CN103008683B - Preparation method for high-efficient monomer silver solution as well as high-efficient monomer silver gel and lotion - Google Patents
Preparation method for high-efficient monomer silver solution as well as high-efficient monomer silver gel and lotion Download PDFInfo
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Abstract
The invention provides a preparation method for high-efficient monomer silver solution. The preparation method comprises the following steps: aqueous solution of silver source compound is mixed with aqueous solution containing protective agent, and then mixed with aqueous solution of reducing agent, and the high-efficient monomer silver solution is obtained through reaction under the condition of stirring; and the stirring speed is 50 r/min-150 r/min, the reaction temperature is minus 5 DEG C to 10 DEG, and the reaction time is 30 min-200 min. According to the invention, the aqueous solution of silver source compound is mixed uniformly with the aqueous solution containing protective agent, so that silver ions are dispersed uniformly, then the aqueous solution of silver source compound is mixed with the aqueous solution of reducing agent, so that the silver ions can be quickly restored into silver atoms, the whole reaction process is carried out at a relatively low temperature, the high-efficient monomer silver prepared has uniform particle diameter, uniform distribution, and good stability, and the reaction time is within 30 min-200 min.
Description
Technical field
The present invention relates to field of medicaments, particularly relate to the preparation method of a kind of efficient monomer silver solution and efficient monomer silver gel and efficient monomer silver washing lotion.
Background technology
Silver as antiseptic have nontoxic, without irritated, have no drug resistance and the multiple advantage such as has a broad antifungal spectrum, it only kills pathogen, do not injure normal cell, it has powerful bactericidal action to pathogenic bacteria of drug-resistant, staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Candida albicans, chlamydia trachomatis and gonococcus etc., can also repair impaired epithelial cell simultaneously.Silver has been described to human body without obvious toxic-side effects in " survey report about silver-colored toxicity " that American Public Health office nineteen ninety announces, local application, silver content is few, is safest application method.Along with the continuous progress of science and technology, people obtain efficient monomer silver much less of common silver granuel footpath, and its particle diameter is between 20 ~ 59nm, because it has larger specific area, so its sterilizing ability is stronger than traditional silver antibacterial agent, and the more little more even bactericidal effect of particle diameter is stronger.
At present, the preparation method of efficient monomer silver has a lot, mainly comprises physical method, chemical method and biological reducing method.Wherein physical method mainly contains sputtering plating, mechanical attrition method and laser burn method, physical method principle is simple, the product of preparation has higher purity, but it requires higher to instrument and equipment, and producing cost is expensive, can only be used for the size of efficient monomer silver particles and the not high industrialization preparation of character requirement.Chemical method mainly contains micro emulsion method, sol-gel process, galvanoplastic, solution phase chemical reduction, photochemical reduction etc., but it is higher that these methods have cost, preparation process is complicated, unstable product quality, silver ion reacts incomplete shortcoming, meanwhile, can not ensure that precipitation does not appear in efficient monomer silver in the process deposited, therefore not yet realize the large-scale production of efficient monomer silver.
Wherein, chemical reduction method is the method for the efficient monomer silver of preparation conventional at present, in order to avoid the efficient monomer Argent grain of preparation is reunited in preparation process, often need to add dispersant and protective agent, Zhang Zongtao etc. take PVP as macromolecule dispersant, take hydrazine hydrate as reducing agent, prepare the ball shape silver powder that average grain diameter is 30 ~ 100nm in aqueous, result shows, higher reaction temperature is conducive to forming little crystal grain silver powder (East China University of Science's journal, 1995, 21:423 ~ 427), but, in the method, higher temperature can make nano silver colloidal sol produce grey black precipitation, even produce silver mirror, greatly have impact on purity and the productive rate of product, Wei Chunping take sodium borohydride as reducing agent, and under the protection of polyvinylpyrrolidone, room temperature reduction liquor argenti nitratis ophthalmicus has synthesized Silver nanoparticles (Liaoning chemical industry, 2010, 7:697 ~ 699), but Silver nanoparticles prepared by the method is more easily reunited, and stability is bad.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of efficient monomer silver solution and efficient monomer silver gel and efficient monomer silver washing lotion, and the efficient monomer silver uniform particle diameter of preparation, is evenly distributed, and has good stability.
The invention provides a kind of preparation method of efficient monomer silver solution, comprising:
By the aqueous solution of silver-colored source compound with containing protectant aqueous solution, then with the aqueous solution of reducing agent, react under the condition of stirring, obtain efficient monomer silver solution;
Wherein, the speed of described stirring is 50r/min ~ 150r/min, and the temperature of described reaction is-5 DEG C ~ 10 DEG C, and the time of described reaction is 30min ~ 200min.
Preferably, the mass ratio of described silver-colored source compound, protective agent and reducing agent is 1:(1 ~ 10): (0.05 ~ 0.5).
Preferably, the speed of described stirring is 90r/min ~ 110r/min.
Preferably, the temperature of described reaction is 0 DEG C ~ 5 DEG C, and the time of described reaction is 150min ~ 180min.
Preferably, in the aqueous solution of described silver-colored source compound, the concentration of silver ion is 3.5g/L ~ 7.0g/L.
Preferably, described silver-colored source compound is selected from silver nitrate or silver ammonia complex.
Preferably, described protective agent is selected from any one or a few in polyvinyl alcohol, polyvinylpyrrolidone, gelatin, monohydric alcohol, polyalcohol, sorbierite, aromatic alcohol wax and polynary arene; Described reducing agent is selected from sodium borohydride, H
2o
2, formaldehyde, hydrazine hydrate, trisodium citrate, ascorbic acid, citric acid, ethanol, sugar, organic amine, any one or a few in polyalcohol and ferrous salt.
Present invention also offers a kind of efficient monomer silver solution prepared according to the method described above.
Present invention also offers a kind of efficient monomer silver gel, mixed by efficient monomer silver solution and assistant agent, described efficient monomer silver solution is above-mentioned efficient monomer silver solution, and in described efficient monomer silver gel, silver content is 200ppm ~ 500ppm.
Present invention also offers a kind of efficient monomer silver washing lotion, mixed by efficient monomer silver solution and water, described efficient monomer silver solution is above-mentioned efficient monomer silver solution, and in described efficient monomer silver washing lotion, silver content is 50ppm ~ 300ppm.
The present invention passes through by the aqueous solution of silver-colored source compound and containing protectant aqueous solution; again with the aqueous solution of reducing agent; stir with the speed of 50r/min ~ 150r/min, at the temperature of-5 DEG C ~ 10 DEG C, carry out reaction 30min ~ 200min, obtain efficient monomer silver solution.The present invention first by the aqueous solution of silver-colored source compound and containing protectant aqueous solution even; silver ion is uniformly dispersed; again with the aqueous solution of reducing agent; silver ion is made to be reduced into silver atoms rapidly; whole course of reaction is carried out all at a lower temperature, and the efficient monomer silver uniform particle diameter of preparation, is evenly distributed; and have good stability, and 30min ~ 200min can complete reaction.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 1 preparation amplifies 200000 times;
Fig. 2 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 1 preparation amplifies 30000 times;
Fig. 3 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 1 preparation is placed 30 days;
Fig. 4 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 3 preparation amplifies 50000 times;
Fig. 5 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 3 preparation is placed 30 days;
Fig. 6 is the scanning electron microscope (SEM) photograph that the Nano silver solution of comparative example 1 of the present invention preparation amplifies 200000 times;
Fig. 7 is the scanning electron microscope (SEM) photograph that the Nano silver solution of comparative example 1 of the present invention preparation amplifies 30000 times;
Fig. 8 is the scanning electron microscope (SEM) photograph that the Nano silver solution of comparative example 1 of the present invention preparation is placed 30 days.
Detailed description of the invention
The invention provides a kind of preparation method of efficient monomer silver solution, comprise the following steps:
By the aqueous solution of silver-colored source compound with containing protectant aqueous solution, then with the aqueous solution of reducing agent, react under the condition of stirring, obtain efficient monomer silver solution;
Wherein, the speed of described stirring is 50r/min ~ 150r/min, and the temperature of described reaction is-5 DEG C ~ 10 DEG C, and the time of described reaction is 30min ~ 200min.
The present invention first by the aqueous solution of silver-colored source compound and containing protectant aqueous solution even; silver ion is uniformly dispersed; again with the aqueous solution of reducing agent; silver ion is made to be reduced into silver atoms rapidly; whole course of reaction is carried out all at a lower temperature, and the efficient monomer silver uniform particle diameter of preparation, is evenly distributed; and have good stability, and 30min ~ 200min can complete reaction.
The present invention is first by the aqueous solution of silver-colored source compound and containing protectant aqueous solution.The aqueous solution of described silver-colored source compound obtains for being dissolved in the water by silver-colored source compound.Described silver-colored source compound is preferably silver nitrate or silver ammonia complex, is more preferably silver nitrate; Described silver ammonia complex is for containing Ag (NO
3)
2 +the compound of ion, the present invention contains Ag (NO to described
3)
2 +the anion of the compound of ion there is no particular/special requirement, is preferably OH
-, Cl
-and NO
3 -in any one or a few, be more preferably OH
-; The source of the present invention to described silver-colored source compound there is no particular/special requirement, can be generally commercially available.The present invention preferably adopts the mode of stirring to be dissolved in the water by silver-colored source compound, and the speed of described stirring is preferably 50r/min ~ 150r/min, is more preferably 90r/min ~ 110r/min; The temperature of described stirring is preferably-5 DEG C ~ 10 DEG C, is more preferably 0 DEG C ~ 5 DEG C; The time of described stirring is preferably 40min ~ 200min, is more preferably 60min ~ 120min.In the aqueous solution of the silver-colored source compound obtained, the concentration of silver ion is preferably 3.5g/L ~ 7.0g/L, is more preferably 4.0g/L ~ 5.2g/L.Described protectant aqueous solution obtains for being dissolved in the water by protective agent; Described protective agent be preferably in polyvinyl alcohol, polyvinylpyrrolidone, gelatin, monohydric alcohol, polyalcohol, sorbierite, aromatic alcohol wax and polynary arene any one or a few, be more preferably polyvinyl alcohol or polyvinylpyrrolidone; The present invention there is no particular/special requirement to described protectant source, can be generally commercially available; The present invention preferably adopts the mode of stirring to be dissolved in the water by protective agent, and the speed of described stirring is preferably 50r/min ~ 150r/min, is more preferably 90r/min ~ 110r/min; The temperature of described stirring is preferably-5 DEG C ~ 10 DEG C, is more preferably 0 DEG C ~ 5 DEG C; The time of described stirring is preferably 40min ~ 200min, is more preferably 60min ~ 120min.What obtain contains in protectant aqueous solution, and protectant concentration is preferably 25g/L ~ 65g/L, is more preferably 35g/L ~ 50g/L.
By the aqueous solution of silver-colored source compound and containing after protectant aqueous solution, the present invention preferably adopts the mode of stirring to make mixing more even, and the speed of described stirring is preferably 50r/min ~ 150r/min, is more preferably 90r/min ~ 110r/min; The temperature of described stirring is preferably-5 DEG C ~ 10 DEG C, is more preferably 0 DEG C ~ 5 DEG C; The time of described stirring is preferably 40min ~ 200min, is more preferably 80min ~ 160min.
By the aqueous solution of silver-colored source compound with containing after protectant aqueous solution, then with the aqueous solution of reducing agent, react under the condition of stirring, efficient monomer silver solution can be obtained.Described reducing agent is preferably sodium borohydride, H
2o
2, formaldehyde, hydrazine hydrate, trisodium citrate, ascorbic acid, citric acid, ethanol, sugar, organic amine, any one or a few in polyalcohol and ferrous salt, be more preferably sodium borohydride or trisodium citrate; The source of the present invention to described reducing agent there is no particular/special requirement, can be generally commercially available; In the aqueous solution of described reducing agent, the concentration of reducing agent is preferably 0.5g/L ~ 1.3g/L, is more preferably 0.8g/L ~ 1.1g/L.The speed of described stirring is preferably 50r/min ~ 150r/min, is more preferably 90r/min ~ 110r/min, most preferably is 100r/min ~ 105r/min; The temperature of described reaction is preferably-5 DEG C ~ 10 DEG C, is more preferably 0 DEG C ~ 5 DEG C, most preferably is 2 DEG C ~ 4 DEG C; The time of described reaction is preferably 30min ~ 200min, is more preferably 150min ~ 180min, most preferably is 160min ~ 170min.In the present invention, the mass ratio of described silver-colored source compound, protective agent and reducing agent is preferably 1:(1 ~ 10): (0.05 ~ 0.5), is more preferably 1:(3 ~ 7): (0.1 ~ 0.3).
The present invention first by the aqueous solution of silver-colored source compound and containing protectant aqueous solution even, thus silver ion is uniformly dispersed, then with the aqueous solution of reducing agent, make silver ion be reduced into silver atoms rapidly, whole course of reaction is carried out all at a lower temperature, avoid temperature too high time, due to Brownian movement aggravation, interparticle collision chance is increased, cause particle agglomeration, there is grey black precipitation, even produce silver mirror, thus affect the shortcoming of product purity and productive rate; By reducing reaction temperature, controlling the Brownian movement speed of molecule, atom, reducing collision, thus reach stable reaction, make the efficient monomer of preparation silver particle size homogeneous, be evenly distributed, simultaneously, complete reaction in the short period of time again, overcome the deficiency that the too low reaction rate of temperature is excessively slow.
After obtaining efficient monomer silver solution, by SEM, its pattern and stability are detected, result shows, efficient monomer silver solution uniform particle diameter provided by the invention, be evenly distributed, and have good stability, in the efficient monomer silver solution obtained, the particle diameter of silver atoms is preferably 20nm ~ 50nm, is more preferably 30nm ~ 40nm; Its silver content is preferably 500ppm ~ 1500ppm, is more preferably 700ppm ~ 1200ppm; Its solution colour is preferably brownish red.
Present invention also offers a kind of efficient monomer silver solution prepared according to the method described above, in described efficient monomer silver solution, the particle diameter of silver atoms is preferably 20nm ~ 50nm, is more preferably 30nm ~ 40nm; Its silver content is preferably 500ppm ~ 1500ppm, is more preferably 700ppm ~ 1200ppm; Its solution colour is preferably brownish red.
Present invention also offers a kind of efficient monomer silver gel, mixed by efficient monomer silver solution and assistant agent, described efficient monomer silver solution is the efficient monomer silver solution prepared according to the method described above, in described efficient monomer silver gel, its silver content is preferably 200ppm ~ 500ppm, is more preferably 250ppm ~ 400ppm; Preferably, described efficient monomer silver solution accounts for the 10wt% ~ 90wt% of described efficient monomer silver solution and assistant agent.The kind of the present invention to described assistant agent there is no particular/special requirement, and can prepare the conventional assistant agent of gel for well known to those skilled in the art, the present invention is preferably Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerin solution and the aqueous solution.The present invention there is no particular/special requirement to the source of described Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerin solution and the aqueous solution and purity, can be generally commercially available, and its purity can be technical grade.
Preferably, the present invention, by the efficient monomer silver solution of preparation and Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerin solution and aqueous solution, prepares efficient monomer silver gel; The ratio of the volume of the volume of the described efficient monomer silver volume of solution and the quality of Acritamer 940 and sodium hydroxide solution, the volume of ethylparaben ethanolic solution, the volume of glycerin solution and the aqueous solution is preferably 1mL:(0.01g ~ 0.03g): (0.005mL ~ 0.02mL): (0.005mL ~ 0.02mL): (0.1mL ~ 0.4mL): (1mL ~ 4mL); The mass concentration of described NaOH is preferably 20% ~ 60%; In described efficient monomer silver solution, silver content is preferably 500ppm ~ 1500ppm.The order by merging of the present invention to described efficient monomer silver solution and Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerin solution and the aqueous solution there is no particular/special requirement, is preferably and Acritamer 940, sodium hydroxide solution, ethylparaben ethanolic solution, glycerin solution, the aqueous solution and efficient monomer silver solution is sequentially added into.
Present invention also offers a kind of efficient monomer silver washing lotion, mixed by efficient monomer silver solution and water, described efficient monomer silver solution is the efficient monomer silver solution prepared according to the method described above, in described efficient monomer silver washing lotion, its silver content is preferably 50ppm ~ 300ppm, is more preferably 100ppm ~ 200ppm; The volume ratio of described efficient monomer silver solution and water is preferably 1:1 ~ 15, is more preferably 1:4 ~ 10.
Concrete, after the efficient monomer silver solution with water dilution of preparation, prepare efficient monomer silver washing lotion.
The efficient monomer silver gel of preparation and efficient monomer silver washing lotion are used for clinical antibacterial tests, result shows, efficient monomer silver gel provided by the invention and efficient monomer silver washing lotion can effectively treat all kinds of vaginitis, prostatitis and acute and chronic rhinitis, obviously can improve symptom, and have no adverse reaction, product safety is effective.
The present invention is by being dissolved in the water silver-colored source compound and protective agent respectively and stirring; obtain the aqueous solution of silver ion respectively and contain protectant aqueous solution; again the two is mixed; again with the aqueous solution of reducing agent; stir with the speed of 50r/min ~ 150r/min; carry out reaction 30min ~ 200min at the temperature of-5 DEG C ~ 10 DEG C, obtain efficient monomer silver solution.The present invention first by the aqueous solution of silver-colored source compound and protectant aqueous solution even; silver ion is uniformly dispersed; again with the aqueous solution of reducing agent; silver ion is made to be reduced into silver atoms rapidly; whole course of reaction is carried out all at a lower temperature, and the efficient monomer silver uniform particle diameter of preparation, is evenly distributed; and have good stability, and 30min ~ 200min can complete reaction.
In order to further illustrate the present invention, below in conjunction with embodiment, the preparation method of efficient monomer silver solution provided by the invention and efficient monomer silver gel and efficient monomer silver washing lotion are described in detail.
Embodiment 1
5g silver nitrate is added in the distilled water of 1000mL2 DEG C, stir 60min with the speed of 100r/min and make it fully dissolve, obtain liquor argenti nitratis ophthalmicus; 25g polyvinyl alcohol is added in the distilled water of 500mL2 DEG C simultaneously, stir 60min with the speed of 100r/min and make it fully dissolve, obtain poly-vinyl alcohol solution; The liquor argenti nitratis ophthalmicus obtained and poly-vinyl alcohol solution are fully mixed, at the temperature of 2 DEG C, stirs 120min with the speed of 100r/min, obtain mixed solution; Then 0.085g sodium borohydride is added in the distilled water of 100mL2 DEG C, stirring 60min with the speed of 100r/min makes it fully dissolve, and slowly join in the mixed solution of silver nitrate and polyvinyl alcohol, at the temperature of 2 DEG C, stir 180min with the speed of 100r/min, obtain efficient monomer silver solution.
Shape measure is carried out with the efficient monomer silver solution of SEM to preparation, testing result is shown in Fig. 1 and Fig. 2, Fig. 1 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 1 preparation amplifies 200000 times, and Fig. 2 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 1 preparation amplifies 30000 times; From Fig. 1 and Fig. 2, in efficient monomer silver solution provided by the invention, the silver atoms contained is of a size of about 20nm, and is evenly distributed.
The efficient monomer silver solution normal temperature lucifuge of preparation is placed 30 days, then by SEM, its pattern is checked, thus detect its stability.Experimental result is shown in Fig. 3, Fig. 3 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 1 preparation is placed 30 days, and as shown in Figure 3, efficient monomer silver solution prepared by the present invention has good stability, after its room temperature lucifuge places 30 days, still for being uniformly distributed.
Embodiment 2
4.0g silver nitrate is added in the distilled water of 1000mL5 DEG C, stir 60min with the speed of 100r/min and make it fully dissolve, obtain liquor argenti nitratis ophthalmicus; 20g polyvinyl alcohol is added in the distilled water of 500mL5 DEG C simultaneously, stir 60min with the speed of 100r/min and make it fully dissolve, obtain poly-vinyl alcohol solution; The liquor argenti nitratis ophthalmicus obtained and poly-vinyl alcohol solution are fully mixed, at the temperature of 5 DEG C, stirs 120min with the speed of 100r/min, obtain mixed solution; Then 0.065g sodium borohydride is added in the distilled water of 100mL5 DEG C, stirring 60min with the speed of 100r/min makes it fully dissolve, and slowly join in the mixed solution of silver nitrate and polyvinyl alcohol, at the temperature of 5 DEG C, stir 180min with the speed of 100r/min, obtain efficient monomer silver solution.
Carry out Shape measure with the efficient monomer silver solution of SEM to preparation, result shows, in efficient monomer silver solution prepared by the present embodiment, the silver atoms contained is of a size of about 20nm, and is evenly distributed.
The efficient monomer silver solution normal temperature lucifuge of preparation is placed 30 days, then by SEM, its pattern is checked, thus detect its stability, experimental result shows, efficient monomer silver solution prepared by the present embodiment has good stability, after its room temperature lucifuge places 30 days, still for being uniformly distributed.
Embodiment 3
5.0g silver nitrate is added in the distilled water of 1000mL4 DEG C, stir 120min with the speed of 100r/min and make it fully dissolve, obtain liquor argenti nitratis ophthalmicus; 18g polyvinylpyrrolidone is added in the distilled water of 500mL4 DEG C simultaneously, stir 120min with the speed of 100r/min and make it fully dissolve, obtain polyvinylpyrrolidonesolution solution; The liquor argenti nitratis ophthalmicus obtained and polyvinylpyrrolidonesolution solution are fully mixed, at the temperature of 4 DEG C, stirs 120min with the speed of 100r/min, obtain mixed solution; Then 0.065g trisodium citrate is added in the distilled water of 100mL4 DEG C, stirring 120min with the speed of 150r/min makes it fully dissolve, and slowly join in the mixed solution of silver nitrate and polyvinylpyrrolidone, at the temperature of 4 DEG C, stir 180min with the speed of 150r/min, obtain efficient monomer silver solution.
Carry out Shape measure with the efficient monomer silver solution of SEM to preparation, testing result is shown in Fig. 4, and Fig. 4 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 3 preparation amplifies 50000 times; As shown in Figure 4, in the efficient monomer silver solution that the present embodiment provides, the silver atoms contained is of a size of about 20nm, and is evenly distributed.
The efficient monomer silver solution normal temperature lucifuge of preparation is placed 30 days, then by SEM, its pattern is checked, thus detect its stability.Experimental result is shown in Fig. 5, Fig. 5 is the scanning electron microscope (SEM) photograph that the efficient monomer silver solution of the embodiment of the present invention 3 preparation is placed 30 days, and as shown in Figure 5, efficient monomer silver solution prepared by the present invention has good stability, after its room temperature lucifuge places 30 days, still for being uniformly distributed.
Comparative example 1
0.0449g polyvinylpyrrolidone is added in beaker, add stirring and dissolving under 30mL deionized water 20 DEG C of conditions, add the silver nitrate aqueous solution of 5mL0.006mol/L more wherein, stir, then in reaction system, dropwise add the concentration that 10mL newly configures is the sodium borohydride aqueous solution of 0.008mol/L, be stirred to solution and become yellow from colourless, obtain Nano silver solution.
Shape measure is carried out with the Nano silver solution of SEM to preparation, testing result is shown in Fig. 6 and Fig. 7, Fig. 6 is the scanning electron microscope (SEM) photograph that the Nano silver solution of comparative example 1 of the present invention preparation amplifies 200000 times, and Fig. 7 is the scanning electron microscope (SEM) photograph that the Nano silver solution of comparative example 1 of the present invention preparation amplifies 30000 times; From Fig. 6 and Fig. 7, in Nano silver solution prepared by comparative example of the present invention, the silver atoms contained is of a size of 50nm ~ 100nm, and has agglomeration.
The Nano silver solution normal temperature lucifuge of preparation is placed 30 days, then by SEM, its pattern is checked, thus detect its stability.Experimental result is shown in Fig. 8, Fig. 8 is the scanning electron microscope (SEM) photograph that the Nano silver solution of comparative example 1 of the present invention preparation is placed 30 days, as shown in Figure 8, and Nano silver solution less stable prepared by comparative example of the present invention, after its room temperature lucifuge places 30 days, there is comparatively significantly agglomeration.
Embodiment 4
By the bacterium stripping property test method of regulation in " the Disposable Sanitary Accessory sanitary standard " of version in 2002, bacteriostatic test is carried out to efficient monomer silver solution, the efficient monomer silver solution of embodiment 3 preparation and the Nano silver solution of comparative example 1 preparation prepared by embodiment 1, the results are shown in Table 1, table 1 is the bacteriostatic test result of the embodiment of the present invention 1, the efficient monomer silver solution of embodiment 3 preparation and the Nano silver solution of comparative example 1 preparation.
The bacteriostatic test result of Nano silver solution prepared by the efficient monomer silver solution of table 1 embodiment of the present invention 1, embodiment 3 preparation and comparative example 1
Embodiment 5
Be that efficient monomer silver solution prepared by the sodium hydroxide solution of 40%, 10mL ethylparaben ethanolic solution, 250mL glycerin solution, the 2500mL aqueous solution and 1000mL embodiment 1 is sequentially added in reactor and is prepared into gel by 20g Acritamer 940,10mL concentration, filling in delivery device, prepare efficient monomer silver gel, wherein silver content is 350ppm.
Embodiment 6
Efficient monomer silver solution 100mL embodiment 1 prepared adds the dilution of 900mL water, and then filling in delivery device, prepare efficient monomer silver washing lotion, wherein silver content is 100ppm.
Embodiment 7
Be that efficient monomer silver solution prepared by the sodium hydroxide solution of 40%, 8mL ethylparaben ethanolic solution, 200mL glycerin solution, the 2000mL aqueous solution and 1000mL embodiment 3 is sequentially added in reactor and is prepared into gel by 16g Acritamer 940,8mL concentration, filling in delivery device, prepare efficient monomer silver gel, wherein silver content is 350ppm.
Embodiment 8
Efficient monomer silver gel prepared by research performation example 5 is to the result for the treatment of of various vaginitis and cervicitis:
Case load:
Select each 72 examples of patient suffering from bacterial vaginosis BV, VVC and cervicitis, totally 216 examples.
The selection of case:
1. age l8 ~ 65 year old, women;
2. the diagnostic criteria of bacterial vaginosis BV, VVC (vulvovaginal candidiasis), cervicitis is met;
3. voluntary participation clinical testing, and sign Informed Consent Form.
Case exclusion standard:
1. age < 18 years old or age > 65 years old;
2. the primary disease person such as conscience kidney or hemopoietic system is merged, mental patient;
3. conceived or women breast-feeding their children;
4. allergic constitution or to the known composition allergy sufferers of this product;
5. anti-inflammatory drug was used to treat in 1 week before medication;
6. other clinical testing person was carried out in 1 week;
7. researcher thinks and should not carry out clinical testing person;
8. diagnostic criteria person is not met;
9. the women (virgin) had sexual intercourse is not had.
Clinical testing procedure:
Adopt open to test from the clinic trial as contrast;
Patients with Bacterial Vaginosis: the efficient monomer silver gel product that embodiment 5 is prepared by patient injects vagina deep, every day 1, often props up 3g, is used in conjunction 7 days;
VVC (vulvovaginal candidiasis): the efficient monomer silver gel that embodiment 5 is prepared by patient injects vagina deep, every day 1, often props up 3g, is used in conjunction 7 days;
Virus in patients with cervicitis: the efficient monomer silver gel that embodiment 5 is prepared by patient injects vagina deep, every day 1, often props up 3g, is used in conjunction 9 days;
Drug withdrawal was followed up a case by regular visits to after 7 days, if the menstrual period then follows up a case by regular visits to after terminating menstrual period.
Clinical evaluation standard:
Recovery from illness: after medication, symptom and sign disappear substantially, integrated value reduces >=90%;
Effective: after medication, cardinal symptom, sign are obviously improved, integrated value reduces >=70%;
Effective: after medication, cardinal symptom, sign are improved, and integrated value reduces >=30%;
Invalid: after medication, cardinal symptom and sign are not improved, integrated value reduces < 30%.
Clinical test results:
1, case performance
The case performance of table 2 embodiment of the present invention 8 gathers
| Sick kind | Enter to organize number | Complete number | Come off number |
| Bacterial vaginosis BV | 72 | 69 | 3 |
| VVC | 72 | 68 | 4 |
| Cervicitis | 72 | 68 | 4 |
2, result of the test
The result of the test of table 3 embodiment of the present invention 8 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver gel treatment bacterial vaginosis BV provided by the invention is 62.32%, total effective rate is 89.86%, total obvious effective rate for the treatment of VVC is 57.35%, total effective rate is 91.18%, total obvious effective rate for the treatment of cervicitis is 57.35%, and total effective rate is 88.24%, can improve the symptom such as itch, abnormal leucorrhea, private parts peculiar smell that it causes, and bad reaction is there is not in process of the test, prove that this product is safe and effective.
Embodiment 9
Efficient monomer silver gel prepared by research performation example 5 is to the result for the treatment of of chronic prostatitis:
Case load:
Select patients with chronic prostatitis totally 72 examples.
The selection of case:
1. age l8 ~ 65 year old, the male sex;
2. the prostatitic diagnostic criteria of non specific chronic is met;
3. voluntary participation clinical testing, and sign Informed Consent Form.
Case exclusion standard:
1. the primary disease person such as conscience kidney or hemopoietic system is merged, mental patient;
2. allergic constitution or to the known composition allergy sufferers of this product;
3. anti-inflammatory drug was used to treat in 1 week before medication;
4. other clinical testing person was carried out in 1 week;
5. researcher thinks and should not carry out clinical testing person;
6. diagnostic criteria person is not met;
7. acute prostatitis patient, patients with prostate cancer.
Clinical testing procedure:
Adopt open to test from the clinic trial as contrast;
The efficient monomer silver gel that example 5 is prepared by patient injects deep rectum, every day 1, often props up 3g, is used in conjunction 15 days.
Clinical evaluation standard:
Recovery from illness: after medication 15d, symptom disappears substantially, integrated value reduces >=95%;
Effective: after medication 15d, symptom is obviously improved, integrated value reduces >=60%;
Effective: after medication 15d, symptom is improved, integrated value reduces >=30%;
Invalid: after medication 15d, symptom is not improved, integrated value reduces < 30%.
Clinical test results:
1, case performance
The case performance of table 4 embodiment of the present invention 9 gathers
| Sick kind | Enter to organize number | Complete number | Come off number |
| Chronic prostatitis | 72 | 69 | 3 |
2, result of the test
The result of the test of table 5 embodiment of the present invention 9 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver gel treatment chronic prostatitis provided by the invention is 44.92%, total effective rate is 89.95%, the symptom such as frequent micturition, odynuria, urine retention, soreness of waist and knee joint, perineum local falling inflation that chronic prostatitis causes can be improved, and bad reaction is there is not in process of the test, prove that this product is safe and effective.
Embodiment 10
Efficient monomer silver washing lotion prepared by research performation example 6 is to the result for the treatment of of acute and chronic rhinitis:
Case load:
Select acute rhinitis, each 72 examples of rhinitis chronic patient, totally 144 examples.
The selection of case:
1. age l8 ~ 65 year old, male or female;
2. the diagnostic criteria of acute and chronic rhinitis is met;
3. voluntary participation clinical testing, and sign Informed Consent Form.
Case exclusion standard:
1. the primary disease person such as conscience kidney or hemopoietic system is merged, mental patient;
2. conceived or women breast-feeding their children;
3. allergic constitution or to the known composition allergy sufferers of this product;
4. anti-inflammatory drug curer was used in 1 week before medication;
5. other clinical testing person was carried out in 1 week;
6. researcher thinks and should not carry out clinical testing person;
7. diagnostic criteria person is not met;
8. sinusitis in patients.
Clinical testing procedure:
Adopt open to test from the clinic trial as contrast;
Using method: efficient monomer silver lotion product prepared by use-case 6, each 4 sprays, often spray about 0.2mL; Acute rhinitis patient every day 3 times, be used in conjunction 7 days; Rhinitis chronic patient every day 4 times, be used in conjunction 7 days.
Clinical evaluation standard:
Clinical cure: after medication 7d, symptom and sign disappear substantially, integrated value reduces >=95%;
Effective: after medication 7d, cardinal symptom and sign are obviously improved, integrated value reduces >=70%;
Effective: after medication 7d, cardinal symptom and sign are improved, and integrated value reduces >=30%;
Invalid: after medication 7d, cardinal symptom and sign are not improved, integrated value reduces < 30%.
Clinical test results:
1, case performance
The case performance of table 6 embodiment of the present invention 10 gathers
2, result of the test
The result of the test of table 7 embodiment of the present invention 10 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver washing lotion treatment acute rhinitis provided by the invention is 56.34%, total effective rate is 94.37%, total obvious effective rate for the treatment of rhinitis chronic is 51.47%, total effective rate is 91.18%, its nasal obstruction caused can be improved, rhinalgia, nasal cavity dryness are itched, nasal congestion, have a running nose, the symptom such as to sneeze, in process of the test, there is not bad reaction, prove that this product is safe and effective.
Embodiment 11
Efficient monomer silver washing lotion prepared by research performation example 6 is to various colpitic result for the treatment of:
Case load:
Each 72 examples of patient of selecting bacteria vaginosis, VVC, totally 144 examples.
The selection of case:
1. age l8 ~ 65 year old, women;
2. bacterial vaginosis BV, VVC is met, i.e. the diagnostic criteria of vulvovaginal candidiasis;
3. voluntary participation clinical testing, and sign Informed Consent Form.
Case exclusion standard:
1. age < 18 years old or age > 65 years old;
2. the primary disease person such as conscience kidney or hemopoietic system is merged, mental patient;
3. conceived or women breast-feeding their children;
4. allergic constitution or to the known composition allergy sufferers of this product;
5. anti-inflammatory drug was used to treat in 1 week before medication;
6. other clinical testing person was carried out in 1 week;
7. researcher thinks and should not carry out clinical testing person;
8. diagnostic criteria person is not met;
9. the women (virgin) had sexual intercourse is not had.
Clinical testing procedure:
Adopt open to test from the clinic trial as contrast;
Patients with Bacterial Vaginosis: after cleaning vulva, the efficient monomer silver lotion product that example 6 is prepared by patient injects vagina deep, and each 1 time sooner or later, each 30mL, is used in conjunction 7 days;
Vulvovaginal candidiasis: using method is each 1 time sooner or later, the efficient monomer silver lotion product prepared by example 6 is with the direct wiping vulva of the mode of dipping in gauze or get product and be about 30mL ~ 40mL and pour in basin, add warm water by the volume ratio of 1:10, carry out vulva cleaning, use 7 days continuously.
Clinical evaluation standard:
Recovery from illness: after medication 7d, symptom and sign disappear substantially, integrated value reduces >=90%;
Effective: after medication 7d, cardinal symptom, sign are obviously improved, integrated value reduces >=70%;
Effective: after medication 7d, cardinal symptom, sign are improved, and integrated value reduces >=30%;
Invalid: after medication 7d, cardinal symptom and sign are not improved, integrated value reduces < 30%.
Clinical test results:
1, case performance
The case performance of table 8 embodiment of the present invention 11 gathers
2, result of the test
The result of the test of table 9 embodiment of the present invention 11 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver washing lotion treatment bacterial vaginosis BV provided by the invention is 60.87%, total effective rate is 89.86%, total obvious effective rate for the treatment of VVC is 57.97%, total effective rate is 91.30%, the symptom such as itch, abnormal leucorrhea, private parts peculiar smell that it causes can be improved, and bad reaction is there is not in process of the test, prove that this product is safe and effective.
Embodiment 12
Efficient monomer silver gel prepared by research performation example 7 is to the result for the treatment of of chronic prostatitis:
Case load:
Select patients with chronic prostatitis totally 72 examples.
The selection of case:
1. age l8 ~ 65 year old, the male sex;
2. the prostatitic diagnostic criteria of non specific chronic is met;
3. voluntary participation clinical testing, and sign Informed Consent Form.
Case exclusion standard:
1. the primary disease person such as conscience kidney or hemopoietic system is merged, mental patient;
2. allergic constitution or to the known composition allergy sufferers of this product;
3. anti-inflammatory drug was used to treat in 1 week before medication;
4. other clinical testing person was carried out in 1 week;
5. researcher thinks and should not carry out clinical testing person;
6. diagnostic criteria person is not met;
7. acute prostatitis patient, patients with prostate cancer.
Clinical testing procedure:
Adopt open to test from the clinic trial as contrast;
The efficient monomer silver gel product that embodiment 7 is prepared by patient injects deep rectum, every day 1, often props up 3g, is used in conjunction 15 days.
Clinical evaluation standard:
Recovery from illness: after medication 15d, symptom disappears substantially, integrated value reduces >=95%; .
Effective: after medication 15d, symptom is obviously improved, integrated value reduces >=60%;
Effective: after medication 15d, symptom is improved, integrated value reduces >=30%;
Invalid: after medication 15d, symptom is not improved, integrated value reduces < 30%.
Clinical test results:
Case performance
The case performance of table 10 embodiment of the present invention 12 gathers
| Sick kind | Enter to organize number | Complete number | Come off number |
| Chronic prostatitis | 72 | 68 | 4 |
Result of the test
The result of the test of table 11 embodiment of the present invention 12 gathers
Result of the test shows: total obvious effective rate of efficient monomer silver gel treatment chronic prostatitis provided by the invention is 45.59%, total effective rate is 88.24%, the symptom such as frequent micturition, odynuria, urine retention, soreness of waist and knee joint, perineum local falling inflation that chronic prostatitis causes can be improved, and bad reaction is there is not in process of the test, prove that this product is safe and effective.
From above-described embodiment and comparative example, the present invention reacts at a lower temperature, efficient monomer silver solution can be prepared in the short period of time, and the efficient monomer silver uniform particle diameter of preparation, be evenly distributed, and have good stability, the efficient monomer silver gel prepared with it and efficient monomer silver washing lotion can effectively treat all kinds of vaginitis, prostatitis and acute and chronic rhinitis.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a preparation method for efficient monomer silver solution, is characterized in that, comprising:
By the aqueous solution of silver-colored source compound with containing protectant aqueous solution, then with the aqueous solution of reducing agent, react under the condition of stirring, obtain efficient monomer silver solution;
Wherein, the speed of described stirring is 90r/min ~ 110r/min, and the temperature of described reaction is-5 DEG C ~ 10 DEG C, and the time of described reaction is 30min ~ 200min.
2. method according to claim 1, is characterized in that, the mass ratio of described silver-colored source compound, protective agent and reducing agent is 1:(1 ~ 10): (0.05 ~ 0.5).
3. method according to claim 1, is characterized in that, the temperature of described reaction is 0 DEG C ~ 5 DEG C, and the time of described reaction is 150min ~ 180min.
4. method according to claim 1, is characterized in that, in the aqueous solution of described silver-colored source compound, the concentration of silver ion is 3.5g/L ~ 7.0g/L.
5. method according to claim 1, is characterized in that, described silver-colored source compound is selected from silver nitrate or silver ammonia complex.
6. method according to claim 1, is characterized in that, described protective agent be selected from polyvinyl alcohol, polyvinylpyrrolidone, gelatin, monohydric alcohol, polyalcohol, sorbierite, aromatic alcohol wax and polynary arene any one or a few; Described reducing agent is selected from sodium borohydride, H
2o
2, formaldehyde, hydrazine hydrate, trisodium citrate, ascorbic acid, citric acid, ethanol, sugar, organic amine, any one or a few in polyalcohol and ferrous salt.
7. the efficient monomer silver solution prepared according to method described in claim 1-6 any one.
8. an efficient monomer silver gel, is mixed by efficient monomer silver solution and assistant agent, and described efficient monomer silver solution is efficient monomer silver solution according to claim 7, and in described efficient monomer silver gel, silver content is 200ppm ~ 500ppm.
9. an efficient monomer silver washing lotion, is mixed by efficient monomer silver solution and water, and described efficient monomer silver solution is efficient monomer silver solution according to claim 7, and in described efficient monomer silver washing lotion, silver content is 50ppm ~ 300ppm.
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| CN105469857B (en) * | 2015-12-28 | 2018-03-02 | 苏州华一新能源科技有限公司 | It is a kind of to be used to nitrogenize silver paste of silicon base and preparation method thereof |
| CN106009442B (en) * | 2016-06-21 | 2019-04-23 | 天津大学 | A kind of preparation method of the polyvinyl alcohol hydrogel of carrying nano silver |
| CN108566954A (en) * | 2017-03-10 | 2018-09-25 | 洛阳惠中兽药有限公司 | A kind of disinfectant and its preparation method and application |
| CN106964785A (en) * | 2017-04-20 | 2017-07-21 | 中国科学院深圳先进技术研究院 | A kind of preparation method of nano-Ag particles |
| CN107398562B (en) * | 2017-07-14 | 2019-06-04 | 山西农业大学 | The preparation method of fulvic acid nano silver gel |
| CN111097922A (en) * | 2020-02-21 | 2020-05-05 | 深圳先进技术研究院 | Nano silver particle and preparation method and application thereof |
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| CN101279376A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of high dispersed superfine spherical silver powder for conductive silver slurry |
| CN102672199A (en) * | 2012-06-01 | 2012-09-19 | 中国科学院理化技术研究所 | Preparation method of silver particle with sheet-strip integrated structural shape |
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| CN101279376A (en) * | 2008-05-15 | 2008-10-08 | 金川集团有限公司 | Preparation of high dispersed superfine spherical silver powder for conductive silver slurry |
| CN102672199A (en) * | 2012-06-01 | 2012-09-19 | 中国科学院理化技术研究所 | Preparation method of silver particle with sheet-strip integrated structural shape |
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