CN103172775A - Preparation method and application of antibiosis composite emulsion containing nano silver particles - Google Patents
Preparation method and application of antibiosis composite emulsion containing nano silver particles Download PDFInfo
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Abstract
The invention discloses a preparation method and an application of an antibiosis composite emulsion containing nano silver particles and belongs to the field of nano composite materials. The method comprises the following steps of: adopting water-soluble silver salt as a precursor, hydrazine hydrate as a reducing agent and ammonia water as a pH value adjusting agent; adopting fatty alcohol-polyoxyethylene ether as a surfactant, acrylic ester as a continuous phase, and respectively adopting a silver salt water solution and a hydrazine hydrate ammonia water solution as dispersion phases to prepare a microemulsion A and a microemulsion B; mixing the microemulsion A and the microemulsion B so as to form a microemulsion C, and carrying out reduction reaction of the silver salt and the hydrazine hydrate in the microemulsion C so as to synthesize the nano silver particles; and finally polymerizing the microemulsion of the acrylic ester so as to obtain the composite emulsion containing the nano silver particles. The composite emulsion containing the nano silver particles has good antibiosis and bactericidal performance, and the antibacterial rates to escherichia coli and staphylococcus aureus are respectively 95.5% and greater than 95.5%.
Description
Technical field
The invention belongs to nano composite material neck city, preparation method and the application thereof of the antibiotic composite emulsion that is specifically related to the synthetic of a kind of nano silver particles and comprises nano Ag particles.
Background technology
Due to quantum effect, small-size effect and specific surface area greatly, nanometer silver has well antibacterial, germicidal action and broad spectrum antibiotic activity thereof, is very promising anti-biotic material of new generation.At present, chemical method is one of main preparation methods of nanometer silver, but the nano silver antimicrobials that the traditional chemical method makes exists and easily to reunite and the easy problem such as oxidized, thereby causes the anti-microbial activity of antiseptic-germicide to reduce.Therefore solving the key issue that the nano silver antimicrobials anti-microbial activity reduces is how to improve dispersiveness and the stability of nano silver particles in antiseptic-germicide, is an important development direction of current nano silver antimicrobials and take the matrix material that comprises nano silver particles that polymkeric substance is dispersion medium and stablizer.
CN101544718A discloses a kind of nano silver particles and has been dispersed in the antimicrobial composite material preparation method in polymeric matrix, the method be take the styrene/methacrylic acid mixtures of methyl esters as external phase, sodium lauryl sulphate is emulsifying agent, silver nitrate aqueous solution or trisodium citrate aqueous solution are disperse phase, primary isoamyl alcohol is the microemulsion that assistant for emulsifying agent preparation contains nano silver particles, then will contain being scattered in distilled water of nano silver particles microemulsion and carry out letex polymerization and obtain nanometer silver/poly-(vinylbenzene-methyl methacrylate) antimicrobial composite material.
CN102165960A discloses a kind of preparation method of nanometer silver antimicrobial mother liquor, at first the method causes the oiliness monomer polymerization with oil-soluble initiator in the aqueous solution, obtain polymer core, then add water-soluble monomer to continue polymerization and form polymer shell, finally add Silver Nitrate to pass through reduction, obtain the nano-antibacterial mother liquor.
The Wu Liguang of Zhejiang Prov Industrial And Commercial University is with polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO, F127) triblock copolymer is tensio-active agent, methyl methacrylate is oil phase, silver nitrate aqueous solution and sodium chloride aqueous solution are the reverse micro emulsion synthesis of nano silver chloride particle that disperse phase is constructed, prepare nano silver/silver chloride/F127-polymethyl methacrylate hybrid separatory membrane (Wu Liguang, Xiang Wen, Du Chunhui by micro-emulsion polymerization again, the research of the controlledly synthesis of Nano AgCl particle and AgCl/F127-PMMA organic/inorganic hybrid membrane in the F127 reverse micro emulsion
chinese Journal of Inorganic Chemistry , 2011,27 (1), 61-65; Wang Jian, Wang Ting, Wu Liguang, the impact of the composition of F127 reverse micro emulsion on the formation of AgCl nano silver particles and AgCl/F127-PMMA hybridized film structure and performance,
chinese Journal of Inorganic Chemistry , 2012,28 (5), 989-994).
It is tensio-active agent that the Wu Liguang of Zhejiang Prov Industrial And Commercial University be take polymerisable 2-acrylamide-2-methylpro panesulfonic acid, glycidyl methacrylate and methyl methacrylate mixture are oil phase, silver nitrate aqueous solution and sodium chloride aqueous solution are the reverse micro emulsion synthesis of nano silver chloride particle that disperse phase is constructed, then prepare by micro-emulsion polymerization that nano silver/silver chloride/poly-(glycidyl methacrylate-methyl methacrylate-acrylamido-methyl propane sulfonic acid) (river increases inorganic, Wu Liguang, Zhou Zhijun, the research of the controlledly synthesis of Nano AgCl particle and AgCl/Poly (GMA-co-MMA-co-AMPS) multipolymer organic/inorganic hybrid membrane in reverse micro emulsion,
sCI , 2011,32 (1), 10-15)
It is tensio-active agent that the Wu Liguang of Zhejiang Prov Industrial And Commercial University be take chlorination-1-dodecyl methyl imidazole ion liquid, methyl methacrylate and acrylamide mixture are oil phase, the silver nitrate aqueous solution aqueous solution is the reverse micro emulsion synthesis of nano silver chloride particle that disperse phase is constructed, prepare nano silver/silver chloride/poly-(methyl methacrylate-acrylamide) hydridization separatory membrane (Teng Yan by micro-emulsion polymerization again, Wang Ting, Du Chunhui, Wu Liguang, in ion liquid microemulsion, the infiltration evaporation of synthetic and AgCl/poly (MMA-co-AM) hybridized film of Nano AgCl separates
the matrix material journal , 2012,29 (6), 42-49).
Relevantly take fatty alcohol-polyoxyethylene ether as tensio-active agent, by reverse micro emulsion synthesis of nano silver particles, then prepare the composite antibiosis emulsion that comprises nano silver particles by micro-emulsion polymerization, have not yet to see report.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of antibiotic composite emulsion preparation method and application thereof that comprises nano silver particles, the method can make nano silver particles be dispersed in polymer emulsion, form the stable composite antibiosis emulsion that comprises nano silver particles, prepared composite antibiosis emulsion anti-microbial property is good.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles is characterized in that comprising the following steps:
1) fatty alcohol-polyoxyethylene ether is joined in acrylate and obtain mixed solution, under ultrasonication, in this mixed solution, add silver salt solution to make microemulsion A;
2) hydrazine hydrate is joined in ammoniacal liquor and be mixed with the hydrazine hydrate ammonia soln; Fatty alcohol-polyoxyethylene ether is joined in acrylate and obtains mixed solution, under ultrasonication, the hydrazine hydrate ammonia soln is added in mixed solution and makes microemulsion B;
3) under ultrasonication by step 2) microemulsion B be added drop-wise in the microemulsion A of step 1), make the microemulsion C that comprises nano silver particles;
4) Diisopropyl azodicarboxylate is joined in the microemulsion C of step 3), carry out polyreaction in 60 ℃ of water-baths, after reaching 30～50mPa.s, polymerization system viscosity stops heating, obtain the antibiotic composite emulsion that comprises nano silver particles, the 0.5wt% that described Diisopropyl azodicarboxylate add-on is the acrylate total amount.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, is characterized in that described fatty alcohol-polyoxyethylene ether is isooctyl alcohol Soxylat A 25-7 or Brij 35.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, it is characterized in that described acrylate is any one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate, is preferably methyl methacrylate.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, is characterized in that the described silver salt of step 1) is Silver Nitrate or silver tetrafluoroborate, is preferably Silver Nitrate.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, it is characterized in that step 1) and 2) in methyl acrylate with volume ratio, the water of fatty alcohol-polyoxyethylene ether, with the volume ratio of fatty alcohol-polyoxyethylene ether, all equate, the volume ratio of acrylate and fatty alcohol-polyoxyethylene ether is 20～30:1; The volume ratio of water and fatty alcohol-polyoxyethylene ether is 0.75～1:1, and wherein water is preparation silver salt solution and hydrazine hydrate ammonia soln water used.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, is characterized in that in the microemulsion A described in step 1), silver salt is 0.1～0.3mol/L with the molecular volume ratio of water.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, is characterized in that step 2) described in microemulsion B in hydrazine hydrate with the molecular volume ratio of water, be 0.3～0.5mol/L; The mass percent of ammonia and water is 25～30wt%.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, the volume ratio that it is characterized in that the microemulsion B described in step 3) and microemulsion A is 1:1, the speed that microemulsion B is added drop-wise in microemulsion A is 0.15～0.3ml/min.
The preparation method of described a kind of antibiotic composite emulsion that comprises nano silver particles, is characterized in that when ultrasonic that ultrasonic frequency is 100Hz, and temperature is 40 ℃.
Described a kind of antibiotic composite emulsion that comprises nano silver particles, the application in intestinal bacteria and streptococcus aureus antibacterial effect.
By adopting aforesaid method, compared with prior art, beneficial effect of the present invention is as follows:
1) the present invention adds silver salt solution fatty alcohol-polyoxyethylene ether and acrylate mixing liquid under ultrasonication, makes microemulsion A; The hydrazine hydrate ammonia soln is added again to fatty alcohol-polyoxyethylene ether and acrylate mixing liquid under ultrasonication, make microemulsion B; Again microemulsion B is added drop-wise in microemulsion A, add Diisopropyl azodicarboxylate to carry out polyreaction, obtain the antibiotic composite emulsion that comprises nano silver particles, its mild condition, easy to operate, can make nano silver particles be dispersed in polymer emulsion, form the stable composite antibiosis emulsion that comprises nano silver particles;
2) the present invention is defined as the charging capacity of Diisopropyl azodicarboxylate the 0.5wt% of methyl acrylate total amount, in polyreaction, make polymerization system viscosity reach 30～50mPa.s, as long as control the time of polyreaction, greatly reduced the reaction conditions controlling factor, simplify operation, improved the reaction precision;
3) the antibiotic composite emulsion that comprises nano silver particles obtained by preparation method of the present invention, its anti-microbial property excellence, be respectively more than 95.5% and 95.5% the antibiotic rate of intestinal bacteria and streptococcus aureus.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in this.
embodiment 1: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 20/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.95/1 of water and isooctyl alcohol Soxylat A 25-7, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.13mol/L, and in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes microemulsion A;
Press the volume ratio 20/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.95/1 of water and isooctyl alcohol Soxylat A 25-7, hydrazine hydrate compares 0.3mol/L with the molecular volume of water, the proportioning of the mass percent 25wt% of ammonia and water, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes microemulsion B;
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.25ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 35mPa.s, obtain the composite emulsion that comprises nano silver particles.
Annotate: the isooctyl alcohol Soxylat A 25-7 in the present embodiment replaces with Brij 35; Any one replacement for methyl methacrylate in β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate, Silver Nitrate replaces with silver tetrafluoroborate, all can obtain same technique effect.
The application of the composite emulsion that comprises nano silver particles in antibiotic that the present embodiment obtains:
Adopt the method for plate culture count, test the antibacterial effect of the prepared composite emulsion that comprises nano silver particles to intestinal bacteria and streptococcus aureus.
Concrete operation step is: it is reference standard experiment preparation that anti-microbial property of the present invention is tested diluent used, and selecting concentration is 5.0 * 10
5the diluent of individual left and right thalline/milliliter, as test bacterium liquid, get 10 milliliters and join containing 25 milliliters of substratum that (its formula is: peptone 2.0 grams, yeast extract 1.0 grams, sodium-chlor 2.0 grams, 220 milliliters of agar-agar 3.0 grams and distilled water) Erlenmeyer flask in, get equally 3 Erlenmeyer flasks, two controlled trials, another is composite emulsion of the present invention; The composite emulsion add-on that comprises nano silver particles is 2g, control group 1: add and do not contain nano silver particles, but other component emulsion identical with the composite emulsion that comprises nano silver particles with concentration; Control group 2: do not add any material (blank); These 3 Erlenmeyer flasks are placed on 40 rev/mins of shaking tables, and 37 ± 1 ℃ of constant temperature, cultivate 24 hours, then gets a certain amount of bacterium liquid and be laid on agar nutrition base, cultivates live bacterial count after 24 hours under 37 ± 1 ℃, and then calculate antibiotic rate.
The composite emulsion that comprises nano silver particles that embodiment 1 makes is respectively 97 ± 0.5% and 97 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus; Control group 1 makes does not contain nano silver particles, but the emulsion that other component is identical with the composite emulsion that comprises nano silver particles with concentration, bacterium can utilize the organism in emulsion to continue to increase as carbon source, therefore 1 pair of intestinal bacteria of control group and streptococcus aureus all do not have antibacterial effect, also contribute to bacterial growth; Control group 2 is blank group, and total plate count also increases, so relative two controlled trials, and the composite emulsion that comprises nano silver particles of the present invention has significant antibacterial effect to intestinal bacteria and streptococcus aureus.
embodiment 2: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 25/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.9/1 of water and isooctyl alcohol Soxylat A 25-7, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.17mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 25/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.9/1 of water and isooctyl alcohol Soxylat A 25-7, hydrazine hydrate compares 0.35mol/L with the molecular volume of water, the proportioning of the mass percent 27wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.30ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 40mPa.s, obtain the composite emulsion that comprises nano Ag particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 2 makes is with embodiment 1, and test result is respectively 96 ± 0.5% and 97 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
embodiment 3: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 30/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.85/1 of water and isooctyl alcohol Soxylat A 25-7, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.22mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 30/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.85/1 of water and isooctyl alcohol Soxylat A 25-7, hydrazine hydrate compares 0.38mol/L with the molecular volume of water, the proportioning of the mass percent 30wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.35ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion E, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 45mPa.s, obtain the composite emulsion that comprises nano silver particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 3 makes is with embodiment 1, and test result is respectively 97 ± 0.5% and 97 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
embodiment 4: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 20/1 of methyl methacrylate and Brij 35, the volume ratio 0.95/1 of water and Brij 35, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.13mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 20/1 of methyl methacrylate and Brij 35, the volume ratio 0.95/1 of water and Brij 35, hydrazine hydrate compares 0.3mol/L with the molecular volume of water, the proportioning of the mass percent 25wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.30ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 40mPa.s, obtain the composite emulsion that comprises nano silver particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 4 makes is with embodiment 1, and test result is respectively 96 ± 0.5% and 97 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
embodiment 5: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 30/1 of methyl methacrylate and Brij 35, the volume ratio 0.85/1 of water and Brij 35, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.22mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 30/1 of methyl methacrylate and Brij 35, the volume ratio 0.85/1 of water and Brij 35, hydrazine hydrate compares 0.38mol/L with the molecular volume of water, the proportioning of the mass percent 30wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.35ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 45mPa.s, obtain the composite emulsion that comprises nano silver particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 5 makes is with embodiment 1, and test result is respectively 96 ± 0.5% and 96 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
embodiment 6: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.95/1 of water and isooctyl alcohol Soxylat A 25-7, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.13mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.95/1 of water and isooctyl alcohol Soxylat A 25-7, hydrazine hydrate compares 0.3mol/L with the molecular volume of water, the proportioning of the mass percent 25wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion C with the speed of 0.25ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion E, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 35mPa.s, obtain the composite emulsion that comprises nano silver particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 6 makes is with embodiment 1, and test result is respectively 95 ± 0.5% and 96 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
embodiment 7: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and Brij 35, the volume ratio 0.9/1 of water and Brij 35, the molecular volume of Silver Nitrate and water is than being the proportioning of 0.18mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and Brij 35, the volume ratio 0.9/1 of water and Brij 35, hydrazine hydrate compares 0.3mol/L with the molecular volume of water, the proportioning of the mass percent 27wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion B and microemulsion D, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.35ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 35mPa.s, obtain the composite emulsion that comprises nano silver particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 7 makes is with embodiment 1, and test result is respectively 95 ± 0.5% and 95 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
embodiment 8: the preparation of the antibiotic composite emulsion that comprises nano silver particles
Press the volume ratio 25/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.9/1 of water and isooctyl alcohol Soxylat A 25-7, the molecular volume of silver tetrafluoroborate and water is than being the proportioning of 0.17mol/L, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Press the volume ratio 25/1 of methyl methacrylate and isooctyl alcohol Soxylat A 25-7, the volume ratio 0.9/1 of water and isooctyl alcohol Soxylat A 25-7, hydrazine hydrate compares 0.35mol/L with the molecular volume of water, the proportioning of the mass percent 27wt% of ammonia and water, the microemulsion B that in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) makes.
Get respectively isopyknic above-mentioned microemulsion A and microemulsion B, in ultrasonic water bath, (ultrasonic frequency 100Hz, 40 ℃ of temperature) is added drop-wise to microemulsion B in microemulsion A with the speed of 0.35ml/min, makes the microemulsion C that comprises nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 ℃ of water-baths, carry out polyreaction, stop heating after polymerization system viscosity reaches 40mPa.s, obtain the composite emulsion that comprises nano Ag particles.
The anti-microbial property testing method of the composite emulsion that comprises nano silver particles that embodiment 8 makes is with embodiment 1, and test result is respectively 97 ± 0.5% and 97 ± 0.5% for the antibiotic rate to intestinal bacteria and streptococcus aureus.
Claims (10)
1. the preparation method of an antibiotic composite emulsion that comprises nano silver particles is characterized in that comprising the following steps:
1) fatty alcohol-polyoxyethylene ether is joined in acrylate and obtain mixed solution, under ultrasonication, in this mixed solution, add silver salt solution to make microemulsion A;
2) hydrazine hydrate is joined in ammoniacal liquor and be mixed with the hydrazine hydrate ammonia soln; Fatty alcohol-polyoxyethylene ether is joined in acrylate and obtains mixed solution, under ultrasonication, the hydrazine hydrate ammonia soln is added in mixed solution and makes microemulsion B;
3) under ultrasonication by step 2) microemulsion B be added drop-wise in the microemulsion A of step 1), make the microemulsion C that comprises nano silver particles;
4) Diisopropyl azodicarboxylate is joined in the microemulsion C of step 3), carry out polyreaction in 60 ℃ of water-baths, after reaching 30～50mPa.s, polymerization system viscosity stops heating, obtain the antibiotic composite emulsion that comprises nano silver particles, the 0.5wt% that described Diisopropyl azodicarboxylate add-on is the acrylate total amount.
2. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, is characterized in that described fatty alcohol-polyoxyethylene ether is isooctyl alcohol Soxylat A 25-7 or Brij 35.
3. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, it is characterized in that described acrylate is any one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate, is preferably methyl methacrylate.
4. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, is characterized in that the described silver salt of step 1) is Silver Nitrate or silver tetrafluoroborate.
5. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, it is characterized in that step 1) and 2) in methyl acrylate with volume ratio, the water of fatty alcohol-polyoxyethylene ether, with the volume ratio of fatty alcohol-polyoxyethylene ether, all equate, the volume ratio of acrylate and fatty alcohol-polyoxyethylene ether is 20～30:1; The volume ratio of water and fatty alcohol-polyoxyethylene ether is 0.75～1:1, and wherein water is preparation silver salt solution and hydrazine hydrate ammonia soln water used.
6. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, is characterized in that in the microemulsion A described in step 1), silver salt is 0.1～0.3mol/L with the molecular volume ratio of water.
7. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, is characterized in that step 2) described in microemulsion B in hydrazine hydrate with the molecular volume ratio of water, be 0.3～0.5mol/L; The mass percent of ammonia and water is 25～30wt%.
8. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, the volume ratio that it is characterized in that the microemulsion B described in step 3) and microemulsion A is 1:1, and the speed that microemulsion B is added drop-wise in microemulsion A is 0.15～0.3ml/min.
9. the preparation method of a kind of antibiotic composite emulsion that comprises nano silver particles as claimed in claim 1, is characterized in that when ultrasonic that ultrasonic frequency is 100Hz, and temperature is 40 ℃.
10. an antibiotic composite emulsion that comprises nano silver particles, the application in intestinal bacteria and streptococcus aureus antibacterial effect.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406548A (en) * | 2013-08-08 | 2013-11-27 | 广西大学 | Silver nano particle and preparation method and application thereof |
| CN105057690A (en) * | 2015-07-20 | 2015-11-18 | 昆明理工大学 | Preparation method of high-dispersibility superfine spherical silver powder |
| CN105199039A (en) * | 2015-09-18 | 2015-12-30 | 浙江工商大学 | Nano-silver/graphene/polymer composite antibacterial emulsion and preparation method thereof |
| CN105214511A (en) * | 2015-09-18 | 2016-01-06 | 浙江工商大学 | A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544718A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544718A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406548A (en) * | 2013-08-08 | 2013-11-27 | 广西大学 | Silver nano particle and preparation method and application thereof |
| CN103406548B (en) * | 2013-08-08 | 2015-11-18 | 广西大学 | Nano silver grain and preparation method thereof and application |
| CN105057690A (en) * | 2015-07-20 | 2015-11-18 | 昆明理工大学 | Preparation method of high-dispersibility superfine spherical silver powder |
| CN105057690B (en) * | 2015-07-20 | 2017-08-25 | 昆明理工大学 | A kind of preparation method of polymolecularity superfine spherical silver powder |
| CN105199039A (en) * | 2015-09-18 | 2015-12-30 | 浙江工商大学 | Nano-silver/graphene/polymer composite antibacterial emulsion and preparation method thereof |
| CN105214511A (en) * | 2015-09-18 | 2016-01-06 | 浙江工商大学 | A kind of Nano Silver/Graphene/Kynoar hybrid membranes and preparation method thereof |
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| CN103172775B (en) | 2015-07-15 |
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Effective date of registration: 20201217 Address after: No. 188, Shengxing Road, Wangdian Town, Xiuzhou District, Jiaxing City, Zhejiang Province Patentee after: SUNYA OPTOELECTRONIC Co.,Ltd. Address before: 310018, No. 18 Jiao Tong Street, Xiasha Higher Education Park, Hangzhou, Zhejiang Patentee before: ZHEJIANG GONGSHANG University |