CN101954274A - Sugary copolymer composite material for reducing phenol-type substances in cigarette smoke and preparation - Google Patents
Sugary copolymer composite material for reducing phenol-type substances in cigarette smoke and preparation Download PDFInfo
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Abstract
The invention discloses a sugary copolymer composite material for reducing phenol-type substances in cigarette smoke and preparation. The composite material takes cellular materials as carriers, polyanion and hydrophilic polycation are alternately loaded on the cellular materials in a layer self-assembly mode, and the hydrophilic polycation is loaded at the outermost layer of the cellular materials. The composite material can be used for preparing cigarette filters and can be prepared into binary composite type cigarette filters or three-section composite type cigarette filters. In the invention, moisture in the composite material is utilized for selectively reducing phenol-type harmful substances in the cigarette smoke, meanwhile, because a plurality of flavor compounds are insoluble in water, loss of flavor components can be avoided, and the inherent quality of cigarettes is kept.
Description
Technical field
The present invention relates to reducing cigarette tar and reducing harm reduction technical field, what be specifically related to content of phenol type substances in a kind of selectivity reducing cigarette fume contains sugared bipolymer composite and preparation method thereof.
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.At various harmful components in the cigarette smoke, the researcher has been developed the multiple harmful technology of falling, and wherein the modification to cigarette filter is the most effective one of the harmful means of falling; By interpolation in cigarette filter or composite nano materials, macromolecular material and biomaterial etc., reach the effect of some harmful components of effective reduction cigarette smoke.
The cigarette smoke composition is very many, mainly is divided into hydrophilic composition and hydrophobicity composition two classes.Result of study shows: with some metallic catalysts, porous or mesoporous adsorption material, nano material, also have of the modification of material such as large biological molecule DNA, lowly played good effect for what hydrophobicity polycyclic aromatic hydrocarbon such as harmful components such as BaP and CO were fallen to cigarette filter; The low CO type cigarette of metallic catalyst has appearred on the market adding in cigarette filter.The researcher finds with materials such as hemoglobin, tea matter composite modified to cigarette filter, perhaps uses NaA type zeolite composite modified to cigarette filter, for the reduction of harmful constituents such as nitroso compound, aldehyde ketone compound certain effect arranged also.
Phenolic compound is a kind of main harmful substance in the cigarette smoke, can through mucocutaneous, respiratory tract and alimentary canal enter in the body with cell magma in protein generation chemical reaction, cause the stupor death of the property accumulated slow poisoning or acute poisoning.Wherein again with the toxicity maximum of phenol, so phenol is listed in one of index compound of cigarette smoke harmful substance, needs monitor and control it.At present, some researchs have begun to pay close attention to the reduction of phenols harmful substance in the cigarette smoke.The extract mixture that discloses among the Chinese patent ZL200710162960.8 some Chinese herbal medicines is incorporated in the pipe tobacco as the method that reduces phenols harmful substance in the cigarette smoke, but the method might influence the normal combustion of pipe tobacco, the mouthfeel of flue gas is affected, even can increases other harmful components.The calixarenes that discloses among the 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 calixarenes self is still waiting to consider.In addition, disclose ionic liquid, metal oxide additive among Chinese patent application CN200810031589.6 and the 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 safe and sanitary problem that is added with ionic liquid or metal oxide also needs further investigation.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, designed and developed the composite of phenols harmful substance contents in the selectivity reducing cigarette fume that a kind of load has the hydrophily polycation.
The present invention also provides the preparation method of the composite of phenols harmful substance contents in a kind of selectivity reducing cigarette fume, and simple controllable is suitable for suitability for industrialized production.
The composite of phenol harmful substance contents in a kind of selectivity reducing cigarette fume, be with the porous material be carrier and on porous material with the mode alternate load polyanion of self assembly layer by layer and the material of hydrophily polycation, and it is outermost for the hydrophily polycation to load on porous material;
Described hydrophily polycation is with the copolymer shown in the following formula I structural formula:
Formula I;
Wherein, R
1Be in glucosyl group, 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; Be used for containing sugared bipolymer and introducing and contain R to described
2The construction unit of group;
N is 1～10 integer;
X: y=10: 1～1: 10, and x: y represents constitutive molar ratio.
The described existing synthetic reaction in sugared bipolymer employing this area that contains prepares, by containing R
2The polymerizable cationic monomer of group according to the polymerization of this area routine with contain R
1The glycosyl two vinyl acetate polymerizations of group and getting, and the synthetic method of putting down in writing in the general research report with reference to people such as Wuqi County (Macromol.Biosci.2006,6,78-83) synthesize.Conventional method is: at first synthetic diacid divinyl ester: diacid and vinylacetate are mixed, and reaction makes diacid divinyl ester under the effect of catalyst; Then; mix with sugar with gained diacid divinyl ester; react under the catalytic action of bacillus alkaline protease, crude product obtains light yellow product glycosyl two vinyl acetates after column chromatography for separation is extracted; again glycosyl two vinyl acetates are mixed with the polymerizable cationic monomer that contains the R2 group; add persulfate aqueous solution, carry out radical polymerization under nitrogen protection, thick polymerizate is after the water dialysis; freeze drying promptly gets the sugared binary copolymerization product that contains finally.
Described sugar can be selected one or more in glucose, fructose, sucrose, maltose, lactose, the gossypose etc. for use.
The described R that contains
2The polymerizable cationic monomer of group can be selected the commercially available prod for use.
The present invention finds that the hydrophily polycation has the ability of moisture water conservation, and the ability of its moisture water conservation has guaranteed the moisture in the composite, makes moisture play the effect that phenol harmful substance selectivity in the cigarette smoke is reduced.Containing in the sugared bipolymer hydrophily polycation shown in the described formula I structural formula contains a large amount of hydroxyl structures, promoted and phenolic compound between active force.
Described porous material is the carrier of additive, and its porous adsorption capacity provides guarantee for the load of hydrophily polycation; The porous material of preferred particulates shape, granular profile can better meet the production demand of cigarette filter.Described granular porous material can be selected this area granular porous material commonly used for use; In the preferred diatomite of described porous material, silica gel, active carbon, macroporous absorbent resin, molecular sieve, zeolite, the sepiolite etc. one or more.
The quality percentage composition of the hydrophily polycation of load in the described composite is preferably 0.05%～5%.Can under the prerequisite of saving cost, more effectively remove the phenols harmful substance.
The particle diameter of described composite is preferably 0.05mm～3mm, and specific area is preferably 20m
2/ g～1500m
2/ g, quality moisture content are preferably 10%～40% (method of testing of quality moisture content is generally: 100 ℃ of dry 2h, according to the calculated mass moisture content of poor quality before and after dry).
Described polyanion is selected a kind of in polyacrylic acid glucose ester, polyacrylic acid gala sugar ester, sodium alginate, CMC, carboxyetbyl chitosan, carboxylic propyl group shitosan, polyacrylic acid, the poly (sodium 4-styrenesulfonate) etc. for use, all can adopt the commercially available prod.
The preparation method of the composite of phenol harmful substance contents in the described selectivity reducing cigarette fume can generally comprise following steps with reference to the self-assembling method layer by layer of existing polycation in this area and polyanion:
(1) porous material and the polyanion aqueous solution are fully mixed, leave standstill the back and filter, the gained filter cake obtains granular solids after drying, finishes the assembling of one deck polyanion individual layer;
(2) aqueous solution with above-mentioned granular solids and hydrophily polycation fully mixes, and leaves standstill the back and filters, and the gained filter cake obtains granular solids after drying, further finishes the assembling of one deck hydrophily polycation individual layer;
(3) according to above-mentioned steps, alternately assemble at porous material surface with polyanion and hydrophily polycation respectively, obtain composite.
In order to reach better effect, preferably:
The mixed proportion of the aqueous solution of the described porous material and the polyanion aqueous solution or hydrophily polycation is: m/v (g/mL)=1～2: 1～5.
In step (1) and the step (2), the condition that leaves standstill is generally 10 ℃～50 ℃ and leaves standstill 20min～2h; Dry condition is generally 60 ℃～90 ℃ dry 2h～120h.
In assembling one deck hydrophily polycation or one deck polyanion is an individual layer, and described composite preferably has 2～20 individual layers.
The concentration of the aqueous solution of described hydrophily polycation or the polyanion aqueous solution is generally 0.2g/L～10g/L.
To be water-keeping material by an effect of carrying of porous material and polyanion construct described composite forms with the hydrophily polycation; Described composite is applied to prepare in the cigarette filter, just can utilizes the phenol harmful substance contents in the moisture selectivity reducing cigarette fume in the composite.
In the filter stick gross mass in the cigarette filter of a cigarette, the quality percentage composition of described composite is preferably 5%～50%.
Described cigarette filter can be the binary compound cigarette filter, comprises common filter stick and the composite filter that superposes along the axial and common filter stick of common filter stick; Described composite filter is made by described composite or by described composite and common filter stick material; 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 two sections common filter sticks and the composite filter that superposes along the axial and common filter stick of common filter stick, and described composite filter is between two sections common filter sticks; Described composite filter is made by described composite or by described composite and common filter stick material; 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 acetate fiber 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 be prepared.
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 Composite Preparation of the present invention can effectively reduce phenol harmful components in the flue gas with the moisture of hydrophily polycation in the composite and absorption as filter medium.Compare with the commercial cigarettes of same specification, adopt the cigarette filter of Composite Preparation of the present invention can make the content of phenol harmful components in the cigarette smoke reduce by 35%～60%.
Because many fragrance organic compounds are water insoluble, composite of the present invention can also be avoided the flavor component loss in the phenol harmful components 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.
The specific embodiment
Contain the synthetic of sugared bipolymer hydrophily polycation: get at first respectively in the 250mL flask that the 0.4mol raw material A joins the mercuric acetate that fills 150mL vinylacetate, 1.0g and acetate in minute copper.Heating and magnetic agitation in 55 ℃ constant temperature oil bath, the concentrated sulfuric acid of dropping 0.25mL mass percentage concentration 98% continues reaction 6.5h after half an hour.After the cooling, add about 2g sodium acetate and fully stir, add saturated sodium bicarbonate solution again, be stirred to bubble collapse, leave standstill, separatory gets crude product with non-water layer decompression distillation, and column chromatography for separation gets product B diacid divinyl ester again.In the conical flask of 250mL, be that 1: 4 ratio adds raw material C and product B, add 1g bacillus alkaline protease and 40mL pyridine then, 50 ℃ of reactions 3 days with the mol ratio of raw material C and product B.After reaction finished, filtration was dezymotized and pyridine is removed in decompression distillation, and crude product uses column chromatography extraction, obtains light yellow product D glycosyl two vinyl acetates, 60 ℃ of vacuum drying.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 peroxydisulfate quality is 2% of raw material E gross mass.Under nitrogen protection, 70 ℃ of stirring reaction 24h pour precipitation in the acetone, filtration, 50 ℃ of vacuum drying 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 freeze dryings get white end product F.
Embodiment 1
Contain synthesizing according to the method described above of sugared bipolymer hydrophily polycation, wherein, raw material A is an adipic acid, raw material C is a glucose, raw material E is an allylamine hydrochloride, product B is an adipic acid divinyl ester, and product D is the glucosyl group hexanedioic acid vinyl ester, synthesizes to obtain containing sugared bipolymer hydrophily polycation.
1647cm in the above-mentioned infrared spectrum that contains sugared bipolymer hydrophily 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:
Determine that according to the above-mentioned magnetic resonance detection data that contain sugared bipolymer hydrophily polycation wherein the mol ratio of x: y is 1: 4.
Contain synthesizing according to the method described above of sugared bipolymer hydrophily polycation, wherein, raw material A is a pimelic acid, raw material C is a gossypose, 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 bipolymer hydrophily polycation.
1645cm in the above-mentioned infrared spectrum that contains sugared bipolymer hydrophily 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:
Determine that according to the above-mentioned magnetic resonance detection data that contain sugared bipolymer hydrophily polycation wherein the mol ratio of x: y is 2.5: 1.
Contain synthesizing according to the method described above of sugared bipolymer hydrophily polycation, wherein, raw material A is a malonic acid, raw material C is a maltose, raw material E is an allylamine hydrochloride, and product B is a malonic acid divinyl ester, and product D is a malt-base malonic acid vinyl acetate, the mol ratio of product D and raw material E 2: 1 synthetic obtains containing sugared bipolymer hydrophily polycation.
1646cm in the above-mentioned infrared spectrum that contains sugared bipolymer hydrophily 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:
Determine that according to the above-mentioned magnetic resonance detection data that contain sugared bipolymer hydrophily polycation wherein the mol ratio of x: y is 1: 1.2.
Contain synthesizing according to the method described above of sugared bipolymer hydrophily polycation, wherein, raw material A is a decanedioic acid, raw material C is a lactose, and raw material E is N, N-DMAA hydrochloride, product B is a decanedioic acid divinyl ester, product D is a lactose base decanedioic acid vinyl acetate, and the mol ratio of product D and raw material E 1: 3 synthetic obtains containing sugared bipolymer hydrophily polycation.
1640cm in the above-mentioned infrared spectrum that contains sugared bipolymer hydrophily 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:
Determine that according to the above-mentioned magnetic resonance detection data that contain sugared bipolymer hydrophily polycation wherein the mol ratio of x: y is 1: 10.
Embodiment 5
Contain synthesizing according to the method described above of sugared bipolymer hydrophily polycation, wherein, raw material A is a dodecanedioic acid, 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 glucosyl group dodecanedioic acid vinyl acetate, and the mol ratio of product D and raw material E obtains containing sugared bipolymer hydrophily polycation at 1: 2.5.
1648cm in the above-mentioned infrared spectrum that contains sugared bipolymer hydrophily 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:
Determine that according to the above-mentioned magnetic resonance detection data that contain sugared bipolymer hydrophily polycation wherein the mol ratio of x: y is 1: 6.5.
Embodiment 6
The water-soluble 5mg/mL of being mixed with of sugared bipolymer that contains among the embodiment 1 is contained the sugared bipolymer aqueous solution (ie in solution A), prepare the aqueous solution (ie in solution B) of the poly (sodium 4-styrenesulfonate) of a 5mg/mL again.Get the 5.0g granular active carbon, mix, stir, under 25 ℃, leave standstill 1h with the 10ml solution B.Filter, all solids in 70 ℃ of baking 48h down, are mixed the solid of gained with the 10mL solution A, stir, under 25 ℃, leave standstill 1h.Filter, the solid that filters gained is dried by the fire 40h down in 80 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 6 times according to the method described above with solution B and solution A respectively again, obtained 14 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 2.5% in the composite.3000～3100cm in the infrared spectrum of this composite
-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 bipolymer.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(20 ± 5) mv, the zeta potential value of composite then becomes-(20 ± 3) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 0.05mm, and specific area is 100m
2/ g, quality moisture content are 20%.
With above-mentioned composite on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make 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 2 that makes 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 composite is 5% of composite filter 2 and common cellulose acetate filter rod 1 gross mass.
Produce the sample cigarette with the common cellulose acetate filter rod that the binary compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in 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 among the embodiment 2 to contain sugared bipolymer water-soluble and be mixed with 0.2mg/mL solution (solution A), prepare the aqueous solution (solution B) of a 0.2mg/mL sodium alginate again.Get 5.0g graininess macroporous absorbent resin, mix, stir, under 30 ℃, leave standstill 1h with the 7.5ml solution B.Filter, all solids are dried by the fire 10h down in 90 ℃.The solid of gained is mixed with the 7.5mL solution A, stir, under 25 ℃, leave standstill 20min.Filter, all solids are dried by the fire 120h down in 60 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 4 times according to the method described above with solution B and solution A respectively again, obtained 10 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 0.05% in the composite.3000cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on the graininess macroporous absorbent resin of sugared bipolymer.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(20 ± 1) mv, the zeta potential value of composite then becomes-(20 ± 2) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 2mm, and specific area is 20m
2/ g, quality moisture content are 40%.
With above-mentioned composite on filter-stick forming device and roll-forming make 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 2 that makes 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 composite is 50% of composite filter 2 and common cellulose acetate filter rod 1 gross mass.
Produce the sample cigarette with the common cellulose acetate filter rod that the binary compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in Table 2.
Table 2 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 8
To contain the water-soluble 10mg/mL of the being mixed with solution of sugared bipolymer (solution A) among the embodiment 3, prepare the aqueous solution (solution B) of a 4mg/mL carboxylic propyl group shitosan again.Get the 5.0g particulate molecular sieve, mix, stir, under 10 ℃, leave standstill 1h with the 15ml solution B.Filter, all solids are dried by the fire 10h down in 90 ℃.The solid of gained is mixed with the 25mL solution A, stir, under 30 ℃, leave standstill 2h.Filter, all solids are dried by the fire 15h down in 90 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 3 times according to the method described above with solution B and solution A respectively again, obtained 8 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 5% in the composite.3000～3100cm in the infrared spectrum of this composite
-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 bipolymer.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(20 ± 3) mv, the zeta potential value of composite then becomes-(17 ± 2) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 0.5mm, and specific area is 200m
2/ g, quality moisture content are 30%.
With above-mentioned composite on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make 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 2 that makes 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 composite is 40% of composite filter 2 and two sections common cellulose acetate filter rod 1 gross masses.
Produce the sample cigarette with the common cellulose acetate filter rod that the three-stage compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in Table 3.
Table 3 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 9
With the aqueous solution that contains the water-soluble 3mg/mL of being mixed with of sugared bipolymer (solution A) among the embodiment 4, prepare the aqueous solution (solution B) of a 2mg/mL polyacrylic acid glucose ester again.Get 5.0g graininess diatom soil, mix, stir, under 50 ℃, leave standstill 20min with the 5ml solution B.Filter, all solids are dried by the fire 24h down in 80 ℃.The solid of gained is mixed with the 25mL solution A, stir, under 25 ℃, leave standstill 1h.Filter, all solids are dried by the fire 48h down in 75 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 8 times according to the method described above with solution B and solution A respectively again, obtained 18 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 2.5% in the composite.1000～1100cm in the infrared spectrum of this composite
-1The appearance of place's characteristic peak has verified that this contains the load success on graininess diatom soil of sugared bipolymer.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(23 ± 1) mv, the zeta potential value of composite then becomes-(20 ± 3) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 0.1mm, and specific area is 800m
2/ g, quality moisture content are 25%.
With above-mentioned composite on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make 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 2 that makes 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 composite is 30% of composite filter 2 and two sections common cellulose acetate filter rod 1 gross masses.
Produce the sample cigarette with the common cellulose acetate filter rod that the three-stage compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in Table 4.
Table 4 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 10
To contain the water-soluble 0.5mg/mL of the being mixed with solution of sugared bipolymer (solution A) among the embodiment 5, prepare the aqueous solution (solution B) of a 6mg/mL CMC again.Get 5.0g graininess sepiolite, mix, stir, under 25 ℃, leave standstill 3h with the 10ml solution B.Filter, all solids are dried by the fire 60h down in 75 ℃.The solid of gained is mixed with the 15mL solution A, stir, under 35 ℃, leave standstill 5h.Filter, all solids are dried by the fire 15h down in 60 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 4 times according to the method described above with solution B and solution A respectively again, obtained 10 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 0.2% in the composite.947cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on the graininess sepiolite of sugared bipolymer.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(20 ± 4) mv, the zeta potential value of composite then becomes-(20 ± 1) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 3mm, and specific area is 100m
2/ g, quality moisture content are 20%.
With above-mentioned composite on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make 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 2 that makes 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 composite is 20% of composite filter 2 and two sections common cellulose acetate filter rod 1 gross masses.
Produce the sample cigarette with the common cellulose acetate filter rod that the three-stage compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in Table 5.
Table 5 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 11
To contain the water-soluble 10mg/mL of the being mixed with solution of sugared bipolymer (solution A) among the embodiment 3, prepare the aqueous solution (solution B) of a 4mg/mL carboxylic propyl group shitosan again.Get the 5.0g particulate molecular sieve, mix, stir, under 10 ℃, leave standstill 1h with the 15ml solution B.Filter, all solids are dried by the fire 10h down in 90 ℃.The solid of gained is mixed with the 25mL solution A, stir, under 30 ℃, leave standstill 2h.Filter, all solids are dried by the fire 15h down in 90 ℃, obtain drying solid, promptly finish 1 self assembly, obtain 2 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 2.2% in the composite.3000～3100cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains sugared bipolymer in particulate molecular sieve load success.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(20 ± 5) mv, the zeta potential value of composite then becomes-(18 ± 3) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 0.5mm, and specific area is 225m
2/ g, quality moisture content are 20%.
With above-mentioned composite on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make 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 2 that makes 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 composite is 40% of composite filter 2 and two sections common cellulose acetate filter rod 1 gross masses.
Produce the sample cigarette with the common cellulose acetate filter rod that the three-stage compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in Table 6.
Table 6 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 12
To contain the water-soluble 1.0mg/mL of the being mixed with solution of sugared bipolymer (solution A) among the embodiment 5, prepare the polyacrylic aqueous solution of a 0.5mg/mL (solution B) again.Get the 5.0g particulate zeolite, mix, stir, under 30 ℃, leave standstill 1h with the 10ml solution B.Filter, all solids are dried by the fire 40h down in 60 ℃.The solid of gained is mixed with the 10mL solution A, stir, under 25 ℃, leave standstill 6h.Filter, all solids are dried by the fire 15h down in 60 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 6 times according to the method described above with solution B and solution A respectively again, obtained 12 individual layers, outermost layer is the above-mentioned sugared bipolymer hydrophily polycation that contains, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 0.5% in the composite.947cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The appearance of two place's characteristic peaks has verified that this contains the load success on particulate zeolite of sugared bipolymer.In addition, monitor by the Zeta potential analyzer, after the assembling of whenever finishing one deck polycation, the zeta potential value of composite all is shown as+(20 ± 2) mv, the zeta potential value of composite then becomes-(20 ± 2) mv value behind continuation assembling one deck polyanion, shows that the mode alternate load with self assembly layer by layer has polyanion and hydrophily polycation on porous material.
After testing, this composite particle diameter is 1.5mm, and specific area is 300m
2/ g, quality moisture content are 25%.
With above-mentioned composite on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make 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 2 that makes 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 composite is 25% of composite filter 2 and two sections common cellulose acetate filter rod 1 gross masses.
Produce the sample cigarette with the common cellulose acetate filter rod that the three-stage compound cigarette filter 3 that makes substitutes in certain brand commercial cigarettes, 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 contrasted 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 results are shown in Table 7.
Table 7 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Claims (10)
1. the composite of phenol harmful substance contents in the selectivity reducing cigarette fume, it is characterized in that, described composite be with the porous material be carrier and on porous material with the mode alternate load polyanion of self assembly layer by layer and the material of hydrophily polycation, and it is outermost for the hydrophily polycation to load on porous material;
Described hydrophily polycation is with the copolymer shown in the following formula I structural formula:
Formula I;
Wherein, R
1Be in glucosyl group, 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 represents constitutive molar ratio.
2. the composite 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 diatomite, Powdered silica gel, active carbon, macroporous absorbent resin, molecular sieve, zeolite, the sepiolite.
3. the composite of phenol harmful substance contents in the selectivity reducing cigarette fume according to claim 1, it is characterized in that described polyanion is a kind of in polyacrylic acid glucose ester, polyacrylic acid gala sugar ester, sodium alginate, CMC, carboxyetbyl chitosan, carboxylic propyl group shitosan, polyacrylic acid, the poly (sodium 4-styrenesulfonate).
4. the composite 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 hydrophily polycation of load in the described composite is 0.05%～5%.
5. according to the preparation method of the composite of phenol harmful substance contents in the described selectivity reducing cigarette fume of claim 1～4, comprising:
(1) porous material and the polyanion aqueous solution are fully mixed, leave standstill the back and filter, the gained filter cake obtains granular solids after drying, finishes the assembling of one deck polyanion individual layer;
(2) aqueous solution with above-mentioned granular solids and hydrophily polycation fully mixes, and leaves standstill the back and filters, and the gained filter cake obtains granular solids after drying, further finishes the assembling of one deck hydrophily polycation individual layer;
(3) according to above-mentioned steps, alternately assemble at porous material surface with polyanion and hydrophily polycation respectively, obtain composite.
6. according to the application in the preparation cigarette filter of the composite of phenol harmful substance contents in each described selectivity reducing cigarette fume of claim 1～4.
7. application according to claim 6 is characterized in that, in the filter stick total amount in the cigarette filter of a cigarette, the quality percentage composition of described composite is 5%～50%.
8. application according to claim 6 is characterized in that described cigarette filter is the binary compound cigarette filter, comprises common filter stick and the composite filter that superposes along the axial and common filter stick of common filter stick; Described composite filter is made by described composite or by described composite and common filter stick material; Composite filter contacts with the pipe tobacco section when being used to prepare cigarette.
9. application according to claim 6, it is characterized in that, described cigarette filter is the three-stage compound cigarette filter, comprises two sections common filter sticks and the composite filter that superposes along the axial and common filter stick of common filter stick, and described composite filter is between two sections common filter sticks; Described composite filter is made by described composite or by described composite and common filter stick material; Common filter stick contacts with the pipe tobacco section when being used to prepare cigarette.
10. application according to claim 9 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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| CN2010102783417A CN101954274B (en) | 2010-09-10 | 2010-09-10 | Sugary copolymer composite material for reducing phenol-type substances in cigarette smoke and preparation |
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| CN102090716A (en) * | 2011-03-03 | 2011-06-15 | 中国海洋大学 | Novel cadmium-removal filter tip |
| CN103561824A (en) * | 2011-02-04 | 2014-02-05 | Hsd欧洲有限公司 | Use of a reticulated dextran polymer as a filter against the inhalation of substances injurious to the health |
| CN104720105A (en) * | 2015-02-11 | 2015-06-24 | 浙江中烟工业有限责任公司 | Composite material for selectively reducing aldehyde material in smoke of cigarette and preparing method and application thereof |
| CN104720104A (en) * | 2015-02-11 | 2015-06-24 | 浙江中烟工业有限责任公司 | Filter tip addition agent for selectively reducing crotonaldehyde in smoke of cigarette and preparing method and application thereof |
| CN108047840A (en) * | 2017-12-21 | 2018-05-18 | 中国烟草总公司郑州烟草研究院 | The liquid coating material of phenol release amount in a kind of filter stick type cigarette mainstream flue gas for reducing paper |
| CN113115980A (en) * | 2021-04-01 | 2021-07-16 | 中国烟草总公司郑州烟草研究院 | Method for reducing phenol content in waste gas |
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| CN103561824A (en) * | 2011-02-04 | 2014-02-05 | Hsd欧洲有限公司 | Use of a reticulated dextran polymer as a filter against the inhalation of substances injurious to the health |
| CN103561824B (en) * | 2011-02-04 | 2016-08-17 | Hsd欧洲有限公司 | Netted dextran polymer is as the application of filter against the inhalation of substances injurious to |
| CN102090716A (en) * | 2011-03-03 | 2011-06-15 | 中国海洋大学 | Novel cadmium-removal filter tip |
| CN104720105A (en) * | 2015-02-11 | 2015-06-24 | 浙江中烟工业有限责任公司 | Composite material for selectively reducing aldehyde material in smoke of cigarette and preparing method and application thereof |
| CN104720104A (en) * | 2015-02-11 | 2015-06-24 | 浙江中烟工业有限责任公司 | Filter tip addition agent for selectively reducing crotonaldehyde in smoke of cigarette and preparing method and application thereof |
| CN104720105B (en) * | 2015-02-11 | 2018-01-30 | 浙江中烟工业有限责任公司 | Composite of aldehyde material and its preparation method and application in a kind of selectivity reducing cigarette fume |
| CN104720104B (en) * | 2015-02-11 | 2018-01-30 | 浙江中烟工业有限责任公司 | Additives of filter tip of crotonaldehyde and its preparation method and application in a kind of selectivity reducing cigarette fume |
| CN108047840A (en) * | 2017-12-21 | 2018-05-18 | 中国烟草总公司郑州烟草研究院 | The liquid coating material of phenol release amount in a kind of filter stick type cigarette mainstream flue gas for reducing paper |
| CN113115980A (en) * | 2021-04-01 | 2021-07-16 | 中国烟草总公司郑州烟草研究院 | Method for reducing phenol content in waste gas |
| CN113115980B (en) * | 2021-04-01 | 2023-06-30 | 中国烟草总公司郑州烟草研究院 | Method for reducing phenol content in waste gas |
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