CN101836655A - Functionalization inorganic antibiosis material and preparation method thereof - Google Patents
Functionalization inorganic antibiosis material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a functionalization inorganic antibiosis material and a preparation method thereof. The functionalization inorganic antibiosis material takes porous inorganic material as carrier. The organic antiseptic with antibiosis group is grafted on the surface of the inorganic material and micromolecule antiseptic is loaded in the pores thereof. The concrete preparation method of the functionalization inorganic antibiosis material is that the covalent grafting modification is carried out on the porous inorganic material, the organic antiseptic with function group is introduced to the surface of the porous inorganic material, at the same time, the micromolecule antiseptic is loaded in the pores of the porous inorganic material, and the synergistic action of the surface grafting and the antiseptic loaded in the micropores can make the novel functionalization inorganic antibiosis material have better antibiosis effect. The novel functionalization inorganic antibiosis material prepared through the method of the invention has better broad spectrum antibiosis effect, and at the same time, has the advantages of low cost and simple preparation technology. The invention can be applied to making paper, dope, nonwoven fiber product and other fields and has good business application prospect.
Description
Technical field
The present invention relates to functional field of new, be specifically related to a kind of functionalization inorganic antibiosis material and preparation method thereof.
Background technology
Anti-biotic material is that a class has antibacterial and new function material bactericidal property." antibiotic " is meant microbial growth, breeding and survivals such as suppressing bacterium, fungi within a certain period of time.The exploitation of anti-biotic material results to the concern of bacterial infection, and along with the rapid raising of people's living standard, people begin more and more to pay close attention to the development and application of antibiotic property functional material.Simultaneously, people also propose more and more higher requirement to anti-biotic material, as human safety, high efficiency and long-lasting etc.
The preparation of anti-biotic material normally adds in common material or compound one or more have the composition of antibacterial functions, or otherwise antibiotic group is incorporated in the middle of the material, makes it obtain antibiotic property.At present comparatively ripe inorganic antibacterial material mainly is photocatalytic activity material such as titanium dioxide and contains the anti-biotic material of metal ions such as silver, copper, zinc, and it is the strongest wherein to contain the anti-microbial property of anti-biotic material of silver ion.
Chinese invention patent ZL03117960.6 discloses the anti-biotic material of the titanium dioxide of photocatalytic activity as antibiotic effective ingredient, this class anti-biotic material is nontoxic, to human body safety, but the titanium dioxide antibiotic material require could be realized the sterilization purpose under ultraviolet excitation, so its application has bigger limitation.
Chinese invention patent ZL01125125.5 discloses a kind of preparation method who contains the inorganic antibacterial material of silver ion.This method is simple to operate, and is with low cost, can make anti-biotic material.U.S. Pat 6,905,711 to disclose with the hydrophilic polymer be carrier, and the antimicrobial silver ion is connected to anti-biotic material on the polymer, is used for the preparation of antibiotic paper and other antimicrobial products.Yet in the practical application of the inorganic antiseptic that contains silver ion, because the load capacity of silver ion is not strong, under situations such as illumination or heating, silver ion can be shaken off the constraint of carrier, generates silver oxide in alkaline environment, and metachromatism takes place.And the anti-biotic material of argentiferous easily generates silver nitride precipitation and reduces the antibiotic property of silver ion when running into the article of chloride ion-containing.In addition, the use of argent can increase the cost of product greatly, and these unfavorable factors have limited the development of the inorganic antibacterial material of metal ion such as silver.
The appearance of organic polymer antibacterial agent has overcome limitation and the deficiency of inorganic antibacterial material on using of photocatalytic activity anti-biotic material and metal ion.The organic polymer antibacterial agent of studying morely at present has guanidinesalt, quaternary ammonium salt, season phosphonium salt, organotin, shitosan and derivative thereof etc., and wherein the guanidinesalt antibacterial agent has good water-solubility, heat endurance and broad spectrum antibacterial performance and paid close attention to widely.The acute toxicity of guanidinesalt is lower simultaneously, can not have a strong impact on health, there is not carcinogenicity in human body, causes the potential threat of sex change and teratogenesis, so guanidinesalt class antibacterial agent has very big potentiality to be exploited, can be applied to fields such as medical treatment, agricultural product protection, food and commodity.U.S. Pat 6031119 discloses a kind of preparation and using method that can be used for the poly-alkylene guanidinesalt of materials such as fiber, paper, glass, resin.The interpolation of guanidine salt polymer can make the product that obtains have broad spectrum antibacterial performance, but because guanidine salt polymer is soluble in water, when simple blend is used in the products such as glass, resin, can make product lose anti-microbial property because of it is water-soluble.Little molecule antibacterial agent has that initial sterilizing power is strong, sterilization is promptly imitated and the characteristics of has a broad antifungal spectrum, its synthetic technology maturation, and price is relatively cheap.But when little molecule antibacterial agent is used for antimicrobial product, oozes out rapidly easily because of its molecular weight is little and to make product lose anti-microbial property.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, functionalization inorganic antibiosis material that a kind of anti-microbial property is lasting, technology is simple, with low cost and preparation method thereof is provided.
In order to solve the defective of above-mentioned prior art, the present invention is connected in the porous inorganic carrier material surface by graft reaction with the organic polymer antibacterial agent, simultaneously the load of little molecule antibacterial agent is inserted in the hole of inorganic carrier material.The use of organic antibacterial agent has overcome the deficiency of photocatalytic activity anti-biotic material and metal ion anti-biotic material, the synergy of organic polymer antibacterial agent and little molecule antibacterial agent has not only improved antibacterial ability, also strengthened its retentivity in antimicrobial product simultaneously, prolong effective antibiotic phase, enlarge the range of application of this new function inorganic antibacterial material.
The present invention is achieved through the following technical solutions:
A kind of preparation method of functionalization inorganic antibiosis material comprises the steps and process conditions:
(1) bridging agent and inorganic carrier material were reacted 2-8 hour in 40 ℃ of-90 ℃ of aqueous solution, obtain the inorganic carrier material of grafting bridging agent; Bridging agent is the 10%-70% of inorganic carrier material weight; Described bridging agent is adipic acid, hexamethylene diamine, epoxychloropropane, γ-glycidoxypropyltrime,hoxysilane or propane diols diglycidyl ether; Described inorganic carrier material is the porous inorganic material, and the aperture is 0.01-10 μ m, and specific surface area is 57.3-400cm
2/ g;
(2) filter to isolate the inorganic carrier material of grafting bridging agent, use distilled water wash then, use organic solvent washing again; Described organic solvent is an acetone or alcohol;
(3) inorganic carrier material and the organic antibacterial agent with the grafting bridging agent reacted 1-6 hour in 50 ℃ of-100 ℃ of water, obtained the inorganic carrier material of grafting organic antibacterial agent after the filtration; Described organic antibacterial agent is that molecular weight is 400-10, the quaternary ammonium salt of 000g/mol, season phosphonium salt class or guanidinesalt class organic polymer material; Organic antibacterial agent is the 0.1-20% of the inorganic carrier material weight of grafting bridging agent;
(4) inorganic carrier material of grafting organic antibacterial agent is inserted in the little molecule antimicrobial that concentration is 20-50mg/ml, after vibrating 12-96 hour under 200-400 rev/min the hunting speed, centrifugal products therefrom obtains functionalization inorganic antibiosis material after 30 ℃ of-80 ℃ of dryings; Described little molecule antibacterial agent be 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, tetracycline hydrochloride and butyl p-hydroxybenzoate; The 5-50% that the little molecule antibacterial agent of load is an inorganic carrier material weight; The solvent of little molecule antibacterial agent is ethanol, acetone or water.
For further realizing purpose of the present invention, described inorganic carrier material is preferably the mesopore molecular sieve of calcium carbonate, imvite, silicate, titanium dioxide or SBA-15.
Described bridging agent is preferably adipic acid, γ-glycidoxypropyltrime,hoxysilane or propane diols diglycidyl ether;
The little molecule antibacterial agent of described load is preferably the 10-30% of inorganic carrier material weight.
A kind of functionalization inorganic antibiosis material, by method for preparing, this material is a carrier with porous inorganic material, the carrier surface grafting has the organic antibacterial agent of antibiotic group, the little molecule antibacterial agent of load in the carrier hole; Described inorganic carrier material is the porous inorganic material, and the aperture is 0.01-10 μ m, and specific surface area is 57.3-400cm
2/ g; Described organic antibacterial agent is that molecular weight is 400-10, the quaternary ammonium salt of 000g/mol, season phosphonium salt class or guanidinesalt class organic polymer material; Described little molecule antibacterial agent is 2,4,4 '-trichlorine 2 '-dihydroxy diphenyl ether, tetracycline hydrochloride and butyl p-hydroxybenzoate.
With respect to prior art, the present invention has the following advantages:
(1) the present invention is incorporated into the porous inorganic carrier material surface with organic polymer antibacterial agent covalence graft, the load of little molecule antibacterial agent is gone in the hole of porous inorganic carrier material, thereby preparation has the functionalization inorganic antibiosis material of the anti-microbial property excellence of long-lasting and slow release;
(2) the porous inorganic carrier material after the graft modification of organic polymer antibacterial agent has good antibacterial performance, in case contact the effect that just can reach sterilization with bacterium, need not ultraviolet excitation, the organic polymer antibacterial agent of covalence graft has the durable antibiotic performance, has overcome limitation and the deficiency of inorganic antibacterial material on using of photocatalytic activity anti-biotic material and metal ion;
(3) the organic polymer antibacterial agent of porous inorganic carrier material covalence graft is at material surface generation antibacterial action, the little molecule antibacterial agent of load plays bactericidal action by slow release, the synergy of the two can improve the anti-microbial property of material greatly, enlarges the range of application of this functionalization inorganic antibiosis material;
(4) the inventive method is simple, and is with low cost, and technical maturity is easy to control.
Description of drawings
Fig. 1 is the infrared spectrum (embodiment 1) before and after the inorganic carrier material grafting organic antibacterial agent
Fig. 2 is the sustained release performance (embodiment 5) of the little molecule antibacterial agent of load in the functionalization inorganic antibiosis material
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples; but the scope of protection of present invention is the scope represented in embodiment of limitation not; all equivalences that spirit essence is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Embodiment 1
10g calcium carbonate powder and 2.36g γ-glycidoxypropyltrime,hoxysilane are added in 100 ml waters, 90 ℃ of lower magnetic force stirring reactions 2 hours.Reaction filters out solids after finishing, and with distillation washing 3 times, washes 3 times with acetone again.Product and 0.1g poly (hexamethylene) hydrochloride are added in 100 ml waters,, obtain the calcium carbonate solid of surface grafting organic antibacterial agent after the filtration 70 ℃ of lower magnetic force stirring reactions 6 hours.Products therefrom is at room temperature dry, then it being joined 200 ml concns is 2 of 50mg/ml, 4,4 '-three chloro-2 '-ethanolic solution of dihydroxy diphenyl ether in, vibration is 72 hours under 400 rev/mins hunting speed, the centrifugal supernatant of removing, products therefrom obtains functionalization inorganic antibiosis material after 60 ℃ of following dryings.
As shown in Figure 1, the infrared spectrum by the calcium carbonate of calcium carbonate and grafting poly (hexamethylene) hydrochloride relatively is 1633cm in wave number in the infrared spectrum of the calcium carbonate after grafting as can be known
-1Tangible absworption peak is arranged, and this is the characteristic absorption peak of poly-hexamethyl guanidinesalt hydrochloride, is the C=N absworption peak in the molecular structure.The wave number of the N-H absworption peak in the poly-hexamethyl guanidinesalt hydrochloride molecular structure is 3285cm
-1, the CH in the molecular structure of poly-hexamethyl guanidinesalt hydrochloride and silane bridging agent
2The wave number of absworption peak is 2932cm
-1, this with and the absworption peak of the OH that combines of calcium carbonate coincide.But the infrared spectrum that contrasts two kinds of materials as can be known, and the calcium carbonate of grafting poly (hexamethylene) hydrochloride increases to some extent in the absorption intensity of this wave-number range.By the infrared spectrum map analysis as can be known, the poly (hexamethylene) hydrochloride is grafted on the calcium carbonate by the silane bridging agent.
Embodiment 2
10g mesoporous molecular sieve SBA-15 powder and 2.7g epoxychloropropane are added in 100 ml waters, 40 ℃ of lower magnetic force stirring reactions 4 hours.Reaction filters out solids after finishing, and with distillation washing 3 times, washes 3 times with ethanol again.Product and 2g chitosan quaternary ammonium salt are added in 100 ml waters,, obtain the mesoporous molecular sieve SBA-15 of surface grafting organic antibacterial agent after the filtration 100 ℃ of lower magnetic force stirring reactions 1 hour.With products therefrom in drying at room temperature, then it being joined 300 ml concns is 20mg/ml 2,4,4 '-three chloro-2 '-ethanolic solution of dihydroxy diphenyl ether in, 96h vibrates under 300 rev/mins hunting speed, the centrifugal supernatant of removing, products therefrom obtains functionalization inorganic antibiosis material after 40 ℃ of following dryings.
Embodiment 3
10g imvite powder and 6.1g propane diols diglycidyl ether are added in 100 ml waters, 50 ℃ of lower magnetic force stirring reactions 8 hours.Reaction filters out solids after finishing, and with distillation washing 3 times, washes 3 times with acetone again.Product and 0.5g poly (hexamethylene) hydrochloride are added in 100 ml waters,, obtain the imvite of surface grafting organic antibacterial agent after the filtration 50 ℃ of lower magnetic force stirring reactions 4 hours.With products therefrom in drying at room temperature, then it is joined in the acetone soln that 200 ml concns are the 30mg/ml butyl p-hydroxybenzoate, the 48h that under 400 rev/mins hunting speed, vibrates, the centrifugal supernatant of removing, products therefrom obtains functionalization inorganic antibiosis material after 30 ℃ of following dryings.
Embodiment 4
10g titania powder and 5.8g hexamethylene diamine are added in 100 ml waters, 90 ℃ of lower magnetic force stirring reactions 6 hours.Reaction filters out solids after finishing, and with distillation washing 3 times, washes 3 times with acetone again.Product and 1g poly (hexamethylene) hydrochloride are added in 100 ml waters,, obtain the titanium dioxide of surface grafting organic antibacterial agent after the filtration 80 ℃ of lower magnetic force stirring reactions 4 hours.With products therefrom in drying at room temperature, then it is added 100ml concentration and be in the acetone soln of butyl p-hydroxybenzoate of 50mg/ml, the 12h that under 400 rev/mins hunting speed, vibrates, the centrifugal supernatant of removing, products therefrom obtains functionalization inorganic antibiosis material after 60 ℃ of following dryings.
10g calcium carbonate powder and 1.8g epoxychloropropane are added in 100 ml waters, 50 ℃ of lower magnetic force stirring reactions 3 hours.Reaction filters out solids after finishing, and with distillation washing 3 times, washes 3 times with acetone again.Product and 0.3g poly (hexamethylene) hydrochloride are added in 100 ml waters,, obtain the calcium carbonate solid of surface grafting organic antibacterial agent after the filtration 90 ℃ of lower magnetic force stirring reactions 6 hours.Products therefrom is at room temperature dry, then it being joined 200 ml concns is 2 of 30mg/ml, 4,4 '-three chloro-2 '-ethanolic solution of dihydroxy diphenyl ether in, vibration is 96 hours under 200 rev/mins hunting speed, the centrifugal supernatant of removing, products therefrom obtains functionalization inorganic antibiosis material after 40 ℃ of following dryings.
As shown in Figure 2, the little molecule antibacterial agent that loads in the functionalization inorganic antibiosis material can slowly release.Slow release speed has influence to grafting poly (hexamethylene) hydrochloride (PHGH) from inorganic carrier material (calcium carbonate) to little molecule antibacterial agent (2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether).Its medium and small molecule antibacterial agent can never discharge in the inorganic carrier material of grafting organic antibacterial agent faster.Little molecule antibacterial agent discharges very fast in the initial period, rate of release slows down gradually then, finally can reach balance.
Embodiment 6
10g mesoporous molecular sieve SBA-15 powder and 1.8g epoxychloropropane are added in 100 ml waters, 40 ℃ of lower magnetic force stirring reactions 5 hours.Reaction filters out solids after finishing, and with distillation washing 3 times, washes 3 times with ethanol again.Product and 0.3g poly (hexamethylene) hydrochloride are added in 100 ml waters,, obtain the mesoporous molecular sieve SBA-15 of surface grafting organic antibacterial agent after the filtration 80 ℃ of lower magnetic force stirring reactions 6 hours.With products therefrom in drying at room temperature, then it being joined 300 ml concns is 20mg/ml2,4,4 '-three chloro-2 '-ethanolic solution of dihydroxy diphenyl ether in, 60h vibrates under 300 rev/mins hunting speed, the centrifugal supernatant of removing, products therefrom obtains functionalization inorganic antibiosis material after 50 ℃ of following dryings.
After testing, the organic antibacterial agent percent grafting of the foregoing description 1-6 and as shown in table 1 to colibacillary anti-microbial property.Wherein, the percent grafting of organic antibacterial agent is meant the percentage that is grafted to the organic antibacterial agent on the inorganic carrier material.Its method of testing is as follows: the inorganic carrier material of grafting organic antibacterial agent is put into thermogravimetric analyzer, and with the thermogravimetric curve of determination of heating rate material between 24-600 ℃ of 20 ℃/min, by analyzing the percent grafting that thermogravimetric curve can obtain organic antibacterial agent.Infrared spectrum (embodiment 1) before and after the inorganic carrier material grafting organic antibacterial agent as shown in Figure 1.
Germicidal efficiency in the table 1 is meant the kill efficiency of the inorganic carrier material of surface grafting organic antibacterial agent to bacterium (Escherichia coli).Succusion is adopted in the test of germicidal efficiency, concrete steps are as follows: at first prepare fresh phosphate buffered solution and high-temperature sterilization, the PBS solution of getting 4.5ml then places test tube, the inorganic carrier material of 0.001g surface grafting organic antibacterial agent is put into test tube and it is shaken up.Escherichia coli suspension (10 with 0.5ml
8CFU/ml) join in the test tube that inorganic carrier material is housed, make colibacillary ultimate density be about 10
6CFU/ml.Test tube at 37 ℃, is taken out behind the vibration 1h in the water bath with thermostatic control oscillator of 200rpm.Get the 0.1ml supernatant and be evenly coated on the agar culture dish, the agar culture dish is put in counts bacteria colony count after cultivating 24h in 37 ℃ the incubator.The result of each sample is 3 agar culture dish results' a mean value.If bacteria colony count excessive (＞250) then should will be cultivated after the supernatant dilution again.Germicidal efficiency is calculated by following formula: clump count * 100% of germicidal efficiency (%)=(clump count of the clump count-sample of blank sample)/blank sample.
By the percent grafting result of the organic antibacterial agent in the table 1 as can be known, the kind of inorganic carrier material and bridging agent, reaction condition and organic antibacterial agent kind all influence to some extent to the percent grafting of organic antibacterial agent on inorganic carrier.At different inorganic carrier materials, organic antibacterial agent can be grafted to the inorganic carrier material surface by selecting suitable bridging agent, the percent grafting of organic antibacterial agent generally can reach 30%-40%.Germicidal efficiency result in the table 1 shows that germicidal efficiency is influenced by the kind of organic antibacterial agent and percent grafting.For the inorganic carrier material of grafting organic antibacterial agent of the same race, the percent grafting of organic antibacterial agent is high more, and then the effect of its kill bacteria is just good more, and germicidal efficiency is high more.
The anti-microbial property (to Escherichia coli) of the inorganic carrier material (0.001g) of table 1 surface grafting organic antibacterial agent
| The sample name | Organic antibacterial agent percent grafting (%) | Germicidal efficiency (%) |
| Embodiment 1 | ??15.4 | ??83 |
| Embodiment 2 | ??10.6 | ??75 |
| Embodiment 3 | ??38.5 | ??98 |
| Embodiment 4 | ??41.2 | ??100 |
| |
??38.7 | ??100 |
| Embodiment 6 | ??40.8 | ??100 |
The functionalization inorganic antibiosis material of the little molecule antibacterial agent of load is as shown in table 2 to the Escherichia coli anti-microbial property among the embodiment 1-6, wherein, little molecule antibacterial agent load capacity refers to load and goes into the little molecule antibacterial agent in the inorganic carrier material of surface grafting organic antibacterial agent and the percentage by weight of inorganic carrier material.Measure the amount that vibration finishes the medium and small molecule antibacterial agent of back solution by ultraviolet-visible spectrometer, by calculating the amount of the little molecule antibacterial agent that can obtain the inorganic carrier material load.The sustained release performance of the little molecule antibacterial agent of load (embodiment 5) as shown in Figure 2 in the functionalization inorganic antibiosis material, as seen from the figure, the little molecule antibacterial agent that load is gone in the inorganic carrier material can slowly release.The anti-microbial property of the little molecule antibacterial agent of functionalization inorganic antibiosis material load is measured by inhibition zone method.At first functionalization inorganic antibiosis material is joined in the cellulosic fibre slurry by 1% of cellulose fiber weight, it is manufactured paper with pulp into paper.Then a certain amount of LB agar is poured in the culture dish, after it at room temperature solidifies, the concentration of other same amount only poured into for half LB agar of the agar of front again form second layer agar layer in the culture dish, this layer is softer slightly than last layer.Then with the bacterial suspension (10 of 0.1ml
8CFU/ml) be uniformly coated on the agar layer surface, the pattern (diameter is 1 centimetre) of a small pieces circle is placed on the agar surface that scribbles bacterium, culture dish is put in 37 ℃ cultivates 24h, antimicrobial efficiency is determined by the size of measuring inhibition zone.As shown in Table 2, the calcium carbonate of the little molecule antibacterial agent of load does not have anti-microbial property, and load the functionalization inorganic antibiosis material of little molecule antibacterial agent all have antibiotic resistance performance, and the load capacity of little molecule antibacterial agent is big more, the diameter of inhibition zone is just big more, shows that the anti-microbial property of functionalization inorganic antibiosis material is just good more.
The anti-microbial property (to Escherichia coli) of the functionalization inorganic antibiosis material of the little molecule antibacterial agent of table 2 load
Annotate: the external diameter of inhibition zone (mm)=antibacterial ring-antibacterial ring internal diameter.
Claims (5)
1. the preparation method of a functionalization inorganic antibiosis material is characterized in that comprising the steps and process conditions:
(1) bridging agent and inorganic carrier material were reacted 2-8 hour in 40 ℃ of-90 ℃ of aqueous solution, obtain the inorganic carrier material of grafting bridging agent; Bridging agent is the 10%-70% of inorganic carrier material weight; Described bridging agent is adipic acid, hexamethylene diamine, epoxychloropropane, γ-glycidoxypropyltrime,hoxysilane or propane diols diglycidyl ether; Described inorganic carrier material is the porous inorganic material, and the aperture is 0.01-10 μ m, and specific surface area is 57.3-400cm
2/ g;
(2) filter to isolate the inorganic carrier material of grafting bridging agent, use distilled water wash then, use organic solvent washing again; Described organic solvent is an acetone or alcohol;
(3) inorganic carrier material and the organic antibacterial agent with the grafting bridging agent reacted 1-6 hour in 50 ℃ of-100 ℃ of water, obtained the inorganic carrier material of grafting organic antibacterial agent after the filtration; Described organic antibacterial agent is that molecular weight is 400-10, the quaternary ammonium salt of 000g/mol, season phosphonium salt class or guanidinesalt class organic polymer material; Organic antibacterial agent is the 0.1-20% of the inorganic carrier material weight of grafting bridging agent;
(4) inorganic carrier material of grafting organic antibacterial agent is inserted in the little molecule antimicrobial that concentration is 20-50mg/ml, after vibrating 12-96 hour under 200-400 rev/min the hunting speed, centrifugal products therefrom obtains functionalization inorganic antibiosis material after 30 ℃ of-80 ℃ of dryings; Described little molecule antibacterial agent is 2,4,4 '-trichlorine 2 '-dihydroxy diphenyl ether, tetracycline hydrochloride and butyl p-hydroxybenzoate; The 5-50% that the little molecule antibacterial agent of load is an inorganic carrier material weight; The solvent of little molecule antibacterial agent is ethanol, acetone or water.
2. according to the preparation method of the functionalization inorganic antibiosis material described in the claim 1, it is characterized in that: described inorganic carrier material is the mesopore molecular sieve of calcium carbonate, imvite, silicate, titanium dioxide or SBA-15.
3. according to the preparation method of the functionalization inorganic antibiosis material described in the claim 1, it is characterized in that: described bridging agent is adipic acid, γ-glycidoxypropyltrime,hoxysilane or propane diols diglycidyl ether.
4. according to the preparation method of the functionalization inorganic antibiosis material described in the claim 1, it is characterized in that: the 10-30% that the little molecule antibacterial agent of described load is an inorganic carrier material weight.
5. by a kind of functionalization inorganic antibiosis material of each described method preparation of claim 1-4, it is characterized in that, this material is a carrier with porous inorganic material, and the carrier surface grafting has the organic antibacterial agent of antibiotic group, the little molecule antibacterial agent of load in the carrier hole; Described inorganic carrier material is the porous inorganic material, and the aperture is 0.01-10 μ m, and specific surface area is 57.3-400cm/g; Described organic antibacterial agent is that molecular weight is 400-10, the quaternary ammonium salt of 000g/mol, season phosphonium salt class or guanidinesalt class organic polymer material; Described little molecule antibacterial agent be 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether, tetracycline hydrochloride and butyl p-hydroxybenzoate.
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