CN105879910A - Poly(styrene-methacrylic acid)/nano-silver composite microsphere and preparation method thereof - Google Patents
Poly(styrene-methacrylic acid)/nano-silver composite microsphere and preparation method thereof Download PDFInfo
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- CN105879910A CN105879910A CN201610302024.1A CN201610302024A CN105879910A CN 105879910 A CN105879910 A CN 105879910A CN 201610302024 A CN201610302024 A CN 201610302024A CN 105879910 A CN105879910 A CN 105879910A
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- styrene
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- nanometer silver
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- 239000004005 microsphere Substances 0.000 title claims abstract description 89
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- -1 Poly(styrene-methacrylic acid) Polymers 0.000 title claims abstract 8
- 239000002131 composite material Substances 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 229910052709 silver Inorganic materials 0.000 claims description 72
- 239000004332 silver Substances 0.000 claims description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000000376 reactant Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000012467 final product Substances 0.000 claims description 13
- NGBNXJUWQPLNGM-UHFFFAOYSA-N silver;azane Chemical compound N.[Ag+] NGBNXJUWQPLNGM-UHFFFAOYSA-N 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical class [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 238000006392 deoxygenation reaction Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229910017611 Ag(NH3)2 Inorganic materials 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract 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 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 229910000033 sodium borohydride Inorganic materials 0.000 description 8
- 239000012279 sodium borohydride Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention belongs to the field of an organic high molecular material and in particular relates to a poly(styrene-methacrylic acid)/nano-silver composite microsphere and a preparation method thereof. The composite microsphere is prepared from a poly(styrene-methacrylic acid) microsphere and nano-silver which is uniformly deposited on the surface of the poly(styrene-methacrylic acid) microsphere, wherein the weight ratio of the nano-silver to the poly(styrene-methacrylic acid) is (20 to 30): 60. The preparation method comprises the following two steps: S1 preparing poly(styrene-methacrylic acid) microsphere emulsion; S2 preparing the poly(styrene-methacrylic acid)/nano-silver composite microsphere. The composite microsphere provided by the invention has the characteristics that the nano-silver has good dispersibility and large specific surface area, is not easy to agglomerate and is high in catalytic efficiency, good in durability and lower in cost; the preparation method provided by the invention is simple in process and a reaction is carried out in a water phase; no toxic reagent is added, the harm to an environment is small and reaction conditions are moderate; common equipment can finish production so that the industrialization of the production is facilitated.
Description
Technical field
The invention belongs to high-molecular organic material field, be specifically related to a kind of poly-(styrene-methyl propylene
Acid)/nanometer silver complex microsphere and preparation method thereof.
Background technology
In recent years, nano structural material is because of its chemistry, physics, biological nature and in numerous applications
Potential application and cause the extensive concern of people.Particularly metal nanoparticle and the burning of correspondence
Thing, such as Ag, Au, Cu, TiO2, ZnO etc..These nano structural materials are in catalyst field
It is widely used in a variety of applications.Wherein, Ag is as the highest catalysis material of a kind of catalytic efficiency, in dirt
The aspects such as water process, photocatalytic degradation and photocatalysis hydrogen production have very important application.But, single
Nanometer silver there are a series of shortcomings such as reunion the most oxidized, easy and high cost as catalysis material.In order to
Solving these problems, a lot of methods have been attempted, and most important of which method mixes Ag exactly to various
Substrate surface.
Summary of the invention
For overcome nanometer silver in prior art as defects such as easily reuniting of existing during catalyst and high costs,
The present invention is using poly-(styrene-t) microsphere as the base material of loading nano silvery, it is contemplated that obtain
A kind of low cost and the good composite of catalytic performance.
The technical scheme that the present invention overcomes defect of the prior art to be used is as follows:
The present invention provides a kind of poly-(styrene-t)/nanometer silver complex microsphere, and it is by poly-(benzene
Ethylene-methyl methacrylate) the nanometer silver composition of microsphere and surface uniform deposition thereof, nanometer silver and poly-(benzene
Ethylene-methyl methacrylate) part by weight be 20-30:60.
Above-mentioned poly-(styrene-t)/nanometer silver complex microsphere, also has further below
Feature.
Further, the mean diameter of described poly-(styrene-t) microsphere is 250-300nm.
Further, the mean diameter of described nanometer silver is 30-50nm.
The present invention also provides for the preparation side of above-mentioned poly-(styrene-t)/nanometer silver complex microsphere
Method, it comprises the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: according to 15 in reaction vessel:
Styrene, methacrylic acid and deionized water are sufficiently mixed by the volume ratio of 1-3:125, are passed through nitrogen drum
Bubble more than deoxygenation 0.5h, be warming up to 70-75 DEG C, add persulfate class initiator, described styrene with
The mol ratio of persulfate class initiator is 50-60:1, under the protection of constant voltage nitrogen, reacts 12-24h, thoroughly
Analysis filters little molecule, to obtain final product；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: by polyvinylpyrrolidine
Poly-(styrene-t) microsphere emulsion prepared by ketone, deionized water and S1 is according to 1:30:4
Weight ratio be sufficiently mixed to obtain reactant liquor, in reactant liquor, then add the silver ammino solution of appropriate new preparation,
Join the Ag (NH that the silver ammino solution in reactant liquor contains3)2OH and poly-(styrene-methyl in reactant liquor
Acrylic acid) part by weight of microsphere emulsion is 0.32-0.95:4, stirs 1-1.5h under room temperature, make silver ammonia from
Son is adsorbed onto poly-(styrene-t) microsphere surface, is warming up to 70-75 DEG C, at nitrogen atmosphere
Lower reaction 7-12h, silver ammonium ion is reduced into nanometer silver uniform deposition at poly-(styrene-methyl propylene
Acid) microsphere surface, it is centrifuged, washs, is dried, to obtain final product.
On the basis of above-mentioned preparation method, it can also be embodied or provide optimum by the present invention further
Select.
Concrete, the persulfate class initiator described in S1 is potassium peroxydisulfate, sodium peroxydisulfate or over cure
Acid ammonium.
Preferably, the styrene described in S1 is 57:1 with the mol ratio of persulfate class initiator
Preferably, using molecular cut off in S1 during dialysis is the bag filter of 3000.
Preferably, the weight average molecular weight of the polyvinylpyrrolidone described in S2 is 13000.
Preferably, the concentration of the silver ammino solution of the new preparation described in S2 is 0.2-0.6mol/L.
Compared with prior art, the invention has the beneficial effects as follows:
1, poly-(styrene-t) microsphere is owing to having carboxyl, and in water, it is with stronger
Negative electricity, thus can well Adsorption For Ag ammonium ion, and then through polyvinylpyrrolidone reduction obtain nanometer silver
And the dispersed surface being deposited on poly-(styrene-t) microsphere obtains complex microsphere, should
Nanometer silver good dispersion on complex microsphere, specific surface area are big and are difficult to reunite, and its catalytic efficiency is high, resistance to
Property is good, cost is relatively low for a long time；
2, the particle diameter of poly-(styrene-t) microsphere is more uniform, and mean diameter is 250-300nm,
The complex microsphere obtained after dispersed deposition nanometer silver can present regular pattern, when it makes as catalyst
Used time, homogeneous size and regular pattern are conducive to accurately controlling its consumption, are conducive to catalysis anti-simultaneously
Ying Qi surface is carried out the most simultaneously, and catalytic efficiency is high；
3, the preparation method that the present invention provides, process is simple and reaction is all carried out in aqueous phase, does not add
Add any toxic reagent, be a kind of eco-friendly method；
4, the preparation method that the present invention provides, reaction condition is gentle, it is not necessary to high temperature, operation with high pressure,
To consersion unit without particular/special requirement, it is easy to industrialized production.
Accompanying drawing explanation
Fig. 1 is that poly-(the styrene-t)/nanometer silver of the embodiment of the present invention 1 preparation is combined micro-
The transmission electron microscope picture of ball；
Fig. 2 is the grain of poly-(styrene-t)/nanometer silver complex microsphere of embodiment 1 preparation
Footpath scattergram；
Fig. 3 is poly-(styrene-t)/nanometer silver complex microsphere catalysis of embodiment 1 preparation
Sodium borohydride (NaBH4) ultra-violet absorption spectrum that reacts of deoxidization, degradation methylene blue (MB)；
Sodium borohydride (NaBH when Fig. 4 is not for adding catalyst4) deoxidization, degradation methylene blue (MB) is instead
The ultra-violet absorption spectrum answered.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with accompanying drawing, example is served only for explaining this
Invention, is not intended to limit the scope of the present invention.
When being not specifically noted, the method for the invention is conventional method, and agents useful for same of the present invention is
Commercial reagent.
Embodiment 1
The preparation of poly-(styrene-t)/nanometer silver complex microsphere, it comprises the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: add in 250mL four-hole bottle
15mL (0.1309mol) styrene, 1mL methacrylic acid and 125mL deionized water, be passed through nitrogen drum
After bubble deoxygenation 0.5h, temperature is risen to 70 DEG C, add 0.625g (0.0023mol) potassium peroxydisulfate and cause
Agent, under constant voltage nitrogen is protected, reacts 24h, and the bag filter using molecular cut off to be 3000 filters little
Molecule, to obtain final product；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: take prepared by 4g S1
Poly-(styrene-t) microsphere emulsion, 30g deionized water and 1g polyvinylpyrrolidone are mixed
Close to add and 100ml there-necked flask obtains reactant liquor, then add the silver ammino solution (0.6 that 10mL newly prepares
Mol/L) enter in reactant liquor, then Ag (NH in reactant liquor3)2The quality of OH is 0.95g, at room temperature stirs
Mix 1h, make silver ammonium ion be adsorbed onto poly-(styrene-t) microsphere surface, be warming up to 70 DEG C,
Reacting 7h under nitrogen atmosphere, silver ammonium ion is reduced into nanometer silver uniform deposition in poly-(styrene-first
Base acrylic acid) microsphere surface, it is centrifuged, washs, is dried, to obtain final product.
Embodiment 2
The preparation of poly-(styrene-t)/nanometer silver complex microsphere, it comprises the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: add in 250mL four-hole bottle
15mL (0.1309mol) styrene, 2mL methacrylic acid and 125mL deionized water, be passed through nitrogen drum
After bubble deoxygenation 0.5h, temperature is risen to 70 DEG C, add 0.708g (0.0026mol) potassium peroxydisulfate and cause
Agent, under constant voltage nitrogen is protected, reacts 18h, and the bag filter using molecular cut off to be 3000 filters little
Molecule, to obtain final product；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: take prepared by 4g S1
Poly-(styrene-t) microsphere emulsion, 30g deionized water and 1g polyvinylpyrrolidone are mixed
Close to add and 100ml there-necked flask obtains reactant liquor, then add the silver ammino solution (0.2 that 10mL newly prepares
Mol/L) enter in reactant liquor, then Ag (NH in reactant liquor3)2The quality of OH is 0.32g, at room temperature stirs
Mix 1h, make silver ammonium ion be adsorbed onto poly-(styrene-t) microsphere surface, be warming up to 70 DEG C,
Reacting 9h under nitrogen atmosphere, silver ammonium ion is reduced into nanometer silver uniform deposition in poly-(styrene-first
Base acrylic acid) microsphere surface, it is centrifuged, washs, is dried, to obtain final product.
Embodiment 3
The preparation of poly-(styrene-t)/nanometer silver complex microsphere, it comprises the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: add in 250mL four-hole bottle
15mL (0.1309mol) styrene, 3mL methacrylic acid and 125mL deionized water, be passed through nitrogen drum
After bubble deoxygenation 0.5h, temperature is risen to 75 DEG C, add 0.590g (0.0022mol) potassium peroxydisulfate and cause
Agent, under constant voltage nitrogen is protected, reacts 12h, and the bag filter using molecular cut off to be 3000 filters little
Molecule, to obtain final product；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: take prepared by 4g S1
Poly-(styrene-t) microsphere emulsion, 30g deionized water and 1g polyvinylpyrrolidone are mixed
Close to add and 100ml there-necked flask obtains reactant liquor, then add the silver ammino solution (0.4 that 10mL newly prepares
Mol/L) enter in reactant liquor, then Ag (NH in reactant liquor3)2The quality of OH is 0.63g, at room temperature stirs
Mix 1h, make silver ammonium ion be adsorbed onto poly-(styrene-t) microsphere surface, be warming up to 75 DEG C,
Under nitrogen atmosphere react 12h, silver ammonium ion be reduced into nanometer silver uniform deposition poly-(styrene-
Methacrylic acid) microsphere surface, it is centrifuged, washs, is dried, to obtain final product.
Embodiment 4
The preparation of poly-(styrene-t)/nanometer silver complex microsphere, it comprises the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: add in 250mL four-hole bottle
15mL (0.1309mol) styrene, 2mL methacrylic acid and 125mL deionized water, be passed through nitrogen drum
After bubble deoxygenation 1h, temperature is risen to 70 DEG C, adds 0.593g (0.0026mol) ammonium persulfate initiator,
Under constant voltage nitrogen is protected, reacting 24h, the bag filter using molecular cut off to be 3000 filters little molecule,
Obtain；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: take prepared by 4g S1
Poly-(styrene-t) microsphere emulsion, 30g deionized water and 1g polyvinylpyrrolidone are mixed
Close to add and 100ml there-necked flask obtains reactant liquor, then add the silver ammino solution (0.4 that 10mL newly prepares
Mol/L) enter in reactant liquor, then Ag (NH in reactant liquor3)2The quality of OH is 0.63g, at room temperature stirs
Mix 1h, make silver ammonium ion be adsorbed onto poly-(styrene-t) microsphere surface, be warming up to 75 DEG C,
Reacting 9h under nitrogen atmosphere, silver ammonium ion is reduced into nanometer silver uniform deposition in poly-(styrene-first
Base acrylic acid) microsphere surface, it is centrifuged, washs, is dried, to obtain final product.
Embodiment 5
The preparation of poly-(styrene-t)/nanometer silver complex microsphere, it comprises the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: add in 250mL four-hole bottle
15mL (0.1309mol) styrene, 2mL methacrylic acid and 125mL deionized water, be passed through nitrogen drum
After bubble deoxygenation 0.8h, temperature is risen to 70 DEG C, add 0.548g (0.0.0023mol) sodium peroxydisulfate and cause
Agent, under constant voltage nitrogen is protected, reacts 24h, and the bag filter using molecular cut off to be 3000 filters little
Molecule, to obtain final product；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: take prepared by 4g S1
Poly-(styrene-t) microsphere emulsion, 30g deionized water and 1g polyvinylpyrrolidone are mixed
Close to add and 100ml there-necked flask obtains reactant liquor, then add the silver ammino solution (0.4 that 10mL newly prepares
Mol/L) enter in reactant liquor, then Ag (NH in reactant liquor3)2The quality of OH is 0.63g, at room temperature stirs
Mix 1h, make silver ammonium ion be adsorbed onto poly-(styrene-t) microsphere surface, be warming up to 75 DEG C,
Reacting 9h under nitrogen atmosphere, silver ammonium ion is reduced into nanometer silver uniform deposition in poly-(styrene-first
Base acrylic acid) microsphere surface, it is centrifuged, washs, is dried, to obtain final product.
Detection example:
Poly-(the styrene-t)/nanometer silver complex microsphere prepared with embodiment 1 is for detection
Sample, obtains its transmission electron microscope picture, grain size distribution and its catalysis sodium borohydride through pertinent instruments test
(NaBH4) uv absorption spectra that reacts of deoxidization, degradation methylene blue (MB).
Fig. 1 is poly-(styrene-t)/nanometer silver complex microsphere that embodiment 1 is prepared
Transmission electron microscope picture, the particle diameter of the most poly-(styrene-t) microsphere is about
250-300nm, and the dispersed deposition in its surface has nanometer silver, the particle diameter of the nanometer silver of deposition is about
30-50nm。
Fig. 2 is poly-(styrene-t)/nanometer silver complex microsphere that embodiment 1 is prepared
Grain size distribution, as can be known from Fig. 2, poly-(styrene-t)/nanometer silver complex microsphere
Particle diameter is distributed between 180-480nm, and mean diameter is 305.3nm, and polydispersity coefficient is 0.33.
Poly-(styrene-t)/nanometer silver complex microsphere catalysis boron of Fig. 3 embodiment 1 preparation
Sodium hydride (NaBH4) ultra-violet absorption spectrum that reacts of deoxidization, degradation methylene blue (MB).Concrete survey
Examination process is: poly-(the styrene-t)/nanometer silver complex microsphere prepared by experimental example 1
Dispersion obtains the dispersion liquid of 0.03mg/mL in deionized water, takes above-mentioned dispersion liquid 1mL and joins 3mL
Concentration is in methylene blue (MB) solution of 3mg/mL, adds 0.5mL in above-mentioned solution simultaneously
Concentration is the sodium borohydride (NaBH of 10mg/mL4) solution, then tested methylene every one minute
Blue ultra-violet absorption spectrum, with the situation illustrating Methylene Blue in Solution to be degraded.Fig. 4 is not for add catalysis
Sodium borohydride (NaBH during agent4) ultra-violet absorption spectrum that reacts of deoxidization, degradation methylene blue (MB),
Its test process is same as described above, difference for do not add poly-(styrene-t)/
Nanometer silver complex microsphere.Knowable to the contrast of Fig. 3 and Fig. 4, poly-(styrene-first prepared by the present invention
Base acrylic acid)/nanometer silver complex microsphere has fine catalytic capability.In order to reflect other of this complex microsphere
Catalytic performance, poly-(styrene-t)/nanometer silver that embodiment 1 is also prepared by the present invention is multiple
Close above-mentioned catalytic degradation test of reforming under similarity condition after microsphere is placed 3 months under the conditions of normal temperature drying,
The ultraviolet absorpting spectrum that test obtains almost is completely superposed with Fig. 3, and this shows to a certain extent, nanometer silver
Stronger at the ratio of poly-(styrene-t) microsphere surface dispersed deposition, the most over time
Elapse and reunite, therefore poly-(styrene-t)/nanometer silver that the present invention provides can effectively prevent
Nanometer silver is reunited, and the durability of its catalytic performance is preferable.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all in the present invention
Spirit and principle within, any modification, equivalent substitution and improvement etc. made, should be included in this
Within bright protection domain.
Claims (9)
1. poly-(styrene-t)/nanometer silver complex microsphere, it is characterised in that
Nanometer silver group by the dispersed deposition of poly-(styrene-t) microsphere and surface thereof
Becoming, nanometer silver is 20-30:60 with the part by weight of poly-(styrene-t).
Poly-(the styrene-t)/nanometer silver of one the most according to claim 1
Complex microsphere, it is characterised in that described poly-(styrene-t) microsphere average
Particle diameter is 250-300nm.
Poly-(the styrene-t)/nanometer silver of one the most according to claim 1
Complex microsphere, it is characterised in that the mean diameter of described nanometer silver is 30-50nm.
4. poly-(styrene-t) as described in any one of claims 1 to 3
The preparation method of/nanometer silver complex microsphere, it is characterised in that comprise the steps:
The preparation of the most poly-(styrene-t) microsphere emulsion: press in reaction vessel
According to the volume ratio of 15:1-3:125 by the most mixed to styrene, methacrylic acid and deionized water
Close, be passed through nitrogen bubble more than deoxygenation 0.5h, be warming up to 70-75 DEG C, add persulfate class
Initiator, described styrene is 50-60:1 with the mol ratio of persulfate class initiator, constant voltage
Under nitrogen protection, reacting 12-24h, dialysis filters little molecule, to obtain final product；
The preparation of the most poly-(styrene-t)/nanometer silver complex microsphere: by polyethylene
Poly-(styrene-t) microsphere emulsion prepared by ketopyrrolidine, deionized water and S1
It is sufficiently mixed to obtain reactant liquor according to the weight ratio of 1:30:4, then adds suitable in reactant liquor
The silver ammino solution of the new preparation of amount, joins what the silver ammino solution in reactant liquor contained
Ag(NH3)2OH and the weight ratio of poly-(styrene-t) microsphere emulsion in reactant liquor
Example is 0.32-0.95:4, stirs 1-1.5h under room temperature, makes silver ammonium ion be adsorbed onto poly-(styrene
-methacrylic acid) microsphere surface, it is warming up to 70-75 DEG C, reacts 7-12h under nitrogen atmosphere,
Silver ammonium ion is reduced into nanometer silver and dispersed is deposited on poly-(styrene-t)
Microsphere surface, is centrifuged, washs, is dried, to obtain final product.
Poly-(the styrene-t)/nanometer silver of one the most according to claim 4
The preparation method of complex microsphere, it is characterised in that the persulfate class initiator described in S1
For potassium peroxydisulfate, sodium peroxydisulfate or Ammonium persulfate..
Poly-(the styrene-t)/nanometer silver of one the most according to claim 4
The preparation method of complex microsphere, it is characterised in that the styrene described in S1 and persulfate
The mol ratio of class initiator is 57:1.
Poly-(the styrene-t)/nanometer silver of one the most according to claim 4
The preparation method of complex microsphere, it is characterised in that in S1, during dialysis, employing molecular cut off is
The bag filter of 3000.
Poly-(the styrene-t)/nanometer silver of one the most according to claim 4
The preparation method of complex microsphere, it is characterised in that the polyvinylpyrrolidone described in S2
Weight average molecular weight is 13000.
Poly-(the styrene-t)/nanometer silver of one the most according to claim 4
The preparation method of complex microsphere, it is characterised in that the silver ammino solution of the new preparation described in S2
Concentration be 0.2-0.6mol/L.
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| CN107243319A (en) * | 2017-07-10 | 2017-10-13 | 湖北大学 | A kind of preparation method of polyacrylic acid modified tourmaline silver composite material |
| CN107456996A (en) * | 2017-07-17 | 2017-12-12 | 湖北大学 | A kind of pH/ responsive to temperature type complex microsphere and its preparation method and application |
| CN110354849A (en) * | 2018-03-26 | 2019-10-22 | 中国石油化工股份有限公司 | Loading type silver catalyst and its preparation method and application |
| CN110669162A (en) * | 2019-10-21 | 2020-01-10 | 长春市联禹化学科技有限公司 | Preparation method of monodisperse polymer/metal conductive microspheres |
| CN112091231A (en) * | 2020-08-25 | 2020-12-18 | 广东工业大学 | Nano silver particles with different shapes and preparation method thereof |
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| CN107243319A (en) * | 2017-07-10 | 2017-10-13 | 湖北大学 | A kind of preparation method of polyacrylic acid modified tourmaline silver composite material |
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| CN110354849A (en) * | 2018-03-26 | 2019-10-22 | 中国石油化工股份有限公司 | Loading type silver catalyst and its preparation method and application |
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| CN110669162A (en) * | 2019-10-21 | 2020-01-10 | 长春市联禹化学科技有限公司 | Preparation method of monodisperse polymer/metal conductive microspheres |
| CN112091231A (en) * | 2020-08-25 | 2020-12-18 | 广东工业大学 | Nano silver particles with different shapes and preparation method thereof |
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