CN109574507A - A kind of nano-level sphere bioactivity glass and preparation method thereof - Google Patents
A kind of nano-level sphere bioactivity glass and preparation method thereof Download PDFInfo
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- CN109574507A CN109574507A CN201910054427.2A CN201910054427A CN109574507A CN 109574507 A CN109574507 A CN 109574507A CN 201910054427 A CN201910054427 A CN 201910054427A CN 109574507 A CN109574507 A CN 109574507A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/108—Forming porous, sintered or foamed beads
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/002—Hollow glass particles
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
Abstract
The present invention provides a kind of nano-level sphere bioactivity glass and preparation method thereof, the following steps are included: surfactant is dissolved in the mixed solvent by (1), mixed solution is obtained, the pH value that basic catalyst adjusts mixed solution is added, obtains alkaline mixed solution；(2) silicon source, calcium source and phosphorus source are sequentially added in the alkaline mixed solution obtained in step (1), carries out continuing high-speed stirred after being added every time, obtains bioactivity glass sol form liquid；(3) by bioactivity glass sol form liquid scrubbing obtained in step (2), hygrometric state gel precipitation is obtained, drying in baking oven is then placed in, obtains bioactivity glass powder；(4) after washing and drying, obtained bioactivity glass powder is placed in high temperature furnace and is heat-treated, nano-level sphere bioactivity glass is obtained.Nano-level sphere bioactivity glass prepared by the present invention has lesser partial size and has complete spherical, can be used for drug loading and bone renovating material.
Description
Technical field
The invention belongs to bioactivity glass technical fields, and in particular to a kind of nano-level sphere bioactivity glass and its
Preparation method.
Background technique
Hench in 1971 etc. is prepared for the bioactivity glass with good biocompatibility using fusion method, by four
The development of more than ten years, the preparation of bioactivity glass mainly has fusion method, sol-gal process and improvement at presentMethod,
Wherein sol-gal process and improvementMethod can be prepared with spherical bioactivity glass；Improvement
It is owned by France in one of soft template method, the spherical biological activity glass of preparation is mainly used for the load of Bone Defect Repari and drug and slow
It releases.
It can be used as the load for needing sustained release drugs in Cytolysosome since nano-scale particle can enter simultaneously indwelling
Body, and bioactivity glass has good bioactivity, decomposition product is ingredient needed for cell, and it is smaller to cell damage,
And degradation rate is moderate, has the potentiality as sustained release drugs carrier.
In the prior art, the synthesis of nano-level sphere bioactivity glass mainly uses cetyl trimethylammonium bromide
(CTAB) etc. surfactants are template, and the bioactivity glass partial size prepared generally is greater than 100nm, and utilizes 3- aminopropan
Base trimethoxy silane can prepare the particle of partial size about 20nm, but its spherical imperfect and reunion is obvious.Due to nano-level sphere
Bioactive glass surface can be larger, easily reunites during the preparation process, forms biggish bioactivity glass group, work as simultaneously
When partial size is smaller, the bioactivity glass of synthesis is spherical often imperfect, is in the prior art several there are no that can prepare partial size
Ten nanometers, the technique of good dispersion, the complete spherical biological activity glass of spheric granules pattern.
Accordingly, it is desirable to provide a kind of be directed to the insufficient improved technology scheme of the above-mentioned prior art.
Summary of the invention
The purpose of the present invention is to provide a kind of nano-level sphere bioactivity glass and preparation method thereof, are provided with preparation
There is the nano-level sphere bioactivity glass compared with small particle, the spherical biological for having meso-hole structure is obtained with simple technology
Activity glass, good dispersion, spheric granules pattern are complete, and the loading and sustained release applied to drug are with a wide range of applications.
To achieve the goals above, the invention provides the following technical scheme:
A kind of preparation method of nano-level sphere bioactivity glass, the preparation method of the activity glass include following step
It is rapid:
(1) surfactant is dissolved in the mixed solvent, obtains mixed solution, basic catalyst is then added and adjusts mixing
The pH value of solution obtains alkaline mixed solution to 9~10；
(2) silicon source, calcium source and phosphorus source are sequentially added in the alkaline mixed solution obtained in step (1), after being added every time
It carries out continuing high-speed stirred, obtains bioactivity glass sol form liquid；
(3) bioactivity glass sol form liquid obtained in step (2) is washed, obtains hygrometric state gel precipitation,
Then hygrometric state gel precipitation is placed in oven and dried, obtains white bioactivity glass powder；
(4) after washing and drying, obtained white bioactivity glass powder is placed in high temperature furnace and is heat-treated,
Surfactant and impurity organic principle are removed, nano-level sphere bioactivity glass is obtained.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that the surface-active in step (1)
Agent is the compound system of nonionic surfactant triblock polymer and cationic surfactant.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that the non-ionic surface active
Agent triblock polymer is P123, molecular formula PEO20PPO70PEO20, PEO is Pluronic F-127 unit, and PPO is polycyclic oxygen third
Alkene unit；
The cationic surfactant is cetyl trimethylammonium bromide.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that P123 and cetyl front three
The mass ratio of base ammonium bromide is (25~150): 1.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that the silicon source in step (2) is positive
Silester；
Calcium source in step (2) is calcium nitrate tetrahydrate；
Phosphorus source in step (2) is orthophosphoric acid.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that the silicon source, calcium source and phosphorus source
Molar ratio be (65~80): (20~30): (2~7)；
The surfactant and the mass ratio of silicon source are (0.755~0.78): 2.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that after silicon source is added in step (2)
The revolving speed of high-speed stirred is 700~1000rpm, and the time is 0.5~2h.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that the base catalysis in step (1)
Agent is ammonium hydroxide；
Preferably, ammonium hydroxide additional proportion is silicon source and ammonium hydroxide volume ratio (2~9): 1.
Preferably, the concentration of ammonium hydroxide is 28%.
In the preparation method of nano-level sphere bioactivity glass as described above, it is preferable that in step (4) in high temperature furnace
The temperature of heat treatment is 500~600 DEG C, 2~5h of soaking time.
A kind of nano-level sphere bioactivity glass of nano-level sphere bioactivity glass preparation method preparation.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:
Nano-level sphere bioactivity glass preparation method of the invention, easy to operate, reaction condition is mild, and raw material is cheap
It is easy to get；Having for 30~90nm of partial size is obtained by the compound system of nonionic surfactant and cationic surfactant to be situated between
The nano-level sphere bioactivity glass of pore structure, partial size maintain the complete pattern of spherical particles while reduction, can be extensive
Loading and controlled release applied to drug.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.Wherein:
Fig. 1 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of the embodiment of the present invention 2；
Fig. 3 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of the embodiment of the present invention 3；
Fig. 4 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of the embodiment of the present invention 4；
Fig. 5 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of the embodiment of the present invention 5；
Fig. 6 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of the embodiment of the present invention 6；
Fig. 7 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of reference examples 1 of the present invention；
Fig. 8 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of reference examples 2 of the present invention；
Fig. 9 is the scanning electron microscope (SEM) photograph of the nano-level sphere bioactivity glass of reference examples 4 of the present invention.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.
The nano-level sphere of a kind of nano-level sphere bioactivity glass provided by the invention and preparation method thereof, preparation is raw
Object activity glass partial size is small, and spheric granules pattern is complete, has good bioactivity, mainly uses non-ionic surface active
The compound system of agent triblock polymer and cationic surfactant cetyl trimethylammonium bromide (CTAB) makees template, adopts
With soft template method synthesis nano spherical biological activity glass.
Preparation method is broadly divided into two big steps: triblock polymer P123 and CTAB being dissolved in the mixed of water and ethyl alcohol first
In bonding solvent and stir evenly, be then added 28% ammonium hydroxide adjust mixed solution pH value after, then be separately added into silicon source, calcium source and
Phosphorus source stirs to get sol form liquid；It will finally be dried after sol form liquid scrubbing, when high temperature furnace high temperature handles one section
Between, obtain the nano-level sphere bioactivity glass of small particle, high-specific surface area and porosity.
The principle that the present invention prepares spherical biological glass is mainly: silicon source hydrolyzes to form spherical silicon oxygen net under alkaline condition
Network, calcium and phosphorus are combined in Si-OH a large amount of on silica network, realize the incorporation of calcium and phosphorus；It is removed by high-temperature process therein
Organic matter obtains nano-level sphere bioactivity glass.The spherolite that preparation method of the invention obtains has lesser partial size, compared with
High-specific surface area and porosity, while having good bioactivity concurrently, there is great application prospect in terms of the load of drug.
A kind of preparation method of nano-level sphere bioactivity glass provided by the invention, comprising the following steps:
(1) surfactant is dissolved in the mixed solvent, obtains mixed solution, basic catalyst is then added and adjusts mixing
The pH value of solution obtains alkaline mixed solution, prepares spherical biological activity glass using soft template method to 9~10；
In a specific embodiment of the present invention, the surfactant in step (1) is nonionic surfactant three block
Polymer and cationic surfactant compound system.
In a specific embodiment of the present invention, nonionic surfactant P123, molecular formula PEO20PPO70PEO20,
PEO is Pluronic F-127 unit, and PPO is polycyclic oxypropylene units；Cationic surfactant is cetyl trimethyl bromination
Ammonium (CTAB).
In a specific embodiment of the present invention, the mass ratio of P123 and CTAB is (25~150): 1 (such as 25:1,30:1,
35:1、40:1、45:1、50:1、55:1、60:1、65:1、70:1、75:1、80:1、85:1、90:1、95:1、100:1、105:1、
110:1、115:1、120:1、125:1、130:1、135:1、140:1、145:1)。
In a specific embodiment of the present invention, mixed solvent is the mixing of water and dehydrated alcohol；
In a specific embodiment of the present invention, basic catalyst is ammonium hydroxide；Preferably, ammonium hydroxide additional proportion is silicon source and ammonia
Water volume ratio (2~9): 1 (such as 2.2:1,2.4:1,2.6:1,2.8:1,3:1,3.2:1,3.4:1,3.6:1,3.8:1,4:1,
4.2:1、4.4:1、4.6:1、4.8:1、5:1、5.2:1、5.4:1、5.6:1、5.8:1、6:1、6.2:1、6.4:1、6.6:1、
6.8:1,7:1,7.2:1,7.4:1,7.6:1,7.8:1,8:1,8.2:1,8.4:1,8.6:1,8.8:1,9:1)；Preferably, ammonia
The concentration of water is 28%.
(2) silicon source, calcium source and phosphorus source are sequentially added in the alkaline mixed solution obtained in step (1), after being added every time
It carries out continuing high-speed stirred, obtains bioactivity glass sol form liquid；
In a specific embodiment of the present invention, the silicon source in step (2) is ethyl orthosilicate；
Calcium source in step (2) is calcium nitrate tetrahydrate；
Phosphorus source in step (2) is orthophosphoric acid.
In a specific embodiment of the present invention, the molar ratio of the silicon source, calcium source and phosphorus source is (65~80): (20~
30): (2~7) (such as 65:20:2,65:20:3,65:20:4,65:20:5,65:20:6,65:20:7,65:25:2,65:25:
3、65:25:4、65:25:5、65:25:6、65:25:7、65:30:2、65:30:3、65:30:4、65:30:5、65:30:6、65:
30:7、70:20:2、70:20:3、70:20:4、70:20:5、70:20:6、70:20:7、70:25:2、70:25:3、70:25:4、
70:25:5、70:25:6、70:25:7、70:30:2、70:30:3、70:30:4、70:30:5、70:30:6、70:30:7、75:
20:2、75:20:3、75:20:4、75:20:5、75:20:6、75:20:7、75:25:2、75:25:3、75:25:4、75:25:5、
75:25:6、75:25:7、75:30:2、75:30:3、75:30:4、75:30:5、75:30:6、75:30:7、80:20:2、80:
20:3、80:20:4、80:20:5、80:20:6、80:20:7、80:25:2、80:25:3、80:25:4、80:25:5、80:25:6、
80:25:7,80:30:2,80:30:3,80:30:4,80:30:5,80:30:6,80:30:7).Preferably, silicon source, calcium source and phosphorus
The molar ratio in source is 70:25:5.
In a specific embodiment of the present invention, surfactant and the mass ratio of silicon source are (0.755~0.78): 2 (such as
0.756:2、0.757:2、0.758:2、0.759:2、0.76:2、0.761:2、0.762:2、0.763:2、0.764:2、0.765:
2、0.766:2、0.767:2、0.768:2、0.769:2、0.77:2、0.771:2、0.772:2、0.773:2、0.774:2、
0.775:2、0.776:2、0.777:2、0.778:2、0.779:2)。
In a specific embodiment of the present invention, the revolving speed that high-speed stirred after silicon source is added in step (2) is 700~
1000rpm (such as 720rpm, 740rpm, 760rpm, 780rpm, 800rpm, 820rpm, 840rpm, 860rpm, 880rpm,
900rpm, 920rpm, 940rpm, 960rpm, 980rpm), the time be 0.5~2h (such as 0.6h, 0.7h, 0.8h, 0.9h, 1h,
1.1h、1.2h、1.3h、1.4h、1.5h、1.6h、1.7h、1.8h、1.9h)。
(3) bioactivity glass sol form liquid obtained in step (2) is washed, obtains hygrometric state gel precipitation,
Then hygrometric state gel precipitation is placed in oven and dried, obtains white bioactivity glass powder.
(4) after washing and drying, white bioactivity glass powder obtained in step (3) is placed in high temperature furnace
Middle heat treatment removes surfactant and impurity organic principle, obtains nano-level sphere bioactivity glass.
In a specific embodiment of the present invention, the temperature being heat-treated in high temperature furnace be 500~600 DEG C (such as 510 DEG C,
520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C), 2~5h of soaking time (such as 3h, 4h, 5h).
Preferably, the temperature being heat-treated in high temperature furnace is 550 DEG C, soaking time 4h.
Embodiment 1
A kind of preparation method of nano-level sphere bioactivity glass provided in this embodiment, comprising the following steps:
(1) 0.75g P123 and 0.02g the CTAB solvent for being added to 40ml dehydrated alcohol and 10ml distilled water are existed first
12h is stirred at 40 DEG C, is made it completely dissolved, mixed solution is obtained；
0.33ml28% ammonium hydroxide is added into mixed solution, pH is about 9, obtains alkaline mixed solution.
(2) 2.2ml ethyl orthosilicate is added in the resulting alkaline mixed solution of step 1), stirs 1h at 40 DEG C, stirs
Mixing speed is 1000rpm, and solution one is obtained after stirring；
1.41g calcium nitrate tetrahydrate is added in solution one, 30min is stirred at 40 DEG C, mixing speed 500rpm is stirred
Solution two is obtained after mixing；
0.1ml orthophosphoric acid is added in solution two, 12h, mixing speed 500rpm, after stirring are stirred at 40 DEG C
Obtain bioactivity glass sol form liquid.
(3) bioactivity glass sol form liquid obtained by step 2) is washed 3 times with distilled water and dehydrated alcohol respectively,
Drying for 24 hours, obtains white bioactivity glass powder at 60 DEG C.
(4) after washing and drying, the white bioactivity glass powder that step 3) is obtained is 550 DEG C in high temperature furnace
Lower high-temperature process 4h removes surfactant and other impurities organic principle, obtains nano-level sphere bioactivity glass.
As shown in Figure 1, nano-level sphere bioactivity glass obtained in the present embodiment is tested, scanning electricity is obtained
Mirror figure, it is known from figures that, the nano-level sphere bioactivity glass average grain diameter prepared in the present embodiment are 37.78nm,
Pattern is spherical shape.
Embodiment 2
A kind of preparation method of nano-level sphere bioactivity glass provided in this embodiment, comprising the following steps:
(1) 0.75g P123 and 0.005g CTAB are added to the solvent of 40ml dehydrated alcohol and 10ml distilled water first
12h is stirred at 40 DEG C, is made it completely dissolved, mixed solution is obtained；
0.33ml28% ammonium hydroxide is added into mixed solution, pH is about 9, obtains alkaline mixed solution.
(2) 2.2ml ethyl orthosilicate is added in the resulting alkaline mixed solution of step 1), stirs 1h at 40 DEG C, stirs
Mixing speed is 1000rpm, and solution one is obtained after stirring；
1.41g calcium nitrate tetrahydrate is added in solution one, 30min is stirred at 40 DEG C, mixing speed 500rpm is stirred
Solution two is obtained after mixing；
0.1ml orthophosphoric acid is added in solution two, 12h, mixing speed 500rpm, after stirring are stirred at 40 DEG C
Obtain bioactivity glass sol form liquid.
(3) bioactivity glass sol form liquid obtained by step 2) is washed 3 times with distilled water and dehydrated alcohol respectively,
Drying for 24 hours, obtains white bioactivity glass powder at 60 DEG C.
(4) after washing and drying, the white bioactivity glass powder that step 3) is obtained is 550 DEG C in high temperature furnace
Lower high-temperature process 4h removes surfactant and other impurities organic principle, obtains nano-level sphere bioactivity glass.
As shown in Fig. 2, nano-level sphere bioactivity glass obtained in the present embodiment is tested, scanning electricity is obtained
Mirror figure after analyzing spectrogram, learns that the nano-level sphere bioactivity glass partial size prepared in the present embodiment is
47.21nm, pattern are spherical shape.
Embodiment 3
By ethyl orthosilicate additional amount is changed to 2.57ml, calcium nitrate tetrahydrate is in step (2) in the present embodiment
0.927g, ortho-phosphoric additional amount are changed to 124 μ l, and other methods step is same as Example 1, and details are not described herein.
As shown in figure 3, nano-level sphere bioactivity glass obtained in the present embodiment is tested, scanning electricity is obtained
Mirror figure after figure is analyzed, learns that the nano-level sphere bioactivity glass partial size prepared in the present embodiment is about 77.65nm,
Pattern is spherical shape.
Embodiment 4
By ethyl orthosilicate additional amount is changed to 2.86ml, calcium nitrate tetrahydrate is in step (2) in the present embodiment
0.73g, orthophosphoric acid are changed to 71 μ 1.Other methods step is same as Example 1, and details are not described herein.
As shown in figure 4, nano-level sphere bioactivity glass obtained in the present embodiment is tested, scanning electricity is obtained
Mirror figure after analyzing figure, learns that the nano-level sphere bioactivity glass partial size prepared in the present embodiment is 86.37nm,
Pattern is spherical shape.
Embodiment 5
The temperature being heat-treated in high temperature furnace in step (1) is changed into 600 DEG C in the present embodiment, other methods step with
Embodiment 1 is identical, and details are not described herein.
As shown in figure 5, nano-level sphere bioactivity glass obtained in the present embodiment is tested, scanning electricity is obtained
Mirror figure after analyzing figure, learns that the nano-level sphere bioactivity glass partial size prepared in the present embodiment is 35.56nm,
Pattern is spherical shape.
Embodiment 6
In the present embodiment 2h, other methods step and reality will be changed into the high temperature furnace high temperature processing time in step (1)
Apply that example 1 is identical, and details are not described herein.
As shown in fig. 6, nano-level sphere bioactivity glass obtained in the present embodiment is tested, scanning electricity is obtained
Mirror figure after analyzing figure, learns that the nano-level sphere bioactivity glass partial size prepared in the present embodiment is 41.35 patterns
For spherical shape.
Reference examples 1
It is identical as example 1 that the additional amount of CTAB in step (1) is changed to 0.1g, other methods and step in this control,
This is repeated no more.
As shown in fig. 7, nano-level sphere bioactivity glass obtained in this reference examples is tested, scanning electricity is obtained
Mirror figure after analyzing figure, learns that the partial size of the spherical biological activity glass prepared in this control is greater than 600nm, pattern is
Spherical shape, and agglomeration is serious.
Reference examples 2
It is identical as example 1 that the additional amount of ammonium hydroxide in step (1) is changed to 2ml, other methods and step in this control, herein
It repeats no more.
As shown in figure 8, nano-level sphere bioactivity glass obtained in this reference examples is tested, scanning electricity is obtained
Mirror figure after analyzing figure, learns that the bioactivity glass agglomeration prepared in this control is serious, substantially not spherical in shape,
For particle agglomeration.
Reference examples 3
By in step (2) in this control, ethyl orthosilicate is added in the resulting alkaline mixed solution of step 1), stirs 1h,
Mixing speed is 200rpm, obtains that gel, other methods and step are identical as example 1, and details are not described herein after stirring.
In this reference examples, spawn is obtained after ethyl orthosilicate is added, nano-level sphere bioactivity cannot be obtained
Glass.
Reference examples 4
By in (2) the step of embodiment 1 in this control, phosphorus source is changed to tricresyl phosphate second rouge, other methods and step and reality
Example 1 is identical, and details are not described herein.
Nano-level sphere bioactivity glass obtained in this reference examples is tested, scanning electron microscope Fig. 9 is obtained, to figure
After being analyzed, the partial size about 42.52nm of the spherical biological activity glass of this reference examples preparation is learnt, pattern is spherical shape, but is rolled into a ball
Poly- phenomenon is serious.
Preparation process uses soft template method in the present invention, and split-phase is not present in liquid phase, and micella size is small, compared to microemulsion
Method, obtained spherical biological activity glass it is smaller.Phosphorus source raw material use orthophosphoric acid in the present invention, can be effectively reduced
Grain diameter.It is added after ethyl orthosilicate and a period of time is stirred persistently with higher revolving speed, calcium source and phosphorus source is then added, so that
Bioactivity glass sol liquid particle in the present invention is tiny, so finally obtain 30~90nm of partial size have meso-hole structure
Nano-level sphere bioactivity glass, and be uniformly dispersed, particle shape spherical in shape.
Due to having a large amount of silicone hydroxyls after teos hydrolysis, gel easily is formed with calcium binding, ball cannot be generated
Shape bioactivity glass, therefore the present invention needs higher mixing speed, to prevent gel-forming, while larger shearing force facilitates
Reduce partial size.
In summary: nano-level sphere bioactivity glass of the invention utilizes nonionic surfactant and cation form
The compound system of face activating agent prepares nano-level sphere bioactivity glass as template, using soft template method, specific to prepare
Method is broadly divided into the progress of two steps, and triblock polymer P123 and CTAB are dissolved in the in the mixed solvent of water and ethyl alcohol first and stirred
It mixes uniformly, basic catalyst ammonium hydroxide is then added and adjusts the pH value of mixed solution, then is separately added into silicon source, calcium source and phosphorus source, stirs
It mixes to obtain sol form liquid；It will finally dry after sol form liquid scrubbing, in high temperature furnace high temperature processing a period of time, obtain small
The nano-level sphere bioactivity glass of partial size, high-specific surface area and porosity.
Nano-level sphere bioactivity glass prepared by the present invention has pore structure abundant, passes through the nonionic of suitable proportion
The compound system of surfactant and cationic surfactant obtains the nanoscale with meso-hole structure of 30~90nm of partial size
Spherical biological activity glass, partial size maintain the pattern of ball-type, can be used for the loading and controlled release of drug while reduction.
Split-phase, prepared micella is not present using soft template method, liquid phase in preparation method in the present invention
Size can be with very little, and the micro emulsion drop of water in preparation method in the prior art such as microemulsion method and organic solvent composition
Size itself is bigger.It is phosphorus source that orthophosphoric acid is used in preparation method of the invention, which can significantly reduce partial size.The present invention
In sequentially add silicon source, calcium source and phosphorus source in the alkaline mixed solution obtained in step (1), easily formed when due to the slow-speed of revolution solidifying
Glue is unable to get nano-level sphere bioactivity glass, therefore carries out continuing high-speed stirred after being added every time, using faster
Speed of agitator also can be effectively reduced grain diameter.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nano-level sphere bioactivity glass, which is characterized in that the preparation method of the activity glass
The following steps are included:
(1) surfactant is dissolved in the mixed solvent, obtains mixed solution, basic catalyst is then added and adjusts mixed solution
PH value to 9~10, obtain alkaline mixed solution；
(2) silicon source, calcium source and phosphorus source are sequentially added in the alkaline mixed solution obtained in step (1), is carried out after being added every time
Continue high-speed stirred, obtains bioactivity glass sol form liquid；
(3) bioactivity glass sol form liquid obtained in step (2) is washed, obtains hygrometric state gel precipitation, then
Hygrometric state gel precipitation is placed in oven and dried, white bioactivity glass powder is obtained；
(4) after washing and drying, obtained white bioactivity glass powder is placed in high temperature furnace and is heat-treated, removed
Surfactant and impurity organic principle, obtain nano-level sphere bioactivity glass.
2. the preparation method of nano-level sphere bioactivity glass as described in claim 1, which is characterized in that in step (1)
Surfactant be nonionic surfactant triblock polymer and cationic surfactant compound system.
3. the preparation method of nano-level sphere bioactivity glass as claimed in claim 2, which is characterized in that the nonionic
Surfactant triblock polymer is P123, molecular formula PEO20PPO70PEO20, PEO is Pluronic F-127 unit, and PPO is
Polycyclic oxypropylene units；
The cationic surfactant is cetyl trimethylammonium bromide.
4. the preparation method of nano-level sphere bioactivity glass as claimed in claim 3, which is characterized in that P123 and 16
The mass ratio of alkyl trimethyl ammonium bromide is (25~150): 1.
5. the preparation method of nano-level sphere bioactivity glass as described in claim 1, which is characterized in that in step (2)
Silicon source be ethyl orthosilicate；
Calcium source in step (2) is calcium nitrate tetrahydrate；
Phosphorus source in step (2) is orthophosphoric acid.
6. the preparation method of nano-level sphere bioactivity glass as claimed in claim 5, which is characterized in that the silicon source,
The molar ratio of calcium source and phosphorus source is (65~80): (20~30): (2~7)；
The surfactant and the mass ratio of silicon source are (0.755~0.78): 2.
7. the preparation method of nano-level sphere bioactivity glass as described in claim 1, which is characterized in that in step (2)
The revolving speed of high-speed stirred is 700~1000rpm after addition silicon source, and the time is 0.5~2h.
8. the preparation method of nano-level sphere bioactivity glass as described in claim 1, which is characterized in that in step (1)
Basic catalyst be ammonium hydroxide；
Preferably, ammonium hydroxide additional proportion is silicon source and ammonium hydroxide volume ratio (2~9): 1；
Preferably, the concentration of ammonium hydroxide is 28%.
9. the preparation method of nano-level sphere bioactivity glass as described in claim 1, which is characterized in that in step (4)
The temperature being heat-treated in high temperature furnace is 500~600 DEG C, 2~5h of soaking time.
10. a kind of nanometer of nano-level sphere bioactivity glass preparation method preparation as described in any one of claims 1 to 9
Grade spherical biological activity glass.
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