CN103172775B - 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, the preparation method of the synthesis being specifically related to a kind of nano silver particles and the antibacterial composite emulsion comprising nano Ag particles and application thereof.
Background technology
Due to quantum effect, small-size effect and great specific surface area, 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 obtained nano silver antimicrobials of conventional chemical methods exists and easily reunites and the easy problem such as oxidized, thus causes the anti-microbial activity of antiseptic-germicide to reduce.Therefore solving key issue that nano silver antimicrobials anti-microbial activity reduces is how to improve the dispersiveness of nano silver particles in antiseptic-germicide and stability, and an important development direction of to take polymkeric substance as the matrix material comprising nano silver particles of dispersion medium and stablizer be current nano silver antimicrobials.
CN101544718A discloses a kind of nano silver particles and is dispersed in antimicrobial composite material preparation method in polymeric matrix, the method with styrene/methacrylic acid mixtures of methyl esters for external phase, sodium lauryl sulphate is emulsifying agent, silver nitrate aqueous solution or trisodium citrate aqueous solution are disperse phase, primary isoamyl alcohol be assistant for emulsifying agent preparation containing the microemulsion of nano silver particles, then carry out letex polymerization obtain nanometer silver/gather (styrene methyl methacrylate) antimicrobial composite material by containing being scattered in distilled water of nano silver particles microemulsion.
CN102165960A discloses a kind of preparation method of nanometer silver antimicrobial mother liquor, the method causes oiliness monomer polymerization with oil-soluble initiator first in aqueous, obtain polymer core, then add water-soluble monomer and continue polymerization formation polymer shell, finally add Silver Nitrate by reduction, obtain 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, nano silver/silver chloride/F127-polymethyl methacrylate hybrid separatory membrane (Wu Liguang is prepared again by micro-emulsion polymerization, Xiang Wen, Du Chunhui, the controlledly synthesis of Nano AgCl particle and the research of AgCl/F127-PMMA organic/inorganic hybrid membrane in F127 reverse micro emulsion,
chinese Journal of Inorganic Chemistry , 2011,27 (1), 61-65, the composition of Wang Jian, Wang Ting, Wu Liguang, F127 reverse micro emulsion is formed AgCl nano silver particles and the impact of AgCl/F127-PMMA hybridized film stuctures and properties,
chinese Journal of Inorganic Chemistry , 2012,28 (5), 989-994).
The Wu Liguang of Zhejiang Prov Industrial And Commercial University with polymerisable 2-acrylamide-2-methylpro panesulfonic acid for tensio-active agent, 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 nano silver/silver chloride/poly-(glycidyl methacrylate-methyl methacrylate-acrylamido-methyl propanesulfonic acid) inorganic (river increasing is prepared by micro-emulsion polymerization, Wu Liguang, Zhou Zhijun, the controlledly synthesis of Nano AgCl particle and the research of AgCl/Poly (GMA-co-MMA-co-AMPS) multipolymer organic/inorganic hybrid membrane in reverse micro emulsion,
sCI , 2011,32 (1), 10-15)
The Wu Liguang of Zhejiang Prov Industrial And Commercial University with chlorination-1-dodecyl methyl imidazole ion liquid for tensio-active agent, methyl methacrylate and acrylamide mixtures 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, nano silver/silver chloride/poly-(methyl methacrylate-acrylamide) hybrid separation membrane (Teng Yan is prepared again by micro-emulsion polymerization, Wang Ting, Du Chunhui, Wu Liguang, in ion liquid microemulsion, the synthesis of Nano AgCl and the infiltration evaporation of AgCl/poly (MMA-co-AM) hybridized film are separated
matrix material journal , 2012,29 (6), 42-49).
Relevant take fatty alcohol-polyoxyethylene ether as tensio-active agent, by reverse micro emulsion synthesis of nano silver particles, then is comprised the composite antibacterial emulsion of nano silver particles by micro-emulsion polymerization preparation, has 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 antibacterial composite emulsion preparation method and the application thereof that comprise nano silver particles, the method can make nano silver particles be dispersed in polymer emulsion, form the stable composite antibacterial emulsion comprising nano silver particles, obtained composite antibacterial emulsion anti-microbial property is good.
Described a kind of preparation method comprising the antibacterial composite emulsion of 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 obtain microemulsion A;
2) hydrazine hydrate is joined in ammoniacal liquor be mixed with hydrazine hydrate ammonia soln; Fatty alcohol-polyoxyethylene ether is joined in acrylate and obtain mixed solution, under ultrasonication, hydrazine hydrate ammonia soln is added obtained microemulsion B in mixed solution;
3) under ultrasonication by step 2) microemulsion B be added drop-wise in the microemulsion A of step 1), the obtained microemulsion C comprising nano silver particles;
4) Diisopropyl azodicarboxylate is joined in the microemulsion C of step 3), polyreaction is carried out in 60 DEG C of water-baths, heating is stopped after reaching 30 ~ 50mPa.s to polymerization system viscosity, obtain the antibacterial composite emulsion comprising nano silver particles, described Diisopropyl azodicarboxylate add-on is the 0.5wt% of acrylate total amount.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, is characterized in that described fatty alcohol-polyoxyethylene ether is isooctanol polyethoxylate or Brij 35.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, it is characterized in that described acrylate is any one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate, be preferably methyl methacrylate.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, is characterized in that the silver salt described in step 1) is Silver Nitrate or silver tetrafluoroborate, is preferably Silver Nitrate.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, it is characterized in that step 1) and 2) in the volume ratio of methyl acrylate and fatty alcohol-polyoxyethylene ether, water all equal with the volume ratio of fatty alcohol-polyoxyethylene ether, 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.
Described a kind of preparation method comprising the antibacterial composite emulsion of 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.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, is characterized in that step 2) described in microemulsion B in hydrazine hydrate be 0.3 ~ 0.5mol/L with the molecular volume ratio of water; The mass percent of ammonia and water is 25 ~ 30wt%.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, is characterized in that the volume ratio of the microemulsion B described in step 3) and microemulsion A is 1:1, and the microemulsion B speed be added drop-wise in microemulsion A is 0.15 ~ 0.3ml/min.
Described a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles, when it is characterized in that ultrasonic, ultrasonic frequency is 100Hz, and temperature is 40 DEG C.
Described a kind of antibacterial composite emulsion comprising 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) silver salt solution is added fatty alcohol-polyoxyethylene ether and crylic acid ester mixture liquid by the present invention under ultrasonication, obtained microemulsion A; Under ultrasonication, hydrazine hydrate ammonia soln is added fatty alcohol-polyoxyethylene ether and crylic acid ester mixture liquid again, obtained microemulsion B; Again microemulsion B is added drop-wise in microemulsion A, add Diisopropyl azodicarboxylate and carry out polyreaction, obtain the antibacterial composite emulsion comprising nano silver particles, its mild condition, easy to operate, nano silver particles can be made to be dispersed in polymer emulsion, to form the stable composite antibacterial emulsion comprising nano silver particles;
2) charging capacity of Diisopropyl azodicarboxylate is defined as the 0.5wt% of methyl acrylate total amount by the present invention, in the polymerization, polymerization system viscosity is made to reach 30 ~ 50mPa.s, as long as control the time of polyreaction, greatly reduce reaction conditions controlling factor, simplify operation, improve reaction precision;
3) by the antibacterial composite emulsion comprising nano silver particles that preparation method of the present invention obtains, its anti-microbial property is excellent, is respectively more than 95.5% and 95.5% to 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 comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 20/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.95/1 of water and isooctanol polyethoxylate, the proportioning that Silver Nitrate is 0.13mol/L with the molecular volume ratio of water, (ultrasonic frequency 100Hz, temperature 40 DEG C) obtained microemulsion A in ultrasonic water bath;
By the volume ratio 20/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.95/1 of water and isooctanol polyethoxylate, hydrazine hydrate compares 0.3mol/L with the molecular volume of water, the proportioning of the mass percent 25wt% of ammonia and water, (ultrasonic frequency 100Hz, temperature 40 DEG C) obtained microemulsion B in ultrasonic water bath;
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.25ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 35mPa.s, stop heating, obtain the composite emulsion comprising nano silver particles.
Note: the isooctanol polyethoxylate Brij 35 in the present embodiment replaces; Any one in methyl methacrylate β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate replaces, and Silver Nitrate silver tetrafluoroborate replaces, and all can obtain same technique effect.
The application in antibacterial of the composite emulsion of what the present embodiment obtained comprise nano silver particles:
Adopt the method for plate culture count, the composite emulsion comprising nano silver particles prepared by test is to the antibacterial effect of intestinal bacteria and streptococcus aureus.
Concrete operation step is: Anti-microbial Performance Tests of the present invention diluent used is reference standard experimental formula, selects concentration to be 5.0 × 10
5the diluent of individual left and right thalline/milliliter, bacterium liquid is used as test, get 10 milliliters and join containing 25 milliliters of substratum that (its formula is: peptone 2.0 grams, Yeast mannan 1.0 grams, 2.0 grams, sodium-chlor, agar-agar 3.0 grams and distilled water 220 milliliters) Erlenmeyer flask in, get 3 Erlenmeyer flasks equally, two controlled trials, another is composite emulsion of the present invention; The composite emulsion add-on comprising nano silver particles is 2g, control group 1: add not containing nano silver particles, but the emulsion that other component is identical with the composite emulsion comprising nano silver particles with concentration; Control group 2: do not add any material (blank); These 3 Erlenmeyer flasks are placed on 40 revs/min of shaking tables, constant temperature 37 ± 1 DEG C, cultivate 24 hours, then get a certain amount of bacterium liquid and be laid in agar Nutrient medium, at 37 ± 1 DEG C, cultivate live bacterial count after 24 hours, and then calculate antibiotic rate.
The antibiotic rate of the composite emulsion comprising nano silver particles to intestinal bacteria and streptococcus aureus that embodiment 1 obtains is respectively 97 ± 0.5% and 97 ± 0.5%; What control group 1 was obtained does not contain nano silver particles, but the emulsion that other component is identical with the composite emulsion comprising nano silver particles with concentration, bacterium can utilize the organism in emulsion to continue to increase as carbon source, therefore control group 1 pair of intestinal bacteria and streptococcus aureus all do not have antibacterial effect, also contribute to bacterium and increase; Control group 2 is blank group, and total plate count also increases, therefore relative two controlled trials, and the composite emulsion comprising nano silver particles of the present invention has significant antibacterial effect to intestinal bacteria and streptococcus aureus.
embodiment 2: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 25/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.9/1 of water and isooctanol polyethoxylate, the proportioning that Silver Nitrate is 0.17mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By the volume ratio 25/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.9/1 of water and isooctanol polyethoxylate, 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.30ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 40mPa.s, stop heating, obtain the composite emulsion comprising nano Ag particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 2 obtains is with embodiment 1, and test result is be respectively 96 ± 0.5% and 97 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
embodiment 3: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 30/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.85/1 of water and isooctanol polyethoxylate, the proportioning that Silver Nitrate is 0.22mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By the volume ratio 30/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.85/1 of water and isooctanol polyethoxylate, 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.35ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion E, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 45mPa.s, stop heating, obtain the composite emulsion comprising nano silver particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 3 obtains is with embodiment 1, and test result is be respectively 97 ± 0.5% and 97 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
embodiment 4: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 20/1 of methyl methacrylate and Brij 35, the volume ratio 0.95/1 of water and Brij 35, the proportioning that Silver Nitrate is 0.13mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.30ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 40mPa.s, stop heating, obtain the composite emulsion comprising nano silver particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 4 obtains is with embodiment 1, and test result is be respectively 96 ± 0.5% and 97 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
embodiment 5: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 30/1 of methyl methacrylate and Brij 35, the volume ratio 0.85/1 of water and Brij 35, the proportioning that Silver Nitrate is 0.22mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.35ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 45mPa.s, stop heating, obtain the composite emulsion comprising nano silver particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 5 obtains is with embodiment 1, and test result is be respectively 96 ± 0.5% and 96 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
embodiment 6: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and isooctanol polyethoxylate, the volume ratio 0.95/1 of water and isooctanol polyethoxylate, the proportioning that Silver Nitrate is 0.13mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and isooctanol polyethoxylate, the volume ratio 0.95/1 of water and isooctanol polyethoxylate, 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion C with the speed of 0.25ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion E, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 35mPa.s, stop heating, obtain the composite emulsion comprising nano silver particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 6 obtains is with embodiment 1, and test result is be respectively 95 ± 0.5% and 96 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
embodiment 7: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 20/1 of β-dimethyl-aminoethylmethacrylate and Brij 35, the volume ratio 0.9/1 of water and Brij 35, the proportioning that Silver Nitrate is 0.18mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion B and microemulsion D respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.35ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 35mPa.s, stop heating, obtain the composite emulsion comprising nano silver particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 7 obtains is with embodiment 1, and test result is be respectively 95 ± 0.5% and 95 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
embodiment 8: the preparation comprising the antibacterial composite emulsion of nano silver particles
By the volume ratio 25/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.9/1 of water and isooctanol polyethoxylate, the proportioning that silver tetrafluoroborate is 0.17mol/L with the molecular volume ratio of water, the microemulsion A that in ultrasonic water bath, (ultrasonic frequency 100Hz, temperature 40 DEG C) is obtained.
By the volume ratio 25/1 of methyl methacrylate and isooctanol polyethoxylate, the volume ratio 0.9/1 of water and isooctanol polyethoxylate, 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, temperature 40 DEG C) is obtained.
Get isopyknic above-mentioned microemulsion A and microemulsion B respectively, in ultrasonic water bath, microemulsion B is added drop-wise in microemulsion A with the speed of 0.35ml/min by (ultrasonic frequency 100Hz, temperature 40 DEG C), the obtained microemulsion C comprising nano silver particles.
The Diisopropyl azodicarboxylate of the 0.5wt% of methyl acrylate total amount is joined in above-mentioned microemulsion C, in 60 DEG C of water-baths, carry out polyreaction, after polymerization system viscosity reaches 40mPa.s, stop heating, obtain the composite emulsion comprising nano Ag particles.
The anti-microbial property testing method comprising the composite emulsion of nano silver particles that embodiment 8 obtains is with embodiment 1, and test result is be respectively 97 ± 0.5% and 97 ± 0.5% to the antibiotic rate of intestinal bacteria and streptococcus aureus.
Claims (10)
1. comprise a preparation method for the antibacterial composite emulsion of nano silver particles, it 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 obtain microemulsion A;
2) hydrazine hydrate is joined in ammoniacal liquor be mixed with hydrazine hydrate ammonia soln; Fatty alcohol-polyoxyethylene ether is joined in acrylate and obtain mixed solution, under ultrasonication, hydrazine hydrate ammonia soln is added obtained microemulsion B in mixed solution;
3) under ultrasonication by step 2) microemulsion B be added drop-wise in the microemulsion A of step 1), the obtained microemulsion C comprising nano silver particles;
4) Diisopropyl azodicarboxylate is joined in the microemulsion C of step 3), polyreaction is carried out in 60 DEG C of water-baths, heating is stopped after reaching 30 ~ 50mPa.s to polymerization system viscosity, obtain the antibacterial composite emulsion comprising nano silver particles, described Diisopropyl azodicarboxylate add-on is the 0.5wt% of acrylate total amount.
2. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, is characterized in that described fatty alcohol-polyoxyethylene ether is isooctanol polyethoxylate or Brij 35.
3. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, is characterized in that described acrylate is any one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate.
4. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, is characterized in that the silver salt described in step 1) is Silver Nitrate or silver tetrafluoroborate.
5. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, is characterized in that step 1) and 2) in the volume ratio of acrylate and fatty alcohol-polyoxyethylene ether be 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. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, it 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, wherein water is prepare silver salt solution water used.
7. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, is characterized in that step 2) described in microemulsion B in hydrazine hydrate be 0.3 ~ 0.5mol/L with the molecular volume ratio of water; The mass percent of ammonia and water is 25 ~ 30wt%, and wherein water is prepare hydrazine hydrate ammonia soln water used.
8. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, it is characterized in that the volume ratio of the microemulsion B described in step 3) and microemulsion A is 1:1, the microemulsion B speed be added drop-wise in microemulsion A is 0.15 ~ 0.3ml/min.
9. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, when it is characterized in that ultrasonic, ultrasonic frequency is 100Hz, and temperature is 40 DEG C.
10. a kind of preparation method comprising the antibacterial composite emulsion of nano silver particles as claimed in claim 1, is characterized in that described acrylate is methyl methacrylate.
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| 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 |
| CN105199039B (en) * | 2015-09-18 | 2017-06-27 | 浙江工商大学 | A kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof |
| CN105214511B (en) * | 2015-09-18 | 2017-11-07 | 浙江工商大学 | A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof |
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