CN110559956B - Hollow porous cellulose microsphere and preparation method and application thereof - Google Patents
Hollow porous cellulose microsphere and preparation method and application thereof Download PDFInfo
- Publication number
- CN110559956B CN110559956B CN201910843541.3A CN201910843541A CN110559956B CN 110559956 B CN110559956 B CN 110559956B CN 201910843541 A CN201910843541 A CN 201910843541A CN 110559956 B CN110559956 B CN 110559956B
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- cellulose
- porous
- pore
- microsphere
- hollow porous
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 208
- 239000001913 cellulose Substances 0.000 title claims abstract description 208
- 239000004005 microsphere Substances 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011148 porous material Substances 0.000 claims abstract description 87
- 230000002378 acidificating effect Effects 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 230000007613 environmental effect Effects 0.000 claims abstract description 6
- 238000011282 treatment Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 38
- 239000000945 filler Substances 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 31
- 239000004088 foaming agent Substances 0.000 claims description 30
- 239000000725 suspension Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000003937 drug carrier Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 10
- 238000011068 loading method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 238000012377 drug delivery Methods 0.000 abstract description 5
- 238000007306 functionalization reaction Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000004627 regenerated cellulose Substances 0.000 abstract description 2
- 230000001172 regenerating effect Effects 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 7
- 210000001724 microfibril Anatomy 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 229920002284 Cellulose triacetate Polymers 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
- 239000002775 capsule Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 244000025254 Cannabis sativa Species 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
- A61K9/1605—Excipients; Inactive ingredients
- A61K9/1629—Organic macromolecular compounds
- A61K9/1652—Polysaccharides, e.g. alginate, cellulose derivatives; Cyclodextrin
-
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- 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
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/043—Carbonates or bicarbonates, e.g. limestone, dolomite, aragonite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Hydrology & Water Resources (AREA)
- Dispersion Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Medicinal Chemistry (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a hollow porous cellulose microsphere and a preparation method and application thereof. The microsphere adopts a cellulose dissolving and regenerating method, takes regenerated cellulose as a framework, combines various organic or inorganic porous materials and an acidic pore-forming agent, prepares composite microspheres combining different inorganic porous materials and cellulose under certain conditions, and washes out the pore-forming agent through an acid solution to form the hollow porous cellulose microsphere. The cellulose microsphere disclosed by the invention contains a large number of hollow porous structures, contains a plurality of functional groups, and has super-strong adsorption capacity and functional loading capacity, the preparation method is simple and convenient in process, the pore structures can be adjusted through the addition of pore-forming agents, the functionalization of wall materials can be adjusted and controlled through active groups, the size of the obtained hollow porous microsphere is easier to control and more uniform, the hollow porous microsphere has a porous structure and super-strong adsorption capacity, is easy to load, adjust and control and release functional substances, and can be applied to the fields of environmental adsorption, water treatment, chemical reaction, drug delivery and the like.
Description
Technical Field
The invention relates to the technical field of porous material preparation, in particular to a hollow porous cellulose microsphere and a preparation method and application thereof.
Background
Since the use of surfactants, different types of microspheres are continuously developed, different products and processes appear, and the porous microsphere material has a wide application prospect and is used as a cheap functional carrier in different industrial fields, wherein the fields comprise food, cosmetics, medicine, coating, catalysts, biomedicine and the like. Compared with the common porous material, the porous microspheres have larger specific surface area, and the shape of the porous microspheres can be square, oval, round and the like. The surface and the inside of the porous microsphere are both porous structures, and the porous material is added, so that the porous microsphere has a porous structure on a support, the microsphere is more favorable for loading a functional target object, and the loading capacity of the porous microsphere is often several times or even more than dozens of times of that of a common porous material. The commonly used preparation methods of the porous microspheres comprise solvent swelling, solution polymerization, a template method and the like, wherein the preparation methods of the solution polymerization method, the conventional template method and the like are complicated, the required equipment requirement is high, the reaction time is long, the environment is not protected and the like, so that the further development of the porous microspheres is limited, and the porosity and the adsorption performance of the commonly prepared materials are limited. CN105214623A discloses a preparation method of a trace heavy metal cellulose triacetate porous microsphere adsorbent, which is characterized in that cellulose triacetate microspheres are formed by agglomerating cellulose triacetate and carbonic acid particles, and a porous structure is formed by corrosion, so that the trace heavy metal cellulose triacetate porous microsphere adsorbent is prepared. The preparation method disclosed by the method is complex in steps, only the adsorption effect on the lead ions is verified, the adsorption performance is limited, and the prepared material does not have obvious porous performance.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and the defects of porosity and adsorption performance of the existing porous cellulose microsphere material and provides a preparation method of hollow porous cellulose microspheres.
The invention aims to provide the hollow porous cellulose microspheres prepared by the method.
The invention also aims to provide application of the hollow porous cellulose microspheres in environmental adsorption, water treatment, chemical reaction and drug delivery.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of hollow porous cellulose microspheres comprises the following steps:
s1, preparing a cellulose solution with the mass percent of 0.1-10%, adding a porous filler, and fully dispersing to prepare a porous material cellulose suspension;
s2, adding an acid-soluble pore-forming agent into the porous material cellulose suspension of S1, and fully dispersing to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the S2 into an acid solution, removing an acid-soluble pore-forming agent to obtain hollow porous cellulose microspheres,
wherein the mass ratio of the porous filler to the cellulose in S1 is (0.2-3) to 1, and the solid content of the cellulose suspension is 2-15 wt%;
the mass ratio of the acidic pore-foaming agent to the cellulose in S2 is (0.2-3): 1.
The composite microsphere adopts a cellulose dissolution regeneration mechanism, takes different types of organic or inorganic porous materials as filler, adds an acidic pore-foaming agent, takes water as a regeneration medium, obtains the porous composite microsphere containing different functional components under certain conditions, and removes the pore-foaming agent by acid washing to form the hollow functionalized microsphere. Compared with the existing porous microspheres, the hollow porous microspheres obtained by the preparation method are easier to control and more uniform in size, the preparation method is simple, convenient and quick, the material sources are wide, the composition of the microspheres is controllable, the composition of the porous microspheres can be regulated and controlled according to application requirements or the functionalized cellulose microspheres are prepared by a chemical method, the application of the fiber material is widened, and the preparation and the application of the cellulose porous material are promoted.
The cellulose is natural cellulose, including wood cellulose, grass cellulose, fruit shell cellulose and the like.
The specific preparation method of the cellulose solution can be as follows: adding a certain amount of cellulose into a solvent capable of dissolving cellulose (an ionic liquid or a sodium hydroxide/urea/thiourea system, a lithium hydroxide/urea system, a NaOH/LiCl/urea system and a sodium hydroxide/urea system), setting the temperature to be a proper temperature, fully dispersing and dissolving the cellulose on a laboratory high-speed dispersion machine, and preparing a transparent cellulose mixed solution.
The porous filler is organic or inorganic porous material, including cellulose microfibril, cellulose nanofilament, inorganic porous material, such as diatomite, zeolite, mesoporous material SBA-15, kaolin, titanium dioxide and alumina.
The acidic pore-foaming agent is an acid-soluble porous inorganic material, such as calcium carbonate, nano titanium dioxide, sodium bicarbonate and the like, and can also be a surfactant or an emulsifier, such as tween 20, tween 60, tween 80 and the like, span 20, span 60, span 80 and the like.
And (3) adding the cellulose mixed solution in the S3 into a dilute acid solution, fully contacting the cellulose balls with the acid solution, regenerating cellulose from the cellulose solution, and soaking overnight until no bubbles are generated, so that the acidic pore-forming agent can be completely removed.
The porous filler used in the invention has good compatibility with cellulose solution, and is insoluble in acid or has good stability in acid. The cellulose solution is fully dispersed and enters the pore channel to form the composite material, after the cellulose solution is regenerated into fibers, the formed cellulose composite microspheres have high strength, good stability and difficult loosening, are not deformed after being stirred for 5 minutes by a high-speed stirrer under 5000 revolutions, contain a large amount of active hydroxyl groups, have the concentration of more than 1mmol/g, have strong loading capacity and are relatively easy for further functionalization.
With the aid of an acid-soluble pore-forming agent, a large number of hollow porous structures can be formed on the surface and inside of the composite microsphere, so that the functionalization and loading capacity of the composite microsphere are further improved.
Preferably, the mass ratio of the porous filler to the cellulose in S1 is 1-4: 1; the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 0.25-2: 1.
Specifically, the mass ratio of the porous filler to the cellulose in S1 may be 1:1, 0.25:1, 3:1, or 4: 1;
the mass ratio of the acidic pore-forming agent to the cellulose in S2 can be 0.25:1, 1:1 or 2: 1.
In order to better prepare the composite microsphere satisfying the porous structure and the modification capability, the mass ratio of the porous filler to the cellulose in S1 is more preferably 3:1, and the mass ratio of the acidic pore-forming agent to the cellulose in S2 is more preferably 2: 1.
Preferably, the pore diameter of the porous filler in S1 is 0.002-10 μm, and the specific surface area is 20-500 m2Per g, pore volume of 0.05-1.5cm3/g。
For example, the porous filler described in S1 may have a pore diameter of 1 μm and a specific surface area of 80m2Per g, pore volume of 0.5cm3/g；
The porous filler in S1 had a pore diameter of 0.25 μm and a specific surface area of 50m2G, pore volume of 0.98cm3/g；
The porous filler in S1 had a pore diameter of 0.01. mu.m, a specific surface area of 500m2G, pore volume 1.16cm3/g；
The pore diameter of the porous filler in S1 was 0.007 μm, and the specific surface area was 100m2Per g, pore volume of 0.5cm3/g。
Wherein, the specific influence of the aperture of the porous filler on the preparation of the hollow porous cellulose microsphere is as follows: the pore diameter of the microsphere changes along with the pore diameter change of the porous filler within a certain range, and the reason that the pore diameter range is limited to be 0.002-10 mu m in the invention is as follows: the method is generally applied to adsorption, the pore diameter of the loaded microsphere is in a micro-nano level, and both overlarge and undersize pore diameters are not beneficial to adsorbing and loading a target object by the microsphere.
The specific influence of the specific surface area of the porous filler on the preparation of the hollow porous cellulose microspheres is as follows: the specific surface area of the porous filler directly influences the specific surface area of the cellulose microspheres, the specific surface area of the cellulose microspheres can be regulated and controlled by the porous filler, and the specific surface area is limited to be 20-500 m2The reason for/g is: the porous filler can be any size, but the compatibility of the fiber solution and the porous filler can be indirectly influenced by the overlarge specific surface area, so that the preparation of the cellulose microspheres is influenced, and a proper range is set.
The specific influence of the pore volume of the porous filler on the preparation of the hollow porous cellulose microspheres is as follows: the pore volume directly influences the cellulose solutionThe degree of the pore channel entering the pore channel further influences the pore volume of the cellulose microspheres, and the pore volume is limited within the range of 0.05-1.5cm3The reason for/g is: the cellulose solution with too small pore volume can not well enter the pore canal, and the cellulose solution with too large pore canal can not be completely filled, so an appropriate range is set.
Preferably, the porous filler in S1 has a pore diameter of 0.25 μm and a specific surface area of 50m2G, pore volume of 0.98cm3/g。
Preferably, the diameter of the acidic pore-foaming agent in S2 is 0.01-100 μm, and the specific surface area is 40-200m2/g。
For example, the acidic porogen described in S2 may have a diameter of 0.03. mu.m and a specific surface area of 40m2/g；
The diameter of the acidic pore-foaming agent in S2 is 0.02 mu m, and the specific surface area is 100m2/g。
The specific influence of the aperture of the acidic pore-foaming agent on the preparation of the hollow porous cellulose microsphere is as follows: the acidic pore-foaming agent can be used as a template agent for preparing the porous cellulose microspheres, so the size of the acidic pore-foaming agent directly determines the pore size of the porous cellulose microspheres, the diameter is limited to be 0.01-100 mu m, the size of the acidic pore-foaming agent is too large, and the prepared hollow porous cellulose microspheres have low strength and are easy to disintegrate.
The specific influence of the specific surface area of the acidic pore-foaming agent on the preparation of the hollow porous cellulose microspheres is as follows: the specific surface area of the acidic pore-foaming agent can directly influence the porous structure of the cellulose microsphere, the larger the specific surface area of the pores of the added pore-foaming agent is, the larger the specific surface area of the formed cellulose microsphere is, and the pore diameter limited by the invention is in the range of 40-200m2And g, if the pore-foaming agent particles are too large, the prepared hollow porous cellulose microspheres are low in strength and easy to disintegrate, and if the pore-foaming agent particles are too small, the porous structure of the cellulose microspheres cannot be formed.
Preferably, the acidic porogen in S2 has a pore diameter of 0.03 μm and a specific surface area of 40m2/g。
Preferably, the concentration of the dilute acid solution in S3 is 0.1-1.0 mol/L.
The acid is added to etch off the acidic pore-forming agent to form a hollow structure, the cellulose suspension is added into the acid solution, on one hand, the cellulose solution can be rapidly regenerated into fibers in the acid aqueous solution, on the other hand, the acidic pore-forming agent can be etched and washed off in the acid to form a hollow porous structure, the effect can be achieved by common dilute acid, the appropriate concentration is 0.1-1.0 mol/L, and the more preferable concentration is 0.1 mol/L.
The invention also discloses the hollow porous cellulose microsphere prepared by the method, wherein the pore diameter of the pore structure of the hollow porous cellulose microsphere is 0.01-1um, and the porosity is 20-70%.
For example, the pore diameter of the pore structure of the hollow porous cellulose microsphere is 0.01-1um, and the porosity is 20-70%
Preferably, the active group of the hollow porous cellulose microsphere is hydroxyl, and the content is more than or equal to 1 mmol/g.
The application of the hollow porous cellulose microspheres in environmental adsorption, water treatment, chemical reaction and drug delivery is also within the protection scope of the invention.
Both the inner part and the surface part of the hollow porous cellulose microsphere can be used for adsorbing and releasing functional substances. The adsorption process and the release process can be controlled by certain conditions such as temperature, functional substances, pH value, light, electricity, sound, magnetism and the like, and the pore-forming agent can be used for adjusting the pore diameter and the specific surface area of the composite microsphere to realize the adjustment of the load of the composite microsphere and the release of a target substance, so that the composite microsphere is widely applied to the fields of environmental adsorption, water treatment, chemical reaction, drug delivery and the like.
The method is simple, convenient and quick, the material source is wide, and the method is suitable for preparing porous microspheres with different materials and different functions based on the reactivity of cellulose in the raw materials and the adsorption capacity of the porous material, and the porous cellulose microspheres can be loaded with different target functional substances, so that the cellulose microspheres with adsorption and release functions are prepared.
Compared with the prior art, the invention has the beneficial effects that:
(1) the cellulose microsphere disclosed by the invention has the porosity of 20-70%, wherein the content of active group hydroxyl is more than or equal to 1mmol/g, and the cellulose microsphere contains a large number of hollow porous structures, contains multiple functional groups, and has super-strong adsorption capacity and functional loading capacity.
(2) The preparation method has simple and convenient process, the pore structure can be adjusted by the adding amount of the pore-foaming agent, the functionalization of the wall material can be adjusted and controlled by the active group, and the size of the obtained hollow porous microsphere is easier to control and more uniform.
(3) The hollow porous cellulose microsphere has a porous structure and super-strong adsorption capacity, is easy to load functional substances, can release the functional substances in a controllable manner, and can be widely applied to the fields of environmental adsorption, water treatment, chemical reaction, drug delivery and the like.
Drawings
FIG. 1 is a schematic view of the preparation and application process of the hollow porous cellulose microsphere of the present invention.
FIG. 2 cellulose/cellulose microfibril composite microsphere
FIG. 3 shows cellulose/cellulose nanofibrils/diatomite composite microspheres.
FIG. 4 shows cellulose/SBA-15 composite microspheres.
FIG. 5 shows the adsorption of composite microspheres (1 is unmodified microspheres; 2 is methylene blue solution; 3 is modified microspheres)
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A hollow porous cellulose microsphere is prepared by the following method:
s1, weighing 4g of wood cellulose powder, adding the wood cellulose powder into 92g of sodium hydroxide/urea mixed solution, placing the mixture into a refrigerator to be frozen to-15 ℃, fully dissolving the mixture in a laboratory high-speed shearing homogenizer to form a transparent cellulose solution to obtain a cellulose solution with the mass percent of 4.1%, adding 4g of cellulose microfibrils after the temperature returns to room temperature, and fully dispersing the cellulose microfibrils on a laboratory high-speed dispersing machine to prepare cellulose suspension with good dispersing performance and the solid content of 8 wt%;
s2, adding 1g of nano calcium carbonate into the porous material cellulose suspension of S1, and stirring and dispersing uniformly to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the step S2 into 1mol/L hydrochloric acid until no bubbles are generated, washing with deionized water, ethanol and acetone, drying at 60 ℃ to obtain the hollow porous microspheres with the capsule walls of regenerated cellulose and cellulose microfibrils,
wherein the mass ratio of the porous filler to the cellulose in S1 is 1:1,
the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 0.25:1,
the cellulose microfibrils have a pore size of 1 μm and a specific surface area of 80m2Per g, pore volume of 0.5cm3/g，
The diameter of the nano calcium carbonate is 0.03 mu m, and the specific surface area is 40m2/g。
Example 2
A hollow porous cellulose microsphere is prepared by the following method:
s1, weighing 4g of grass cellulose powder, adding the grass cellulose powder into 92g of NaOH/LiCl/urea mixed solution, placing the mixture into a refrigerator to be frozen to-15 ℃, fully dissolving the mixture in a laboratory high-speed shearing homogenizer to form a transparent cellulose solution, obtaining the cellulose solution with the mass percent of 4.1%, adding 0.5g of cellulose nanofibril and diatomite respectively after the temperature returns to the room temperature, and fully dispersing the mixture on a laboratory high-speed dispersing machine to prepare cellulose suspension with good dispersing performance and the solid content of 5 wt%;
s2, adding 1g of nano titanium dioxide into the porous material cellulose suspension of S1, and stirring and dispersing uniformly to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the step S2 into 1mol/L hydrochloric acid until no bubbles are generated, washing with deionized water, ethanol and acetone, drying at 60 ℃ to obtain the hollow porous microspheres with the walls of regenerated cellulose-cellulose nanofibril-diatomite,
wherein the mass ratio of the porous filler to the cellulose in S1 is 0.25:1,
the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 0.25:1,
the diatomaceous earth has a pore diameter of 0.25 μm and a specific surface area of 50m2G, pore volume of 0.98cm3/g，
The diameter of the nano titanium dioxide is 0.02 mu m, and the specific surface area is 100m2/g。
Example 3
A hollow porous cellulose microsphere is prepared by the following method:
s1, weighing 1g of filter paper cotton cellulose, drying, shearing, adding into 23g of ionic liquid, keeping the room temperature, continuously stirring, fully dissolving to form a transparent cellulose solution to obtain a cellulose solution with the mass percent of 4.2%, adding SBA-151 g after the temperature returns to the room temperature, and fully dispersing on a laboratory high-speed dispersion machine to prepare a cellulose suspension with good dispersion performance and the solid content of 4 wt%;
s2, adding 1g of Tween 60 into the porous material cellulose suspension of S1, and stirring and dispersing uniformly to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the step S2 into 1mol/L hydrochloric acid until no bubbles are generated, cleaning with deionized water, ethanol and acetone, drying at 60 ℃ to obtain the porous microspheres with hollow capsule walls of regenerated cellulose-SBA-15,
wherein the mass ratio of the porous filler to the cellulose in S1 is 1:1,
the mass ratio of the acidic pore-foaming agent to the cellulose in S2 is 1:1,
the pore diameter of SBA-15 is 0.01 mu m, the specific surface area is 500m2G, pore volume 1.16cm3/g。
Example 4
A hollow porous cellulose microsphere is prepared by the following method:
s1, weighing 1g of filter paper cotton cellulose, drying, shearing, adding into 23g of ionic liquid, keeping the room temperature, continuously stirring, fully dissolving to form a transparent cellulose solution to obtain a cellulose solution with the mass percent of 4.2%, adding 0.5g of zeolite powder and diatomite respectively after the temperature returns to the room temperature, and fully dispersing on a laboratory high-speed dispersion machine to prepare a cellulose suspension with good dispersibility and a solid content of 4 wt%;
s2, adding 1g of nano calcium carbonate into the porous material cellulose suspension of S1, and stirring and dispersing uniformly to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the step S2 into 1mol/L hydrochloric acid until no bubbles are generated, washing with deionized water, ethanol and acetone, drying at 60 ℃ to obtain the hollow porous microspheres with the walls of regenerated cellulose-zeolite powder-diatomite,
wherein the mass ratio of the porous filler to the cellulose in S1 is 1:1,
the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 1:1,
the zeolite powder has a pore diameter of 0.007 μm and a specific surface area of 100m2Per g, pore volume of 0.5cm3/g，
The diatomite has a pore diameter of 0.25 μm and a specific surface area of 50m2Per g, pore volume 0.98cm3/g，
The diameter of the nano calcium carbonate is 0.03 mu m, and the specific surface area is 40m2/g。
Example 5
A hollow porous cellulose microsphere is prepared by the following method:
s1, weighing 4g of cellulose powder extracted from peanut shells, adding the cellulose powder into a sodium hydroxide/urea mixed solution, putting the mixture into a refrigerator, freezing the mixture to-15 ℃, fully dissolving the mixture in a laboratory high-speed shearing homogenizer to form a transparent cellulose solution, obtaining a cellulose solution with the mass percent of 10%, adding 6g of cellulose nanofibrils and microfibrils respectively after the temperature returns to room temperature, fully dispersing the mixture in a laboratory high-speed dispersing machine, and preparing cellulose microfibril-nanofibril cellulose suspension with good dispersion performance and the solid content of 8 wt%;
s2, adding 8g of nano calcium carbonate into the porous material cellulose suspension of S1, and stirring and dispersing uniformly to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the step S2 into 1mol/L hydrochloric acid until no bubbles are generated, washing with deionized water, ethanol and acetone, and drying at 60 ℃ to obtain the porous microspheres with hollow capsule walls of regenerated cellulose-cellulose microfibril-cellulose nanofilaments.
Wherein the mass ratio of the porous filler to the cellulose in S1 is 3:1,
the mass ratio of the acidic pore-foaming agent to the cellulose in S2 is 2:1,
the diatomite has a pore diameter of 0.25 μm and a specific surface area of 50m2Per g, pore volume 0.98cm3/g，
The diameter of the nano calcium carbonate is 0.03 mu m, and the specific surface area is 40m2/g。
Example 6
A hollow porous cellulose microsphere is prepared by the following method:
s1, weighing 1g of filter paper cotton cellulose, drying, shearing, adding into 23g of ionic liquid, keeping the room temperature, continuously stirring, fully dissolving to form a transparent cellulose solution to obtain a cellulose solution with the mass percent of 4.2%, adding 0.5g of zeolite powder and diatomite respectively after the temperature returns to the room temperature, and fully dispersing on a laboratory high-speed dispersion machine to prepare a cellulose suspension with good dispersibility and a solid content of 4 wt%;
s2, adding 1g of nano calcium carbonate into the porous material cellulose suspension of S1, and then stirring and dispersing uniformly to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the step S2 into 0.1mol/L hydrochloric acid until no bubbles are generated, washing with deionized water, ethanol and acetone, drying at 60 ℃ to obtain the hollow porous microspheres with the capsule walls of regenerated cellulose-zeolite powder-diatomite,
wherein the mass ratio of the porous filler to the cellulose in S1 is 1:1,
the mass ratio of the acidic pore-foaming agent to the cellulose in S2 is 1:1,
the zeolite powder has pore diameter of 0.007 μm and specific surface area of 100m2Per g, pore volume of 0.5cm3/g，
The diatomite has a pore diameter of 0.25 μm and a specific surface area of 50m2Per g, pore volume 0.98cm3/g，
The diameter of the nano calcium carbonate is 0.03 mu m, and the specific surface area is 40m2/g。
Example 7
A hollow porous cellulose microsphere is prepared by the following method:
s1, preparing a cellulose solution with the mass percent of 5%, adding a porous filler diatomite, and fully dispersing to prepare a porous material cellulose suspension;
s2, adding acid-soluble pore-foaming agent nano calcium carbonate into the porous material cellulose suspension of S1, and fully dispersing to prepare a cellulose mixed solution;
s3, adding an acid solution into the cellulose mixed solution of S2 in a dropwise or spraying manner, removing the acid-soluble pore-forming agent to obtain hollow porous cellulose microspheres,
wherein the mass ratio of the porous filler to the cellulose in the S1 is 4:1, and the solid content of the cellulose mixed solution is 8 wt%;
the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 1: 1.
Comparative example 1
A hollow porous cellulose microsphere is prepared by the following method:
s1, preparing a cellulose solution with the mass percent of 5%, adding porous filler diatomite, and fully dispersing to prepare a porous material cellulose suspension;
s2, adding acid-soluble pore-foaming agent nano calcium carbonate into the porous material cellulose suspension of S1, and fully dispersing to prepare a cellulose mixed solution;
s3, adding an acid solution into the cellulose mixed solution of S2 in a dropwise or spraying manner, removing the acid-soluble pore-forming agent to obtain hollow porous cellulose microspheres,
wherein the mass ratio of the porous filler to the cellulose in the S1 is 4:1, and the solid content of the cellulose mixed solution is 8 wt%;
the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 0.1: 1.
Comparative example 2
Cellulose microspheres prepared by the following method:
s1, preparing a cellulose solution with the mass percent of 5%, adding a porous filler diatomite, and fully dispersing to prepare a porous material cellulose suspension;
s2, adding acid-soluble pore-forming agent nano calcium carbonate into the porous material cellulose suspension of S1, fully dispersing to prepare a cellulose mixed solution,
s3, adding an acid solution into the cellulose mixed solution of S2 in a dropwise or spraying manner to remove the acid-soluble pore-forming agent, wherein the solution has too high viscosity, the cellulose mixed solution is gelatinized and cannot be formed into balls, and the cellulose microspheres cannot be prepared.
Wherein the mass ratio of the porous filler to the cellulose in S1 is 6:1, and the solid content of the cellulose mixed solution is 8 wt%;
the mass ratio of the acidic pore-foaming agent to the cellulose in the S2 is 0.1: 1.
Result detection
(1) Hollow structure detection
The hollow structures of the hollow porous cellulose microspheres prepared in the examples and the comparative examples are tested, including the detection of the hollow pore diameter and the porosity
The detection method comprises the following steps: using Brunauer-Emmett-Teller (BET) N2The physical adsorption method measures the specific surface area, pore volume, etc. of the sample. The tests were carried out on an automatic gas adsorption analyzer (Belsorp-Max BEL Inc, Osaka, Japan) using high purity nitrogen as a carrier gas. The porous microspheres were degassed at 80 ℃ for 12h and then measured for N at-160.15 ℃2And (4) adsorbing.
The results are shown in Table 1.
(2) Reactive group detection
The content of active group hydroxyl of the hollow porous cellulose microspheres prepared in the examples and the comparative examples is detected,
the detection method comprises the following steps: the hydroxyl value is determined on the basis of an acylation method (also called an esterification method), namely, hydroxyl in a sample and acid anhydride are subjected to quantitative acylation reaction to generate ester and acid, and after excessive acid anhydride is hydrolyzed into acid, alkali standard solution is used for titration, and finally, the hydroxyl content is calculated.
The results are shown in Table 1.
TABLE 1
The hollow porous cellulose microspheres required to be prepared by the invention need to be controlled within a certain aperture range, the aperture is between 0.1um and 1um, the aperture is less than 0.1um, the functional components are not favorably loaded in the later period, and the performance such as the specific surface area of the material cannot be improved due to overlarge aperture. The porosity of the microspheres prepared by the embodiment of the invention is about 30%, and the hydroxyl content is more than 1 mmol/g.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. A preparation method of hollow porous cellulose microspheres is characterized by comprising the following steps:
s1, preparing a cellulose solution with the mass percent of 0.1-10%, adding a porous filler, and fully dispersing to prepare a porous material cellulose suspension;
s2, adding an acid-soluble pore-forming agent into the porous material cellulose suspension of S1, and fully dispersing to prepare a cellulose mixed solution;
s3, adding the cellulose mixed solution in the S2 into an acid solution, removing an acid-soluble pore-forming agent to obtain hollow porous cellulose microspheres,
wherein the mass ratio of the porous filler to the cellulose in S1 is 1-3: 1, and the solid content of the cellulose suspension is 5-10 wt%;
the mass ratio of the acidic pore-foaming agent to the cellulose in S2 is 2:1,
the pore diameter of the porous filler in S1 is 0.25-1 μm, and the specific surface area is 50-80 m2Per g, pore volume of 0.5-0.98cm3/g，
The diameter of the acidic pore-foaming agent in S2 is 0.02-0.03 mu m, and the specific surface area is 40-100 m2/g。
2. The method for preparing hollow porous cellulose microspheres according to claim 1, wherein the concentration of the acid solution is 0.1 to 1.0 mol/L.
3. The hollow porous cellulose microsphere prepared by the preparation method of claim 1 or 2, wherein the pore diameter of the pore structure of the hollow porous cellulose microsphere is 0.01-1um, and the porosity is 20-70%.
4. The hollow porous cellulose microsphere of claim 3, wherein the active group of the hollow porous cellulose microsphere is hydroxyl group, and the content is not less than 1 mmol/g.
5. The hollow porous cellulose microsphere of claim 4, wherein the active group of the hollow porous cellulose microsphere is hydroxyl and the content is 1.21 to 1.54 mmol/g.
6. Use of hollow porous cellulose microspheres according to claim 3 for environmental adsorption, water treatment, chemical reactions and the preparation of pharmaceutical carriers.
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| FR3138813A1 (en) * | 2022-08-11 | 2024-02-16 | Sas Woodoo | METHOD FOR OBTAINING A LIGNO-CELLULOSIC COMPOSITE MATERIAL AND COMPOSITE MATERIAL OBTAINED BY THIS PROCESS |
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| US4303431A (en) * | 1979-07-20 | 1981-12-01 | Torobin Leonard B | Method and apparatus for producing hollow microspheres |
| CN101250267B (en) * | 2008-04-14 | 2011-09-14 | 武汉大学 | Preparation method of cellulose microsphere |
| CN102557714B (en) * | 2012-01-09 | 2016-01-20 | 江南大学 | A kind of duct amplification method of porous ceramics microballoon |
| US9271937B2 (en) * | 2012-05-31 | 2016-03-01 | Covidien Lp | Oxidized cellulose microspheres |
| CN102863655B (en) * | 2012-09-24 | 2015-03-25 | 厦门大学 | Chain-ball-shaped magnetic chitosan/acetate cellulose and preparation method thereof |
| CN103566846B (en) * | 2013-11-07 | 2015-12-30 | 华北电力大学（保定） | A kind of porous functionalization microcapsules, Preparation method and use |
| CN103724635B (en) * | 2013-12-06 | 2016-01-20 | 中国烟草总公司郑州烟草研究院 | Preparation method of a kind of cellulose acetate porous microsphere and products thereof |
| CN103756016B (en) * | 2013-12-25 | 2016-05-25 | 武汉工程大学 | A kind of size homogeneous cellulose microsphere and its production and use |
| KR101741982B1 (en) * | 2015-01-22 | 2017-05-31 | 주식회사 셀루메드 | Porous biodegradable polymer microsphere for dual-loaded drug delivery and method for producing thereof |
| CN109134944A (en) * | 2018-08-28 | 2019-01-04 | 安徽聚欣新材料科技有限公司 | A kind of porous small ball and its application with different chemical functional groups |
| CN109232993A (en) * | 2018-08-28 | 2019-01-18 | 安徽聚欣新材料科技有限公司 | A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball |
| CN109647296A (en) * | 2019-01-18 | 2019-04-19 | 东华大学 | A kind of Porous hollow microballoon and its preparation method and application |
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