CN102432898B - Preparation method of Ag/TiO2 whisker-medical polyurethane composite material - Google Patents
Preparation method of Ag/TiO2 whisker-medical polyurethane composite material Download PDFInfo
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- CN102432898B CN102432898B CN 201110212176 CN201110212176A CN102432898B CN 102432898 B CN102432898 B CN 102432898B CN 201110212176 CN201110212176 CN 201110212176 CN 201110212176 A CN201110212176 A CN 201110212176A CN 102432898 B CN102432898 B CN 102432898B
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Abstract
The invention provides a preparation method of a Ag/TiO2 whisker-medical polyurethane composite material. The preparation method is characterized by comprising the following steps of: a, preparing 0.01-1M silver-salt solution, adding a positive-hole trapping agent and removing oxygen in a reaction system; b, adding TiO2 whiskers into the reaction system according to the mass ratio of silver to TiO2 of (1:1)-(1:50) in the silver-salt solution, stirring and adsorbing for 0.5-8h; c, under the stirring and anaerobic conditions, adopting a photochemical reduction method to reduce silver ions so as to prepare silver particles on the surfaces of the TiO2 whiskers; d, after the reaction is finished, filtering, obtaining the TiO2 whiskers carrying the silver particles, drying the TiO2 whiskers under the vacuum condition till the weight is constant, and storing for spare use; e, under room temperature, preparing polyurethane solution according to the proportion of the medical polyurethane to an organic solvent of (1:3)-(1:30); and f, adding the Ag/TiO2 whiskers obtained in the step d into the medical polyurethane solution obtained in the step e, fully stirring to lead the Ag/TiO2 whiskers to be distributed uniformly in the medical polyurethane solution, then adopting a solvent volatilization method to prepare a polyurethane film with uniformly-dispersed Ag/TiO2 whiskers, drying the polyurethane film under the vacuum condition till the weight is constant, and storing for spare use. The Ag particles are prepared by the photo-reduction method, and the Ag particles carried by the Ag/TiO2 whiskers are not easy to fall, so that the possible biotoxicity possible to exist in the nano silver particles can be reduced furthest.
Description
Technical field
The present invention relates to a kind of preparation method of antimicrobial composite material, especially a kind of Ag/TiO that is applied to medical material and medical instruments field
2Whisker-medical polyurethane composite manufacture method.
Background technology
High molecular polymer is an important branch of biomaterial, is widely used in the manufacturing of clinical intervention material because of its outstanding mechanical properties and biocompatibility.Yet bacterial adhesion is the subject matter that gets involved medical material with infecting, and therefore design prepares the polymkeric substance with antibacterial properties and seems particularly important.
Nanometer silver is used widely at biomedicine field as anti-biotic material owing to antibiotic characteristics and the antibacterial mechanisms of its uniqueness.The same with other nano material, nanometer silver is after entering life entity, with the life entity identical conventional substances of chemical property, biological activity and the chemical ingredients produce that interacts a great difference is arranged, might bring infringement to human health, and become the inducement of some diseases.Undersized nano-Ag particles may cause some new, potential toxicity problems, for example has in the biological assessment of nano grain of silver of different-grain diameter, and the nanoparticle toxicity of 15nm is much larger than 55nm.Studies show that in recent years: along with the increase of concentration, certain toxic side effect appears in nanometer silver.
Metal nanometer composite material take polymkeric substance as matrix; its action principle is that each molecule by polymkeric substance provides a plurality of connecting portions simultaneously and the particle effect; and very effectively be fixed; and can also act on forming the self-assembly of various nanostructures by static, hydrogen bond, charge transfer and other, nanoparticle is played a very good protection.Simultaneously, the nano silver polymer matrix material provides a well basis for nanometer silver in the combination of material surface and the long-acting release of germ resistance silver ions.
In medical macromolecular materials, polyurethane material has good tissue consistency and blood compatibility, good toughness, solvent resistance, hydrolytic resistance, anti-microorganism, nontoxicity, the good wear-resistant performance that waits excellence.Titanium dioxide (TiO
2) with the erosion resistance of its good biocompatibility (nontoxic, harmless, non-corrosiveness), excellence and the approval that special photochemical properties obtains Chinese scholars.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.Titanium dioxide crystal whisker is the oxide material with specific function, has widely application at functional materials and composite manufacture field.Ag/TiO
2Whisker-medical polyurethane matrix material namely is to possess urethane, TiO
2, and the antimicrobial composite material of nanometer silver three advantage, it is take urethane as main body, TiO
2Whisker is carrier, and nano-Ag particles is attached on the whisker.Yet existing preparation method can't guarantee that also the nano-Ag particles reliable attachment is at TiO
2The whisker surface.
In view of this, be necessary existing Ag/TiO
2Whisker-medical polyurethane composite manufacture method is improved, to address the above problem.
Summary of the invention
The object of the present invention is to provide a kind of Ag/TiO
2Whisker-medical polyurethane composite manufacture method, the matrix material that obtains by the method not only possesses urethane, TiO
2, and nanometer silver three's advantage, and can guarantee that the nano-Ag particles reliable attachment is at TiO
2The whisker surface.
One of for achieving the above object, a kind of Ag/TiO of the present invention
2Whisker-medical polyurethane composite manufacture method, it comprises the steps:
A. prepare the silver salt solution of 0.01～1M, and add positive hole trapping agents, remove the oxygen in the reaction system;
B. according to silver in the silver salt solution and TiO
2Mass ratio be that the ratio of 1:1～1:50 adds TiO in reaction system
2Whisker, and whip attachment 0.5～8h;
C. stir and oxygen free condition under, adopt the photoreduction method to reduce silver ions, with at TiO
2The silver-colored particle of whisker surface preparation;
D. after question response finishes, filter the TiO that obtains to support silver-colored particle
2Whisker, and save backup after under vacuum condition, being dried to constant weight;
E. at room temperature, the ratio according to medical polyurethane and organic solvent is the ratio preparation polyurethane solution of 1:3～1:30;
F. the Ag/TiO that steps d is obtained
2Whisker joins in the medical polyurethane solution of step e acquisition, and fully stirs so that Ag/TiO
2Whisker evenly distributes in medical polyurethane solution, then adopts the solvent evaporation method preparation to have Ag/TiO
2The homodisperse polyurethane film of whisker, and save backup after under vacuum condition, being dried to constant weight.
As a further improvement on the present invention, described silver salt solution is silver nitrate solution.
As a further improvement on the present invention, described positive hole trapping agents is Virahol or ethanol or formic acid.
As a further improvement on the present invention, the deoxidation method among the described step a is biexhaust pipe method or nitrogen bubbling law.
As a further improvement on the present invention, described TiO
2The length-to-diameter ratio of whisker is greater than 8, and its diameter is nanometer or micron order; Described TiO
2Whisker be configured as rutile-type or Detitanium-ore-type or TiO
2(B) or plate titanium type or their combination.
As a further improvement on the present invention, the light source of described photoreduction method is 5w～2kw, and light application time is 10min～8h.
As a further improvement on the present invention, the diameter range of described silver-colored particle is 20nm～2 μ m.
As a further improvement on the present invention, in the film by step f acquisition, described Ag/TiO
2The mass ratio of whisker and urethane is 0.01% ~ 5%.
As a further improvement on the present invention, described medical polyurethane comprises that medical polyester is that urethane or polyethers are that urethane or aromatic isocyanate are that urethane or aliphatic isocyanates are urethane.
As a further improvement on the present invention, the organic solvent that adopts among the described step e is selected from tetrahydrofuran (THF) or dimethyl formamide or N,N-DIMETHYLACETAMIDE ketone or alkoxide solvent or their combination.
Compared with prior art, the invention has the beneficial effects as follows: by photoreduction met hod, utilize titania surface generation unbound electron under the illumination condition, silver ion reduction generates nano particle.There are special strong interaction in the nano-Ag particles and the carrier titanium oxide that generate by this method, make the nanometer silver difficult drop-off, thereby farthest reduce the bio-toxicity that nano-Ag particles may exist, and give full play to the antimicrobial effect of silver-colored particle.In addition, by controlled light intensity, the concentration of silver salt and time, can regulate Ag particle diameter and distribution thereof; And the employing photoreduction met hod need not to use any reductive agent, not only improves the biocompatibility of product, and has simplified preparation process, reduces cost.In addition, the composite material film preparation process is simple, and is low for equipment requirements, easily realizes suitability for industrialized production, and the thin film stability of preparation is good, and the surface property of urethane is not affected, and simultaneously, the mechanical property of matrix material gets a promotion.
Embodiment
Below in conjunction with embodiment the present invention is described in detail; but these embodiments do not limit the present invention, and the conversion on the reaction conditions 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.
In the present embodiment, TiO
2The length-to-diameter ratio of whisker is greater than 8, and its diameter is at nanometer or micron order; The configuration of titanium oxide whisker can be rutile-type, Detitanium-ore-type, TiO
2(B), a kind of in the plate titanium type or their combination.
Medical polyurethane can be that urethane, polyethers are that urethane, aromatic isocyanate are that urethane, aliphatic isocyanates are a kind of in the urethane or their combination for the medical grade polyester.
In the present embodiment, Ag/TiO
2Whisker-medical polyurethane composite manufacture method comprises the steps:
A. compound concentration is the silver salt solution of 0.01 ~ 1M, adds an amount of positive hole trapping agents, adopts biexhaust pipe method or nitrogen bubbling law, removes the oxygen in the reaction system.Wherein silver salt can be soluble silver salt, such as Silver Nitrate; Hole trapping agents comprises Virahol, ethanol and formic acid etc.;
B. the mass ratio according to silver and titanium oxide whisker is 1:1 ~ 1:50, adds titanium oxide whisker in silver salt solution, whip attachment 0.5 ~ 8h;
C. under stirring and anaerobic state, adopt UV Light reduction silver ions, to prepare silver-colored particle in titania surface.Wherein intensity of illumination is 5w ~ 2kw, and the reaction times is 10min ~ 8h;
D. after reaction finished, with a large amount of unreacted solution of water washing and filtering, vacuum-drying was preserved use to constant weight;
E. under the room temperature, under 18～25 ℃ of conditions, according to medical polyurethane and organic solvent mass ratio 1:3 ~ 1:30 dissolve complete.Organic solvent can be a kind of or its combination of the ketones such as tetrahydrofuran (THF), dimethyl formamide, N,N-DIMETHYLACETAMIDE and dimethyl sulfoxide (DMSO) or alkoxide solvent;
F. Ag/TiO
2Whisker and medical polyurethane solution stirring are even, adopt the solvent evaporation method preparation to have Ag/TiO
2The homodisperse polyurethane film of whisker.Vacuum-drying is spent the night, and saves backup after constant weight.Homodisperse Ag/TiO wherein
2Whisker and urethane mass ratio are 0.01% ~ 5%.The method of solvent evaporates film forming can adopt the methods such as film forming in the stink cupboard, solvent Indoor Natural volatilization film forming, vacuum-drying film forming, forced air drying film forming.By these methods, can regulate temperature, humidity and the airflow on surface of solvent evaporates environment.As, the adjusting ambient temperature is 15～40 ℃.
Prepare the Ag particle by photoreduction met hod, can make TiO
2The Ag particle difficult drop-off of whisker carrying.And by controlled light intensity, the concentration of silver salt and time can be regulated Ag particle diameter and distribution thereof, typical diameter range 20nm ~ 2 μ m.
The present invention will be further described below in conjunction with specific embodiment.
Embodiment one:
Taking by weighing 1.7g Silver Nitrate compound concentration is the silver nitrate solution of 0.1M, adds 5ml ethanol as positive hole trapping agents, adopts nitrogen bubbling law continuous bubbling 1h, removes the oxygen in the reaction system.The TiO that adds the anatase octahedrite configuration
2Whisker 2g stirs under magneticaction, makes 2g TiO
2The abundant Adsorption For Ag ion of whisker, the reaction times is 4h.
Then, reaction conditions is controlled under stirring and the anaerobic state, adopts 8w black lamp photoreduction silver ions, the reaction times is 4h.After reaction finished, with a large amount of water suction filtration flushing samples, vacuum-drying was preserved use to constant weight.
Under 18～25 ℃ of conditions, get 20g medical fat family's urethane and 200g tetrahydrofuran (THF), preparation medical fat family urethane macromolecular solution.After medical fat family urethane dissolves fully, get 0.014g Ag/TiO
2Whisker and 77g medical polyurethane stir 4h, and reacted solution is poured in surface clean, the smooth glassware, adopt solvent evaporation method to prepare film forming, save backup after constant weight.
The film that obtains of embodiment thus, Ag/TiO
2Whisker can Uniform Dispersion, and the particle diameter of Ag particle is about 100nm, and the antibacterial effect in the 48h is good.
Embodiment two:
Taking by weighing 0.85g Silver Nitrate compound concentration is the silver nitrate solution of 0.05M, adds the 3ml Virahol as positive hole trapping agents, adopts nitrogen bubbling law continuous bubbling 1h, removes the oxygen in the reaction system.The TiO that adds the anatase octahedrite configuration
2Whisker 2g, magnetic agitation absorption 4h.
Then, under stirring and anaerobic state, adopt 500w high-voltage lamp irradiation reaction system, make silver ions under illumination condition, be reduced to simple substance silver, the reaction times is 2h.After reaction finished, with a large amount of water suction filtration flushing samples, vacuum-drying was preserved use to constant weight.
Under 18～25 ℃ of conditions, take by weighing 20g medical fat family's urethane and 200g DMF, the preparation medical fat family urethane macromolecular solution take DMF as organic solvent.
After urethane dissolves fully, get 0.035g Ag/TiO
2Whisker and 77g medical polyurethane stir 4h, reacted solution are poured in surface clean, the smooth glassware into the solvent evaporates film forming.Sample vacuum-drying is spent the night, and saves backup after constant weight.
The film that obtains of embodiment thus, Ag/TiO
2Whisker can Uniform Dispersion, and the particle diameter of Ag particle is about 500nm～1200nm, and the antibacterial effect in the 48h is good.
Embodiment three:
Take by weighing Silver Nitrate 1.7g, compound concentration is the silver nitrate solution of 0.1M, adds the 3ml Virahol as positive hole trapping agents, adopts nitrogen bubbling law continuous bubbling 1h, removes the oxygen in the reaction system.Add appearance and cover TiO
2(B) endo conformation is the TiO of anatase octahedrite
2Whisker 1g.Under magneticaction, stir, make 1g TiO
2The abundant Adsorption For Ag ion of whisker, the reaction times is 4h.
Then, under stirring and anaerobic state, adopt 100w high-voltage lamp photoreduction silver ions, the reaction times is 4h.After reaction finished, with a large amount of water suction filtration flushing samples, vacuum-drying was preserved use to constant weight.
Under 18～25 ℃ of conditions, get 40g medical fat family's urethane and 200g tetrahydrofuran (THF), the preparation medical fat family urethane macromolecular solution take tetrahydrofuran (THF) as organic solvent.。
Treat that urethane dissolves fully, get 0.035g Ag/TiO
2Whisker and 42g medical fat family urethane stir 4h, and reacted solution is poured in surface clean, the smooth glassware, adopt solvent evaporation method to prepare film forming, save backup after constant weight.
The film that obtains of embodiment thus, Ag/TiO
2Whisker can Uniform Dispersion, and the particle diameter of Ag particle is 200 ~ 400nm, and the antibacterial effect in the 48h is good.
Above listed a series of detailed description only is specifying for feasibility embodiment of the present invention; they are not to limit 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 (9)
1. Ag/TiO
2Whisker-medical polyurethane composite manufacture method, it is characterized in that: the method comprises the steps:
A. prepare the silver salt solution of 0.01～1M, and add positive hole trapping agents, remove the oxygen in the reaction system;
B. according to silver in the silver salt solution and TiO
2Mass ratio be that the ratio of 1:1～1:50 adds TiO in reaction system
2Whisker, and whip attachment 0.5～8h;
C. stir and oxygen free condition under, adopt the photoreduction method to reduce silver ions, with at TiO
2The silver-colored particle of whisker surface preparation;
D. after question response finishes, filter the TiO that obtains to support silver-colored particle
2Whisker, and save backup after under vacuum condition, being dried to constant weight;
E. at room temperature, the ratio according to medical polyurethane and organic solvent is the ratio preparation polyurethane solution of 1:3～1:30;
F. the Ag/TiO that steps d is obtained
2Whisker joins in the medical polyurethane solution of step e acquisition, and fully stirs so that Ag/TiO
2Whisker evenly distributes in medical polyurethane solution, then adopts the solvent evaporation method preparation to have Ag/TiO
2The homodisperse polyurethane film of whisker, Ag/TiO in the described film
2The mass ratio of whisker and urethane is 0.01% ~ 5%, and saves backup be dried to constant weight under vacuum condition after.
2. preparation method according to claim 1, it is characterized in that: described silver salt solution is silver nitrate solution.
3. preparation method according to claim 1, it is characterized in that: described positive hole trapping agents is Virahol or ethanol or formic acid.
4. preparation method according to claim 1, it is characterized in that: the deoxidation method among the described step a is biexhaust pipe method or nitrogen bubbling law.
5. preparation method according to claim 1 is characterized in that: described TiO
2The length-to-diameter ratio of whisker is greater than 8, and its diameter is nanometer or micron order; Described TiO
2Whisker be configured as rutile-type or Detitanium-ore-type or plate titanium type or their combination.
6. preparation method according to claim 1, it is characterized in that: the light source of described photoreduction method is 5w～2kw, light application time is 10min～8h.
7. preparation method according to claim 1, it is characterized in that: the diameter range of described silver-colored particle is 20nm～2 μ m.
8. preparation method according to claim 1, it is characterized in that: described medical polyurethane comprises that medical polyester is that urethane or polyethers are that urethane or aromatic isocyanate are that urethane or aliphatic isocyanates are urethane.
9. preparation method according to claim 1, it is characterized in that: the organic solvent that adopts among the described step e is selected from tetrahydrofuran (THF) or dimethyl formamide or N,N-DIMETHYLACETAMIDE ketone or alkoxide solvent or their combination.
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Citations (1)
| 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 |
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| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 光化学还原法制备Ag-TiO2抗菌材料的制备及性能研究;周新文等;《化工新材料》;20061130;第34卷(第11期);第67－70页 * |
| 周新文等.光化学还原法制备Ag-TiO2抗菌材料的制备及性能研究.《化工新材料》.2006,第34卷(第11期),第67－70页. |
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