CN104587489B - Halloysite nanotube drug sustained-release material and preparation method thereof - Google Patents
Halloysite nanotube drug sustained-release material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a halloysite nanotube drug sustained-release material and a preparation method thereof. The drug sustained-release material is prepared by the following steps: performing acid corrosion to a halloysite nanotube to obtain a dilated nanotube, loading the drug into an inner cavity of the halloysite nanotube, and coating an organosilane polymerized hydrophobic layer onto the surface of the drug-carried halloysite nanotube, wherein the during the coating of the organosilane polymerized hydrophobic layer, organosilane I is firstly used for modifying the outer surface of the halloysite nanotube, and then organosilane II is added to form the organosilane polymerized hydrophobic layer on the surface of the nanotube. Compared with the prior art, the sustained release material has universality on a hydrophobic drug and a hydrophile drug, the drug release time can be effectively prolonged, the encapsulation efficiency is high, and the administration safety of the drug can be improved.
Description
Technical field
The invention belongs to Thermosensitive Material Used for Controlled Releasing of Medicine field, and in particular to a kind of halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine and its system
Preparation Method.
Background technology
In recent years, China's slow releasing pharmaceutical used presentation steady-state growth situation always.Release/controlled release preparation is clinical conventional
One of pharmaceutical dosage form, due to sustained release preparation have can reduce take number of times, improve patient compliance, blood concentration fluctuation compared with
It is little, method of administration variation, excitant is little and curative effect persistently, the advantage such as safety, so many medicines all attempt to develop into it is slow
Release formulation, makes research project of the pharmacy corporation with very big practical value.Slow-release material be conducive to improve curative effect of medication,
Toxic and side effect is reduced, the pain of the multiple medication of patient can be mitigated, be significant for clinical application level is improved.
《Print during chemical industry》(2013,27(9):5-8) at present the bio-pharmaceutical sustained release macromolecular material of exploitation is mainly day
Right macromolecule, semi-synthetic macromolecule, synthesis macromolecule.Wherein CNT, shitosan, sodium alginate and PLA etc. are current
More material is applied in drug controlled release system, middle utilization water soluble polymer sodium alginate modification encapsulating Ao Shali is had been reported that
The CNT of platinum has obtained oxaliplatin-sodium alginate-multi-walled carbon nano-tubes to improve the biocompatibility of CNT
Compound, as a result proves that good medicament slow release effect can be played.《Jiangsu's agriculture science》(2013,41(7):299-302)
Report by model drug of oxaliplatin and study multi-walled carbon nano-tubes as the feasibility of slow-released carrier, by water-soluble high score
Sub- moditied processing carboxylic carbon nano-tube (MWCNT COOH), improves its surface nature, as a result show the oxaliplatin that obtains-
Chitin-sodium alginate-multi-walled carbon nano-tubes compound, slow release effect is good.《Chemistry and bioengineering》(2014,31
(2):35-37) report and adopt emulsion-solvent evaporation method, with Biodegradable material PLA as carrier, doctor is added wherein
It is micro- that medicine level azithromycin and a certain amount of nano ferriferrous oxide prepare polylactic acid/nano ferroso-ferric oxide load Azithromycin slow-release
Ball, as a result shows that there is microballoon obvious medicament slow release to act on.But, although above-mentioned compound can play certain sustained release effect
Really, but it is only capable of being used in the sustained release of certain specific medicine, not with universality.
Although additionally, having some slow releasing pharmaceutical products at present, it is still present, and envelop rate is relatively low, absorb limited, system
Agent quality is unstable, dosage more difficult control the problems such as.And the high cost of its preparation, the complex operation of preparation process.
The content of the invention
It is an object of the invention to provide it is a kind of for hydrophobic drug and hydrophilic medicament have universality, can be effective
The halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine for extend pharmaceutical release time, envelop rate height, improving drug administration security.
Another object of the present invention is to provide a kind of preparation method of above-mentioned slow-release material simple to operate, low cost.
Technical scheme：
A kind of halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine, the Thermosensitive Material Used for Controlled Releasing of Medicine by halloysite nanotubes by carrying out sour
Halloysite nanotubes of the erosion with after the nanotube for obtaining dilatation, by drug loading in halloysite nanotubes inner chamber, after medicine is carried
Surface coating organosilan polymerization hydrophobic layer is obtained；Wherein, coat during organic polymerizable silane hydrophobic layer, first using organosilicon
Alkane coupling agent I is modified halloysite nanotubes outer surface, adds organo silane coupling agent II, so as in galapectite nanometer
Pipe surface coats to form organic polymerizable silane hydrophobic layer, organo silane coupling agent I be tetraethoxysilane, organo silane coupling agent
II one kind or several in n-octytriethoxysilane, hexadecyl, VTES
Kind.
The organosilan polymerization hydrophobic layer thickness of above-mentioned formation is 20～50nm.
The preparation method of above-mentioned slow-release material, comprises the following steps：
(1) corrosion of halloysite nanotubes
Galapectite powder is corroded with dilute acid soln, is washed, is dried, and the dilatation galapectite for obtaining inner wall section corrosion is received
Mitron；
(2) drug loading
By medicine dissolving to be loaded in solvent, then the halloysite nanotubes of dilatation are soaked in above-mentioned solution,
Guarantee system is in vacuum environment, cleans, is dried to obtain load medicine halloysite nanotubes；
(3) hydrophobic layer modification
A, by carry medicine halloysite nanotubes dissolved with solvent, add organo silane coupling agent I it is right at 30～70 DEG C
Halloysite nanotubes outer surface is modified；
B, the halloysite nanotubes after modification are scattered in solvent, add organo silane coupling agent II at 90～130 DEG C
Under form organic polymerizable silane hydrophobic layer in halloysite nanotubes Surface coating；
Wherein, organo silane coupling agent I is tetraethoxysilane, and organo silane coupling agent II is selected from n-octyl triethoxy
One or more in silane, hexadecyl, VTES.
In (3rd) step, it is 1 to carry medicine halloysite nanotubes with the mass ratio of organo silane coupling agent I：2.0～5.0.
In (3rd) step, carry per 1g in medicine halloysite nanotubes and add 5～20mL ammoniacal liquor.
In (3rd) step, the halloysite nanotubes after modification are 1 with the mass ratio of organo silane coupling agent II：2.5～7.0.
In (2nd) step, halloysite nanotubes are 1 with the mass ratio of medicine：0.5～5.
Medicine of the present invention is preferably included as brufen, C14H10Cl2NNaO2 or Ofloxacin.
Acid in acid corrosion of the present invention is dilute acid soln, and concentration is preferably 1.0～5.0mol/L.
Olefin(e) acid solution is preferably dilution heat of sulfuric acid.
The load medicine time of halloysite nanotubes is advisable for 24～48h.
One or more in described solvent preferred alcohol, isopropanol, toluene or hexamethylene.
Beneficial effects of the present invention
The universality of slow-release material of the present inventor for being used in medicine in prior art is low, and high cost is delayed
Release the present situation of effect on driving birds is not good etc., there is provided one kind has universality, low cost, envelop rate for hydrophobic drug and hydrophilic medicament
It is high, the quality of the pharmaceutical preparations is stable, dosage is easily controlled, the bag that can effectively extend pharmaceutical release time, improve drug administration security
It is covered with the halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine of machine polymerizable silane hydrophobic layer.Specifically, slow-release material of the invention is by choosing
It is raw material to take halloysite nanotubes, acid corrosion is carried out to obtain the nanotube of dilatation to halloysite nanotubes first, afterwards by medicine
Thing is loaded among inner chamber, hence it is evident that increase drugloading rate to reach more high-drug-effect；Secondly by first using specific organosilan I pair
Halloysite nanotubes outer surface is modified, and is added specific organosilan II and is formed organic polymerizable silane in nanotube surface
Hydrophobic layer, controls the thickness degree of hydrophobic layer, reaches preferable sustained drug release effect.
The present invention from corrosion after galapectite as slow releasing carrier material, also carry out hydrophobic layer modification, by hydrophobic layer with
Galapectite is combined and is employed together in sustained release, obtains good slow release effect.By the nanometer material for corroding the dilatation inner chamber for obtaining
Material, improves envelop rate.From the TEM figures of Fig. 1 as can be seen that the cavity inside diameter of original halloysite nanotubes is 10- in a figures
The galapectite obtained after corroding in 15nm, b figure carries out load medicine, and internal diameter expands as 25-35nm.It can be seen that, the galapectite material after corrosion
Material can improve entrapment efficiency really.
Using modified galapectite material as nano drug-carrying material in the present invention, method of administration and the administration of medicine can be not only made
Mode variation, so as to provide more selections for following preparation.And the nano drug-carrying material of the present invention has increase medicine
Absorption, improve medicine bioavilability advantage, pharmaceutically-active time lengthening can be made, be conducive to increase medicine with inhale
Receive position biofilm contact area, hence it is evident that increase and improve absorption and the bioavilability of medicine.For the treatment of some diseases,
General drug metabolism is fast, need repeated multiple times administration, and increases complication odds, and the present invention efficiently solves this hardly possible
Topic.The present invention enhances the stability of medicine factor to external world by forming the environment more closed.The biological stability of medicine
Strengthened, medicine can keep the integrality of its structure before site of action is reached, so as to improve the biologically active of medicine.
When the drug concentration of the present invention is 50mg/ml, drugloading rate is up to 150mg/g.
And the preparation method of the present invention is simple, low cost, the excellent performance of the slow-release material for preparing.
Description of the drawings
Fig. 1 is that angstrom trachelospermum jasminoide nanotube that embodiment 1 is obtained carries medicine and the transmission electron microscope picture after the modifying and decorating of surface.Wherein,
Fig. 1 (a) is the halloysite nanotubes of cavity, and Fig. 1 (b) is to carry the halloysite nanotubes after medicine, and Fig. 1 (c) is to be covered with organosilan
The halloysite nanotubes material of polymerization hydrophobic layer；From a, as can be seen that medicine has successfully been loaded in angstrom trachelospermum jasminoide nanotube in b figures
In chamber, the obvious internal diameter expansion of angstrom trachelospermum jasminoide nanotube after corrosion improves drugloading rate；As can be seen that organosilan gathers from c figures
Close hydrophobic layer and be successfully coated on halloysite nanotubes surface after load medicine.
Fig. 2 is the medicament slow release performance figure of the halloysite nanotubes material that embodiment 4 is obtained.
Fig. 3 is the medicament slow release performance figure of the halloysite nanotubes material that embodiment 1 is obtained.
Fig. 4 is the medicament slow release performance comparison diagram of the halloysite nanotubes material that embodiment 1 and comparative example 3 are obtained.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
(1) corrosion of halloysite nanotubes (HNTs)
Take 4g galapectite powder to be scattered in the dilution heat of sulfuric acid of 200mL 3mol/L, after ultrasonic disperse, in 70 DEG C of water-baths
Middle magnetic agitation 12h, with a large amount of distillation water washings to neutrality, 60 DEG C of dryings of vacuum, obtains the dilatation angstrom Lip river of inner wall section corrosion
Stone nanotube.
(2) load of brufen (IBU)
Take 1g Ibuprofen samples to be placed in conical flask, dissolved completely with the ethanol of 40mL, then add the dilatation of 1g
Halloysite nanotubes ultrasonic disperse, and guarantee system is in vacuum environment, and constant temperature oscillation 24h is reaching the mesh of drug loading
, to be cleaned with second alcohol and water completely, vacuum drying obtains HNTs-IBU.
(3) hydrophobic layer modification
A, by the HNTs-IBU of the 0.5g solvent (ethanol of 200mL：Water=4:1) ultrasonic dissolution is carried out, in 45 DEG C of magnetic force
Stirring half an hour add 8.335mL ammoniacal liquor after a while, later add 1.75g tetraethoxysilanes (TEOS), whole reaction system in
45 DEG C of water-bath 12h.After the completion of reaction, cleaned with second alcohol and water respectively to neutrality, centrifugation, vacuum drying obtains HNTs-
IBU@TEOS。
B, take 0.5g HNTs-IBU@TEOS ultrasonic disperses in the dry toluene of 25mL, add the n-octyl three of 2.32g
Ethoxysilane (OTES) back flow reaction 24h in 90 DEG C of oil baths.After the completion of reaction, cleaned into ethanol and toluene respectively
Property, centrifugation, vacuum drying obtains HNTs-IBU@TEOS@OTES.So organosilan polymerization hydrophobic layer is formed in galapectite and receives
Nanotube surface.
(4) external sustained release performance
The external sustained release behavior of HNTs-IBU@TEOS@OTES nano-tube support materials is carried out in dissolving-out tester, 0.4g
Nano material be infiltrated in the pH 7.4PBS cushioning liquid of 500mL, 100rpm/min, 37 DEG C, in a certain time interval,
Take the release liquid of 1.0mL respectively, and fill into the fresh pH 7.4PBS cushioning liquid of 1.0mL, the solution for taking out is passed through into 0.45
μm nylon leaching film, then by its concentration of ultraviolet determination.
Comparative example 1
(3rd) step hydrophobic layer modification in embodiment 1 is only modified from single organosilan to halloysite nanotubes, is grasped
Make as follows：0.5g HNTs-IBU ultrasonic disperses are taken in the dry toluene of 25mL, the n-octyl triethoxysilicane of 2.32g is added
Alkane (OTES) back flow reaction 24h in 90 DEG C of oil baths.
The nano particle obtained after the completion of bearing reaction aggregates into the big bulk of viscosity.
Comparative example 2
The temperature 45 C for using is changed to into 20 DEG C in (3rd) step hydrophobic layer modification a steps in embodiment 1, remaining is walked according to a
Rapid mode carries out operating as follows：Take the HNTs-IBU of the 0.5g solvent (ethanol of 200mL：Water=4:1) ultrasound is carried out molten
Solution, in 20 DEG C of magnetic agitation half an hour 8.335mL ammoniacal liquor is added after a while, and 1.75g tetraethoxysilanes (TEOS) are added later, whole
Individual reaction system is in 20 DEG C of water-bath 12h.Find that product is sticked in bottle wall mostly after the completion of reaction, centre is milky molten
Agent, it is impossible to cleaned.
Comparative example 3
The portfolio ratio of organosilan in (3rd) step hydrophobic layer modification in embodiment 1 is changed to into m (OTES)：m(HNTs-
IBU@TEOS)=8 with obtain different-thickness organosilan be polymerized hydrophobic layer, remaining is grasped according to the mode of embodiment 1
Make, operate as follows：
A, by the HNTs-IBU of the 0.5g solvent (ethanol of 200mL：Water=4:1) ultrasonic dissolution is carried out, in 45 DEG C of magnetic force
Stirring half an hour add 8.335mL ammoniacal liquor after a while, later add 1.75g tetraethoxysilanes (TEOS), whole reaction system in
45 DEG C of water-bath 12h.After the completion of reaction, cleaned with second alcohol and water respectively to neutrality, centrifugation, vacuum drying obtains HNTs-
IBU@TEOS。
B, take 0.5g HNTs-IBU@TEOS ultrasonic disperses in the dry toluene of 25mL, add the ethoxy of n-octyl three of 4g
Base silane (OTES) back flow reaction 24h in 90 DEG C of oil baths.After the completion of reaction, cleaned to neutrality with ethanol and toluene respectively, from
The heart, vacuum drying obtains HNTs-IBU@TEOS@OTES.
The material slow-release effect such as Fig. 4 for obtaining, it can be seen that medicine is difficult to be discharged from material, affects medicine
Absorption process and curative effect.
Embodiment 2
(1) corrosion of halloysite nanotubes
Take 4g galapectite powder to be scattered in the dilution heat of sulfuric acid of 200mL 5mol/L, after ultrasonic disperse, in 80 DEG C of water-baths
Middle magnetic agitation 12h, with a large amount of distillation water washings to neutrality, 70 DEG C of dryings of vacuum, obtains the dilatation angstrom Lip river of inner wall section corrosion
Stone nanotube.
(2) load of Ofloxacin (OFL)
Take 1g Ofloxacin samples to be placed in conical flask, dissolved completely with the dilute acetic acid solution of 30mL pH 3.0, and
The halloysite nanotubes ultrasonic disperse of the dilatation of 2g is added afterwards, and guarantee system is in vacuum environment, constant temperature oscillation 48h is reaching
The purpose of drug loading, is cleaned completely with dilute acetic acid solution water, and vacuum drying obtains HNTs-OFL.
(3) hydrophobic layer modification
A, by the HNTs-OFL of the 0.5g solvent (isopropanols of 200mL：Water=5:1) ultrasonic dissolution is carried out, in 45 DEG C of magnetic
Power stirring adds after a while 8.335mL ammoniacal liquor, and 1.75g tetraethoxysilanes (TEOS) are added later, and whole reaction system is in 60 DEG C
Water-bath 12h.After the completion of reaction, cleaned with second alcohol and water respectively to neutrality, centrifugation, vacuum drying obtains HNTs-OFL
TEOS。
B, take 0.5g HNTs-OFL@TEOS ultrasonic disperses in the dry toluene of 25mL, add the n-octyl three of 2.32g
Ethoxysilane (OTES) back flow reaction 24h in 100 DEG C of oil baths.After the completion of reaction, cleaned into ethanol and toluene respectively
Property, centrifugation, vacuum drying obtains HNTs-OFL@TEOS@OTES.So organosilan polymerization hydrophobic layer is formed in galapectite and receives
Nanotube surface.
(4) external sustained release performance
The external sustained release behavior of HNTs-OFL@TEOS@OTES nano-tube support materials is carried out in dissolving-out tester, 0.5g
Nano material be infiltrated in the pH 7.4PBS cushioning liquid of 500mL, 100rpm/min, 37 DEG C, in a certain time interval,
Take the release liquid of 5.0mL respectively, and fill into the fresh pH 7.4PBS cushioning liquid of 5.0mL, the solution for taking out is passed through into 0.45
μm nylon leaching film, then by its concentration of ultraviolet determination.
Embodiment 3
(1) corrosion of halloysite nanotubes
Take 4g galapectite powder to be scattered in the dilution heat of sulfuric acid of 200mL 4mol/L, after ultrasonic disperse, in 80 DEG C of water-baths
Middle magnetic agitation 12h, with a large amount of distillation water washings to neutrality, 70 DEG C of dryings of vacuum, obtains the dilatation angstrom Lip river of inner wall section corrosion
Stone nanotube.
(2) load of brufen (IBU)
Take 2g Ibuprofen samples to be placed in conical flask, dissolved completely with the ethanol of 50mL, then add the dilatation of 2g
Halloysite nanotubes ultrasonic disperse, and guarantee system is in vacuum environment, and constant temperature oscillation 24h is reaching the mesh of drug loading
, to be cleaned with second alcohol and water completely, vacuum drying obtains HNTs-IBU.
(3) hydrophobic layer modification
A, by the HNTs-IBU of the 0.5g solvent (ethanol of 200mL：Water=5:1) ultrasonic dissolution is carried out, in 60 DEG C of magnetic force
Stirring adds after a while 8.335mL ammoniacal liquor, and 2.25g tetraethoxysilanes (TEOS) are added later, and whole reaction system is in 60 DEG C of water
Bath reaction 12h.After the completion of reaction, cleaned with second alcohol and water respectively to neutrality, centrifugation, vacuum drying obtains HNTs-IBU TEOS.
B, take 0.5g HNTs-IBU@TEOS ultrasonic disperses in the dry toluene of 25mL, add the ethoxy of n-octyl three of 3g
Base silane (OTES) back flow reaction 24h in 120 DEG C of oil baths.After the completion of reaction, cleaned to neutrality with ethanol and toluene respectively, from
The heart, vacuum drying obtains HNTs-IBU@TEOS@OTES.So organosilan polymerization hydrophobic layer is formed in halloysite nanotubes
Surface.
(4) external sustained release performance
The external sustained release behavior of HNTs-IBU@TEOS@OTES nano-tube support materials is carried out in dissolving-out tester, 0.5g
Nano material be infiltrated in the pH 7.4PBS cushioning liquid of 500mL, 100rpm/min, 37 DEG C, in a certain time interval,
Take the release liquid of 5.0mL respectively, and fill into the fresh pH 7.4PBS cushioning liquid of 5.0mL, the solution for taking out is passed through into 0.45
μm nylon leaching film, then by its concentration of ultraviolet determination.
Embodiment 4
(1) corrosion of halloysite nanotubes
Take 4g galapectite powder to be scattered in the dilution heat of sulfuric acid of 200mL 5mol/L, after ultrasonic disperse, in 75 DEG C of water-baths
Middle magnetic agitation 12h, with a large amount of distillation water washings to neutrality, 70 DEG C of dryings of vacuum, obtains the dilatation angstrom Lip river of inner wall section corrosion
Stone nanotube.
(2) load of C14H10Cl2NNaO2 (DS)
Take 2g Diclofenac sodium samples to be placed in conical flask, dissolved completely with the ethanol of 40mL, then add 1g's
The halloysite nanotubes ultrasonic disperse of dilatation, and guarantee system is in vacuum environment, constant temperature oscillation 24h is reaching drug loading
Purpose, is cleaned completely with second alcohol and water, and vacuum drying obtains HNTs-DS.
(3) hydrophobic layer modification
A, by the HNTs-DS of the 0.5g solvent (isopropanols of 200mL：Water=3:1) ultrasonic dissolution is carried out, in 50 DEG C of magnetic force
Stirring adds after a while 8.335mL ammoniacal liquor, and 2.25g tetraethoxysilanes (TEOS) are added later, and whole reaction system is in 45 DEG C of water
Bath reaction 12h.After the completion of reaction, cleaned with second alcohol and water respectively to neutrality, centrifugation, vacuum drying obtains HNTs-DS TEOS.
B, take 0.5g HNTs-DS@TEOS ultrasonic disperses in the dry toluene of 25mL, add the ethoxy of n-octyl three of 3g
Base silane (OTES) back flow reaction 24h in 120 DEG C of oil baths.After the completion of reaction, cleaned to neutrality with ethanol and toluene respectively, from
The heart, vacuum drying obtains HNTs-DS@TEOS@OTES.So organosilan polymerization hydrophobic layer is formed in halloysite nanotubes table
Face.
(4) external sustained release performance
The external sustained release behavior of HNTs-DS@TEOS@OTES nano-tube support materials is carried out in dissolving-out tester, 0.3g
Nano material be infiltrated in the pH 7.4PBS cushioning liquid of 500mL, 100rpm/min, 37 DEG C, in a certain time interval,
Take the release liquid of 3.0mL respectively, and fill into the fresh pH 7.4PBS cushioning liquid of 3.0mL, the solution for taking out is passed through into 0.45
μm nylon leaching film, then by its concentration of ultraviolet determination.
Claims (8)
1. a kind of halloysite nanotubes Thermosensitive Material Used for Controlled Releasing of Medicine, it is characterised in that the Thermosensitive Material Used for Controlled Releasing of Medicine is by by galapectite nanometer
Pipe carries out acid corrosion with after the nanotube for obtaining dilatation, by drug loading in halloysite nanotubes inner chamber, carry medicine after angstrom
Lip river stone nanotube surface coats organic polymerizable silane hydrophobic layer and obtains；Wherein, during coating organic polymerizable silane hydrophobic layer,
First halloysite nanotubes outer surface is modified using organo silane coupling agent I, add organo silane coupling agent II, so as to
Organic polymerizable silane hydrophobic layer is formed in halloysite nanotubes Surface coating, organo silane coupling agent I is tetraethoxysilane, is had
Machine silane coupling agent II is selected from n-octytriethoxysilane, hexadecyl, VTES
In one or more；
It is 1 that medicine halloysite nanotubes are carried with the mass ratio of organo silane coupling agent I：2.0～5.0；
Halloysite nanotubes after modification are 1 with the mass ratio of organo silane coupling agent II：2.5～6.0.
2. the slow-release material according to claim 1, it is characterised in that the organosilan polymerization hydrophobic layer thickness of formation is
20～50nm.
3. the slow-release material according to claim 1, it is characterised in that described medicine be brufen, C14H10Cl2NNaO2 or
Ofloxacin.
4. the preparation method of the slow-release material described in any one of claim 1-3, it is characterised in that comprise the following steps：
(1) corrosion of halloysite nanotubes
Galapectite powder is corroded with dilute acid soln, is washed, is dried, and obtains the dilatation galapectite nanometer of inner wall section corrosion
Pipe；
(2) drug loading
By medicine dissolving to be loaded in solvent, then the halloysite nanotubes of dilatation are soaked in above-mentioned solution, it is ensured that
System is in vacuum environment, cleans, is dried to obtain load medicine halloysite nanotubes；
(3) hydrophobic layer modification
A, medicine halloysite nanotubes will be carried dissolved with solvent, add ammoniacal liquor, add organo silane coupling agent I 30～
Halloysite nanotubes outer surface is modified at 70 DEG C；
B, the halloysite nanotubes after modification are scattered in solvent, add organo silane coupling agent II at 90～130 DEG C
Coat to form organic polymerizable silane hydrophobic layer in nanotube surface；
Wherein, organosilan I is tetraethoxysilane, and organosilan II is selected from n-octytriethoxysilane, cetyl three
One or more in Ethoxysilane, VTES.
5. preparation method according to claim 4, it is characterised in that in (3rd) step, medicine halloysite nanotubes are carried per 1g
Middle addition 5～20mL ammoniacal liquor.
6. preparation method according to claim 4, it is characterised in that in (2nd) step, halloysite nanotubes and medicine
Mass ratio is 1：0.5～5.
7. the preparation method according to claim 4, it is characterised in that the concentration of described dilute acid soln is 1.0～
5.0mol/L。
8. the preparation method according to claim 4, it is characterised in that described solvent selected from ethanol, isopropanol, toluene
Or one or more in hexamethylene.
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