CN101390524A - Argentine-loaded hydroxylapatite and preparation method thereof - Google Patents
Argentine-loaded hydroxylapatite and preparation method thereof Download PDFInfo
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- CN101390524A CN101390524A CNA2008101528974A CN200810152897A CN101390524A CN 101390524 A CN101390524 A CN 101390524A CN A2008101528974 A CNA2008101528974 A CN A2008101528974A CN 200810152897 A CN200810152897 A CN 200810152897A CN 101390524 A CN101390524 A CN 101390524A
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Abstract
The invention discloses an AgxCa10-x(PO4)6(OH)2 and a preparation method; the AgxCa10-x(PO4)6(OH)2 is the hydroxyapatite loaded with silver irons; the preparation method has the following steps: based on the mass ratio of 1:30-10, the AgNO3 aqueous solution with the mass concentration of 8%-25% is mixed with hydroxyapatite and stirred in the dark at 15-30 DEG C for 15-30 hours, and then treated with ion exchange reaction and filtered; the solid is dried and calcined at 800-1000 DEG C to prepare the AgxCa10-x(PO4)6(OH)2. The vector matrix hydroxyapatite molecues of the AgxCa10-x(PO4)6(OH)2 contain hydroxy groups which can produce force with cellulose molecules to improve the combination fastness between antibacterial agent and cotton fiber; after the ordinary cotton fabric is antimicrobially treated with AgxCa10-x(PO4)6(OH)2, the cotton fabric with broad antimicrobial spectrum, good human body compatibility, high safety and good washing fastness can be obtained.
Description
Technical field
The present invention relates to a kind of hydroxyapatite and preparation method, particularly relate to a kind of argentum-carried hydroxylapatite and preparation method.
Background technology
The research of China's anti-biotic material is mainly in the mid-90 in 20th century, and except use to some extent in only a few fields such as anticorrosion with coat, other field almost is blank entirely.China's anti-biotic material industry development was very fast in recent years, large quantities of enterprises and universities and colleges, scientific research institution's hand-in-glove have had development at full speed in a plurality of fields such as the industrialization of natural antibacterial agent, inorganic antiseptic, organic antibacterial agent, photocatalyst-type anti-biotic agent and anti-biotic material and application and developments.Development of China's anti-biotic material at present and application have obtained very big progress, and an emerging antibiotic industry begins to take shape.
Natural antibacterial agent is mainly the extract of natural animal-plant, and it is to be the antibacterial agent that people utilized the earliest, because most of natural antibacterial agents are subjected to the restriction of resource and processing conditions, application has certain difficulty, at present can't large-scale production.
In the production and the breeding that suppress noxious bacteria, mould, thereby reach in the antibiotic method of kill bacteria, the development of diversified organic antibacterial agent and exploitation were once once occupying main status.Organic antibacterial agent mainly is divided into: quaternary ammonium salt, phenolic ether class, phenol, thiazoles, isothiazole class, imidazoles and pyridines etc., its sterilization speed is fast, antibacterial efficacy is high, easy to process but organic antibacterial agent exists antibiotic kind single, poor stability, material itself can produce the microorganism drug resistance, poor chemical stability, shortcomings such as poor heat resistance have limited its application in article of manufacture, especially the application in the medical and health industry.
Inorganic antiseptic is a class anti-biotic material of 20th century the mid-80 fast development, compares with organic antibacterial agent, and all there is clear superiority in inorganic antiseptic at aspects such as safety, persistence, continuity and warm tolerances, has become the main flow of antibacterial agent research.Inorganic antiseptic can be divided into two classes by the mechanism that it acts on microorganism: a class is to be that the metallic compound with antibacterial action of representative combines with inorganic carrier and is prepared from silver, is referred to as silver-series antibacterial agent; Another kind of is to be that the material with photocatalysis of representative is made antibiotic main body with the titanium, is the photochemical catalyst of extensive use as titanium dioxide, is referred to as the photocatalyst of titanium dioxide series antibacterial agent.The sterilization of catalysis material antibacterial agent can only could produce under the condition that the light irradiation is arranged, and its effect because of intensity of illumination and light source kind difference, does not have sterilization or antibacterial action at this type of antibacterial agent of light dark place substantially yet.
At present silver-series antibacterial agent is according to the difference of carrier, and mainly be divided into: (1) zeolite with carrying silver antibacterial agent: zeolite is the aluminium silicate mineral that a class has the alkaline earth metal of cation exchange capacity (CEC), by ion exchange with Ag
+Be attached to the antibacterial agent that makes in its structure.This antibacterial agent is mainly used in products such as the fiber, plastics of low temperature process.(2) carry silver-colored bentonite bactericidal agent: bentonite is a kind of clay of natural layer structure, has good monovalent cation switching performance, can be by cation exchange with Ag
+Introduce interlayer and make a year silver-colored bentonite bactericidal agent.This kind antibacterial agent since the interlayer structure of bentonite carrier to Ag
+Active force a little less than, make Ag
+Just discharge faster at the use initial stage, cause Ag
+Concentration is higher and bring murder by poisoning, is detrimental to health, so use few.(3) carry silver-colored silica gel antibacterial agent: silica gel has very big specific surface area, Ag
+Mainly combine with it and form complex compound Na by suction-operated
p[Ag
q(S
2O
3)], and utilize sol-gel process to form SiO on its surface
2Layer and the antibacterial agent that makes.The antibiotic effective ingredient of this antibacterial agent is not Ag
+Ion, but the complex of silver, thereby they are a lot of a little less than with respect to the antibacterial ability of other silver-series antibacterial agents.(4) carry silver-colored phosphate antibiosis agent: existing this type of antibacterial agent mainly is to be carrier with phosphoric acid titanium salt or phosphoric acid zirconates, contains the cation of a large amount of ion exchange carried out in the crystal structure that has, by ion exchange with little alkali metal ion Ag
+Ion exchange is come out, thereby obtains the antibacterial agent of slow releasing function.This class antibacterial agent is mainly used in the ceramic product of high temperature process.More than these silver-series antibacterial agents if be used for the antibiotic finish of cotton gauze fiber, all exists to combine the low problem of fastness with cotton fiber because do not exist in their molecular structure can with the group of gossypin molecule generation active force.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of argentum-carried hydroxylapatite is provided.
Second purpose of the present invention provides a kind of preparation method of argentum-carried hydroxylapatite.
Technical scheme of the present invention is summarized as follows:
A kind of argentum-carried hydroxylapatite is a negative Ag-bearing on hydroxyapatite.
A kind of preparation method of argentum-carried hydroxylapatite, be made up of following steps: in mass ratio is 1: the ratio of 30-10 is the AgNO of 8%-25% with mass concentration
3The aqueous solution mixes with hydroxyapatite, and in lucifuge, 15-30 ℃ is stirred 15-30h down, carries out ion-exchange reactions, filters, and with the solid oven dry, calcining 3-6h makes a kind of argentum-carried hydroxylapatite under 800～1000 ℃.
Described hydroxyapatite is to make with following method: in the ratio of mass ratio 1: 1.5-3, with CaCO
3And CaHPO
4After being mixed into mixture, in mixture: the mass ratio of absolute ethyl alcohol is that the ratio of 5-8:1 adds described mixture in the described absolute ethyl alcohol, add the fatty alcohol-polyoxyethylene ether that accounts for described mixture quality 5%-8% again, stir, ball milling 3-7h in ball mill puts into and is equivalent to volume of mixture 20-30 deionized water doubly behind the ball milling, at 60～80 ℃ of reaction 3-7h, suction filtration, solid oven dry at 900～1100 ℃ of calcining 4-8h, promptly make hydroxyapatite.
Argentum-carried hydroxylapatite [Ag of the present invention
xCa
10-x(PO
4)
6(OH)
2] middle carrier matrix hydroxyapatite [Ca
10(PO
4)
6(OH)
2] be a kind of traditional biomaterial, compatible functional with human body extensively is used as artificial tooth and artifical bone.Structurally, hydroxyapatite is a kind of microporous materials, but the multiple metal cation of sorption, and ion-exchange reactions takes place with it.In numerous common metal ion, the antibacterial action of silver occupy the first, thereby by chemical method hydroxyapatite is carried the argentum-carried hydroxylapatite that obtains after the silver processing and have antibiotic and compatible good, the promptly safe characteristics of human body.Exist in the argentum-carried hydroxylapatite molecule of the present invention to produce the oh group of active force, thereby can well improve the fastness problem that combines of antibacterial agent and cotton fiber with cellulosic molecule; After common cotton fabric carried out antibiotic finish with argentum-carried hydroxylapatite, the antibiotic fabric that obtains except have has a broad antifungal spectrum, the human body compatibility is good, outside the safe characteristics, the fabric washing fastness after the arrangement also is better than other silver-series antibacterial agent finish fabrics.
Description of drawings
Fig. 1 is medical standard hydroxyapatite X-ray diffraction analysis spectrogram;
Fig. 2 prepares hydroxyapatite X-ray diffraction analysis spectrogram for the present invention;
Fig. 3 is an argentum-carried hydroxylapatite X-ray diffraction analysis spectrogram of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
A kind of argentum-carried hydroxylapatite, negative Ag-bearing on hydroxyapatite.
Embodiment 2
A kind of preparation method of argentum-carried hydroxylapatite, be made up of following steps: in mass ratio is 1: 30 ratio, is 8% AgNO with mass concentration
3The aqueous solution mixes with hydroxyapatite, and in lucifuge, 25 ℃ are stirred 25h down, carry out ion-exchange reactions, filter, and with the solid oven dry, calcining 6h makes a kind of argentum-carried hydroxylapatite under 800 ℃.
Hydroxyapatite is by embodiment 5 preparations.
A kind of preparation method of argentum-carried hydroxylapatite, be made up of following steps: in mass ratio is the ratio of 1:10, is 25% AgNO with mass concentration
3The aqueous solution mixes with hydroxyapatite, stirs 20h down for 20 ℃ in lucifuge, carries out ion-exchange reactions, filters, and with the solid oven dry, calcining 3h makes a kind of argentum-carried hydroxylapatite under 1000 ℃.
Hydroxyapatite is by embodiment 5 preparations.
Embodiment 4
A kind of preparation method of argentum-carried hydroxylapatite, be made up of following steps: in mass ratio is the ratio of 1:20, is 20% AgNO with mass concentration
3The aqueous solution mixes with hydroxyapatite, and in lucifuge, 30 ℃ are stirred 15h down, carry out ion-exchange reactions, filter, and with the solid oven dry, calcining 4h makes a kind of argentum-carried hydroxylapatite under 900 ℃.
Hydroxyapatite is by embodiment 6 preparations.
Embodiment 5
A kind of preparation method of argentum-carried hydroxylapatite, be made up of following steps: in mass ratio is the ratio of 1:25, is 15% AgNO with mass concentration
3The aqueous solution mixes with hydroxyapatite, and in lucifuge, 15 ℃ are stirred 30h down, carry out ion-exchange reactions, filter, and with the solid oven dry, calcining 5h makes a kind of argentum-carried hydroxylapatite under 850 ℃.
Embodiment 6
Hydroxyapatite is to make with following method: in 1: 3 ratio of mass ratio, with CaCO
3And CaHPO
4After being mixed into mixture, in mixture: the mass ratio of absolute ethyl alcohol is that the ratio of 8:1 adds described mixture in the described absolute ethyl alcohol, add the fatty alcohol-polyoxyethylene ether that accounts for described mixture quality 5% again, stir, ball milling 5h in ball mill puts into the deionized water that is equivalent to 22 times of volume of mixture behind the ball milling, at 75 ℃ of reaction 4h, suction filtration, solid oven dry at 900 ℃ of calcining 8h, promptly make hydroxyapatite.
Embodiment 7
Hydroxyapatite is to make with following method: in 1: 1.5 ratio of mass ratio, with CaCO
3And CaHPO
4After being mixed into mixture, in mixture: the mass ratio of absolute ethyl alcohol is that 5: 1 ratio adds described mixture in the described absolute ethyl alcohol, add the fatty alcohol-polyoxyethylene ether that accounts for described mixture quality 6% again, stir, ball milling 6h in ball mill puts into the deionized water that is equivalent to 30 times of volume of mixture behind the ball milling, at 70 ℃ of reaction 5h, suction filtration, solid oven dry at 1100 ℃ of calcining 4h, promptly make hydroxyapatite.
Embodiment 8
Hydroxyapatite is to make with following method: in 1: 2 ratio of mass ratio, with CaCO
3And CaHPO
4After being mixed into mixture, in mixture: the mass ratio of absolute ethyl alcohol is that 6: 1 ratio adds described mixture in the described absolute ethyl alcohol, add the fatty alcohol-polyoxyethylene ether that accounts for described mixture quality 8% again, stir, ball milling 3h in ball mill puts into the deionized water that is equivalent to 25 times of volume of mixture behind the ball milling, at 60 ℃ of reaction 7h, suction filtration, solid oven dry at 1000 ℃ of calcining 6h, promptly make hydroxyapatite.
Embodiment 9
Hydroxyapatite is to make with following method: in 1: 2.5 ratio of mass ratio, with CaCO
3And CaHPO
4After being mixed into mixture, in mixture: the mass ratio of absolute ethyl alcohol is that 7: 1 ratio adds described mixture in the described absolute ethyl alcohol, add the fatty alcohol-polyoxyethylene ether that accounts for described mixture quality 5% again, stir, ball milling 7h in ball mill puts into the deionized water that is equivalent to 20 times of volume of mixture behind the ball milling, at 80 ℃ of reaction 3h, suction filtration, solid oven dry at 950 ℃ of calcining 7h, promptly make hydroxyapatite.
Hydroxyapatite also can adopt the commercially available prod.
Experiment is executed
By negative Ag-bearing on two kinds of provable hydroxyapatites of method.
Method one: precipitation detection method
Take a morsel the argentum-carried hydroxylapatite for preparing in beaker, add an amount of 1: 1 hydrochloric acid, fully after the vibration, with its suction filtration, get its filter residue, repeatedly wash with deionized water, suction filtration is got its filter residue oven dry.Add the capacity red fuming nitric acid (RFNA) in filter residue, heating is all dissolved until solid matter.When treating that solution temperature is reduced to room temperature, sodium chloride solution is splashed into wherein, produce white flocculent deposit in the visible system, illustrate to have silver in the former prepared product.
Method two: X-ray diffraction spectrum analysis method
Medical standard hydroxyapatite, Experiment Preparation hydroxyapatite, Experiment Preparation argentum-carried hydroxylapatite are made X-ray diffraction analysis.(analysis of spectra is seen Fig. 1-3)
Go out peak standard (ASTM) according to internal authority X-ray diffraction spectrogram, when the angle of diffraction is 30.8 °, secondly highest peak appears in hydroxyapatite, locates all to have the big peak of hydroxyapatite at 26 °, 32.2 °, 32.9 °, 46.75 °, 49.5 °, 50.5 °, 51.6 ° etc. respectively.Fig. 2 is enough identical corresponding to the appearance energy of hydroxyapatite among Fig. 1, and Fig. 2 contrasts ASTM and draws the peak angle of diffraction and also can coincide.The hydroxyapatite crystal formation structural development of illustrative experiment preparation is good.
Fig. 3 compares with Fig. 2, and peak shape has occurred than obvious variation, and Fig. 3 locates out strong peak at 34.1 °, and this peak has sheltered that hydroxyapatite is former locationally to go out the peak at this.In addition, 38 ° to locate out the last one unimodal, locates out strong peak in for 44.1 °.(λ, function calculation θ) also contrasts X-ray diffraction elemental characteristic standard scale, confirms out that it is silver element that the peak characterizes material through d=f.The silver of having judged on the hydroxyapatite load thus.
A kind of argentum-carried hydroxylapatite of the present invention is carried out the process introduction of padding finishing to cotton fiber kind fabrics such as hospital gauzes as antibacterial finishing agent:
Above-mentioned literal is changed into:
Pad technological process: cotton fibers such as medical absorbent cotton/gauze kind fabric → immersion soak → pressure rolling → immerse again soak → pressure rolling → preliminary drying → bake
Soak is formed by weight percentage: a kind of argentum-carried hydroxylapatite 1%～3% of the present invention, and calgon 0.05～0.5%, deacetyl chitin 3%～8%, citric acid 0.02%～0.1%, surplus is a water.
The preliminary drying temperature: 90 ℃, preliminary drying 1-3min, baking temperature scope: 130～170 ℃, bake 1-4min.
Hospital gauze after treatment is with reference to the textile industry standard FZ/T01021-92 of People's Republic of China (PRC) antibacterial fabric performance test, with test specimens (present embodiment carries out gauze padding finishing after as antibacterial finishing agent to hospital gauze with argentum-carried hydroxylapatite) be put in the conical flask respectively to (common cotton) in the same old way, inoculate with test organisms, after the inoculation, to wash and measure bacterial number immediately to the bacterium that goes up in the same old way, after the sample constant temperature culture, the washing bacterium is also measured bacterial number.The result shows that it is 100% that the bacterium of test specimens reduces percentage.
A kind of argentum-carried hydroxylapatite of the present invention has has a broad antifungal spectrum, the human body compatibility is good, safe characteristics, arrangement After the fabric washing fastness also be better than other silver-series antibacterial agent finish fabrics.
Claims (3)
1. an argentum-carried hydroxylapatite is characterized in that negative Ag-bearing on hydroxyapatite.
2. the preparation method of an argentum-carried hydroxylapatite, it is characterized in that being made up of following steps: in mass ratio is the ratio of 1:30-10, is the AgNO of 8%-25% with mass concentration
3The aqueous solution mixes with hydroxyapatite, and in lucifuge, 15-30 ℃ is stirred 15-30h down, carries out ion-exchange reactions, filters, and with the solid oven dry, calcining 3-6h makes a kind of argentum-carried hydroxylapatite under 800～1000 ℃.
3. the preparation method of a kind of argentum-carried hydroxylapatite according to claim 2 is characterized in that described hydroxyapatite is to make with following method: in the ratio of mass ratio 1: 1.5-3, with CaCO
3And CaHPO
4After being mixed into mixture, in mixture: the mass ratio of absolute ethyl alcohol is that the ratio of 5-8:1 adds described mixture in the described absolute ethyl alcohol, add the fatty alcohol-polyoxyethylene ether that accounts for described mixture quality 5%-8% again, stir, ball milling 3-7h in ball mill puts into and is equivalent to volume of mixture 20-30 deionized water doubly behind the ball milling, at 60～80 ℃ of reaction 3-7h, suction filtration, solid oven dry at 900～1100 ℃ of calcining 4-8h, promptly make hydroxyapatite.
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|---|---|---|---|
| CN2008101528974A CN101390524B (en) | 2008-11-07 | 2008-11-07 | Argentine-loaded hydroxylapatite and preparation method thereof |
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| CN101390524B CN101390524B (en) | 2012-05-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107189372A (en) * | 2017-06-26 | 2017-09-22 | 俞惠英 | A kind of antibacterial polyester film and preparation method thereof |
| CN110141684A (en) * | 2019-05-20 | 2019-08-20 | 江苏科技大学 | A kind of hydro-thermal sterilizing methods of hydroxyapatite coating layer surface in situ synthetic antimicrobial silver orthophosphate |
| CN110306345A (en) * | 2019-05-29 | 2019-10-08 | 安徽元和工贸有限责任公司 | A kind of preparation method of medical antibacterial cotton gauze |
| CN111054404A (en) * | 2020-01-08 | 2020-04-24 | 沈阳师范大学 | Preparation method of flaky hydroxyapatite carrier and supported nano-silver catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480401B (en) * | 2013-09-30 | 2015-05-13 | 江苏理工学院 | Preparation method of HAP (hydroxyapatite)-supported aluminum trichloride catalyst |
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2008
- 2008-11-07 CN CN2008101528974A patent/CN101390524B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189372A (en) * | 2017-06-26 | 2017-09-22 | 俞惠英 | A kind of antibacterial polyester film and preparation method thereof |
| CN110141684A (en) * | 2019-05-20 | 2019-08-20 | 江苏科技大学 | A kind of hydro-thermal sterilizing methods of hydroxyapatite coating layer surface in situ synthetic antimicrobial silver orthophosphate |
| CN110141684B (en) * | 2019-05-20 | 2020-10-09 | 江苏科技大学 | Hydrothermal sterilization method for in-situ synthesis of antibacterial silver phosphate on surface of hydroxyapatite coating |
| CN110306345A (en) * | 2019-05-29 | 2019-10-08 | 安徽元和工贸有限责任公司 | A kind of preparation method of medical antibacterial cotton gauze |
| CN110306345B (en) * | 2019-05-29 | 2022-07-08 | 青岛中腾生物技术有限公司 | Preparation method of medical antibacterial cotton gauze |
| CN111054404A (en) * | 2020-01-08 | 2020-04-24 | 沈阳师范大学 | Preparation method of flaky hydroxyapatite carrier and supported nano-silver catalyst |
| CN111054404B (en) * | 2020-01-08 | 2022-12-23 | 沈阳师范大学 | Preparation method of flaky hydroxyapatite carrier and supported nano-silver catalyst |
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| CN101390524B (en) | 2012-05-23 |
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