CN101250267A - Cellulose microsphere as well as preparation method and use thereof - Google Patents
Cellulose microsphere as well as preparation method and use thereof Download PDFInfo
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- CN101250267A CN101250267A CNA2008100473141A CN200810047314A CN101250267A CN 101250267 A CN101250267 A CN 101250267A CN A2008100473141 A CNA2008100473141 A CN A2008100473141A CN 200810047314 A CN200810047314 A CN 200810047314A CN 101250267 A CN101250267 A CN 101250267A
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Abstract
The invention discloses cellulose microsphere, and a preparation process and the application. The cellulose microsphere is prepared through dispersing cellulose solution in organic solvent which comprises emulsifier or composite emulsifier, solidifying in constant temperature for 1-10hr to shape after stirring to evenly disperse drops, then adding diluted acid to make cellulose regenerate into microsphere, standing and stratifying, filtering to obtain cellulose particles, finally obtaining cellulose microsphere after decantation. The solution of cellulose and the preparation of cellulose microsphere are physical processes without chemical reaction. The whole preparation technology is simple, has short time consumption, and organic solvent can be repeatedly used. The process has low device demand, which is convenient for industrial production. The cellulose microsphere which is prepared through adopting the process has favorable mechanical property, excellent flow-ability, heat stability and swelling resistance property, oxidation resistance ability, biodegrability resistance and acidic and alkali degradation capability, and has extensive usage.
Description
Technical field
The present invention relates to a kind of cellulose microsphere and its production and use, belong to chemical field.
Background technology
Mierocrystalline cellulose is natural resource the abundantest on the earth, that can recover, have inexpensive, degradable and environment do not produced characteristics such as pollution, so countries in the world is all attached great importance to cellulosic research and development.
Mierocrystalline cellulose is by linear polymer that β-(1 → 4)-D-glycosidic link is formed by connecting by the cellobiose repeating unit, hydroxyl on each dehydrated glucose unit is positioned at C-2, C-3 and C-6 position, reaction property with typical primary alconol and secondary alcohol, can pass through a series of chemical modification, produce the functional high molecule material of different purposes.The development and the application of cellulose adsorbent and ion-exchanger start from the beginning of the fifties, have the Mierocrystalline cellulose commodity selling of multiple brand and series at present both at home and abroad, because the limitation of preparation means, plain sorbent material of commercial fibre and ion-exchanger mostly are powdery or microgranular greatly, and pore structure is not so good, this just restricts its use range significantly, and the ball shaped cellulose sorbent material has just in time remedied the shortcoming of existing goods, can control cell size, granularity, it is big to have specific surface, advantages such as transparent performance and hydraulic performance are good, be easy to operate on processing and the suitable post, and can be used to analyzing blood, remove the antigen in the blood plasma, the absorption serum protein, the separation and purification bacterial, preparation and separating chiral compound, the purifying chloroplast DNA, adsorbing metal ions, separate transition metal ion, reclaim valuable gold, therefore the enrichments of radioactive metal etc. cause lot of domestic and international scientific effort interest all about the preparation of ball shaped cellulose and the research of application.
The modal preparation method of ball shaped cellulose sorbent material is emulsification-solidification method (also claiming the collosol and gel phase conversion method, Sol-gel transition method), and the preparation method generally can be divided into following step: the preparation of cellulose gum or cellulose solution; The preparation of cellulose bead body is comprising the regeneration of curing that cellulose solution is dispersed into spherical drop, drop and cellulose bead body; Cellulose microsphere functionalized.The solvent that is used for dissolving cellulos at present mainly contains cuprammonium complexing solvent, cadmium ethylenediamine complexing solvent, amine oxidation system, lithium chloride/N,N-DIMETHYLACETAMIDE, ionic liquid, carbamate system, oxidation sodium/water, alkali/urea or thiocarbamide/aqueous systems equal solvent, because the solvent that has is still at the experimental stage, although existing manufacturing feasibility and the prospect of realizing that has can't be as the stock liquid of preparation cellulose bead body.Therefore the lot of domestic and international researcher selected inexpensive, raw material sources easily viscose prepare the Mierocrystalline cellulose spheroid.But traditional viscose prepares a large amount of waste liquid, waste gas and the waste materials of generation in the Mierocrystalline cellulose spheroid process, causes serious pollution to environment.And the cellulose bead body great majority of preparation contain residual groups or by solvent contamination own, limited its in application biological and medically.These have restricted the development of cellulose microsphere on certain program.
Summary of the invention
Purpose of the present invention provides a kind of cellulose microsphere and its production and use in order to overcome above-mentioned the deficiencies in the prior art exactly, with alkali/urea or the direct dissolving cellulos of the plain solvent of thiocarbamide/water cellulose, the preparation cellulose solution adopts collosol and gel normal temperature phase conversion method to prepare cellulose microsphere then.Present method manufacturing process is simple, produces not have to poison, and solvent is nontoxic and reusable, and product is easy to aftertreatment, environmentally safe.
Realize that the technical scheme that the object of the invention adopts is: a kind of cellulose microsphere, particle diameter are 1～2500um, and mean pore size is 200～1000um, and specific surface area is 500～800m
2/ g, water ratio 86～93%, skeletal density 1.45～1.50g/ml, apparent density 1.01～1.05g/ml, pore volume 1.00～5.00ml/g, cell size 90～95%.
Described cellulose microsphere makes by the following method: at first produce cellulose solution, adopt collosol and gel normal temperature phase conversion method to prepare cellulose microsphere then.It may further comprise the steps: with alkali/urea or thiocarbamide/water is solvent, high-speed stirring dissolving cellulos at low temperatures, and the high speed centrifugation deaeration removal of impurity gets cellulose solution then.Cellulose solution is scattered in the organic solvent that contains emulsifying agent or compound emulsifying agent, be stirred to the drop back ambient cure 1-10hr that is uniformly dispersed and be shaped, add dilute hydrochloric acid then and make cellulose regenerated formation microballoon, standing demix, the upper strata is an organic solvent, lower floor is a water, and cellulose grain is deposited in lower floor, filter cellulose grain, topple over and upper organic phase, it can directly recycle, and removes water, and cellulose grain gets cellulose microsphere with the distilled water decantate for several times.Contain 20% alcoholic acid redistilled water 0～5 ℃ of preservation with putting into behind the 10% aqueous ethanolic solution washing by soaking 3～5 times.
Above-mentioned used organic solvent is kerosene, transformer oil, pump oil, 200
#Gasoline, turbine wet goods mineral oil or whiteruss, the perhaps mixed organic solvents of two or more composition in them, consumption of organic solvent be the cellulose solution volume 3-10 doubly; Emulsifying agent or compound emulsifying agent are Twin-80, Span-80, oleic acid or potassium oleate, the perhaps blending emulsifiers of two or more composition in them, and the emulsifying agent volumetric usage is 0.1～10% of an organic solvent volume.
The preparation of described cellulose solution may further comprise the steps: Mierocrystalline cellulose is dissolved in the solvent of alkali/urea or thiocarbamide/water, high-speed stirring is until cellulose dissolution at low temperatures, and the high speed centrifugation deaeration removal of impurity gets cellulose solution then.
The cellulose microsphere specific surface area that the method for the invention makes is big, grain size homogeneous and can being controlled by processing parameter; Pore size distribution is wide can be regulated by adding linking agent; Hydroxyl is rich on the surface, does not have other residual groups, can widen its Application Areas by surface chemical modification or surface group derivatize, is suitable for being used to mutually to separate and adsorb or the carrier of catalyzed reaction as chromatographic stationary.Nontoxic, the good biocompatibility of this cellulose microsphere, and operation and reactivity worth are good, are used to prepare magnetic microsphere, and the carrier of enzyme or other biomaterial also is used for blood purification and is convenient to fluorescent mark as fluorescent probe.
Compared with prior art, innovation of the present invention is as follows:
The present invention is a raw material with the natural polymer Mierocrystalline cellulose of originating abundant, is dissolved in the solvent of alkali/urea or thiocarbamide/water and makes cellulose solution.Adopt normal temperature collosol and gel phase inversion (Sol-Gel) method to prepare cellulose microsphere then.The preparation of cellulosic dissolving and cellulose microsphere all is a physical process, and chemical reaction does not take place.Whole preparation process is succinct, weak point consuming time, and used organic solvent is reusable.Present method is not high to equipment requirements, is convenient to suitability for industrialized production.Other group of cellulose microsphere noresidue that present method makes and other reagent, the cleaning that has kept cellulose microsphere, and cellulose microsphere has mechanical property, good flowing property, thermostability and swell-resistant energy, resistance of oxidation, antibiont degradation capability and antiacid alkaline degradation ability preferably, and is of many uses.Can be used for separating and adsorb or the carrier and the preparation magnetic microsphere of catalyzed reaction.Because the nontoxic and good biocompatibility of Mierocrystalline cellulose is so more have superiority at carrier, blood-purifying adsorbing agent and the fluorescent microsphere probe as enzyme or other biomaterial.Can degrade under field conditions (factors) behind the product abandonment, help environment protection.
Description of drawings
Fig. 1 is the scanning electron microscope close-up view of the cellulose microsphere of the embodiment of the invention 1 preparation
Fig. 2 is the scanning electron microscope close-up view of the single cellulose microsphere of the embodiment of the invention 1 preparation
Fig. 3 is the scanning electron microscope surface tissue figure of the cellulose microsphere of the embodiment of the invention 1 preparation
Embodiment
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
Be pre-chilled to-12 ℃ with the NaOH/ aqueous solution of urea and make dissolution with solvents preparation of cellulose cellulose solution, in being furnished with the 500ml there-necked flask of condensation reflux unit and water bath with thermostatic control, add 300ml kerosene and transformer oil mixed solvent, with the 3mlTwin-80/Span-80 compound emulsifying agent, after stirring, the cellulose solution 100ml that slowly adds above-mentioned preparation, add in 60min and finish, the control stirring velocity is 200r/min, emulsification 30min under the normal temperature.Keep identical condition to continue Procuring 1hr, dripping dilute acid is acidified to pH to be that neutrality makes cellulose regenerated subsequently.Stop to stir, standing demix, the upper strata is an organic solvent, and lower floor is a water, and cellulose grain is deposited in lower floor.Topple over and upper organic phase, it can directly recycle, remove water, cellulose grain with the distilled water decantate for several times the back with behind the 10% aqueous ethanolic solution washing by soaking 3～5 times cellulose microsphere, put into and contain 20% ethanol redistilled water 0～5 ℃ of preservation.
The above-mentioned cellulose microsphere median size that makes is 2500um, and mean pore size is 1000um, and specific surface area is 500m
2/ g, water ratio are 93%, and pore volume is 5.00ml/g, and cell size is 95%.The scanning electron microscope close-up view of the cellulose microsphere that present embodiment makes as shown in Figure 1, the scanning electron microscope close-up view of single cellulose microsphere is as shown in Figure 2.The scanning electron microscope surface tissue of cellulose microsphere as shown in Figure 3.
Embodiment 2
Be pre-chilled to-12 ℃ with the NaOH/ aqueous solution of urea and make dissolution with solvents preparation of cellulose cellulose solution, in being furnished with the 500ml there-necked flask of condensation reflux unit and water bath with thermostatic control, add 300ml whiteruss and 9mlSpan-80, after stirring, the cellulose solution 50ml that slowly adds above-mentioned preparation, in 30min, add and finish, the control stirring velocity is 800r/min, emulsification 30min under the normal temperature.Keep identical condition to continue Procuring 1hr, dripping 10% hcl acidifying subsequently, to be to pH that neutrality makes cellulose regenerated.Stop to stir, standing demix, the upper strata is an organic solvent, and lower floor is a water, and cellulose grain is deposited in lower floor.Topple over and upper organic phase, it can directly recycle, remove water, cellulose grain with the distilled water decantate for several times the back with behind the 10% aqueous ethanolic solution washing by soaking 3～5 times cellulose microsphere, put into and contain 20% ethanol redistilled water 0～5 ℃ of preservation.
The above-mentioned cellulose microsphere median size that makes is 600um, and mean pore size is 800um, and specific surface area is 750m
2/ g, water ratio 90%, pore volume 4.51ml/g, cell size 92%.
Embodiment 3
Be pre-chilled to-12 ℃ with the NaOH/ aqueous solution of urea and make dissolution with solvents preparation of cellulose cellulose solution, in being furnished with the 500ml there-necked flask of condensation reflux unit and water bath with thermostatic control, add 300ml200
#Whiteruss and 30mlSpan-80 and potassium oleate compound emulsifying agent after stirring, slowly add the cellulose solution 30ml of above-mentioned preparation, add to finish in 15min, and the control stirring velocity is 1000r/min, emulsification 30min under the normal temperature.Keep identical condition to continue Procuring 4hr, drip rare pH of being acidified to of 10% subsequently and be that neutrality makes is cellulose regenerated.Stop to stir, standing demix, the upper strata is an organic solvent, and lower floor is a water, and cellulose grain is deposited in lower floor.Topple over and upper organic phase, it can directly recycle, remove water, cellulose grain with the distilled water decantate for several times the back with behind the 10% aqueous ethanolic solution washing by soaking 3～5 times cellulose microsphere, put into and contain 20% ethanol redistilled water 0～5 ℃ of preservation.
The above-mentioned cellulose microsphere median size that makes is 1um, and mean pore size is 200um, and specific surface area is 800m
2/ g, water ratio 86%, pore volume 1.00ml/g, cell size 90%.
Embodiment 4
Be pre-chilled to-5 ℃ with the NaOH/ thiourea solution and make dissolution with solvents preparation of cellulose cellulose solution, in being furnished with the 500ml there-necked flask of condensation reflux unit and water bath with thermostatic control, add 300ml pump oil and turbine oil mixed solvent and 9ml oleic acid and potassium oleate compound emulsifying agent, after stirring, the cellulose solution 50ml that slowly adds above-mentioned preparation, in 45min, add and finish, the control stirring velocity is 600r/min, emulsification 30min under the normal temperature.Keep identical condition to continue Procuring 6hr, dripping 10% hcl acidifying subsequently, to be to pH that neutrality makes cellulose regenerated.Stop to stir, standing demix, the upper strata is an organic solvent, and lower floor is a water, and cellulose grain is deposited in lower floor.Topple over and upper organic phase, it can directly recycle, remove water, cellulose grain with the distilled water decantate for several times the back with behind the 10% aqueous ethanolic solution washing by soaking 3～5 times cellulose microsphere, put into and contain 20% ethanol redistilled water 0～5 ℃ of preservation.
The above-mentioned cellulose microsphere median size that makes is 450um, and mean pore size is 800um, and specific surface area is 750m
2/ g, water ratio 90%, pore volume 4.35ml/g, cell size 94%.
Embodiment 5
Be pre-chilled to-12 ℃ with the LiOH/ aqueous solution of urea and make dissolution with solvents preparation of cellulose cellulose solution, in being furnished with the 500ml there-necked flask of condensation reflux unit and water bath with thermostatic control, add 300ml200
#Oil and whiteruss mixed solvent and 15mlSpan-80 emulsifying agent after stirring, slowly add the cellulose solution 30ml of above-mentioned preparation, add to finish in 15min, and the control stirring velocity is 1000r/min, emulsification 30min under the normal temperature.Keep identical condition to continue Procuring 10hr, dripping 10% hcl acidifying subsequently, to be to pH that neutrality makes cellulose regenerated.Stop to stir, standing demix, the upper strata is an organic solvent, and lower floor is a water, and cellulose grain is deposited in lower floor.Topple over and upper organic phase, it can directly recycle, remove water, cellulose grain with the distilled water decantate for several times the back with behind the 10% aqueous ethanolic solution washing by soaking 3～5 times cellulose microsphere, put into and contain 20% ethanol redistilled water 0～5 ℃ of preservation.
The above-mentioned cellulose microsphere median size that makes is 1um, and mean pore size is 1000um, and specific surface area is 800m
2/ g, water ratio 86%, pore volume 1.85ml/g, cell size 90%.
Embodiment 6
Be pre-chilled to-5 ℃ with the LiOH/ thiourea solution and make dissolution with solvents preparation of cellulose cellulose solution, in being furnished with the 500ml there-necked flask of condensation reflux unit and water bath with thermostatic control, add 300ml200
#Gasoline and turbine oil mixed solvent and 3ml oleic acid after stirring, slowly add the cellulose solution 50ml of above-mentioned preparation, add to finish in 30min, and the control stirring velocity is 600r/min, emulsification 30min under the normal temperature.Keep identical condition to continue Procuring 6hr, dripping 10% hcl acidifying subsequently, to be to pH that neutrality makes cellulose regenerated.Stop to stir, standing demix, the upper strata is an organic solvent, and lower floor is a water, and cellulose grain is deposited in lower floor.Topple over and upper organic phase, it can directly recycle, remove water, cellulose grain with the distilled water decantate for several times the back with behind the 10% aqueous ethanolic solution washing by soaking 3～5 times cellulose microsphere, put into and contain 20% ethanol redistilled water 0～5 ℃ of preservation.
The above-mentioned cellulose microsphere median size that makes is 100um, and mean pore size is 850um, and specific surface area is 600m
2/ g, water ratio 82%, pore volume 4.95ml/g, cell size 94%.
The above-mentioned cellulose microsphere that makes can be used to prepare cellulose magnetic microsphere, comprise following two kinds of methods: the magnetic particles such as ferric oxide that 1, when the preparation cellulose solution, add excess of imports paramagnetic, prepare the magnetic fibre cellulose solution earlier by direct embedding, by the method for the invention balling-up, obtain magnetic microsphere again; 2, after employing the method for the invention makes cellulose microsphere, adopt the original position method of formation, in the hole of microballoon, adopt chemical process to generate the magnetic particles such as ferric oxide of superparamagnetism, obtain magnetic microsphere.The above-mentioned cellulose microsphere that makes also can directly or behind the derivatize can be used as blood-purifying adsorbing agent, is used for adsorbing toxic substance in the blood.In addition, cellulose microsphere also can adopt entrapping method, absorption method, e to be used for the fixing of enzyme or other biomaterial and fluorescent substance, the carrier and the fluorescent microsphere probe of preparation enzyme or other biomaterial.
Claims (9)
1. cellulose microsphere, particle diameter is 1～2500um, and mean pore size is 200～1000um, and specific surface area is 500～800m
2/ g, water ratio 86～93%, pore volume 1.00～5.00ml/g, cell size 90～95%.
2. the preparation method of the described cellulose microsphere of claim 1, it is characterized in that may further comprise the steps: cellulose solution is scattered in the organic solvent that contains emulsifying agent or compound emulsifying agent, being stirred to the drop back ambient cure 1-10hr that is uniformly dispersed is shaped, add diluted acid then and make cellulose regenerated formation microballoon, standing demix, filter cellulose grain, behind the decantate cellulose microsphere.
3. according to the preparation method of the described cellulose microsphere of claim 2, it is characterized in that: Mierocrystalline cellulose is dissolved in the solvent of alkali/urea or thiocarbamide/water, high-speed stirring is until cellulose dissolution at low temperatures, and the high speed centrifugation deaeration removal of impurity gets cellulose solution then.
4. according to the preparation method of the described cellulose microsphere of claim 2, it is characterized in that: used organic solvent is kerosene, transformer oil, pump oil, 200
#Gasoline, turbine wet goods mineral oil or whiteruss, the perhaps mixed organic solvents of two or more composition in them, organic solvent be the cellulose solution volume 3-10 doubly.
5. according to the preparation method of the described cellulose microsphere of claim 2, it is characterized in that: used emulsifying agent or compound emulsifying agent are the emulsifying agent that is used to prepare water-in-oil emulsion, and its volume is 1～10% of an organic solvent volume.
6. according to the preparation method of claim 2 or 5 described cellulose microspheres, it is characterized in that: emulsifying agent or compound emulsifying agent are in Twin-80, Span-80, oleic acid or the potassium oleate, perhaps the blending emulsifiers of two or more composition in them.
7. according to the preparation method of the described cellulose microsphere of claim 2, it is characterized in that: stirring velocity is: 200～1000r/min.
8. according to the preparation method of the described cellulose microsphere of claim 2, it is characterized in that: dripping dilute acid is acidified to pH, and to be that neutrality makes cellulose regenerated.
9. the described cellulose microsphere of claim 1 is in the carrier of preparation magnetic microsphere, enzyme or other biomaterial and the application in blood-purifying adsorbing agent and the fluorescent microsphere probe.
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