constituent in the flue gas with the moisture of wetting ability polycation in the additive and absorption as filtration medium.Compare with the commercial cigarettes of same specification, adopt the cigarette filter of additive preparation of the present invention can make the content of phenol objectionable constituent in the cigarette smoke reduce by 40%～60%.
Because many fragrance organic cpds are water insoluble, additive of the present invention can also be avoided the flavour ingredient loss in the phenol objectionable constituent in reducing flue gas simultaneously, keeps the interior quality of cigarette.
Description of drawings
Fig. 1 is the structural representation that the cigarette of binary compound cigarette filter of the present invention is housed;
Fig. 2 is the structural representation that the cigarette of three-stage compound cigarette filter of the present invention is housed;
Among Fig. 1 and Fig. 2,1 is common filter stick, and 2 is composite filter, and 3 is cigarette filter, and 4 is the pipe tobacco section.
Embodiment
Contain the synthetic of sugared copolymer wetting ability polycation: get at first respectively in the 250mL flask that the 0.4mol raw material A joins the mercuric acetate that fills 150mL vinyl acetate, 1.0g and acetate in minute copper.Heating and magnetic agitation in 55 ℃ constant temperature oil bath, the vitriol oil of dropping 0.25mL mass percentage concentration 98% continues reaction 6.5h after half a hour.After the cooling, add about 2g sodium-acetate and fully stir, add saturated sodium hydrogen carbonate solution again, be stirred to bubble collapse, leave standstill, separatory gets crude product with non-water layer underpressure distillation, and column chromatography for separation gets product B diacid divinyl ester again.In the Erlenmeyer flask of 250mL, be that 1: 4 ratio adds raw material C and product B with the mol ratio of raw material C and product B, add 1g bacillus alkaline protease and 40mL pyridine then, 50 ℃ were reacted 3 days.After reaction finished, filtration was dezymotized and pyridine is removed in underpressure distillation, and crude product uses column chromatography extraction, obtains light yellow product D glycosyl two vinyl acetates, 60 ℃ of vacuum-dryings.With product D and raw material E with mol ratio 1: 1 in the 25mL round-bottomed flask, add the potassium persulfate solution of 6mg/mL, making the Potassium Persulphate quality is 2% of raw material E total mass.Under nitrogen protection, 70 ℃ of stirring reaction 24h pour deposition in the acetone, filtration, 50 ℃ of vacuum-dryings acquisition crude products into.Crude product was dialysed 3 days to big water gaging after being dissolved in suitable quantity of water, and-45 ℃ of lyophilizes get white final product F.
Contain synthesizing according to the method described above of sugared copolymer wetting ability polycation; Wherein, raw material A is a hexanodioic acid, and raw material C is a glucose; Raw material E is an allylamine hydrochloride; Product B is a hexanodioic acid divinyl ester, and product D is the glucone hexanedioic acid vinyl ester, synthesizes to obtain containing sugared copolymer wetting ability polycation.
1647cm in the above-mentioned infrared spectrum that contains sugared copolymer wetting ability polycation
-1Disappearance, the 3000～3100cm of the two key characteristic peaks of the C=C at place
-1The appearance and the 1000～1100cm of uncle's ammonium salt characteristic peak at place
-1Locate the maintenance at sugared C-O vibration performance peak, product polymerization success be described, have following structural formula:
Confirm that according to the above-mentioned magnetic resonance detection data that contain sugared copolymer wetting ability polycation wherein the mol ratio of x: y is 1: 4.
Contain synthesizing according to the method described above of sugared copolymer wetting ability polycation, wherein, raw material A is a pimelic acid; Raw material C is a raffinose; Raw material E is a N-methacrylic amine hydrochlorate, and product B is a pimelic acid divinyl ester, and product D is a cotton seed glycosyl pimelic acid vinyl acetate; The mol ratio of product D and raw material E 5: 1 synthetic obtains containing sugared copolymer wetting ability polycation.
1645cm in the above-mentioned infrared spectrum that contains sugared copolymer wetting ability polycation
-1Disappearance, the 3000cm of the two key characteristic peaks of the C=C at place
-1The appearance and the 1000～1100cm of the secondary ammonium salt characteristic peak at place
-1Locate the maintenance at sugared C-O vibration performance peak, product polymerization success be described, have following structural formula:
Confirm that according to the above-mentioned magnetic resonance detection data that contain sugared copolymer wetting ability polycation wherein the mol ratio of x: y is 2.5: 1.
Contain synthesizing according to the method described above of sugared copolymer wetting ability polycation, wherein, raw material A is a propanedioic acid; Raw material C is a SANMALT-S; Raw material E is an allylamine hydrochloride, and product B is a propanedioic acid divinyl ester, and product D is a malt-base propanedioic acid vinyl acetate; The mol ratio of product D and raw material E 2: 1 synthetic obtains containing sugared copolymer wetting ability polycation.
1646cm in the above-mentioned infrared spectrum that contains sugared copolymer wetting ability polycation
-1Disappearance, the 3000～3100cm of the two key characteristic peaks of the C=C at place
-1The appearance and the 1000～1100cm of uncle's ammonium salt characteristic peak at place
-1Locate the maintenance at sugared C-O vibration performance peak, product polymerization success be described, have following structural formula:
Confirm that according to the above-mentioned magnetic resonance detection data that contain sugared copolymer wetting ability polycation wherein the mol ratio of x: y is 1: 1.2.
Contain synthesizing according to the method described above of sugared copolymer wetting ability polycation, wherein, raw material A is a sebacic acid; Raw material C is a lactose, and raw material E is N, N-DMAA hydrochloride; Product B is a sebacic acid divinyl ester; Product D is a lactose base sebacic acid vinyl acetate, and the mol ratio of product D and raw material E 1: 3 synthetic obtains containing sugared copolymer wetting ability polycation.
1640cm in the above-mentioned infrared spectrum that contains sugared copolymer wetting ability polycation
-1The disappearance and the 1000～1100cm of the two key characteristic peaks of the C=C at place
-1Locate the maintenance at sugared C-O vibration performance peak, product polymerization success be described, have following structural formula:
Confirm that according to the above-mentioned magnetic resonance detection data that contain sugared copolymer wetting ability polycation wherein the mol ratio of x: y is 1: 10.
Embodiment 5
Contain synthesizing according to the method described above of sugared copolymer wetting ability polycation; Wherein, raw material A is a dodecanedioic acid, and raw material C is a glucose; Raw material E is the methylacryoyloxyethyl trimethyl ammonium chloride; Product B is a dodecanedioic acid divinyl ester, and product D is a glucone dodecanedioic acid vinyl acetate, and the mol ratio of product D and raw material E obtains containing sugared copolymer wetting ability polycation at 1: 2.5.
1648cm in the above-mentioned infrared spectrum that contains sugared copolymer wetting ability polycation
-1Disappearance, the 947cm of the two key characteristic peaks of the C=C at place
-1The appearance and the 1000～1100cm of the quaternary ammonium salt characteristic peak at place
-1Locate the maintenance at sugared C-O vibration performance peak, product polymerization success be described, have following structural formula:
Confirm that according to the above-mentioned magnetic resonance detection data that contain sugared copolymer wetting ability polycation wherein the mol ratio of x: y is 1: 6.5.
Embodiment 6
With the said polycation solution that contains the water-soluble 5mg/mL of being mixed with of sugared copolymer among the embodiment 1; Again the 5.0g granular active carbon is immersed in the above-mentioned said polycation solution of 10ml; Soak 6h, filter, the gained solid dries by the fire 10h down in 60 ℃; Obtain additive, the quality percentage composition of the polycation of load is 2.5% in the additive.Through the infrared spectrum characterization analysis, 3000～3100cm in the infrared spectrum of this additive
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on granular active carbon of sugared copolymer, and obtaining load has the granular porous material that contains sugared copolymer.
Through detecting, this additive particle diameter is 0.05mm, and specific surface area is 100m
2/ g, quality water ratio are 20%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming process composite filter 2; Being raw material with the acetate silk makes common cellulose acetate filter rod 1 according to the preparation method of composite filter 2.The composite filter that makes 2 is axially superposeed with common cellulose acetate filter rod 1 along common cellulose acetate filter rod 1; Make binary compound cigarette filter 3; Wherein, Composite filter 2 is 2: 1 with the length ratio of common cellulose acetate filter rod 1, and the addition of additive is 5% of composite filter 2 and common cellulose acetate filter rod 1 total mass.
Common cellulose acetate filter rod with the binary compound cigarette filter that makes 3 substitutes in certain brand commercial cigarettes is produced the sample cigarette, and composite filter 2 one ends contact with pipe tobacco section 4 in the sample cigarette.Aldehydes matter in the sample cigarette flue gas is measured, and contrasts with the commercial cigarettes of pipe tobacco of the same race (adopting the common cellulose acetate filter rod of same size).(Cerulean measures on UK) content of phenol type substances according to the Cerulean SM450 type that the is defined in smoking machine of ISO3308 in the cigarette smoke.The result sees table 1.
Table 1 combined type cigarette filter of the present invention is to the harmful effect of falling of aldehydes matter
Embodiment 7
With the said polycation solution that contains the water-soluble 0.2mg/mL of being mixed with of sugared copolymer among the embodiment 2; Again 5.0g particulate state macroporous adsorbent resin is immersed in the above-mentioned said polycation solution of 7.5ml; Soak 7h, filter, the gained solid dries by the fire 9h down in 65 ℃; Obtain additive, the quality percentage composition of the polycation of load is 0.05% in the additive.3000cm in the infrared spectrum of this additive
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks,, and the measured value of zeta current potential is+20mV, verified that this contains the load success on the particulate state macroporous adsorbent resin of sugared copolymer, obtaining load has the granular porous material that contains sugared copolymer.
Through detecting, this additive particle diameter is 2mm, and specific surface area is 20m
2/ g, quality water ratio are 40%.
With above-mentioned additive on filter-stick forming device and roll-forming process composite filter 2; Being raw material with the acetate silk makes common cellulose acetate filter rod 1 according to the preparation method of composite filter 2.The composite filter that makes 2 is axially superposeed with common cellulose acetate filter rod 1 along common cellulose acetate filter rod 1; Make binary compound cigarette filter 3; Wherein, Composite filter 2 is 1: 2 with the length ratio of common cellulose acetate filter rod 1, and the addition of additive is 50% of composite filter 2 and common cellulose acetate filter rod 1 total mass.
Common cellulose acetate filter rod with the binary compound cigarette filter that makes 3 substitutes in certain brand commercial cigarettes is produced the sample cigarette, and composite filter 2 one ends contact with pipe tobacco section 4 in the sample cigarette.Aldehydes matter in the sample cigarette flue gas is measured, and contrasts with the commercial cigarettes of pipe tobacco of the same race (adopting the common cellulose acetate filter rod of same size).The detection method of content of phenol type substances is with embodiment 6 in the cigarette smoke.The result sees table 2.
Table 2 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols objectionable impurities
Embodiment 8
With the said polycation solution that contains the water-soluble 10mg/mL of being mixed with of sugared copolymer among the embodiment 3; Again the 5.0g particulate molecular sieve is immersed in the above-mentioned said polycation solution of 25ml; Soak 7h, filter, the gained solid dries by the fire 10h down in 60 ℃; Obtain additive, the quality percentage composition of the polycation of load is 5% in the additive.3000～3100cm in the infrared spectrum of this additive
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on particulate molecular sieve of sugared copolymer, and obtaining load has the granular porous material that contains sugared copolymer.
Through detecting, this additive particle diameter is 0.5mm, and specific surface area is 200m
2/ g, quality water ratio are 30%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming process composite filter 2; Being raw material with the acetate silk makes common cellulose acetate filter rod 1 according to the preparation method of composite filter 2.The composite filter that makes 2 is placed between two sections common cellulose acetate filter rods 1; And along common cellulose acetate filter rod 1 axial and two sections common cellulose acetate filter rods 1 stacks; Make three-stage compound cigarette filter 3; Wherein, composite filter 2 is 0.5: 1 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of additive is 40% of composite filter 2 and two sections common cellulose acetate filter rod 1 total masses.
Common cellulose acetate filter rod with the three-stage compound cigarette filter that makes 3 substitutes in certain brand commercial cigarettes is produced the sample cigarette, and an end of one section common cellulose acetate filter rod 1 contacts with pipe tobacco section 4 in the sample cigarette.Aldehydes matter in the sample cigarette flue gas is measured, and contrasts with the commercial cigarettes of pipe tobacco of the same race (adopting the common cellulose acetate filter rod of same size).The detection method of content of phenol type substances is with embodiment 6 in the cigarette smoke.The result sees table 3.
Table 3 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols objectionable impurities
Embodiment 9
With the said polycation solution that contains the water-soluble 3mg/mL of being mixed with of sugared copolymer among the embodiment 4; Again 5.0g particulate state diatom soil is immersed in the above-mentioned said polycation solution of 25ml; Soak 6h, filter, the gained solid dries by the fire 10h down in 60 ℃; Obtain additive, the quality percentage composition of the polycation of load is 2.5% in the additive.1000～1100cm in the infrared spectrum of this additive
-1The appearance of characteristic peak, and the measured value of zeta current potential is+23mV, verified that this contains the load success on particulate state diatom soil of sugared copolymer, obtaining load has the granular porous material that contains sugared copolymer.
Through detecting, this additive particle diameter is 0.1mm, and specific surface area is 800m
2/ g, quality water ratio are 25%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming process composite filter 2; Being raw material with the acetate silk makes common cellulose acetate filter rod 1 according to the preparation method of composite filter 2.The composite filter that makes 2 is placed between two sections common cellulose acetate filter rods 1; And along common cellulose acetate filter rod 1 axial and two sections common cellulose acetate filter rods 1 stacks; Make three-stage compound cigarette filter 3; Wherein, composite filter 2 is 1: 1 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of additive is 30% of composite filter 2 and two sections common cellulose acetate filter rod 1 total masses.
Common cellulose acetate filter rod with the three-stage compound cigarette filter that makes 3 substitutes in certain brand commercial cigarettes is produced the sample cigarette, and an end of one section common cellulose acetate filter rod 1 contacts with pipe tobacco section 4 in the sample cigarette.Aldehydes matter in the sample cigarette flue gas is measured, and contrasts with the commercial cigarettes of pipe tobacco of the same race (adopting the common cellulose acetate filter rod of same size).The detection method of content of phenol type substances is with embodiment 6 in the cigarette smoke.The result sees table 4.
Table 4 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols objectionable impurities
Embodiment 10
With the said polycation solution that contains the water-soluble 0.5mg/mL of being mixed with of sugared copolymer among the embodiment 5; Again 5.0g particulate state sepiolite is immersed in the above-mentioned said polycation solution of 15ml; Soak 5h, filter, the gained solid dries by the fire 10h down in 60 ℃; Obtain additive, the quality percentage composition of the polycation of load is 0.2% in the additive.947cm in the infrared spectrum of this additive
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on the particulate state sepiolite of sugared copolymer, and obtaining load has the granular porous material that contains sugared copolymer.
Through detecting, this additive particle diameter is 3mm, and specific surface area is 100m
2/ g, quality water ratio are 20%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming process composite filter 2; Being raw material with the acetate silk makes common cellulose acetate filter rod 1 according to the preparation method of composite filter 2.The composite filter that makes 2 is placed between two sections common cellulose acetate filter rods 1; And along common cellulose acetate filter rod 1 axial and two sections common cellulose acetate filter rods 1 stacks; Make three-stage compound cigarette filter 3; Wherein, composite filter 2 is 2: 1 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of additive is 20% of composite filter 2 and two sections common cellulose acetate filter rod 1 total masses.
Common cellulose acetate filter rod with the three-stage compound cigarette filter that makes 3 substitutes in certain brand commercial cigarettes is produced the sample cigarette, and an end of one section common cellulose acetate filter rod 1 contacts with pipe tobacco section 4 in the sample cigarette.Aldehydes matter in the sample cigarette flue gas is measured, and contrasts with the commercial cigarettes of pipe tobacco of the same race (adopting the common cellulose acetate filter rod of same size).The detection method of content of phenol type substances is with embodiment 6 in the cigarette smoke.The result sees table 5.
Table 5 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols objectionable impurities
Embodiment 11
With the said polycation solution that contains the water-soluble 0.1mg/mL of being mixed with of sugared copolymer among the embodiment 5; Again the Powdered silica gel of 5.0g is immersed in the above-mentioned said polycation solution of 10ml; Soak 6h, filter, the gained solid dries by the fire 10h down in 60 ℃; Obtain additive, the quality percentage composition of the polycation of load is 0.1% in the additive.947cm in the infrared spectrum of this additive
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on Powdered silica gel of sugared copolymer, and obtaining load has the granular porous material that contains sugared copolymer.
Through detecting, this additive particle diameter is 0.3mm, and specific surface area is 800m
2/ g, quality water ratio are 40%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming process composite filter 2; Being raw material with the acetate silk makes common cellulose acetate filter rod 1 according to the preparation method of composite filter 2.The composite filter that makes 2 is placed between two sections common cellulose acetate filter rods 1; And along common cellulose acetate filter rod 1 axial and two sections common cellulose acetate filter rods 1 stacks; Make three-stage compound cigarette filter 3; Wherein, composite filter 2 is 1.8: 1 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of additive is 25% of composite filter 2 and two sections common cellulose acetate filter rod 1 total masses.
Common cellulose acetate filter rod with the three-stage compound cigarette filter that makes 3 substitutes in certain brand commercial cigarettes is produced the sample cigarette, and an end of one section common cellulose acetate filter rod 1 contacts with pipe tobacco section 4 in the sample cigarette.Aldehydes matter in the sample cigarette flue gas is measured, and contrasts with the commercial cigarettes of pipe tobacco of the same race (adopting the common cellulose acetate filter rod of same size).The detection method of content of phenol type substances is with embodiment 6 in the cigarette smoke.The result sees table 6.
Table 6 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols objectionable impurities
Claims (9)
1. the additive of phenol harmful substance contents in the selectivity reducing cigarette fume is characterized in that, described additive be with the porous material be carrier and on porous material load the material of wetting ability polycation;
Described wetting ability polycation is with the multipolymer shown in the following formula I structural formula:
The formula I;
Wherein, R
1Be in glucone, fructosyl, sucrose base, malt-base, lactose base, the cotton seed glycosyl one or more;
Contain R
2The polymerizable cationic monomer of group is allylamine hydrochloride, N, a kind of in N-DMAA hydrochloride, N-methacrylic amine hydrochlorate, methylacryoyloxyethyl trimethyl ammonium chloride, the dimethyl diallyl ammonium chloride;
N is 1～10 integer;
X: y=10: 1～1: 10, and x: y representes constitutive molar ratio.
2. the additive of phenol harmful substance contents in the selectivity reducing cigarette fume according to claim 1; It is characterized in that described porous material is one or more in zeyssatite, silica gel, gac, macroporous adsorbent resin, molecular sieve, zeolite, the sepiolite.
3. the additive of phenol harmful substance contents is characterized in that in the selectivity reducing cigarette fume according to claim 1, and the quality percentage composition of the wetting ability polycation of load in the described additive is 0.05%～5%.
4. the additive of phenol harmful substance contents is characterized in that in the selectivity reducing cigarette fume according to claim 1, and the particle diameter of described additive is 0.05mm～3mm, and specific surface area is 20m
2/ g～1500m
2/ g, quality water ratio are 10%～40%.
5. according to the application in the preparation cigarette filter of the additive of phenol harmful substance contents in each described selectivity reducing cigarette fume of claim 1～4.
6. application according to claim 5 is characterized in that, in the filter stick total amount in the cigarette filter of a cigarette, the quality percentage composition of described additive is 5%～50%.
7. application according to claim 5 is characterized in that described cigarette filter is the binary compound cigarette filter, comprises common filter stick and the axial and synergetic composite filter of common filter stick along common filter stick; Described composite filter is perhaps processed by described additive and common filter stick material by described additive; Composite filter contacts with the pipe tobacco section when being used to prepare cigarette.
8. application according to claim 5; It is characterized in that; Described cigarette filter is the three-stage compound cigarette filter, comprises the axial and synergetic composite filter of common filter stick of the common filter stick of two sections common filter sticks and edge, and described composite filter is between two sections common filter sticks; Described composite filter is perhaps processed by described additive and common filter stick material by described additive; Common filter stick contacts with the pipe tobacco section when being used to prepare cigarette.
9. application according to claim 8 is characterized in that, described composite filter is 0.5～2: 1 with the length ratio of the common filter stick of each section.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102788336A CN101974124B (en) | 2010-09-10 | 2010-09-10 | Sugar-containing bipolymer additive for reducing phenol substance contained in cigarette smoke |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102788336A CN101974124B (en) | 2010-09-10 | 2010-09-10 | Sugar-containing bipolymer additive for reducing phenol substance contained in cigarette smoke |
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| CN101974124A CN101974124A (en) | 2011-02-16 |
| CN101974124B true CN101974124B (en) | 2012-08-22 |
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| CN106076250A (en) * | 2016-06-24 | 2016-11-09 | 广东中烟工业有限责任公司 | A kind of preparation method and application of adsorbing material |
| CN112674384A (en) * | 2019-10-17 | 2021-04-20 | 宁波合康生物医药科技有限公司 | Additive for reducing harmful substances in smoke and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049184A (en) * | 2006-04-03 | 2007-10-10 | 云南瑞升烟草技术（集团）有限公司 | Application of organic acid salt of multihydroxyl in preparing cigarette of reducing releasing tar and carbon monoxide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049184A (en) * | 2006-04-03 | 2007-10-10 | 云南瑞升烟草技术（集团）有限公司 | Application of organic acid salt of multihydroxyl in preparing cigarette of reducing releasing tar and carbon monoxide |
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