CN100522180C - Anti-infection nano montmorillonite and its preparation method - Google Patents
Anti-infection nano montmorillonite and its preparation method Download PDFInfo
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- CN100522180C CN100522180C CNB2005100365533A CN200510036553A CN100522180C CN 100522180 C CN100522180 C CN 100522180C CN B2005100365533 A CNB2005100365533 A CN B2005100365533A CN 200510036553 A CN200510036553 A CN 200510036553A CN 100522180 C CN100522180 C CN 100522180C
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Abstract
The invention relates to an infection-resisting nano montmorillonite and method for preparation, which comprises 100 weight parts of montmorillonite, 10-60 weight parts of quaternary ammonium salt, and 10-48 weight parts of infection-resisting substance. The invention also discloses its preparing process.
Description
Technical field
The present invention relates to field of inorganic materials, particularly infection inorganic material and preparation method thereof.
Background technology
Montmorillonitum (MMT) be bentonite again, belongs to a kind of mineral Chinese medicine.The eighties in 20th century, American-European countries was used for pharmaceutical excipient with Montmorillonitum, and included the U.S., Europe and British Pharmacopoeia in.The Western medicine dioctahedral smectite (Smeeta) (being Montmorillonitum) that France IPSEN drugmaker produces is the medicine that is applied to treat digestive system disease in recent years.Montmorillonitum is widely used in clinical as protection digestive tract mucosa and the medicine that reaches complementary infection purpose by the absorption antibacterial; its pharmacological action is: (1) Montmorillonitum granule tool lamellar structure and heterogeneity CHARGE DISTRIBUTION; toxin to the virus in the digestive tract, antibacterial and generation thereof has fixedly inhibitory action; and Montmorillonitum does not enter blood circulation; excrete together with fixed antibacterial about 6h, take free of toxic effects for a long time.(2) Montmorillonitum combines by electrostatic interaction with mucous glycoprotein, and can the thickness of rete malpighii be increased by the local irritant effect of gastrointestinal mucosal being increased the synthetic quantity of mucous glycoprotein, toughness strengthens, strengthened the barrier function of mucosa, improved the defense function of mucosal barrier attack factor.(3) can balance parasitic flora of Montmorillonitum and amount that digestive tract endocrine type immunoglobulin (SIgA) is repaired increase, thereby improve the immunologic function of health, the invasion and attack of the opposing various attack factor.(4) Montmorillonitum has antiacid effect, and the pepsin in medicine pepsin and the gastric juice is had antagonism.(5) Montmorillonitum can activate proconvertin, VIII, XII, has the effect of digestive tract local hemostasis.
Though Montmorillonitum has certain specific surface area and cation exchange capacity, and absorption property is better, but the hydrophilic that Montmorillonitum surface silicon oxide structure is extremely strong and the hydrolysis of interlayer cation make its surface have the thin moisture film of one deck usually, and can not adsorb hydrophobic Organic substance (as oils and fats) effectively.
Intercalation is compound to be a kind of most important method of preparation nano material.Natural Montmorillonitum is a phyllosilicate, and its molecule space has bigger hole, and its construction unit is by two silicon-oxy tetrahedrons, and silica of sandwich is octahedra to be constituted, and its chemical formula is (M+nH
2O) (Al
4-yMgy) Si
8O
20(OH)
4(M=Na wherein
+, Ca
2+, Mg
2+Or the like), its structure lamella is a nanoscale, about 1 nanometer of its elementary layer spacing is easily carried out exchange reaction with inorganic, alkyl quaternary ammonium salts or other organic cations and neutral molecule and is generated the Montmorillonitum (nanometer Montmorillonitum) that organises, make its purposes more extensively, performance is unique more.Present Montmorillonitum by the graft process preparation, its purpose is to improve the mechanical performance and the hot property of Montmorillonitum mostly, be mainly used in industries such as printing ink, high-grade paint, engineering plastics, and to using organic cation such as alkyl quaternary ammonium salts and infection material intercalation Montmorillonitum and preparation method thereof not to appear in the newspapers.
Summary of the invention
The object of the present invention is to provide a kind of anti-infection nano montmorillonite.
Another object of the present invention provides the preparation method of anti-infection nano montmorillonite.
Anti-infection nano montmorillonite of the present invention consists of (weight portion)
Montmorillonitum: 100;
Intercalator: 10～60;
Infection material: 10～48.
Montmorillonitum of the present invention is the Na-Montmorillonitum.The Na-Montmorillonitum can prepare with following method: the raw material Montmorillonitum (is mainly contained Na
+, Ca
2+, Mg
2+Ion) stirs in 10 parts of saturated deionized water solutions of the NaCl 100-300 part, form stable aaerosol solution; Aaerosol solution stirred 5～6 hours down at 30～40 ℃.Sucking filtration is used the deionized water wash filtrate then.Be deposited in 70 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20～30 μ m, promptly obtains the Na-Montmorillonitum.
Intercalator used in the present invention can be a quaternary ammonium salt.Quaternary ammonium salt commonly used has Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, hexadecyltrimethylammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl hexadecyldimethyl benzyl ammonium ammonium chloride, two dodecyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride (DTAB), Tetradecyl Trimethyl Ammonium Bromide, cetyl trimethyl ammonium bromide (CTAB), the octadecyl trimethylammonium bromide, octadecyl hexadecyldimethyl benzyl ammonium ammonium bromide, didodecyldimethylammbromide bromide, alkyl dimethyl benzyl and two alkyl-dimethyl ammonium chloride (Bardac 208M), DDAC (Bardac 2280), Quaternium 24 (Bardac LF-80), octyl-decyl alkyl dimethyl ammonium chloride/Quaternium 24 (Bardac 2080), diisobutyl phenoxy group ethoxyethyl dimethyl benzyl list water ammonium chloride (Hyamine 1622 Crystals, Benzethonium Chloride benzethonium chloride) wherein one or more.Intercalator preferably Quaternium 24 (Bardac LF-80), two alkyl-dimethyl ammonium chloride (Bardac 208M), DDAC (Bardac2280), didecyl dimethyl ammonium bromide, benzethonium chloride wherein one or more.Preferably 25～60 parts of quaternary ammonium salt consumptions of the present invention (weight portion/100 weight portion Na-Montmorillonitums).
Infection material of the present invention is for medically using the infection material always.Infection material of the present invention can be antifungal such as miconazole nitrate, econazole nitrate; Can be aminoglycosides infection materials such as amikacin sulfate, gentamycin; Can be Tetracyclines infection materials such as tetracycline, doxycycline; Can also be sulphuric acid hibitane, rifampicin.Infection material used in the present invention preferably econazole nitrate, miconazole nitrate, amikacin sulfate, tetracycline, rifampicin is wherein a kind of.Preferably 15～40 parts of infection material consumptions of the present invention (weight portion/100 weight portion Na-Montmorillonitums).
Anti-infection nano montmorillonite preparation method of the present invention is the solution intercalation complex technique of using always.
Anti-infection nano montmorillonite preparation method of the present invention, contain following steps:
A. (the deionized water quality: stirring forms stable suspersion solution Na-Montmorillonitum quality=10: 1～30: 1) at deionized water with the Na-Montmorillonitum; Add intercalator, stir intercalation after 2～8 hours down, filter at 80～90 ℃, washing filter thing, dripping silver nitrate in cleaning mixture does not have precipitation.With intercalation Montmorillonitum drying, ball milling after the washing, obtaining particle diameter is the intercalation nano Montmorillonitum of 20～30 μ m.
B. the intercalation nano Montmorillonitum with above-mentioned gained stirs in solvent, forms stable suspersion solution; Add the infection material, stir intercalation 2～8 o'clock at normal temperatures after, filter, remove and desolvate; Filter thing with solvent wash then, intercalation Montmorillonitum drying, ball milling with after the washing obtain the anti-infection nano montmorillonite that particle diameter is 20～30 μ m.
Anti-infection nano montmorillonite preparation method of the present invention stirs preferably 85 ℃ of intercalation temperature among the step a, stirring the intercalation time better is 3～6 hours, preferably 4 hours.In step a, the deionized water quality: the Na-Montmorillonitum is best in quality to be 20: 1.
Anti-infection nano montmorillonite preparation method of the present invention, solvent for use is a kind of in ethanol (dehydrated alcohol), deionized water, the chloroform among the step b, solvent quality: Na-Montmorillonitum quality is 5: 1～50: 1, preferably 10: 1.Stirring the intercalation time in step b better is 3～5 hours, preferably 4 hours.
Insert quaternary ammonium salt and infection material between montmorillonite layer, the preparation anti-infection nano montmorillonite improves the Montmorillonitum specific surface area, strengthens the adsorptivity to antibacterial, virus and toxin etc.; Owing to, strengthen the directed anti-infectious function of anti-infectives to the absorption of antibacterial, virus.Montmorillonitum is as infection material carrier, and the slow release of control infection material strengthens the anti-infective action effect.Montmorillonitum is not absorbed by digestive tract simultaneously, and the anti-infectives of intercalation is not absorbed and enters blood circulation, reduces the side effect of anti-infectives to human body.
Quaternary ammonium salts agent of the present invention is modified montmorillonite used, and the distance after the modification between montmorillonite layer increases, and becomes lipophile by hydrophilic, and organic absorption properties such as oils and fats are strengthened.
For a better understanding of the present invention, the infection of following description of test anti-infection nano montmorillonite of the present invention, slowly discharge and control the oils and fats effect.
1, the fungistatic effect of infection material intercalation nano Montmorillonitum
On different MH culture medium, inoculate escherichia coli, staphylococcus aureus, Candida albicans respectively.On the MH culture medium, beat the hole of 2mm diameter according to the sterile working, the infection material intercalation nano Montmorillonitum of quality such as precision takes by weighing and the powder (in contrast) of Montmorillonitum, click and enter respectively in the hole of MH culture medium, in incubator 37 ℃ cultivate 24h after, observe the bacterial growth situation, parallel test 3 times is write down its antibacterial ring size respectively, calculating mean value.
The biocidal property effect of table 1 intercalation nano Montmorillonitum
Anti-infection nano montmorillonite suppresses the escherichia coli grown cultures and the results are shown in Figure 3.
The result: Montmorillonitum, CTAB intercalation nano Montmorillonitum do not have biocidal property, and other quaternary ammonium salts or infection material intercalation Montmorillonitum have biocidal property.
2. cetyl trimethyl ammonium bromide (CTAB) intercalation nano Montmorillonitum is to the absorption of antibacterial
Get conical flask and add a certain amount of cetyl trimethyl ammonium bromide intercalation nano Montmorillonitum, Montmorillonitum is as blank, add a certain amount of bacterium liquid more respectively, jolting 20 minutes, leave standstill after 6 hours and draw supernatant, behind the doubling dilution on the MH culture medium viable bacteria plate count, calculate average clump count.Be calculated as follows both adsorption rates to staphylococcus aureus; Adsorption rate=(bacterial concentration in bacterial concentration in the 1-developmental tube supernatant/blank pipe supernatant) * 100%.
Table 2 MMT and CTAB/MMT nano composite material are to the absorption of staphylococcus aureus
The result: cetyl trimethyl ammonium bromide intercalation nano Montmorillonitum to the adsorption rate of antibacterial apparently higher than Montmorillonitum to the antibacterial adsorption rate.
3, the releasing effect of infection material intercalation nano Montmorillonitum antibacterials.
3 parts of the infection material intercalation nano Montmorillonitums of quality such as take by weighing,, be suspended in 0.9% saline (perhaps coordinative solvent) with the filter paper parcel, soak 24h, 48h, 72h, ... take out, with ultraviolet spectrophotometer test infection material release time be 2-72 hour.
The slow release result of the medical compound substance of table 3 UV spectrophotometer measuring miconazole nanometer
4, oily nanometer Montmorillonitum absorb oil of control and protein effect.
Albumin (ALB) adsorption experiment method precision respectively takes by weighing: CTAB intercalation nano Montmorillonitum, each 100mg of Montmorillonitum, add human albumin 2ml respectively, and 37 ℃ of concussions of constant temperature 3 hours, 4500r/min draws supernatant after centrifugal 10 minutes to be measured.
Detection method adopts the blood automatic biochemical analyzer to measure the variation of absorption front and back albumin (g/L), and adsorption rate is calculated as follows:
A％＝(C0-Ct)/C0×100％
C0: the content of absorption prealbumin (ALB);
Ct: absorption t content of ALB in the serum after the time.
Table 4 different material is to albuminous absorption result
1. blank group measured value before adsorbing; 2. Montmorillonitum adsorbs the back measured value; 3CTAB intercalation nano Montmorillonitum absorption back value
Vegetable oil absorption and detection method: get a centrifuge tube before the experiment, weigh, precision takes by weighing a certain amount of Montmorillonitum, CTAB intercalation nano Montmorillonitum then, join in the centrifuge tube, draw a certain amount of vegetable oil and add centrifuge tube, seal, jolting centrifuge tube certain hour leaves standstill, centrifugal, abandoning supernatant, reuse organic solvent washing centrifuge tube, intercalation Montmorillonitum, filter, centrifuge tube and filter paper are put into vacuum drying oven and are dried to constant weight, and taking-up is weighed, calculate the recruitment of intercalation Montmorillonitum, be the amount of its absorption vegetable oil.
Table 5 nano composite material is to the absorption result of vegetable oil
The result: CTAB intercalation Montmorillonitum, DDAC (Bardac 2280) intercalation Montmorillonitum to the adsorptivity of vegetable oil apparently higher than the adsorptivity of Montmorillonitum to vegetable oil.
Description of drawings
Fig. 1 is the infrared spectrogram of Montmorillonitum.Curve 1 is the infrared spectrogram of Na-Montmorillonitum among the figure; Curve 2 is infrared spectrograms of cetyl trimethyl ammonium bromide intercalation Montmorillonitum; Curve 3 is infrared spectrograms of cetyl trimethyl ammonium bromide/miconazole Montmorillonitum.
Fig. 2 is the XRD figure of Montmorillonitum.Curve 1 is the XRD figure of Na-Montmorillonitum among the figure; Curve 2 is XRD figure of cetyl trimethyl ammonium bromide intercalation Montmorillonitum; Curve 3 is XRD figure of cetyl trimethyl ammonium bromide/miconazole Montmorillonitum.
Fig. 3 is the inhibition escherichia coli grown cultures result of Montmorillonitum; 1 is that Dodecyl trimethyl ammonium chloride intercalation Montmorillonitum suppresses escherichia coli grown cultures result among the figure; The 2nd, cetyl trimethyl ammonium bromide intercalation Montmorillonitum suppresses escherichia coli grown cultures result; The 3rd, cetyl trimethyl ammonium bromide and miconazole intercalation Montmorillonitum suppress escherichia coli grown cultures result; The 4th, F-80 and miconazole intercalation Montmorillonitum suppress escherichia coli grown cultures result.
The specific embodiment
Following examples make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
1. prepare the Na-Montmorillonitum: the raw material Montmorillonitum (is mainly contained Na
+, Ca
2+, Mg
2+Ion)
20g stirs in the saturated deionized water solution of 500mLNaCl, forms stable aaerosol solution; Aaerosol solution stirred 5 hours down at 35 ℃.Sucking filtration is used the deionized water wash filtrate 4 times then.Be deposited in 70 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20～30 μ m, promptly obtains Na-Montmorillonitum (its infrared spectrum is seen Fig. 1, and its XRD figure is seen Fig. 2).
2. preparation nanometer Montmorillonitum: 10g Na-Montmorillonitum is added the 200ml deionized water, stir and form stable aaerosol solution; Add the 6g cetyl trimethyl ammonium bromide, 85 ℃ of following stirring reactions 5 hours.Sucking filtration uses the deionized water wash filtrate for several times then, removes halide ion wherein, 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 13g quaternary ammonium salts nanometer Montmorillonitum (its infrared spectrum is seen Fig. 1, and its XRD figure is seen Fig. 2).Confirmed 50% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and gravimetric analysis.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: 10g Na-Montmorillonitum is added the 180ml deionized water for stirring form stable aaerosol solution; Add 4.0g Bardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 5 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 nanometer Montmorillonitum.Collect all filtrates, with the filtering with microporous membrane of 0.45um, get an amount of filtrate, use Biomat-5 type ultraviolet spectrophotometer and measure the ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2.2g, promptly Quaternium 24 is at 10g Na-Montmorillonitum intercalation 1.8g.Confirmed 45% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: 10g Na-Montmorillonitum is added the 200ml deionized water, stir and form stable aaerosol solution; Add 6.0gBardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 5 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 Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt amount 2.7g with the filtering with microporous membrane of 0.45um.Be that Quaternium 24 is at 10g Na-Montmorillonitum intercalation 3.3g.Confirmed 55% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: 10g Na-Montmorillonitum is added the 200ml deionized water, stir and form stable aaerosol solution; Add 8.0g Bardac LF-80 (Quaternium 24), 85 ℃ of following stirring reactions 5 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 Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 3.2g with the filtering with microporous membrane of 0.45um.Be Quaternium 24 at 10g Na-Montmorillonitum intercalation 4.8g, confirmed 60% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 5
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 250mL deionized water for stirring, is formed stable aaerosol solution; Then the 4g Dodecyl trimethyl ammonium chloride is added in the aaerosol solution; With mixed liquor 90 ℃ of following stirring reactions 8 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2g with the filtering with microporous membrane of 0.45um.Be Dodecyl trimethyl ammonium chloride at 10g Na-Montmorillonitum intercalation 2g, confirmed 50% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. the preparation quadratic-layer is inserted nanometer Montmorillonitum: the quaternary ammonium salt-modified nanometer Montmorillonitum of above-mentioned gained is mixed with the 6g Dodecyl trimethyl ammonium chloride, adding deionized water 400ml, with mixed liquor 90 ℃ of following stirring reactions 5 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 4.5g with the filtering with microporous membrane of 0.45um.Be quadratic-layer when inserting Dodecyl trimethyl ammonium chloride confirmed other 25% Dodecyl trimethyl ammonium chloride insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis at 10g Na-Montmorillonitum intercalation 1.5g.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: with embodiment 5.
3. the preparation quadratic-layer is inserted nanometer Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with the 10g Dodecyl trimethyl ammonium chloride, adding deionized water 300ml, with mixed liquor 90 ℃ of following stirring reactions 5 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 7g with the filtering with microporous membrane of 0.45um.Be quadratic-layer when inserting Dodecyl trimethyl ammonium chloride confirmed other 30% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis at 10g Na-Montmorillonitum intercalation 3g.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: with embodiment 5.
3. the preparation quadratic-layer is inserted nanometer Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with the 6g Quaternium 24, adding deionized water 300ml, with mixed liquor 90 ℃ of following stirring reactions 5 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 4.62g with the filtering with microporous membrane of 0.45um.Be Quaternium 24 at 10g Na-Montmorillonitum intercalation 138g, confirmed 23% Quaternium 24 insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 250mL deionized water for stirring, is formed stable aaerosol solution; Then the 4g Dodecyl trimethyl ammonium chloride is added in the aaerosol solution; With mixed liquor 85 ℃ of following stirring reactions 8 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 12g quaternary ammonium salts nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2g with the filtering with microporous membrane of 0.45um.Be Dodecyl trimethyl ammonium chloride at 10g Na-Montmorillonitum intercalation 2g, confirmed 50% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. the preparation quadratic-layer is inserted nanometer Montmorillonitum: get the above-mentioned quaternary ammonium salts nanometer Montmorillonitum that obtains and mix with the 8g Quaternium 24, adding deionized water 300ml, with mixed liquor 85 ℃ of following stirring reactions 5 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 16.5g quaternary ammonium salts nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 6.03g with the filtering with microporous membrane of 0.45um.Be Quaternium 24 at 10g Na-Montmorillonitum intercalation 1.97g, confirmed 24.6% Quaternium 24 insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 9
1. prepare the Na-Montmorillonitum: with embodiment 1
2. preparation nanometer Montmorillonitum: Na-montmorillonite 2 0g is stirred in 500mL deionized water disperse medium, form stable aaerosol solution; Then the 10g benzethonium chloride is added in the aaerosol solution; With mixed liquor 85 ℃ of following stirring reactions 6 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 montmorillonite.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light absorbance, calculate residue quaternary ammonium salt amount 4.6g with the filtering with microporous membrane of 0.45um.Be that benzethonium chloride is at 20g Na-Montmorillonitum intercalation 5.4g.Confirmed 54% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. prepare miconazole nitrate intercalation Montmorillonitum: the quaternary ammonium salt-modified organic montmorillonite 25.4g of above-mentioned gained is added in the 400ml ethanol, stir and form steady suspension, add the 15g miconazole nitrate, stirred 4 hours under the room temperature, sucking filtration is used the washing with alcohol 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 miconazole nitrate intercalation Montmorillonitum.Receive all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 12g with the filtering with microporous membrane of 0.45um.Be that miconazole nitrate is at 10g Na-Montmorillonitum intercalation 1.5g.Confirmed 20% miconazole nitrate insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 300mL deionized water for stirring, is formed stable aaerosol solution; Then the 6g DDAC is added in the aaerosol solution; With mixed liquor 90 ℃ of following stirring reactions 6 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 3.12g with the filtering with microporous membrane of 0.45um.Be that DDAC is at 10g Na-Montmorillonitum intercalation 2.88g.Confirmed 48% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation miconazole nitrate intercalation nano Montmorillonitum: get above-mentioned gained quaternary ammonium salts Montmorillonitum and mix with the 7g miconazole nitrate, adding ethanol 300ml is with mixed liquor stirring reaction 6 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 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 miconazole nitrate intercalation nano Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 5.74g with the filtering with microporous membrane of 0.45um.Be miconazole nitrate at 10g Na-Montmorillonitum intercalation 1.26g, confirmed 18% miconazole nitrate insertion montmorillonite nano sheet with XRD test and IR test and ultraviolet spectrometry gravimetric analysis
Interlayer.
Embodiment 11
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 300mL deionized water for stirring, is formed stable aaerosol solution; Then the 7g DDAC is added in the aaerosol solution; With mixed liquor 90 ℃ of following stirring reactions 6 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 3.5g with the filtering with microporous membrane of 0.45um.Be DDAC at 10g Na-Montmorillonitum intercalation 3.5g, confirmed 50% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation miconazole nitrate intercalation nano Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with the 10g miconazole nitrate, and adding ethanol 350ml is with mixed liquor stirring reaction 6 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 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 miconazole nitrate intercalation nano Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 6.5g with the filtering with microporous membrane of 0.45um.Be that miconazole nitrate is at 10g Na-Montmorillonitum intercalation 3.5g.Confirmed 35% miconazole insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 12
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 280mL deionized water for stirring, is formed stable aaerosol solution; Then the 8g DDAC is added in the aaerosol solution; With mixed liquor 90 ℃ of following stirring reactions 6 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 3.4g with the filtering with microporous membrane of 0.45um.Be DDAC at 10g Na-Montmorillonitum intercalation 4.6g, confirmed 57.5% DDAC insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation miconazole nitrate intercalation nano Montmorillonitum: get above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum and mix with the 12g miconazole nitrate, adding ethanol 300ml is with mixed liquor stirring reaction 6 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 gets miconazole nitrate intercalation nano Montmorillonitum.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 0.45um.Be miconazole nitrate at 10g Na-Montmorillonitum intercalation 4.8g, confirmed 40% miconazole nitrate insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 13
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 300mL deionized water for stirring, is formed stable aaerosol solution; Then the 10g DDAC is added in the aaerosol solution; With mixed liquor 80 ℃ 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 4g with the filtering with microporous membrane of 0.45um.Be DDAC at 10g Na-Montmorillonitum intercalation 6g, confirmed 60% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation sulphuric acid hibitane intercalation nano Montmorillonitum: the above-mentioned quaternary ammonium salts Montmorillonitum that obtains is mixed with the sulphuric acid hibitane of 5g, and adding ethanol 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 the sulphuric acid 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 sulphuric acid hibitane intercalation nano Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 3.5g with the filtering with microporous membrane of 0.45um.Be the sulphuric acid hibitane at 10g Na-Montmorillonitum intercalation 1.5g, confirmed 30% sulphuric acid hibitane insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 14
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 500mL deionized water for stirring, is formed stable aaerosol solution; Then the 4g hexadecyltrimethylammonium chloride is added in the aaerosol solution; With mixed liquor 80 ℃ of following stirring reactions 4.5 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2g with the filtering with microporous membrane of 0.45um.Be hexadecyltrimethylammonium chloride at 10g Na-Montmorillonitum intercalation 2g, confirmed 50% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation sulphuric acid hibitane intercalation nano Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with 6.5g sulphuric acid hibitane, and adding ethanol 460ml is with mixed liquor stirring reaction 5 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 the sulphuric acid hibitane, is deposited in 70 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly gets sulphuric acid hibitane intercalation nano Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 3.0g with the filtering with microporous membrane of 0.45um.Be that the sulphuric acid hibitane is at 10g Na-Montmorillonitum intercalation 2.6g.Confirmed 40% sulphuric acid hibitane insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 15
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: 10g Na-Montmorillonitum is added the 200ml deionized water, stir and form stable aaerosol solution; Add 6.0g Bardac LF-80 (Quaternium 24), 80 ℃ of following stirring reactions 8 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 Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt amount 2.7g with the filtering with microporous membrane of 0.45um.Be Quaternium 24 at 10g Na-Montmorillonitum intercalation 3.3g, confirmed 55% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation sulphuric acid hibitane intercalation nano Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with 10g sulphuric acid hibitane, and adding ethanol 280ml is with mixed liquor stirring reaction 5 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 the sulphuric acid 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 sulphuric acid hibitane intercalation nano Montmorillonitum.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 0.45um.Be the sulphuric acid hibitane at 10g Na-Montmorillonitum intercalation 3.8g, confirmed 38% sulphuric acid hibitane insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 16
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: with embodiment 15.
3. preparation sulphuric acid hibitane intercalation nano Montmorillonitum: get above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum and mix with 12g sulphuric acid hibitane, adding ethanol 450ml is with mixed liquor stirring reaction 5 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 the sulphuric acid 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 sulphuric acid hibitane intercalation nano Montmorillonitum.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 0.45um.Be the sulphuric acid hibitane at 10g Na-Montmorillonitum intercalation 4.8g, confirmed 40% sulphuric acid hibitane insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 17
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: with embodiment 9.
3. preparation amikacin sulfate intercalation Montmorillonitum: get the above-mentioned quaternary ammonium salts nanometer Montmorillonitum that obtains and mix with the 10g amikacin sulfate, adding 230ml deionized water, with mixed liquor 40 ℃ of following stirring reactions 5 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 60 ℃ of following vacuum dryings to constant weight, and ball milling to particle diameter is 20-30 μ m, promptly obtains amikacin sulfate intercalation Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 7.5g with the filtering with microporous membrane of 0.45um.Be amikacin sulfate at 10g Na-Montmorillonitum intercalation 1.25g, confirmed 25% amikacin sulfate insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 18
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 5g in the 80mL deionized water for stirring, is formed stable aaerosol solution; Then the 5g benzethonium chloride is added in the aaerosol solution; With mixed liquor 90 ℃ of following stirring reactions 7.5 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2g with the filtering with microporous membrane of 0.45um.Be benzethonium chloride at 5g Na-Montmorillonitum intercalation 3g, confirmed 60% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation amikacin sulfate intercalation Montmorillonitum: get above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum and mix with the 8g amikacin sulfate, adding deionized water 80ml, with mixed liquor 40 ℃ of following stirring reactions 5 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 amikacin sulfate intercalation Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 5.6g with the filtering with microporous membrane of 0.45um.Be that amikacin sulfate is at 5g Na-Montmorillonitum intercalation 2.4g; Confirmed 30% amikacin sulfate insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 19
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g is stirred in 250mL deionized water disperse medium, form stable aaerosol solution; Then 6gBardac LF-80 (Quaternium 24) is added in the aaerosol solution; With mixed liquor 80 ℃ of following stirring reactions 8 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 Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2.4g with the filtering with microporous membrane of 0.45um.Be that Quaternium 24 is at 10g Na-Montmorillonitum intercalation 3.6g; Confirmed 60% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. prepare the rifampicin Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is added in the 150ml chloroform, stir and form steady suspension, add 5g rifampicin powder, stirring is 4 hours under the room temperature, and sucking filtration is used chloroform washing and filtering thing 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 rifampicin intercalation Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 3.5g with the filtering with microporous membrane of 0.45um.Be that rifampicin is at 10g Na-Montmorillonitum intercalation 1.5g; Confirmed 30% rifampicin insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 20
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: with embodiment 19.
3. prepare infection material intercalation nano Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is added in the 100ml dehydrated alcohol, stir and form steady suspension, add tetracycline 5g, miconazole 5g, stirred 4 hours under the room temperature, sucking filtration is used the washing with alcohol 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 tetracycline, miaow bran azoles intercalation nano Montmorillonitum.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 0.45um.Be that the infection material is at 10g Na-Montmorillonitum intercalation 4g; Confirmed 40% medicine insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 21
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 200mL deionized water for stirring, is formed stable aaerosol solution; Then 6g Bardac LF-80 (Quaternium 24) is added in the aaerosol solution; 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2.4g with the filtering with microporous membrane of 0.45um.Be that Quaternium 24 is at 10g Na-Montmorillonitum intercalation 3.6g; Confirmed 60% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation tetracycline intercalation nano Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with the 8g 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 tetracycline intercalation nano Montmorillonitum.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 0.45um.Be that tetracycline is at 10g Na-Montmorillonitum intercalation 2g; Confirmed 30% tetracycline insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Embodiment 22
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 300mL deionized water for stirring, is formed stable aaerosol solution; Then the 10g DDAC is added in the aaerosol solution; With mixed liquor 80 ℃ of following stirring reactions 8 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 4g with the filtering with microporous membrane of 0.45um.Be that DDAC is at 10g Na-Montmorillonitum intercalation 6g; Confirmed 60% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation tetracycline intercalation nano Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with the 10g tetracycline, and adding ethanol 100ml is with mixed liquor stirring reaction 5 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 tetracycline intercalation nano Montmorillonitum.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 0.45um.Be that tetracycline is at 10g Na-Montmorillonitum intercalation 4g; Confirmed 40% tetracycline insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 220mL deionized water for stirring, is formed stable aaerosol solution; Then the 5g benzethonium chloride is added in the aaerosol solution; 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 2.5g with the filtering with microporous membrane of 0.45um.Be that benzethonium chloride is at 10g Na-Montmorillonitum intercalation 2.5g; Confirmed 50% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation amikacin sulfate intercalation Montmorillonitum: get the above-mentioned quaternary ammonium salts nanometer Montmorillonitum that obtains and mix with the 5g amikacin sulfate, adding 100ml deionized water, with mixed liquor 40 ℃ of following stirring reactions 6 hours.Sucking filtration, use the deionized water wash filtrate for several times then, use Biomat-5 type UV spectrophotometer measuring filtrate and do not have amikacin sulfate, be deposited in 60 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is 20-30 μ m, promptly obtains amikacin sulfate intercalation Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 2g with the filtering with microporous membrane of 0.45um.Be that amikacin sulfate is at 10g Na-Montmorillonitum intercalation 3g; XRD test and IR test and ultraviolet spectrometry gravimetric analysis have confirmed 20% amikacin sulfate insertion montmorillonite nano sheet interlayer.
Embodiment 24
1. prepare the Na-Montmorillonitum: with embodiment 1.
2. preparation nanometer Montmorillonitum: Na-Montmorillonitum 10g in the 100mL deionized water for stirring, is formed stable aaerosol solution; Then the 8g DDAC is added in the aaerosol solution; With mixed liquor 90 ℃ of following stirring reactions 7.5 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 nanometer Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residue quaternary ammonium salt 3.5g with the filtering with microporous membrane of 0.45um.Be that DDAC is at 10g Na-Montmorillonitum intercalation 4.5g; Confirmed 56.25% quaternary ammonium salt insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
3. preparation amikacin sulfate intercalation Montmorillonitum: above-mentioned gained quaternary ammonium salts nanometer Montmorillonitum is mixed with the 8g amikacin sulfate, adding deionized water 100ml, with mixed liquor 40 ℃ of following stirring reactions 5 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 amikacin sulfate intercalation Montmorillonitum.Collect all filtrates,, get an amount of filtrate and use Biomat-5 type ultraviolet spectrophotometer mensuration ultraviolet light light absorption value, calculate residual drug 5.76g with the filtering with microporous membrane of 0.45um.Be that amikacin sulfate is at 10g Na-Montmorillonitum intercalation 2.24g; Confirmed 28% amikacin sulfate insertion montmorillonite nano sheet interlayer with XRD test and IR test and ultraviolet spectrometry gravimetric analysis.
Claims (10)
1. anti-infection nano montmorillonite, make by following parts by weight of component:
Na-Montmorillonitum: 100; Intercalator: 10～60; Infection material: 10～48; Wherein:
The Na-Montmorillonitum is to stir in 10 parts of saturated deionized water solutions of the NaCl 100-300 part of raw material Montmorillonitum, to form stable aaerosol solution; Aaerosol solution stirred 5～6 hours down at 30～40 ℃; Sucking filtration is used the deionized water wash filtrate then; Be deposited in 70 ℃ of following vacuum dryings to constant weight, ball milling to particle diameter is that 20～30 μ m obtain;
Intercalator is a quaternary ammonium salt;
The infection material is a kind of in miconazole nitrate, econazole nitrate, amikacin sulfate, gentamycin, tetracycline, doxycycline, sulphuric acid hibitane and the rifampicin.
2. the described anti-infection nano montmorillonite of claim 1 is characterized in that intercalator is one or more in Quaternium 24, DDAC, didecyl dimethyl ammonium bromide and the benzethonium chloride.
3. claim 1 or 2 described anti-infection nano montmorillonites, wherein the intercalator consumption is 25～60 weight portions/100 weight portion Na-Montmorillonitums.
4. the described anti-infection nano montmorillonite of claim 1 is characterized in that the infection material is a kind of in econazole nitrate, miconazole nitrate, amikacin sulfate, tetracycline and the rifampicin.
5. claim 1 or 4 described anti-infection nano montmorillonites, wherein the consumption of infection material is 15～40 weight portions/100 weight portion Na-Montmorillonitums.
6. the preparation method of the described anti-infection nano montmorillonite of claim 1, contain following steps:
A. the Na-Montmorillonitum is pressed the deionized water quality: Na-Montmorillonitum quality=added deionized water for stirring and form stable suspersion solution in 10: 1～30: 1; Add intercalator, stirred intercalation 2～8 hours down, filter at 80～90 ℃, washing filter thing, dripping silver nitrate in cleaning mixture does not have precipitation; With Montmorillonitum drying, ball milling after the washing, obtaining particle diameter is the intercalation nano Montmorillonitum of 20～30 μ m;
B. the intercalation nano Montmorillonitum of above-mentioned gained is pressed solvent quality: Na-Montmorillonitum quality=in solvent, stirred formation stable suspersion solution in 5: 1～50: 1, described solvent is ethanol, deionized water or chloroform; Add the infection material, at room temperature stir intercalation after 2～8 hours, filter, remove and desolvate; Filter thing with solvent wash then, intercalation Montmorillonitum drying, ball milling with after the washing obtain the anti-infection nano montmorillonite that particle diameter is 20～30 μ m.
7. the described anti-infection nano montmorillonite preparation method of claim 6, it is characterized in that solvent quality among the step b: Na-Montmorillonitum quality is 20: 1.
8. the described anti-infection nano montmorillonite preparation method of claim 6 is characterized in that stirring the intercalation temperature among the step a is 85 ℃.
9. the described anti-infection nano montmorillonite preparation method of claim 6 is characterized in that stirring the intercalation time among the step a is 4 hours.
10. the described anti-infection nano montmorillonite preparation method of claim 6 is characterized in that stirring the intercalation time among the step b is 4 hours.
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