CN1943804A - The medical use anti-infection polymeric material and its preparation method - Google Patents
The medical use anti-infection polymeric material and its preparation method Download PDFInfo
- Publication number
- CN1943804A CN1943804A CNA2006101229013A CN200610122901A CN1943804A CN 1943804 A CN1943804 A CN 1943804A CN A2006101229013 A CNA2006101229013 A CN A2006101229013A CN 200610122901 A CN200610122901 A CN 200610122901A CN 1943804 A CN1943804 A CN 1943804A
- Authority
- CN
- China
- Prior art keywords
- infection
- montorillonite clay
- preparation
- load
- medical use
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention provides an anti-infective medical polymer material, comprising 100 dose of heat curable silicone rubber, 2.5 to 15 dose of Na-montmorillonite, 0.75 to 6.2 dose of quaternary ammonium salt intercalation compounds, 0.3 to 5.6 doses of antibiotics. Preparation method of the materials is: convert the montmorillonite clay to Na-montmorillonite, and then intercalate quaternary ammonium salts to montmorillonite to obtain the organic-montmorillonite with anti-infective drugs attached to it, and compound with heat curable silicone rubber at last. The material has a long anti-infection time, good physical and mechanical properties, and not easy to age. It can be used in the preparation of various medical catheters, such as catheters, deep venous catheters, drainage tubes, trachea intubation and so on.
Description
Technical field
The present invention relates to field of medical materials, be specifically related to medical use anti-infection polymeric material.
Background technology
Medical catheter is to use medical instruments very widely on the hospital clinical, comprises catheter, drainage tube, tracheal intubation etc.Because these conduits are kept somewhere for a long time at human body, often cause conduit infections relating problem.The measure of Clinical Processing conduit infections relating and the problem of existence have at present: 1, in time change conduit, can increase patient's the misery and the chance of infection but change conduit repeatedly; 2, prevention flushing, but multinomial studies show that with not flushing group do not have significant difference; 3, use antibiotic, but in case the conduit infections relating occurs, very difficult biomembrane, the often poor effect passed through of antibiotic.
The polymer that is used to prepare medical catheter at present has following several:
1, natural emulsion: big to the human body zest, biocompatibility is poor;
2, polrvinyl chloride: form biomembrane easily, cause the conduit infections relating;
3, vacuum plating silver infection material: cost an arm and a leg, and silver has toxicity to liver, kidney, nervous system and mucosa
4, silicone rubber: little to the human body stimulation, be not easy to form biomembrane, antibiotic substance can also be combined in catheter surface or intermediary to the infection material.
Because it is little that silicone rubber has the human body stimulation, be difficult for forming biomembrane and can being widely used in the preparation of medical catheter in conjunction with the characteristics of antibacterials.Silicone rubber and the bonded mode of antibacterials have following two kinds at present:
(1) surface combination: the antibacterials content by surface combination is low, and comes off easily and cause the infection time shorter;
(2) sandwich method: promptly antibacterials are put in the middle of the material by the method for physics and chemistry, this method complex process is difficult to realize industrialization.
Montorillonite clay claims " bentonite " again, its molecule space has bigger hole, montorillonite clay mineral crystal grain is tiny, has bigger external surface area, simultaneously since interlaminar action power a little less than, interlayer can be peeled off, expand under the effect of solvent, is separated into thinner single-chip, makes montorillonite clay have bigger specific surface area.Utilize this character of montorillonite clay exchangeable cations, available cationic surfactant carries out modification to it to be handled, and increases specific surface area, makes the organo montmorillonite that purposes is extensive more, performance is unique more.The nanometer polymerization material of intercalation compounding preparation is mainly used in industries such as printing ink, high-grade paint, engineering plastics, also is useful on the report of silicone rubber intercalation, mainly is the physical mechanics property that changes product.Be scattered in the silicone rubber about the carrier of montorillonite clay as the infection material, and be applied to medical apparatus and instruments relevant report also arranged.The Zhongshan University side of wishing penetrating judgment is awarded by polymer modification montmorillonite intercalation complex method and is developed silicone rubber/montmorillonite load antibacterials nanometer polymerization material, have control medicament slow release effect (
Http: // 202.116.65.193/jinpin2005/zonghe/paper/4/03014.docInventor's collaborative project), but there are several problems in this silastic material: (1) anti-microbial property instability, and the release experiment of antibacterials just by 72h, can not prove the infection effect that can reach needed more than 20 days clinically; (2) used silastic material is a room temperture rubber vulcanization, in south, summer temperature is higher, high temperature can cause the molecular structure of room temperture rubber vulcanization to change, thereby reduce the catheter fever mechanical property: the method for this material of (3) preparation is a solwution method, use a large amount of organic solvent chloroforms, environment is brought a series of pollution.
Summary of the invention
The purpose of this invention is to provide a kind of medical use anti-infection polymeric material.
Another object of the present invention provides the preparation method of this medical use anti-infection polymeric material.
The technical solution of realization above-mentioned purpose of the present invention is:
A kind of medical use anti-infection polymeric material is made up of the component of following weight portion: 100 parts of high-temperature silicon disulfide rubbers, 0.43～9 part of Na-montorillonite clay, 0.25～6.2 part of quaternary ammonium salts agent, 0.3～5.8 part of antibacterials; Wherein, the Na-montorillonite clay is made by following method: use the saturated deionized water of NaCl with the Ca in the montorillonite clay
2+, Mg
2+Be replaced as Na
+, filter, wash, be dried to constant weight then, promptly.
A kind of medical use anti-infection polymeric material of the present invention, the optimum ratio of each component is: 100 parts of high-temperature silicon disulfide rubbers, 5～9 parts of Na-montorillonite clays, 1～5 part of quaternary ammonium salts agent, 3～5 parts of antibacterials.
Medical use anti-infection polymeric material of the present invention, wherein, described high-temperature silicon disulfide rubber is common medical grade silicone rubber, specifically is a kind of in dimethyl silicone rubber, Methylethyl silicone rubber, methyl phenyl vinyl silicone rubber, the fluorosioloxane rubber, preferably Methylethyl silicone rubber.Described quaternary ammonium salts agent can be Quaternium 24, DDAC, benzethonium chloride wherein one or more.Described antibacterials can be antifungal drugs, as econazole nitrate, miconazole nitrate; Also can be antibiotic, as amikacin sulfate, tetracycline, rifampicin, gentamycin, doxycycline; Can also be the non-antibiotic bacteriostatic, as hibitane.
Medical use anti-infection polymeric material of the present invention, its preparation method is made up of the following step:
(1) preparation of Na-montorillonite clay: montorillonite clay (is mainly contained Na
+, Ca
2+, Mg
2+Ion) in 10～30 times the saturated deionized water solution of NaCl, stirs, form steady suspension, stirred 5～6 hours down at 30～40 ℃ again, sucking filtration, filter thing with deionized water wash, then at 70 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20～30 μ m;
(2) preparation of organo montmorillonite: with the deionized water for stirring of step (1) gained Na-montorillonite clay 20 times of times of weight, form suspension, add intercalator again, stirred 4 hours down at 85 ℃, filter, washing filter thing is removed halide ion, and dry in vacuum drying oven then, ball milling to particle diameter is 20-50 μ m;
(3) preparation of antibacterials load montorillonite clay: step (2) gained organo montmorillonite is stirred in the solvent of 10 times of times of weight, form suspension, add antibacterials again, stirred 4 hours down for 40 ℃ in room temperature or constant temperature, filter, dry in vacuum drying oven then, ball milling to particle diameter is 20-50 μ m;
(4) compound: that step (3) gained infection load montorillonite clay and high-temperature silicon disulfide rubber is compound.
The preparation method of medical use anti-infection polymeric material of the present invention, the described solvent of this method are the wherein a kind of of dehydrated alcohol or deionized water.
Medical use anti-infection composite material and preparation method thereof of the present invention, wherein step (4) adopts the preparation method of high-temperature silicon disulfide rubber elastomeric compound, and those skilled in the art can also adopt corresponding complex method according to concrete high-temperature silicon disulfide rubber.
The preparation method of medical use anti-infection polymeric material of the present invention, the compound employing fusion intercalation of infection load montorillonite clay and high-temperature silicon disulfide rubber complex method wherein, be specially: (152 * 305mm) is mixing with 160 pairs of roller mills of Φ to get rubber and antibiotic load montorillonite clay, friction ration is 1: 1.42, and two roll temperatures are below 40 ℃; Mixing evenly after, extrude the thin slice of 2-3mm, parked 24 hours; Add vulcanizing agent DCP then, with 25 tons of hydraulic flat forcing press top boards sample preparation of dull and stereotyped heating, 170 ℃ of curing temperatures, cure time got final product in 10 minutes.
In actual production process, need be to load amikacin sulfate montorillonite clay medical use anti-infection polymeric material sampling Detection of the present invention and monitoring.Concrete detection method is as follows: get one section material sample, make 1cm * 1cm thin slice, carry out FT-IR (fourier-transform infrared) test: FT-IR tests the infrared spectrometer that used instrument is a U.S. Nicolet company, and test mode is taked surface reflectance, and the surface of sample is analyzed; Can find to cover the characteristic absorption peak that holds in the palm soil and institute's carrying medicament respectively from the gained infrared spectrum, i.e. the material that explanation is tested is a material of the present invention.The characteristic absorption peak of montorillonite clay is: 1030cm
-1Neighbouring is Si-O-Si skeletal vibration peak, 400～600cm
-1Internal vibration peak for silicon-oxy tetrahedron and alumina octahedral.
Medical use anti-infection polymeric material of the present invention utilizes the organo montmorillonite granule to be carrier, and anti-infectives effectively and uniformly is dispersed in the silastic polymer, and infection has good infection effect for up to more than 30 days; Employed silicone rubber is high-temperature silicon disulfide rubber, adds montorillonite clay and inserts between silastic-layer, makes polymeric material of the present invention have good thermodynamic property and physical and mechanical property, can not be subjected to influence of temperature variation during use; Polymeric material of the present invention has been avoided the use of hazardous solvent in preparation process, reduced the pollution to environment.
For a better understanding of the present invention, will test by some below and prove its effect.
1, the mensuration of the different antibiotic substance montorillonite clays of load:
Take by weighing the different antibacterials montorillonite clays of a certain amount of load, place corresponding different solvent, with apparatus,Soxhlet's circulation extracting 24h, cross the antibiotic substance that the absorption of montorillonite clay appearance is earned in diafiltration, dry then, grinding, cross 200 mesh sieves, be used for the montorillonite clay (seeing Fig. 1,2) of the different antibiotic substance of XRD and infrared spectrum measurement load.Fig. 1 is the XRD figure of montorillonite clay and modified montmorillonoid, wherein curve 1 is the Na-montorillonite clay, curve 2 is the montorillonite clays of load amikacin sulfate, curve 3 is the montorillonite clays of load miconazole, curve 4 is the montorillonite clays of load tetracycline, curve 5 is the montorillonite clays of load hibitane, according to Bragg equation n λ=2dsin θ, calculate to such an extent that the interlamellar spacing of montorillonite clay is 1.31nm, and be respectively 1.49nm, 2.26nm, 1.59nm through the organoclay interlamellar spacing of amikacin sulfate, miconazole, tetracycline, hibitane modification, 1.58nm interlamellar spacing all is greatly improved.Fig. 2 is the infrared spectrogram of montorillonite clay and modified montmorillonoid, curve 1 is the Na-montorillonite clay among the figure, and curve 2 is the montorillonite clays of load amikacin sulfate, and curve 3 is the montorillonite clays of load miconazole, curve 4 is the montorillonite clays of load tetracycline, and curve 5 is the montorillonite clays of load hibitane.From this infrared spectrogram as can be seen, the montorillonite clay after the modification all has the characteristic absorption peak of modification medicine respectively except the characteristic peak that original soil is arranged.Fig. 1 and Fig. 2 have proved that the antibiotic substance intercalation enters between montmorillonite layer.
2, medical use anti-infection polymeric material XRD test:
(152 * 305mm) is mixing, and friction ration is 1: 1.42, and two roll temperatures are below 40 ℃ with 160 pairs of roller mills of Φ to get a certain amount of rubber and antibiotic load montorillonite clay; Mixing evenly after, extrude the thin slice of 2-3mm, parked 24 hours; Add vulcanizing agent DCP then, with 25 tons of hydraulic flat forcing press top boards sample preparation of dull and stereotyped heating, 170 ℃ of curing temperatures, cure time 10 minutes obtains silicone rubber infection polymeric material, is used for XRD test (see figure 3).Among Fig. 3, curve 1 is the pure silicon elastomeric material, curve 2 is medical use anti-infection composites, as can be seen from the figure, after modified montmorillonoid is added to silicone rubber, its angle of diffraction further moves to little angular direction, calculates to such an extent that its interlamellar spacing is 4.85nm by Bragg equation, illustrates that antibacterials have entered between the silicone rubber effectively.
3, the slow release of antibacterials:
The medical use anti-infection polymeric material of the present invention of load miaow bran azoles is prepared into 6mm diameter, disk that 1mm is thick, and it is standby to sterilize; Silicone rubber plate is suspended in 0.9% saline (perhaps coordinative solvent), soaks 1day, 2day, 3day...35day.Changed a liquid in per 24 hours, with ultraviolet spectrophotometer test antibiotic substance release time be 28-35 days.
The release result of the medical polymeric material of table 1 UV spectrophotometer measuring load miaow bran azoles nanometer
| Time (day) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 |
| Drug level (mg/ml) | 0.45 | 0.43 | 0.42 | 0.39 | 0.37 | 0.35 | 0.34 | 0.31 | 0.30 | 0.27 | 0.25 | 0.18 |
| Medication amount (mg) | 0.90 | 0.86 | 0.84 | 0.78 | 0.74 | 0.70 | 0.68 | 0.62 | 0.60 | 0.54 | 0.50 | 0.36 |
| Time (day) | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 |
| Drug level (mg/ml) | 0.156 | 0.152 | 0.134 | 0.128 | 0.093 | 0.089 | 0.082 | 0.075 | 0.066 | 0.062 | 0.059 | 0.056 |
| Medication amount (mg) | 0.312 | 0.304 | 0.268 | 0.256 | 0.186 | 0.178 | 0.164 | 0.150 | 0.132 | 0.124 | 0.118 | 0.112 |
| Time (day) | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 | 33 | 34 | 35 | |
| Drug level (mg/ml) | 0.055 | 0.052 | 0.051 | 0.047 | 0.043 | 0.040 | 0.038 | 0.032 | 0.031 | 0.028 | 0.025 | |
| Medication amount (mg) | 0.110 | 0.104 | 0.102 | 0.094 | 0.086 | 0.080 | 0.076 | 0.064 | 0.062 | 0.056 | 0.050 |
4, bacteriostatic experiment
(1) biomembranous preparation
With following material be prepared into 6mm diameter, disk that 1mm is thick, standby behind the autoclaving; The medical use anti-infection composite is suspended in staphylococcus epidermidis (Escherichia coli bacteria liquid, Candida albicans) the bacterium liquid, soaks, obturage with anti-pollution around the flat board, place 37 ℃ of incubators to cultivate, the per 24 hours once fresh bacterium liquid of replacing with sealing film.All the outward appearance with positive controls is identical to be cultured to the whole samples of perusal, does the colony counting of biomembrane antibacterial then.Record incubation time, effect.
Matched group: all-silicon rubber sheet;
1: one sublevel of sample is inserted the montorillonite clay silicone rubber infection polymeric material of bromo geramine;
2: one sublevels of sample are inserted Quaternium 24 montorillonite clay silicone rubber infection polymeric material;
Sample 3: load tetracycline montorillonite clay silicone rubber infection polymeric material;
Sample 4: load rifampicin montorillonite clay silicone rubber infection polymeric material;
Sample 5: load hibitane montorillonite clay silicone rubber infection polymeric material;
Sample 6: load miconazole montorillonite clay silicone rubber infection polymeric material;
Sample 7: load amikacin sulfate montorillonite clay silicone rubber infection polymeric material.
Above sample is preparation under the same reaction condition, and the ratio of infection slow-released carrier and silicone rubber is 15: 85.
The biomembrane cultivation results of the medical use anti-infection composite of the different infection materials of table 2 load
| Time (my god) | Matched | Sample | 1 | | | | | | Sample 7 |
| 1 | ++++ | - | - | - | - | - | - | - | |
| 2 | ++++ | - | - | - | - | - | - | - | |
| 3 | ++++ | - | - | - | - | - | - | - | |
| 4 | ++++ | - | - | - | - | - | - | - | |
| 5 | ++++ | - | - | - | - | - | - | - | |
| 6 | ++++ | + | - | - | - | - | - | - | |
| 7 | ++++ | + | - | + | - | - | - | - | |
| 8 | ++++ | ++ | - | + | + | + | + | - | |
| 9 | ++++ | ++ | - | + | + | + | + | - | |
| 10 | ++++ | ++ | - | ++ | ++ | + | + | - | |
| 11 | ++++ | ++ | ++ | ++ | ++ | + | ++ | + | |
| 12 | ++++ | +++ | ++ | ++ | ++ | ++ | ++ | + | |
| 13 | ++++ | ++++ | +++ | +++ | ++ | ++ | ++ | + | |
| 14 | ++++ | ++++ | ++++ | +++ | +++ | ++ | ++ | ++ | |
| 15 | ++++ | ++++ | ++++ | ++++ | +++ | +++ | +++ | ++ | |
| 16 | ++++ | ++++ | ++++ | ++++ | +++ | +++ | +++ | ++ | |
| 17 | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | +++ | ++ | |
| 18 | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | ++ | |
| 19 | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | +++ | |
| 20 | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | +++ | |
| 21 | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ | ++++ |
("-" expression is organized perusal in contrast with the all-silicon rubber sheet in the table, and bacterium liquid is clarified fully; "+", " ++ ", " +++" are represented different bacterial turbidities respectively with " ++ ++ ", and wherein " ++ ++ " expression is in full accord with matched group)
(2) colony counting of biomembrane antibacterial
Take out each 5 on above-mentioned material diaphragm, wash planktonic bacteria off 5 times with 0.9% normal saline 2m1 flushing, place the test tube that contains the aseptic MH meat soup of 1ml, sonic oscillation (59KHz, 100%power, 15min) biomembrane is peeled off fully from the material diaphragm, draw the 100ul culture fluid, with 10 times of gradient serial dilutions to 10000 times, add in the aseptic plate with the 0.1ml amount respectively, and pour the MH agar 20ml that is cooled to 40 ℃ into, mixing, cooling is hatched 18h for rearmounted 37 ℃, observes the colony growth situation, does colony counting.The parallel repetition of above-mentioned experiment 3 times.Calculate actual clump count as follows: actual clump count (CFU/cm
3)=naked eyes can be counted clump count * extension rate/volume; Common logarithm (the lgCFU/cm for the treatment of excess syndrome border clump count
3) be standard colony counting unit.
Biomembrane bacterial colony count on the table 3 anti-infection nano medical composite material
| Material | Average actual colony counting (CFU/cm 3，x±s) | Average colony counting (lgCFU/cm 3，x±s) |
| Matched group | (6.98±1.25)×10 3 | 3.84±0.07 |
| Sample 1 | (6.54±0.60)×10 3 | 3.81±0.07 |
| Sample 2 | (5.72±0.66)×10 3 | 3.76±0.04 |
| Sample 3 | (3.54±0.56)×10 3 | 3.54±0.04 |
Matched group in the table: all-silicon rubber sheet; 1: one sublevel of sample is inserted the montorillonite clay silicone rubber infection composite of bromo geramine; 2: one sublevels of sample are inserted Quaternium 24 montorillonite clay silicone rubber infection composite; Sample 3: load miconazole montorillonite clay silicone rubber infection composite.Has tangible antibacterial action from bacteriostatic experiment medical use anti-infection polymeric material of the present invention as can be seen.
5, DSC test
DSC 204 F1 differential scanning calorimetric analysis instrument, sample 10.0mg, heating rate 20K/min,
Temperature range-80～200 ℃.The differential scanning calorimetric analysis instrument can be used for measuring the thermal property of material, can use crystallization temperature T
mExpress.The crystallization temperature Tm relation of medical use anti-infection polymeric material of the present invention and pure silicon rubber as shown in Figure 4.By curve 1 and 2 as can be known, the T of medical use anti-infection polymeric material of the present invention
m(36.7 ℃) are than the T of pure silicon rubber
m(39.1 ℃) have improved 2.4 ℃, and this is because the adding with crystal structure montorillonite clay makes T
mImprove, thus the resistance to elevated temperatures of raising material, and the thermal property of medical use anti-infection polymeric material is greatly improved.
6, Mechanics Performance Testing
Carry out the silicone rubber stretching experiment by GB528-82: pure silicon rubber and medical use anti-infection composite are made dumbbell shape, test on the RIGER universal tensile testing machine, draw speed is 500mm/min, hot strength, the elongation at break of record sample.
Carry out above sample anti tear experiment by GB530-81, sample is made perpendicular type, tests on the RIGER universal tensile testing machine, and draw speed is 500mm/min, the record tearing toughness.
All experimental temperatures are 23 ℃, and the test specimen number is 5, get its meansigma methods, and the result is as shown in table 4.Can obviously find out by table 4, the medical use anti-infection composite all is significantly improved than pure silicon rubber at hot strength, elongation at break and tearing toughness, the organo montmorillonite that load infection material is described evenly and has effectively entered between the silicone rubber, thereby improves its mechanical property.
The Mechanics Performance Testing of table 4 medical use anti-infection polymeric material of the present invention
| Hot strength (MPa) | Elongation at break (%) | Tearing toughness (N/mm) | |
| Pure silicon rubber | 9.30 | 24.31 | 750 |
| The medical use anti-infection composite | 9.38 | 25.40 | 775 |
7, TEM test
Medical use anti-infection polymeric material of the present invention is used tem observation, and as shown in Figure 5, the illiteracy holder soil of visible load antibacterials is evenly distributed in the silicone rubber.
From above-mentioned experimental result as can be known, polymeric material of the present invention not only can well be controlled the slow release of antibiotic substance, makes the infection time surpass 30 days, also has the thermodynamic property and the physical and mechanical property of material preferably.
Description of drawings
Fig. 1 is the XRD figure of montorillonite clay and modified montmorillonoid, and wherein curve 1 is the Na-montorillonite clay; Curve 2 is the montorillonite clays of load amikacin sulfate; Curve 3 is the montorillonite clays of load miconazole; Curve 4 is the montorillonite clays of load tetracycline; Curve 5 is the montorillonite clays of load hibitane;
Fig. 2 is the infrared spectrogram of montorillonite clay and modified montmorillonoid.Curve 1 is the Na-montorillonite clay among the figure; Curve 2 is the montorillonite clays of load amikacin sulfate; Curve 3 is the montorillonite clays of load miconazole; Curve 4 is the montorillonite clays of load tetracycline; Curve 5 is the montorillonite clays of load hibitane;
Fig. 3 is the XRD figure of medical use anti-infection composite.Wherein, curve 1 is the XRD figure of silastic material; Curve 2 medical use anti-infection polymeric material XRD figure of the present invention;
Fig. 4 is the DSC variation diagram of silicone rubber and polymeric material of the present invention, and wherein, curve 1 is the DSC figure of silastic material; Curve 2 medical use anti-infection polymeric material DSC figure of the present invention;
Fig. 5 is the TEM figure of medical use anti-infection polymeric material of the present invention.
The specific embodiment
Embodiment one
1. preparation Na-montorillonite clay: raw material montorillonite clay 20g is stirred in the saturated deionized water solution of 500mLNaCl, form steady suspension; Suspension stirred 5 hours down at 30 ℃, and sucking filtration is used the deionized water wash filtrate 3 times then.Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the Na-montorillonite clay.
2. preparation organo montmorillonite: Na-montorillonite clay 20g is stirred in 400mL deionized water disperse medium, form steady suspension; Then the 18g benzethonium chloride is added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains quaternary ammonium salt-modified organic illiteracy and takes off.
3. preparation load amikacin sulfate montorillonite clay: get the above-mentioned organo montmorillonite that obtains and mix with the amikacin sulfate of 15g, adding 200ml deionized water, with mixed liquor 40 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, and capillary electrophoresis detects filtrate does not have amikacin sulfate, is deposited in 60 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains montmorillonite load antibiotic substance carrier.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual sulfuric acid amikacin 6g with the filtering with microporous membrane of 0.45um.Be amikacin sulfate at 20g organo montmorillonite intercalation 9g, promptly to account for the complex percentage composition be 31.03% to antibacterials.
4. prepare load amikacin sulfate medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load amikacin sulfate montorillonite clay 3.5g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load amikacin sulfate medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 1.27g, benzethonium chloride 1.15g, amikacin sulfate 1.08g.
Get one section above-mentioned material sample, make 1cm * 1cm thin slice, carry out FT-IR (fourier-transform infrared) test: FT-IR tests the infrared spectrometer that used instrument is a U.S. Nicolct company, and test mode is taked surface reflectance, and the surface of sample is analyzed; Find 400～1333cm from the gained infrared spectrum
-1Finger print region has following characteristic absorption peak: 1030cm
-1Neighbouring is Si-O-Si skeletal vibration peak, 400～600cm
-1Internal vibration peak for silicon-oxy tetrahedron and alumina octahedral; At 1550cm
-1And 1650cm
-1Near stronger absworption peak is arranged, this is an amide groups in the amikacin sulfate molecular structure
Characteristic absorption peak, illustrate that load has the illiteracy holder soil of amikacin sulfate effectively to enter between the polymeric material.
Embodiment two
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: 5g Na-montorillonite clay is added the 100ml deionized water, stir and form steady suspension; Add 1g Dodecyl trimethyl ammonium chloride and 1g cetyl trimethyl ammonium bromide, 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Br up to filtrate
-(detect Br till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. preparation load econazole montorillonite clay: the above-mentioned modified organo montmorillonite that obtains is added the 50ml dehydrated alcohol, stir and form steady suspension, add the 2g econazole, stirred 4 hours under the room temperature, sucking filtration is used the absolute ethanol washing filtrate 4 times then.To constant weight, ball milling to particle diameter is 20-30 μ m to precipitate at 60 ℃ of following vacuum dryings, promptly obtains the montorillonite clay of load econazole.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 1g with the filtering with microporous membrane of 0.45um.Be econazole at 5g organo montmorillonite intercalation 1g, promptly to account for the complex percentage composition be 16.67% to antibacterials.
4. prepare load econazole medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load econazole montorillonite clay 3g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load econazole medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 1.78g, Dodecyl trimethyl ammonium chloride and cetyl trimethyl ammonium bromide be 0.71g altogether, econazole 0.5g.
Embodiment three
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: Na-montorillonite clay 30g is stirred in 600mL deionized water disperse medium, form steady suspension; Then 15g DDAC and 15g hexadecyltrimethylammonium chloride are added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. preparation load gentamycin montorillonite clay: the organo montmorillonite of above-mentioned preparation is added in the 300ml deionized water, stir and form steady suspension, add 4,000,000 units (about 40g) gentamycin, stirred 4 hours under the room temperature, sucking filtration is used the deionized water wash filtrate 4 times then.Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load gentamycin.Collect all filtrates, filtering with microporous membrane with 0.45um, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue gentamycin 28g, be gentamycin at 30g organo montmorillonite intercalation 12g, promptly to account for the complex percentage composition be 28.57% to antibacterials.
4. preparation load gentamycin covers medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load gentamycin montorillonite clay 3g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load gentamycin medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 1.07g, DDAC and hexadecyltrimethylammonium chloride be 1.07g altogether, gentamycin 0.86g.
Embodiment four
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: Na-montorillonite clay 10g in the 200mL deionized water for stirring, is formed steady suspension; Then the 6g hexadecyltrimethylammonium chloride is added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. preparation load miconazole nitrate montorillonite clay: get above-mentioned gained organo montmorillonite and mix with the 10g miconazole nitrate, adding dehydrated alcohol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have miconazole nitrate, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer and soak through and decide the ultraviolet light light absorption value, calculate residual drug 5.2g with the filtering with microporous membrane of 0.45um.Be miconazole nitrate at 10g organo montmorillonite intercalation 4.8g, promptly to account for the complex percentage composition be 32.43% to antibacterials.
4. preparation medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, above-mentioned miconazole nitrate load montorillonite clay g, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load miconazole nitrate medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 0.43g, hexadecyltrimethylammonium chloride 0.25g, miconazole nitrate 0.32g.
Embodiment five
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: Na-montorillonite clay 20g is stirred in 400mL deionized water disperse medium, form steady suspension; Then 10g DDAC and 10g benzethonium chloride are added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. prepare load hibitane antibiotic montmorillonite: get above-mentioned gained organo montmorillonite and mix, add dehydrated alcohol 200mL, with mixed liquor mechanical agitation reaction at room temperature 4 hours with the hibitane of 20g.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains montmorillonite load antibiotic substance carrier.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue hibitane 12g with the filtering with microporous membrane of 0.45um.Be hibitane at 20g organo montmorillonite intercalation 8g, promptly to account for the complex percentage composition be 28.57% to antibacterials.
4. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned hibitane antibiotic montmorillonite 5g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 1.78g, the DDAC benzethonium chloride is 1.78g altogether, hibitane 1.43g.
Embodiment six
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: Na-montorillonite clay 10g in the 200mL deionized water for stirring, is formed steady suspension; Then the 10g DDAC is added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 70 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the quaternary ammonium salts nano imvite.
3. preparation load hibitane montorillonite clay: get above-mentioned gained quaternary ammonium salts nano imvite and mix with the 12g hibitane, adding dehydrated alcohol 100ml is with mixed liquor stirring reaction 5 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load hibitane.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 7.2g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 4.8g, promptly to account for the complex percentage composition be 32.43% to antibacterials.
4. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 18g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 6.08g, DDAC 6.08g, hibitane 5.8g.
Embodiment seven
1. preparation Na-montorillonite clay; With embodiment one.
2. preparation organo montmorillonite: Na-montorillonite clay 8g is stirred in 160mL deionized water disperse medium, form steady suspension; Then the 8g DDAC is added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. preparation load antibiotic substance montorillonite clay: get above-mentioned gained organo montmorillonite and mix with the 10g miconazole nitrate, adding dehydrated alcohol 80ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have miconazole nitrate, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains load nitric acid and narrows the montorillonite clay of health azoles.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue miconazole nitrate 6g with the filtering with microporous membrane of 0.45 μ m.Be miconazole nitrate at 8g organo montmorillonite intercalation 4g, promptly to account for the complex percentage composition be 33.3% to antibacterials.
4. prepare load nitric acid miaow health medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 15g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load nitric acid miaow health medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 5g, DDAC 5g, nitric acid miaow health 5g.
Embodiment eight
1. preparation Na-montorillonite clay: with embodiment one
2. preparation organo montmorillonite: Na-montorillonite clay 5g is stirred in 100mL deionized water disperse medium, form steady suspension; Then the 5g benzethonium chloride is added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. preparation load antibiotic substance montorillonite clay: get above-mentioned gained organo montmorillonite and mix with the 5g amikacin sulfate, adding deionized water 50ml, with mixed liquor 40 ℃ of following stirring reactions of constant temperature 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have amikacin sulfate, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load amikacin sulfate.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual sulfuric acid amikacin 2.6g with the filtering with microporous membrane of 0.45um.Be amikacin sulfate at 5g organo montmorillonite intercalation 2.4g, it is 32.43% that antibacterials account for the complex percentage composition.
4. prepare load amikacin sulfate antibacterial medical polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 9g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load amikacin sulfate medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 3.04g, benzethonium chloride 3.04g, amikacin sulfate 2.92g.
Embodiment nine
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: 10g Na-montorillonite clay is added the 200ml deionized water, stir and form steady suspension; Add 8.0g Bardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains quaternary ammonium salt modified montmorillonoid.
3. preparation is covered the load antibiotic substance and taken off soil: get above-mentioned gained organo montmorillonite and mix with the 15g hibitane, adding dehydrated alcohol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains montmorillonite load antibiotic substance carrier.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 10.2g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 4.8g, it is 32.43% that antibacterials account for the complex percentage composition.
4. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 10g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 3.75g, Quaternium 24 3g, hibitane 3.24g.
Embodiment ten
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: Na-montorillonite clay 10g in the 500mL deionized water for stirring, is formed steady suspension; Then 4g DDAC and 4g Quaternium 24 are added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains quaternary ammonium salt modified montmorillonoid.
3. preparation load antibiotic substance montorillonite clay: get above-mentioned gained organo montmorillonite and mix with the 10g hibitane, adding dehydrated alcohol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load hibitane.Collect all filtrates,, get an amount of filtrate and use Biomat～5 type ultraviolet spectrophotometers mensuration ultraviolet light light absorption value, calculate residual drug 5.2g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 4.8g, it is 32.43% that antibacterials account for the complex percentage composition.
4. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 12g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 4.51g, the DDAC Quaternium 24 is 3.6g altogether, hibitane 3.89g.
Embodiment 11
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: with embodiment one.
3. preparation load miconazole nitrate montorillonite clay: with embodiment one.
4. prepare load miconazole nitrate medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 10g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load miconazole nitrate medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 4.3g, hexadecyltrimethylammonium chloride 2.5g, miconazole nitrate 3.2g.
Embodiment 12
1. preparation Na-montorillonite clay, preparation organo montmorillonite: with embodiment one.
2. preparation load antibiotic substance montorillonite clay: the organo montmorillonite of getting the above-mentioned gained of 10g mixes with the amikacin sulfate of 8g, the montorillonite clay of adding 100ml deionized water disperse medium, with mixed liquor 40 ℃ of following stirring reactions of constant temperature 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, is deposited in 60 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load amikacin sulfate.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual sulfuric acid amikacin 5g with the filtering with microporous membrane of 0.45 μ m.Be amikacin sulfate at 10g organo montmorillonite intercalation 3g, it is 23.08% that antibacterials account for the complex percentage composition.
3. prepare load amikacin sulfate medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 15g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load amikacin sulfate medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 7.2g, hexadecyltrimethylammonium chloride 4.33g, amikacin sulfate 3.46g.
Embodiment 13
1. with embodiment one: preparation Na-montorillonite clay, preparation organo montmorillonite
2. preparation load antibiotic substance montorillonite clay: get a certain amount of organo montmorillonite 10g and mix with the hibitane of 5g, adding dehydrated alcohol 100ml disperse medium is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load hibitane.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue hibitane 3g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 2g, it is 16.67% that antibacterials account for the complex percentage composition.
3. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 15g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 7.8g, hexadecyltrimethylammonium chloride 4.69g, hibitane 2.5g.
Embodiment 14
1. preparation Na-montorillonite clay, preparation organo montmorillonite: with embodiment one.
2. preparation load antibiotic substance montorillonite clay: get a certain amount of organo montmorillonite 10g and mix with the hibitane of 8g, adding dehydrated alcohol 100ml disperse medium is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load hibitane.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue hibitane 4g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 4g, it is 28.57% that antibacterials account for the complex percentage composition.
3. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 5g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 2.93g, hexadecyltrimethylammonium chloride 0.64g, hibitane 1.43g.
Embodiment 15
1. preparation Na-montorillonite clay: with embodiment 1.
2. preparation organo montmorillonite: 10g Na-montorillonite clay is added the 200ml deionized water, stir and form steady suspension; Add 6.0g Bardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the quaternary ammonium salts montorillonite clay.
3. preparation load hibitane nano imvite: above-mentioned gained quaternary ammonium salts nano imvite is mixed with the 10g hibitane, and adding ethanol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the washing with alcohol filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains load hibitane nano imvite.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 6.2g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 3.8g, it is 27.53% that antibacterials account for the complex percentage composition.
4. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, above-mentioned hibitane intercalation nano montorillonite clay 5g, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 2.26g, Quaternium 24 1.36g, hibitane 1.38g.
Embodiment 16
1. preparation Na-montorillonite clay: with embodiment 1.
2. preparation organo montmorillonite: Na-montorillonite clay 10g in the 200mL deionized water for stirring, is formed steady suspension; Then the 10g DDAC is added in the suspension; With mixed liquor 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the quaternary ammonium salts nano imvite.
3. preparation load tetracycline nano imvite: above-mentioned gained quaternary ammonium salts nano imvite is mixed with the 10g tetracycline, and adding ethanol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the washing with alcohol filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have tetracycline, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains load tetracycline nano imvite.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 6g with the filtering with microporous membrane of 0.45 μ m.Be tetracycline at 10g organo montmorillonite intercalation 4g, it is 28.57% that antibacterials account for the complex percentage composition.
4. prepare load tetracycline medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, above-mentioned tetracycline intercalation nano montorillonite clay 10g, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load tetracycline medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 3.57g, Quaternium 24 3.57g, tetracycline 2.86g.
Embodiment 17
1. preparation Na-montorillonite clay: with embodiment 1.
2. preparation organo montmorillonite: 10g Na-montorillonite clay is added the 200ml deionized water, stir and form steady suspension; Add 6.0g Bardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the quaternary ammonium salts montorillonite clay.
3. preparation load doxycycline nano imvite: above-mentioned gained quaternary ammonium salts nano imvite is mixed with the 10g doxycycline, and adding ethanol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the washing with alcohol filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of doxycycline intercalation nano.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 6.2g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 3.8g, it is 27.54% that antibacterials account for the complex percentage composition.
4. prepare load hibitane medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, above-mentioned doxycycline intercalation nano montorillonite clay 5g, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load doxycycline medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 2.26g, Quaternium 24 1.35g, doxycycline 1.38g.
Embodiment 18
1. preparation Na-montorillonite clay: with embodiment 1.
2. preparation organo montmorillonite: 10g Na-montorillonite clay is added the 200ml deionized water, stir and form steady suspension; Add 6.0g Bardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Cl up to filtrate
-(detect Cl till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the quaternary ammonium salts montorillonite clay.
3. preparation load rifampicin nano imvite: above-mentioned gained quaternary ammonium salts nano imvite is mixed with the 10g rifampicin, and adding ethanol 100ml is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the washing with alcohol filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains load rifampicin nano imvite.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 6.2g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 3.8g, it is 27.54% that antibacterials account for the complex percentage composition.
4. prepare load rifampicin medical use anti-infection polymeric material: get medical methyl vinyl silicone rubber 100g, above-mentioned rifampicin intercalation nano montorillonite clay 5g, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load rifampicin medical use anti-infection polymeric material, methyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 2.26g, Quaternium 24 1.35g, rifampicin 1.38g.
Embodiment 19
1. preparation Na-montorillonite clay: with embodiment one.
2. preparation organo montmorillonite: 5g Na-montorillonite clay is added the 100ml deionized water, stir and form steady suspension; Add 1g Dodecyl trimethyl ammonium chloride and 1g cetyl trimethyl ammonium bromide, 85 ℃ of following stirring reactions 4 hours.Sucking filtration uses the deionized water wash filtrate for several times then, does not have Br up to filtrate
-(detect Br till detecting with silver nitrate aqueous solution
-).Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains organo montmorillonite.
3. preparation load econazole montorillonite clay: the above-mentioned modified organo montmorillonite that obtains is added the 50ml dehydrated alcohol, stir and form steady suspension, add the 2g econazole, stirred 4 hours under the room temperature, sucking filtration is used the absolute ethanol washing filtrate 4 times then.Be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load econazole.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 1g with the filtering with microporous membrane of 0.45 μ m.Be econazole at 5g organo montmorillonite intercalation 1g, it is 16.67% that antibacterials account for the complex percentage composition.
4. prepare load econazole medical use anti-infection polymeric material: get medical dimethyl base silicone rubber 100g, the above-mentioned load econazole montorillonite clay 15g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load econazole medical use anti-infection polymeric material, dimethyl base silicone rubber 100g wherein, Na-montorillonite clay 8.93g, Dodecyl trimethyl ammonium chloride and cetyl trimethyl ammonium bromide be 3.57g altogether, econazole 2.5g.
1. preparation Na-montorillonite clay, preparation organo montmorillonite: with embodiment one.
2. preparation load antibiotic substance montorillonite clay: get a certain amount of organo montmorillonite 10g and mix with the hibitane of 8g, adding dehydrated alcohol 100ml disperse medium is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and the UV spectrophotometer measuring filtrate does not have hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load hibitane.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue hibitane 4g with the filtering with microporous membrane of 0.45 μ m.Be hibitane at 10g organo montmorillonite intercalation 4g, it is 28.57% that antibacterials account for the complex percentage composition.
3. prepare load hibitane medical use anti-infection polymeric material: get medical methyl phenyl vinyl silicone rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 5g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3m, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, methyl phenyl vinyl silicone rubber 100g wherein, Na-montorillonite clay 2.23g, hexadecyltrimethylammonium chloride 1.33g, hibitane 1.43g.
Embodiment 21
1. preparation Na-montorillonite clay, preparation organo montmorillonite: with embodiment one.
2. preparation load antibiotic substance montorillonite clay: get a certain amount of organo montmorillonite 10g and mix with the amikacin of 8g, adding dehydrated alcohol 100m1 disperse medium is with mixed liquor stirring reaction 4 hours at room temperature.Sucking filtration uses the absolute ethanol washing filtrate for several times then, and UV spectrophotometer measuring filtrate amikacin is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains the montorillonite clay of load amikacin.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue amikacin 4g with the filtering with microporous membrane of 0.45 μ m.Be amikacin at 10g organo montmorillonite intercalation 4g, it is 28.57% that antibacterials account for the complex percentage composition.
3. prepare load amikacin medical use anti-infection polymeric material: get medical fluorosioloxane rubber 100g, the above-mentioned load antibiotic substance montorillonite clay 5g that obtains, with in 160 pairs of roller mills of Φ (152 * 305mm) carry out mixing, friction ration is 1: 1.42, two roll temperatures are below 40 ℃, mixing evenly after, go out the thin slice of 2-3mm, parked 24 hours.Get vulcanizing agent DCP 2g then, 25 tons of hydraulic flat forcing press top boards sample preparation with the flat board heating, 170 ℃ of curing temperatures, cure time 10 minutes, obtain load hibitane medical use anti-infection polymeric material, fluorosioloxane rubber 100g wherein, Na-montorillonite clay 2.23g, hexadecyltrimethylammonium chloride 1.33g, amikacin 1.43g.
Claims (7)
1, a kind of medical use anti-infection polymeric material of the present invention is made up of the component of following weight portion: 100 parts of high-temperature silicon disulfide rubbers, 0.43～9 part of Na-montorillonite clay, 0.25～6.2 part of quaternary ammonium salts agent, 0.3～5.8 part of antibacterials; Wherein the Na-montorillonite clay is made by following method: use the saturated deionized water of NaCl with the Ca in the montorillonite clay
2+, Mg
2+Be replaced as Na
+, filter, wash, be dried to constant weight then, promptly.
2, according to the described a kind of medical use anti-infection polymeric material of claim 1, it is characterized in that the proportioning of each component is: 100 parts of high-temperature silicon disulfide rubbers, 5～9 parts of Na-montorillonite clays, 1～5 part of quaternary ammonium salts agent, 3～5 parts of antibacterials.
3,, it is characterized in that described high-temperature silicon disulfide rubber is dimethyl silicone rubber, Methylethyl silicone rubber, methyl phenyl vinyl silicone rubber or fluorosioloxane rubber according to claim 1 or 2 described a kind of medical use anti-infection polymeric materials.
4,, it is characterized in that described high-temperature silicon disulfide rubber is a Methylethyl silicone rubber according to claim 1 or 2 described a kind of medical use anti-infection polymeric materials.
5, according to claim 1 or 2 described a kind of medical use anti-infection polymeric materials, it is characterized in that described quaternary ammonium salts agent can be Quaternium 24, DDAC, benzethonium chloride wherein one or more.
6,, it is characterized in that described antibacterials can be econazole nitrate, miconazole nitrate, amikacin sulfate, tetracycline, rifampicin, gentamycin, doxycycline or hibitane according to claim 1 or 2 described a kind of medical use anti-infection polymeric materials.
7, the preparation method of claim 1 or 2 described a kind of medical use anti-infection polymeric materials, this method is made up of the following step:
(1) preparation of Na-montorillonite clay: montorillonite clay is stirred in 10～30 times the saturated deionized water solution of NaCl, form steady suspension, stirred 5～6 hours down at 30～40 ℃ again, sucking filtration, filter thing with deionized water wash, then at 70 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20～30 μ m;
(2) preparation of organo montmorillonite: with the deionized water for stirring of step (1) gained Na-montorillonite clay, form suspension, add intercalator again at 20 times, stirred 4 hours down at 85 ℃, filter, washing filter thing is removed halide ion, and dry in vacuum drying oven then, ball milling to particle diameter is 20-50 μ m;
(3) preparation of infection load montorillonite clay: step (2) gained organo montmorillonite is stirred in 10 times deionized water or dehydrated alcohol, form suspension, add the infection material again, stirred 4 hours down for 40 ℃ in room temperature or constant temperature, filter, dry in vacuum drying oven then, ball milling to particle diameter is 20-50 μ m;
(4) compound: that step (3) gained infection load montorillonite clay and high-temperature silicon disulfide rubber is compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101229013A CN100490908C (en) | 2006-10-23 | 2006-10-23 | The medical use anti-infection polymeric material and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101229013A CN100490908C (en) | 2006-10-23 | 2006-10-23 | The medical use anti-infection polymeric material and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1943804A true CN1943804A (en) | 2007-04-11 |
| CN100490908C CN100490908C (en) | 2009-05-27 |
Family
ID=38043594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101229013A Expired - Fee Related CN100490908C (en) | 2006-10-23 | 2006-10-23 | The medical use anti-infection polymeric material and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100490908C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965639A (en) * | 2013-01-25 | 2014-08-06 | 圣光医用制品有限公司 | Antibacterial anticoagulant high polymer material, and preparation method and application thereof |
| CN105462261A (en) * | 2015-12-22 | 2016-04-06 | 合肥仲农生物科技有限公司 | Anti-infection nano composite material |
| CN105454232A (en) * | 2016-01-25 | 2016-04-06 | 郑叶芳 | Montmorillonite-based antibacterial agent and preparation method thereof |
| CN105713256A (en) * | 2016-03-23 | 2016-06-29 | 苏州市贝克生物科技有限公司 | Corrosion-resistant medical rubber and preparation method thereof |
| CN106012503A (en) * | 2015-09-02 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Montmorillonite coated polyamide composite high temperature resistant material |
| CN107412873A (en) * | 2017-05-02 | 2017-12-01 | 北京化工大学 | A kind of high anti-tear antibiotic property breast prosthesis impervious barrier material preparation method |
| CN114191688A (en) * | 2021-12-23 | 2022-03-18 | 山东百多安医疗器械股份有限公司 | Adjustable defecation anal tube with prompt function and manufacturing method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11771716B2 (en) | 2019-06-12 | 2023-10-03 | King Fahd University Of Petroleum And Minerals | Nanoclays for the control of melanoma cell proliferation and cell viability |
-
2006
- 2006-10-23 CN CNB2006101229013A patent/CN100490908C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965639A (en) * | 2013-01-25 | 2014-08-06 | 圣光医用制品有限公司 | Antibacterial anticoagulant high polymer material, and preparation method and application thereof |
| CN103965639B (en) * | 2013-01-25 | 2018-05-01 | 圣光医用制品有限公司 | Antibiosis anticoagulative blood high molecular material and its preparation method and application |
| CN106012503A (en) * | 2015-09-02 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Montmorillonite coated polyamide composite high temperature resistant material |
| CN105462261A (en) * | 2015-12-22 | 2016-04-06 | 合肥仲农生物科技有限公司 | Anti-infection nano composite material |
| CN105454232A (en) * | 2016-01-25 | 2016-04-06 | 郑叶芳 | Montmorillonite-based antibacterial agent and preparation method thereof |
| CN105713256A (en) * | 2016-03-23 | 2016-06-29 | 苏州市贝克生物科技有限公司 | Corrosion-resistant medical rubber and preparation method thereof |
| CN107412873A (en) * | 2017-05-02 | 2017-12-01 | 北京化工大学 | A kind of high anti-tear antibiotic property breast prosthesis impervious barrier material preparation method |
| CN114191688A (en) * | 2021-12-23 | 2022-03-18 | 山东百多安医疗器械股份有限公司 | Adjustable defecation anal tube with prompt function and manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100490908C (en) | 2009-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1943804A (en) | The medical use anti-infection polymeric material and its preparation method | |
| Yan et al. | Biosynthesis of bacterial cellulose/multi-walled carbon nanotubes in agitated culture | |
| Barot et al. | Physicochemical and biological assessment of silver nanoparticles immobilized Halloysite nanotubes-based resin composite for dental applications | |
| CN1301751C (en) | Infection-resistant medical devices | |
| Etemadi et al. | Study on the reinforcing effect of nanodiamond particles on the mechanical, thermal and antibacterial properties of cellulose acetate membranes | |
| Song et al. | Preparation of the superhydrophobic nano-hybrid membrane containing carbon nanotube based on chitosan and its antibacterial activity | |
| CN105596367B (en) | Using chitosan-poloxamer as nano silver antimicrobial gel of gel-type vehicle and its preparation method and application | |
| CN109096740A (en) | Antibacterial antistatic TPU film material and preparation method thereof | |
| CN113016823B (en) | Preparation method of photo-thermal antibacterial near-infrared bimetallic nanoparticles | |
| CN1668191A (en) | Skin cleanser compositions and methods of use | |
| CN111793336B (en) | Preparation method of antibacterial polylactic acid master batch | |
| Han et al. | Degradable GO-Nanocomposite hydrogels with synergistic photothermal and antibacterial response | |
| CN111793337B (en) | Antibacterial polylactic acid master batch and application thereof | |
| TWI666270B (en) | An antibacterial composite and method for preparing the same | |
| Singh et al. | Macromolecular chitosan/ciprofloxacin pro-drugs: synthesis, physico-chemical and biological assess-ment for drug delivery systems | |
| CN106145216A (en) | One breeding enterprise sewage-treating agent and its preparation method and application | |
| Smirnov et al. | Study of the structures of biofilms formed by Salmonella typhimurium bacteria on abiotic surfaces by the methods of light and transmission electron microscopy | |
| CN1850289A (en) | Antibactrial wound suturing-free tissue adhesive | |
| CN1048628C (en) | Prepn of cyclopropyloxacini injecta | |
| TWI506269B (en) | Use of fluorescent saccharide-based derivative | |
| CN1765368A (en) | Anti-infection nano montmorillonite and its preparation method | |
| Hamid et al. | Synthesis of Acrylamide-Graphene Oxide Polymer for Antibacterial Application | |
| CN1850290A (en) | Wound suturing-free tissue adhesive | |
| CN1739507A (en) | Medicine composition for treating mixed infectious disease | |
| CN1743007A (en) | Inflammation-resistant modified imvite and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090527 Termination date: 20111023 |