CN104151471B - Nano silver/polystyrene hollow composite microsphere and preparation method thereof - Google Patents
Nano silver/polystyrene hollow composite microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN104151471B CN104151471B CN201410317883.9A CN201410317883A CN104151471B CN 104151471 B CN104151471 B CN 104151471B CN 201410317883 A CN201410317883 A CN 201410317883A CN 104151471 B CN104151471 B CN 104151471B
- Authority
- CN
- China
- Prior art keywords
- silver
- polystyrene
- nanometer silver
- complex microsphere
- polystyrene hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 43
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 35
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title abstract description 38
- 239000002131 composite material Substances 0.000 title abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000004332 silver Substances 0.000 claims abstract description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 4
- -1 silver ions Chemical class 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 244000061458 Solanum melongena Species 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 125000002560 nitrile group Chemical group 0.000 abstract description 2
- 238000005191 phase separation Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 239000003242 anti bacterial agent Substances 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a nano-silver/polystyrene hollow composite microsphere and a preparation method thereof, which take acrylic acid and acrylonitrile as functional monomers, prepare polystyrene microspheres with the surfaces modified by carboxyl and nitrile groups together by adopting a double-in-situ miniemulsion polymerization process, prepare hollow polystyrene microspheres with silicon dioxide as cores by utilizing the phase separation effect of the extended polystyrene and ethyl orthosilicate, the in-situ hydrolysis of the ethyl orthosilicate and the in-situ polymerization of styrene, then dropwise add silver nitrate, and prepare the nano-silver/polystyrene hollow composite microsphere under the reduction effect of hydrazine hydrate by electrostatically adsorbing silver ions. The method provided by the invention has the advantages of simple process, mild conditions and easiness in control, and the obtained microspheres are uniform in nano-silver coating and high in coating rate.
Description
Technical field
The invention belongs to inorganic/polymer composites field, particularly relate to nanometer silver/polystyrene hollow complex microsphere and
Its preparation method.
Background technology
Antibacterial product is known as being environmental protection and healthy product by countries in the world, and there are the biggest need in market at home and abroad
Ask, be widely used in the fields such as plastics, fiber, medical treatment, building, chemical industry；Person to person, people have fundamentally been stopped in its use
And the cross infection between thing, thing and thing.Anti-biotic material is just towards nano-antibacterial technology and inorganic/polymer nano nano antibacterial at present
Material direction is developed.Nano-class antibacterial material refers to make nano-class antibacterial agent by certain method and technology, then make its with
Antibacterial carrier is combined, and preparation has the material of antibacterial functions.Research shows, in numerous metallic elements, silver be sterilizing ability
By force, and nontoxic, tasteless, Heat stability is good, is one of presently preferred antibacterial.Therefore, the research master to nano anti-biotic material
Nano silver particles to be concentrated on makees the nanometer silver system anti-biotic material of antibacterial；Silver-series antibacterial agent no doubt has sterilizing ability strong, big
The plurality of advantages such as specific surface area, superpower activity and permeability；But silver easily variable color itself, manufacture difficult, expensive, limit
Its application.Thus prepare inorganic/polymer anti-biotic material by compound to nano silver particles and polymer, both retain the main of bi-component
Characteristic, also obtains the excellent properties that stock blend does not possesses.
Owing to the specific surface area of nanometer silver is very big, surface atom number is many, surface energy is high and there is substantial amounts of surface defect,
Easily there is agglomeration between granule, be difficult to after reunion by mechanical method its depolymerization, the anti-of material can be largely effected on
Bacterium performance.Therefore preparing the core content of antimicrobial composite material is to control nanometer silver degree of scatter in the polymer and particle diameter divides
Cloth.At present, polymer is modified, increases the interaction between nanometer silver and polymer, the group of nanometer silver can be reduced
Poly-effect.Accordingly, it would be desirable to study novel polymerization technique further, the functional groups such as carboxyl, itrile group, hydroxyl amino are introduced
In polymer, thus effectively solve the stabilization problem of nanometer silver.
Summary of the invention
It is an object of the invention to provide a kind of nanometer silver/polystyrene hollow complex microsphere and preparation method thereof.
The present invention adopts the following technical scheme that to achieve these goals
Nanometer silver/polystyrene hollow complex microsphere, it is characterised in that: it is to be hollow kernel with silicon dioxide, polyphenyl
Ethylene is shell, and surface in situ reduction generates the complex microsphere of nanometer silver；It is made up of the raw material of following weight parts:
Styrene 8-10
γ-methacryloxypropyl trimethoxy silane 0.6-0.8
Tetraethyl orthosilicate 4-6
Divinylbenzene 0.5-1
Hexadecane 0.7-0.9
Azodiisobutyronitrile 0.10-0.20
Methacrylic acid 1.5-2
Acrylonitrile 0.9-1.1
Hydrazine hydrate 9-10
Polyvinyl pyrrolidone 0.3-0.5
Silver nitrate 0.3-0.5
Dodecyl sodium sulfate 0.01-0.05
Water 90-100
The ammonia 1.0-1.5 of mass fraction about 28%.
Described nanometer silver/polystyrene hollow complex microsphere, it is characterised in that: described nanometer silver/polystyrene is empty
Heart complex microsphere uses mini-emulsion polymerization in situ to prepare.
Described nanometer silver/polystyrene hollow complex microsphere, it is characterised in that: described nanometer silver/polystyrene is empty
The particle diameter of heart complex microsphere is 500nm.
Described nanometer silver/polystyrene hollow complex microsphere, it is characterised in that: comprise the following steps:
(1) styrene, hexadecane, γ-methacryloxypropyl trimethoxy silane, positive silicic acid are taken by weight
Ethyl ester, divinylbenzene, methacrylic acid, azodiisobutyronitrile fully dissolve after mixing as oil phase, then take ten by weight
Dialkyl sulfonates is soluble in water to be slowly added to oil phase in aqueous phase, pre-emulsification 0.4-0.5h as aqueous phase, utilizes under ice-water bath
High-speed shearing equipment is fine crankshaft 5-6min under the rotating speed of about 16000rpm, and is immediately transferred in there-necked flask, stirring
The most logical nitrogen 0.5-1h, to get rid of system air, at 65-70 DEG C after water-bath 1-1.5h, drips acrylonitrile by weight,
Continue reaction 1.5-2h, then drip ammonia by weight, continue reaction；
(2) silver nitrate, polyvinyl pyrrolidone are the most fully mixed, after continuing reaction about 6h, by 10 seconds/
The mixed liquor of silver nitrate and polyvinyl pyrrolidone is joined in reaction system by the rate of addition of left and right, and room temperature stands 2-
3h, then drip hydrazine hydrate by weight, present aubergine to reaction system, centrifugal, purification, to obtain final product.
The principle of the present invention is:
With acrylic acid and acrylonitrile as function monomer, double mini-emulsion polymerization technique in situ is used to prepare surface by carboxyl and nitrile
The polystyrene microsphere that base is jointly modified, utilizes the polystyrene and the phase separation of tetraethyl orthosilicate and positive silicic acid second increased
The in-situ hydrolysis of ester and cinnamic in-situ polymerization, prepared kernel is the hollow polystyrene microsphere of silicon dioxide, drips nitre afterwards
Acid silver, by Electrostatic Absorption silver ion, under the reduction of hydrazine hydrate, prepares nanometer silver/polystyrene hollow and is combined micro-.
The present invention, with carboxyl and nitrile-group modification polymer, utilizes the phase between the polymer-modified and tetraethyl orthosilicate increased
Separation principle, is coated with tetraethyl orthosilicate in the polymer, hydrolyzes under the effect of ammonia, forms silicon dioxide granule, volume
Reducing, form hollow structure, drip silver nitrate solution afterwards, modified polystyrene Electrostatic Absorption silver ion, with hydrazine hydrate for also
Former dose, in-situ reducing generates nano silver particles, prepares nano silver/polymer complex microsphere.
Beneficial effects of the present invention:
(1) use mini-emulsion polymerization technique to prepare the surface microsphere by the modification jointly of carboxyl, itrile group, there is polymerization technique
Simply, reaction condition is gentle, reacts the features such as easily controllable and operation.
(2) modified microsphere room temperature Adsorption For Ag ion is used, silver/polymer composite microsphere prepared by in-situ reducing nanometer silver,
There is microsphere surface nano silver particles be uniformly dispersed, the features such as the monodispersity of microsphere is good.
(3) silver/polymer composite microsphere prepared by this method, the absorption of silver ion and degree of scatter can be changed by acrylonitrile
Property microsphere control, simple and convenient, it is easy to implement.
(4) preparation of silver/polymer composite microsphere, can be in field application such as anti-biotic materials.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of nanometer silver/polystyrene hollow complex microsphere；
Detailed description of the invention,
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Prepare silicon dioxide/polystyrene microsphere and include following raw materials according:
Styrene 8 parts
γ-methacryloxypropyl trimethoxy silane 0.6 part
Tetraethyl orthosilicate 5 parts
Divinylbenzene 0.6 part
Hexadecane 0.8 part
Azodiisobutyronitrile 0.15 part
Methacrylic acid 1.6
Acrylonitrile 1 part
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.01 part
95 parts of water
Ammonia 1.5 parts (mass fraction 28%)
Concrete preparation method is as follows:
Weigh styrene, hexadecane, γ-methacryloxypropyl trimethoxy silane, tetraethyl orthosilicate, divinyl
Base benzene, methacrylic acid, azodiisobutyronitrile, as oil phase, weigh dodecyl sodium sulfate soluble in water as aqueous phase, treat oil
It is slowly added to after being uniformly mixed mutually in aqueous phase, room temperature magnetic agitation pre-emulsification 30min, then utilizes at a high speed under ice-water bath
Shearing equipment is fine crankshaft 5min under the rotating speed of 16000rpm, transfers to mixture equipped with thermometer, agitator and returned cold
In tetra-mouthfuls of round-bottomed flasks of 250mL of solidifying pipe, logical N under stirring230min, then water-bath 68 DEG C reaction 1h, drips acrylonitrile,
Continue reaction 1.5h, then drip NH3·H2O continues reaction.
Prepare nanometer silver/polystyrene hollow complex microsphere and include following raw materials according:
Polyvinyl pyrrolidone 0.3 part
Silver nitrate 0.3 part
Hydrazine hydrate 10 parts
Concrete preparation method is as follows:
Weigh silver nitrate, polyvinyl pyrrolidone, magnetic agitation mix homogeneously, after above-mentioned steps reaction 6h, start
Being added drop-wise in reaction system by the rate of addition of 10 seconds/, room temperature stands 2h, drips hydrazine hydrate afterwards, presents purple to reaction system
Redness, centrifugal, purification, to obtain final product, structure chart is as shown in Figure 1.
Embodiment 2
Prepare silicon dioxide/polystyrene microsphere and include following raw materials according:
Styrene 8 parts
γ-methacryloxypropyl trimethoxy silane 0.8 part
Tetraethyl orthosilicate 5 parts
Divinylbenzene 0.6 part
Hexadecane 0.8 part
Azodiisobutyronitrile 0.15 part
Methacrylic acid 1.6
Acrylonitrile 1 part
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.01 part
95 parts of water
Ammonia 1.5 parts (mass fraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
Raw material and the concrete preparation method of preparing nanometer silver/polystyrene hollow complex microsphere are as follows
(with embodiment 1)
Embodiment 3
Prepare silicon dioxide/polystyrene microsphere and include following raw materials according:
Styrene 8 parts
γ-methacryloxypropyl trimethoxy silane 0.6 part
Tetraethyl orthosilicate 5 parts
Divinylbenzene 0.6 part
Hexadecane 0.8 part
Azodiisobutyronitrile 0.15 part
Methacrylic acid 1.6
Acrylonitrile 0 part
Disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.01 part
95 parts of water
Ammonia 1.5 parts (mass fraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
Raw material and the concrete preparation method of preparing nanometer silver/polystyrene hollow complex microsphere are as follows
(with embodiment 1)
Embodiment 4
Prepare silicon dioxide/polystyrene microsphere and include that following raw materials according and concrete preparation method are as follows
(with embodiment 1)
Prepare nanometer silver/polystyrene hollow complex microsphere and include following raw materials according:
Polyvinyl pyrrolidone 0.4 part
Silver nitrate 0.4 part
Hydrazine hydrate 10 parts
Concrete preparation method is as follows:
(with embodiment 1).
Claims (3)
1. nanometer silver/polystyrene hollow complex microsphere, it is characterised in that: it is to be hollow kernel with silicon dioxide, polyphenyl second
Alkene is shell, and surface in situ reduction generates the complex microsphere of nanometer silver；It is made up of the raw material of following weight parts:
Styrene 8-10
γ-methacryloxypropyl trimethoxy silane 0.6-0.8
Tetraethyl orthosilicate 4-6
Divinylbenzene 0.5-1
Hexadecane 0.7-0.9
Azodiisobutyronitrile 0.10-0.20
Methacrylic acid 1.5-2
Acrylonitrile 0.9-1.1
Hydrazine hydrate 9-10
Polyvinyl pyrrolidone 0.3-0.5
Silver nitrate 0.3-0.5
Dodecyl sodium sulfate 0.01-0.05
Water 90-100
The ammonia 1.0-1.5 of mass fraction about 28%；
The preparation method of described nanometer silver/polystyrene hollow complex microsphere, comprises the following steps:
(1) styrene, hexadecane, γ-methacryloxypropyl trimethoxy silane, positive silicic acid second are taken by weight
Ester, divinylbenzene, methacrylic acid, azodiisobutyronitrile fully dissolve after mixing as oil phase, then take 12 by weight
Sodium alkyl sulfonate is soluble in water to be slowly added to oil phase in aqueous phase, pre-emulsification 0.4-0.5h as aqueous phase, utilizes height under ice-water bath
Speed shearing equipment fine crankshaft 5-6min under the rotating speed of about 16000rpm, and be immediately transferred in there-necked flask, under stirring
Logical nitrogen 0.5-1h, to get rid of system air, at 65-70 DEG C after water-bath 1-1.5h, drips acrylonitrile by weight, continues
Continuous reaction 1.5-2h, then drip ammonia by weight, continue reaction；
(2) silver nitrate, polyvinyl pyrrolidone are the most fully mixed, after continuing reaction about 6h, by 10 seconds/left sides
The mixed liquor of silver nitrate and polyvinyl pyrrolidone is joined in reaction system by right rate of addition, and room temperature stands 2-3h,
Drip hydrazine hydrate the most by weight, present aubergine to reaction system, centrifugal, purification, to obtain final product.
Nanometer silver the most according to claim 1/polystyrene hollow complex microsphere, it is characterised in that: described nanometer silver/
Polystyrene hollow complex microsphere uses mini-emulsion polymerization in situ to prepare.
Nanometer silver the most according to claim 1/polystyrene hollow complex microsphere, it is characterised in that: described nanometer silver/
The particle diameter of polystyrene hollow complex microsphere is 500nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410317883.9A CN104151471B (en) | 2014-07-03 | 2014-07-03 | Nano silver/polystyrene hollow composite microsphere and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410317883.9A CN104151471B (en) | 2014-07-03 | 2014-07-03 | Nano silver/polystyrene hollow composite microsphere and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104151471A CN104151471A (en) | 2014-11-19 |
| CN104151471B true CN104151471B (en) | 2016-11-16 |
Family
ID=51877112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410317883.9A Expired - Fee Related CN104151471B (en) | 2014-07-03 | 2014-07-03 | Nano silver/polystyrene hollow composite microsphere and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104151471B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892833B (en) * | 2015-05-21 | 2017-03-29 | 安徽大学 | A kind of preparation method of the hollow microgel of polyacrylic acid |
| CN105153453B (en) * | 2015-07-01 | 2018-06-15 | 安徽大学 | Nanometer Copper/polymeric hollow complex microsphere and preparation method thereof |
| CN105895192B (en) * | 2016-06-24 | 2017-10-20 | 四川艾尔法泰克科技有限公司 | Low-temperature conductive silver paste and preparation method thereof |
| CN112225973B (en) * | 2020-10-13 | 2023-02-03 | 河南工业大学 | Insect-proof packaging material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007078038A1 (en) * | 2005-12-30 | 2007-07-12 | Cheil Industries Inc. | Thermoplastic nanocomposite resin composite materials |
| CN101381423A (en) * | 2008-09-10 | 2009-03-11 | 厦门大学 | Method for preparing silver-coating polystyrene nano granule |
-
2014
- 2014-07-03 CN CN201410317883.9A patent/CN104151471B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007078038A1 (en) * | 2005-12-30 | 2007-07-12 | Cheil Industries Inc. | Thermoplastic nanocomposite resin composite materials |
| CN101381423A (en) * | 2008-09-10 | 2009-03-11 | 厦门大学 | Method for preparing silver-coating polystyrene nano granule |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104151471A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104151471B (en) | Nano silver/polystyrene hollow composite microsphere and preparation method thereof | |
| CN105754021B (en) | A kind of grain magnetic polymer microsphere preparation method | |
| CN100425627C (en) | Preparation process of magnetic partical/polymer/silicon dioxide structure magnetic microball | |
| CN103342991B (en) | Composite nanocapsule phase-change material and preparation method thereof | |
| CN106268680A (en) | Magnetic Nano microcapsule adsorbent and its preparation method and application | |
| CN103223322B (en) | Preparation method of nanosilver and sulfydryl jointly modified magnetic microspheres | |
| CN103194134B (en) | Preparation method of antibacterial coating | |
| CN101544718A (en) | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix | |
| CN104530294A (en) | High-strength silicon dioxide and clay dual nano-composite hydrogel and preparation method thereof | |
| CN102964539A (en) | Preparation method of porous magnetic polystyrene microspheres | |
| CN114160061B (en) | Bionic structure antibacterial microcapsule and preparation method and application thereof | |
| CN104072659A (en) | Magnetic resin microspheres and preparation method thereof | |
| CN106478903A (en) | A kind of nanometer silver antimicrobial emulsion | |
| CN103936019B (en) | A kind of preparation method of homogeneous magnetic nanometer silicon dioxide particle | |
| CN107768061B (en) | A kind of preparation method of packet silicon nanoscale magnetic bead | |
| CN103054831B (en) | Magnetic silicon dioxide/polystyrene composite shell-structure nano microcapsules and preparation method thereof | |
| He et al. | Morphology design and synthesis of magnetic microspheres as highly efficient reusable catalyst for organic dyes | |
| CN106430222B (en) | A kind of nano silica microsphere and preparation method thereof | |
| CN101927147B (en) | Nano-scale magnetic silicon dioxide composite microsphere and preparation method thereof | |
| CN103396505A (en) | Preparation method of pure cationic nanosphere | |
| CN104485191A (en) | Magnetic hollow nanometer ball and preparation method thereof | |
| Liu et al. | Synthesis of tri-layer hybrid microspheres with magnetic core and functional polymer shell | |
| CN101444712B (en) | Method for producing size-controllable magnetic hollow spheres | |
| WO2011019180A3 (en) | Electrostatic image-developing toner | |
| CN104558993A (en) | Modified polyvinyl alcohol membrane and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161116 |