CN109604619A - A kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain - Google Patents
A kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain Download PDFInfo
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- CN109604619A CN109604619A CN201910056301.9A CN201910056301A CN109604619A CN 109604619 A CN109604619 A CN 109604619A CN 201910056301 A CN201910056301 A CN 201910056301A CN 109604619 A CN109604619 A CN 109604619A
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- photopolymerization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
- B22F1/147—Making a dispersion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
Abstract
The invention discloses a kind of methods that styrene-based class monomer uv photopolymerization prepares Nano silver grain; belong to metal powder preparation technical field; the present invention provides light polymerization process to synthesize Nano silver grain; the silver nano-grain of polymerization not only can be almost separated into individual particle, but also vinyl monomer can be adsorbed on the surface of silver nano-grain to play a protective role.In the suspension of the silver nano-grain for the polymerization prepared by discharge-induced explosion method, cause the free radical polymerization of vinyl monomer by ultraviolet radiation, to prepare the monodispersed silver nano-grain with respective ligand.Vinyl monomer is attached on silver nano-grain surface by " photopolymerization and photo-grafting " mechanism, it can be reacted with the oxide skin(coating) of silver nano-grain outer surface by the free radical polyalcohol that ultraviolet induction is formed, the silver nano-grain for promoting polymerization is separated from each other.The silver nano-grain of polymer wrapped shows excellent colloidal stability in various organic solvents.
Description
Technical field
The invention belongs to metal powder preparation technical fields, and in particular to a kind of styrene-based class monomer uv photopolymerization
The method for preparing Nano silver grain.
Background technique
Nano silver grain refers to that crystallite dimension is the ultra-fine ag material of nanoscale, and nano silver particles are due to its good conduction
Property, so that it is occupied extremely important status in microelectronic field.Skin effect, quantum size effect of nano silver particles etc., make
It also has some special purposes, such as surface-enhanced Raman application, medical application.Aspect that there are three main application fields,
Including high-end silver paste, the antibiotic paint of conductive coating and medical field.
The synthetic method for the Nano silver grain being most widely used at present has vaporization condensation process, discharge-induced explosion method and mechanochemistry
Method；Vaporization condensation process energy consumption is big, at high cost, partial size is difficult to control, product stability is poor；The silver nano-grain of discharge-induced explosion method production
Size is larger, Yi Juhe, low stability, thus its application is extremely restricted；Mechanochemical reaction is ground by long-time,
It cannot be guaranteed that all raw materials can participate in reacting, it, can not be with homogeneous reaction because contact surface is smaller after all for solid-phase sequencing
It compares.Therefore how it is original prepare nano silver method on the basis of can preferably control the size of nano silver, improve purity,
Reducing cost will be following some problems urgently to be solved.
Summary of the invention
The purpose of the present invention is provide a kind of simple and effective photopolymerization side for deficiency present in existing preparation method
Method synthesizes Nano silver grain, not only the silver nano-grain of polymerization can be almost separated into individual particle, but also vinyl monomer
The surface of silver nano-grain can be adsorbed on to play a protective role.In the silver nanoparticle for the polymerization prepared by discharge-induced explosion method
In the suspension of grain, vinyl monomer (styrene, methyl methacrylate, N- isopropyl propylene are caused by ultraviolet radiation
Amide and methacrylic acid 2- (dimethylamino) ethyl ester) free radical polymerization, to prepare single point with respective ligand
Scattered silver nano-grain.Vinyl monomer is attached on silver nano-grain surface by " photopolymerization and photo-grafting " mechanism, i.e.,
It can be reacted, be promoted poly- with the oxide skin(coating) of silver nano-grain outer surface by the free radical polyalcohol that ultraviolet induction is formed
The silver nano-grain of conjunction is separated from each other.The silver nano-grain of polymer wrapped shows excellent colloid in various organic solvents
Stability.
The present invention is achieved through the following technical solutions:
A kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain, the specific steps are as follows:
(1), discharge-induced explosion method prepares silver nano-grain；
In an argon atmosphere, by diameter be 0.2mm, purity more than or equal to 95% filamentary silver be fixed on high-field electrode it
Between, with mechanical device continued power, charger capacitor is 96 μ F, and electrode discharge voltage is 4.0-4.4kV, in high-density current
Under, to filamentary silver heating (104K it) and brings it about and is radially expanded, filamentary silver is made to vaporize to form silver-colored steam, then condensation forms diameter and exists
The silver nano-grain of 50-200nm, and be collected in the collector full of argon gas；
(2), uv photopolymerization method separates and stablizes Nano silver grain；
Silver nano-grain prepared by step (1) is dispersed in the mixed solution of vinyl monomer and toluene, wherein Yin Na
The mass volume ratio of the mixed solution of rice grain and vinyl monomer and toluene is 1:1-1:20, vinyl monomer and toluene
Volume ratio is 10:1-1:10；Solution is handled, oxygen is completely removed, mixed solution is then made to be in the atmosphere of nitrogen
In, then mixed solution is placed in photochemical reactor, under ultraviolet light irradiation condition, mixed solution is stirred
8-12h are centrifuged after mixed solution is changed into uniform dark solution by beige suspension liquid, circulation 5-7 times into
Row purifying, to remove remaining polystyrene and unreacted styrene monomer in mixed solution, to obtain diameter 30-
The silver nano-grain of 300nm.
Further, high-density current described in step (1) is (1-5) 1012A/m2。
Further, Photoreactor described in step (2) transmitting a length of 300-400nm of ultraviolet light wave, wavelength be λ=
350nm, general power~5mW/cm2。
Further, stirring rate described in step (2) is 800-1000rpm.
Further, centrifugation rate described in step (2) is 10000rpm, time 15min.
Further, vinyl monomer described in step (2) is styrene, methyl methacrylate, N- isopropyl propylene
Amide or methacrylic acid 2- (dimethylamino) ethyl ester.
The principle of the present invention is as follows:
Under ultraviolet light, photopolymerization reaction occurs in toluene solution for vinyl monomer (0.10g/mL), herein instead
During answering, ultraviolet light can make vinyl monomer scission of link generate free radical, which can be with the oxidation on Nano silver grain surface
Silver layer reacts, by reacting the oxide layer between the Nano silver grain for removing aggregation, to realize state of aggregation nano grain of silver
The separation of son.Simultaneously, the phase emergencing copolymer generated in this photopolymerization reaction can be grafted to Nano silver grain by covalent bond
Surface, to improve glue of the Nano silver grain in a variety of organic solvents (toluene, tetrahydrofuran, dimethylformamide etc.)
Body stability.
Compared with prior art, advantages of the present invention is as follows:
1, the partial size of method preparation of the invention can control, product stability it is high；
2, preparation method of the invention dispersin polymerization nano silver particles simultaneously, it is carried out cladding improve moisture-resistant and
Inoxidizability.
3, light polymerization process used by method of the invention is simple to operation, at low cost, and can promote and apply not office
It is limited to a kind of polymer.
Detailed description of the invention
Fig. 1 is apparatus structure schematic diagram used in discharge-induced explosion method of the invention；
In figure: power supply module 1, explosion chamber 2, filter chamber 3, wire supply chamber 4, supply coil 5, condenser type energy storage device
6, brush 7, inductance 8, discharge loop resistance 9, exploding wire 10, synchronously control panel 11, high voltage converter 12；
Fig. 2 is TEM and the SEM figure of Nano silver grain prepared by the embodiment of the present invention 1；
Wherein, a is the TEM figure of the set Nano silver grain of discharge-induced explosion method preparation, and b is that uv photopolymerization method separates and stablizes
The TEM of Nano silver grain schemes, and c is the SEM figure of the set Nano silver grain of discharge-induced explosion method preparation, and d is the separation of uv photopolymerization method
And stablize the SEM figure of Nano silver grain；
Fig. 3 a is discharge-induced explosion Nano silver grain size distribution histogram；
Fig. 3 b is the high resolution transmission electron microscopy of discharge-induced explosion Nano silver grain；
Fig. 3 c is XPS spectrum figure of the discharge-induced explosion Nano silver grain before and after argon plasma etching；
Fig. 4 is TEM figure of the present invention using the Nano silver grain of differing ethylene base monomer preparation；
Wherein, a is that embodiment 1 uses methyl methacrylate, and b is that embodiment 2 uses methacrylic acid 2- (dimethylamino
Base) ethyl ester, c is that embodiment 3 uses n-isopropyl acrylamide.
Specific embodiment
The present invention is described further with reference to the accompanying drawing.
Embodiment 1
Electric detonation explosion unit works as shown in Figure 1, the voltage of 220/380V is converted to constant height by high voltage converter 11
Voltage U0, and voltage U0 is added on power supply module 1, and is charged for condenser type energy storage device 6.In wire supply chamber 4, by
It supplies coil 5 and conveys wire to explosion chamber 2.After charging, condenser type energy storage device 6 is controlled by synchronously control panel 11
By commutating device 7 and inductance 8 discharges into exploding wire 10., there is particulate cloud after explosion in electric wire explosion.Hanging nanometer
Particle enters in filter chamber 3.
A kind of method that methyl methacrylate monomer uv photopolymerization prepares Nano silver grain, the specific steps are as follows:
(1), discharge-induced explosion method prepares silver nano-grain；
In an argon atmosphere, by diameter be 0.2mm, purity more than or equal to 95% filamentary silver be fixed on high-field electrode it
Between, with mechanical device continued power, charger capacitor is 96 μ F, and electrode discharge voltage is 4.0, under high-density current, to silver
Silk is heated and is brought it about and is radially expanded, and filamentary silver is made to vaporize to form silver-colored steam, and then condensation forms diameter in the silver of 50-200nm
Nano particle, and be collected in the collector full of argon gas；
(2), uv photopolymerization method separates and stablizes Nano silver grain；
Silver nano-grain prepared by step (1) is dispersed in the mixed solution of vinyl monomer and toluene, wherein Yin Na
The mass volume ratio of the mixed solution of rice grain and styrene and toluene is 1:1, the volume of vinyl monomer styrene and toluene
Than for 1:1；Solution is handled, oxygen is completely removed, is in mixed solution in the atmosphere of nitrogen, it then will mixing
Solution is placed in photochemical reactor, under ultraviolet light irradiation condition, is stirred 12h to mixed solution, mixed solution by
It after beige suspension liquid is changed into uniform dark solution, is centrifuged, recycles 5 times and purified, it is molten to remove mixing
Remaining polystyrene and unreacted styrene monomer in liquid, to obtain diameter in the silver nano-grain of 30-300nm, such as
In Fig. 2 b shown in transmission electron microscope (TEM) figure.
Fig. 2 a and Fig. 2 c are respectively the Nano silver grain that discharge-induced explosion method is prepared, as we can see from the figure this particle
Aggregation extent is very serious；Fig. 2 b and d are respectively the Nano silver grain of this method preparation, and as can be seen from the figure most of particle is in
It is now single particle structure.
Embodiment 2
Using another vinyl monomer --- methyl methacrylate is poly- to carry out same light as reaction raw materials
Reaction is closed to have the function that separation and stablize Nano silver grain.The rate of polymerization and styrene list of methyl methacrylate monomer
Body is similar, therefore the ratio of the monomer and solvent toluene is also in the same manner as in Example 1, and keeps the ratio of silver particles and solution
It is constant, to realize similar separating effect.Specifically, the mixing of silver nano-grain and methyl methacrylate monomer and toluene
The mass volume ratio of solution is (1:1), and the mixed proportion of methyl methacrylate monomer and toluene is (1:1).Remaining reaction item
Part and step are identical with example 1.Obtained result is as shown in transmission electron microscope (TEM) figure in Fig. 4 b, partial size model
Enclosing is 50-150nm.
Embodiment 3
Using another vinyl monomer --- methacrylic acid 2- (dimethylamino) ethyl ester comes as reaction raw materials
Same photopolymerization reaction is carried out to have the function that separation and stablize Nano silver grain.Due under the same reaction conditions,
The rate of polymerization of methacrylic acid 2- (dimethylamino) ethyl ester is higher than styrene monomer and methyl methacrylate monomer, because
This needs to reduce the ratio of the monomer and solvent toluene, and keeps the constant rate of silver particles and solution, similar to realize
Separating effect.Specifically, the mass volume ratio of silver nano-grain and methyl methacrylate monomer and the mixed solution of toluene is
The mixed proportion of 1:1, methyl methacrylate monomer and toluene is 1:2.Remaining reaction condition and step and complete phase in example 1
Together.For obtained result as shown in transmission electron microscope (TEM) figure in Fig. 4 b, particle size range is 60-200nm.
Embodiment 4
Using vinyl monomer --- n-isopropyl acrylamide is anti-to carry out same photopolymerization as reaction raw materials
It should be to have the function that separation and stablize Nano silver grain.Under the same reaction conditions, n-isopropyl acrylamide monomer
Rate of polymerization is similar with methacrylic acid 2- (dimethylamino) acetate monomer, therefore, monomer and solvent toluene and silver granuel
Son is identical with example two as the ratio of solution.Specifically, silver nano-grain and methyl methacrylate monomer and toluene
The mass volume ratio of mixed solution is 1:1, and the mixed proportion of methyl methacrylate monomer and toluene is 1:2.Remaining reaction item
Part and step are identical with example 1.Obtained result is as shown in transmission electron microscope (TEM) figure in Fig. 4 c, partial size model
Enclosing is 80-200nm.
Claims (6)
1. a kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain, which is characterized in that specific steps
It is as follows:
(1), discharge-induced explosion method prepares silver nano-grain；
In an argon atmosphere, it is that the filamentary silver of 0.2mm, purity more than or equal to 95% is fixed between high-field electrode by diameter, uses
Mechanical device continued power, charger capacitor are 96 μ F, and electrode discharge voltage is 4.0-4.4kV, under high-density current, to silver
Silk is heated and is brought it about and is radially expanded, and filamentary silver is made to vaporize to form silver-colored steam, and then condensation forms diameter in the silver of 50-200nm
Nano particle, and be collected in the collector full of argon gas；
(2), uv photopolymerization method separates and stablizes Nano silver grain；
Silver nano-grain prepared by step (1) is dispersed in the mixed solution of vinyl monomer and toluene, wherein silver nanoparticle
Grain is 1:1-1:20, the volume of vinyl monomer and toluene with the mass volume ratio of vinyl monomer and the mixed solution of toluene
Than for 10:1-1:10；Solution is handled, oxygen is completely removed, is in mixed solution in the atmosphere of nitrogen, so
Mixed solution is placed in photochemical reactor afterwards, under ultraviolet light irradiation condition, 8-12h are stirred to mixed solution,
It after mixed solution is changed into uniform dark solution by beige suspension liquid, is centrifuged, recycles 5-7 times and purified,
To remove remaining polystyrene and unreacted styrene monomer in mixed solution, to obtain diameter 30-300nm's
Silver nano-grain.
2. a kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain as described in claim 1,
It is characterized in that, high-density current described in step (1) is (1-5) 1012A/m2。
3. a kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain as described in claim 1,
It is characterized in that, a length of 300-400nm of ultraviolet light wave of the transmitting of Photoreactor described in step (2), wavelength is λ=350nm, total work
Rate~5mW/cm2。
4. a kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain as described in claim 1,
It is characterized in that, stirring rate described in step (2) is 800-1000rpm.
5. a kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain as described in claim 1,
It is characterized in that, centrifugation rate described in step (2) is 10000rpm, time 15min.
6. a kind of method that styrene-based class monomer uv photopolymerization prepares Nano silver grain as described in claim 1,
It is characterized in that, vinyl monomer described in step (2) is styrene, methyl methacrylate, n-isopropyl acrylamide or first
Base acrylic acid 2- (dimethylamino) ethyl ester.
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Cited By (1)
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| CN112704734A (en) * | 2019-10-25 | 2021-04-27 | 吉林大学 | Metallic aluminum nano adjuvant, vaccine composition, preparation method and application thereof |
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Application publication date: 20190412 |