CN1729787A - Liquid nanometer simple substance silver antibacterial agent and preparation method thereof - Google Patents
Liquid nanometer simple substance silver antibacterial agent and preparation method thereof Download PDFInfo
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- CN1729787A CN1729787A CN 200510036375 CN200510036375A CN1729787A CN 1729787 A CN1729787 A CN 1729787A CN 200510036375 CN200510036375 CN 200510036375 CN 200510036375 A CN200510036375 A CN 200510036375A CN 1729787 A CN1729787 A CN 1729787A
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Abstract
Disclosed is a liquid state nano antimicrobial agent of Argentine simple substance, which comprises the following constituents (by weight percent): argentic salt 2-5%, nano Argentine generating agent 0.5-5%, Argentine complexing agent 0.5-8%, and water 82-97%. In the preparation, ionic type high molecular polymer is used as the Argentine complexing agent.
Description
Technical field
The present invention relates to a kind of antibacterial agent, being specifically related to is the preparation method of a kind of liquid nanometer simple substance silver antibacterial agent and this antibacterial agent.
Background technology
In people's living environment, exist various harmful microorganisms, life to the mankind produces harmful effect, investigate according to Britain Scotland telephone operator, flu, pharyngitis, epidemic meningitis, hepatitis, blood-shoot-eye illness, skin disease, tens kinds of infectious diseases such as pulmonary tuberculosis can be through using this approach of phone spread out.It is found that a kind of enterogastritis that produces because of the food that is subjected to germ contamination in the edible refrigerator, have sore throat that feel sick, dizzy " refrigerator syndrome " closes disease ".Therefore, various and people of the research closely-related various anti-biotic material of living has become current heat subject.
Anti-biotic material refers under the prerequisite that does not change original material traditional performance, safety and processing characteristics, gives material good antibacterial effect.In the preparation of anti-biotic material, it is particularly crucial that the application of antibacterial agent seems.
Antibacterial agent is pressed the difference of composition, can be divided into three major types such as natural antimicrobial agent, organic antibacterial agent, inorganic antiseptic.
Natural antimicrobial agent has shitosan, natural extract etc.Natural antimicrobial agent refining refinement and getting from animals and plants mainly contains the shitosan of refining refinement from the shell of crab and shrimp.Natural antimicrobial agent is owing to its poor heat resistance, and duration of efficacy is short, is subjected to the restriction of safety and processing conditions simultaneously, is difficult to realize extensive industrialization.
The principal item of organic antibacterial agent has quaternary ammonium salts, phenols, pyridines, nitrile, biguanides, alcohols, pyridines, organic metal class, thiazoles, imidazoles.This type of antibacterial antiplaque agent efficient height, speed of action is fast, and is easy to process, but temperature tolerance is poor, and weather resistance is poor, easily separates out in solvent environment, easily produces drug resistance, and catabolite is poisonous, and in many instances, application all is restricted.
Inorganic antiseptic can be divided into three major types: the first kind is metal ion (as metal ions such as silver, copper, zinc etc., using maximum is a silver ion) antibacterial agent; Second class is with TiO
2, ZnO is the photocatalysis class antibacterial agent of representative; The 3rd class is a Nano Silver simple substance antibacterial agent.
First kind inorganic antiseptic is to utilize ion-exchange, fusion method and absorption method etc. to introduce antibiotic ion, its antibiotic mechanism is the metal ion dissolution type, promptly in the antibacterial agent use, the sulfydryl that exists in the metal ion of stripping and microbial body internal protein, the nucleic acid (SH), amino (NH gradually
2) wait the functional group of sulfur-bearing, ammonia to react, destroy the activity of enzyme in cell membrane or the cellular plasm, thereby had antibacterial ability.This class antibacterial agent safety is good, be to use a more class antibacterial agent at present, but its poor stability, easy to change is a dusty material simultaneously, needs to disperse once more before application.
The warm tolerance of the second class inorganic antiseptic is than first kind inorganic antiseptic height, but must have the existence of ultraviolet irradiation, oxygen or water just can play bactericidal action, also has scattering problem once more simultaneously, and application is restricted.
In recent years, nano simple substance silver powder has caused that people pay close attention to widely because it has excellent security and anti-microbial property, becomes the third generation inorganic antiseptic of superior performance.Chinese patent CN 1266761A discloses a kind of preparation method of nano-scale silver powder; this method is that silver nitrate is made silver ammino solution; under agitation be added to gradually and contain in protectant reductant solution; silver in the silver ammino solution is reduced into nano level silver powder; after filtration, washing, vacuum drying, obtain the nano-silver powder of average grain diameter in the 50-100 nanometer.But because this nano-silver powder is a dusty material, its surface area is very big, be very easy to reunite, go to toward need or adding surfactant and disperse again in application by mechanical external force such as ultrasonic by it, dispersion effect is poor, and usage amount is bigger, and cost is higher, use thereby limited this product, generally only be applied in the field of medicaments at present.
Chinese patent CN 1586774A discloses a kind of preparation method of nano silver colloid aqueous solution; this method adopts double injecting control technology; under the stirring of agitator, two simultaneously injection of silver-colored ammonia spirit and the reductant aqueous solution obtained product in the reaction system that contains the protectant aqueous solution.Two control technologys are adopted in this invention, and the equipment cost height owing to used ammoniacal liquor, can cause product pH value too high in the prescription, and sharp aroma is arranged, and application will be restricted; Adopt double injecting control technology simultaneously, content at initial reaction stage reductant and silver is lower, silver ion in the adding system can not fast, fully be reduced into simple substance silver, like this, unreacted silver ion can be adsorbed on the surface of newborn simple substance silver, the reductant reduction that is added subsequently, and make that the Nano Silver particle diameter continues to increase, cause the product particle diameter inhomogeneous, particle diameter wider distribution (1-50nm), activity is lower.
Chinese patent CN 1583332A also discloses a kind of nano silver colloidal sol and preparation method thereof, using under the condition of disperseing protecting colloid and reductant, obtains the Nano Silver that particle size range is 1-50nm.But technical scheme from this patent CN 1583332A and patent CN 1586774A disclosure, the deficiency that all has following three aspects in two patent applications: first, two patent application methods all can not be used running water, and have been to use distilled water and the pure water that obtains through handling.This is because contain more Cl in the running water
-, can react with silver ion, generate the AgCl precipitation of white, on the one hand, can reduce Ag
+Valid density, the AgCl particle of Sheng Chenging is equivalent to add nucleator simultaneously, makes the nano silver particles of generation become big.Therefore, in existing Nano Silver technology of preparing, all use distilled water or pure water, to get rid of Cl
-Interference.But distilled water or pure water are all handled running water through Special Equipment or technology and are obtained, not only power consumption but also water consumption (as when the preparation distilled water, needing to use a large amount of water to make water vapour be cooled to distilled water).Like this, can increase production cost greatly, increase by a procedure again simultaneously, prolong the production cycle; The product particle diameter that obtains in the second, the two patent application method is bigger, wider range (1-50nm).And nanometer particle size is more little and it is narrow more to distribute, and it is active just high more, and antibacterial effect and processability are then good more; The three, two applies for a patent the silver salt that uses in the method all only is silver nitrate, cost height (in the preparation process of Nano Silver, the cost of silver salt is one of most critical factor of the whole product cost of influence).In the technical field of current Nano Silver preparation, though silver nitrate price height is widely adopted owing to it can be dissolved in distilled water or the pure water well; The silver chlorate price is very high, and is water insoluble again, generally is not used; Silver potassium cyanide contains potassium cyanide owing in the product, and is poisonous, generally do not use; Silver sulfate, price is more much lower than silver nitrate, and safety is also very good, but because it is slightly soluble in water, also is not applied to preparing Nano Silver at present.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned prior art defective, provides that a kind of silver salt range of choice is big, the product granularity is little and narrow distribution range (0.5-7nm), antibiotic, germicidal efficiency is high, cost is low a kind of liquid nanometer simple substance silver antibacterial agent and preparation method.
For solving the problems of the technologies described above, technical scheme proposed by the invention is:
A kind of liquid nanometer simple substance silver antibacterial agent is characterized in that being become to be grouped into by following weight percentage: silver salt: 2-5%, and Nano Silver generates agent: 0.5%-5%, silver-colored complexing agent: 0.5%-8%, water: 82-97%;
Described silver-colored complexing agent is one or more combination in betaine type polymer, polycarboxylic acids and salt thereof, poly and the salt thereof;
Described silver salt is a kind of in silver nitrate, the silver sulfate or both combinations;
It is one or more combination in hydrogen peroxide, potassium borohydride, sodium borohydride, the hydrazine hydrate that described Nano Silver generates agent;
Described water is distilled water, deionized water and running water.
A kind of preparation method of liquid nanometer simple substance silver antibacterial agent is characterized in that: adopt the ionic high molecular polymer with static, steric effect as silver-colored complexing agent, with the Ag in the silver salt
+Complexing fully takes place, and controls in strictness and under its flow condition Nano Silver is generated agent and spray in above-mentioned reactant, and high-speed stirred, make Ag
+Be reduced into nanometer simple substance silver, and form the long-chain steric hindrance and the electric double layer protection of high molecular polymer, nanometer simple substance silver for a long time, stably is dispersed in the water, and its concrete steps are:
(1) generates an amount of water of adding in the agent at Nano Silver, be mixed and made into Nano Silver and generate the agent aqueous solution, in silver-colored complexing agent, add suitable quantity of water mixed preparing silver complexing agent aqueous solution simultaneously;
(2) silver-colored complexing agent aqueous solution is added in the reactor, under the mixing speed of 600-800r/min, add silver salt, make silver ion and silver-colored complexing agent that complex reaction fully take place at high speed dispersor;
(3) control under the condition that its flow is 500-1000ml/min in strictness, by spray thrower Nano Silver is generated the agent aqueous solution and spray in step (2) the gained solution, after spray finishes, continued stirring reaction 0.5-2 hour, can obtain product.
The present invention compared with prior art has following two significant advantages:
1) the ionic high molecular polymer that has static, steric effect by employing is as silver-colored complexing agent, can with the Ag in the silver salt
+Complexing fully taking place, can use cheap and good-quality running water and silver sulfate as raw material, greatly reduce production cost, shortens the production cycle;
2) adopt high-speed stirred to disperse to combine among its preparation technology with spray, Nano Silver generation agent is sprayed onto in the complex solution of silver salt and the generation of silver-colored complexing agent quantitatively, can increase considerably the contact area of Nano Silver generation agent and silver ion, reduce the reunion of silver-colored particle, help the generation of granule nanometer simple substance silver, can obtain effective component content height, granularity is littler, distribution is narrower, antimicrobial efficiency is higher liquid nanometer simple substance silver antibacterial agent.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of liquid nano argent antibacterial agent of the present invention.
Embodiment
The present invention is the improvement that the defective that occurs according to aforementioned prior art is carried out.Little for obtaining particle diameter, active constituent content height, the simple substance silver that production cost is low, the present invention has passed through screening and test repeatedly to the raw material and the proportioning of its component.Usually, the main component silver salt that constitutes Nano Silver is silver nitrate, silver chlorate, silver sulfate etc. substantially, and wherein silver chlorate is water insoluble, and cost is very high, does not generally use; Though the silver sulfate price is more much lower than silver nitrate,, limited its use, so prior art is used silver nitrate mostly owing to itself be insoluble in the characteristic of water.The present invention is through repetition test, selects in betaine type polymer, polycarboxylic acids and salt thereof, poly and the salt thereof one or more be combined in the preparation Nano Silver process as silver-colored complexing agent for use, and they are safe, the Ag that can come out with silver sulfate ionization
+Chemical action (its course of reaction is as shown below) taking place, form higher, the water-soluble silver complex of stability, impels reaction (1) constantly to carry out to the ionization direction, final silver sulfate sediment dissolving, clear solution becomes colorless.
Simultaneously, because the electrically charged and long-chain coiled structure of above-mentioned silver-colored complexing agent has charge effect and space steric effect, can prevent silver-colored agglomeration of particles, Ag effectively
+After being reduced into nanometer simple substance silver, can for a long time, stably be dispersed in the water, be much better than general protectant, therefore, the silver salt that uses can be silver nitrate, silver sulfate, the scope of application of having extended silver salt.
In the preparation process of Nano Silver, very strict to the requirement of water.General distilled water, the pure water of adopting in the prior art, though and running water is good and cheap, seldom adopt, this is owing to contain more Cl in the running water
-, can react with silver ion, generate the AgCl precipitation of white, on the one hand, can reduce Ag
+Valid density, the AgCl particle of Sheng Chenging is equivalent to add nucleator simultaneously, makes the nano silver particles of generation become big.Therefore, in preparation Nano Silver process, must use distilled water or pure water in the prior art, to get rid of Cl
-Interference.The applicant after research repeatedly again through overtesting, though the silver nitrate of running water preparation or silver sulfate solution are because of part A g
+Become AgCl and the muddy phenomenon that is white in color, but mixed the stirring through after a while with silver-colored complexing agent again, white precipitate can disappear, and becomes colourless transparent solution again.This is because silver-colored complexing agent used in the present invention and silver ion have stronger complexing power, form more stable silver complex, cause reaction (1) constantly to carry out ionization reaction to right, the AgCl that generates is dissolved again, solved the defective that can not adopt running water in the prior art, its mechanism is as follows:
In weight proportion, different concentration is selected resulting reactant quality difference, and silver salt is as the important component of Nano Silver preparation, the increase of its concentration, can reduce production costs significantly on the one hand, cost of transportation, packing cost, make extensive industrialization become possibility; Can widen range of application on the other hand, because antibacterial agent concentration is high more, its consumption will be few more, processing characteristics then good more (can not cause bigger influence) then to the processing technology of original material, but when silver salt concentration was excessive, reaction velocity was accelerated, and the silver-colored nucleus collision probability of formation increases, mutual coalescence takes place easily, form bulky grain, cause product cut size to become big, even precipitate, therefore, the concentration of silver salt must be controlled in the suitable scope; And Nano Silver generation agent concentration is also influential to product granularity, this is because Nano Silver generation agent concentration is low excessively, the silver ion Restore All can not be become simple substance silver, its excessive concentration, can cause the quickening of reaction velocity, the crystal seed that forms is bigger, and the crystal grain that forms also has little time diffusion with regard to coalescence, causes the particle diameter of product to become big gradually; The silver complexing agent concentration is also very big to the influence of product granularity, when silver-colored complexing agent concentration is low excessively, is difficult to the nanometer simple substance silver that generates is played better protective effect, and silver particles will be reunited, its excessive concentration, and its protective effect increases not obvious.Therefore, the selection proportioning of silver salt, silver-colored complexing agent, Nano Silver generation agent is particularly important.
The present invention is preferred through integrating, and each weight percentages of components is: silver salt: 2-5%, Nano Silver generates agent: 0.5%-5%, silver-colored complexing agent: 0.5%-8%, water: 82-97%.Wherein silver salt can adopt silver nitrate or silver sulfate, also two kinds of silver salt can be used in combination; One or more combination in silver complexing agent employing betaine type polymer, polycarboxylic acids and salt, poly and the salt thereof; It is one or more combination in hydrogen peroxide, potassium borohydride, sodium borohydride, the hydrazine hydrate that Nano Silver generates agent.
Different with the prior art proportioning, the present invention has improved the content of silver salt and silver-colored complexing agent as one feels fit, to improve the content of product effective ingredient, further reduces the production and transport cost.For reducing the coalescence that mentioned component produces owing to the raising of concentration, in concrete step of preparation process, adopt high speed dispersor to carry out dispersed with stirring, can produce very strong shearing force during stirring, the nanometer simple substance silver that generates can be spread out well, and use spray thrower Nano Silver to be generated under as the condition of 500-1000ml/min agent to be sprayed onto quantitatively in the complex solution that silver salt and silver-colored complexing agent generate at flow, can increase considerably the contact area of Nano Silver generation agent and silver ion, avoid causing the generation of silver-colored particle agglomeration phenomenon, help the generation of granule nanometer simple substance silver owing to local concentration is too high.The selection of flow should mixing speed be complementary when disperseing during spray, and flow is too big, and employed equipment cost can corresponding improve, and flow hour does not then reach designing requirement, the quality that effect when reducing reaction and reactant generate.
Through comparative trial, under identical condition, the nano silver antimicrobials that adopts distilled water and running water to obtain, its key property unanimity as raw material.Therefore, the present invention can adopt running water to make raw material, can save the required cost (comprising equipment, water rate, the electricity charge etc.) of preparation distilled water so greatly, makes the production cycle more shorten, the easier realization of industrialization.
Embodiment one:
(1) 0.5% betaine type polymer and 47% running water are mixed into the betaine type aqueous solutions of polymers; Then 0.5% hydrogen peroxide and 50% running water are mixed into aqueous hydrogen peroxide solution;
(2) the betaine type aqueous solutions of polymers is added in the reactor, under the mixing speed of 800r/min, add 2% silver nitrate, stirred about 1.5 hours, make silver ion and betaine type polymer solution that complex reaction fully take place at high speed dispersor;
(3) at last with aqueous hydrogen peroxide solution, by spray thrower and under the flow-control of per minute 1000ml, spray in step (2) gained solution, after spray finishes, continue stirring reaction and stirred 1 hour, can obtain liquid nanometer simple substance silver antibacterial agent.
Embodiment two:
(1) distilled water with 5% poly and 44% is mixed into the poly-poly aqueous solution; Then 3% sodium borohydride and 45% distilled water are mixed into sodium borohydride aqueous solution;
(2) the poly aqueous solution is added in the reactor, under the mixing speed of 700r/min, add 3% silver sulfate, stir and made silver ion and poly solution that complex reaction fully takes place in 1 hour at high speed dispersor;
(3) at last with sodium borohydride aqueous solution, by spray thrower and under the flow-control of per minute 800ml, spray in step (2) the gained solution, after spray finishes, continue stirring reaction and stirred 1 hour, can obtain liquid nanometer simple substance silver antibacterial agent.
Embodiment three:
(1) 4% poly, 4% betaine type polymer and 40% running water are mixed into silver-colored complexing agent aqueous solution; Then the running water of 3% hydrogen peroxide, 2% hydrazine hydrate and 42% is mixed into Nano Silver and generates the agent aqueous solution;
(2) silver-colored complexing agent aqueous solution is added in the reactor, under the mixing speed of 700r/min, the silver sulfate of adding 5%, stirring made silver ion and poly solution that complex reaction fully take place in 1 hour at high speed dispersor;
(3) at last with silver-colored complexing agent aqueous solution, by spray thrower and under the flow-control of per minute 500ml, spray in step (2) the gained solution, after spray finishes, continue stirring reaction and stirred 2 hours, can obtain liquid nanometer simple substance silver antibacterial agent.
Above-mentioned product is by the examining report at microorganism detection center, Guangdong Province as can be known: the liquid nanometer simple substance silver antibacterial agent that is made by the present invention all has very excellent anti-microbial property to colon bacillus (ATCC25922), staphylococcus aureus (ATCC 6538), candida albicans (ATCC10231), pseudomonas aeruginosa (ATCC 9027), Friedlander (ATCC 10031), salmonella typhimurium (NICPBP 50115), bacillus subtilis black mutation (ATCC 9372) etc., and its minimum inhibitory concentration is all less than 10mg/L; To colon bacillus (ATCC25922), staphylococcus aureus (ATCC 6538), candida albicans (ATCC 10231), pseudomonas aeruginosa (ATCC 9027), bacillus subtilis black mutation (ATCC 9372) all has very strong bactericidal properties, its sterilizing rate reaches more than 99.999%, it is a kind of desirable novel sterilization, antibacterial agent, have broad application prospects, can directly add coating to, commodity, pottery, in the textile, prepare various anti-biotic materials, simultaneously behind the dilute with water, also can directly be used as disinfectant and use, be used for surgical hand, sanitary washing, skin, the sterilization of body surface and medicine equipment.
Fig. 1 is the TEM figure of liquid nano argent antibacterial agent of the present invention.This transmission electron microscope TEM figure shows: the silver-colored complexing agent that the present invention uses is except giving birth to the complexing with silver hair, because the particularity of its structure, silver had charge stable effect and sterically hindered stabilizing effect simultaneously, silver-colored agglomeration of particles can be prevented very effectively, thereby dispersed extraordinary liquid nanometer simple substance silver antibacterial agent can be obtained; This nanometer simple substance silver presents single dispersion situation in solution, particle diameter is distributed as 0.5-7nm.
Claims (7)
1, a kind of liquid nanometer simple substance silver antibacterial agent is characterized in that being become to be grouped into by following weight percentage:
Silver salt: 2-5%, Nano Silver generates agent: 0.5%-5%
Silver complexing agent: 0.5%-8%, water: 82-97%.
2, a kind of liquid nanometer simple substance silver antibacterial agent according to claim 1 is characterized in that described silver-colored complexing agent is one or more combination in betaine type polymer, polycarboxylic acids and salt thereof, poly and the salt thereof.
3, liquid nanometer simple substance silver antibacterial agent according to claim 1 is characterized in that: described silver salt is a kind of in silver nitrate, the silver sulfate or both combinations.
4, liquid nanometer simple substance silver antibacterial agent according to claim 1 is characterized in that: it is one or more combination in hydrogen peroxide, potassium borohydride, sodium borohydride, the hydrazine hydrate that described Nano Silver generates agent.
5, the liquid nanometer simple substance silver antibacterial agent of stating according to claim 1 is characterized in that: described water is distilled water, deionized water and running water.
6, a kind of preparation method of liquid nanometer simple substance silver antibacterial agent is characterized in that: adopt the ionic high molecular polymer with static, steric effect as silver-colored complexing agent, with the Ag in the silver salt
+Complexing fully takes place, and controls in strictness and under its flow condition Nano Silver is generated agent and spray in above-mentioned reactant, and high-speed stirred, make Ag
+Be reduced into nanometer simple substance silver, and form the long-chain steric hindrance and the electric double layer protection of high molecular polymer, nanometer simple substance silver for a long time, stably be dispersed in the water.
7, the preparation method of a kind of liquid nanometer simple substance silver antibacterial agent according to claim 6 is characterized in that comprising following concrete steps:
(1) generates an amount of water of adding in the agent at Nano Silver, be mixed and made into Nano Silver and generate the agent aqueous solution, in silver-colored complexing agent, add suitable quantity of water mixed preparing silver complexing agent aqueous solution simultaneously;
(2) silver-colored complexing agent aqueous solution is added in the reactor, under the mixing speed of 600-800r/min, add silver salt, make silver ion and silver-colored complexing agent that complex reaction fully take place at high speed dispersor;
(3) control under the condition that its flow is 500-1000ml/min in strictness, by spray thrower Nano Silver is generated the agent aqueous solution and spray in step (2) the gained solution, after spray finishes, continued stirring reaction 0.5-2 hour, can obtain product.
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| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN101999409A (en) * | 2010-09-30 | 2011-04-06 | 王平康 | Nano silver-zinc complex antibacterial disinfectant and preparation method thereof |
| CN102159083A (en) * | 2008-09-17 | 2011-08-17 | 塔明克公司 | Antimicrobial composition |
| CN102535175A (en) * | 2010-11-23 | 2012-07-04 | 罗门哈斯公司 | Method for durable fabric treatment |
| CN102699340A (en) * | 2012-04-13 | 2012-10-03 | 上海上星家居用品有限公司 | Preparation method of colourless transparent rapid sterilization reactive oxygen composite nanometer silver sol |
| WO2014000638A1 (en) * | 2012-06-29 | 2014-01-03 | Rohm And Haas Company | Silver-containing composition |
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| CN101926363B (en) * | 2009-06-23 | 2013-01-30 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN101999409A (en) * | 2010-09-30 | 2011-04-06 | 王平康 | Nano silver-zinc complex antibacterial disinfectant and preparation method thereof |
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| CN102699340A (en) * | 2012-04-13 | 2012-10-03 | 上海上星家居用品有限公司 | Preparation method of colourless transparent rapid sterilization reactive oxygen composite nanometer silver sol |
| WO2014000638A1 (en) * | 2012-06-29 | 2014-01-03 | Rohm And Haas Company | Silver-containing composition |
| CN104522050B (en) * | 2015-01-07 | 2018-01-09 | 安徽瀚驰生物科技有限公司 | A kind of compound disinfectant and processing technology of Nano Silver and polyhexamethylene guanide |
| CN104522050A (en) * | 2015-01-07 | 2015-04-22 | 安徽瀚驰生物科技有限公司 | Composite bactericide of nano-silver and polyhexamethylene guanidine and processing technology of composite bactericide |
| CN107694319A (en) * | 2017-09-18 | 2018-02-16 | 佛山市启振环保科技有限公司 | A kind of air peculiar smell remover and preparation method thereof |
| CN109128211A (en) * | 2018-08-16 | 2019-01-04 | 山东大学 | The method of micro-nano silver particle is prepared in water solution system |
| CN109128211B (en) * | 2018-08-16 | 2021-10-26 | 山东大学 | Method for preparing micro-nano silver particles in aqueous solution system |
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