CN102294052B - Preparation method of medical high polymer based silver nano material - Google Patents
Preparation method of medical high polymer based silver nano material Download PDFInfo
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- CN102294052B CN102294052B CN 201110212173 CN201110212173A CN102294052B CN 102294052 B CN102294052 B CN 102294052B CN 201110212173 CN201110212173 CN 201110212173 CN 201110212173 A CN201110212173 A CN 201110212173A CN 102294052 B CN102294052 B CN 102294052B
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Abstract
The invention provides a preparation method of a medical high polymer based silver nano material, comprising the following steps: a, at room temperature, according to the weight ratio of a medical high polymer material to an organic solvent of 1:3-1:30, preparing a medical high polymer organic solvent, to control the viscosity within 150-1500 cp; b, adding Ag/TiO2 whisker with the mass concentration of 0.01-0.3% in the medical high polymer organic solvent prepared by the step a, stirring violently to mix uniformly; c, controlling the temperature and humidity in a specific condition, pouring the mixed solution obtained by the step b in a container, preparing a film by volatilization of solvent, wherein, Ag/TiO2 whisker forms a concentration gradient in the polymer solution according to its own gravity; and d, letting the solvent be subject to complete volatilization to form the film to obtain the medical high polymer based silver nano composite material, cleaning the material, carrying out drying under vacuum until the weight is constant, and then storing for use. Because the concentration of Ag/TiO2 whisker in the composite material distributes in gradient, the material can realize the long release of silver ions, so that the material has a long time of antiseptic effect.
Description
Technical field
The present invention relates to a kind of preparation method of anti-biotic material, especially a kind of nanometer silver preparation methods that is applied to the medical high polymer base of medical material and medical instruments field.
Background technology
At present, bacterial infection, thrombosis and calcification are to contact the three big major complications that bio-medical material and medical apparatus and instruments face for blood, and infecting becomes one of topmost disease harm.In the U.S., in the institute or the bacterial infection relevant with hospital, be positioned at the 5th of the cause of death, be only second to after heart disease, cancer, apoplexy and pneumonia and the influenza.The Center for Disease Control (CDC) of the U.S. (CDC) estimates, hospital to every patient's of nosocomial infection diagnosis and treatment cost above 2300 dollars.At present maximum in the metal ion antibacterial research is the antibacterial that contains silver ion, and U.S. scientist studies show that, silver ion has and destroys antibacterial, the respiratory function of virus and the function of somatoblast.The nanometer silver ultramicro powder that research is made under nanometer technology makes nanometer silver increase greatly with the probability that the microorganism surface contacts.Therefore, the anti-microbial property of nanometer silver is far longer than traditional silver-series antibacterial agent.Nanometer silver has good antibacterial effect to gram negative bacteria and gram positive bacteria.
The antibacterial characteristics of nanometer silver makes it to be widely used in biomedical materials field such as medical catheter class material, dental materials, medical equipment and implant.And in most of silver-containing antibacterial polymer, mainly be contain elemental silver and or highly-water-soluble silver salt and silver composite, all exist in aqueous environment and to discharge the slow or silver ion of silver ion speed and discharge problems such as too fast.In addition, also have a lot of problems to remain further investigation about the toxicity of nanometer silver, if but can effectively control nano-Ag particles or concentration of silver ions, just can guarantee nanometer silver safety in vivo.Therefore, on the manufacturing process of nanometer silver, how to keep efficient, lasting and controlled release silver ion is emphasis and the difficult point of nano silver antibacterial material research always.
Polymer is the metal nanometer composite material of matrix, its action principle be each molecule by polymer provide a plurality of connecting portions simultaneously with the self assembly of granule, nanoparticle is played a very good protection.Simultaneously, nanometer silver/polymer composites provides a well basis for nanometer silver in the combination of material surface and the long-acting release of antibiotic property silver ion.In nanometer silver/polymer composites, nanometer silver can be dispersed in the polymeric matrix uniformly, and the material of this method preparation can effectively be avoided the reunion of nano-particle.The nano-complex of medical high polymer polymer and silver be expected on the one hand can by polymer fixedly nano-Ag particles prevent that nano-particle from entering blood and tissue, can realize permanent silver ion release in addition on the one hand.
Though found the breach for the safety issue that under the anti-microbial property prerequisite that keeps silver ion, improves silver ion in the prior art, but exist the problem of aspects such as safety, antibiotic property and silver ion release in the present composite, can not well satisfy actual needs.
In view of this, be necessary the nanometer silver preparation methods of existing medical high polymer base is improved, to address the above problem.
Summary of the invention
The object of the present invention is to provide a kind of nanometer silver preparation methods of medical high polymer base, there are a graded in the concentration of the nano-Ag particles that makes by this method or particle diameter, thereby the silver ion in the realization material discharges for a long time, and then has long antibacterial effect.
For achieving the above object, the nanometer silver preparation methods of a kind of medical high polymer base of the present invention, it comprises the steps:
A. at room temperature, according to the ratio of medical macromolecular materials and organic solvent mass ratio 1:3 ~ 1:30, preparation medical high polymer organic solution makes range of viscosities control at 150 ~ 1500cp;
B. be that 0.01% ~ 3% Ag/TiO2 whisker adds in the medical high polymer solution of step a configuration with mass concentration, strong agitation is so that the two abundant mix homogeneously;
C. 10 ~ 80 ℃ of temperature, under the condition of relative humidity 30 ~ 90%, the mixed solution that step b obtains is poured in the vessel, adopted the solvent evaporates thin films; Wherein the Ag/TiO2 whisker distributes according to the Concentraton gradient that self gravitation is formed in the macromolecular solution;
D. solvent volatilizees after the film forming fully, obtains the nano silver composite material of medical high polymer base, and after it was cleaned up, vacuum drying was preserved to the constant weight and used.
As a further improvement on the present invention, described medical macromolecular materials comprise medical polyurethane or medical polyvinyl or medical polyethylene or medical polylactic acid or medical grade silicon rubber or medical polyether-ketone.
As a further improvement on the present invention, described organic solvent comprises oxolane, N, dinethylformamide, dimethyl acetylamide, dichloromethane, chloroform, heptane, cyclohexane extraction, butanone, acetone or ethanol.
As a further improvement on the present invention, described Ag/TiO2 whisker refers to support on the titanium oxide whisker surface material of different-grain diameter nano-Ag particles, and the particle size range of described nano-Ag particles is 20 ~ 800nm.
As a further improvement on the present invention, the mass content of described nano-Ag particles is less than or equal to 3%.
Compared with prior art, the invention has the beneficial effects as follows: because the concentration in gradient of Ag/TiO2 whisker in composite distributes, the perhaps concentration of nano-Ag particles or particle diameter distribution gradient in composite, make material can realize that silver ion discharges for a long time, thereby have long antibacterial effect.And, according to the requirement to antibiotic property, can regulate the concentration change of nano-Ag particles and the thickness of thin film thereof.In addition, the composite that makes by this method can be given full play to the cooperative effect of medical macromolecular materials and nanometer silver, reduces the use of nanometer silver, saves cost.In addition, the medical high polymer that this preparation method is suitable for is more, applied range; And the film preparation process is simple, and is low for equipment requirements, easily realizes suitability for industrialized production.
Description of drawings
The sketch map that Fig. 1 distributes for the concentration in gradient of Ag/TiO2 whisker in macromolecular material of preparing by a specific embodiment of preparation method of the present invention.
The sketch map that Fig. 2 distributes for the concentration in gradient of nano-Ag particles in macromolecular material of preparing by another specific embodiment of preparation method of the present invention.
Fig. 3 is the sketch map of the particle diameter distribution gradient of nano-Ag particles in macromolecular material prepared by another specific embodiment of preparation method of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing the present invention is described in detail; but these embodiments do not limit the present invention, and the conversion on the reaction condition that those of ordinary skill in the art does according to these embodiments, reactant or the raw material consumption all is included in protection scope of the present invention.
Functionally gradient material (FGM) refers to class composition structure and performance at material thickness or length direction is continuous or the heterogeneous body composite of quasi-continuous variation.
In first embodiment, adopt the Ag/TiO2 whisker as antibiotic raw material.The Ag/TiO2 whisker refers to support on titanium oxide (TiO2) whisker surface the material of nano-Ag particles.Whisker refers to a kind of fiber of growing into the monocrystalline form under the manual control condition, its diameter very little (micron number magnitude), do not contain the defective (crystal boundary, dislocation, hole etc.) that exists in the common material, its atomic arrangement high-sequential, thereby its intensity is close to the perfect crystal theoretical value, and its mechanical strength equals in abutting connection with interatomic force.
The Ag/TiO2 whisker can pass through silver salt, as silver nitrate solution and titanium dioxide (TiO2) whisker stir and oxygen free condition under, adopt photoreduction method reduction silver ion, with acquisition at TiO2 whisker surface preparation nano-Ag particles.The configuration of TiO2 whisker can be rutile-type, Detitanium-ore-type, TiO2(B), a kind of in the plate titanium type or their combination.
In the present embodiment, the nanometer silver preparation methods of medical high polymer base comprises the steps:
A. under the room temperature, complete according to the ratio dissolving of medical macromolecular materials and organic solvent mass ratio 1:3 ~ 1:30 under 18 ~ 25 ℃ of conditions, and according to the strict medical high polymer solution viscosities of controlling of the difference of concentration, typical viscosity is controlled at 150 ~ 1500cp.Medical macromolecular materials comprise polyurethane, the polrvinyl chloride of medical grade, polyethylene, polylactic acid, silicone rubber and polyether-ether-ketone etc.The organic solvent of dissolving medical macromolecular materials comprises oxolane, N, dinethylformamide, dimethyl acetylamide, dichloromethane, chloroform, heptane, cyclohexane extraction, butanone, acetone, ethanol etc.;
B. be that 0.01% ~ 3% Ag/TiO2 crystal whisker materials adds medical high polymer solution, strong agitation, mixing according to mass concentration.Wherein the nano-Ag particles particle size range of TiO2 whisker is 20 ~ 800nm;
C. control under the temperature and humidity situation, mixed solution is poured in the vessel, adopt the solvent evaporates thin films.The method of solvent evaporates film forming can adopt the methods such as film forming, vacuum drying film forming, forced air drying film forming of volatilizing naturally in film forming, the solvent compartment in the fume hood.The temperature of solvent evaporates is 10 ~ 80 ℃ in the film forming procedure, relative humidity 30 ~ 90%.Rely on interaction and the effect of Ag/TiO2 whisker self gravitation of Ag/TiO2 whisker and solution, form the Concentraton gradient of Ag/TiO2 whisker in macromolecular material as shown in Figure 1.By the viscosity of control macromolecular solution, can control the mutual relation of whisker self gravitation and buoyancy.When whisker gravity is big, will in the solvent evaporates process, slowly fall, thereby form functionally gradient material (FGM);
D. after solvent volatilized film forming fully, distilled water cleaned up, and vacuum drying is preserved use to constant weight.
In second embodiment, adopt nano-Ag particles as antibiotic raw material, its preparation method comprises the steps:
A. under the room temperature, under 18 ~ 25 ℃ of conditions, complete according to the ratio dissolving of medical macromolecular materials and organic solvent mass ratio 1:3 ~ 1:30.Medical macromolecular materials comprise polyurethane, the polrvinyl chloride of medical grade, polyethylene, polylactic acid, silicone rubber and polyether-ether-ketone etc.The organic solvent of dissolving medical high polymer comprises oxolane, N, dinethylformamide, dimethyl acetylamide, dichloromethane, chloroform, heptane, cyclohexane extraction, butanone, acetone, ethanol etc.;
B. be that 0.01% ~ 3% nano-Ag particles joins medical high polymer solution, strong agitation, mixing with mass concentration;
C. control under the temperature and humidity situation, mixed solution is poured in the vessel, adopt the solvent evaporates thin films, the equally distributed thin film of preparation nano-Ag particles.Wherein the nano-Ag particles particle size range is 20 ~ 800nm.The method of solvent evaporates film forming can adopt the methods such as film forming, vacuum drying film forming, forced air drying film forming of volatilizing naturally in film forming, the solvent compartment in the fume hood.The temperature of solvent evaporates is 10 ~ 80 ℃ in the film forming procedure, relative humidity 30 ~ 90%;
D. the solvent film forming of volatilizing fully changes nano-Ag particles concentration or particle diameter, repeats b and c step, obtains the anti-biotic material with gradient characteristic.The composite that the concentration in gradient of nano-Ag particles as shown in Figure 2 distributes, and the composite of the particle diameter distribution gradient of nano-Ag particles as shown in Figure 3;
E. after solvent volatilized film forming fully, the composite distilled water cleaned up, and vacuum drying is preserved use to constant weight.
In the composite that makes by said method, the mass content of nano-Ag particles (nano-Ag particles that comprises TiO2 whisker surface) is no more than 3%, and nano-Ag particles (nano-Ag particles that comprises TiO2 whisker surface) particle size range is 20 ~ 800nm.Because the concentration in gradient of Ag/TiO2 whisker in composite distributes, perhaps the concentration of nano-Ag particles or particle diameter distribution gradient in composite makes material can realize that silver ion discharges for a long time, thereby has long antibacterial effect.By experiment, the thin film of preparation still has good antibacterial property after continuous 20 days cleaning.
The present invention will be further described below in conjunction with specific embodiment.
Embodiment one: with the Ag/TiO2 whisker as antibiotic raw material
Take by weighing 23g polyurethane master batch and 100g oxolane, the polyurethane master batch is dissolved in the oxolane, preparation polyurethane high molecule solution.
After treating that polyurethane dissolves fully, add the anatase type tio2 whisker that the 0.4g surface supports the silver nano-grain of 110nm, fully stir 4h, the two is uniformly dispersed mutually.
Be about at room temperature, relative humidity under 50% the condition, will contain Ag/TiO2 whisker solution and be placed in the rustless steel container and leave standstill, adopt solvent evaporation method to prepare film forming, wherein the concentration in gradient of Ag/TiO2 whisker in material distributes, as shown in Figure 1.
Prepared functionally gradient material (FGM) is cleaned up in distilled water, and vacuum drying is preserved to the constant weight standby.
Embodiment two: be antibiotic raw material with nano-Ag particles
At room temperature, according to polylactic acid and chloroform mass ratio 1:8 preparation polylactic acid chloroformic solution.
The way that adopts in-situ reducing or directly add nano-Ag particles disposes respectively and contains 20nm, each portion of polylactic acid chloroformic solution of 40nm and 100nm nano-Ag particles, and wherein the quality of nano-Ag particles is 1% of polylactic acid quality, strong agitation, mixing.
25 ℃ of control temperature, humidity 80%, the nano-Ag particles mixed solution that will contain 100nm is poured in the glass culture dish, adopts solvent evaporation method to be prepared into the thin film that nano-Ag particles is evenly distributed.
On the surface of existing antibacterial film, select the polylactic acid chloroformic solution of the nano-Ag particles of 40nm and 20nm successively then, mixing, film forming, the anti-biotic material that acquisition has the particle diameter graded, as shown in Figure 3.
The gained functionally gradient material (FGM) adopts distilled water to clean up, and vacuum drying is preserved use to constant weight.
Embodiment three: with the Ag/TiO2 whisker as antibiotic raw material
Take by weighing 18g polyurethane master batch and 100g oxolane organic solvent, the polyurethane master batch is dissolved in the oxolane, preparation polyurethane high molecule solution.
After treating that polyurethane dissolves fully, add rutile-Detitanium-ore-type Ag/TiO2 whisker that the 0.4g surface supports the nano-Ag particles about 500nm, fully stir 4h, in whipping process, solution surface is exposed in the unlimited fume hood, makes partial solvent volatilize.
In room temperature, relative humidity is under 50% the condition, will contain Ag/TiO2 whisker solution left standstill, the solvent evaporates film forming.
The functionally gradient material (FGM) that makes cleans up in distilled water, and vacuum drying is preserved use to constant weight.
Embodiment four: be antibiotic raw material with nano-Ag particles
Under the room temperature, according to polyurethane and oxolane mass ratio 1:5 obtain solution, complete dissolve polyurethane.
Dispose the nanometer silver mass concentration respectively and be each 40ml of polyurethane solutions of 0.02%, 0.3% and 1% 100nm nano-Ag particles, strong agitation, mixing.
30 ℃ of temperature of control, humidity 70%, it is in the 16cm glass culture dish that 1% mixed solution that will contain the 100nm nano-Ag particles is poured diameter into, adopts the solvent evaporates thin films, the equally distributed thin film of preparation nano-Ag particles, the solvent back of volatilizing fully becomes smooth thin film.
Then on the surface of existing antibacterial film, select the polyurethane solutions of 0.3% and 0.02% nano-Ag particles successively, mixing, film forming obtains to have the anti-biotic material that Concentraton gradient changes, as shown in Figure 2.
Functionally gradient material (FGM) adopts distilled water to clean up, and vacuum drying is preserved use to constant weight.
Above listed a series of detailed description only is specifying at feasibility embodiment of the present invention; they are not in order to limiting protection scope of the present invention, allly do not break away from equivalent embodiment or the change that skill spirit of the present invention does and all should be included within protection scope of the present invention.
Claims (5)
1. the nanometer silver preparation methods of a medical high polymer base, it is characterized in that: this preparation method comprises the steps:
A. at room temperature, according to the ratio of medical macromolecular materials and organic solvent mass ratio 1:3 ~ 1:30, preparation medical high polymer organic solution makes range of viscosities control at 150 ~ 1500cp;
B. be that 0.01% ~ 3% Ag/TiO2 whisker adds in the medical high polymer solution of step a configuration with mass concentration, strong agitation is so that the two abundant mix homogeneously;
C. 10 ~ 80 ℃ of temperature, under the condition of relative humidity 30 ~ 90%, the mixed solution that step b obtains is poured in the vessel, adopted the solvent evaporates thin films; Wherein the Ag/TiO2 whisker distributes according to the Concentraton gradient that self gravitation is formed in the macromolecular solution;
D. solvent volatilizees after the film forming fully, obtains the nano silver composite material of medical high polymer base, and after it was cleaned up, vacuum drying was preserved to the constant weight and used.
2. preparation method according to claim 1, it is characterized in that: described medical macromolecular materials comprise medical polyurethane or medical polyvinyl or medical polyethylene or medical polylactic acid or medical grade silicon rubber or medical polyether-ketone.
3. preparation method according to claim 1, it is characterized in that: described organic solvent comprises oxolane, N, dinethylformamide, dimethyl acetylamide, dichloromethane, chloroform, heptane, cyclohexane extraction, butanone, acetone or ethanol.
4. preparation method according to claim 1, it is characterized in that: described Ag/TiO2 whisker refers to support on the titanium oxide whisker surface material of different-grain diameter nano-Ag particles, the particle size range of described nano-Ag particles is 20 ~ 800nm.
5. preparation method according to claim 4, it is characterized in that: the mass content of described nano-Ag particles is less than or equal to 3%.
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| CN103040631B (en) * | 2013-01-23 | 2016-03-30 | 常州南京大学高新技术研究院 | A kind of antimicrobial form inorganic crystal whisker functional composite material and method for making thereof and purposes |
| CN106139255A (en) * | 2015-04-17 | 2016-11-23 | 天津市赛宁生物工程技术有限公司 | A kind of collagen protein combines new material and the preparation method of the medical sponge support of calcium phosphate |
| CN106633808A (en) * | 2016-10-31 | 2017-05-10 | 湖南科技大学 | Preparation method of eggshell powder based synthetic paper |
| CN106860911A (en) * | 2017-03-16 | 2017-06-20 | 湖北大学 | A kind of surface of metal titanium antimicrobial composite coating and preparation method thereof |
| CN109266011A (en) * | 2018-09-03 | 2019-01-25 | 苏州歌诗夫新材料有限公司 | Medical bottle stopper silica gel material without fluorescer and preparation method thereof |
| CN111117042A (en) * | 2020-02-12 | 2020-05-08 | 张勇 | Method for manufacturing medical protective sintered breathable material with sterilization channel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255274A (en) * | 2008-04-22 | 2008-09-03 | 东南大学 | Composite nano silver-polyurethane antibiotic material and preparation thereof |
| CN102010514A (en) * | 2010-11-02 | 2011-04-13 | 东南大学 | Method and device for preparing nano silver- and porous structure-containing medical high molecular material |
| CN102014975A (en) * | 2008-02-29 | 2011-04-13 | 史密夫和内修有限公司 | Gradient coating for biomedical applications |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102014975A (en) * | 2008-02-29 | 2011-04-13 | 史密夫和内修有限公司 | Gradient coating for biomedical applications |
| CN101255274A (en) * | 2008-04-22 | 2008-09-03 | 东南大学 | Composite nano silver-polyurethane antibiotic material and preparation thereof |
| CN102010514A (en) * | 2010-11-02 | 2011-04-13 | 东南大学 | Method and device for preparing nano silver- and porous structure-containing medical high molecular material |
Non-Patent Citations (2)
| Title |
|---|
| 何伟.新型纳米银/聚氨酯胆道支架表面抗菌涂层的体外抑菌试验.《中国组织工程研究与临床康复》.2011,第15卷(第3期),第454页. |
| 新型纳米银/聚氨酯胆道支架表面抗菌涂层的体外抑菌试验;何伟;《中国组织工程研究与临床康复》;20110115;第15卷(第3期);第454页 * |
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