CN104151471A - Nano-silver/polystyrene hollow composite microspheres and preparation method thereof - Google Patents
Nano-silver/polystyrene hollow composite microspheres and preparation method thereof Download PDFInfo
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- CN104151471A CN104151471A CN201410317883.9A CN201410317883A CN104151471A CN 104151471 A CN104151471 A CN 104151471A CN 201410317883 A CN201410317883 A CN 201410317883A CN 104151471 A CN104151471 A CN 104151471A
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Abstract
The invention discloses nano-silver/polystyrene hollow composite microspheres and a preparation method thereof. The preparation method comprises the following steps: by taking acrylic acid and acrylonitrile as functional monomers, preparing polystyrene microspheres of which the surfaces are jointly modified by carboxyl and nitrile groups by adopting a dual-in-situ miniemulsion polymerization process, preparing hollow polystyrene microspheres taking silicon dioxide as cores by utilizing the growing phase separation effect of polystyrene and tetraethyl orthosilicate, in-situ hydrolysis of tetraethyl orthosilicate and in-situ polymerization of styrene, then dropping silver nitrate, adsorbing silver ions by static electricity, and preparing the nano-silver/polystyrene hollow composite microspheres under the reduction action of hydrazine hydrate. The method provided by the invention has the advantages of simple process, mild conditions and easiness in control, the obtained microspheres are uniformly coated with nano-silver, and the coating rate is high.
Description
Technical field
The invention belongs to inorganic/polymer composites field, relate in particular to nanometer silver/polystyrene hollow compound microsphere and preparation method thereof.
Background technology
It is environmental protection and healthy product that antimicrobial prod is known as by countries in the world, and there is very large demand in market at home and abroad, is widely used in the fields such as plastics, fiber, medical treatment, building, chemical industry; The cross infection between person to person, people and thing, thing and thing has fundamentally been stopped in its use.Anti-biotic material is just towards nano-antibacterial technology and inorganic/polymer nanocomposite anti-biotic material future development at present.Nano-class antibacterial material refers to by certain method and technology makes nano-class antibacterial agent, then makes itself and antibacterial carrier compound, and preparation has the material of antibacterial.Research shows, in numerous metallic elements, silver is that sterilizing ability is the strongest, and nontoxic, tasteless, and Heat stability is good is one of first-selected at present antiseptic-germicide.Therefore, the research of nano anti-biotic material mainly being concentrated on to nano silver particles, to make the nanometer silver of antiseptic-germicide be anti-biotic material; Silver-series antibacterial agent no doubt has the specific surface area that sterilizing ability is strong, large, the superpower plurality of advantages such as activity and perviousness; But very easily variable color of silver itself, manufacture difficulty, expensive, limit its application.Thereby by inorganic to nano silver particles and the compound preparation of polymkeric substance/polymkeric substance anti-biotic material, both retained the main characteristics of two-pack, also obtain the excellent properties that stock blend does not possess.
Because the specific surface area of nanometer silver is very large, surface atom number is many, surface can be high and have a large amount of surface imperfection, and agglomeration very easily occurs between particle, reunite and be difficult to afterwards by mechanical method, to its depolymerization, can greatly affect the anti-microbial property of material.Therefore the core content of preparing antimicrobial composite material is to control degree of scatter and the size distribution of nanometer silver in polymkeric substance.At present, polymkeric substance is carried out to modification, increase the interaction between nanometer silver and polymkeric substance, can reduce the agglomeration of nanometer silver.Therefore, further the novel polymerization technique of research, is incorporated into the functional groups such as carboxyl, itrile group, hydroxyl amino in polymkeric substance, thereby effectively solves the stabilization problem of nanometer silver.
Summary of the invention
The object of this invention is to provide a kind of nanometer silver/polystyrene hollow compound microsphere and preparation method thereof.
The present invention adopts following technical scheme to achieve these goals:
Nanometer silver/polystyrene hollow compound microsphere, is characterized in that: it is taking silicon-dioxide as hollow kernel, and polystyrene is shell, and surface in situ reduction generates the complex microsphere of nanometer silver; It is to be made up of the raw material of following weight parts:
Vinylbenzene 8-10
γ-methacryloxypropyl trimethoxy silane 0.6-0.8
Tetraethoxy 4-6
Vinylstyrene 0.5-1
N-Hexadecane 0.7-0.9
Diisopropyl azodicarboxylate 0.10-0.20
Methacrylic acid 1.5-2
Vinyl cyanide 0.9-1.1
Hydrazine hydrate 9-10
Polyvinylpyrolidone (PVP) 0.3-0.5
Silver Nitrate 0.3-0.5
Sodium laurylsulfonate 0.01-0.05
Water 90-100
The ammoniacal liquor 1.0-1.5 of massfraction 28% left and right.
Described nanometer silver/polystyrene hollow compound microsphere, is characterized in that: described nanometer silver/polystyrene hollow compound microsphere adopts original position mini-emulsion polymerization to prepare.
Described nanometer silver/polystyrene hollow compound microsphere, is characterized in that: the particle diameter of described nanometer silver/polystyrene hollow compound microsphere is 500nm.
Described nanometer silver/polystyrene hollow compound microsphere, is characterized in that: comprise the following steps:
(1) get by weight vinylbenzene, n-Hexadecane, γ-methacryloxypropyl trimethoxy silane, tetraethoxy, Vinylstyrene, methacrylic acid, Diisopropyl azodicarboxylate fully dissolve mix rear as oil phase, get by weight again sodium laurylsulfonate soluble in water as water, oil phase is slowly added in water, pre-emulsification 0.4-0.5h, under ice-water bath, utilize high-speed shearing equipment thin emulsification 5-6min under the rotating speed of 16000rpm left and right, and be transferred to immediately in there-necked flask, under whipped state, logical nitrogen 0.5-1h is to get rid of system air, at 65-70 DEG C after water-bath 1-1.5h, drip by weight vinyl cyanide, continue reaction 1.5-2h, drip by weight again ammoniacal liquor, continue reaction,
(2) fully mix by weight Silver Nitrate, Polyvinylpyrolidone (PVP), continue behind reaction 6h left and right, by the rate of addition of 10 seconds/left and right, the mixed solution of Silver Nitrate and Polyvinylpyrolidone (PVP) is joined in reaction system, normal temperature leaves standstill 2-3h, drip by weight again hydrazine hydrate, present red-purple to reaction system, centrifugal, purify, to obtain final product.
Principle of the present invention is:
Taking vinylformic acid and vinyl cyanide as function monomer, adopt the polystyrene microsphere of two original position mini-emulsion polymerization technique preparations surface by carboxyl and the common modification of itrile group, utilize the polystyrene and the phase separation of tetraethoxy and the in-situ hydrolysis of tetraethoxy and the cinnamic in-situ polymerization that increase, making kernel is the hollow polystyrene microballoon of silicon-dioxide, rear dropping Silver Nitrate, by electrostatic adhesion silver ions, under the reductive action of hydrazine hydrate, prepare nanometer silver/polystyrene Hollow Compound micro-.
The present invention is with carboxyl and nitrile-group modification polymkeric substance, utilize the phase separation principle between the polymer-modified and tetraethoxy increasing, tetraethoxy is coated in polymkeric substance, under the effect of ammoniacal liquor, be hydrolyzed, form silicon dioxide granule, volume-diminished, forms hollow structure, rear dropping silver nitrate solution, the polystyrene electrostatic adhesion silver ions of modification, taking hydrazine hydrate as reductive agent, in-situ reducing generates nano silver particles, prepares nanometer silver/polymer composite microsphere.
Beneficial effect of the present invention:
(1) adopt the microballoon of mini-emulsion polymerization technique preparation surface by carboxyl, the common modification of itrile group, there is polymerization technique simple, reaction conditions gentleness, reaction is easy to the features such as control and operation.
(2) features such as adopt modification microballoon normal temperature Adsorption For Ag ion, silver/polymer composite microsphere prepared by in-situ reducing nanometer silver, has microsphere surface nano silver particles and be uniformly dispersed, and the monodispersity of microballoon is good.
(3) the standby silver/polymer composite microsphere of this legal system, the absorption of silver ions and degree of scatter can be controlled by vinyl cyanide modification microballoon, simple and convenient, easy to implement.
(4) preparation of silver/polymer composite microsphere, can be in field application such as anti-biotic materials.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of nanometer silver/polystyrene hollow compound microsphere;
embodiment,
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
8 parts of vinylbenzene
0.6 part of γ-methacryloxypropyl trimethoxy silane
5 parts of tetraethoxys
0.6 part of Vinylstyrene
0.8 part of n-Hexadecane
0.15 part of Diisopropyl azodicarboxylate
Methacrylic acid 1.6
1 part of vinyl cyanide
0.01 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
95 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
Take vinylbenzene, n-Hexadecane, γ-methacryloxypropyl trimethoxy silane, tetraethoxy, Vinylstyrene, methacrylic acid, Diisopropyl azodicarboxylate is as oil phase, take sodium laurylsulfonate soluble in water as water, after being uniformly mixed, oil phase slowly adds in water, room temperature magnetic agitation pre-emulsification 30min, then under ice-water bath, utilize high-speed shearing equipment thin emulsification 5min under the rotating speed of 16000rpm, mixture is transferred to thermometer is housed, in the 250mL four-hole round-bottomed flask of agitator and reflux condensing tube, logical N under whipped state
230min, then 68 DEG C of reaction 1h of water-bath, drip vinyl cyanide, continue reaction 1.5h, then drip NH
3h
2o continues reaction.
Prepare nanometer silver/polystyrene hollow compound microsphere and comprise following raw materials according:
0.3 part of Polyvinylpyrolidone (PVP)
0.3 part of Silver Nitrate
10 parts of hydrazine hydrates
Concrete preparation method is as follows:
Take Silver Nitrate, Polyvinylpyrolidone (PVP), magnetic agitation mixes, after above-mentioned steps reaction 6h, start to be added drop-wise in reaction system by the rate of addition of 10 seconds/, normal temperature leaves standstill 2h, rear dropping hydrazine hydrate, present red-purple to reaction system, centrifugal, purification, to obtain final product, and structure iron as shown in Figure 1.
Embodiment 2
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
8 parts of vinylbenzene
0.8 part of γ-methacryloxypropyl trimethoxy silane
5 parts of tetraethoxys
0.6 part of Vinylstyrene
0.8 part of n-Hexadecane
0.15 part of Diisopropyl azodicarboxylate
Methacrylic acid 1.6
1 part of vinyl cyanide
0.01 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
95 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
The raw material and the concrete preparation method that prepare nanometer silver/polystyrene hollow compound microsphere are as follows
(with embodiment 1)
Embodiment 3
Prepare silicon-dioxide/polystyrene microsphere and comprise following raw materials according:
8 parts of vinylbenzene
0.6 part of γ-methacryloxypropyl trimethoxy silane
5 parts of tetraethoxys
0.6 part of Vinylstyrene
0.8 part of n-Hexadecane
0.15 part of Diisopropyl azodicarboxylate
Methacrylic acid 1.6
0 part of vinyl cyanide
0.01 part of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate
95 parts, water
1.5 parts of ammoniacal liquor (massfraction 28%)
Concrete preparation method is as follows:
(with embodiment 1)
The raw material and the concrete preparation method that prepare nanometer silver/polystyrene hollow compound microsphere are as follows
(with embodiment 1)
Embodiment 4
Prepare silicon-dioxide/polystyrene microsphere comprise following raw materials according and concrete preparation method as follows
(with embodiment 1)
Prepare nanometer silver/polystyrene hollow compound microsphere and comprise following raw materials according:
0.4 part of Polyvinylpyrolidone (PVP)
0.4 part of Silver Nitrate
10 parts of hydrazine hydrates
Concrete preparation method is as follows:
(with embodiment 1).
Claims (4)
1. nanometer silver/polystyrene hollow compound microsphere, is characterized in that: it is taking silicon-dioxide as hollow kernel, and polystyrene is shell, and surface in situ reduction generates the complex microsphere of nanometer silver; It is to be made up of the raw material of following weight parts:
Vinylbenzene 8-10
γ-methacryloxypropyl trimethoxy silane 0.6-0.8
Tetraethoxy 4-6
Vinylstyrene 0.5-1
N-Hexadecane 0.7-0.9
Diisopropyl azodicarboxylate 0.10-0.20
Methacrylic acid 1.5-2
Vinyl cyanide 0.9-1.1
Hydrazine hydrate 9-10
Polyvinylpyrolidone (PVP) 0.3-0.5
Silver Nitrate 0.3-0.5
Sodium laurylsulfonate 0.01-0.05
Water 90-100
The ammoniacal liquor 1.0-1.5 of massfraction 28% left and right.
2. nanometer silver/polystyrene hollow compound microsphere according to claim 1, is characterized in that: described nanometer silver/polystyrene hollow compound microsphere adopts original position mini-emulsion polymerization to prepare.
3. nanometer silver/polystyrene hollow compound microsphere according to claim 1, is characterized in that: the particle diameter of described nanometer silver/polystyrene hollow compound microsphere is 500nm.
4. nanometer silver/polystyrene hollow compound microsphere as claimed in claim 1, is characterized in that: comprise the following steps:
(1) get by weight vinylbenzene, n-Hexadecane, γ-methacryloxypropyl trimethoxy silane, tetraethoxy, Vinylstyrene, methacrylic acid, Diisopropyl azodicarboxylate fully dissolve mix rear as oil phase, get by weight again sodium laurylsulfonate soluble in water as water, oil phase is slowly added in water, pre-emulsification 0.4-0.5h, under ice-water bath, utilize high-speed shearing equipment thin emulsification 5-6min under the rotating speed of 16000rpm left and right, and be transferred to immediately in there-necked flask, under whipped state, logical nitrogen 0.5-1h is to get rid of system air, at 65-70 DEG C after water-bath 1-1.5h, drip by weight vinyl cyanide, continue reaction 1.5-2h, drip by weight again ammoniacal liquor, continue reaction,
(2) fully mix by weight Silver Nitrate, Polyvinylpyrolidone (PVP), continue behind reaction 6h left and right, by the rate of addition of 10 seconds/left and right, the mixed solution of Silver Nitrate and Polyvinylpyrolidone (PVP) is joined in reaction system, normal temperature leaves standstill 2-3h, drip by weight again hydrazine hydrate, present red-purple to reaction system, centrifugal, purify, to obtain final product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892833A (en) * | 2015-05-21 | 2015-09-09 | 安徽大学 | Preparation method of polyacrylic acid hollow microgel |
| CN105153453A (en) * | 2015-07-01 | 2015-12-16 | 安徽大学 | Nano-copper/polymer hollow composite microsphere and preparation method thereof |
| CN105895192A (en) * | 2016-06-24 | 2016-08-24 | 四川艾尔法泰克科技有限公司 | Low-temperature conductive silver slurry and preparation method thereof |
| CN112225973A (en) * | 2020-10-13 | 2021-01-15 | 河南工业大学 | Insect-proof packaging material and preparation method thereof |
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| 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 active Active
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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892833A (en) * | 2015-05-21 | 2015-09-09 | 安徽大学 | Preparation method of polyacrylic acid hollow microgel |
| CN105153453A (en) * | 2015-07-01 | 2015-12-16 | 安徽大学 | Nano-copper/polymer hollow composite microsphere and preparation method thereof |
| CN105153453B (en) * | 2015-07-01 | 2018-06-15 | 安徽大学 | Nanometer Copper/polymeric hollow complex microsphere and preparation method thereof |
| CN105895192A (en) * | 2016-06-24 | 2016-08-24 | 四川艾尔法泰克科技有限公司 | Low-temperature conductive silver slurry and preparation method thereof |
| CN112225973A (en) * | 2020-10-13 | 2021-01-15 | 河南工业大学 | Insect-proof packaging material 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 |
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