CN101919591B - Poly glucosamine hexanedioic acid vinyl ester material for reducing content of phenol type substances - Google Patents
Poly glucosamine hexanedioic acid vinyl ester material for reducing content of phenol type substances Download PDFInfo
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- CN101919591B CN101919591B CN2010102788779A CN201010278877A CN101919591B CN 101919591 B CN101919591 B CN 101919591B CN 2010102788779 A CN2010102788779 A CN 2010102788779A CN 201010278877 A CN201010278877 A CN 201010278877A CN 101919591 B CN101919591 B CN 101919591B
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- 239000000126 substance Substances 0.000 title claims abstract description 39
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- 239000000463 material Substances 0.000 title claims abstract description 19
- MSWZFWKMSRAUBD-IVMDWMLBSA-N 2-amino-2-deoxy-D-glucopyranose Chemical compound N[C@H]1C(O)O[C@H](CO)[C@@H](O)[C@@H]1O MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 title claims description 40
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 title claims description 40
- 229960002442 glucosamine Drugs 0.000 title claims description 40
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- 239000002131 composite material Substances 0.000 claims abstract description 149
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- 230000009931 harmful effect Effects 0.000 claims abstract description 43
- HDRHEOGKFZKCPD-UHFFFAOYSA-N 6-ethenoxy-6-oxohexanoic acid;hydrochloride Chemical compound Cl.OC(=O)CCCCC(=O)OC=C HDRHEOGKFZKCPD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 30
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
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- JZQAAQZDDMEFGZ-UHFFFAOYSA-N bis(ethenyl) hexanedioate Chemical compound C=COC(=O)CCCCC(=O)OC=C JZQAAQZDDMEFGZ-UHFFFAOYSA-N 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- Cigarettes, Filters, And Manufacturing Of Filters (AREA)
Abstract
本发明公开了一种降低苯酚类物质含量的聚氨基葡萄糖己二酸乙烯酯材料。该复合材料是以多孔材料为载体并在多孔材料上以层层自组装的方式交替负载聚阴离子和亲水性聚阳离子的材料，且负载在多孔材料最外层的为亲水性聚阳离子；所述的亲水性聚阳离子为聚氨基葡萄糖己二酸乙烯酯盐酸盐。该复合材料可用于制备卷烟滤嘴，可制备成二元复合式卷烟过滤嘴或者三段复合式卷烟过滤嘴。本发明利用复合材料中的水分选择性降低卷烟烟气中的苯酚类有害物质，同时由于许多香味有机化合物不溶于水，可以避免香味成分损失，保持卷烟的内在品质。
The invention discloses a polyglucosamine vinyl adipate material with reduced content of phenolic substances. The composite material is a material in which a porous material is used as a carrier and polyanions and hydrophilic polycations are alternately loaded on the porous material in a layer-by-layer self-assembly manner, and the outermost layer of the porous material is a hydrophilic polycation; The hydrophilic polycation is polyglucosamine vinyl adipate hydrochloride. The composite material can be used to prepare cigarette filters, and can be prepared into binary composite cigarette filters or three-stage composite cigarette filters. The present invention utilizes the water in the composite material to selectively reduce the phenolic harmful substances in the cigarette smoke, and at the same time, because many flavor organic compounds are insoluble in water, the loss of flavor components can be avoided and the inner quality of the cigarette can be maintained.
Description
Technical field
The present invention relates to reducing cigarette tar and reducing harm reduction technical field, be specifically related to the poly glucosamine hexanedioic acid vinyl ester composite 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.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.
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.
Described hydrophily polycation is selected the poly glucosamine hexanedioic acid vinyl ester hydrochloride for use, wherein contains a large amount of hydroxyl structures, can promote and phenolic compound between active force.
Described poly glucosamine hexanedioic acid vinyl ester hydrochloride prepares according to existing polymerization, but this material synthesizes (Biotechnol.Lett., 2001,23,1981 with reference to people's such as Wuqi County research report; Chinese Chemical Letters, 2002,12,416.).Conventional method is: synthesizing adipic acid divinyl ester at first: adipic acid and vinylacetate are mixed, and reaction makes adipic acid divinyl ester under the effect of catalyst; Then; mix with aminoglucose hydrochloride with gained adipic acid divinyl ester; under the catalytic action of bacillus alkaline protease, react; crude product is after column chromatography for separation is extracted; obtain light yellow product glucosamine hexanedioic acid vinyl ester hydrochloride, again this product is carried out radical polymerization (potassium peroxydisulfate is made initator) under nitrogen protection, thick polymerizate is after the water dialysis; freeze drying promptly gets poly glucosamine hexanedioic acid vinyl ester hydrochloride finally.
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 more effectively remove the phenols harmful substance under the prerequisite of saving cost.
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 2～24 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 40%～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
Poly glucosamine hexanedioic acid vinyl ester hydrochloride synthetic: get at first respectively in the 250mL flask that the 0.4mol adipic acid 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 adipic acid divinyl ester again.Add the aminoglucose hydrochloride of 0.3mol and the adipic acid divinyl ester of 0.1mol in the conical flask of 250mL, add 1g bacillus alkaline protease and 40mL pyridine again, 50 ℃ were reacted 3 days.After reaction finished, filtration was dezymotized and pyridine is removed in decompression distillation, and crude product uses column chromatography extraction, obtains light yellow product glucosamine hexanedioic acid vinyl ester hydrochloride, 80 ℃ of vacuum drying.In product glucosamine hexanedioic acid vinyl ester hydrochloride, add the potassium persulfate solution of 6mg/mL, making the potassium peroxydisulfate quality is 2% of glucosamine hexanedioic acid vinyl ester hydrochloride gross mass.Under nitrogen protection, 80 ℃ of stirring reaction 12h 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 poly glucosamine hexanedioic acid vinyl ester hydrochloride.1647cm in the infrared spectrum of above-mentioned product
-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 is described.
The aqueous solution (solution A) of preparation 5mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride and the aqueous solution (solution B) of 5mg/mL polyacrylic acid gala sugar ester.Get the 5.0g particulate zeolite, mix, stir, under 15 ℃, leave standstill 1h with the 7.5ml solution B.Filter, all solids are dried by the fire 72h down in 60 ℃.The solid of gained is mixed with the 10mL solution A, stir, under 30 ℃, leave standstill 1h.Filter, the solid that filters gained is dried by the fire 50h down in 75 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 10 times according to the method described above with solution B and solution A respectively again, obtained 22 individual layers, outermost layer is above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, 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 load success on particulate zeolite of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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 1.0mm, and specific area is 400m
2/ g, quality moisture content are 40%.
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 1: 1 with the length ratio of common cellulose acetate filter rod 1, and the addition of composite is 30% 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 phenols harmful substance
With the water-soluble aqueous solution (solution A) of 5mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride and the aqueous solution (solution B) of 3mg/mL sodium alginate of being mixed with of poly glucosamine hexanedioic acid vinyl ester hydrochloride.Get the Powdered silica gel of 5.0g, mix, stir, under 25 ℃, leave standstill 3h with the 7.5ml solution B.Filter, all solids are dried by the fire 72h down in 60 ℃.The solid of gained is mixed with the 5mL solution A, stir, under 25 ℃, leave standstill 1h.Filter, the solid that filters gained is dried by the fire 50h down in 75 ℃, 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 8 individual layers, outermost layer is above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 2% in the composite.3000～3100cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The load success on Powdered silica gel of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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+(22 ± 3) mv, the zeta potential value of composite then becomes-(19 ± 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 0.2mm, and specific area is 650m
2/ g, quality moisture content are 25%.
Above-mentioned composite roll-forming on filter-stick forming device is made 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: 2 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of composite is 50% 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 1 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
With the water-soluble aqueous solution (solution A) of 0.2mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride and the aqueous solution (solution B) of 6mg/mL CMC of being mixed with of poly glucosamine hexanedioic acid vinyl ester hydrochloride.Get 5.0g graininess macroporous absorbent resin, mix, stir, under 15 ℃, leave standstill 2h with the 4ml solution B.Filter, all solids are dried by the fire 48h down in 60 ℃.The solid of gained is mixed with the 10mL solution A, stir, under 20 ℃, leave standstill 2h.Filter, the solid that filters gained is dried by the fire 50h down in 75 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 5 times according to the method described above with solution B and solution A respectively again, obtained 12 individual layers, outermost layer is above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 0.05% in the composite.3000～3100cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The load success on the graininess macroporous absorbent resin of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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+(22 ± 3) mv, the zeta potential value of composite then becomes-(16 ± 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 2mm, and specific area is 20m
2/ g, quality moisture content are 20%.
Above-mentioned composite roll-forming on filter-stick forming device is made 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: 1.5 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of composite is 10% 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 1 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
With the water-soluble aqueous solution (solution A) and the polyacrylic aqueous solution of 5mg/mL (solution B) that is mixed with 10mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride of poly glucosamine hexanedioic acid vinyl ester hydrochloride.Get the 5.0g particulate molecular sieve, mix, stir, under 20 ℃, leave standstill 2h with the 8ml solution B.Filter, all solids are dried by the fire 72h down in 60 ℃.The solid of gained is mixed with the 5mL solution A, stir, under 30 ℃, leave standstill 2h.Filter, the solid that filters gained is dried by the fire 50h 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 above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 2% in the composite.3000～3100cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The load success on particulate molecular sieve of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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+(22 ± 3) 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 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 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 1.5: 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).The detection method of content of phenol type substances is with embodiment 1 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 5
With the water-soluble aqueous solution (solution A) of 7mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride and the aqueous solution (solution B) of 5mg/mL poly (sodium 4-styrenesulfonate) of being mixed with of poly glucosamine hexanedioic acid vinyl ester hydrochloride.Get 5.0g graininess sepiolite, mix, stir, under 20 ℃, leave standstill 1h with the 6ml solution B.Filter, all solids are dried by the fire 72h down in 60 ℃.The solid of gained is mixed with the 4mL solution A, stir, under 35 ℃, leave standstill 2h.Filter, the solid that filters gained is dried by the fire 50h down in 75 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 2 times according to the method described above with solution B and solution A respectively again, obtained 3 individual layers, outermost layer is above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 0.05% in the composite.3000～3100cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The load success on the graininess sepiolite of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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-(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 3mm, and specific area is 100m
2/ g, quality moisture content are 10%.
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 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 1 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 6
With the water-soluble aqueous solution (solution A) of 4mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride and the aqueous solution (solution B) of 4mg/mL carboxylic propyl group shitosan of being mixed with of poly glucosamine hexanedioic acid vinyl ester hydrochloride.Get the 5.0g granular active carbon, mix, stir, under 20 ℃, leave standstill 1.5h with the 10ml solution B.Filter, all solids are dried by the fire 72h down in 60 ℃.The solid of gained is mixed with the 8mL solution A, stir, under 30 ℃, leave standstill 3h.Filter, the solid that filters gained is dried by the fire 50h down in 75 ℃, obtain drying solid, promptly finish 1 self assembly, drying solid is handled after 10 times according to the method described above with solution B and solution A respectively again, obtained 22 individual layers, outermost layer is above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, 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 load success on the graininess sepiolite of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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-(16 ± 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 0.05mm, and specific area is 100m
2/ g, quality moisture content are 35%.
Above-mentioned composite roll-forming on filter-stick forming device is made 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 15% 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 1 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 7
With the water-soluble aqueous solution (solution A) of 4mg/mL poly glucosamine hexanedioic acid vinyl ester hydrochloride and the aqueous solution (solution B) of 4mg/mL carboxylic propyl group shitosan of being mixed with of poly glucosamine hexanedioic acid vinyl ester hydrochloride.Get the 5.0g granular active carbon, mix, stir, under 20 ℃, leave standstill 1.5h with the 10ml solution B.Filter, all solids are dried by the fire 72h down in 60 ℃.The solid of gained is mixed with the 8mL solution A, stir, under 30 ℃, leave standstill 3h.Filter, the solid that filters gained is dried by the fire 50h down in 75 ℃, obtain drying solid, promptly finish 1 self assembly, obtain 2 individual layers, outermost layer is above-mentioned poly glucosamine hexanedioic acid vinyl ester hydrochloride hydrophily polycation, get final product the high-moisture-retention composite, the quality percentage composition of the polycation of load is 0.05% in the composite.3000～3100cm in the infrared spectrum of this composite
-1With 1000～1100cm
-1The load success on the graininess sepiolite of this poly glucosamine hexanedioic acid vinyl ester hydrochloride has been verified in the appearance of two place's characteristic peaks.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-(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 1.5mm, and specific area is 300m
2/ g, quality moisture content are 10%.
Above-mentioned composite roll-forming on filter-stick forming device is made 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 1.5: 1 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 1 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 the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
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, 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 each 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; One of two sections common filter sticks section contacts with the pipe tobacco section when being used for preparing 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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| CN102090716A (en) * | 2011-03-03 | 2011-06-15 | 中国海洋大学 | Novel cadmium-removal filter tip |
| KR101852925B1 (en) | 2011-11-29 | 2018-04-30 | 삼성전자주식회사 | Hybrid porous structured material, method of preparing hybrid porous structure material, membrane including hybrid porous structured material, and water treatment device including membrane including hybrid porous structured material |
| KR102088915B1 (en) | 2013-05-31 | 2020-04-14 | 삼성전자주식회사 | Hybrid porous structured material, method of preparing hybrid porous structure material, membrane including hybrid porous structured material, and water treatment device including membrane including hybrid porous structured material |
| CN104738814B (en) * | 2015-02-11 | 2018-01-30 | 浙江中烟工业有限责任公司 | A micro-nano structure filter additive for reducing phenol in cigarette smoke and its preparation method and application |
| CN107028218B (en) * | 2017-05-25 | 2019-10-11 | 云南中烟工业有限责任公司 | A kind of method for preparing geranyl acetone sustained-release material |
| CN107199015A (en) * | 2017-06-29 | 2017-09-26 | 滁州卷烟材料厂 | A kind of preparation method of sepiolite base volume cigarette filter tip adsorbent |
| CN110250567A (en) * | 2019-05-08 | 2019-09-20 | 中山市博海精细化工有限公司 | A kind of environment-friendly cigarette filter tip filler and preparation method |
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