CN103611505B - Preparation method, product and application of copper ion functionalized porous cellulose composite microsphere - Google Patents
Preparation method, product and application of copper ion functionalized porous cellulose composite microsphere Download PDFInfo
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Abstract
The invention discloses a preparation method, a product and application of a copper ion functionalized porous cellulose composite microsphere. Based on the combination of a double-emulsion-solvent elimination method and an ionic crosslinked technique, the method comprises the following steps: firstly, preparing a water-in-oil type W1/O emulsion by emulsifying an internal water phase W1 consisting of a carboxyl or amido-functionalized hydrophilia high molecular material solution and an oil phase O consisting of an organic solution of oil solubility cellulose, subsequently adding the W1/O emulsion into an outer water phase consisting of a copper ion water, eliminating an organic solvent by using a solvent volatilization or diffusion method, and performing ionic crosslinked reaction so as to prepare the copper ion functionalized porous cellulose composite microsphere. The particle size of the copper ion functionalized porous cellulose composite microsphere is within the range of 10.0-2,000 micrometers, the pore volume is 0.5-8.0mL/g, the aperture is 20-2,000nm, the specific surface area is 1.0-60m<2>/g, and the copper ion content is 0.1-10.0%. The material is added into cigarette filters, so that the emission amount of hydrogen cyanide in fume is reduced by greater 25%.
Description
technical field:
The invention belongs to cigarette filter-tip additive agent field, particularly a kind of preparation method and products thereof of porous cellulose complex microsphere of copper ion functionalization and application.
background technology:
Hydrogen cyanide is one of cigarette smoke harmful components, and the research both at home and abroad in the burst size reducing hydrogen cyanide in cigarette smoke mainly comprises catalytic oxidation and absorption method.Catalytic oxidation often uses noble metal catalyst, required Catalyst Production cost is higher, preparation process is complicated, and such as nm of gold is carried on catalyst carrier A l2O3 or TiO2 obtaining reducing hydrogen cyanide in cigarette mainstream flue gas by Chinese patent 200410023246.7.Reduce in flue gas hydrogen cyanide release quantifier elimination in absorption method, the most frequently used is activated carbon.Such as, patent WO2007117115 utilizes the high-specific surface area of active carbon effectively to adsorb the material such as tar, HCN in flue gas.But active carbon often has a negative impact to cigarette odor-absorbing as filter stick additive, such as, cigarette fragrance saturation degree declines.For features such as the acidity of hydrogen cyanide and the high complexing powers of cyanogen root, basic matterial, carrying transition metal sill are used to reduce in the research of cigarette mainstream flue gas hydrogen cyanide.US Patent No. 3878289 adopts Al2O3 and the SiO2 of carrying alkali metal hydroxide to reach the object reducing HCN burst size in cigarette smoke.The modified porous material that Chinese patent 200910172250.2 obtains containing quaternary amine alkali group by carrying out modification to porous carrier, it can reduce hydrogen cyanide more than 30%.The active carbon that transition metal floods is joined filter tip by US2007/0295346, can reduce the HCN in cigarette smoke.Chinese patent 201010542254.8 by by have compared with bigger serface porous carrier as ion exchange resin, ion-exchange fibre and macroporous absorbent resin etc. from obtain complex materials after different complexing of metal ion, it is applied to cigarette with the form of binary compound filter candle, and in alternative reduction cigarette mainstream flue gas, HCN reaches more than 25%.But above-mentioned material all exists shortcoming to a certain degree, such as material therefor is friendly not to environment, and the adsorption effect of hydrogen cyanide is obvious not, and inhaling taste to cigarette has impact, and preparation process is complicated, and cost is more high, and its application is restricted.
Cellulose is the natural macromolecular material that occurring in nature enriches the most, and it belongs to renewable resource, biodegradable, is the macromolecular material of a class environment and biology close friend.Be raw material with cellulose and its derivates, prepare high-valued product significant.Chinese patent 201210070945.1 is base material with cellulose, take macromolecular material as composite, with the aqueous solution of alkali/aqueous solution of urea or alkali/thiocarbamide for solvent, obtains cellulose composite microsphere by sol-gel transition and cross-linking agents.Chinese patent 200610010145.5 is by cellulose, and dyestuff and blowing agent are dissolved in the aqueous solution of urea, thiocarbamide, NaOH and auxiliary agent formation; Adopt to rotate and make drop and use inorganic acid aqueous solution solidification drop to obtain the fluffy colored fiber crude granule of porous.Said method or preparation process are comparatively loaded down with trivial details, or cellulose microsphere granule interior combines comparatively tight, and adsorption capacity is strong not, limits its application.
summary of the invention:
The preparation method of the porous cellulose complex microsphere of a kind of copper ion functionalization that object of the present invention provides based on above-mentioned prior art situation just and with application.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for the porous cellulose complex microsphere of copper ion functionalization, the method combines based on double emulsion-removal of solvents method and ionomer technology, comprises following concrete steps:
(1) aqueous solution of the hydrophilic high molecular material of carboxyl or functional amido is formed in aqueous phase W1 join emulsification in the oil phase O that oil-soluble cellulose organic solution forms and obtain water-in-oil type W1/O emulsion;
(2) W1/O emulsion is added in the outer aqueous phase W2 of copper ion aqueous solution formation and obtain W1/O/W2 double emulsion, solvent volatilization or diffusion method is adopted to remove organic solvent, drop solidifies, in drop solidification process, hydrophilic high molecular material generation ionomer in copper ion in outer aqueous phase W2 and interior aqueous phase W1 reacts and is compound in microballoon, and after filtration, washing, drying obtain the porous cellulose complex microsphere of copper ion functionalization.
The hydrophilic high molecular material of described carboxyl or functional amido be carboxymethyl cellulose, CMS, CMC, shitosan, carboxymethyl cyclodextrin, polyacrylic one or more, its concentration in interior aqueous phase W1 is 0.5 ~ 5.0 wt%.
The preparation method of the porous cellulose complex microsphere of described copper ion functionalization, is characterized in that: in described outer aqueous phase W2, copper ion concentration is 0.01 ~ 0.5 mol/L.
Described oil-soluble cellulose is cellulose acetate, ethyl cellulose or both mixtures, and its concentration in oil phase O is 1.0 ~ 10.0 wt%.
Described oil phase solvent is the mixture of one or any two kinds in ethyl acetate, methyl acetate, carrene, chloroform.
Described interior aqueous phase, oil phase, outer aqueous phase mass ratio are 0.05 ~ 1.3: 1: 2 ~ 20.
When preparing W1/O emulsion and W1/O/W2 emulsion, add emulsifying agent as required, as polyvinyl alcohol, lauryl sodium sulfate, sucrose ester, Tween-80, Si Pan-20 or Si Pan-80, the addition of emulsifying agent is 0.2-2.0%, and emulsifying agent can make an addition in interior aqueous phase, oil phase or outer aqueous phase.
The porous cellulose complex microsphere of the copper ion functionalization prepared by said method, this complex microsphere is made up of cellulose acetate or ethyl cellulose and the crosslinked hydrophilic macromolecule of copper ion, microspherulite diameter is in 10 ~ 2000 micrometer ranges, SEM shows that microballoon has the pore structure of intercommunication, mercury injection method test shows that microballoon pore volume is at 0.5 ~ 8.0 mL/g, aperture is at 20 ~ 12000 nm, and nitrogen adsorption assay shows that microballoon BET specific surface area is at 1 ~ 60 m
2it is 0.1 ~ 10.0 wt% that/g, ICP-MS measure microballoon content of copper ion.
Porous cellulose complex microsphere is added in cigarette filter as composite filter tip additive particle, hydrogen cyanide burst size more than 25% in main flume can be reduced.
The porous cellulose complex microsphere of copper ion functionalization provided by the invention reduces that hydrogen cyanide burst size in flue gas mainly realizes based on the complexing of hydrogen cyanide and copper ion, and the pore structure of microballoon intercommunication ensure that the fast transport of flue gas and effective contact area.
The invention has the beneficial effects as follows: the hydrophilic component such as carboxymethyl cellulose, CMS, shitosan, CMC, carboxymethyl cyclodextrin that (1) microballoon inner dispersion provided by the invention has copper ion crosslinked, these components give the multifrequency nature of complex microsphere, such as, the introducing of copper ion improves the performance that complex microsphere reduces hydrogen cyanide in flue gas; The pore structure of microballoon has not only been enriched in the introducing of hydrophilic component, and can make the moisture in microballoon absorption air, improves the ability that it reduces harmful ingredients in flue gas further.(2) this microballoon base material is cellulose acetate or ethyl cellulose, and its chemical constitution is similar to existing cigarette filter filter material (existing commercially fine based on vinegar), inhales taste substantially without impact to cigarette.
detailed description of the invention:
The present invention is further described below in conjunction with embodiment, but content of the present invention be limited to this.
embodiment 1
(1) configuration of interior aqueous phase, oil phase, outer aqueous phase:
3.0 g carboxymethyl celluloses are dissolved in 97 g water and obtain interior aqueous phase;
10.0g cellulose acetate dissolves is obtained oil phase in 90.0g ethyl acetate;
Outer aqueous phase is obtained by 12.5g cupric sulfate pentahydrate, 0.10g polyvinyl alcohol dissolution to 1000 g water.
(2) preparation of W1/O emulsion: be added to by aqueous phase in 100g in 100g oil phase, uses high-speed emulsifying machine 10000rpm emulsification evenly to obtain W1/O emulsion;
(3) preparation of microballoon: above-mentioned W1/O emulsion is instilled in the outer aqueous phase of 1000 g, keep temperature to be 50
oc, mechanical agitation, rotating speed 200 rpm, solvent flashing, solidification obtains microballoon, and washing drying obtains microballoon.
Microsphere average grain diameter 210 microns, BET specific surface area 13.1 m
2/ g, copper content 5.1%, pore volume 2.6mL/g, mean pore sizes is 942nm.
embodiment 2
(1) configuration of interior aqueous phase, oil phase, outer aqueous phase:
1.5g carboxymethyl cellulose is dissolved in 43.5 g water and obtains interior aqueous phase;
5g ethyl cellulose is dissolved in 95g carrene and obtains oil phase;
Outer aqueous phase is obtained by 25g cupric sulfate pentahydrate, 0.20g polyvinyl alcohol dissolution to 1000g water.
(2) preparation of W1/O emulsion: aqueous phase in 50g is added to 100g oil phase, uses high-speed emulsifying machine emulsification evenly to obtain W1/O emulsion;
(3) preparation of microballoon: by the outer aqueous phase of above-mentioned W1/O emulsion instillation 1000g, keep temperature to be 30
oc, mechanical agitation, rotating speed 300rpm, solvent flashing, solidification obtains microballoon, and washing drying obtains microballoon.
Microsphere average grain diameter 300 microns, BET specific surface area 5.2 m
2/ g, copper content 3.7%, pore volume 1.9 mL/g, mean pore sizes is 2250 nm.
embodiment 3
(1) configuration of interior aqueous phase, oil phase, outer aqueous phase:
2g CMS is dissolved in 48g water and obtains interior aqueous phase;
5g ethyl cellulose is dissolved in 95g carrene and obtains oil phase;
Outer aqueous phase is obtained by 12.5g cupric sulfate pentahydrate, 0.20g polyvinyl alcohol dissolution to 1000g water.
(2) preparation of W1/O emulsion: aqueous phase in 20g is added to 100g oil phase, uses high-speed emulsifying machine emulsification evenly to obtain W1/O emulsion;
(3) preparation of microballoon: by the outer aqueous phase of above-mentioned W1/O emulsion instillation 1000g, mechanical agitation, rotating speed 300rpm, room temperature solvent flashing, solidification obtains microballoon, and washing drying obtains microballoon.
Microsphere average grain diameter 160 microns, BET specific surface area 4.1 m
2/ g, copper content 2.9%, pore volume 2.2 mL/g, mean pore sizes is 980 nm.
embodiment 4
(1) configuration of interior aqueous phase, oil phase, outer aqueous phase:
1.5g CMC is dissolved in 48.5g water and obtains interior aqueous phase;
5g ethyl cellulose is dissolved in 95g carrene and obtains oil phase;
Outer aqueous phase is obtained by 12.5g cupric sulfate pentahydrate, 0.20g polyvinyl alcohol dissolution to 1000g water.
(2) preparation of W1/O emulsion: aqueous phase in 50g is added to 100g oil phase, uses high-speed emulsifying machine emulsification evenly to obtain W1/O emulsion;
(3) preparation of microballoon: by the outer aqueous phase of above-mentioned W1/O emulsion instillation 1000g, mechanical agitation, rotating speed 300rpm, room temperature solvent flashing, solidification obtains microballoon, and washing drying obtains microballoon.
Microsphere average grain diameter 160 microns, BET specific surface area 17 m
2/ g, pore volume 6.5 mL/g, mean pore sizes is 1040 nm.
embodiment 5
(1) configuration of interior aqueous phase, oil phase, outer aqueous phase:
10g carboxymethyl-beta-cyclodextrin is dissolved in 90g water and obtains interior aqueous phase;
5g cellulose acetate dissolves is obtained oil phase in 95g ethyl acetate;
Outer aqueous phase is obtained by 12.5g cupric sulfate pentahydrate, 0.20g polyvinyl alcohol dissolution to 1000g water.
(2) preparation of W1/O emulsion: aqueous phase in 80 g is added to 100 g oil phases, uses high-speed emulsifying machine emulsification evenly to obtain W1/O emulsion;
(3) preparation of microballoon: by the outer aqueous phase of above-mentioned W1/O emulsion instillation 1000g, mechanical agitation, rotating speed 100 rpm, room temperature solvent flashing, solidification obtains microballoon, and washing drying obtains microballoon.
Microsphere average grain diameter 360 microns, BET specific surface area 7.0 m
2/ g, pore volume 4.8mL/g, mean pore sizes 320nm.
embodiment 6
(1) configuration of interior aqueous phase, oil phase, outer aqueous phase:
8g carboxymethyl-beta-cyclodextrin, 2g carboxymethyl cellulose are dissolved in 90g water and obtain interior aqueous phase;
By 5g ethyl cellulose, 2g cellulose acetate dissolves obtains oil phase in 93g ethyl acetate/dichloromethane (mass ratio 1:1) mixed solvent;
Outer aqueous phase is obtained by 10.0 g copper chlorides, 0.20g polyvinyl alcohol dissolution to 1000g water.
(2) preparation of W1/O emulsion: aqueous phase in 40 g is added to 100 g oil phases, uses high-speed emulsifying machine emulsification evenly to obtain W1/O emulsion;
(3) preparation of microballoon: by the outer aqueous phase of above-mentioned W1/O emulsion instillation 300g, mechanical agitation, rotating speed 300rpm, room temperature solvent flashing, solidification obtains microballoon, and washing drying obtains microballoon.
Microsphere average grain diameter 360 microns, BET specific surface area 39 m
2/ g, pore volume 7.8mL/g, mean pore sizes 540nm.
embodiment 7
Microballoon in embodiment 1-3 is used as composite filter tip additive particle, numbering is respectively 1#, 2# and 3#, microballoon addition is 15 milligrams/, take regular-size cigarette as control sample, according to standard aspiration condition again smoking machine carry out cigarette smoking experiment, measure the content of HCN in main flume, result is as follows:
| Microsphere sample | Contrast | 1# | 2# | 3# |
| HCN content ug/cig | 102.4 | 51.1 | 65.4 | 74.4 |
| HCN reduced rate | - | 50.1% | 36.1% | 27.3% |
Claims (4)
1. a preparation method for the porous cellulose complex microsphere of copper ion functionalization, is characterized in that: the method combines based on double emulsion-removal of solvents method and ionomer technology, comprises following concrete steps:
(1) the hydrophilic high molecular material aqueous solution of carboxyl or functional amido is formed in aqueous phase W1 join emulsification in the oil phase O that oil-soluble cellulose organic solution forms and obtain water-in-oil type W1/O emulsion;
(2) W1/O emulsion is added in the outer aqueous phase W2 of copper ion aqueous solution formation and obtain W1/O/W2 double emulsion, solvent volatilization or diffusion method is adopted to remove organic solvent, drop solidifies, in drop solidification process, hydrophilic high molecular material generation ionomer in copper ion in outer aqueous phase W2 and interior aqueous phase W1 reacts and is compound in microballoon, and after filtration, washing, drying obtain the porous cellulose complex microsphere of copper ion functionalization;
The hydrophilic high molecular material of described carboxyl or functional amido be carboxymethyl cellulose, CMS, CMC, shitosan, carboxymethyl cyclodextrin, polyacrylic one or more, its concentration in interior aqueous phase W1 is 0.5 ~ 5.0 wt%;
In described outer aqueous phase W2, copper ion concentration is 0.01 ~ 0.5 mol/L;
Described oil-soluble cellulose is cellulose acetate, ethyl cellulose or both mixtures, and its concentration in oil phase O is 1.0 ~ 10.0 wt%;
The mass ratio of described interior aqueous phase, oil phase, outer aqueous phase is 0.05 ~ 1.3: 1: 2 ~ 20.
2. the preparation method of the porous cellulose complex microsphere of copper ion functionalization according to claim 1, is characterized in that: described oil phase solvent is the mixture of one or any two kinds in ethyl acetate, methyl acetate, carrene, chloroform.
3. the porous cellulose complex microsphere of the copper ion functionalization prepared by claim 1 method, it is characterized in that: this complex microsphere is made up of cellulose acetate or ethyl cellulose and the crosslinked hydrophilic macromolecule of copper ion, microballoon has the pore structure of intercommunication, particle diameter is in 10 ~ 2000 micrometer ranges, pore volume is at 0.5 ~ 8.0 mL/g, aperture at 20 ~ 12000 nm, BET specific surface area 1.0 ~ 60 m
2/ g, in microballoon, content of copper ion is 0.1 ~ 10.0 wt%.
4. the application of the porous cellulose complex microsphere of the copper ion functionalization prepared by claim 1 method, it is characterized in that: porous cellulose complex microsphere is added in cigarette filter as composite filter tip additive particle, hydrogen cyanide burst size more than 25% in main flume can be reduced.
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| CN105004819B (en) * | 2015-08-19 | 2017-03-15 | 福建中烟工业有限责任公司 | A kind of method of hydrogen cyanide content in measure cigarette mainstream flue gas |
| BR112018008308A2 (en) * | 2015-10-30 | 2018-10-30 | Toray Industries | cellulose derivative microparticle, dispersion, method for microparticle production, composite microparticle and preparation |
| CN108212114A (en) * | 2018-02-08 | 2018-06-29 | 福州大学 | A kind of copper ion trace composite adsorbing material and preparation method thereof |
| CN113368838B (en) * | 2021-06-15 | 2022-11-29 | 青岛科技大学 | Biomass nano-cellulose porous material with surface loaded with nano-transition metal oxide and preparation method thereof |
| CN116210686B (en) * | 2023-01-13 | 2024-03-08 | 天津市汉邦植物保护剂有限责任公司 | Copper gluconate preparation and preparation method thereof |
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