CN106629745B - A kind of hollow SiO of cellulose load2The preparation method of microballoon catalytic carrier - Google Patents
A kind of hollow SiO of cellulose load2The preparation method of microballoon catalytic carrier Download PDFInfo
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- CN106629745B CN106629745B CN201710014898.1A CN201710014898A CN106629745B CN 106629745 B CN106629745 B CN 106629745B CN 201710014898 A CN201710014898 A CN 201710014898A CN 106629745 B CN106629745 B CN 106629745B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- B01J32/00—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention discloses a kind of celluloses to load hollow SiO2The preparation method of microballoon catalytic carrier.It is the sphere aggregates that form polyelectrolyte polyacrylic acid in its poor solvent for template to use the main points of method, and ethyl orthosilicate is silicon source predecessor, and SiO is obtained after hydrolyzing, polymerizeing2/ PAA core-shell particles, product are washed through centrifugation, can remove polyelectrolyte polymers to form hollow SiO2Then microballoon is loaded on cellulose and obtains the hollow SiO of cellulose load2Microballoon catalytic carrier.This method is fast and convenient, hollow SiO2Microballoon disperses and uniform particle diameter, production cost are low, and application value is high.The present invention is both utilized biodegradable green material, is reduced environmental pollution using native cellulose as load carriers, while cellulose macromolecule itself has good adsorption function, loading functional good.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose catalytic carrier, more particularly to a kind of cellulose loads hollow SiO2
The preparation method of microballoon catalytic carrier, belongs to field of material engineering technology.
Background technology
Silica (SiO2), since it is with good mechanical strength, thermal stability and chemical inertness, in scientific research and life
Production field suffers from important role.Again because of SiO2Colloid has high stability, nano core-shell knot in liquid medium
Structure precipitation process and the controllability of thickness of the shell are good.In addition, the SiO being prepared by colloidal sol-gel method2Surface is with a large amount of
Silanol group, the often place of Polymer adsorption, it is many in polarity, highly polar homopolymer and copolymer can pass through hydrogen
Key is attracted to its surface.So SiO2It is that very handy core-shell type coats medium.
Hollow SiO2Micro-sphere material has in the fields such as the loading of catalysis, drug and dyestuff and release, absorption potentially answers
With value, the extensive concern of people is caused.Although existing SiO2There are many reports for the preparation method of hollow ball, but exist mostly
The deficiencies of time cost is longer, laboratory strength is excessive.And most of methods for preparing hollow microsphere need to remove template, and one
As need to select appropriate chemical solvent to dissolve or combustion decomposition template can obtain hollow-core construction at a high temperature of certain.Porous material
Expect the features such as adjustable and queueing discipline, high specific surface area and big adsorption capacity, urging with pore passage structure size due to it
The fields such as change, separation, absorption, biomaterial, sensor advanced composite material (ACM) and photoelectronics, electromagnetism, materialogy, environmentology
It has a wide range of applications.
In porous material preparation field, Chinese patent (CN201610244127.7) is " with a kind of nonionic/anion binding
Type surfactant be soft template silicon dioxide microsphere preparation " disclose reversible addion-fragmentation chain transfer method polymerization
The star amphiphilic block copolymer using cagelike silsesquioxane as core is obtained, it contains hydrophilic polymethoxy polyethylene glycol propylene
Acid esters section, hydrophobic polymethyl methacrylate section, hydrophobic polystyrene section and cagelike silsesquioxane core；Mesoporous dioxy
It is soft template that silicon nitride material, which prepares mainly star amphiphilic block copolymer, and ethyl orthosilicate is silicon source, and tetrahydrofuran/hydrochloric acid is molten
Liquid is mixed solvent, and selectivity volatilization tetrahydrofuran is realized.A kind of Chinese patent (CN201610094136.2) " controllably water suction two
The preparation method of silicon oxide microsphere " controllably absorbs water earth silicon material, and macroscopic view has micro-sphere structure, microcosmic to have meso-hole structure,
Simultaneously synthesizing hybridisation silica gel has high activity surface, narrow pore-size distribution and excellent mechanical stability, the controllable water suction
The preparation method of silicon dioxide microsphere material can be quick, and simplicity prepares the silicon dioxide microsphere with controllable water imbibition performance.In
State's patent (CN201610108385.2) " a kind of monitoring of near infrared light, controlled drug release mesoporous silicon dioxide micro-sphere and its
The mesoporous silicon dioxide micro-sphere that synthetic method " is related to is multilayered structure：Most kernel is a smooth nano SiO 2 particle,
For adjusting microspherulite diameter and load near-infrared nanocrystalline body, these near-infrared nanocrystalline bodies are excited in certain wavelength near infrared light
Under, lower transformation can occur, that is, send out the near infrared light of specific wavelength；Secondary outer layer is one layer of smooth silica shell,
Near-infrared nanocrystalline body for fixing and protecting internal layer；Outermost layer is mesoporous silicon oxide shell, is used for load target drug
With the quencher molecule of near infrared light nanocrystal and connect or coat responsive polymer, to realize that controlled drug discharges.The U.S. is special
Sharp (US4132560) " Pigmented microporous silica microspheres " provides one kind and passing through acidifying water
The method that packet oil emu prepares microballoon, the silicon dioxide microsphere after coloring can be used as opacifier for coating composition and as filling out
Manufacture of the material for paper.United States Patent (USP) (US4011096) " Vesiculated silica microspheres " provides one
The silicon dioxide microsphere of the method that the double emulsions of kind acidification oil packet oil-in-water prepare microballoon, bubbles can be used as opacifier for coating
Composition and applying filler are in papermaking.Up to now, it yet there are no using cellulose as skeleton, it is negative by Moist chemical synthesis cellulose
Carry hollow SiO2The related process technologies of microballoon catalytic carrier occur.
Cellulose provided by the invention loads hollow SiO2Microballoon catalytic carrier is by polyelectrolyte polyacrylic acid (PAA)
The sphere aggregates formed in its poor solvent are template, and ethyl orthosilicate (TEOS) is silicon source predecessor, through hydrolyzing, gathering
SiO is obtained after conjunction2/ PAA core-shell particles, product are washed through centrifugation, can remove polyelectrolyte polymers to form SiO2It is hollow micro-
Then ball is loaded on cellulose and obtains the hollow SiO of cellulose load2Microballoon catalytic carrier.This method is fast and convenient,
SiO2Tiny balloon disperses and uniform particle diameter, production cost are low, and application value is high.The present invention is carried using native cellulose as load
Body had both taken full advantage of biodegradable green material, has reduced environmental pollution, while cellulose macromolecule itself is with good
The cellulose of good adsorption function, generation loads hollow SiO2Microballoon catalytic carrier loading functional is good, application field it is wide and
Foreground is huge.The cellulose of preparation loads hollow SiO2Microballoon catalytic carrier is suitable for catalysis, medical and magnetic, photoelectric material etc.
The application in field has the production meaning of reality.
Invention content
To overcome traditional Si O2The defects of preparation process present in tiny balloon synthetic method is cumbersome, time-consuming, changes simultaneously
Kind SiO2It is equal to prepare fast and convenient operating method, dispersion and grain size for the problems such as tiny balloon reunion is serious, grain size is inhomogenous
One, production cost is low, the high SiO of application value2Tiny balloon, the object of the present invention is to provide a kind of load of cellulose is hollow
SiO2The preparation method of microballoon catalytic carrier.
To achieve the above object, the technical scheme is that using following steps：
1) polyacrylic acid of 0.1-0.2g is placed in conical flask, at ambient temperature, is added 1-2mL's a concentration of 25%
Polyacrylic acid is dissolved into transparent clear solution by ammonium hydroxide, stirs and pour into rapidly the ethyl alcohol of 20-40mL a concentration of 99.7%, molten
Liquid becomes milky, then divides 0.5-1mL ethyl orthosilicates 4 times, each interval time 1-3h, injects in reaction solution, continues
3-5h is stirred, is dried after centrifuging and being washed with distilled water 5 times and obtains hollow SiO2Microballoon；
2) the hollow SiO for obtaining step 1)2Cyanuric Chloride is added in microballoon, and 3-5 h are reacted under condition of ice bath, then will
Cellulose powder is dissolved in n,N-Dimethylformamide, by the hollow SiO of load2Warp is added in 70-90 DEG C of shaking bath in microballoon
The cellulose powder reaction 1-3h of n,N-Dimethylformamide dissolving is crossed, reaction product washing is filtered 5 times and dried to get to load
The cellulose of completion loads hollow SiO2Microballoon catalytic carrier.
The hollow SiO2The mass ratio of microballoon and Cyanuric Chloride is 1-3:1.
The mass ratio of the cellulose powder and N,N-dimethylformamide is 1-3:2.
The hollow SiO2The mass ratio of microballoon and cellulose powder is 2-3:10.
The cellulose is one kind in rice straw, straw and bagasse source fiber element.
Compared with the background art, the invention has the advantages that：
Present invention improves traditional Si O2Preparation process present in tiny balloon synthetic method is cumbersome and time-consuming, SiO2It is empty
The problems such as reunion of heart microballoon is serious, grain size is inhomogenous has prepared fast and convenient operating method, dispersion and uniform particle diameter, production
It is at low cost, the high SiO of application value2Tiny balloon, using long chain cellulose as skeleton adulteration SiO2Tiny balloon not only increases
SiO2The whole adsorptivity of tiny balloon carrier, while also improving the added value of plant cellulose and not causing environmental pressure,
It has important practical significance.
Description of the drawings
Fig. 1 is that cellulose prepared by embodiment 1 loads hollow SiO2The SiO of microballoon catalytic carrier2The transmitted electron of microballoon is aobvious
Micro mirror figure (left figure：20000 times of amplification；Right figure amplifies 40000 times)；
Fig. 2 is that cellulose prepared by embodiment 1 loads hollow SiO2The N of microballoon catalytic carrier2Adsorption-desorption curve.
Specific implementation mode
The present invention is further explained in the light of specific embodiments.
Embodiment 1:
1) polyacrylic acid of 0.1g is placed in conical flask, at ambient temperature, the ammonium hydroxide of 2mL a concentration of 25% is added
Polyacrylic acid is dissolved into transparent clear solution, stirs and pour into rapidly the ethyl alcohol of 25mL a concentration of 99.7%, solution becomes breast
Then white divides the ethyl orthosilicate of 0.5mL 4 times, per minor tick in corresponding time 2h injections reaction solution.Continue to stir
5h is centrifuged and is obtained hollow SiO after being washed with distilled water 5 drying2Microballoon；
2) the hollow SiO for obtaining step 1)2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 1:1 reaction mass ratio adds
Enter Cyanuric Chloride and react 4h under condition of ice bath, rice straw cellulose powder is then pressed into rice straw cellulose powder and N, N- dimethyl formyls
Amine 1:2 mass ratio is dissolved in n,N-Dimethylformamide, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and cellulose powder
2:10 reaction mass in 80 DEG C of shaking bath than being added the cellulose powder reaction by N,N-dimethylformamide dissolving
2h, reaction product washing is filtered 5 times and dried loads hollow SiO to get the cellulose completed to load2Microballoon catalytic carrier
(a)。
Embodiment 2:
1) polyacrylic acid of 0.15g is placed in conical flask, at ambient temperature, the ammonia of 1.5mL a concentration of 25% is added
Polyacrylic acid is dissolved into transparent clear solution by water, stirs and pour into rapidly the ethyl alcohol of 20mL a concentration of 99.7%, and solution becomes
Then milky divides the ethyl orthosilicate of 0.5mL 4 times, per minor tick in corresponding time 3h injections reaction solution.Continue to stir
3h is centrifuged and is obtained hollow SiO after being washed with distilled water 5 drying2Microballoon；
2) the hollow SiO for obtaining step 1)2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 2:1 reaction mass ratio adds
Enter Cyanuric Chloride and react 3h under condition of ice bath, Wheat straw fiber element powder is then pressed into Wheat straw fiber element powder and N, N- dimethyl formyls
Amine 3:2 mass ratio is dissolved in n,N-Dimethylformamide, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and cellulose powder
3:10 reaction mass in 80 DEG C of shaking bath than being added the cellulose powder reaction by N,N-dimethylformamide dissolving
1h, reaction product washing is filtered 5 times and dried loads hollow SiO to get the cellulose completed to load2Microballoon catalytic carrier
(b)。
Embodiment 3:
1) polyacrylic acid of 0.2g is placed in conical flask, at ambient temperature, the ammonium hydroxide of 1mL a concentration of 25% is added
Polyacrylic acid is dissolved into transparent clear solution, stirs and pour into rapidly the ethyl alcohol of 40mL a concentration of 99.7%, solution becomes breast
Then white divides the ethyl orthosilicate of 0.75mL 4 times, per minor tick in corresponding time 1h injections reaction solution.Continue to stir
5h is centrifuged and is obtained hollow SiO after being washed with distilled water 5 drying2Microballoon；
2) the hollow SiO for obtaining step 1)2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 3:1 reaction mass ratio adds
Enter Cyanuric Chloride and react 4h under condition of ice bath, Bagasse-cellulose powder is then pressed into Bagasse-cellulose powder and N, N- dimethyl
Formamide 1:2 mass ratio is dissolved in n,N-Dimethylformamide, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and fiber
Plain powder 2:10 reaction mass in 70 DEG C of shaking bath than being added the cellulose powder by N,N-dimethylformamide dissolving
2h is reacted, reaction product washing is filtered 5 times and dried loads hollow SiO to get the cellulose completed to load2Microballoon catalysis carries
Body (c).
Embodiment 4:
1) polyacrylic acid of 0.1g is placed in conical flask, at ambient temperature, the ammonium hydroxide of 2mL a concentration of 25% is added
Polyacrylic acid is dissolved into transparent clear solution, stirs and pour into rapidly the ethyl alcohol of 30mL a concentration of 99.7%, solution becomes breast
Then white divides the ethyl orthosilicate of 1mL 4 times, per minor tick in corresponding time 2h injections reaction solution.Continue to stir 4h,
It centrifuges and obtains hollow SiO after being washed with distilled water 5 drying2Microballoon；
2) the hollow SiO for obtaining step 1)2Microballoon presses hollow SiO2Microballoon and Cyanuric Chloride 1:1 reaction mass ratio adds
Enter Cyanuric Chloride and react 5h under condition of ice bath, rice straw cellulose powder is then pressed into rice straw cellulose powder and N, N- dimethyl formyls
Amine 2:2 mass ratio is dissolved in n,N-Dimethylformamide, by the hollow SiO of load2Microballoon presses hollow SiO2Microballoon and cellulose powder
3:10 reaction mass in 90 DEG C of shaking bath than being added the cellulose powder reaction by N,N-dimethylformamide dissolving
3h, reaction product washing is filtered 5 times and dried loads hollow SiO to get the cellulose completed to load2Microballoon catalytic carrier
(d)。
Measure four kinds of hollow SiO prepared by embodiment 1,2,3,42The particle size of microballoon, while tester calculates it and bears
The load factor being loaded onto on cellulose.Table 1 is four kinds of hollow SiO prepared by embodiment 1,2,3,42The particle size of microballoon measures knot
Fruit and the load factor result being loaded on cellulose.By data in table 1 it is found that using preparation method of the present invention acquisition
Cellulose loads hollow SiO2Microballoon catalytic carrier (a), cellulose load hollow SiO2Microballoon catalytic carrier (b), cellulose load
Hollow SiO2Microballoon catalytic carrier (c), cellulose load hollow SiO2The SiO of microballoon catalytic carrier (d)2Microsphere average grain diameter exists
248-356nm is loaded to the load factor on cellulose in 11.5-15.3%, illustrates hollow SiO prepared by this method2It is micro-
Ball, which is loaded to really on cellulose, has synthesized the hollow SiO of cellulose load2Microballoon catalytic carrier and have preferable load effect.
Such as Fig. 1, hollow SiO is prepared from embodiment 12The transmission electron microscope figure of microballoon can be seen that, what embodiment 1 synthesized
SiO2Microsphere diameter about 250nm, it is about 40nm to have apparent hollow structure, wall thickness, and hollow wall is smoother, and no internal penetration becomes
Gesture.Such as Fig. 2, the cellulose prepared from embodiment 1 loads hollow SiO2The N of microballoon catalytic carrier2It can in adsorption-desorption isothermal
To find out, sample maximum is characterized in that absorption branch and desorption branch are misaligned, an apparent H3 type hysteresis loop occurs, shows in sample
With the presence of non-uniform slit-shaped duct.The specific surface area of sample is 26.83m2/g.Pore size distribution curve occurs one in 3.5nm
A sharp peak, it is 3.5nm to illustrate its aperture largely, that is, illustrates that microballoon is implicitly present in meso-hole structure, further for microballoon from now on
Carrier using providing condition.
Table 1
Listed above is only specific embodiments of the present invention.Present invention is not limited to the above embodiments, can also there are many
Deformation.All deformations that those skilled in the art directly can export or associate from present disclosure, should all
It is considered protection scope of the present invention.
Claims (5)
1. a kind of cellulose loads hollow SiO2The preparation method of microballoon catalytic carrier, which is characterized in that include the following steps：
1) polyacrylic acid of 0.1-0.2g is placed in conical flask, at ambient temperature, the ammonium hydroxide of 1-2mL a concentration of 25% is added
Polyacrylic acid is dissolved into transparent clear solution, stirs and pour into rapidly the ethyl alcohol of 20-40mL a concentration of 99.7%, solution becomes
Then milky divides 0.5-1mL ethyl orthosilicates 4 times, each interval time 1-3h, inject in reaction solution, continues to stir 3-
5h is dried after centrifuging and being washed with distilled water 5 times and is obtained hollow SiO2Microballoon；
2) the hollow SiO for obtaining step 1)2Cyanuric Chloride is added in microballoon, 3-5h is reacted under condition of ice bath, then by cellulose
Powder is dissolved in n,N-Dimethylformamide, by the hollow SiO of load2Microballoon is added in 70-90 DEG C of shaking bath and passes through N, N- bis-
The cellulose powder of methylformamide dissolving reacts 1-3h, and reaction product washing is filtered 5 times and dried to get the fibre completed to load
Dimension element loads hollow SiO2Microballoon catalytic carrier.
2. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, feature exist
In：The hollow SiO2The mass ratio of microballoon and Cyanuric Chloride is 1-3:1.
3. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, feature exist
In：The mass ratio of the cellulose powder and N,N-dimethylformamide is 1-3:2.
4. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, feature exist
In：The hollow SiO2The mass ratio of microballoon and cellulose powder is 2-3:10.
5. a kind of cellulose according to claim 1 loads hollow SiO2The preparation method of microballoon catalytic carrier, feature exist
In：The cellulose is one kind in rice straw, straw and bagasse source fiber element.
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| CN1223231A (en) * | 1997-11-13 | 1999-07-21 | 德古萨股份公司 | Mouldings based on pyrogenic silicon dioxide |
| CN100494057C (en) * | 2006-10-09 | 2009-06-03 | 中国科学技术大学 | Preparation process of hollow silica ball |
| JP2010037137A (en) * | 2008-08-05 | 2010-02-18 | Sony Corp | Hollow particle and method for producing the same |
| CN103203206B (en) * | 2012-01-12 | 2016-08-03 | 山东嘉源检测技术有限公司 | Cellulose/titanium dioxide/silica aerogel and preparation method thereof |
| CN103285920B (en) * | 2013-05-27 | 2015-04-08 | 东华大学 | Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof |
| CN104190333B (en) * | 2014-01-10 | 2016-01-06 | 齐鲁工业大学 | A kind of preparation method of fluorescent hollow silicon dioxide microsphere |
| CN105038495A (en) * | 2015-07-08 | 2015-11-11 | 当涂县科辉商贸有限公司 | Nanometer cellulose-loaded super thermal-insulation heat-preserving paint and preparation method thereof |
| CN105037766B (en) * | 2015-09-18 | 2018-10-12 | 哈尔滨理工大学 | SiO2The preparation method of hollow ball/graphene oxide/polyimide composite film |
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