Summary of the invention
The present invention is based on phenol type substances principle soluble in water, designed and developed the additive of phenols harmful substance contents in the selectivity reducing cigarette fume that a kind of load has the hydrophily polycation.
The additive of phenol harmful substance contents in a kind of selectivity reducing cigarette fume, be with the porous material be carrier and on porous material load the material of hydrophily polycation.
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 additive, 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, one or more in the preferred diatomite of described porous material, silica gel, active carbon, macroporous absorbent resin, molecular sieve, zeolite, the sepiolite etc. for use.
The quality percentage composition of the hydrophily polycation of load in the described additive is preferably 0.05%~5%, can more effectively remove the phenols harmful substance under the prerequisite of saving cost.
The particle diameter of described additive 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).
The preparation method of described additive comprises: the mode of hydrophily polycation by common dipping absorption loaded on the porous material, make additive; Concrete steps comprise: the aqueous solution of porous material and hydrophily polycation is fully mixed, leave standstill the back and filter, the solid matter vacuum drying with filtration obtains obtains additive.
The concentration of the aqueous solution of described hydrophily polycation is preferably 0.2g/L~10g/L.
To be water-keeping material by an effect of carrying of porous material construct described additive forms with the hydrophily polycation; Described additive is applied to prepare in the cigarette filter, just can utilizes the phenol harmful substance in the moisture selectivity reducing cigarette fume in the additive.
In the filter stick gross mass in the cigarette filter of a cigarette, the quality percentage composition of described additive is preferably 5%~50%.
Described cigarette filter can be the binary compound cigarette filter, comprises common filter stick and the composite filter that superposes along the axial and common filter stick of common filter stick; Described composite filter is made by described additive or by described additive 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 additive or by described additive 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 additive preparation of the present invention can effectively reduce phenol harmful components in the flue gas with the moisture of hydrophily polycation in the additive and absorption as filter medium.Compare with the commercial cigarettes of same specification, adopt the cigarette filter of additive preparation of the present invention can make the content of phenol harmful components in the cigarette smoke reduce by 40%~60%.
Because many fragrance organic compounds are water insoluble, additive 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.
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.
Embodiment 1
With the water-soluble said polycation solution that is mixed with 5mg/mL of poly glucosamine hexanedioic acid vinyl ester hydrochloride, again the Powdered silica gel of 2.0g is immersed in the above-mentioned said polycation solution of 25ml, soak 4h, filter, the gained solid dries by the fire 12h down in 60 ℃, obtain additive, the quality percentage composition of the polycation of load is 5% in the additive.Through the infrared spectrum characterization analysis, 3000~3100cm in the infrared spectrum of this additive
-1With 1000~1100cm
-1The appearance of two place's characteristic peaks, and the measured value of zeta current potential is+26mV, verify the load success on Powdered silica gel of poly glucosamine hexanedioic acid vinyl ester hydrochloride, obtained the granular porous material that load has the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
After testing, this additive particle diameter is 0.25mm, specific area 900m
2/ g, quality moisture content are 40%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming 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 additive 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
Embodiment 2
With the water-soluble said polycation solution that is mixed with 5mg/mL of poly glucosamine hexanedioic acid vinyl ester hydrochloride, again 5.0g graininess diatom soil is immersed in the above-mentioned said polycation solution of 30ml, soak 4h, filter, the gained solid dries by the fire 12h down in 60 ℃, obtain additive, the quality percentage composition of the polycation of load is 2% in the additive.Through the infrared spectrum characterization analysis, 3000~3100cm in the infrared spectrum of this additive
-1With 1000~1100cm
-1The appearance of two place's characteristic peaks, and the measured value of zeta current potential is+20V, verify the load success on graininess diatom soil of poly glucosamine hexanedioic acid vinyl ester hydrochloride, obtained the granular porous material that load has the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
After testing, this additive particle diameter is 0.1mm, and specific area is 700m
2/ g, quality moisture content are 25%.
Above-mentioned additive roll-forming on filter-stick forming device is made composite filter 2; With the acetate silk is that raw material makes common cellulose acetate filter rod 1 according to composite filter 2 preparation methods.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 additive 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 2.
Table 2 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 3
With the water-soluble said polycation solution that is mixed with 1mg/mL of poly glucosamine hexanedioic acid vinyl ester hydrochloride, again the 5.0g particulate molecular sieve is immersed in the above-mentioned said polycation solution of 10ml, soak 3h, filter, the gained solid dries by the fire 12h down in 60 ℃, obtain additive, the quality percentage composition of the polycation of load is 0.05% in the additive.Through the infrared spectrum characterization analysis, 3000~3100cm in the infrared spectrum of this additive
-1With 1000~1100cm
-1The appearance of two place's characteristic peaks, and the measured value of zeta current potential is+29mV, verify the load success on particulate molecular sieve of poly glucosamine hexanedioic acid vinyl ester hydrochloride, obtained the granular porous material that load has the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
After testing, this additive particle diameter is 0.8mm, and specific area is 150m
2/ g, quality moisture content are 10%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming make composite filter 2; With the acetate silk is that raw material makes common cellulose acetate filter rod 1 according to composite filter 2 preparation methods.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: 1.5 with the length ratio of common cellulose acetate filter rod 1, and the addition of additive is 50% of composite filter 2 and common cellulose acetate filter rod 1 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 3.
Table 3 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance
Embodiment 4
With the water-soluble said polycation solution that is mixed with 5mg/mL of poly glucosamine hexanedioic acid vinyl ester hydrochloride, again 3.0g graininess macroporous absorbent resin is immersed in the above-mentioned said polycation solution of 15ml, soak 4h, filter, the gained solid dries by the fire 12h down in 60 ℃, obtain additive, the quality percentage composition of the polycation of load is 2% in the additive.Through the infrared spectrum characterization analysis, 3000~3100cm in the infrared spectrum of this additive
-1With 1000~1100cm
-1The appearance of two place's characteristic peaks, and the measured value of zeta current potential is+15mV, verify the load success on the graininess macroporous absorbent resin of poly glucosamine hexanedioic acid vinyl ester hydrochloride, obtained the granular porous material that load has the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
After testing, this additive particle diameter is 1.5mm, and specific area is 40m
2/ g, quality moisture content are 35%.
With above-mentioned additive 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 additive is 15% of composite filter 2 and two sections sour fibrous filter candle 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 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 said polycation solution that is mixed with 3mg/mL of poly glucosamine hexanedioic acid vinyl ester hydrochloride, again the 5.0g granular active carbon is immersed in the above-mentioned said polycation solution of 15ml, soak 6h, filter, the gained solid dries by the fire 12h down in 60 ℃, obtain additive, the quality percentage composition of the polycation of load is 0.5% in the additive.Through the infrared spectrum characterization analysis, 3000~3100cm in the infrared spectrum of this additive
-1With 1000~1100cm
-1The appearance of two place's characteristic peaks, and the measured value of zeta current potential is+25mV, verify the load success on granular active carbon of poly glucosamine hexanedioic acid vinyl ester hydrochloride, obtained the granular porous material that load has the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
After testing, this additive particle diameter is 0.075mm, and specific area is 300m
2/ g, quality moisture content are 25%.
With above-mentioned additive on the acetate silk that is added on shredding on the filter-stick forming device uniformly and roll-forming 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 1.5: 1 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of additive is 40% of composite filter 2 and two sections sour fibrous filter candle 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 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 said polycation solution that is mixed with 2mg/mL of poly glucosamine hexanedioic acid vinyl ester hydrochloride, again 4.0g graininess sepiolite is immersed in the above-mentioned said polycation solution of 30ml, soak 7h, filter, the gained solid dries by the fire 12h down in 60 ℃, obtain additive, the quality percentage composition of the polycation of load is 1.2% in the additive.Through the infrared spectrum characterization analysis, 3000~3100cm in the infrared spectrum of this additive
-1With 1000~1100cm
-1The appearance of two place's characteristic peaks, and the measured value of zeta current potential is+21mV, verify the load success on the graininess sepiolite of poly glucosamine hexanedioic acid vinyl ester hydrochloride, obtained the granular porous material that load has the poly glucosamine hexanedioic acid vinyl ester hydrochloride.
After testing, this additive particle diameter is 3mm, and specific area is 135m
2/ g, quality moisture content are 15%.
Above-mentioned additive 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 with the length ratio of the common cellulose acetate filter rod 1 of each section, and the addition of additive is 30% of composite filter 2 and two sections sour fibrous filter candle 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 6.
Table 6 combined type cigarette filter of the present invention is to the harmful effect of falling of phenols harmful substance