CN103691967B - A kind of simple method for preparing of novel extensive nano-silver hydrosol - Google Patents
A kind of simple method for preparing of novel extensive nano-silver hydrosol Download PDFInfo
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- CN103691967B CN103691967B CN201410009948.3A CN201410009948A CN103691967B CN 103691967 B CN103691967 B CN 103691967B CN 201410009948 A CN201410009948 A CN 201410009948A CN 103691967 B CN103691967 B CN 103691967B
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- hydrosol
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Abstract
The present invention relates to a kind of simple method for preparing of novel extensive nano-silver hydrosol.The method adopts solution phase chemical reduction on convention stir tank and reactor equipment, oximes reducing agent is utilized to be silver-colored simple substance by silver ion reduction soluble in water, the silver-colored simple substance restored by water-soluble high-molecular compound parcel, dispersion, forms the stable hydrosol rapidly.The deoxygenation that the present invention's oxime compound used (acetaldoxime, acetoxime or diacetylmonoxime) is outstanding and reduction double action make the nano-Ag particles even size distribution be prepared into, and highly stable.The preparation of nano-silver hydrosol of the present invention, raw material is easy to get, and technique is simple, and production cost is low, is suitable for large-scale mass production.Nano-silver hydrosol anti-microbial property prepared by the present invention is good, use safety, and the antibacterial functions that can be widely used in fabric, footwear material, leather etc. arranges.
Description
[technical field]
The present invention relates to a kind of fibrous woven technical field.More specifically, the present invention relates to a kind of simple method for preparing of novel extensive nano-silver hydrosol.
[background technology]
Nano Silver, as a kind of emerging functional material, is widely used in antistatic material, catalysis material, battery electrode material, low temperature superconducting material, conductive paste material and biological sensing material.In addition, nano silver particles has very strong broad-spectrum bactericidal capacity, good bio-compatibility, is difficult to produce the advantages such as drug resistance, also in an increasingly wide range of applications in fields such as medical and health.Therefore the preparation of Nano Silver is subject to extensive concern, the method of bibliographical information is a lot, has summed up: chemical reduction method, biological reducing are sent out, microemulsion method, gamma Rays method, magnetron sputtering method, photoreduction met hod, laser ablation, electrochemical process, seed mediator method, chemical vapour deposition technique, supercritical fluid method etc.These methods have all successfully prepared nano level silver particles above, and have unique application performance.But higher to equipment requirement for the physical method of representative with supercritical fluid method, magnetron sputtering method, laser ablation and gamma Rays method etc. in these methods, be difficult to large-scale production; It is loaded down with trivial details, a large amount of with an organic solvent etc. that microemulsion method, seed mediator method, biological reducing method etc. prepare formality as new method; Electrochemical production speed is slow, and the protective agent of necessary high concentration, and having the silver particles of more Large stone in cathodic deposition, this makes the cost preparing Nano Silver improve; And chemical reduction method is simple to operate, cost is lower, being convenient to large-scale production, is the maximum method of research report.
Chinese patent CN1583332A discloses a kind of nano silver colloidal sol and preparation method thereof: obtained by silver nitrate, water, reducing agent and protecting colloid.In aqueous systems, even if there is the protection of protecting colloid, nano-Ag particles is also easy to reunite, and the shelf stability of nano silver colloidal sol can be caused to decline, when concentration silver-colored in system is especially higher or reducing agent reducing power used is stronger.
Chinese patent CN1669914A discloses a kind of preparation method of nano silver colloidal sol: the system choosing silver nitrate aqueous solution and surfactant, regulates to obtain nano silver colloidal sol by temperature.Because this system does not use specific reducing agent, although silver sol is relatively stable, but most of silver ion is not reduced and forms monomer silver in system, this part silver ion be not reduced in the basic conditions, have chlorion to exist or under the condition such as illumination, can finally be reduced to silver and reunite, and this process is not controlled, which limits its application.
US Patent No. 6979491Antimicrobialyarnhavingnanosilverparticlesandmeth odsformanufacturingthesame: this Nano Silver is obtained by the aqueous solution of nitrate and reducing agent glucose, vitamin and hydrazine hydrate; because this Nano Silver is without dispersant or protective agent, nano-Ag particles is easy to reunite.
US Patent No. 20090104437Scalablesilvernano-particlecolloid: this Nano Silver is obtained by the aqueous solution of silver nitrate, borane reducing agent sodium hydride and stabilizing agent natrium citricum, the reducing power of sodium borohydride is very strong, and obtained nano-Ag particles is large.
Chinese patent CN101633045A discloses a kind of nano silver colloidal sol of ethanol system, and anti-microbial property is good, highly stable, and production cost is low, but a large amount of inflammable and explosive alcohol solvent contained, easily cause storage, transport difficult.
Chinese patent CN102197826A discloses a kind of novel method preparing alkaline nano silver on a large scale, its reducing agent is the larger material of the toxicity such as sodium borohydride, hydrazine hydrate, also use a large amount of nonaqueous solvents, when the alkaline nano silver of preparation is used for antibiotic finish fabric, also may cause damage to fiber.
Chinese patent CN102935513A discloses a kind of stable nano silver colloidal sol and preparation method thereof, and its Nano Silver can store 6-24 month, and preparation process needs just can complete by ultrasonic and ultraviolet equipment.
Chinese patent CN102941353A discloses a kind of preparation method of polysaccharide nano silver colloidal sol; use modification/grafting polyglucose as reducing agent and stability protective agent; its technique is simple; security is high; but polyglucose class material reproducibility is weak; need the longer reaction time (5-10 hour), and modification/grafting polyglucose is not the raw material that existing market is easy to get, large-scale production may be restricted.
Chinese patent CN103143724A discloses a kind of preparation method of different-shape nano silver sol, reducing agent used is sodium dithionite, the sulfate radical that reaction system produces may impact the stable of Nano Silver, and belong to strong basicity system (pH value is 11), also may cause damage to fiber for during antibiotic finish fabric.
Chinese patent CN103203466A discloses a kind of preparation method of different-grain diameter Nano Silver, and reducing agent relates to the materials such as the larger formaldehyde of toxicity, sodium borohydride, hydrazine hydrate.Comprehensive literature report is known: the common reducing agent of chemical preparation Nano Silver has formaldehyde, sodium borohydride, citrate, DMF, EG, ascorbic acid, hydrazine hydrate, aldehyde, plant extracts, H
2, reduced sugar (as glucose, maltose) etc.; formaldehyde, sodium borohydride, hydrazine hydrate etc. that wherein large-scale production is commonly used are all the materials that toxicity is very large; and remain in Nano Silver system and be difficult to remove; the present invention prepares the reducing agent using oxime compound to prepare as Nano Silver, there is not yet Research Literature report.
At present, market needs all the time a kind of use safety, the nano-silver hydrosol of constant product quality, need a kind of simple to operate, cost is lower, granularity holds manageable nano-silver hydrosol large-scale producing method.For this reason, the present inventor completes the present invention finally through lot of experiments.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of simple method for preparing of novel extensive nano-silver hydrosol.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of simple method for preparing of novel extensive nano-silver hydrosol.The method step is as follows:
Steps A: 0.2-5 parts by weight water-soluble silver salt and 30-40 weight parts water are added in agitator tank, stir 5-20min at temperature 20-60 DEG C, makes described silver salt dissolve completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 0.5-10 weight portion oximes reducing agent, 0.3-15 weight portion macromolecule dispersion protective agent are added in reactor together with 30-69 weight parts water, stir 10-20min at temperature 20-60 DEG C, form homogeneous transparent solution; Then above-mentioned steps A gained silver salt solution point 3-5 in 30-60min is criticized and add, continue reaction 60-120min under identical condition; Finally under same mixing speed, increase the temperature to 65-80 DEG C, 30-60min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
A preferred embodiment of the invention, described water soluble silver salt, oximes reducing agent and macromolecule dispersion protective agent weight ratio is (0.5-1): (2-2.5): (1-3), is preferably (0.6-0.8): (2.2-2.4): (1.5-2).
According to another kind of preferred embodiment of the present invention, described water soluble silver salt is at least one in silver nitrate, silver acetate or silver ammino solution.
According to another kind of preferred embodiment of the present invention, described oximes reducing agent is at least one in acetaldoxime, acetoxime or diacetylmonoxime.
According to another kind of preferred embodiment of the present invention, described macromolecule dispersion protective agent is at least one in water soluble starch, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) or CMC.
According to another kind of preferred embodiment of the present invention, described water is deionized water or distilled water.
The principle of institute of the present invention foundation is: the present invention adopts solution phase chemical reduction on convention stir tank and reactor equipment, reducing agent is utilized to be silver-colored simple substance by silver ion reduction soluble in water, the silver-colored simple substance restored by water-soluble high-molecular compound parcel, dispersion, forms the stable hydrosol rapidly.The present invention's reducing agent used be oxime compound as acetaldoxime, acetoxime or diacetylmonoxime etc., these oxime compounds have stronger reproducibility, generally use as boiler water new type deoxidizer at present.In the present invention, oxime compound has deoxygenation and silver ion reduction double action, and this is control key technology of the present invention, and current research document not yet has report.
In process prepared by nano-silver hydrosol, oxygen in reaction system is removed by oxime compound in time, can ensure that the high-activity nano silver just generated avoids oxidized well, improve the stability of Nano Silver, often adopt the method for logical nitrogen flooding oxygen to reach this object in some preparation in the past, nitrogen is easy to lose, and the present invention's oxime compound used uninterruptedly can play phlogistication, so the Nano Silver performance prepared is more stable.In addition, the catabolite of oxime compound is NH3, N2, H2O, micro-acetic acid, produces, have no adverse effects to environmental system without formic acid.The reaction equation of oxime compound deoxygenation is as follows:
Oxime compound has very strong reduction to silver ion, and key reaction formula may be as follows:
In preparation process of the present invention, employ macromolecular water-soluble compound as dispersed nano-silver particles protective agent, high-activity nano Argent grain can be stoped well to assemble, reunite, sol system long-term stability is existed.Meanwhile, in order to improve the stability of nano silver colloidal sol, after reduction reaction terminates, Small molecular volatile matter reaction generated by vacuum exhaust and the extracting of residue oximes reducing agent are gone out, and also ensure that the purity of nano silver colloidal sol like this, make it use safer.
In more detail the present invention will be described below.
The present invention relates to a kind of simple method for preparing of novel extensive nano-silver hydrosol.The method step is as follows:
Steps A: 0.2-5 parts by weight water-soluble silver salt and 30-40 weight parts water are added in agitator tank, stir 5-20min at temperature 20-60 DEG C, makes described silver salt dissolve completely, obtains a kind of homogeneous transparent solution, for subsequent use.
A preferred embodiment of the invention, described water soluble silver salt is at least one in silver nitrate, silver acetate or silver ammino solution.
Silver nitrate, CAS is numbered 7761-88-8, and chemical formula is AgNO
3, clear crystal, soluble in water or ammoniacal liquor, meets organic matter and becomes grey black, decomposite silver.The present invention's silver nitrate used is chemical pure or analyzes pure level, commercially available.
Silver acetate, is silver acetate, and CAS is numbered 563-63-3, and chemical formula is CH3COOAg, and white, to near-white flash of light acicular crystal or crystalline powder, is slightly soluble in water, is dissolved in hot water and dust technology, decomposes.The present invention's silver acetate used is chemical pure or analyzes pure level, commercially available.
Silver ammino solution, is toillen's reagent again, and chemical formula is [Ag (NH3)] OHXH O, has the colourless transparent liquid of ammonia taste, a kind of weak oxidant, is usually used in making glass liner and differentiating reduced sugar.The present invention's silver ammino solution used is commercially available or is reacted by reagent silver nitrate and ammoniacal liquor and oneself produce.
Preferably, water soluble silver salt of the present invention is silver nitrate.
According to another kind of preferred embodiment of the present invention, described water is deionized water or distilled water.
According to another kind of preferred embodiment of the present invention, described agitator tank material is the one in stainless steel, enamel or pottery.Agitator tank also can be aqueous phase tank, can stir material, mixture, mediation, the process such as homogeneous, be widely used in the industries such as coating, medicine, building materials, chemical industry, pigment, resin, food, scientific research.The present invention's agitator tank used is the stainless steel product of Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province production and sales.
Step B: first 0.5-10 weight portion oximes reducing agent, 0.3-15 weight portion macromolecule dispersion protective agent are added in reactor together with 30-69 weight parts water, stir 10-20min at temperature 20-60 DEG C, form homogeneous transparent solution; Then above-mentioned steps A gained silver salt solution point 3-5 in 30-60min is criticized and add, continue reaction 60-120min under identical condition; Finally under same mixing speed, increase the temperature to 65-80 DEG C, 30-60min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims.
A preferred embodiment of the invention, described oximes reducing agent is at least one in acetaldoxime, acetoxime or diacetylmonoxime.
Oxime compound (DMKO, methyl ethyl ketoxime (diacetylmonoxime), acetaldoxime) is as the new type deoxidizer patented technology that is Drew chemical company of the U.S. disclosed in 1984; there is low toxicity, efficient, speed is fast and there is passivation protection effect; all there are the product of oximes boiler water deoxidant in Nolco company of the U.S. (water treatment company the biggest in the world), Drew company etc.; and obtain in the developed country such as American-European-Japanese and apply widely; China also succeeds in developing in nineteen nineties, and achieves successful popularization.
Acetaldoxime, CAS is numbered 107-29-9, and chemical formula is CH
3cH=NOH, outward appearance is white liquid or solid, relative density 0.966g/mL, boiling point 114.5 DEG C, index of refraction 1.415, soluble in water, alcohol or ether, belong to low toxicity material, its LD50 is 1900mg/kg, main with being used as organic synthesis intermediate, pesticide methomyl intermediate, boiler water deoxidant.The present invention's acetaldoxime used is the product of Shandong Wan Duofu fine chemistry Co., Ltd production and sales.
Acetoxime (being called for short DMKO), be also called DMKO, chemical formula is (CH
3)
2c=NOH relative density: 0.9113g/mL, fusing point: 60 DEG C, flash-point: 47.2 DEG C, boiling point: 134.8 DEG C, toxicity LD50:5500mg/kg, soluble in water and alcohol, ether equal solvent, aqueous solution saturation solubility is 25% (mass percent), it is water-soluble in neutral, and facile hydrolysis in diluted acid, can make potassium permanganate fade at normal temperatures.Be mainly used in feedwater chemistry oxygen scavenger in Industrial Boiler; compared with conventional boiler oxygen scavenging chemical; have that consumption is few, oxygen removal efficiency is high, the feature such as nontoxic, non-environmental-pollution; being the Shut-down Protection of subcritical boiler and the best medicine of Passivation Treatment, is also the ideal product replacing the traditional chemical oxygen scavengers such as hydrazine in middle high-pressure boiler feedwater.The product of the dignified Chemical Company in the present invention Nanjing used or the production and sales of Shanghai Nuo Tai Chemical Co., Ltd..
Diacetylmonoxime, has another name called methyl ethyl ketoxime, and CAS is numbered 96-29-7, and structural formula is
, colorless oil transparency liquid.Water-soluble: 114g/L (25 DEG C), and be dissolved in most organic solvents such as ethanol, methyl alcohol, rosin, ether, ketone, hydrocarbon.Proportion (20 DEG C): 0.923g/mL; Fusing point :-29.5 DEG C, boiling point: 152 ~ 153 DEG C; Relative steam density (atmospheric density=1): 3.0; Refractive power (20 DEG C): 1.4410.Belong to low toxicity material, its LD50 is that 2800mg/kg and metal ion have stronger complexing, volatile, can react with hydrochloric acid, sulfuric acid, and release butanone.Its purposes widely, is mainly used as the anti skinning agent of coating, paint and ink, isocyanate blocking agents, the intermediate of organosilicon cross-linking agent, the viscosity stabiliser of oxidation drying adhesive, boiler deoxidant, metal conditioner, desulfurizing agent and organic synthesis intermediate etc.The present invention's diacetylmonoxime used is the product of Zhejiang Jin Hua new material limited company production and sales.
Preferably, oximes reducing agent of the present invention is acetaldoxime or acetoxime.
More preferably, oximes reducing agent of the present invention is acetoxime.
According to another kind of preferred embodiment of the present invention, described macromolecule dispersion protective agent is at least one in water soluble starch, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) or CMC.
Water soluble starch, CAS is numbered 9005-84-9, and outward appearance is white amorphous powder, and taste is micro-sweet, has the intrinsic smell of water-soluble starch, can in cold water whole instant solution, solution is as clear as crystal.The present invention's water soluble starch used is the product of Yun Feng starch Co., Ltd of Nantong City production and sales.
Polyvinylpyrrolidone (PVP), white or off-white powder or particle, have hygroscopicity, and odorless or micro-smelly, water-soluble, alkali, acid and polar organic solvent, have very strong expansion character, have strong complexing power, also have good adhesive effect.The polyvinylpyrrolidone that the present invention uses is current commercially product sold, such as Boai NKY Pharmaceutical Co., Ltd with trade name NKY PVPK product sold, Jiaozhuo Zhong Wei Chemical Co., Ltd. with trade name PVP-K homopolymerization series product sold or Shanghai Wei Tong material Science and Technology Ltd. with trade name polyvinylpyrrolidone product sold.Preferably, described polyvinylpyrrolidone (PVP) molecular weight is 30000-90000.
The series of products of PEG (polyethylene glycol) are nontoxic, nonirritant, have good water-soluble, and have good intermiscibility with many organic matter components.They have excellent lubricity, moisture retention, dispersiveness, bonding agent, antistatic additive and softening agent etc., all have and apply very widely in the industries such as cosmetics, pharmacy, chemical fibre, rubber, plastics, papermaking, paint, plating, agricultural chemicals, intermetallic composite coating and food processing.The polyethylene glycol of the food-grade that LG-DOW company produces, cosmetics and pharmaceutical grade have passed U.S. FDA certification, meets American Pharmacopeia (USP), NF (NF), Food Chemical Codex (FCC) standard.The serial sell goods that PEG used in the present invention is LG-DOW company, Hai'an petrochemical plant is produced.Preferably, the molecular weight of described PEG (polyethylene glycol) is 200-4000.
Polyvinyl alcohol (PVA), CAS is numbered 9002-89-5, white plates, cotton-shaped or pulverulent solids, tasteless, water-soluble, be insoluble to gasoline, kerosene, vegetable oil, benzene, toluene, dichloroethanes, carbon tetrachloride, acetone, ethyl acetate, methyl alcohol, ethylene glycol etc., be slightly soluble in dimethyl sulfoxide (DMSO), important industrial chemicals, for the manufacture of Pioloform, polyvinyl acetal, resistance to gasoline pipeline and vinylon synthetic fibers, fabric-treating agent, emulsifying agent, paper coating, adhesive etc.The present invention PVA used is the product of Jinan Ming Zhou Chemical Co., Ltd. production and sales.
Sodium carboxymethylcellulose (CMC), CAS is numbered 9004-32-4, white or milky fibrous powder or particle, density 0.5-0.7g/mL, almost odorless, tasteless, tool hygroscopicity, be easy to be dispersed in water into clear gum solution, insoluble in the organic solvents such as ethanol.Be used as thickener in food industry, in medical industry, be used as pharmaceutical carrier, be used as adhesive in daily chemical industry, resist dignified dose again.The protecting colloid etc. of sizing agent and printing gum is used as in printing and dyeing industry.The present invention CMC used is the product of Changzhou Guo Yu Environmental Protection Technology Co., Ltd production and sales.
CMC, CAS is numbered 83512-85-0, white or micro-yellow, tasteless, unsetting translucent solid.Chance water is instant, aqueous solution clear, and stable in properties, is a kind of water-solubility chitosan derivative, has numerous characteristics, and as antibiotic property is strong, having preservation, is a kind of polyampholyte etc.Cosmetics, fresh-keeping, medical etc. in have multiple application, be also that Recent study obtains one of more chitosan derivatives.The present invention's CMC used is the product of Beijing Hua Maike biotechnology Co., Ltd production and sales.
Preferably, macromolecule dispersion protective agent of the present invention is at least one in polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) or sodium carboxymethylcellulose (CMC).
According to the another kind of preferred embodiment that this law is bright, described reactor is stainless steel, pottery or enamel material.Preferably, described reactor is pottery or enamel material.Described reactor is Weihai Chemical Machinery Co., Ltd., Wuxi Su Yang Chemical Equipment Co., Ltd. product sold.
According to another kind of preferred embodiment of the present invention, the mixing speed of described reactor is 400-800rpm, and reduction reaction temperature is 20-60 DEG C.
Preferably, the mixing speed of reactor of the present invention is 500-600rpm, and reduction reaction temperature is 25-40 DEG C.
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
A preferred embodiment of the invention, the present invention prepared nano-silver hydrosol to be sealed in plastic containers, with to prevent be oxidized by the oxygen in air, cause system unstable.
According to another kind of preferred embodiment of the present invention, the present invention prepared the silver particles content of nano-silver hydrosol be 1000-30000ppm, described silver particles particle diameter is 1-90nm, preserve under described particle diameter room temperature 180 days constant.
Preferably, in nano-silver hydrosol of the present invention, the particle diameter of silver ion is 10-60nm.
According to another kind of preferred embodiment of the present invention, the prepared minimal inhibitory concentration of nano-silver hydrosol to Escherichia coli and staphylococcus aureus obtained of the present invention is less than 30ppm, and is 40-120ppm for the preferred concentration of textiles antibacterial finishing.
The following detailed description of the Performance Detection test of nano-silver hydrosol prepared by the present invention.
Detection method and testing result as follows.
The UV-Vis spectra test of A, nano-silver hydrosol of the present invention:
By prepared nano-silver hydrosol distilled water diluting to measurement desired concn scope, get 4mL liquid to be measured and be placed in quartz colorimetric utensil, with Cary50 type ultraviolet-visible spectrophotometer, obtain its uv-visible absorption spectroscopy, scanning wavelength scope is 200 ~ 800nm.Its result of the test is shown in accompanying drawing 1.
In general, due to the plasmon absorption on Nano Silver surface, nano silver colloidal sol can have a stronger absworption peak at 390 ~ 440nm, and form (shape and particle diameter) and the character of solution of the position of absworption peak and peak shape and nano silver colloidal sol are relevant.The nano-silver hydrosol that as seen from Figure 1 prepared by the present invention has a very strong absworption peak at 418nm place, and its plasmon absorption peak is symmetrical, and this says in colloidal sol that having the less Nano Silver of particle exists, and domain size distribution is more even.
X-ray diffraction (XRD) test of B, nano-silver hydrosol of the present invention:
XRD uses D/max-rA to turn target multiple crystal X-ray diffractometer analysis (Japanese Rigaku produces), and its condition is as follows: copper target (CuKa), X-ray wavelength 1.5406nm, sweep limits are 10-90 °, sweep speed is 0.02 degree/second.Nano silver colloidal sol of the present invention is dripped on slide, carries out X-ray diffraction analysis, it the results are shown in accompanying drawing 2, there is the characteristic absorption peak of elemental silver in this figure, in 2 θ=38.2 °, there are 5 obvious diffraction maximums at 44.38 °, 64.49 °, 74.36 °, 81.51 ° places, data consistent on each peak value and standard card JCPDS card 04-0783, the respectively diffraction of corresponding centroid cubic crystal system (fcc) elemental silver (111), (200), (220), (311), (222) crystal face.Exist without other assorted peaks in figure, illustrate that the Nano Silver purity obtained by the present invention is higher.
Transmission electron microscope (TEM) test of C, nano-silver hydrosol of the present invention:
Tem study uses JEM-1200EX(Japan JEOL to produce), measure under operating voltage 160KV.Selection silver content is that the nano silver colloidal sol of the present invention of 100ppm has carried out transmission electron microscope test, and it the results are shown in accompanying drawing 3.This result shows, the particle diameter of nano silver colloidal sol of the present invention is 1-30nm.Carried out transmission electron microscope test after this sample is preserved 90 days at 25 DEG C, it the results are shown in accompanying drawing 4.This result shows that the particle diameter of nano silver colloidal sol of the present invention is still 1-30nm.Meanwhile, also carried out the similar test of preserving 180 days, obtained substantially identical result.As can be seen here, nano-silver hydrosol of the present invention has extraordinary stability.
Minimal inhibitory concentration (MIC) test of D, nano-silver hydrosol of the present invention:
Test according to Ministry of Public Health's disinfection technology standard (version in 2002) 2.1.7.3, test bacterial classification is Escherichia coli and staphylococcus aureus, and its result of the test is listed in table 1.
Minimal inhibitory concentration (MIC) result of the test of table 1 nano-silver hydrosol
The antibacterial effect evaluation test that B, nano-silver hydrosol of the present invention are applied on pure cotton fabric:
Nano-silver hydrosol of the present invention is pressed Nano Silver 50ppm concentration process pure cotton fabric, and by the washing procedure of standard FZ/T73023-2006 " antibiosis knitting product appendix C antibiotic fabric sample decantation test method ", 50 washings are carried out to the fabric of antibiotic finish, then carry out antibacterial test by standard GB/T20944.2-2007 " the evaluation part 2 of antibacterial textile performance: absorption process " to the antibiotic fabric before and after washing, test bacterial classification is Escherichia coli, staphylococcus aureus and Candida albicans.Its result of the test is listed in table 2.
The pure cotton fabric Anti-microbial Performance Tests result that table 2 Nano Silver arranges
The above results clearly illustrates that, in nano-silver hydrosol prepared by the present invention, Argent grain exists with Nano grade, and distribution is relatively more even, and particle diameter is at 1-30nm, and store after 180 days, its particle size is substantially unchanged, highly stable; Nano-silver hydrosol prepared by the present invention is all less than 30ppm to Escherichia coli, staphylococcus aureus minimal inhibitory concentration (MIC), and bacteriostatic activity is remarkable; The antibiotic rate of the pure cotton fabric of nano silver colloidal sol process using the present invention to prepare to Escherichia coli, staphylococcus aureus and Candida albicans is all greater than 99%, and after 50 washings its antibiotic rate still higher than 90%.
[beneficial effect]
The present invention has following beneficial effect:
Use equipment is few, and technique is simple, pollution-free, environmentally friendly, is convenient to large-scale industrial production; Nano-silver hydrosol prepared by the present invention is safe to use, anti-microbial property is good, stability is splendid, after 50 washings to the antibiotic rate of Escherichia coli, staphylococcus aureus and Candida albicans still higher than 90%, described silver particles particle diameter at room temperature preserve 180 days constant.The antibacterial functions that can be applicable to fabric, footwear material, leather etc. arranges, and production cost is low, has the very strong market competitiveness.
[accompanying drawing explanation]
Fig. 1 is the UV-Vis spectra figure of nano-silver hydrosol of the present invention.
The X-ray diffractogram (XRD) of Fig. 2 nano-silver hydrosol of the present invention.
Fig. 3 is the transmission electron microscope figure (TEM) of nano-silver hydrosol of the present invention.
Fig. 4 is that nano-silver hydrosol of the present invention is at the transmission electron microscope picture of placement after 90 days (TEM).
[detailed description of the invention]
The present invention will be understood better by these embodiments following.
embodiment 1:the preparation of nano-silver hydrosol of the present invention
Steps A: 1 weight portion silver nitrate and 30 weight parts waters are added in the stainless steel agitator tank that Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province produces, 5-8min is stirred at temperature 20-25 DEG C, described silver salt is dissolved completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 2 weight portion acetaldoximes, 1.5 parts by weight water-soluble starch are added together with 65.5 weight parts waters in the glassed steel reaction vessels that Weihai Chemical Machinery Co., Ltd. produces, under temperature 20-35 DEG C of 400-600rpm rotating speed, stir 10-20min, form homogeneous transparent solution; Then in 30min, divide 3 batches by above-mentioned steps A gained silver salt solution to add, continue reaction 100min under identical condition; Finally under same mixing speed, increase the temperature to 75-80 DEG C, 40-50min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
embodiment 2:the preparation of nano-silver hydrosol of the present invention
Steps A: 0.5 weight portion silver acetate and 30 weight parts waters are added in the stainless steel agitator tank that Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province produces, 10-15min is stirred at temperature 50-60 DEG C, described silver salt is dissolved completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 1 weight portion acetaldoxime, 2 weight portion PVP are added together with 66.5 weight parts waters in the glassed steel reaction vessels that Weihai Chemical Machinery Co., Ltd. produces, stir 10-15min under under temperature 50-60 DEG C of 400-600rpm rotating speed, form homogeneous transparent solution; Then in 30min, divide 3 batches by above-mentioned steps A gained silver salt solution to add, continue reaction 80min under identical condition; Finally under same mixing speed, increase the temperature to 75-80 DEG C, 40-50min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
embodiment 3:the preparation of nano-silver hydrosol of the present invention
Steps A: 10 weight portion silver ammino solutions and 30 weight parts waters are added in the stainless steel agitator tank that Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province produces, 5min is stirred at temperature 20-25 DEG C, described silver salt is dissolved completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 5 pbw acetone oximes, 10 weight portion PVP are added together with 45 weight parts waters in the glassed steel reaction vessels that Weihai Chemical Machinery Co., Ltd. produces, stir 10-15min under under temperature 30-40 DEG C of 400-600rpm rotating speed, form homogeneous transparent solution; Then in 40min, divide 4 batches by above-mentioned steps A gained silver salt solution to add, continue reaction 100min under identical condition; Finally under same mixing speed, increase the temperature to 65-70 DEG C, 30-40min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
embodiment 4:the preparation of nano-silver hydrosol of the present invention
Steps A: 5 weight portion liquid silver nitrates and 35 weight parts waters are added in the stainless steel agitator tank that Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province produces, 10-15min is stirred at temperature 20-25 DEG C, described silver salt is dissolved completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 10 pbw acetone oximes, 10 weight portion PEG are added together with 40 weight parts waters in the glassed steel reaction vessels that Weihai Chemical Machinery Co., Ltd. produces, stir 10-15min under under temperature 20-30 DEG C of 400-600rpm rotating speed, form homogeneous transparent solution; Then in 40min, divide 4 batches by above-mentioned steps A gained silver salt solution to add, continue reaction 120min under identical condition; Finally under same mixing speed, increase the temperature to 65-70 DEG C, 30-40min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
embodiment 5:the preparation of nano-silver hydrosol of the present invention
Steps A: 2 weight portion liquid silver acetates and 30 weight parts waters are added in the stainless steel agitator tank that Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province produces, 15-20min is stirred at temperature 50-60 DEG C, described silver salt is dissolved completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 4 weight portion diacetylmonoximes, 15 weight portion CMC are added together with 49 weight parts waters in the glassed steel reaction vessels that Weihai Chemical Machinery Co., Ltd. produces, stir 15-20min under under temperature 50-60 DEG C of 400-600rpm rotating speed, form homogeneous transparent solution; Then in 40min, divide 4 batches by above-mentioned steps A gained silver salt solution to add, continue reaction 100min under identical condition; Finally under same mixing speed, increase the temperature to 65-70 DEG C, 40-50min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
embodiment 6:the preparation of nano-silver hydrosol of the present invention
Steps A: 5 weight portion liquid silver ammino solutions and 30 weight parts waters are added in the stainless steel agitator tank that Yancheng City Qi Lian power equipment Co., Ltd of Jiangsu Province produces, 5-7min is stirred at temperature 20-25 DEG C, described silver salt is dissolved completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 7.5 pbw acetone oximes, 10 weight portion Carboxy Chitosans are added together with 52.5 weight parts waters in the glassed steel reaction vessels that Weihai Chemical Machinery Co., Ltd. produces, stir 10-15min under under temperature 40-50 DEG C of 400-600rpm rotating speed, form homogeneous transparent solution; Then in 30min, divide 3 batches by above-mentioned steps A gained silver salt solution to add, continue reaction 70min under identical condition; Finally under same mixing speed, increase the temperature to 65-70 DEG C, 30-40min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained clear homogeneous liquid is released, packs, namely complete the preparation of nano-silver hydrosol.
Adopt the method for testing described in this description, test the anti-microbial property of nano-silver hydrosol prepared by the present embodiment 1-6, its test result is listed in table 3 and table 4.
The MIC result of the test of Nano Silver glue prepared by table 3: embodiment 1-6
Nano-silver hydrosol prepared by table 4: embodiment 1-6 is application in pure cotton fabric arranges
Antibacterial tests result (Nano Silver working concentration is 50ppm)
Claims (10)
1. a simple method for preparing for novel extensive nano-silver hydrosol, is characterized in that the step of the method is as follows:
Steps A: 0.2-5 parts by weight water-soluble silver salt and 30-40 weight parts water are added in agitator tank, stir 5-20min at temperature 20-60 DEG C, makes described water soluble silver salt dissolve completely, obtains a kind of homogeneous transparent solution, for subsequent use;
Step B: first 0.5-10 weight portion oximes reducing agent, 0.3-15 weight portion macromolecule dispersion protective agent are added in reactor together with 30-69 weight parts water, stir 10-20min at temperature 20-60 DEG C, form homogeneous transparent solution; Then above-mentioned steps A gained silver salt solution point 3-5 in 20-60min is criticized and add, at temperature 20-60 DEG C, continue reaction 60-120min; Finally under same mixing speed, increase the temperature to 65-80 DEG C, 30-60min is vacuumized to reactor simultaneously, the volatile components in reaction system is removed, reclaims;
Step C): step B gained homogeneous transparent solution is released, packs, namely complete the preparation of nano-silver hydrosol.
2. preparation method according to claim 1, is characterized in that described water soluble silver salt, oximes reducing agent and macromolecule dispersion protective agent weight ratio is (0.5-1): (2-2.5): (1-3).
3. preparation method according to claim 1, is characterized in that described water soluble silver salt is at least one in silver nitrate, silver acetate or silver ammino solution.
4. preparation method according to claim 1, is characterized in that described oximes reducing agent is at least one in acetaldoxime, acetoxime or diacetylmonoxime.
5. preparation method according to claim 1, is characterized in that described macromolecule dispersion protective agent is at least one in water soluble starch, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) or CMC.
6. preparation method according to claim 1, is characterized in that described water is deionized water or distilled water.
7. preparation method according to claim 1, is characterized in that the material of described agitator tank and reactor is the one in stainless steel, enamel or pottery.
8. preparation method according to claim 1, it is characterized in that the mixing speed of described reactor is 400-800rpm, reduction reaction temperature is 20-60 DEG C.
9. any one of claim 1-8, described in claim, method obtains nano-silver hydrosol, it is characterized in that the silver particles content of described nano-silver hydrosol is 1000-30000ppm, described silver particles particle diameter is 1-90nm, under described silver particles particle diameter room temperature preserve 180 days constant.
10. any one of claim 1-8, described in claim, method obtains nano-silver hydrosol, it is characterized in that the minimal inhibitory concentration of described nano-silver hydrosol to Escherichia coli and staphylococcus aureus is less than 30ppm, and be 40-120ppm for the preferred concentration of textiles antibacterial finishing.
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| CN104186545B (en) * | 2014-08-09 | 2017-08-22 | 三河市京纳环保技术有限公司 | A kind of zeolite carries the new extensive simple method for preparing of zinc inorganic antiseptic |
| CN104325154A (en) * | 2014-11-28 | 2015-02-04 | 夏正付 | Preparation technology of ultrafine copper powder |
| CN105734187B (en) * | 2016-02-29 | 2017-11-03 | 上海应用技术学院 | A kind of fragrant leather care products and its preparation method and application |
| CN107008921B (en) * | 2017-03-31 | 2019-01-04 | 昆明理工大学 | Method for preparing nano silver |
| CN107520461A (en) * | 2017-07-31 | 2017-12-29 | 华南理工大学 | It is a kind of that Nano Silver prepared and preparation method thereof and the application in anti-bacteria paper are reduced using maize straw extract |
| CN109452309A (en) * | 2018-12-21 | 2019-03-12 | 三河市京纳环保技术有限公司 | A kind of preparation method of silicon substrate carrying silver antimicrobials |
| CN110014166A (en) * | 2019-02-28 | 2019-07-16 | 东华大学 | A method for synthesizing nano-silver using black rice pigment green |
| CN111066784A (en) * | 2019-12-24 | 2020-04-28 | 中国农业科学院农业环境与可持续发展研究所 | Ag/AgCl/cellulose composite antibacterial material and preparation method and application thereof |
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