CN102553545A - Cellulose composite microsphere and preparation method thereof - Google Patents
Cellulose composite microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cellulose composite microsphere, a preparation method thereof and application. The particle size of the cellulose composite microsphere is 1mum-1200mum, the specific surface area of the cellulose composite microsphere is 100m<2>/g-500m<2>/g, and the aperture of the cellulose composite microsphere is 200nm-900nm. The preparation method comprises the following steps of: preparing a mixture solution of cellulose and a composite material by using the cellulose as a matrix, a polymer material as composite material and a water solution of alkali/urea or alkali/thiourea as a solvent, and obtaining the cellulose composite microsphere through sol-gel phase transition and cross-linking agent cross linkage. The advantages of cellulose microsphere are reserved by the cellulose composite microsphere, and due to the adding of the composite material, new functional groups are simultaneously added for the surface of the microsphere and further decoration and modification are facilitated. An organic solvent used in the preparation method disclosed by the invention can be reused, the whole preparation technology is simple, low in time consuming, undemanding for equipment and convenient for industrial production, and the prepared cellulose composite microsphere has a good flow property and mechanical property and a wide application.
Description
Technical field
The present invention relates to a kind of cellulosic material class adsorbent, relate in particular to a kind of cellulose complex microsphere, belong to chemical field.
Background technology
Cellulose is the abundantest natural reproducible resource, and according to scientist's estimation, reach 1,000 hundred million ton or more through biosynthetic renewable cellulose every year.Because cellulose has inexpensive, degradable and advantage such as pollution of ecological environment not, therefore, in today that problem of environmental pollution increasingly sharpens, countries in the world are paid attention to the performance study and the exploitation of this natural macromolecular material of cellulose more.
Cellulose is homogeneous and one of the simplest polymer in the polysaccharide field; It is made up of D-dehydration glucopyranoside (AGU); Be formed by connecting with (1-4) glycosidic bond each other; Many hydroxyls being arranged on the macromolecular chain, have stronger reactivity worth and interaction performance, is comparatively desirable carrier material and sorbing material therefore.The research of cellulose carrier and sorbing material starts from the fifties in last century, existing at present multiple commercial cellulose commodity.Yet present commercial cellulose products mainly is to be solvent preparation with cellulose copper ammon solution, cellulose cadmium ethylenediamine solution, cellulose tartaric acid ferrous solution, cellulose NMMO solution or viscose liquid.These solvents all are poisonous and harmfuls or inflammable and explosive, produce a large amount of waste water, waste gas, waste material in the production process, and environment is caused very big pollution; Products obtained therefrom is Powdered or graininess mostly; Adsorbance is low, and withstand voltage properties is poor, and these shortcomings have greatly limited its range of application.Simultaneously; Be subject to cellulosic self-characteristic, these cellulose commodity show higher characterization of adsorption to metal ion and hydroaropic substance, but for the lyophobic dust adsorption capacity a little less than; And single surface functional group also is unfavorable for the further modification and the modification of product.These shortcomings have limited the range of application of cellulose commodity greatly.
Chinese patent 1660129A discloses a kind of preparation method of agent of cyclodextrin-cellulose for adsorbing uric acid; This agent of cyclodextrin-cellulose for adsorbing uric acid is that cellulose is dissolved in the NaOH aqueous solution; In aqueous slkali, add crosslinking agent, carry out polymerization in 2～10 hours, add cyclodextrin then and continue polymerization 2～6 hours at 30～60 ℃; Dry then, pulverizing obtains.Prepared agent of cyclodextrin-cellulose for adsorbing uric acid specific area, adsorption capacity and the mechanical performance of this method all remains further to be improved.
Summary of the invention
The purpose of this invention is to provide that one type of specific area is big, the preparation method and the purposes of high adsorption capacity, the simple cellulose complex microsphere of preparation method and this cellulose microsphere.
The objective of the invention is to realize like this: a kind of cellulose complex microsphere is provided; Said cellulose complex microsphere is base material with the cellulose; With cyclodextrin, shitosan or sodium alginate as composite; The aqueous solution with alkali and aqueous solution of urea or alkali and thiocarbamide is solvent, the mixed solution of preparation cellulose/composite, then through colloidal sol mutually to gel phase transformation with crosslinking agent is crosslinked prepares.Whole preparation process is simple, produces not have to poison, and the product post processing is easy, environmentally safe.Gained cellulose complex microsphere particle diameter is 1～1200um, and specific area is 100～500m
2/ g, the aperture is 200～900nm.Said colloidal sol is that the cellulose composite solution is scattered in the organic solvent of emulsifying agent or compound emulsifying agent to the gel phase transition process, and after 200～1200r/min was stirred to dropping liquid and is uniformly dispersed, normal temperature cure 1～8h was shaped under identical mixing speed.Said crosslinking agent is glutaraldehyde, ethylene glycol diglycidylether or epoxychloropropane.
The present invention also provides a kind of preparation method of above-mentioned cellulose complex microsphere, may further comprise the steps:
1) preparation of cellulose/composite solution: preparation alkali and the aqueous solution of urea or the aqueous solution of alkali and thiocarbamide; Be refrigerated to-12 ℃～-5 ℃, add cellulose and composite then, after the stirring and dissolving; Evacuation and centrifugal degassing and removal of impurities; Obtain the cellulose composite solution, said composite is cyclodextrin, shitosan or sodium alginate;
2) preparation of cellulose complex microsphere: the cellulose composite solution is scattered in the organic solvent of emulsifying agent or compound emulsifying agent, after 200～1200r/min was stirred to dropping liquid and is uniformly dispersed, normal temperature cure 1～8h was shaped under identical mixing speed; Be heated to 40～80 ℃, add crosslinking agent reaction 2～8h, adding diluted acid to solution system is acid (pH＜5); Make cellulose composite material regeneration microballoon, standing demix, the upper strata is an organic facies; Lower floor is a water; Pour out upper organic phase, behind the filtration drying, promptly obtain the cellulose complex microsphere.
Said organic solvent is a n-hexane, benzinum, or atoleine, and the perhaps mixed organic solvents of two or more in them, the organic solvent volume is 2～10 times of cellulose solution.
Said emulsifying agent is this Pan series emulsifying agent, and Pan 60 like that, this Pan 85, and perhaps twain series emulsifier, like Tween 80, polysorbate85, the perhaps blended emulsifier of two kinds in them or two or more compositions.
Said crosslinking agent is glutaraldehyde, ethylene glycol diglycidylether or epoxychloropropane.
With the cellulose complex microsphere water or the washing with alcohol that obtain, obtain pure cellulose complex microsphere, obtain the cellulose composite particles after freeze drying or the oven dry.
Said cellulose complex microsphere is applied to separation and the purifying of protein, enzyme, nucleic acid, polysaccharide large biological molecule, and the absorption of water, oil, heavy metal ion, dyestuff and essence and flavoring agent.
The invention has the beneficial effects as follows: cellulose complex microsphere adsorbent can be controlled cell size, and specific area is big, porosity is high, and adsorbance is big, and machinery and good flowing properties have remedied the deficiency of existing goods.The adding of composite has increased the multifrequency nature of cellulose microsphere; For example; The pore structure of cellulose microsphere has been enriched in the adding of cyclodextrin, has improved the recognition capability of cellulose microsphere for organic molecule, inorganic ions, lyophobic dust, has expanded the range of application of cellulose microsphere; The adding of shitosan and sodium alginate micro ball makes cellulose microsphere have more various surface-active functional group, helps the further modification and the modification of complex microsphere.In addition, the adding of three kinds of composites is further improved the absorption property of cellulose microsphere and improves.Therefore, this type of cellulose complex microsphere can be applied to separation and the purifying of large biological molecules such as protein, enzyme, nucleic acid, polysaccharide, and the absorption of water, oil, heavy metal ion, dyestuff and essence and flavoring agent.
The present invention is a base material with extensive, the cheap cellulose of raw material sources; Respectively with cyclodextrin, sodium alginate or shitosan as composite; The aqueous solution with alkali/aqueous solution of urea or alkali/thiocarbamide is solvent; Prepared the cellulose composite solution, changed mutually and the crosslinked cellulose complex microsphere that prepared of crosslinking agent through collosol and gel then.Whole preparation process is simple, and weak point consuming time is not high to equipment requirements, is convenient to commercial production, and the preparation process does not have violent chemical reaction, mild condition, and used organic solvent is all reusable, and is with low cost, free from environmental pollution.When gained cellulose complex microsphere has been preserved the advantage of cellulose family microballoon; The microsphere surface that is incorporated as of composite has increased new functional group; Help the further modification and the modification of microballoon, and further improve the absorption property of cellulose microsphere.Therefore; The cellulose complex microsphere of the present invention's preparation is of many uses; Can be applied to the absorption of heavy metal ion, dyestuff and essence and flavoring agent; Simultaneously, because cellulose and the nontoxic and good biocompatibility of used composite, this complex microsphere can be applied to separation and purifying and the controlled delivery of pharmaceutical agents release of protein, enzyme, nucleic acid, this type of polysaccharide large biological molecule.
Description of drawings
Fig. 1 is the present invention and other the different cellulose microspheres retention rate comparison diagram to menthol.
The specific embodiment
The present invention is base material with the cellulose; With macromolecular material cyclodextrin, sodium alginate or shitosan is composite; The aqueous solution with alkali/aqueous solution of urea or alkali/thiocarbamide is solvent; The mixed solution of preparation cellulose composite material changes and the crosslinked cellulose complex microsphere that prepared of crosslinking agent through collosol and gel then mutually.
The preparation technology of above-mentioned cellulose complex microsphere can be divided into two steps: the preparation of cellulose/composite solution and the preparation of cellulose complex microsphere.
The preparation of cellulose/composite solution: preparation alkali and the aqueous solution of urea or the aqueous solution of alkali and thiocarbamide, be refrigerated to-12 ℃～-5 ℃, add cellulose and composite then, after the stirring and dissolving, evacuation and centrifugal degassing and removal of impurities obtain the cellulose composite solution.
The preparation of cellulose complex microsphere: the cellulose composite solution is scattered in the organic solvent of emulsifying agent or compound emulsifying agent, after 200～1200r/min was stirred to dropping liquid and is uniformly dispersed, normal temperature cure 1～8h was shaped under identical mixing speed; Be heated to 40～80 ℃, add crosslinking agent reaction 2～8h, adding diluted acid to solution system is acid (pH＜5); Make cellulose composite material regeneration microballoon, standing demix, the upper strata is an organic facies; Lower floor is a water; Pour out upper organic phase, behind the filtration drying, promptly obtain the cellulose complex microsphere.Organic solvent is a benzinum, n-hexane, atoleine, the perhaps mixed organic solvents of two or more in them, organic solvent volume be cellulose composite solution volume 2-10 doubly.Emulsifying agent is this Pan series emulsifying agent, and Pan 60 like that, this Pan 85, and perhaps twain series emulsifier, like Tween 80, polysorbate85, the perhaps blended emulsifier of two kinds in them or two or more compositions.Said crosslinking agent is glutaraldehyde, ethylene glycol diglycidylether or epoxychloropropane.
Following instance will further specify method provided by the invention.
Embodiment 1:
Preparation 100g NaOH (5g)/urea (14g) aqueous solution is refrigerated to-12 ℃ after the dissolving, add the 5g cellulose then, behind the vigorous stirring dissolving cellulos, adds cyclodextrin 3g, and vigorous stirring dissolving cyclodextrin also is uniformly dispersed composite solution.In being furnished with the 500mL there-necked flask of reflux condensing tube and water bath with thermostatic control, add 200mL atoleine and 4g Si Pan 80 emulsifying agents, after 600r/min stirs it is uniformly dispersed, slowly add the cellulose composite solution 80mL of method for preparing; Normal temperature stirs 2h down; Be heated to 40 ℃, add the 1g glutaraldehyde, behind the reaction 2h; Hydrochloric acid to the solution of adding 10% is acid (pH＜5), makes the regeneration of cellulose complex microsphere.Stop to stir, standing demix, the upper strata is an organic facies, and lower floor is a water, and the compound cellulose solids precipitation is at lower floor's aqueous phase.Pour out upper organic phase, separate obtaining the composite fibre crude granule from lower floor's aqueous phase.Gained cellulose complex microsphere particle washs with distilled water immersion, promptly gets pure cellulose complex microsphere.The cellulose complex microsphere average grain diameter that makes is 800um, and average pore size is 400nm, and specific area is 400m
2/ g.
Embodiment 2:
Preparation 100g LiOH (8g)/urea (16g) aqueous solution is refrigerated to-10 ℃ after the dissolving, add the 5g cellulose then, behind the vigorous stirring dissolving cellulos, adds shitosan 1g, and vigorous stirring dissolving shitosan also is uniformly dispersed composite solution.The mixed solvent (volume ratio is 1/1) that in being furnished with the 500mL there-necked flask of reflux condensing tube and water bath with thermostatic control, adds 300mL n-hexane and atoleine; With 4g Si Pan 60 and 6g Si Pan 85 blended emulsifiers, after 700r/min stirs it is uniformly dispersed, slowly add the cellulose composite solution 50mL of method for preparing; After stirring 3h; Be heated to 50 ℃, add ethylene glycol diglycidylether 1.5g, after continuing to react 3h; Hydrochloric acid to the solution of adding 10% is acid (pH＜5), makes the regeneration of cellulose complex microsphere.Stop to stir, standing demix, the upper strata is an organic facies, and lower floor is a water, and cellulose complex microsphere solids precipitation is at lower floor's aqueous phase.Pour out upper organic phase, separate obtaining cellulose complex microsphere particle from aqueous phase.Gained cellulose complex microsphere particle is used alcohol-pickled washing, promptly gets pure cellulose complex microsphere.The cellulose complex microsphere average grain diameter that makes is 400um, and average pore size is 300nm, and specific area is 350m
2/ g.
Embodiment 3:
Preparation 100g LiOH (5g)/thiocarbamide (14g) aqueous solution is refrigerated to-7 ℃ after the dissolving, add the 5g cellulose then, behind the vigorous stirring dissolving cellulos, adds sodium alginate 5g, and vigorous stirring dissolving sodium alginate also is uniformly dispersed composite solution.After the mixed solvent (volume ratio is 1/1) and the 30g Tween 80 that in being furnished with the 500mL there-necked flask of reflux condensing tube and water bath with thermostatic control, add 300mL benzinum and n-hexane, 1200r/min stir it are uniformly dispersed; Slowly add the cellulose composite solution 100mL of method for preparing, stirring at normal temperature 8h is heated to 80 ℃; Add epoxychloropropane 2g, after continuing to react 8h, hydrochloric acid to the solution of adding 10% is acid (pH＜5); Make the regeneration of cellulose complex microsphere, stop to stir standing demix; The upper strata is an organic facies, and lower floor is a water, and cellulose complex microsphere solids precipitation is at lower floor's aqueous phase.Pour out upper organic phase, separate obtaining cellulose complex microsphere particle from aqueous phase.Gained cellulose complex microsphere particle is used alcohol-pickled washing, promptly gets pure cellulose complex microsphere.The cellulose complex microsphere average grain diameter that makes is 20um, and average pore size is 300nm, and specific area is 350m
2/ g.
Embodiment 4:
Preparation 100g NaOH (10g)/thiocarbamide (8g) aqueous solution is refrigerated to-5 ℃ after the dissolving, add the 5g cellulose then, behind the vigorous stirring dissolving cellulos, adds cyclodextrin 5g, and vigorous stirring dissolving cyclodextrin also is uniformly dispersed composite solution.After the mixed solvent (volume ratio is 1/1) and the 2g polysorbate60 emulsifying agent that in being furnished with the 500mL there-necked flask of reflux condensing tube and water bath with thermostatic control, add 300mL benzinum and atoleine, 200r/min stir it are uniformly dispersed; Slowly add the cellulose composite solution 100mL of method for preparing, stirring at normal temperature 1h is heated to 60 ℃; Add glutaraldehyde 0.5g; After continuing reaction 7h, hydrochloric acid to the solution of adding 10% is acid (pH＜5), makes the regeneration of cellulose complex microsphere.Stop to stir, standing demix, the upper strata is an organic facies, and lower floor is a water, and the cellulose complex microsphere is deposited in lower floor.Pour out upper organic phase, remove water, promptly get the cellulose complex microsphere.Gained cellulose complex microsphere washs with alcohol immersion, promptly gets pure cellulose complex microsphere.The cellulose complex microsphere average grain diameter that makes is 1200um, and average pore size is 600nm, and specific area is 250m
2/ g.
Embodiment 5:
Take by weighing dry cellulose microsphere, cellulose/cyclodextrin complex microsphere, cellulose/sodium alginate complex microsphere and each 2g of cellulose/chitosan microball respectively; Join in the edible oil respectively; 37 ℃ of following 150r/min vibration absorption are isolated microballoon after 6 hours, weighing oil suction microballoon hygrometric state weight.Different microballoons are seen table 1 to the saturated extent of adsorption of edible oil.
Embodiment 6:
Take by weighing dry cellulose microsphere, cellulose/cyclodextrin complex microsphere, cellulose/sodium alginate complex microsphere and each 2g of cellulose/chitosan microball respectively; Joining concentration respectively is in the BSA solution of 0.5mg/mL; 37 ℃ of following 150r/min vibration absorption; Isolate microballoon after 2 hours, the content of BSA is measured through ultraviolet specrophotometer in the solution.Adsorption isothermal curve is used Languir curve simulation, coefficient R
2All more than 0.95.Different microballoons are seen table 1 to the saturated extent of adsorption of BSA.
Embodiment 7:
Take by weighing dry cellulose microsphere, cellulose/cyclodextrin complex microsphere, cellulose/sodium alginate complex microsphere and each 2g of cellulose/chitosan microball respectively; Join respectively in the methylene blue solution that concentration is 0.5mmol/mL; 37 ℃ of following 150r/min vibration absorption; Isolate microballoon after 6 hours, the content of methylene blue is measured through ultraviolet specrophotometer in the solution.Adsorption isothermal curve is used Languir curve simulation, coefficient R
2All more than 0.95.Different microballoons are seen table 1 to the saturated extent of adsorption of methylene blue.
Embodiment 8:
Take by weighing dry cellulose microsphere, cellulose/cyclodextrin complex microsphere, cellulose/sodium alginate complex microsphere and each 2g of cellulose/chitosan microball respectively; Join concentration respectively and be in the ethanolic solution of menthol of 0.5mg/mL; 37 ℃ of following 150r/min vibration absorption; Isolate microballoon after 6 hours, the content of menthol passes through gas chromatographic measurement in the ethanolic solution.Adsorption isothermal curve is used Languir curve simulation, coefficient R
2All more than 0.95.Different microballoons are seen table 1 to the saturated extent of adsorption of menthol.
Embodiment 9:
Take by weighing dry cellulose microsphere, cellulose/cyclodextrin complex microsphere, cellulose/sodium alginate complex microsphere and each 2g of cellulose/chitosan microball respectively; Join concentration respectively and be in the ethanolic solution of menthol of 0.5mg/mL; 37 ℃ of following 150r/min vibration absorption were isolated microballoon after 6 hours, in 60 ℃ of baking ovens, placed after 2 hours; Gained is contained in the microballoon tiling and surface plate of menthol, measure the reserve capability of microballoon menthol.Different microballoons are as shown in Figure 1 to the retention rate of menthol.
The cellulose complex microsphere of method for preparing has purposes widely, and this microballoon can be applied to separation and the purifying of large biological molecules such as protein, enzyme, nucleic acid, polysaccharide, and the absorption of water, oil, heavy metal ion, dyestuff and essence and flavoring agent.
Table 1:
Claims (9)
1. cellulose complex microsphere; It is characterized in that, be base material with the cellulose, is composite with cyclodextrin, shitosan or sodium alginate; The aqueous solution with alkali/aqueous solution of urea or alkali/thiocarbamide is solvent; The mixed solution of preparation cellulose composite material obtains the cellulose complex microsphere to the transformation and the crosslinking agent of gel phase through colloidal sol then mutually fully, and said crosslinking agent is glutaraldehyde, ethylene glycol diglycidylether or epoxychloropropane; Said cellulose complex microsphere particle diameter is 1～1200 um, and specific area is 100～500m
2/ g, the aperture is 200～900nm.
2. the preparation method of an a kind of cellulose complex microsphere as claimed in claim 1 is characterized in that, may further comprise the steps:
1) preparation of cellulose/composite solution: preparation alkali and the aqueous solution of urea or the aqueous solution of alkali and thiocarbamide; Be refrigerated to-12 ℃～-5 ℃, add cellulose and composite then, after the stirring and dissolving; Evacuation and centrifugal degassing and removal of impurities; Obtain the cellulose composite solution, said composite is cyclodextrin, shitosan or sodium alginate;
2) preparation of cellulose complex microsphere: the cellulose composite solution is scattered in the organic solvent of emulsifying agent or compound emulsifying agent, after 200～1200r/min was stirred to dropping liquid and is uniformly dispersed, normal temperature cure 1～8h was shaped under identical mixing speed; Be heated to 40～80 ℃, add crosslinking agent reaction 2～8h, adding diluted acid to solution system is acid (pH＜5); Make cellulose composite material regeneration microballoon, standing demix, the upper strata is an organic facies; Lower floor is a water; Pour out upper organic phase, behind the filtration drying, promptly obtain the cellulose complex microsphere.
3. the preparation method of a kind of cellulose complex microsphere according to claim 2 is characterized in that, said organic solvent is a n-hexane; Benzinum; Or atoleine, the perhaps mixed organic solvents of two or more in them, the organic solvent volume is 2～10 times of cellulose solution.
4. the preparation method of a kind of cellulose complex microsphere according to claim 2 is characterized in that, said emulsifying agent is this Pan's series emulsifying agent, perhaps twain series emulsifier, perhaps blended emulsifier of two kinds of compositions in them.
5. the preparation method of a kind of cellulose complex microsphere according to claim 4 is characterized in that, said this Pan's series emulsifying agent comprises this Pan 60, this Pan 85.
6. the preparation method of a kind of cellulose complex microsphere according to claim 4 is characterized in that, said twain series emulsifier comprises Tween 80, polysorbate85.
7. the preparation method of a kind of cellulose complex microsphere according to claim 2 is characterized in that, said crosslinking agent is glutaraldehyde, ethylene glycol diglycidylether or epoxychloropropane.
8. the preparation method of a kind of cellulose complex microsphere according to claim 2; It is characterized in that; With the cellulose complex microsphere water or the washing with alcohol that obtain, obtain pure cellulose complex microsphere, obtain the cellulose composite particles after freeze drying or the oven dry.
9. a kind of cellulose complex microsphere according to claim 1 is applied to separation and the purifying of protein, enzyme, nucleic acid, polysaccharide large biological molecule, and the absorption of water, oil, heavy metal ion, dyestuff and essence and flavoring agent.
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