CN117323974A - Preparation method of polyaniline modified hydrophilic nano hollow microcapsule - Google Patents
Preparation method of polyaniline modified hydrophilic nano hollow microcapsule Download PDFInfo
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- 229920000767 polyaniline Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003094 microcapsule Substances 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- 238000003756 stirring Methods 0.000 claims description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002088 nanocapsule Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims 2
- 239000013315 hypercross-linked polymer Substances 0.000 claims 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011068 loading method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 14
- 239000003814 drug Substances 0.000 description 7
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 229940079593 drug Drugs 0.000 description 6
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OVBPIULPVIDEAO-UHFFFAOYSA-N N-Pteroyl-L-glutaminsaeure Natural products C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)NC(CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229960000304 folic acid Drugs 0.000 description 3
- 235000019152 folic acid Nutrition 0.000 description 3
- 239000011724 folic acid Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- MWWSFMDVAYGXBV-RUELKSSGSA-N Doxorubicin hydrochloride Chemical compound Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 MWWSFMDVAYGXBV-RUELKSSGSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000008307 w/o/w-emulsion Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229960002918 doxorubicin hydrochloride Drugs 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J13/025—Applications of microcapsules not provided for in other subclasses
-
- 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
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/25—Coated, impregnated or composite adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of carbon dioxide capture, and particularly relates to a preparation method of polyaniline modified hydrophilic nano hollow microcapsules, which comprises three steps of preparing super-crosslinked hollow microcapsules (HCP-HC), preparing sulfonated HCP-HC (S-HCP-HC) and preparing PAN modified S-HCP-HC (PANI@S-HCP-HC), wherein the composite material has electrochemical activity based on the conductivity of polyaniline, the S-HCP-HC has the advantages of hydrophilicity, adjustable structure, large specific surface area, good stability, multiple structures, low price, capability of loading other metals and the like, PANI is combined with the sulfonated HCP-HC, the hydrophilicity of the S-HCP-HC enables the PANI to enter the pore structure of the S-HCP-HC, the PANI@S-HCP-HC has good morphology, and the high specific surface area is kept; the method has the advantages of scientific and reliable principle, simple procedure operation, mild reaction conditions, no need of special reaction equipment and expensive catalyst, and low production cost.
Description
Technical field:
the invention belongs to the technical field of carbon dioxide capture,in particular to a preparation method of polyaniline modified hydrophilic nano hollow microcapsule for preparing a carbon capture electrode for CO 2 Is a chemical capture of (a).
The background technology is as follows:
with the deepening of the industrialization degree, the concentration of greenhouse gases in the atmosphere, especially CO, is continuously increased 2 Global climate is warming, so that the problems of extreme weather increase, energy crisis and the like promote the research of carbon dioxide conversion. The general strategy of carbon capture and utilization aims at converting carbon dioxide into economically valuable chemicals for recovery, and has important significance for protecting the global ecological environment and promoting sustainable development of human society.
At present, the hollow organic microporous microcapsule is widely applied in the fields of catalysis, electrochemistry and medicine. For example, chinese patent 201310371108.7 discloses a preparation method of a hollow PLGA drug-loaded microcapsule based on polyethylene glycol and folic acid grafted polyethyleneimine modification, comprising: (1) Dissolving folic acid FA in a solvent, adding N-hydroxysuccinimide NHS and carbodiimide EDC, adding amino polyethylene glycol carboxylic acid NH2-PEG-COOH, stirring at 25-28 ℃ for reacting for 2-3d, dialyzing, freeze-drying, re-dissolving in the solvent, adding N-hydroxysuccinimide NHS and carbodiimide EDC, adding polyethylenimine PEI, stirring at 25-28 ℃ for reacting for 2-3d, dialyzing, and freeze-drying to obtain PEI-PEG-FA polymer; (2) Dissolving polylactic-co-glycolic acid PLGA in an organic solvent to obtain an oil phase; dissolving doxorubicin hydrochloride DOX & HCl in ultrapure water to obtain a water phase; then mixing the oil phase and the water phase, and carrying out ultrasonic treatment in ice water bath for 20-30s to obtain water-in-oil W/O emulsion; (3) Adding the W/O emulsion into a polyvinyl alcohol PVA water solution, and homogenizing under the ice water bath condition to obtain a water-in-oil-in-water W/O/W emulsion; (4) Adding the W/O/W emulsion into isopropanol water solution, stirring for 1-4h, and centrifugally washing to obtain PLGA-DOX drug-loaded hollow microcapsules; (5) Dispersing the PLGA-DOX drug-loaded hollow microcapsule in water, adding PEI-PEG-FA polymer aqueous solution, stirring for 15-30min, centrifugally washing, dispersing in water, freeze-drying to obtain the polyethylene glycol and folic acid grafted polyethyleneimine modified PLGA drug-loaded hollow microcapsule with good drug slow release performance and tumor cell targeted treatment effect, thereby providing reference for the development of multifunctional targeted pharmaceutical preparations. Chinese patent 201210549671.4 discloses a porous polymer hollow microcapsule, which is prepared by the following steps: step one: adding nano silicon dioxide particles into absolute ethyl alcohol, performing ultrasonic dispersion, adding ammonia water, then adding a silane coupling agent 3- (methacryloyloxy) propyl trimethoxy silane to obtain a mixed solution, stirring for 12-36 hours to perform surface modification on the nano silicon dioxide particles, centrifuging the mixed solution, pouring out supernatant, and washing 3-5 times by using absolute ethyl alcohol or methanol to obtain surface modified nano silicon dioxide particles; step two: dispersing surface modified nano silicon dioxide particles in absolute ethyl alcohol by ultrasonic, then adding sodium dodecyl benzene sulfonate, sodium bicarbonate and water, stirring for 30-90 minutes by ultrasonic, adding monomer styrene and comonomer divinylbenzene to obtain mixed solution, stirring for 30-90 minutes at 40-60 ℃, heating to 70-90 ℃, adding an initiator, stirring for 1-5 hours, centrifuging the mixed solution, pouring out supernatant, washing for 1-2 times by using absolute ethyl alcohol or methanol, and drying to obtain core-shell particles of poly (styrene-divinylbenzene) coated nano silicon dioxide; step three: stirring core-shell particles of poly (styrene-divinylbenzene) coated nano silicon dioxide, a cross-linking agent and an organic solvent for 1-5 hours at normal temperature, magnetically stirring for 0.1-2 hours, then adding Lewis acid serving as a catalyst, keeping magnetically stirring, heating to 30-60 ℃, reacting for 2-12 hours at the temperature, heating to 70-120 ℃, reacting for 10-72 hours at the temperature to obtain a very viscous solid-liquid mixture, filtering the very viscous solid-liquid mixture to obtain brown solid, washing the solid with diethyl ether and methanol for 1-5 times to remove residual cross-linking agent, solvent and catalyst, extracting with methanol for 12-36 hours to remove residual catalyst Lewis acid, removing nano silicon dioxide particles with hydrofluoric acid, and drying to obtain a high polymer carrier for drug loading and release, catalyst loading or ion adsorbent: yellow brown or purple porous polymer hollow microcapsules.
Polyaniline as the earliest discovered conductive polymer, has low cost and easy combinationThe composite material has the characteristics of high conductivity, multiple oxidation states, high pseudocapacitance and the like, and is widely applied to the fields of paint, batteries, wave absorbing materials, sensors, conductive fibers and the like. In addition to this, studies have found that: solid amine-based adsorbents at lower CO 2 Under partial pressure condition, the catalyst has higher adsorption capacity, lower regeneration temperature (less than 100 ℃), and less corrosion to equipment. Based on CO 2 Interaction with amino groups to form carbamic acid, carbamates and bicarbonates, polyaniline has great potential in applications for capturing carbon dioxide. Therefore, the polyaniline and the hollow microcapsule are expected to be compounded to obtain a cheap composite material with electric activity and specific surface area, and capture carbon dioxide, thereby having positive social and economic values.
The invention comprises the following steps:
the invention aims to overcome the defects in the prior art, and seeks to design a preparation method of a polyaniline modified hydrophilic nano hollow microcapsule so as to solve the problems of a non-porous structure of a polyaniline material, small specific surface area and poor conductivity of a super-crosslinked polymer.
In order to achieve the above purpose, the specific technical process of the preparation method of the polyaniline modified hydrophilic hollow nanocapsules comprises three steps of preparing super-crosslinked hollow microcapsules (HCP-HC), preparing sulfonated HCP-HC (S-HCP-HC) and preparing PAN modified S-HCP-HC (PANI@S-HCP-HC):
(1) Preparation of HCP-HC
First, the volume ratio was set to 2:13 KH-570 and ethanol into commercially available SiO 2 In the nanoparticle ethanol dispersion liquid, reacting for 24 hours, washing and centrifuging the obtained product with methanol for 3 times, and vacuum drying for 24 hours to obtain vinyl modified SiO 2 ；
Wherein SiO is 2 The particle size of the nano particles is 50-300 nm, ethanol: siO (SiO) 2 The ratio of nanoparticles was 25mL:1g;
again, sodium Dodecyl Benzene Sulfonate (SDBS) and NaHCO 3 Dissolving in distilled water to obtain aqueous solution, and modifying SiO with vinyl group 2 Dispersing in ethanol, adding into aqueous solution, stirring continuously to obtain stable emulsion, and adding into water solutionAdding styrene and Divinylbenzene (DVB), heating to 85deg.C, and dropwise adding potassium persulfate (KPS) water solution to obtain SiO 2 @PS-DVB；
Wherein, SDBS: naHCO (NaHCO) 3 The mass ratio of (3): 20, the volume of distilled water is 100mL; vinyl modified SiO 2 : the proportion of ethanol is 3mg:25mL; distilled water: ethanol: the volume ratio of the styrene is 10:1:1, a step of; the volume of DVB is 2-25% of the volume of styrene; the concentration of the KPS aqueous solution is 0.1g/mL;
then, siO is added 2 Swelling PS-DVB in a mixed solution of Dichloroethane (DCE) and dimethoxymethane (FDA) for 1h, and adding FeCl at 35deg.C 3 Raising the temperature to 45 ℃, reacting for 5 hours, heating the reaction product to 80 ℃, keeping for 19 hours, cleaning and filtering to obtain SiO 2 @HCPs；
Wherein SiO is 2 @ PS-DVB: DCE: the FDA ratio was 1g:20mL:1.73mL; feCl 3 : the FDA ratio was 3.32g:1.73mL;
finally, etching SiO with hydrofluoric acid 2 Filtering and washing the @ HCPs to obtain brown HCP-HC, and drying the HCP-HC in a vacuum environment at 60 ℃ for 24 hours for later use;
(2) Preparation of S-HCP-HC
Stirring and adding HCP-HC into concentrated sulfuric acid, stirring for 4 hours at 35 ℃, carefully cleaning and filtering with ethanol, and drying in an environment at 60 ℃ to obtain S-HCP-HC;
wherein, concentrated sulfuric acid: the HCP-HC ratio was 10mL:1g;
(3) Preparation of PANI@S-HCP-HC
Mixing concentrated hydrochloric acid and aniline, adding water, stirring at room temperature for 3 hours, adding S-HCP-HC, stirring for 6 hours, dripping Ammonium Persulfate (APS) aqueous solution, reacting at room temperature for 2 hours, washing the filtered product with water and ethanol, and drying in an environment with the temperature of 60 ℃ to obtain PANI@S-HCP-HC;
wherein, S-HCP-HC: the proportion of water is 0.2g:1mL; S-HCP-HC: the proportion of aniline is 1g:1-4mL; concentrated hydrochloric acid: the volume ratio of aniline is 4:1, a step of; APS: the proportion of aniline is 0.12g:1mL of aqueous APS solution was 1mL in volume.
The PANI@S-HCP-HC disclosed by the invention is used for preparing an electrochemical carbon dioxide capturing material: the PANI@S-HCP-HC carbon capture electrode can improve the specific surface area of polyaniline, and the aperture and the conductivity of an electrochemical carbon dioxide capture material can be adjusted by controlling the addition amount of the polyaniline, so that the electrochemical carbon dioxide capture is effectively promoted;
the specific preparation process comprises the following steps: dispersing PANI@S-HCP-HC and carbon nanotubes in ethanol to obtain a dispersion liquid, adding Polytetrafluoroethylene (PTFE) as a binder, carrying out ultrasonic treatment to uniformly mix the dispersion liquid, dripping the dispersion liquid on a polished glassy carbon electrode by using a micropipette, and drying the mixture in an environment with the temperature of 60 ℃ for 1h to obtain a PANI@S-HCP-HC carbon capture electrode; wherein the mass percentage concentration of PTFE is 1%; pani@s-HCP-HC: carbon nanotubes: the ratio of PTFE is 4:5:1.
compared with the prior art, the invention has the advantages of electrochemical activity of the composite material based on the conductivity of polyaniline, hydrophile, adjustable structure, large specific surface area, good stability, various structures, low price, capability of loading other metals and the like, and combines PANI with sulfonated HCP-HC, and the hydrophilicity of S-HCP-HC enables PANI to enter into the pore structure of S-HCP-HC, so that PANI@S-HCP-HC has good morphology and keeps high specific surface area; the method has the advantages of scientific and reliable principle, simple procedure operation, mild reaction conditions, no need of special reaction equipment and expensive catalyst, and low production cost.
Description of the drawings:
FIG. 1 is a cyclic voltammogram of PANI@S-HCP-HC and S-HCP-HC prepared in an example of the present invention.
The specific embodiment is as follows:
the invention is further described below by way of example with reference to the accompanying drawings.
Example 1:
the specific technical process of the polyaniline modified hydrophilic nano hollow microcapsule preparation method related to the embodiment is as follows:
the mixed solution composed of 500mL of ethanol and 40mL of TEOS is vigorously and mechanically stirred, and 40mL of NH is added 3 ·H 2 O, stirStirring for 24h to obtain a dispersion, dripping a mixture of 4mL KH-570 and 26mL ethanol into the dispersion, reacting for 24h, washing the centrifugal reaction product with methanol for 3 times, and vacuum drying for 24h to obtain SiO 2 ；
0.036g SDBS and 0.24g NaHCO 3 Dissolving in 100mL distilled water to obtain an aqueous solution, and mixing 1.2mg SiO 2 Dispersing in 10mL of ethanol, adding into aqueous solution, continuously stirring to obtain stable emulsion, adding 10mL of styrene and DVB with volume ratio of 5% of styrene into the emulsion, raising the temperature to 85deg.C, and dropwise adding 1mL of KPS aqueous solution with concentration of 0.1g/mL to obtain SiO 2 @PS-DVB；
1g of SiO 2 PS-DVB is put into a mixed solution composed of 20mL of DCE and 1.73mL of FDA to be swelled for 1h, and 3.32g of FeCl is added at the temperature of 35 DEG C 3 Raising the temperature to 45 ℃, reacting for 5 hours, heating the reaction product to 80 ℃, keeping for 19 hours, cleaning and filtering to obtain SiO 2 @HCPs；
Etching SiO with hydrofluoric acid 2 Filtering and washing the mixture at the temperature of 60 ℃ to obtain brown HCP-HC, and drying the HCP-HC in a vacuum environment at the temperature of 60 ℃ for 24 hours;
5mL of concentrated sulfuric acid is added into 0.5g of HCP-HC by stirring, the mixture is stirred for 4 hours at the temperature of 35 ℃, then the mixture is carefully washed and filtered by ethanol, and the mixture is dried at the temperature of 60 ℃ to obtain S-HCP-HC;
after 0.2mL of concentrated HCl and 0.1mL of aniline are mixed, 1mL of water is added, stirring is carried out at room temperature for 3h, 0.2g S-HCP-HC is added, stirring is carried out for 6h, 1mL of 0.012g/mL of APS aqueous solution is dripped, reaction is carried out at room temperature for 2h, the obtained product is washed and filtered by water and ethanol, and the obtained product is dried in an environment with the temperature of 60 ℃ to obtain PANI@S-HCP-HC.
Example 2:
the procedure of the preparation method of pani@s-HCP-HC according to this example is the same as that of example 1, except that: the concentrated HCl had a volume of 0.3mL, the aniline had a volume of 0.07mL, and the APS aqueous solution had a concentration of 0.016g/mL.
Example 3:
the procedure of the preparation method of pani@s-HCP-HC according to this example is the same as that of example 1, except that: the concentrated HCl had a volume of 0.4mL, the aniline had a volume of 0.05mL, and the APS aqueous solution had a concentration of 0.024g/mL.
Example 4:
the CV curves of the working electrodes prepared in examples 1, 2 and 3, PANI@S-HCP-HC and S-HCP-HC, over a potential range of-0.2 to 0.8V at a scan rate of 100mV/S, are shown in FIG. 1, and the increase in the CV curve area of the PANI@S-HCP-HC compared to the S-HCP-HC indicates that the PANI improves the electrochemical performance of the S-HCP-HC; pani@s-HCP-HC exhibits pseudocapacitive properties comprising two pairs of redox peaks, wherein a/a 'is due to the transition of emeraldine-penicillin aniline and B/B' is due to the redox transition of PANI between the semiconductor and conductive state, the area of the CV curve increasing with increasing PANI.
Claims (10)
1. The preparation method of the polyaniline modified hydrophilic nano hollow microcapsule comprises three steps of preparing the super-crosslinked hollow microcapsule, preparing sulfonated HCP-HC and preparing PAN modified S-HCP-HC, and is characterized in that:
(1) Preparation of HCP-HC
First, a mixture of KH-570 and ethanol was dropped into SiO 2 In the ethanol dispersion liquid of the nano particles, the reaction is carried out, the obtained product is washed and centrifuged by methanol, and the vinyl modified SiO is obtained by vacuum drying 2 ；
Again, sodium dodecyl benzene sulfonate and NaHCO 3 Dissolving in distilled water to obtain aqueous solution, and modifying SiO with vinyl group 2 Dispersing in ethanol, adding into aqueous solution, continuously stirring to obtain stable emulsion, adding styrene and divinylbenzene into the emulsion, heating, and dropwise adding potassium persulfate aqueous solution to obtain SiO 2 @PS-DVB；
Then, siO is added 2 Swelling PS-DVB in mixed solution of dichloroethane and dimethoxymethane, and adding FeCl 3 Reacting, heating, maintaining, cleaning and filtering the reaction product to obtain SiO 2 @HCPs；
Finally, etching SiO with hydrofluoric acid 2 Filtering and washing the mixture at the temperature of HCPs to obtain HCP-HC, and drying the HCP-HC in a vacuum environment;
(2) Preparation of S-HCP-HC
Adding HCP-HC into concentrated sulfuric acid under stirring, washing with ethanol, filtering, and drying to obtain S-HCP-HC;
(3) Preparation of PANI@S-HCP-HC
Mixing concentrated hydrochloric acid and aniline, adding water, stirring, adding S-HCP-HC, stirring, dripping ammonium persulfate aqueous solution, reacting, washing the filtered product with water and ethanol, and drying to obtain PANI@S-HCP-HC.
2. The preparation method of the polyaniline modified hydrophilic hollow nanocapsules according to claim 1, which is characterized by comprising the following specific technical processes:
(1) Preparation of HCP-HC
First, the volume ratio was set to 2:13 KH-570 and ethanol into commercially available SiO 2 In the nanoparticle ethanol dispersion liquid, reacting for 24 hours, washing and centrifuging the obtained product with methanol for 3 times, and vacuum drying for 24 hours to obtain vinyl modified SiO 2 ；
Again, sodium dodecyl benzene sulfonate and NaHCO 3 Dissolving in distilled water to obtain aqueous solution, and modifying SiO with vinyl group 2 Dispersing in ethanol, adding into aqueous solution, stirring continuously to obtain stable emulsion, adding styrene and divinylbenzene into the emulsion, heating to 85deg.C, and dropwise adding potassium persulfate aqueous solution to obtain SiO 2 @PS-DVB；
Then, siO is added 2 Swelling PS-DVB in a mixed solution of dichloroethane and dimethoxymethane for 1 hr, and adding FeCl at 35deg.C 3 Raising the temperature to 45 ℃, reacting for 5 hours, heating the reaction product to 80 ℃, keeping for 19 hours, cleaning and filtering to obtain SiO 2 @HCPs；
Finally, etching SiO with hydrofluoric acid 2 Filtering and washing the @ HCPs to obtain brown HCP-HC, and drying the HCP-HC in a vacuum environment at 60 ℃ for 24 hours for later use;
(2) Preparation of S-HCP-HC
Stirring and adding HCP-HC into concentrated sulfuric acid, stirring for 4 hours at 35 ℃, carefully cleaning and filtering with ethanol, and drying in an environment at 60 ℃ to obtain S-HCP-HC;
(3) Preparation of PANI@S-HCP-HC
Mixing concentrated hydrochloric acid and aniline, adding water, stirring at room temperature for 3 hours, adding S-HCP-HC, stirring for 6 hours, dripping ammonium persulfate aqueous solution, reacting at room temperature for 2 hours, washing the filtered product with water and ethanol, and drying in an environment with the temperature of 60 ℃ to obtain PANI@S-HCP-HC.
3. The method for preparing the polyaniline modified hydrophilic nanocapsules according to claim 1 or 2, wherein pani@s-HCP-HC is used for preparing an electrochemical capture carbon dioxide material: the PANI@S-HCP-HC carbon capture electrode adjusts the pore diameter and the conductivity of the electrochemical capture carbon dioxide material by controlling the addition amount of aniline.
4. The method for preparing the polyaniline modified hydrophilic hollow nanocapsules according to claim 1 or 2, wherein in the step (1), siO 2 The particle size of the nano particles is 50-300 nm, ethanol: siO (SiO) 2 The ratio of nanoparticles was 25mL:1g; SDBS:
NaHCO 3 the mass ratio of (3): 20, the volume of distilled water is 100mL; vinyl modified SiO 2 : the proportion of ethanol is 3mg:25mL; distilled water: ethanol: the volume ratio of the styrene is 10:1:1, a step of; the volume of DVB is 2-25% of the volume of styrene; the concentration of the KPS aqueous solution is 0.1g/mL; siO (SiO) 2 @ PS-DVB: DCE: the FDA ratio was 1g:20mL:1.73mL; feCl 3 : the FDA ratio was 3.32g:1.73mL.
5. The method for preparing polyaniline modified hydrophilic hollow nanocapsules according to claim 1 or 2, wherein in step (2), concentrated sulfuric acid: the HCP-HC ratio was 10mL:1g.
6. The method for preparing the polyaniline modified hydrophilic nanocapsules according to claim 1 or 2, wherein in the step (3), S-HCP-HC: the proportion of water is 0.2g:1mL; S-HCP-HC: the proportion of aniline is 1g:1-4mL; concentrated hydrochloric acid: the volume ratio of aniline is 4:1, a step of; APS: the proportion of aniline is 0.12g:1mL of aqueous APS solution was 1mL in volume.
7. The preparation method of the polyaniline modified hydrophilic hollow nanocapsules according to claim 3, wherein the specific preparation process comprises the following steps: dispersing PANI@S-HCP-HC and carbon nanotubes in ethanol to obtain a dispersion liquid, adding a binder, performing ultrasonic treatment, dripping on a glassy carbon electrode, and drying for 1h to obtain the PANI@S-HCP-HC carbon capture electrode.
8. The method for preparing polyaniline modified hydrophilic hollow nanocapsules according to claim 7, wherein the binder is polytetrafluoroethylene.
9. The method for preparing the polyaniline modified hydrophilic hollow nanocapsules according to claim 7, wherein the polyaniline modified hydrophilic hollow nanocapsules are dried in an environment at a temperature of 60 ℃.
10. The preparation method of the polyaniline modified hydrophilic hollow nanocapsules according to claim 7, wherein the mass percentage concentration of PTFE is 1%; pani@s-HCP-HC: carbon nanotubes: the ratio of PTFE is 4:5:1.
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| CN117861630B (en) * | 2024-01-27 | 2024-06-04 | 杭州捷瑞智能装备股份有限公司 | Preparation method of modified silica gel adsorbent |
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