CN100575420C - The mixture of poly m-phenylene diamine and nanometer silver and in-situ reduction preparation method thereof - Google Patents
The mixture of poly m-phenylene diamine and nanometer silver and in-situ reduction preparation method thereof Download PDFInfo
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- CN100575420C CN100575420C CN200710037533A CN200710037533A CN100575420C CN 100575420 C CN100575420 C CN 100575420C CN 200710037533 A CN200710037533 A CN 200710037533A CN 200710037533 A CN200710037533 A CN 200710037533A CN 100575420 C CN100575420 C CN 100575420C
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Abstract
The invention discloses the preparation method of a kind of poly m-phenylene diamine/nano metal mixture.The in-situ reduction preparation method of said poly m-phenylene diamine of the present invention and nano-ag composite at first is to prepare poly m-phenylene diamine with chemical oxidization method, then silver ion solution is joined the poly m-phenylene diamine internal reaction, filters at last to get final product.Different with the method for galvanic deposit in-situ reducing metal ion, be spontaneous carrying out by conductive polymers original position reducing metal ionic method from aqueous metal salt, need not electrical drive power.Obviously this method is not only energy-conservation, and equipment is simple, easily realizes large-scale operation.Adopt the prepared poly m-phenylene diamine of this method/silver-colored nano-complex, the particle diameter of silver particles and content are subjected to the influence in concentration of silver ions and reaction times, and the particle diameter of silver particles in mixture can be low to moderate 10～20nm.
Description
Technical field
The present invention relates to preparation method's technical field of poly m-phenylene diamine/nano metal organic-inorganic composite body.
Background technology
In recent years, the research of p-poly-phenyl two amine compounds is in the ascendant, and the polyphenyl diamines can form various matrix materials with elemental metals, polynite, carbon nanotube, polyvinyl alcohol etc. respectively, and they have all shown the functional of excellence.Polyphenyl diamines/carbon mano-tube composite has great specific surface area owing to having the nanometer micropore structure, metal ion had very strong adsorptive power, by the modified electrode of its assembling to the trace cadmium ion, the cupric ion ion has excellent detectivity, detecting concentration is low to moderate 0.25 and 0.33ppb respectively, the linear probing scope is 5～100ppb, be a kind of electrochemical sensor [Gao X H of excellent performance, Wei W Z, Yang L, et al.Carbon nanotubes/poly (1,2-diaminobenzene) nanoporous composite film electrodeprepared by multipluse potentiostatic electropolymerization and its application to determination oftrace heavy metal ions.Electroanalysis, 2006,18 (5): 485-492].In the mixture of polyphenyl diamines and nano metal, successfully prepared the mixture of poly-o-phenylenediamine at present with gold, platinum, nail, tin etc.And obtained better application.For example, poly-o-phenylenediamine and golden micron particle mixture can pass through in-situ polymerization in-situ compositing (Liao F.Simple preparation ofmonodisperse, large gold spheres.Materials Letters, 2005, self-assembly method (YuanR 59:3132-3134) or layer by layer, Zhang L Y, Li Q F, Chai Y Q, Cao S R.A label-free amperometric immunosenor based onmulti-layer assembly of polymerized o-phenylenediamine and gold nanoparticles for determinationof Japanese B encephalitis vaccine.Analytica Chimica Acta, 2005,531:1-5.Zhang L Y, Yuan R, Huang X Q, et al.Potentiometric immunosensor based on antiserum of Japanese B encephalitisimmobilized in nano-Au/polymerized o-phenylenediamine film.Electrochemistry Communications, 2004,6:1222-1226) preparation.Because the Au nanoparticle has huge specific surface area, can be connected with various biomolecules, therefore Au nanoparticle and polyphenyl diamines can be made the biosensor of respective substance behind compound immobilized antigen afterwards of electrode surface or antibody, having preferably to Japanese B encephalitis vaccine, antitrypsin, responding ability and broad get the concentration-response scope.And can realize the regeneration of transmitter, access times can be up to more than 30 times repeatedly.Poly m-phenylene diamine and golden nanometer particle mixture can be by composite algorithm preparations layer by layer.Utilize poly m-phenylene diamine/ferrocene/HRP/ golden nanometer particle mixture can prepare the hydrogen peroxide transmitter, the linear range of this transmitter is 1.3 * 10
-7Mol/L～8 * 10
-6Mol/L, the time of response only is 30s.
Except above-mentioned employing electrochemical polymerization method makes the method for polymkeric substance and nano-Au composite, also have photoreduction met hod, additional reducing agent reduction method etc., but these procedures comparatively complexity, complex operation, energy expenditure are big, and reaction is subjected to more condition restriction and is difficult to apply.As the electrochemical process that is most widely used need be prior to adopting electrochemical process deposition one layer of polymeric film on the electrode, then again with certain electrochemical method deposited gold nanoparticle in polymeric film, adopt this method to need consumed power and be subjected to the restriction of electrode surface area size and can not carry out scale operation.In addition, in Bao Dao polyphenyl diamines and the metal composite research at home and abroad, majority is the preparation research of poly-o-phenylenediamine and metal composite, does not also see the report about the preparation method of the mixture of poly m-phenylene diamine and nanometer silver.
Summary of the invention
Purpose of the present invention just provides a kind of easy and simple to handle, the poly m-phenylene diamine that cost is low and the in-situ reduction preparation method of nano-ag composite, and this method is better than existing the most widely used electrochemical process on output.
Another object of the present invention provides the mixture of prepared poly m-phenylene diamine of above-mentioned preparation method and nanometer silver.
For reaching above-mentioned purpose, the technical scheme that the present invention takes is:
The in-situ reduction preparation method of poly m-phenylene diamine and nano-ag composite at first is to prepare poly m-phenylene diamine with chemical oxidization method, then silver ion solution is added the poly m-phenylene diamine internal reaction, filters at last and promptly obtains poly m-phenylene diamine and nano-ag composite.
The in-situ reduction preparation method of above-mentioned poly m-phenylene diamine and nano-ag composite, the concrete steps that wherein said chemical oxidization method prepares poly m-phenylene diamine are: add mphenylenediamine monomer and oxygenant in the acid reaction medium respectively, after waiting to dissolve oxidizing agent solution added the mphenylenediamine monomer solution, it is reacted completely, and aftertreatment can obtain the poly m-phenylene diamine powder.
Said oxygenant can be ammonium sulfate, Sodium Persulfate or potassium bichromate etc.Oxygenant and monomeric mol ratio be preferably 0.5: 1～and 3: 1.Because polymeric reaction temperature has considerable influence to polymerization rate, it is all unfavorable to the polyreaction of mphenylenediamine to cross low or too high temperature of reaction, and therefore in the present invention, polymeric reaction temperature is preferably 30～70 ℃.The present invention adopts currently known methods polymerisate to be separated aftertreatments such as purification, and this aftertreatment comprises removes the monomer of not participating in reaction that remains in the reaction mixture, the oligopolymer that reaction generates, and residual oxygenant.Treatment step is: filtration, deionized water wash, precipitation and drying.
Said silver ion solution is preferably Silver Nitrate.
Beneficial effect of the present invention: different with the method for galvanic deposit in-situ reducing metal ion, be spontaneous carrying out by conductive polymers original position reducing metal ionic method from aqueous metal salt, need not electrical drive power.Obviously this method is not only energy-conservation, and equipment is simple, easily realizes large-scale operation.Adopt the prepared poly m-phenylene diamine of this method/silver-colored nano-complex, the particle diameter of silver particles and content are subjected to the influence in concentration of silver ions and reaction times, and the particle diameter of silver particles in mixture can be low to moderate 10～20nm.
Description of drawings
Fig. 1 illustrates that for being to adopt the poly m-phenylene diamine of local reduction way preparation and the TEM photo of nano-ag composite in the silver nitrate solution of 0.5mmol/L at starting point concentration silver particles is 10～20nm.
Fig. 2 illustrates that for being to adopt the poly m-phenylene diamine of local reduction way preparation and the TEM photo of nano-ag composite in the silver nitrate solution of 2.5mmol/L at starting point concentration silver particles is 50～100nm.
Fig. 3 for be the poly m-phenylene diamine that adopts the local reduction way preparation in the silver nitrate solution of 2.5mmol/L at starting point concentration with nano-ag composite in the electron diffraction photo of silver-colored monocrystalline, illustrate that silver-colored is monocrystal particle.
Embodiment
Take by weighing 4.3256g (0.04mol) mphenylenediamine and be dissolved in the hydrochloric acid soln of 100mL 1mol/L, take by weighing 27.384g (0.12mol) ammonium persulphate at 3: 1 by oxygen list mol ratio and be dissolved in the hydrochloric acid soln that 100mL concentration is 1mol/L.Under 30 ℃ oxidizing agent solution is added drop-wise in the monomer solution.Dropping oxidizing agent picks up counting, coreaction 24h.The attitude black powder shaped polymer that obtains mixing soaks, stirs 24h with it in ammoniacal liquor or sodium hydroxide solution, filters, and washing, after the drying, the poly m-phenylene diamine of the attitude that can obtain mixing.Output 4.25g, productive rate 98.3%.
Embodiment 2
Take by weighing 4.3256g (0.04mol) mphenylenediamine and be dissolved in the hydrochloric acid soln of 100mL 1mol/L, take by weighing 9.126g (0.04mol) ammonium persulphate at 1: 1 by oxygen list mol ratio and be dissolved in the hydrochloric acid soln that 100mL concentration is 1mol/L.Under 65 ℃ oxidizing agent solution is added drop-wise in the monomer solution.Dropping oxidizing agent picks up counting, coreaction 24h.The attitude black powder shaped polymer that obtains mixing soaks, stirs 24h with it in ammoniacal liquor or sodium hydroxide solution, filters, and washing, after the drying, the poly m-phenylene diamine of the attitude that can obtain mixing.Output 3.50g, productive rate 80.9%.
Embodiment 3～4
Get embodiment 1 product 50mg, stirring reaction 24h in the silver ion solution of 30 ℃ of following input 25mL starting point concentration 0.5mmol/L, silver content is 5.1wt% in poly m-phenylene diamine and the nano-ag composite, silver-colored grain diameter is 10～20nm (Fig. 1).Accordingly, under the similarity condition, changing initial concentration of silver ions is 2.5mmol/L, silver-colored grain diameter is 50～100nm (Fig. 2) in poly m-phenylene diamine and the nano-ag composite, particularly specifically, in Nano silver grain, some is a monocrystal particle, can be confirmed by the electron diffraction collection of illustrative plates (Fig. 3).
Get embodiment 1 product 50mg, stirring reaction 24h in 30 ℃ of silver ion solutions that drop into down 25mL starting point concentration 0.49mmol/L filters, poly m-phenylene diamine and nano-ag composite, detect through laser particle analyzer, the mixture median size is 3.63 μ m; Under the similarity condition, changing initial concentration of silver ions is 2.5mmol/L, 4.0mmol/L, 10.7mmol/L, 21.6mmol/L 42.9mmol/L detects through laser particle analyzer, the mixture median size is respectively: 3.14 μ m, 2.93 μ m, 3.83 μ m, 4.43 μ m, 2.85 μ m.
Embodiment 11～15
Get embodiment 1 product 50mg, stirring reaction 1h in 30 ℃ of silver ion solutions that drop into down 25mL starting point concentration 5mmol/L filters, poly m-phenylene diamine and nano-ag composite, detect through laser particle analyzer, the mixture median size is 4.95 μ m; Under the similarity condition, the change reaction times is 3h, 6h, and 12h, 24h detects through laser particle analyzer, and the mixture median size is respectively: 4.11 μ m, 4.05 μ m, 4.78 μ m, 2.93 μ m.
By above embodiment as seen, local reduction way can be used for preparing poly m-phenylene diamine and nano-ag composite, and is simple to operate, only needs to add in certain density silver nitrate solution a certain amount of poly m-phenylene diamine, and stir and to get final product, need not increase equipment and additional reducing agent expense.
Claims (2)
1, the in-situ reduction preparation method of poly m-phenylene diamine and nano-ag composite, it is characterized in that, at first be to prepare poly m-phenylene diamine with chemical oxidization method, then the 50mg poly m-phenylene diamine is joined in the 25ml silver ion solution under 30 ℃ and react 24h, wherein, the starting point concentration of silver ions is 0.5mmol/L or 2.5mmol/L in the described silver ion solution, filters at last to get final product; The concrete steps that wherein said chemical oxidization method prepares poly m-phenylene diamine are: take by weighing the 4.3256g mphenylenediamine and be dissolved in the hydrochloric acid soln of 100mL 1mol/L, taking by weighing the 27.384g ammonium persulphate at 3: 1 by oxygen list mol ratio is dissolved in the hydrochloric acid soln that 100mL concentration is 1mol/L, under 30 ℃ oxidizing agent solution is added drop-wise in the monomer solution, dropping oxidizing agent picks up counting, coreaction 24h, attitude black powder shaped polymer obtains mixing, it is soaked, stirs 24h in ammoniacal liquor or sodium hydroxide solution, filter, washing, the poly m-phenylene diamine of the attitude that obtains after the drying mixing.
2, the in-situ reduction preparation method of poly m-phenylene diamine as claimed in claim 1 and nano-ag composite is characterized in that: said silver ion solution is meant silver nitrate solution.
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| CN101220150B (en) * | 2008-01-29 | 2010-06-02 | 同济大学 | Copolymer of m-phenylenediamine and sulfonation m-phenylenediamine, and method for producing the same |
| CN101787124A (en) * | 2010-04-02 | 2010-07-28 | 南京大学 | Conductive polymetaphenylene diamine high polymer and preparation method and application thereof |
| CN102746667A (en) * | 2012-07-12 | 2012-10-24 | 新疆大学 | Polyaniline/nanogold composite material synthesized by solid-phase method |
| CN111185240B (en) * | 2020-02-24 | 2022-08-05 | 万华化学集团股份有限公司 | Phenylenediamine-containing organic porous polymer supported catalyst, preparation method thereof and method for preparing m-xylylenediamine by hydrogenation |
| CN113257586B (en) * | 2021-06-03 | 2023-04-07 | 中南大学 | Preparation and application method of silver-carbon composite electrode material |
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Non-Patent Citations (7)
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| Novel Multifunctional Polymer from Aromatic DiaminesbyOxidative Polymerizations. Li X. G., Huang M. R., Duan W. Yang Y. L.Chemical Reviews,Vol.102 No.9. 2002 |
| Novel Multifunctional Polymer from Aromatic DiaminesbyOxidative Polymerizations. Li X. G.,Huang M.R.,Duan W.Yang Y.L.Chemical Reviews,Vol.102 No.9. 2002 * |
| Poly(m-phenylenediamine): Synthesis and Characterization byX-ray Photoelectron Spectroscopy. Chan H. S. O., Ng S. C., Hor T. S., Sun J., Tan K. L., Tan B.T. G.European Polymer Journal,Vol.27 No.11. 1991 |
| Poly(m-phenylenediamine): Synthesis and Characterization byX-ray Photoelectron Spectroscopy. Chan H.S.O.,Ng S.C.,Hor T.S.,Sun J.,Tan K.L.,Tan B.T.G.European Polymer Journal,Vol.27 No.11. 1991 * |
| Preparation of Nanosized Metallic Particles in Polyaniline. Wang J., Neoh K. G., Kang E. T.Journal of Colloid and Interface Science,Vol.239 No.1. 2001 |
| Preparation of Nanosized Metallic Particles in Polyaniline. Wang J., Neoh K.G.,Kang E. T.Journal of Colloid and Interface Science,Vol.239 No.1. 2001 * |
| Rapid and Effective Adsorption of Lead Ions onFine Poly(phenylenediamine) Microparticles. Huang M. R., Peng Q. Y., Li X. G.Chemistry-A European Journal,Vol.12 No.16. 2006 |
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