CN102059347B - Nano silver capable of being scattered in hydrophobic system and preparation method and application thereof - Google Patents
Nano silver capable of being scattered in hydrophobic system and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses nano silver capable of being scattered in a hydrophobic system and a preparation method and the application thereof. The preparation method comprises the steps of: adding modifiers during the later period of preparing conventional nano silver so as to obtain the nano silver capable of being scattered in the hydrophobic system. Because the modifiers are added during the later period of preparing the conventional nano silver, the obtained modified nano silver has high surface activation, good scattering performance, and excellent electric conduction performance. The method has broad range of applications, and can be used for modifying various features of nano silver. The nano silver capable of being scattered in the hydrophobic system has strong washing fastness and still keeps good scattering performance after being washed for several times, the preparation method of the nano silver has simple technology, low cost, and broad application range. The invention overcomes a series of defects of the prior art.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of be dispersed in Nano Silver in the hydrophobic type system and preparation method thereof and application.
Background technology
Come from the microstructure of self uniqueness, nano particle has small-size effect, skin effect, quantum size effect and macro quanta tunnel effect, thereby can demonstrate the heat that is different from conventional material, light, electricity, magnetic, catalysis and the effect such as responsive.
In the conducting metal field, silver is not only one of best metal material of conductance, and be also conductive metal material of unique a kind of its oxide, also has simultaneously good anti-microbial property, therefore silver is a kind of very important raw material of industry in the modern industry field, is playing the part of very important role in the national product life.
The silver great majority that are applied in industrial circle at present all are the silver powder of micron level.With respect to the silver powder of micron level, the Nano Silver of Nano grade has the excellent special effectses such as quantum size effect, skin effect, small-size effect and macro quanta tunnel effect.Therefore the silver powder of Nano grade has good application at aspects such as microelectronics, photoelectron, catalysis, biology sensor, data storage, magnetic device, medicinal antibiosis, SERSs.
In recent years, the preparation method of Nano Silver and synthetic technology have obtained very big development.The preparation method of Nano Silver has many kinds, be broadly divided into physical method and chemical method two large classes, comprise chemical reduction method, microwave reduction, ultrasonic auxiliary synthetic method, magnetron sputtering method, template, photoreduction met hod, crystal seed method, polyalcohol method, microemulsion method, electrochemical process, biological reducing method etc.The pattern of synthesizing nano-silver is also very abundant, from the graininess of one dimension, spherical Nano Silver, to the wire of two dimension, bar-shaped, banded, tubular nanometer is silver-colored, also has the Nano Silver of the patterns such as dendroid, cubic, cylindrical shape, triangular prism, shape hedgehog, octahedron of three-dimensional.
Nano Silver is mainly used to prepare catalysis material, anti-biotic material and electronic polymer material.The same with other nano material, Nano Silver has higher surface energy, when it is filled in polymer or the dispersion solvent system as a kind of filler, is easy to flock together, thereby can reduces the performance of material, also can improve the cost of material.The dispersiveness of improving Nano Silver not only can improve the performance of material, also can reduce the filling rate of Nano Silver, improves contact rate, reduction contact resistance between the nano silver particles, and therefore dispersiveness is the very important parameter of Nano Silver in application.
How to improve the dispersiveness of Nano Silver in the hydrophobicity system and become the study hotspot of Nano Silver, also more about patent, the bibliographical information of this respect both at home and abroad at present, specifically following patent is arranged:
Chinese patent CN 1903946A (a kind of preparation method of high dispersed nano-silver particle) adopts chemical reduction method; take polyalcohol as reducing agent and solvent; in the situation that macromolecule dispersant exists, silver nitrate is at high temperature reduced obtain high dispersed nano-silver particle.The shortcoming that the present invention mentions the Nano Silver process for dispersing is: resulting Nano Silver mainly is granular, its dispersiveness is to utilize polyvinylpyrrolidone or poly-carboxyl class comb-shaped polymer that the coating of Nano Silver is realized, the Nano Silver processed like this substantially on being insulated property polymer overmold, thereby so that the electric conductivity that Nano Silver has lost.
Chinese patent CN 101544718A (a kind of nano silver particles is dispersed in the preparation method of the antimicrobial composite material in the polymeric matrix) preparation styrene/methacrylic acid methyl esters mix monomer, lauryl sodium sulfate mixed monomer solution, silver nitrate aqueous solution and trisodium citrate aqueous solution; Respectively silver nitrate aqueous solution and trisodium citrate aqueous solution are mixed according to volume ratio with the lauryl sodium sulfate mixed monomer solution, make the microemulsion that contains silver nitrate and the microemulsion that contains trisodium citrate; Then two kinds of microemulsions are mixed, obtaining mix monomer is the stable microemulsion that contains nano silver particles of continuous phase, and then this microemulsion is dispersed in prepares ordinary emulsion in the distilled water, again logical nitrogen deoxygenation, carrying out emulsion polymerization, use again the sodium chloride break milk separation, washing.The prepared nano particle of the present invention can be dispersed in the polymeric system, but the preparation method of the Nano Silver that provides is not only loaded down with trivial details, and its dispersiveness is that the modifying surface owing to the Surfactant SDS Nano Silver produces, because the surface of this surfactant and Nano Silver is strong not strong with joint efforts, therefore be easy in the process of washing, washing off, thus so that the dispersiveness of Nano Silver reduction.
Chinese patent CN 101249566A (a kind of preparation method of monodisperse silver nano) is blended in PVP and silver nitrate among the PEG according to certain mol proportion, can obtain monodispersed rice shape Nano Silver after stirring at a certain temperature.The single dispersed nano silver of mentioning among the present invention mainly is to make under the protection of PVP, because being good for of PVP and Nano Silver surface is strong not with joint efforts, so after PVP washes away, also can easily assemble when the Nano Silver of this graininess pattern disperses in polymer.
Chinese patent CN 1966586A (a kind of reactive, monodispersed surface modify silver nano-grain and preparation method thereof) with the dialkyl disulfides base for the phosphoric acid modification sodium borohydride the resulting graininess Nano Silver of reduction silver nitrate during as reducing agent.Although method provided by the present invention is simple, and prepared graininess Nano Silver has preferably stability in nonpolar and weak polar solvent, but the cost of dialkyl dithiophosphoric acid provided by the present invention is higher, and mainly be the dispersiveness that improves the graininess Nano Silver, and the not solution of problem of easily assembling after disperseing in polymer for the Nano Silver of the patterns such as wire, bar-shaped, dendroid, hedgehog, cylindrical shape.
Chinese patent CN 1416988A (oil soluble metal silver nano-powder and preparation method thereof) utilizes the thiophosphate organic compound to carry out surface coordination stable metal silver nanoparticle, its prepared Nano Silver can be dispersed in benzene, form colloidal dispersion in the non-polar solvens such as gasoline, and can repeatedly be extracted as powder.The present invention also is the solution that proposes for the scattering problem of particle diameter graininess Nano Silver between 1～20nm, rather than is well suited for disperseing the Nano Silver of wire, other pattern such as bar-shaped.
Chinese patent CN 101279376A mainly relates to the preparation method of conductive silver paste usefulness high dispersive superfine nano silver in the electronics industry, mainly be to adopt PVAC polyvinylalcohol to realize take formaldehyde as reducing agent as dispersant, the dispersion of resulting silver slurry after the reduction silver ammino solution.This paper adopts PVA as dispersant, and there are the following problems: (1) PVA although can improve its dispersiveness in polymer, can reduce the conductance of Nano Silver after Nano Silver is coated; (2) PVA and Nano Silver strong make a concerted effort more weak, thereby meeting so that this coating material easily come off; (3) its prepared Nano Silver mainly is the Nano Silver between 0.3～1 μ m, and range of application is narrower.
Chinese patent CN 101569937A (a kind of conductive silver paste preparation method of high dispersed nano-silver) is under the condition that stirs, liquor argenti nitratis ophthalmicus and reducing agent are added in the hyper-dispersant solution simultaneously, in the constant situation of the reaction temperature that keeps reaction system and pH value, obtain the high dispersed nano-silver of the different-grain diameter of 0.1～5.0 μ m by adjustment mixing speed and reaction time.The advantage of this patent utilizes hyper-dispersant and reducing agent to join in the reaction system simultaneously, but the hyper-dispersant that utilizes of mentioning in this patent also only is that the graininess Nano Silver is played peptizaiton, and can not disperse the Nano Silver of wire, the pattern such as bar-shaped; And the method proposes for chemical reduction reaction, does not mention the Nano Silver that can use other method preparation in the patent, thereby has limited its range of application.At present domesticly also preferably solution was not proposed for the dispersion problem of Nano Silver in polymer of the patterns such as wire, bar-shaped, dendroid, hedgehog, cylindrical shape.
Yuusuke YASUDA etc. adopt the organic polymer that contains 30 carbon atoms of having an appointment in the molecule that nano-Ag particles and Nano Silver oxide are carried out modification in US Patent No. 20100270515A1, and the modified Nano silver that obtains can be used as the conductive adhesive in the electronic polymer.The prepared modified Nano silver of method that this part provides in the patent of in April, 2010 application has dispersed preferably, but mainly is for the nano-Ag particles of particle diameter about 100nm.
Adopt a kind of amino polymer of having an opportunity of end that contains such as (CH among the US Patent No. 20100266688A1
3O
3Si (CH
2)
3NHCH
2CH
2NH
2Deng to carrying out modification with nano-Ag particles, this silver atoms has very strong adhesion with amino, and this silver atoms is a kind of netted dispersed structure.The prepared material of this patent mainly is used for preparing anti-biotic material, and the Nano Silver of institute's modification has good dispersiveness, but mainly is the modification for silver atoms.
Mention among the Japan Patent WO 2010098402A1 and adopt a kind of (CH that contains
2)
nThe organic polymer of COOH structure carries out surface modification to trickle metallic particles such as golden particulate, silver-colored particulate, copper particulate etc., then is dispersed in and is used for preparing conductive membrane, elecroconductive thin line, electrode material in the polymer.The method that metal particle is adopted that the present invention proposes, not only complicated, and building between macromolecule modifier and the metallic particles is strong not with joint efforts, easily washes away, thereby causes dispersed the reduction.
Mayer etc. adopt respectively KBH in the presence of poly-HPMA
4With the standby Ag nano particle of UV radiation reduction legal system, they find that the Ag particle that adopts the reduction of UV radiation method to prepare is unstable, and adopt KBH
4The Ag particle that reducing process prepares can stably be deposited some months.(A.B.R.Mayer?and?J.E.Mark.Poly(2-hydroxyalkyl?methacrylates)as?stabilizers?for?colloidal?noblemetal?nanoparticles.Polymer.41，4，2000，1627-1631)。
Tanushree Bala etc. are at document: Tanushree Bala, Anita Swami, B.L.V.Prasad, the dispersion for Nano Silver of mentioning among Murali Sastry.Phase transfer of oleic acid capped NicoreAgshellnanoparticles assisted by the flexibility of oleic acid on the surface of silver.Journal of Colloid and Interface Science 283 (2005) 422-431 also is the solution that proposes for the dispersiveness of nanoparticle.
The seminar at the places such as Yi Li adopts terephthalic acids, to benzene two eyeballs, 4-eyeball yl benzoic acid carries out surface modification to the Nano Silver that is filled in the Nano grade in the used for electronic packaging conducting resinl, namely utilize pi-conjugated self assembly molecule line to connect conducting particles and matrix resin, find that these self assembly molecule lines can improve conductance, and the Nano Silver of this favorable dispersibility can be applied in (Rongwei Zhang in the conducting resinl field of microelectronics Packaging, Yi Li, Myung Jin Yim, Member, IEEE, Kyoung Sik Moon.Enhanced Electrical Properties ofAnisotropic Conductive Adhesive With π-Conjugated Self-AssembledMolecular Wire Junctions.IEEE TRANSACTIONS ON COMPONENTSAND PACKAGING TECHNOLOGIE S, VOL.32, NO.3, SEPTEMBER2009).
In sum: Nano Silver is a kind of very useful nano material, and dispersiveness is the key issue of Nano Silver required solution in application.Present researcher both domestic and external is for proposing a lot of solutions about the dispersion problem of Nano Silver in the hydrophobic polymer system, but according to reporting for work of existing domestic and foreign literature and patent, also do not carry the dispersion problem of Nano Silver in polymer that can effectively side by side solve different-shape (as: spherical, graininess, wire, bar-shaped, dendroid, hedgehog, cylindrical shape etc.).
Summary of the invention
Primary and foremost purpose of the present invention is to overcome the shortcoming of prior art with not enough, a kind of Nano Silver that the fine dispersion effect can be arranged in hydrophobic polymer or dicyandiamide solution is provided, this Nano Silver has different morphologies, such as graininess, spherical, wire, bar-shaped, dendroid, hedgehog etc.
Another object of the present invention is to provide the preparation method of above-mentioned Nano Silver.
A further object of the present invention is to provide the application of above-mentioned Nano Silver.
Purpose of the present invention is achieved through the following technical solutions:
A kind of Nano Silver that is dispersed in the hydrophobic type system has the structure shown in the following general formula:
(Ag)
h—{(Ag)
m—(X—R)
n}
y
Wherein, h is 100～10000000; Y is 10～100000; M is 10～100000; X is-NR
2,-NR
3,-NH
2,-COOH ,-COO
-,-S0
3H ,-SO
3,-SH ,-PO
2- 4Or-OH; R is the polymer of more than one materials in alkyl, styrene, vinylacetate, acrylonitrile, methyl methacrylate or the methyl acrylate, and the molecular weight of this polymer is 10～1000000; N is 10～100000.
The above-mentioned Nano Silver that is dispersed in the hydrophobic type system, its preparation method is:
Get the reaction of silver nitrate and hydrazine hydrate, add dressing agent in the reaction later stage, react again 0～120min, obtain the Nano Silver in spherical the be dispersed in hydrophobic type system.
The above-mentioned Nano Silver that is dispersed in the hydrophobic type system, its preparation method or:
Get after propane diols, sodium chloride and the silver nitrate reaction 1～6 hour, add dressing agent, react again 0～120min, obtain the Nano Silver in the be dispersed in hydrophobic type system of wire.
The above-mentioned Nano Silver that is dispersed in the hydrophobic type system, its preparation method or:
Get after ethylene glycol, vulcanized sodium and the silver nitrate reaction 1～6 hour, add dressing agent, react again 0～120min, obtain the Nano Silver in bar-shaped the be dispersed in hydrophobic type system.
The above-mentioned Nano Silver that is dispersed in the hydrophobic type system, its preparation method be also:
Get after the dispersion liquid that contains zinc and the silver nitrate reaction 1～6 hour, add dressing agent, react again 0～120min, obtain the Nano Silver in the be dispersed in hydrophobic type system of dendroid shape.
Described dressing agent has the structure shown in the following general formula:
X——R
Wherein, X is-NR
2,-NR
3,-NH
2,-COOH ,-COO
-,-S0
3H ,-SO
3,-SH ,-PO
2- 4Or-OH; R is the polymer of more than one materials in alkyl, styrene, vinylacetate, acrylonitrile, methyl methacrylate or the methyl acrylate, and the molecular weight of this polymer is 10～1000000.
The mol ratio of described dressing agent and silver nitrate is 1: 10～8: 10.
The Nano Silver that is dispersed in the hydrophobic type system of the present invention can be applicable in the fields such as anti-biotic material, microelectronics Packaging conducting resinl, conductive silver paste material, electrode of solar battery material, flexible transparent conductive film.
The present invention has following advantage and effect with respect to prior art:
(1) has the nano-silver surface modified method that patent documentation is reported for work, mainly be in the last handling process that Nano Silver prepares, to carry out, when in the last handling process of Nano Silver, carrying out modification, because this moment, the surface-active of silver was passivated, and closed thereby cause the Nano Silver dressing agent to be difficult to valence bond.This patent utilizes one-step method that the mode of Nano Silver dressing agent by chemical reaction self-assembled to the Nano Silver surface in the reaction later stage of preparation Nano Silver to get on.Because in the chemical reaction later stage, the apparent activation energy of Nano Silver is higher, therefore can realize preferably modification and the fine dispersion in polymer.
(2) the Nano Silver method of modifying of the present invention's proposition is by one-step method that the Nano Silver dressing agent is surperficial at Nano Silver by the chemical means self assembly, therefore prepared Nano Silver not only has good dispersiveness in hydrophobic polymer and organic solvent, and the conductance of Nano Silver can not reduce because of surface modification.
(3) the present invention not only provides a kind of synthetic method with hydrophobic Nano Silver coating material, also can according to actual conditions by the strand length of adjusting coating material and the consumption of dressing agent, realize the difference dispersion of Nano Silver in hydrophobic polymer of different nature or solvent.
(4) provided by the present invention have hydrophobic Nano Silver coating material and not only can be used to modify spherical or the graininess Nano Silver, also can be used to modify other patterns, such as the Nano Silver of the patterns such as: wire, bar-shaped, dendroid, hedgehog, cylindrical shape.
(5) dressing agent provided by the present invention, and after modifying by the method for modifying mentioned in the literary composition has very strong valence bond to the surface of silver and closes ability, but the repeatedly washing of organic solvent-resistant, and repeatedly continuing to keep its good dispersiveness after the washing.Simultaneously, the Nano Silver after the modification not only can be dispersed in the organic solvents such as benzene, toluene, carrene, dibutyl phthalate, and can be extracted as repeatedly the Nano Silver use.
(6) the present invention adopts one-step method to realize nano-silver surface modified, thereby can realize that the Nano Silver of different shaped looks is in the dispersion of hydrophobic solvent or polymeric system, the method is with respect to traditional post treatment method, and the technique of the method for modifying that this patent provides is simpler, method is more reliable, cost is cheaper.
Description of drawings
Fig. 1 is the TEM picture of spherical Nano Silver.
Fig. 2 is the microphotograph before and after the spherical Nano Silver modification; Wherein, before left figure is modification, after right figure is modification.
Fig. 3 is the Nano Silver for preparing of embodiment 1 through the dispersion effect figure in diisobutyl phthalate after the washing repeatedly; Wherein, E be ten times the washing after, C be eight times the washing after, B be six times the washing after, A be four times the washing after.
Fig. 4 is the TEM picture of wire Nano Silver.
Fig. 5 is deployment conditions comparison in carrene and water after the modification of wire Nano Silver; Wherein, the 1. dispersion effect picture in cyclohexane before the modification, 2: the dispersion effect picture water after the modification in water, 3: the dispersion effect picture after the modification in carrene.
Fig. 6 is the TEM picture of rod-like nano silver.
Fig. 7 is the dispersion effect figure in the solvent dibutyl phthalate before and after the modification of rod-like nano silver; Wherein, before left figure is modification, after right figure is modification.
Fig. 8 is the TEM picture of wire Nano Silver.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Example one
1, the Nano Silver dressing agent is synthetic:
Get 4.2g polyoxyethylene 400 grease acid esters, the 2.5g N-tert-butyl group-Serine, 3.2gDMAP, 4.2gEDCHCl, insert in the 250ml reaction flask, add again the 180ml carrene, place under the room temperature, high-speed stirred stops reaction after 2～3 days, take out sample and purify through washing, remove unreacted completely serine and catalyst DMAP, EDC hydrochloride.Get a required end and contain amino, an other end contains the Nano Silver dressing agent of hydrophobic-type component.The structural formula of this dressing agent such as figure below:
2, spherical Nano Silver is synthetic:
Get the 0.17g silver nitrate and be dissolved in the 20ml deionized water, place the 100ml reaction bulb, 25 ℃ of lower high-speed stirred, (purity: 60%) slowly drip in the aqueous solution of silver nitrate, dropping is reacted about 2-3 hour after finishing again to get the 20ml hydrazine hydrate again.The TEM photo of prepared spherical Nano Silver as shown in Figure 1.
3, the modification on spherical Nano Silver surface:
Get the synthetic Nano Silver dressing agent of 0.135g step 1, it is dissolved in the 20ml methyl alcohol, when above-mentioned Nano Silver preparation feedback proceeds to about 2 hours, in the situation that reaction system continues to stir, the methanol solution that will contain again the Nano Silver modification of above-mentioned steps 1 slowly drips wherein, react 120min again, prepare the Nano Silver in spherical the be dispersed in hydrophobic type system, the structure of this Nano Silver is as follows:
N=m=13800 wherein; H=3980000; Y=4500
4. performance test
(1) electric conductivity
The dispersibility Nano Silver of this patent preparation can be applicable to anti-biotic material, the microelectronics Packaging conducting resinl, the conductive silver paste material, the electrode of solar battery material, the fields such as flexible transparent conductive film, the conductive effect for preparing Nano Silver in order to characterize this patent, the Nano Silver that the present embodiment step 3 is obtained according to document (Ke Yupeng. the microelectronics assembling is with the research of high-performance nano silver conductive adhesive: [master thesis]. Changsha: Central South University, 2007:20-40) be prepared into conducting resinl, then carry out with reference to GJB GJB548A-1996 method 5011, and adopt the four point probe anchor clamps of DC digital resistance meter SB2231 and a special use to test, and the best experimental data that provides in measured data and the document is compared.Concrete outcome such as following table.
Data show in the table: after the experimental technique that the process this patent provides was processed, the nano-silver conductive rate of gained improved a lot, thereby can reduce the Nano Silver filling rate in the material.
(2) dispersive property
The dispersion effect of Nano Silver as shown in Figure 2 before and after the modification.
(3) wash-resistant property
The Nano Silver that step 3 is obtained (passes through respectively toluene, benzene, cyclohexane through repeatedly washing, n-hexane, carrene, chloroform, methyl alcohol, absolute ethyl alcohol, n-formyl sarcolysine base pyrrolidones) afterwards, be dispersed in the diisobutyl phthalate the experiment effect photo as shown in Figure 3, wherein E be ten times the washing after, C be eight times the washing after, B be six times the washing after, A be four times the washing after.
Example two
1, the Nano Silver dressing agent is synthetic:
In three mouthfuls of reaction flasks of 500ml, pass into nitrogen, and keep high speed machine to stir, eliminate the oxygen in the reaction bulb, then the 0.121molN-tert-butyl group-Serine and 0.109mol triethylamine are dissolved in the anhydrous tetrahydro furan that 300ml processed, and this solution joined in above-mentioned three mouthfuls of reaction flasks, be placed on again-20 ℃ of lower cooling and stirring, and add lentamente the treated anhydrous lauroyl chloride of 0.198mol, this reaction remains on-20 ℃ of lower reactions 10 hours, and then-5 ℃ of lower reactions 5 hours, and then the solvent decompression distillation in this system is eliminated.Obtain the head product lauroyl-N-tert-butyl group-Serine, get again the trifluoroacetic acid of the lauroyl of the 60.2mmol-N-tert-butyl group-Serine and 0.301mol, join 100cm
2Carrene at room temperature react again about one hour, again with the unreacted in this solution system completely TFA remove.Then using again 4moldm
-3Hydrochloric acid it is carried out acidifying, with methyl alcohol it is carried out crystallization and purification again after the acidifying, can obtain needed product lauroyl-Serine.The one end contains can be good for the group that is combined in the Nano Silver surface, and the other end contains hydrophobic components, can be used to Nano Silver is carried out modification.The structural formula of lauroyl-Serine is as shown below:
2, the wire Nano Silver is synthetic
Get the propane diols that 5ml dewaters, join in the 25ml single port reaction flask, 160 ℃ of lower stir abouts 1 hour, add again the sodium chloride propylene glycol solution (concentration: 1mM) of 0.1ml, after the 5min, in system, drip the propylene glycol solution that 10ml contains the 0.32g silver nitrate again.After dripping end, keep mixing speed and reaction temperature constant, continue again reaction about 3 hours, just can make diameter 50～60nm, the wire nanometer of length about about 2～5 μ m, its TEM picture is as shown in Figure 4.
3, the modification on wire Nano Silver surface
In step 2; when stirring 2h behind the dropping silver nitrate; the similar growth of wire Nano Silver is got the dressing agent about 0.05g fully, i.e. lauroyl-Serine of preparing of step 1; it is dissolved among the DMSO; keep reaction temperature constant, again it is added drop-wise in the reaction system of step 2 lentamente, react again 120min; prepare the Nano Silver in the be dispersed in hydrophobic type system of wire, the structure of this Nano Silver is as follows:
Wherein, n=m=14500; H=26890000; Y=2300
4, performance test
(1) electric conductivity
The dispersibility Nano Silver of this patent preparation can be applicable to anti-biotic material, the microelectronics Packaging conducting resinl, the conductive silver paste material, the electrode of solar battery material, the fields such as flexible transparent conductive film, in order to characterize the conductive effect of this patent Nano Silver, the Nano Silver that the present embodiment step 3 is obtained according to document (Ke Yupeng. the microelectronics assembling is with the research of high-performance nano silver conductive adhesive: [master thesis]. Changsha: Central South University, method 2007:20-40) is prepared into conducting resinl, then test with reference to GJB GJB548A-1996 method 5011, and adopting the four point probe anchor clamps of DC digital resistance meter SB2231 and a special use to test, the best experimental data that provides in data that will be measured and the document compares.Concrete outcome such as following table.
Data show in the table: after the experimental technique that the process this patent provides was processed, the nano-silver conductive rate of gained improved a lot, thereby can reduce the Nano Silver filling rate in the material.
(2) dispersive property
The dispersion effect of Nano Silver as shown in Figure 5 before and after the modification.
Example three
1, dressing agent is synthetic:
Get 160ml styrene, 150mg initiator A IBN (azodiisobutyronitrile), 510mg chain-transferring agent thioacetic acid; wiring solution-forming joins in the 250ml single port reaction flask; under the ice-water bath condition, pass into continuously nitrogen 1h; with thorough displacement oxygen wherein, then under stirring under the protection of nitrogen and slowly with heating water bath to 60 ℃ beginning polymerisation.After the 60min, change water-bath into ice bath, stop its reaction, make the thioacetic acid base polystyrene.The structural formula of this dressing agent is as shown below, wherein n=10000:
2, rod-like nano silver is synthetic
Get the ethylene glycol that 5ml dewaters, join in the 25ml single port reaction flask, 180 ℃ of lower stir abouts 1 hour, ethylene glycol solution (the concentration: 1mM) that adds again 0.5ml Containing Sulfur sodium, after the 5min, in above-mentioned reaction system, drip the ethylene glycol solution that 10ml contains the 0.32g silver nitrate again, after dripping end, keep mixing speed and reaction temperature constant, continue again reaction 3 hours, just can make diameter 500～800nm, the rod-like nano silver of length about about 10～50 μ m, its pattern picture is as shown in Figure 6
3, the modification of rod-like nano silver surface
In step 2, when stirring 2h behind the dropping silver nitrate, the similar growth of rod-like nano silver fully, get 1.2g thioacetic acid base polystyrene, it is dissolved in the dimethyl sulfoxide (DMSO), keep reaction temperature constant, again this solution is added drop-wise in the reaction system of step 2 lentamente, react 120min again, prepare the Nano Silver in bar-shaped the be dispersed in hydrophobic type system, the structure of this Nano Silver is as follows:
Wherein, x=10000, y=10000, m=235000, n=3560, h=4320000
4, performance test
(1) electric conductivity
The dispersibility Nano Silver of this patent preparation can be applicable to anti-biotic material, the microelectronics Packaging conducting resinl, the conductive silver paste material, the electrode of solar battery material, the fields such as flexible transparent conductive film, the conductive effect for preparing Nano Silver in order to characterize this patent, the Nano Silver that the present embodiment step 3 is obtained according to document (Ke Yupeng. the microelectronics assembling is with the research of high-performance nano silver conductive adhesive: [master thesis]. Changsha: Central South University, method 2007:20-40) is prepared into conducting resinl, then carry out with reference to GJB GJB548A-1996 method 5011, and adopting the four point probe anchor clamps of DC digital resistance meter SB2231 and a special use to test, the best experimental data that provides in data that will be measured and the document compares.Concrete outcome such as following table.
Data show in the table: after the experimental technique that the process this patent provides was processed, the nano-silver conductive rate of gained improved a lot, thereby can reduce the Nano Silver filling rate in the material.
(2) dispersive property
The dispersion effect of Nano Silver as shown in Figure 7 before and after the modification.
Example four
1, dressing agent is synthetic:
In three mouthfuls of reaction flasks of 500ml, pass into nitrogen, and keep high speed machine to stir, eliminate the oxygen in the reaction bulb, then the 0.121molN-tert-butyl group-Serine and 0.109mol triethylamine are dissolved in the anhydrous tetrahydro furan that 300ml processed, and this solution joined in above-mentioned three mouthfuls of reaction flasks, be placed on again-20 ℃ of lower cooling and stirring, and add lentamente the treated anhydrous stearyl chloride of 0.198mol, this reaction remains on-20 ℃ of lower reactions 10 hours, and then-5 ℃ of lower reactions 5 hours, and then the solvent decompression distillation in this system is eliminated.Obtain the head product stearyl-N-tert-butyl group-Serine, get again the trifluoroacetic acid of the stearyl of the 60.2mmol-N-tert-butyl group-Serine and 0.301mol, join 100cm
2Dioxane at room temperature react again about one hour, again with the unreacted in this solution system completely TFA remove.And then use 4moldm
-3Hydrochloric acid it is carried out acidifying, with methyl alcohol it is carried out crystallization and purification again after the acidifying, can obtain needed product stearyl-Serine.The one end contains can be good for the group that is combined in the Nano Silver surface, and the other end contains hydrophobic components, can be used to Nano Silver is carried out modification.
2, dendritic nano-silver is synthetic
With the 100g zinc metal sheet with in the ultrasonic ethanolic solution that is dispersed in 10mL, under 25 ℃, the dispersion liquid of getting 1m zinc is added drop-wise to the liquor argenti nitratis ophthalmicus that 20ml concentration is 0.03M slowly, after stirring 6 hours, just can make dendritic nano-silver, its length is about 5～10 μ m, and the diameter of its trunk portion and resin part is about 20～30nm, and its pattern as shown in Figure 8.
3, the finishing of dendritic nano-silver
In step 2; when stirring the 40min left and right sides behind the dropping silver nitrate; get stearyl-Serine synthetic in the 0.1g step 1; it is dissolved in the n-formyl sarcolysine base pyrrolidones; keep reaction temperature constant, again it is added drop-wise in the reaction system of step 2 slowly, react again 120min; prepare the dendritic Nano Silver that is dispersed in the hydrophobic type system, the structure of this Nano Silver is as follows:
Wherein, m=14500, n=8564, h=54200000, y=2360
4, performance test
(1) electric conductivity
The dispersibility Nano Silver of this patent preparation can be applicable to anti-biotic material, the microelectronics Packaging conducting resinl, the conductive silver paste material, the electrode of solar battery material, the fields such as flexible transparent conductive film, the conductive effect for preparing Nano Silver in order to characterize this patent, the Nano Silver that the present embodiment step 3 is obtained according to document (Ke Yupeng. the microelectronics assembling is with the research of high-performance nano silver conductive adhesive: [master thesis]. Changsha: Central South University, method 2007:20-40) is prepared into conducting resinl, then carry out with reference to GJB GJB548A-1996 method 5011, and adopting the four point probe anchor clamps of DC digital resistance meter SB2231 and a special use to test, the best experimental data that provides in data that will be measured and the document compares.Concrete outcome such as following table:
Data show in the table: after the experimental technique that the process this patent provides was processed, the nano-silver conductive rate of gained improved a lot, thereby can reduce the Nano Silver filling rate in the material.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (3)
1. Nano Silver that can be dispersed in the hydrophobic type system is characterized in that having following structure:
Wherein, x=10000, y=10000, m=235000, n=3560, h=4320000;
Perhaps following structure:
Wherein, m=14500, n=8564, h=54200000, y=2360.
2. the described a kind of application that is dispersed in Nano Silver in the hydrophobic type system of claim 1.
3. according to claim 2 described a kind of application that is dispersed in Nano Silver in the hydrophobic type system is characterized in that: the described Nano Silver that is dispersed in the hydrophobic type system is used as the microelectronics Packaging conducting resinl.
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| CN101554664A (en) * | 2009-05-20 | 2009-10-14 | 广东风华高新科技股份有限公司 | Method for preparing nano-scale silver powder |
| CN101698235A (en) * | 2009-10-30 | 2010-04-28 | 北京化工大学 | Method for preparing high-purity nano silver by gas assistance in liquid phase |
| KR20100115201A (en) * | 2009-04-17 | 2010-10-27 | 웅진케미칼 주식회사 | Nano-silver controled particles size and preparing thereof |
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| CN101554664A (en) * | 2009-05-20 | 2009-10-14 | 广东风华高新科技股份有限公司 | Method for preparing nano-scale silver powder |
| CN101698235A (en) * | 2009-10-30 | 2010-04-28 | 北京化工大学 | Method for preparing high-purity nano silver by gas assistance in liquid phase |
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