CN103724635B - Preparation method of a kind of cellulose acetate porous microsphere and products thereof - Google Patents
Preparation method of a kind of cellulose acetate porous microsphere and products thereof Download PDFInfo
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- CN103724635B CN103724635B CN201310647628.6A CN201310647628A CN103724635B CN 103724635 B CN103724635 B CN 103724635B CN 201310647628 A CN201310647628 A CN 201310647628A CN 103724635 B CN103724635 B CN 103724635B
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Abstract
The invention discloses preparation method of a kind of cellulose acetate porous microsphere and products thereof, its preparation method comprises the following steps, to the cellulose acetate dissolves of glycerine triacetate be mixed with in organic solvent, then the aqueous solution adding pore-creating agent wherein obtains water-in-oil-type W/O emulsion, finally W/O emulsion is added in the outer aqueous phase aqueous solution, remove organic solvent and obtain cellulose acetate porous microsphere.Cellulose acetate porous microsphere median size provided by the invention is 20.0 ~ 2000 microns, BET specific surface area 1.0 ~ 50.0m2/g, and aperture is at 50 ~ 20000nm, and pore volume is at 0.5 ~ 10.0mL/g, and in microballoon, glycerine triacetate content is 1.0 ~ 20.0%.Cellulose acetate porous microsphere provided by the invention has the vesicular structure of intercommunication, and pore volume is large, pore structure and particle diameter controllable, and this structure is conducive to its application in fractionation by adsorption, water treatment, bio-medical field.
Description
technical field:
The invention belongs to macromolecular material field, particularly a kind of preparation method of cellulose acetate porous microsphere and the product prepared by the method thereof.
background technology:
Cellulose acetate is a kind of important derivatived cellulose, and it is cellulosic acetic ester.Cellulose acetate has the characteristics such as nontoxic, biodegradable.Wherein, degree of substitution with acetyl group cellulose acetate between 2.0 ~ 2.7 is called as Cellulose diacetate, and it is widely used as cigarette filter filament (cigarette diacetate fiber).
In order to the filter stick making cigarette diacetate fiber roll into has suitable hardness, industrial often at a certain amount of glycerine triacetate of tow surface applying, its consumption is generally 4.0% ~ 12.0% of diacetate fiber quality.In the filter stick course of processing, inevitably produce discarded cigarette diacetate fiber.But because these discarded pipe tobaccos are often containing a certain amount of glycerine triacetate, limit its recycling.The treatment process of discarded tow is that fixed point is burned at present, although stopped discarded tow to enter the approach that false smoke manufactures link, also brings the waste of resource.
Cellulose acetate porous microsphere not only remains the character of cellulose acetate material itself; and due to the microtexture of porous microsphere uniqueness; as porousness, larger specific surface area etc.; its industrial Applicability is paid close attention to gradually, is expected to be used widely in fields such as separation, absorption, bio-medical, environment protection.Patent US4663667 adopts the precipitator method to prepare porous cellulose acetate microballoon, by by cellulose acetate dissolves in the acetum of high density, then instill precipitation in low-concentration acetic acid solution and obtain cellulose acetate porous microsphere.Patent US461892 take halohydrocarbon as solvent, by suspended dispersed legal system for porous cellulose acetate microballoon.Discarded cellulose acetate tow containing softening agent is dissolved in mixed solvent by Chinese patent CN201110222485.5, obtain polymer slurries, then polymer slurries is joined in dispersion liquid, fully be mixed to get suspension, by reducing cellulose acetate dissolves degree, separate out cellulose acetate microballoon.But, under normal circumstances, adopt the cellulose acetate microballoon prepared by above method often atresia or pore volume less, pore structure is easy-regulating not, and its application is limited.
summary of the invention:
The cellulose acetate porous microsphere that the object of the present invention is to provide a kind of preparation method of cellulose acetate porous microsphere and prepared by the method.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for cellulose acetate porous microsphere, the method comprises the following steps:
(1) cellulose acetate dissolves being mixed with glycerine triacetate is obtained the cellulose acetate organic solution that concentration is 1.0 ~ 10.0% in organic solvent;
(2) joined by the pore-creating agent aqueous solution in above-mentioned cellulose acetate organic solution, emulsification obtains water-in-oil-type W/O emulsion;
(3) W/O emulsion added in the outer aqueous phase aqueous solution and obtain W/O/W double emulsion, remove organic solvent, microballoon solidifies, and obtains described cellulose acetate porous microsphere after washing drying after filtration.
The described pore-creating agent aqueous solution is the carbonate solution of concentration 1.0 ~ 20.0%, bicarbonate solution or both mixing solutionss; Described carbonate is volatile salt, sodium carbonate, salt of wormwood; Supercarbonate is bicarbonate of ammonia, sodium bicarbonate, saleratus.
In the described outer aqueous phase aqueous solution, pH value is 1.0 ~ 9.0.
It is described that to be mixed with glycerine triacetate massfraction in the cellulose acetate of glycerine triacetate be 1.0 ~ 30.0%.This cellulose acetate being mixed with glycerine triacetate can for discarded cigarette cellulose acetate tow, also can mix gained mixture for discarded cigarette cellulose acetate tow further with glycerine triacetate, or be cellulose acetate and glycerine triacetate mixing gained mixture.
The degree of substitution with acetyl group of described cellulose acetate is 2.0 ~ 2.7.
Described organic solvent is the mixed solvent of a kind of or two kinds of arbitrary proportions in ethyl acetate, methyl acetate, methylene dichloride, trichloromethane.
The mass ratio of the described pore-creating agent aqueous solution, cellulose acetate organic solution and the outer aqueous phase aqueous solution is 0.1 ~ 0.5:1:5 ~ 20.
When preparing W/O emulsion and W/O/W emulsion, emulsifying agent can be added as required, as polyvinyl alcohol, tween-80 etc., the addition of emulsifying agent preferably 0.2 ~ 2.0%.
When preparing W/O/W emulsion, preparation temperature is preferably 20 ~ 50
oc carries out.
The cellulose acetate porous microsphere utilizing aforesaid method to prepare, scanning electron microscope test display microballoon has the pore structure of intercommunication, and median size is 20 ~ 2000 microns; Nitrogen adsorption methods measures and shows that the BET specific surface area of microballoon is at 1.0 ~ 50.0m
2/ g; Mercury penetration method measures and shows that microballoon aperture is at 50 ~ 20000nm, and pore volume is at 0.5 ~ 10.0mL/g; In microballoon, glycerine triacetate massfraction is 1.0% ~ 20%.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention and Chinese patent CN102911379(and CN201110222485.5, background technology part was mentioned) method preparing cellulose acetate microballoon announced compares, although the raw material used is similar, but the cellulose acetate microballoon hole that it prepares is not communicated with, pore volume less (related data of not reporting for work), aperture is less (20 ~ 200nm) also.The present invention adopts double emulsion and pore-creating agent foaming to combine, and the cellulose acetate microballoon prepared has the pore structure of intercommunication, pore volume large (can up to 10mL/g), and pore size distribution is wider, there is oversized hole (can up to 20 microns).Simultaneously pore structure and particle diameter controllable, the structure of this uniqueness is conducive to its application in fractionation by adsorption, water treatment, bio-medical field.Such as, providing support as can be Growth of Cells during cell cultures microcarrier, being conducive to the transmission of nutritive substance; During as flue gas sorbing material, oversized hole is conducive to the fast transport of flue gas, and the adsorbable flue gas objectionable impurities in less hole.
(2) cellulose acetate porous microsphere provided by the invention contains a certain amount of glycerine triacetate, be conducive to medicine, spices fixing, the absorption of flue gas special component.
(3) raw material of cellulose acetate porous microsphere provided by the invention both can be new cellulose acetate and the mixture of glycerine triacetate, also can be discarded cellulose acetate tow (containing glycerine triacetate) and the mixture with glycerine triacetate thereof, be conducive to turning waste into wealth, realize the efficiency utilization of resource.
Accompanying drawing explanation
Scanning electronic microscope (SEM) photo of the cellulose acetate porous microsphere of Fig. 1 prepared by the embodiment of the present invention 3.
Embodiment
The present invention is further described below in conjunction with embodiment, but is not restriction the present invention.
Embodiment 1
The cellulose acetate tow sample (wherein glycerine triacetate content is 8.0%, and cellulose acetate substitution value is 2.5) that 5.0g is discarded is dissolved in 95.0g ethyl acetate and obtains cellulose acetate solution; Add the aqueous solution of 5.0g containing 5% bicarbonate of ammonia, 1% polyvinyl alcohol wherein, use ultrasonic cell disruptor emulsification to obtain W/O emulsion in 3 minutes; Above-mentioned W/O emulsion is slowly added 800g containing 0.2% polyvinyl alcohol the aqueous solution in, 400rpm mechanical stirring obtains W/O/W emulsion, normal temperature volatile organic solvent, solidification, after filtration, washing and drying obtain cellulose acetate porous microsphere.
Microballoon BET specific surface area 9.2m
2/ g, particle diameter is 50 ~ 1200 microns, median size 300 microns, mean pore size 2.2 microns, microballoon pore volume 3.1mL/g, and in microballoon, glycerine triacetate content is 3.5%.
Embodiment 2
By cellulose acetate tow sample (wherein glycerine triacetate content is 8.0%, and cellulose acetate substitution value is 2.5) discarded for 8.0g and 2.0g glycerine triacetate blended after, be dissolved in 90.0g ethyl acetate and obtain cellulose acetate solution; Add the aqueous solution of 5.0g containing 5% sodium bicarbonate, 1% polyvinyl alcohol wherein, use ultrasonic cell disruptor emulsification to obtain W/O emulsion in 10 minutes; Above-mentioned W/O emulsion is slowly added 800g containing 0.2% polyvinyl alcohol, in 1% vinegar aqueous acid, 600rpm mechanical stirring obtains W/O/W emulsion, normal temperature volatile organic solvent, solidification, after filtration, washing drying obtains cellulose acetate porous microsphere.
Microballoon BET specific surface area 7.8m
2/ g, particle diameter is 50 ~ 450 microns, median size 220 microns, mean pore size 1.2 microns, microballoon pore volume 7.1mL/g, and in microballoon, glycerine triacetate content is 15.5%.
Embodiment 3
1 part of glycerine triacetate and 4 parts of cellulose acetates (substitution value 2.4) are obtained through the granulation of spiral blending extrusion the cellulose acetate being mixed with glycerine triacetate, and wherein glycerine triacetate accounts for 20%.Get the above-mentioned cellulose acetate dissolves being mixed with glycerine triacetate of 5.0g and obtain cellulose acetate solution in 95.0g ethyl acetate/dichloromethane mixed solvent (mass ratio 1:1); Add the aqueous solution of 10.0g containing 10% bicarbonate of ammonia, 1% polyvinyl alcohol wherein, emulsification obtains W/O emulsion; Above-mentioned W1/O emulsion is slowly added 800g containing in the aqueous solution of 0.2% polyvinyl alcohol, 400rpm stirs and obtains W/O/W emulsion, heating 40
oc volatile organic solvent, solidification, after filtration, washing and drying obtain cellulose acetate porous microsphere.
Fig. 1 is the stereoscan photograph of cellulose acetate porous microsphere prepared by the present embodiment, and microballoon presents the vesicular structure of height.Microballoon BET specific surface area 11.3m
2/ g, particle diameter is 30 ~ 400 microns, median size 200 microns, mean pore size 3.2 microns, pore volume 6.3mL/g, and glycerine triacetate content is 11.2%.
Embodiment 4
After 1.5g glycerine triacetate and 3.5g cellulose acetate (substitution value 2.4) are mixed, add 95g ethyl acetate/dichloromethane mixed solvent (mass ratio 1:1) and obtain cellulose acetate solution; Add the aqueous solution of 10g containing 5% bicarbonate of ammonia, 5% volatile salt, 1% polyvinyl alcohol wherein, emulsification obtains W/O emulsion; Above-mentioned W/O emulsion is slowly added 1200g containing in the aqueous solution of 0.1% polyvinyl alcohol, 200rpm stirring obtains W/O/W emulsion, stirs solidification, and filtration, washing also drying obtain cellulose acetate porous microsphere.
Microballoon BET specific surface area 20m
2/ g, particle diameter is 30 ~ 800 microns, median size 280 microns, mean pore size 0.5 micron, pore volume 9.2mL/g, and triacetin ester content is 17.0%.
Claims (6)
1. a preparation method for cellulose acetate porous microsphere, is characterized in that: concrete steps are as follows:
(1) cellulose acetate dissolves being mixed with glycerine triacetate is obtained the cellulose acetate organic solution that concentration is 1.0 ~ 10.0% in organic solvent; The described cellulose acetate being mixed with glycerine triacetate is discarded cigarette cellulose acetate tow, discarded cigarette cellulose acetate tow and glycerine triacetate mix gained mixture further or cellulose acetate and glycerine triacetate mixing gained mixture;
(2) joined by the pore-creating agent aqueous solution in above-mentioned cellulose acetate organic solution, emulsification obtains water-in-oil emulsion W/O emulsion; The described pore-creating agent aqueous solution is the carbonate solution of concentration 1.0 ~ 20.0%, bicarbonate solution or both mixing solutionss; Described carbonate is volatile salt, sodium carbonate, salt of wormwood; Supercarbonate is bicarbonate of ammonia, sodium bicarbonate, saleratus;
(3) W/O emulsion is added in the outer aqueous phase aqueous solution obtain W/O/W double emulsion, remove organic solvent, microballoon solidifies, in microballoon solidification process, form porous microsphere because pore-creating agent produces gas, after washing drying after filtration, obtain described cellulose acetate porous microsphere;
The mass ratio of the described pore-creating agent aqueous solution, cellulose acetate organic solution and the outer aqueous phase aqueous solution is 0.1 ~ 0.5:1:5 ~ 20.
2. the preparation method of cellulose acetate porous microsphere according to claim 1, is characterized in that: in the described outer aqueous phase aqueous solution, pH value is 1.0 ~ 9.0.
3. the preparation method of cellulose acetate porous microsphere according to claim 1, is characterized in that: described in be mixed with glycerine triacetate mass percent in the cellulose acetate of glycerine triacetate be 1 ~ 30%.
4. the preparation method of cellulose acetate porous microsphere according to claim 1, is characterized in that: described organic solvent is the mixing of a kind of or two kinds of arbitrary proportions in ethyl acetate, methyl acetate, methylene dichloride, trichloromethane.
5. the preparation method of cellulose acetate porous microsphere according to claim 1, is characterized in that: when preparing W/O/W emulsion, preparation temperature is preferably 20 ~ 50
oc carries out.
6. the cellulose acetate porous microsphere prepared by claim 1 method, is characterized in that: this microballoon has the pore structure of intercommunication, and microsphere average grain diameter is 20 ~ 2000 microns, BET specific surface area 1.0 ~ 50.0m
2/ g, aperture is at 50 ~ 20000nm, and pore volume is at 0.5 ~ 10.0mL/g, and in microballoon, glycerine triacetate massfraction is 1.0% ~ 20%.
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| CN105413646B (en) * | 2015-12-04 | 2018-08-21 | 河海大学 | A kind of preparation method of porous cellulose acetate microsphere adsorbing agent |
| CN107164090A (en) * | 2017-05-31 | 2017-09-15 | 东南大学 | A kind of cigarette perfume microcapsule and preparation method |
| CN110559956B (en) * | 2019-09-06 | 2022-06-21 | 广东省生物工程研究所（广州甘蔗糖业研究所） | Hollow porous cellulose microsphere and preparation method and application thereof |
| CN111454468B (en) * | 2020-03-27 | 2021-04-20 | 西安交通大学 | Shape-controllable intelligent response microsphere and preparation method thereof |
| CN115109300A (en) * | 2021-03-17 | 2022-09-27 | 四川大学 | Preparation method of macroporous cellulose diacetate microspheres |
| CN115109301A (en) * | 2021-03-18 | 2022-09-27 | 四川大学 | Preparation method of hollow open cellulose diacetate microspheres |
| CN114405483B (en) * | 2021-12-13 | 2024-03-26 | 健帆生物科技集团股份有限公司 | Porous cellulose microsphere adsorbent with core-shell structure, preparation method and application |
| CN114471709B (en) * | 2022-01-04 | 2023-12-19 | 济南大学 | Iron-doped cellulose-based microsphere with high catalytic performance as well as preparation method and application thereof |
| CN114656677B (en) * | 2022-02-11 | 2022-12-16 | 华南理工大学 | Lignin porous microsphere based on W/O/W type multiple emulsion solvent volatilization and preparation method and application thereof |
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| CN102911379B (en) * | 2011-08-04 | 2014-04-23 | 南通醋酸纤维有限公司 | Method for preparing cellulose acetate microspheres and product prepared by method |
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