CN109261087A - Hollow microcapsule and its preparation method and application - Google Patents
Hollow microcapsule and its preparation method and application Download PDFInfo
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- CN109261087A CN109261087A CN201811433653.3A CN201811433653A CN109261087A CN 109261087 A CN109261087 A CN 109261087A CN 201811433653 A CN201811433653 A CN 201811433653A CN 109261087 A CN109261087 A CN 109261087A
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920001661 Chitosan Polymers 0.000 claims abstract description 48
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 43
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 42
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 42
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 42
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 42
- 238000001338 self-assembly Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 23
- 239000002245 particle Substances 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 238000005253 cladding Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 59
- 239000010410 layer Substances 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 30
- 229910021641 deionized water Inorganic materials 0.000 description 30
- 239000000243 solution Substances 0.000 description 26
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 18
- 239000007787 solid Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 238000010586 diagram Methods 0.000 description 12
- 229960004756 ethanol Drugs 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 11
- 229960000935 dehydrated alcohol Drugs 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000002775 capsule Substances 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011162 core material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012686 silicon precursor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000002594 sorbent Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 206010011732 Cyst Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Cosmetics (AREA)
Abstract
The present invention provides a kind of hollow microcapsule and its preparation method and applications, the hollow microcapsule is by the mesoporous silicon oxide using surface with positive charge as template, alternately the chitosan of cladding carboxymethyl cellulose and surface with positive charge carries out LBL self-assembly, obtains after finally removing removing template.Hollow microcapsule pattern of the invention is uniform, and particle diameter distribution is narrow, and high mechanical strength is not easily broken, while wall material uses biomass film, is easy degradation, environment friendly and pollution-free.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of hollow microcapsule and its preparation method and application.
Background technique
Microcapsules are mainly made of softgel shell and capsule-core.Softgel shell is usually made of thin-film material, general comparatively robust, and capsule-core
It can be solid particle and be also possible to liquid, the diameter of microcapsules is generally 5~200 μm, and wall thickness is generally 0.2 micron and arrives
Between several microns.Microcapsules can be single layer structure in various shapes, cyst walls such as ball-type, grain type, kidney type, bar shapeds, can also
To be multilayered structure, and capsule-core can be one or more shapes.Microcapsules have the advantages that convenient transportation, when microcapsules core material
It when for liquid, is wrapped up by capsule material and forms microcapsules solid form, this produces great convenience to storage, transport, micro-
The technology of capsule mainly can be applied to the fields such as printing, pharmacy, makeup, food, weaving and agricultural.Currently, preparing micro- glue
Capsule mainly includes complex coacervation, emulsion process, layer-by-layer, solvent evaporation method, spray drying process, wherein layer assembly
Technology has many advantages, such as controllable film thickness, permeability.
The LBL self-assembly skill based on polymer zwitterion electrostatic interaction is being researched and proposed in the 1990s, having
Art.Then gradually developing to laminated assembling technology technology using colloidal particle is template assemblies into the particle with nucleocapsid structure,
Removing template is removed by the methods of dissolving or melting, to prepare hollow microcapsule.
Summary of the invention
In the prior art, that there are pattern and partial sizes is uneven for the hollow microcapsule prepared, mechanical strength it is not high it is easily rupturable with
And not environmentally the problem of.
In order to solve the problems in the prior art, the present invention provides a kind of hollow microcapsule and its preparation method and applications.This
The hollow microcapsule pattern of invention is uniform, and particle diameter distribution is narrow, and high mechanical strength is not easily broken, while wall material is thin using biomass
Film is easy degradation, environment friendly and pollution-free.
Specifically, the present invention provides the following technical scheme that
A kind of hollow microcapsule is by the mesoporous silicon oxide using surface with positive charge as template, is alternately coated
The chitosan of carboxymethyl cellulose and surface with positive charge carries out LBL self-assembly, obtains after finally removing removing template.
Preferably, in above-mentioned hollow microcapsule, the aperture of the mesoporous silicon oxide is 3-5nm.
Preferably, in above-mentioned hollow microcapsule, the Kong Rongwei 0.3-1cm of the mesoporous silicon oxide3/g。
Preferably, in above-mentioned hollow microcapsule, the Kong Rongwei 0.5-0.9cm of the mesoporous silicon oxide3/g。
The preparation method of above-mentioned hollow microcapsule, this method include the following steps:
1) mesoporous silicon oxide by surface with positive charge is soluble in water, obtains template liquid；
2) carboxymethyl cellulose is added in the template liquid of step 1), obtains the template liquid of assembling carboxymethyl cellulose layer；
3) chitosan of the surface with positive charge is added in the template liquid of step 2), is obtained on carboxymethyl cellulose layer
Assemble the template liquid of chitosan layer；
4) it with the template liquid of step 3), repeats alternately step 2) and step 3) carries out LBL self-assembly, until reaching
The target microcapsules number of plies, obtains microcapsules liquid；
5) it is added in hydrofluoric acid or sodium hydrate aqueous solution and vibrates after drying the microcapsules liquid of step 4), it is dried to obtain
The hollow microcapsule.
Preferably, in above-mentioned preparation method, in step 1), the surface passes through with the mesoporous silicon oxide of positive charge
It is obtained after mesoporous silicon oxide is added to stir process in ammonium hydroxide, drying.
Preferably, in above-mentioned preparation method, in step 2), the mass ratio of the carboxymethyl cellulose and template is 3:5-
20。
Preferably, in above-mentioned preparation method, in step 3), chitosan of the surface with positive charge is by by 0.2-
0.4g chitosan obtains after being dissolved in the acetic acid that 200ml concentration is 0.1-0.15M.
Preferably, in above-mentioned preparation method, in step 3), the matter of chitosan and template of the surface with positive charge
Amount is than being 2:5-20.
Preferably, further include following step between step 4) and step 5) in above-mentioned preparation method: by glutaraldehyde plus
Enter into the microcapsules liquid of step 4), 12-24h is stirred under the conditions of 40-50 DEG C, cooling, washing, after obtaining glutaraldehyde cross-linking
Microcapsules liquid.
Application of the above-mentioned hollow microcapsule in pharmacy, printing and cosmetic field
The invention has the benefit that
Hollow microcapsule of the present invention, by the mesoporous silicon oxide using surface with positive charge as template, alternately
It coats the chitosan of carboxymethyl cellulose and surface with positive charge and carries out LBL self-assembly, obtained after finally removing removing template.This
The hollow microcapsule pattern of invention is uniform, and particle diameter distribution is narrow, and high mechanical strength is not easily broken, while wall material is thin using biomass
Film is easy degradation, environment friendly and pollution-free.
Detailed description of the invention
Nitrogen adsorption-desorption isotherm of mesoporous silicon oxide prepared by Fig. 1 embodiment one.
The graph of pore diameter distribution of mesoporous silicon oxide prepared by Fig. 2 embodiment one.
The grain size distribution of hollow microcapsule prepared by Fig. 3 embodiment one.
The stress-strain diagram of hollow microcapsule prepared by Fig. 4 embodiment one.
The grain size distribution of hollow microcapsule prepared by Fig. 5 embodiment two.
The stress-strain diagram of hollow microcapsule prepared by Fig. 6 embodiment two.
The grain size distribution of hollow microcapsule prepared by Fig. 7 embodiment three.
The stress-strain diagram of hollow microcapsule prepared by Fig. 8 embodiment three.
The grain size distribution of the hollow microcapsule of Fig. 9 example IV preparation.
The stress-strain diagram of the hollow microcapsule of Figure 10 example IV preparation.
The grain size distribution of hollow microcapsule prepared by Figure 11 comparative example one.
The stress-strain diagram of hollow microcapsule prepared by Figure 12 comparative example one.
Specific embodiment
In order to solve, the hollow microcapsule pattern prepared and partial size existing in the prior art are uneven, mechanical strength is not high
Easily rupturable and preparation method not environmentally the problem of, the present invention provides a kind of hollow microcapsule and its preparation method and application, it is described in
Empty microcapsules are by the mesoporous silicon oxide using surface with positive charge as template, alternately coat carboxymethyl cellulose and surface
Chitosan with positive charge carries out LBL self-assembly, obtains after finally removing removing template.
In a kind of preferred embodiment of the invention, the aperture of the mesoporous silicon oxide is 3-5nm.
In a kind of preferred embodiment of the invention, the Kong Rongwei 0.3-1cm of the mesoporous silicon oxide3/ g, more preferably
For 0.5-0.9cm3/g。
In a kind of preferred embodiment of the invention, the preparation method of above-mentioned hollow microcapsule, the specific steps are as follows:
1) preparation of mesoporous silicon oxide: 1-6g surfactant cetyl trimethylammonium bromide (CTAB) is dissolved in
In 100g dehydrated alcohol and the mixed liquor of 288g deionized water, 25%~28% ammonium hydroxide 16g is then added, is stirred at room temperature
The solution of 30min formation clear；0.8g ethyl orthosilicate is added into solution, after being vigorously stirred 4-8h, next
In 7h, each hour, 0.8g ethyl orthosilicate was added dropwise into solution, then proceeded to be stirred to react 8h.After reaction by gained liquid
Body 6000r/min is centrifuged 15min；Extracting waste precipitating, is successively washed with deionized water and EtOH Sonicate, is centrifuged, obtain white solid
Powder；Extracting waste solid powder 1g is dissolved in the mixed solution of 10ml deionized water, 150ml dehydrated alcohol and 0.5-2g ammonium nitrate
In, 60 DEG C of reflux 12h are to extract template CTAB, and centrifugation, repetition extraction procedure is primary, and deionized water and second are successively used in centrifugation
Alcohol washing, 80 DEG C of vacuum drying are used deionized water and ethanol washing afterwards for 24 hours, are roasted to get the mesoporous silicon oxide；
2) preparation of mesoporous silicon oxide of the surface with positive charge: the mesoporous silicon oxide of 0.1g step 1) preparation is weighed
It as template, is dissolved in the ammonium hydroxide of 30ml, has Jie of positive charge after stirring 15min, 80 DEG C of dry 6h to surface
Hole silica；
3) preparation of chitosan of the surface with positive charge: 0.2-0.4g chitosan is weighed, being dissolved in 200ml concentration is
In the acetic acid of 0.1-0.15M, 30min is stirred to get the chitosan solution of positive charge is had to surface；
4) surface of step 2) preparation the preparation of template liquid: is dissolved in 20ml water with the mesoporous silicon oxide of positive charge
In, it stirs evenly to get template liquid is arrived；
5) assemble one layer of carboxymethyl cellulose template liquid preparation: weigh a certain amount of carboxymethyl cellulose, by itself plus
In the template liquid for entering step 4) preparation, the mass ratio of the carboxymethyl cellulose and template is 3:5-20, stir 10min to get
To the template liquid of one layer of carboxymethyl cellulose of assembling；
6) it assembles the preparation of the template liquid of one layer of carboxymethyl cellulose and one layer of chitosan: weighing a certain amount of step 3) preparation
Surface have positive charge chitosan solution, be added into step 5) preparation one layer of carboxymethyl cellulose of assembling template liquid
In, the mass ratio of chitosan and template of the surface with positive charge is 2:5-20, stirs 20min to get one layer of assembling is arrived
The template liquid of carboxymethyl cellulose and one layer of chitosan；
7) preparation of microcapsules liquid: repeating alternately step 5) and step 6) carries out LBL self-assembly, until alternately inhaling
Attached carboxymethyl cellulose and chitosan are until reach the required microcapsules number of plies to get to microcapsules liquid；
8) preparation of the microcapsules liquid after glutaraldehyde cross-linking: glutaraldehyde is added in the microcapsules liquid of step 7), in 40-
12-24h is stirred under the conditions of 50 DEG C, cooling, washing is three times to get to the microcapsules liquid after glutaraldehyde cross-linking.
9) preparation of hollow microcapsule: hydrogen fluorine will be added after the microcapsules liquid drying after the glutaraldehyde cross-linking of step 8) preparation
8h is vibrated in acid or sodium hydrate aqueous solution, is washed, arrives the hollow microcapsule after 80 DEG C of dry 6h.
The present invention also provides above-mentioned hollow microcapsule pharmacy, printing and cosmetic field application.
Hollow microcapsule and its preparation method and application of the invention are further illustrated below by specific embodiment.
In following embodiments, the measuring method of stress-strain diagram are as follows: by hollow microcapsule sample be placed on a 2mm ×
The groove of 2.5cm × 2cm, slight oscillatory obtain more real microcapsules accumulation body, then whole using these microcapsules as one
Body is piled into thin piece of certain thickness and area, carries out static pressure to microcapsules with the speed of 1mm/min, until microcapsules are complete
Broken, abscissa is strain (stress removes area), and ordinate is stress.
In the following embodiments, the information of each reagent used and instrument is as shown in Table 1 and Table 2.
Agents useful for same information table in 1 embodiment of table
In the following embodiments, chitosan viscosity average molecular weigh used is 50000~100000.
Device therefor information table in 2 embodiment of table
Embodiment one
1. the preparation of mesoporous silicon oxide: 2g surfactant cetyl trimethylammonium bromide (CTAB) is dissolved in 100g
In dehydrated alcohol and the mixed liquor of 288g deionized water, 25%~28% ammonium hydroxide 16g is then added, 30min shape is stirred at room temperature
At the solution of clear；0.8g ethyl orthosilicate is added into solution, after being vigorously stirred 4h, in next 7h, each
Hour, 0.8g ethyl orthosilicate was added dropwise into solution, then proceeded to be stirred to react 8h.After reaction by gained liquid 6000r/
Min is centrifuged 15min；Extracting waste precipitating, is successively washed with deionized water and EtOH Sonicate, is centrifuged, obtain white solid powder；It takes white
Color solid powder 1g is dissolved in the mixed solution of 10ml deionized water, 150ml dehydrated alcohol and 1g ammonium nitrate, 60 DEG C of reflux 12h
To extract template CTAB, centrifugation, repetition extraction procedure is primary, and deionized water and ethanol washing, 80 DEG C of vacuum are successively used in centrifugation
Dry to use deionized water and ethanol washing afterwards for 24 hours, 550 DEG C of roastings are to get the mesoporous silicon oxide.Fig. 1 and Fig. 2 is respectively this
Nitrogen adsorption-the desorption isotherm and graph of pore diameter distribution of the mesoporous silicon oxide of embodiment preparation, are analyzed it is found that the present embodiment system
The mesoporous pore size of standby mesoporous silicon oxide is 3-5nm, Kong Rongwei 0.541cm3/g；
2. the preparation of mesoporous silicon oxide of the surface with positive charge: weighing the mesoporous silicon oxide of 0.1g step 1 preparation
It as template, is dissolved in the ammonium hydroxide of 30ml, has Jie of positive charge after stirring 15min, 80 DEG C of dry 6h to surface
Hole silica；
3. the preparation of chitosan of the surface with positive charge: weighing 0.2g chitosan, being dissolved in 200ml concentration is 0.1M
Acetic acid in, stir 30min to get to surface have positive charge chitosan solution；
4. the preparation of template liquid: surface prepared by step 2 is dissolved in 20ml water with the mesoporous silicon oxide of positive charge,
It stirs evenly to get template liquid is arrived；
5. assembling the preparation of the template liquid of one layer of carboxymethyl cellulose: weighing 0.03g carboxymethyl cellulose, be added into step
In the template liquid of rapid 4 preparation, the mass ratio of the carboxymethyl cellulose and template is 3:10, stirs 10min to get assembling one is arrived
The template liquid of layer carboxymethyl cellulose；
6. the preparation of the template liquid of one layer of carboxymethyl cellulose of assembling and one layer of chitosan: weighing the preparation of 20ml step 3
Surface has the chitosan solution of positive charge, is added into the template liquid of one layer of carboxymethyl cellulose of assembling of step 5 preparation,
The mass ratio of chitosan and template of the surface with positive charge is 1:5, stirs 20min to get one layer of carboxymethyl of assembling is arrived
The template liquid of cellulose and one layer of chitosan；
7. the preparation of microcapsules liquid: repeating alternately step 5 and step 6 carries out LBL self-assembly, until alternating sorbent
Carboxymethyl cellulose and chitosan arrive microcapsules liquid to 3 layers；
8. the preparation of the microcapsules liquid after glutaraldehyde cross-linking: 0.1ml glutaraldehyde is added in the microcapsules liquid of step 7,
18h is stirred under the conditions of 40 DEG C, cooling, washing is three times to get to the microcapsules liquid after glutaraldehyde cross-linking.
9. the preparation of hollow microcapsule: 20ml will be added after the microcapsules liquid drying after glutaraldehyde cross-linking prepared by step 8
2% hydrofluoric acid in vibrate 8h, wash, to get to the hollow microcapsule after 80 DEG C of dry 6h.
Fig. 3 be hollow microcapsule manufactured in the present embodiment grain size distribution, as seen from the figure, prepared particle diameter distribution compared with
It is narrow, illustrate that partial size is more uniform, and partial size is smaller.
Fig. 4 is the stress-strain diagram of hollow microcapsule manufactured in the present embodiment, as seen from the figure, prepared hollow micro- glue
Capsule has preferable compression strength.
Embodiment two
1. the preparation of mesoporous silicon oxide: 4g surfactant cetyl trimethylammonium bromide (CTAB) is dissolved in 100g
In dehydrated alcohol and the mixed liquor of 288g deionized water, 25%~28% ammonium hydroxide 16g is then added, 30min shape is stirred at room temperature
At the solution of clear；0.8g ethyl orthosilicate is added into solution, after being vigorously stirred 6h, in next 7h, each
Hour, 0.8g ethyl orthosilicate was added dropwise into solution, then proceeded to be stirred to react 8h.After reaction by gained liquid 6000r/
Min is centrifuged 15min；Extracting waste precipitating, is successively washed with deionized water and EtOH Sonicate, is centrifuged, obtain white solid powder；It takes white
Color solid powder 1g is dissolved in the mixed solution of 10ml deionized water, 150ml dehydrated alcohol and 1.5g ammonium nitrate, 60 DEG C of reflux
12h to extract template CTAB, centrifugation, repeat extraction procedure it is primary, centrifugation, successively use deionized water and ethanol washing, 80 DEG C
Deionized water and ethanol washing are used in vacuum drying afterwards for 24 hours, and 550 DEG C of roastings are to get the mesoporous silicon oxide, nitrogen adsorption result
Show that its mesoporous pore size is 3-5nm, Kong Rongwei 0.887cm3/g；；
2. the preparation of mesoporous silicon oxide of the surface with positive charge: weighing the mesoporous silicon oxide of 0.1g step 1 preparation
It as template, is dissolved in the ammonium hydroxide of 30ml, has Jie of positive charge after stirring 15min, 80 DEG C of dry 6h to surface
Hole silica；
3. the preparation of chitosan of the surface with positive charge: weighing 0.3g chitosan, being dissolved in 200ml concentration is
In the acetic acid of 0.12M, 30min is stirred to get the chitosan solution of positive charge is had to surface；
4. the preparation of template liquid: surface prepared by step 2 is dissolved in 20ml water with the mesoporous silicon oxide of positive charge,
It stirs evenly to get template liquid is arrived；
5. assembling the preparation of the template liquid of one layer of carboxymethyl cellulose: weighing 0.06g carboxymethyl cellulose, be added into step
In the template liquid of rapid 4 preparation, the mass ratio of the carboxymethyl cellulose and template is 3:5, stirs 10min to get assembling one is arrived
The template liquid of layer carboxymethyl cellulose；
6. the preparation of the template liquid of one layer of carboxymethyl cellulose of assembling and one layer of chitosan: weighing the preparation of 27ml step 3
Surface has the chitosan solution of positive charge, is added into the template liquid of one layer of carboxymethyl cellulose of assembling of step 5 preparation,
The mass ratio of chitosan and template of the surface with positive charge is 2:5, stirs 20min to get one layer of carboxymethyl of assembling is arrived
The template liquid of cellulose and one layer of chitosan；
7. the preparation of microcapsules liquid: repeating alternately step 5 and step 6 carries out LBL self-assembly, until alternating sorbent
Carboxymethyl cellulose and chitosan arrive microcapsules liquid to 3 layers；
8. the preparation of the microcapsules liquid after glutaraldehyde cross-linking: 0.1ml glutaraldehyde is added in the microcapsules liquid of step 7,
12h is stirred under the conditions of 40 DEG C, cooling, washing is three times to get to the microcapsules liquid after glutaraldehyde cross-linking.
9. the preparation of hollow microcapsule: 20ml will be added after the microcapsules liquid drying after glutaraldehyde cross-linking prepared by step 8
2% hydrofluoric acid in vibrate 8h, wash, to get to the hollow microcapsule after 80 DEG C of dry 6h.
Fig. 5 is the grain size distribution of hollow microcapsule manufactured in the present embodiment, as seen from the figure, prepared hollow microcapsule
Particle diameter distribution is relatively narrow, and bigger than the partial size of embodiment 1, is 680nm or so.
Fig. 6 is the stress-strain diagram of hollow microcapsule manufactured in the present embodiment, as seen from the figure, prepared hollow micro- glue
The stress-strain diagram of capsule and embodiment 1 it is very close, deformation is slightly less than embodiment 1, illustrates that its crushing resistance is more preferable.
Embodiment three
1. the preparation of mesoporous silicon oxide: 6g surfactant cetyl trimethylammonium bromide (CTAB) is dissolved in 100g
In dehydrated alcohol and the mixed liquor of 288g deionized water, 25%~28% ammonium hydroxide 16g is then added, 30min shape is stirred at room temperature
At the solution of clear；0.8g ethyl orthosilicate is added into solution, after being vigorously stirred 8h, in next 7h, each
Hour, 0.8g ethyl orthosilicate was added dropwise into solution, then proceeded to be stirred to react 8h.After reaction by gained liquid 6000r/
Min is centrifuged 15min；Extracting waste precipitating, is successively washed with deionized water and EtOH Sonicate, is centrifuged, obtain white solid powder；It takes white
Color solid powder 1g is dissolved in the mixed solution of 10ml deionized water, 150ml dehydrated alcohol and 2g ammonium nitrate, 60 DEG C of reflux 12h
To extract template CTAB, centrifugation, repetition extraction procedure is primary, and deionized water and ethanol washing, 80 DEG C of vacuum are successively used in centrifugation
Dry to use deionized water and ethanol washing afterwards for 24 hours, 550 DEG C of roastings are to get the mesoporous silicon oxide, nitrogen adsorption result table
It is bright, mesoporous pore size 3-5nm, Kong Rongwei 0.651cm3/g；；
2. the preparation of mesoporous silicon oxide of the surface with positive charge: weighing the mesoporous silicon oxide of 0.1g step 1 preparation
It as template, is dissolved in the ammonium hydroxide of 30ml, has Jie of positive charge after stirring 15min, 80 DEG C of dry 6h to surface
Hole silica；
3. the preparation of chitosan of the surface with positive charge: weighing 0.4g chitosan, being dissolved in 200ml concentration is
In the acetic acid of 0.15M, 30min is stirred to get the chitosan solution of positive charge is had to surface；
4. the preparation of template liquid: surface prepared by step 2 is dissolved in 20ml water with the mesoporous silicon oxide of positive charge,
It stirs evenly to get template liquid is arrived；
5. assembling the preparation of the template liquid of one layer of carboxymethyl cellulose: weighing 0.015g carboxymethyl cellulose, be added into
In template liquid prepared by step 4, the mass ratio of the carboxymethyl cellulose and template is 3:20, stirs 10min to get assembling is arrived
The template liquid of one layer of carboxymethyl cellulose；
6. the preparation of the template liquid of one layer of carboxymethyl cellulose of assembling and one layer of chitosan: weighing the table of 5ml step 3 preparation
Face has the chitosan solution of positive charge, is added into the template liquid of one layer of carboxymethyl cellulose of assembling of step 5 preparation, institute
The mass ratio for stating chitosan and template of the surface with positive charge is 1:10, stirs 20min to get one layer of carboxymethyl fibre of assembling is arrived
The template liquid of dimension element and one layer of chitosan；
7. the preparation of microcapsules liquid: repeating alternately step 5 and step 6 carries out LBL self-assembly, until alternating sorbent
Carboxymethyl cellulose and chitosan arrive microcapsules liquid to 3 layers；
8. the preparation of the microcapsules liquid after glutaraldehyde cross-linking: 0.1ml glutaraldehyde is added in the microcapsules liquid of step 7,
It is stirred under the conditions of 50 DEG C for 24 hours, cooling, washing is three times to get to the microcapsules liquid after glutaraldehyde cross-linking.
9. the preparation of hollow microcapsule: 20ml will be added after the microcapsules liquid drying after glutaraldehyde cross-linking prepared by step 8
2% hydrofluoric acid in vibrate 8h, wash, to get to the hollow microcapsule after 80 DEG C of dry 6h.
Fig. 7 is the grain size distribution of hollow microcapsule manufactured in the present embodiment, as seen from the figure, prepared hollow microcapsule
Partial size be 480nm, the slightly above partial size of embodiment 1, and particle diameter distribution is relatively narrow, distribution is concentrated.
Fig. 8 is the stress-strain diagram of hollow microcapsule manufactured in the present embodiment, as seen from the figure, prepared hollow micro- glue
The hollow microcapsule that there is capsule preferable compression strength and embodiment 1, embodiment 2 to prepare is not much different.
Example IV
1. the preparation of mesoporous silicon oxide: 1g surfactant cetyl trimethylammonium bromide (CTAB) is dissolved in 100g
In dehydrated alcohol and the mixed liquor of 288g deionized water, 25%~28% ammonium hydroxide 16g is then added, 30min shape is stirred at room temperature
At the solution of clear；0.8g silicon precursor is added into solution, after being vigorously stirred 4h, in next 7h, Mei Ge little
When into solution be added dropwise 0.8g silicon precursor, then proceed to be stirred to react 8h.After reaction by gained liquid 6000r/min from
Heart 10min；Extracting waste precipitating, is successively washed with deionized water and EtOH Sonicate, is centrifuged, obtain white solid powder；Extracting waste is solid
Body powder 1g is dissolved in the mixed solution of 10ml deionized water, 150ml dehydrated alcohol and 0.5g ammonium nitrate, 60 DEG C of reflux 12h with
Template CTAB is extracted, centrifugation, repetition extraction procedure is primary, centrifugation, successively uses deionized water and ethanol washing, and 80 DEG C of vacuum are dry
It is dry for 24 hours afterwards use deionized water and ethanol washing, 800 DEG C roasting to get the mesoporous silicon oxide, nitrogen adsorption the result shows that,
Its mesoporous pore size is 10-20nm, Kong Rongwei 0.0125cm3/g。
Remaining step is identical as 1 step 2~9 of embodiment.
Fig. 9 is the grain size distribution of hollow microcapsule manufactured in the present embodiment, as seen from the figure, prepared hollow microcapsule
Particle diameter distribution in 600-960nm, compared with the hollow microcapsule of 1-3 of embodiment of the present invention preparation, particle diameter distribution is wide, partial size point
Cloth is uneven.
Figure 10 is the stress-strain diagram of hollow microcapsule manufactured in the present embodiment, and as seen from the figure, prepared is hollow micro-
Capsule has preferable compression strength, and compression strength is slightly below the hollow microcapsule of embodiment 1-3 preparation.
Comparative example one
1. the preparation of silica: it is anhydrous that 1g surfactant cetyl trimethylammonium bromide (CTAB) being dissolved in 100g
In ethyl alcohol and the mixed liquor of 288g deionized water, then be added 25%~28% ammonium hydroxide 16g, be stirred at room temperature 30min formed it is clear
Clear bright solution；Into solution be added 0.8g silicon precursor, after being vigorously stirred 4h, in next 7h, each hour to
0.8g silicon precursor is added dropwise in solution, then proceedes to be stirred to react 8h.Gained liquid 4000r/min is centrifuged after reaction
10min；Extracting waste precipitating, is successively washed with deionized water and EtOH Sonicate, is centrifuged, obtain white solid powder；Extracting waste solid
Powder 1g is dissolved in the mixed solution of 10ml deionized water, 150ml dehydrated alcohol and 0.5g ammonium nitrate, and 60 DEG C of reflux 12h are to take out
Template CTAB is mentioned, is centrifuged, repetition extraction procedure is primary, centrifugation, successively uses deionized water and ethanol washing, 80 DEG C of vacuum drying
For 24 hours afterwards use deionized water and ethanol washing, 500 DEG C roasting to get arrive silica, nitrogen adsorption the result shows that, aperture compared with
Small is 1-2nm, Kong Rongwei 0.008cm3/g。
Remaining step is identical as 1 step 2~9 of embodiment.
Figure 11 is the grain size distribution of the hollow microcapsule of this comparative example preparation, as seen from the figure, prepared hollow micro- glue
The particle diameter distribution of capsule is in 500-1000nm, and compared with the hollow microcapsule of 1-4 of embodiment of the present invention preparation, particle diameter distribution is wider,
It is more uneven.
Figure 12 is the stress-strain diagram of the hollow microcapsule of this comparative example preparation, as seen from the figure, with embodiment 1-4 phase
Than prepared hollow microcapsule should change greatly under same stress condition, and compression strength is worse.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (12)
1. a kind of hollow microcapsule, which is characterized in that the hollow microcapsule be by with surface have positive charge mesoporous two
Silica is template, alternately coats the chitosan of carboxymethyl cellulose and surface with positive charge and carries out LBL self-assembly, finally
It is obtained after removing removing template.
2. hollow microcapsule according to claim 1, wherein the aperture of the mesoporous silicon oxide is 3-5nm.
3. hollow microcapsule according to claim 1 or claim 2, wherein the Kong Rongwei 0.3-1cm of the mesoporous silicon oxide3/g。
4. any one of -3 hollow microcapsule according to claim 1, wherein the Kong Rongwei 0.5- of the mesoporous silicon oxide
0.9cm3/g。
5. the preparation method of the described in any item hollow microcapsules of claim 1-4, wherein this method includes the following steps:
1) mesoporous silicon oxide by surface with positive charge is soluble in water, obtains template liquid；
2) carboxymethyl cellulose is added in the template liquid of step 1), obtains the template liquid of assembling carboxymethyl cellulose layer；
3) chitosan of the surface with positive charge is added in the template liquid of step 2), is obtained in carboxymethyl cellulose layer over-assemble
The template liquid of chitosan layer；
4) it with the template liquid of step 3), repeats alternately step 2) and step 3) carries out LBL self-assembly, until reaching target
The microcapsules number of plies obtains microcapsules liquid；
5) it is added in hydrofluoric acid or sodium hydrate aqueous solution and vibrates after drying the microcapsules liquid of step 4), be dried to obtain in described
Empty microcapsules.
6. preparation method according to claim 5, wherein in step 1), the surface has the mesoporous dioxy of positive charge
SiClx after mesoporous silicon oxide is added to stir process in ammonium hydroxide, drying by obtaining.
7. preparation method according to claim 5 or 6, wherein in step 2), the matter of the carboxymethyl cellulose and template
Amount is than being 3:5-20.
8. according to the described in any item preparation methods of claim 5-7, wherein in step 3), the surface is with positive charge
Chitosan after 0.2-0.4g chitosan is dissolved in the acetic acid that 200ml concentration is 0.1-0.15M by obtaining.
9. according to the described in any item preparation methods of claim 5-8, wherein in step 3), the surface is with positive charge
Chitosan and the mass ratio of template are 2:5-20.
10. according to the described in any item preparation methods of claim 5-9, wherein further include following between step 4) and step 5)
Step: glutaraldehyde is added in the microcapsules liquid of step 4), and 12-24h is stirred under the conditions of 40-50 DEG C, cooling, and washing obtains
Microcapsules liquid after to glutaraldehyde cross-linking.
11. a kind of hollow microcapsule is obtained by the described in any item preparation methods of claim 5-10.
12. hollow microcapsule described in claim 1-4 or 11 is in the application of pharmacy, printing and cosmetic field.
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