CN102717064B - Hyperbranched nano-silver taking amphiphilic polymer as stabilizing agent and preparation method thereof - Google Patents
Hyperbranched nano-silver taking amphiphilic polymer as stabilizing agent and preparation method thereof Download PDFInfo
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- CN102717064B CN102717064B CN201210233273.1A CN201210233273A CN102717064B CN 102717064 B CN102717064 B CN 102717064B CN 201210233273 A CN201210233273 A CN 201210233273A CN 102717064 B CN102717064 B CN 102717064B
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Abstract
The invention relates to hyperbranched nano-silver and a preparation method thereof, and particularly relates to hyperbranched nano-silver taking an amphiphilic polymer as a stabilizing agent and a preparation method thereof. The preparation method comprises the following steps: dissolving the amphiphilic polymer in water, carrying out ice bath, adding a certain amount of reductive agent, and stirring; and dropwise adding blended ice silver nitrate solution in the solution to obtain nano-silver solution, wherein the concentration of the amphiphilic copolymer stabilizing agent is 0.001-0.01g/ml, the concentration of the water-soluble reductive agent is 0.005-0.01mol/L, and the concentration of the silver nitrate solution is 0.001-0.01mol/L. The amphiphilic polymer has selective adsorption on crystal planes of formed nano-particles to enable metal atoms to grow on specific crystal planes so as to form the nano-silver with a hyperbranched structure. The particle size of the prepared nano-silver is 5-20nm, and the nano-silver has large specific surface area, thus having very strong catalytic properties, and potential application in the aspect of antibacterial performance.
Description
Technical field
The present invention relates to hyperbranched Nano Silver and preparation method thereof, hyperbranched Nano Silver that the amphipathic high polymer of particularly take is stabilizing agent and preparation method thereof.
Background technology
Nano metal material has been widely used in fields such as catalysis, photoelectronics, information storage and imaging techniques, it take noble metal gold, silver, copper etc. is representative, wherein nano silver material is with its excellent conduction and thermal conductivity, and the high stability under varying environment, the person's that obtains nano materials research concern widely, it has very excellent performance at aspects such as electronics, optics, antibacterial and catalysis, can be widely used in catalyst material, battery electrode material, optical material, anti-biotic material, coating etc.Research shows, the performance of Nano Silver excellence depends primarily on the shape of Nano Silver, size and structure etc.For Nano Silver morphology Control aspect, by different dimensions, Nano Silver is divided into 1-dimention nano silver, two-dimensional nano silver and three-dimensional nano silver at present.1-dimention nano silver mainly comprises Nano Silver rod, nano-silver thread, Nano Silver band, Nano Silver pipe etc.; Two-dimensional nano silver mainly contains Nano Silver triangular prism and nanometer silver plate etc.; Three-dimensional Ag nano particle comprises the structures such as nano-Ag particles, the dendritic crystalline substance of Nano Silver, Nano Silver cubic block, Nano Silver tetrahedron, Nano Silver decahedron and Nano Silver bipyramid.(the ZhangW.C such as Zhang; WUX.L; ChenH.T.; etal.Self-organized formation of silver nanowire; nanocubes and bypyramids via a so1vothermal method.Aeta Materialia; 2008; 56 (11): 2508-2513) traditional polyalcohol method is combined with hydro-thermal method; introduce a certain amount of sodium chloride; chlorion wherein can be combined with silver ion and be generated AgCl colloid; when AgCl colloid concentration is lower, it is as the crystal seed that generates nano-silver thread; When AgCl colloid concentration is higher, this colloid, as inhibitor, is conducive to generate Nano Silver cubic block.(the Aherne D such as Aherne D, LedwithD.M, GaraM., etal..Optical properties and growth aspects of silver nanoprisms produeed by a highly reproducible and rapid synihesis at roomtemperature.AdVanced Functional Materials, 2008, 18 (14): 2005-2016) at room temperature, introduce silver-colored crystal seed, adopt ascorbic acid reduction silver ion, the kayexalate (PSSS) of take is stabilizing agent, synthesize (the Zheng X W such as Nano Silver triangular prism .zheng, Zhu L Y, Yan AH, et al.J Co lloid Interf Sci, 2003, 268 (2): 357) in mixed surfactant CTAB and lauryl sodium sulfate (SDS), by weak reductant ascorbic acid (AsA) reduction AgNO
3, preparation Ag nano wire and dendroid particle.
Summary of the invention
The object of this invention is to provide a kind of hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent and preparation method thereof of take.
Described composition of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent is amphipathic high polymer and silver, and described amphipathic high polymer is amphipathic maleic acid long-chain fatty alcohol macrogol ester and cinnamic copolymer.
Nano Silver prepared by the present invention is not used any organic solvent, meets the requirement of environmental protection.Prepared particle diameter of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent is 5～20nm, has very bigger serface, thereby has very strong catalytic performance, also has potential utilization simultaneously aspect anti-microbial property.
Described amphipathic high polymer is amphipathic maleic acid long-chain fatty alcohol macrogol ester and cinnamic copolymer, and its structural formula is:
Described preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent is as follows:
Amphipathic high polymer is dissolved in the water, and ice bath, adds water-soluble reducing agent, then adds the ice liquor argenti nitratis ophthalmicus preparing, the hyperbranched Nano silver solution that to obtain take amphipathic high polymer be stabilizing agent.
The concentration of described amphipathic high polymer can be 0.001～0.01g/ml, and the concentration of water-soluble reducing agent can be 0.005～0.01mol/L, and described liquor argenti nitratis ophthalmicus concentration can be 0.001～0.01mol/L.
Described water-soluble reducing agent can be selected from ascorbic acid, sodium borohydride or natrium citricum etc.
The preparation method of described amphipathic high polymer is as follows:
Amphipathic maleic acid long-chain fatty alcohol macrogol ester is dissolved in solvent, stirs and make its form with micella dispersed at 20～80 ℃, obtain micellar solution; Under nitrogen protection, add successively monomer and initator, react after 5～24h at 40～100 ℃, obtain amphipathic high polymer.
Described amphipathic maleic acid long-chain fatty alcohol macrogol ester, monomer, initator and solvent are amphipathic maleic acid long-chain fatty alcohol macrogol ester 0.01%～1%, monomer 1%～10%, initator 0.001%～0.1% by mass percentage, surplus is solvent, and described solvent can adopt deionized water etc.
Described amphipathic maleic acid long-chain fatty alcohol macrogol ester, is obtained through two step esterifications by maleic acid and long-chain fatty alcohol and polyethylene glycol, its molecular structure as shown in the formula:
The degree of polymerization that wherein n is polyethylene glycol, n=4～18; M is the chain length of long-chain fatty alcohol, m=11～25; The molecular weight of polyethylene glycol is 200～8000; The carbon chain lengths of fatty alcohol is 12～26 carbon atoms.
Described monomer can be selected from a kind of in styrene, acrylic acid, ethyl acrylate, butyl acrylate etc.
Described initator can be selected from least one in azodiisobutyronitrile, ABVN, benzoyl peroxide, potassium peroxydisulfate, ammonium persulfate etc.
The preparation method following (synthetic method is referring to the applicant's formerly patent application CN200910112693.2) of described amphipathic maleic acid long-chain fatty alcohol macrogol ester:
1) maleic anhydride, long-chain fatty alcohol and polymerization inhibitor are dissolved in solvent, at 50～120 ℃, react after 2～48h, obtain maleic acid monoesters:
2) by maleic acid monoesters, polyethylene glycol, polymerization inhibitor, catalyst dissolution in solvent, under reflux temperature, react after 2～28h, steaming desolventizes, and obtains maleic acid long-chain fatty alcohol polyethylene glycol dibasic acid esters.
Mol ratio between described maleic anhydride, long-chain fatty alcohol and polyethylene glycol is 1: (0.5～2): (0.25～4).
Described polymerization inhibitor is the compound that can stablize, catch free radical, preferably phenolic compound, particularly preferably hydroquinones.
Described catalyst can be selected from a kind of in machine sulfonic acid, heteroacid ester, inorganic acid etc., and described machine sulfonic acid can be selected from toluenesulfonic acid etc., and described heteroacid ester can be selected from titanate esters etc., and described inorganic acid can be selected from the concentrated sulfuric acid etc.
Described solvent can be selected from toluene or to toluene etc.
The consumption of described polymerization inhibitor is 0.01%～5% of raw material total amount by mass percentage.
The consumption of described catalyst is 0.01%～5% of raw material total amount by mass percentage.
The consumption of described solvent is 50%～500% of raw material total amount by mass percentage.
The present invention is reduced agent reduction at low temperatures based on silver nitrate, first nucleation forms Nano silver grain, Nano silver grain is combined with amphipathic stabilizing agent, stabilizing agent has selective absorption performance to some crystal face of nano particle, thereby restriction metallic atom is increased on specific minute surface, thereby form the Nano Silver of dissaving structure.
Accompanying drawing explanation
Fig. 1 is for take the TEM figure of the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent.In Fig. 1, scale 200nm.
Fig. 2 is the enlarged image of hyperbranched Nano Silver.In Fig. 2, scale 20nm.
From Fig. 1 and 2, can find out.Nano-silver thread is mutually gone here and there and is formed the Nano Silver with dissaving structure together, and the diameter of Nano Silver branch is 10～20nm.
The specific embodiment
Below by specific embodiment, the present invention is further illustrated.
Embodiment 1
1, the preparation of the different alcohol dibasic acid esters of double bond containing maleic acid in the middle of strand
4.9g (0.05mol) maleic anhydride, 13.5g (0.05mol) 18 alcohol, 0.5g hydroquinones (polymerization inhibitor) and 30g toluene are mixed; Mixed liquor is poured in round-bottomed flask, react 8h at the temperature of 80 ℃ after maleic acid 18 alcohol monoesters.Getting 4.6g (0.0125mol) maleic acid 18 alcohol monoesters, 7.5g (0.0125mol) Macrogol 600,0.5g hydroquinones, 0.2g p-methyl benzenesulfonic acid (catalyst) and 40g toluene mixes; Mixed liquor is poured in round-bottomed flask, react 12h under reflux temperature after maleic acid 18 alcohol Macrogol 600 dibasic acid esters.
2, the preparation of amphipathic high polymer
0.3g maleic acid 18 alcohol Macrogol 600 dibasic acid esters are dissolved in 50ml deionized water under 65 ℃, nitrogen and stirring condition; form stable maleic acid 18 alcohol Macrogol 600 dibasic acid esters micellar solutions; in solution, add 1ml styrene; after emulsification a period of time; add initator, after nitrogen protection reaction 12h, obtain amphipathic high polymer.
The preparation of the hyperbranched Nano Silver that 3, amphipathic high polymer is stabilizing agent
The amphipathic high polymer of 2ml is dissolved in the water, and ice bath, adds 0.01g sodium borohydride (reducing agent), stirs; The 0.017g ice liquor argenti nitratis ophthalmicus preparing (silver nitrate is dissolved in 20ml ice deionized water) is dropwise added to solution in step 1, the hyperbranched Nano silver solution (as illustrated in fig. 1 and 2) that the amphipathic high polymer of take is stabilizing agent.
Embodiment 2～7
The preparation of the different alcohol dibasic acid esters of double bond containing maleic acid and the preparation of amphipathic high polymer be with embodiment 1 in the middle of strand, changes the amount of amphipathic high polymer stabilizing agent, the amount of the amount of reducing agent and kind and change silver nitrate, specifically in Table 1.
Table 1 changes the amount of each component and prepares hyperbranched Nano Silver
Claims (10)
1. the hyperbranched Nano Silver that the amphipathic high polymer of take is stabilizing agent, is characterized in that its composition is amphipathic high polymer and silver, and described amphipathic high polymer is amphipathic maleic acid long-chain fatty alcohol macrogol ester and cinnamic copolymer, and its structural formula is:
2. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 1, is characterized in that its concrete steps are as follows:
Amphipathic high polymer is dissolved in the water, and ice bath, adds water-soluble reducing agent, then adds the ice liquor argenti nitratis ophthalmicus preparing, the hyperbranched Nano silver solution that to obtain take amphipathic high polymer be stabilizing agent;
The concentration of described amphipathic high polymer is 0.001～0.01g/ml, and the concentration of water-soluble reducing agent is 0.005～0.01mol/L, and described ice liquor argenti nitratis ophthalmicus concentration is 0.001～0.01mol/L.
3. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 2, is characterized in that described water-soluble reducing agent is selected from ascorbic acid, sodium borohydride or natrium citricum.
4. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 2, is characterized in that the preparation method of described amphipathic high polymer is as follows:
Amphipathic maleic acid long-chain fatty alcohol macrogol ester is dissolved in solvent, stirs and make its form with micella dispersed at 20～80 ℃, obtain micellar solution; Under nitrogen protection, add successively monomer and initator, react after 5～24h at 40～100 ℃, obtain amphipathic high polymer.
5. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 4, it is characterized in that described amphipathic maleic acid long-chain fatty alcohol macrogol ester, monomer, initator and solvent are amphipathic maleic acid long-chain fatty alcohol macrogol ester 0.01%～1%, monomer 1%～10%, initator 0.001%～0.1% by mass percentage, surplus is solvent, and described solvent adopts deionized water.
6. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 4, it is characterized in that described amphipathic maleic acid long-chain fatty alcohol macrogol ester, by maleic acid and long-chain fatty alcohol and polyethylene glycol, through two step esterifications, obtained, its molecular structure as shown in the formula:
The degree of polymerization that wherein n is polyethylene glycol, n=4～18; M is the chain length of long-chain fatty alcohol, m=11～25; The molecular weight of polyethylene glycol is 200～8000; The carbon chain lengths of fatty alcohol is 12～26 carbon atoms.
7. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 4, is characterized in that described monomer is selected from a kind of in styrene, acrylic acid, ethyl acrylate, butyl acrylate; Described initator is selected from least one in azodiisobutyronitrile, ABVN, benzoyl peroxide, potassium peroxydisulfate, ammonium persulfate.
8. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 4, is characterized in that the preparation method of described amphipathic maleic acid long-chain fatty alcohol macrogol ester is as follows:
1) maleic anhydride, long-chain fatty alcohol and polymerization inhibitor are dissolved in solvent, at 50～120 ℃, react after 2～48h, obtain maleic acid monoesters:
2) by maleic acid monoesters, polyethylene glycol, polymerization inhibitor, catalyst dissolution in solvent, under reflux temperature, react after 2～28h, steaming desolventizes, and obtains maleic acid long-chain fatty alcohol polyethylene glycol dibasic acid esters;
Mol ratio between described maleic anhydride, long-chain fatty alcohol and polyethylene glycol is 1: (0.5～2): (0.25～4);
Described polymerization inhibitor is for stablizing, catch the compound of free radical;
Described catalyst is selected from a kind of in organic sulfonic acid, heteroacid ester, inorganic acid, and described organic sulfonic acid is selected from toluenesulfonic acid, and described heteroacid ester is selected from titanate esters, and described inorganic acid is selected from the concentrated sulfuric acid;
Described solvent is selected from toluene or to toluene;
The consumption of described polymerization inhibitor is 0.01%～5% of raw material total amount by mass percentage;
The consumption of described catalyst is 0.01%～5% of raw material total amount by mass percentage;
The consumption of described solvent is 50%～500% of raw material total amount by mass percentage.
9. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 8, is characterized in that described polymerization inhibitor is selected from phenolic compound.
10. preparation method of take the hyperbranched Nano Silver that amphipathic high polymer is stabilizing agent as claimed in claim 9, is characterized in that described polymerization inhibitor is selected from hydroquinones.
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