CN104225660A - Bioactive glass fibre-polycaprolactone composite film as well as preparation method and application of same - Google Patents

Bioactive glass fibre-polycaprolactone composite film as well as preparation method and application of same Download PDF

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CN104225660A
CN104225660A CN201410466451.4A CN201410466451A CN104225660A CN 104225660 A CN104225660 A CN 104225660A CN 201410466451 A CN201410466451 A CN 201410466451A CN 104225660 A CN104225660 A CN 104225660A
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bioactive glass
glass fiber
polycaprolactone
composite membrane
polycaprolactone composite
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CN104225660B (en
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陈晓峰
刘惠
李贤�
林泽峰
李玉莉
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South China University of Technology SCUT
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Abstract

The invention belongs to the field of biomedical composite materials, and discloses a bioactive glass fibre-polycaprolactone composite film as well as a preparation method and an application of the same. The bioactive glass fibre-polycaprolactone composite film is mainly obtained by preparing bioactive glass fibres with nanopores by combining an electrospinning technology with a sol-gel method, then dispersing the bioactive glass fibres in polycaprolactone-containing solution, spreading on a glass dish, and drying. The bioactive glass fibre-polycaprolactone composite film is of a hierarchical porous structure, the diameters of large pores on the film are 20-100 microns, and the diameters of small pores on the film are less than 2 microns. The bioactive glass fibre-polycaprolactone composite film is good in medicine-carrying and gene-carrying potentials, and good in application prospect in the aspects of hard tissue repair and skin auxiliary materials due to the hierarchical porous structure.

Description

Bioactive glass fiber-polycaprolactone composite membrane and preparation method thereof and application
Technical field
The invention belongs to bio-medical composition field, be specifically related to a kind of bioactive glass fiber-polycaprolactone composite membrane and preparation method thereof and application.
Background technology
1969, prosperous strange (Hench) taught first passage fusion method and obtains 45S5 (45%SiO 2-24.5%Na 2o-24.5%CaO-6%P 2o 5) bio-vitric, and use it for the test of Mus femur planting model, under finding fluid environment, its surface energy forms hydroxyapatite crystal fast, this crystal is combined with the oozy collagen fiber of adjacent osteocyte, forms the interface cohesion suitable with host bone intensity.And the later stage finds, adjustment bio-vitric composition can make itself and soft tissue form reasonable interface cohesion.The eighties in 20th century is for reparation and the periodontal disease injury repairing of clinical middle otica.
The good biological activity of bioactivity glass, biocompatibility etc. make it develop in recent years more to grow, 1991, Heng Qi seminar uses sol-gel process to prepare stable bioactivity glass, this method has derived serial of methods subsequently, as template, method of electrostatic spinning etc., obtain the bioactivity glass of a lot of different component and pattern.
The people such as Kim utilize method of electrostatic spinning to obtain biological activity glass nano-fibre (Adv.Funct.Mater.2006 first, 16,1529), it can not only play the effect of fibrous template in Bone Defect Repari, also has superior biological activity and Osteoblast Differentiation potential.The people such as Hong utilize the characteristic that is separated (Adv.Funct.Mater.2010,20,1503) of electrospinning process, and obtained hollow bioactive glass fiber, has good medicine and carry and sustained release performance.
The biological activity of bioactive glass fiber excellence ascribes plasma diffusing W,Mo fast to, but surrounding materials calcium, phosphate radical plasma concentration can be made too high, comparatively large to the toxicity of cell, is unfavorable for the reparation being directly used in the tissue such as bone or skin.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of bioactive glass fiber-polycaprolactone composite membrane, and the bioactive glass fiber that described preparation method obtains-polycaprolactone composite membrane has graded porous structure;
Another object of the present invention is to the bioactive glass fiber-polycaprolactone composite membrane providing above-mentioned preparation method to obtain, described bioactive glass fiber-polycaprolactone composite membrane has good biocompatibility, biological activity and medicine carrying thing/year gene ability, and can control the release of contained medicine or gene;
Another object of the present invention is the application providing above-mentioned bioactive glass fiber-polycaprolactone composite membrane, and it has the potential repaired for skin wound as dressing, and is used for Bone Defect Repari as bioactivity coatings.
Object of the present invention is achieved through the following technical solutions:
A preparation method for bioactive glass fiber-polycaprolactone composite membrane, comprises the steps:
(1) 50 ~ 150mg bioactive glass fiber being joined 10mL mass volume ratio is in the polycaprolactone-acetic acid solution of 8% ~ 12%, stirring or ultrasonic wave concussion make bioactive glass fiber be uniformly dispersed in polycaprolactone-acetic acid solution, carry out magnetic agitation 30min again, obtain bioactive glass fiber-polycaprolactone mixed solution;
(2) getting bioactive glass fiber described in 4 ~ 10mL-polycaprolactone mixed solution, to join diameter be in the glass dish of 10cm, and vacuum drying 2 days, obtains described bioactive glass fiber-polycaprolactone composite membrane.
Preferably, in the described polycaprolactone-acetic acid solution of step (1), the molecular weight of polycaprolactone is 40000 ~ 80000;
Preferably, the preparation method of step (1) described bioactive glass fiber is:
(I) ethanol, water and 2mol/L hydrochloric acid solution are mixed, add template, magnetic agitation mix homogeneously, then add ethyl orthosilicate (TEOS), triethyl phosphate (TEP) and lime nitrate successively, stir and obtain bio-vitric precursor solution;
Preferably, the consumption of step (I) described water is 1mL, and the consumption of described 2mol/L hydrochloric acid solution is 1mL, and the consumption volume ratio of described ethanol and water is (6 ~ 14): 1;
Preferably, described in step (I), the mol ratio of water and described ethyl orthosilicate is (2.5 ~ 3.5): 1;
Preferably, step (I) described ethyl orthosilicate, triethyl phosphate and lime nitrate mol ratio are: ethyl orthosilicate: lime nitrate: triethyl phosphate=(60 ~ 90): (36 ~ 6): 8;
According to described ethyl orthosilicate, triethyl phosphate and lime nitrate mol ratio, in the bioactive glass fiber finally obtained, the mol ratio of silicon oxide, calcium oxide and phosphorus pentoxide is: silicon oxide: calcium oxide: phosphorus pentoxide=(60 ~ 90): (36 ~ 6): 4;
Preferably, described template is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer (P123), and the consumption of described template is 0 ~ 2g;
(II) described bio-vitric precursor solution is sealed ageing 0.5 ~ 4 day at ambient temperature, obtain the bio-vitric precursor solution after ageing;
(III) get the bio-vitric precursor solution after ageing described in 5mL to mix with isopyknic ethanol, then the binding agent adding 300 ~ 500mg mixes to and obtains clear solution;
Preferably, step (III) described bonding agent is polyvinyl butyral resin (PVB);
(IV) get 5mL step (III) described clear solution with syringe and carry out electrostatic spinning, clear solution extruded velocity is set as 0.5 ~ 1.0mL/h, applying electric field is 1.4 ~ 2KV/cm, the thick product of bioactive glass fiber of electrostatic spinning formation is received with aluminium-foil paper, obtain the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in vacuum drying oven dry 3 days;
(V) thick for the bioactive glass fiber on aluminium-foil paper product film is taken off after completing by drying, thick for described bioactive glass fiber product film is placed in 650 DEG C of environment heat treatments 3 hours, obtains described bioactive glass fiber.
A kind of bioactive glass fiber-polycaprolactone composite membrane obtained by above-mentioned preparation method.
Described bioactive glass fiber-polycaprolactone composite membrane has graded porous structure, and described bioactive glass fiber is dispersed in surface and the inside of described polycaprolactone film;
Preferably, there are in described bioactive glass fiber-polycaprolactone composite membrane three class aperture specifications, wherein the diameter of first kind hole is 20 ~ 100 μm, and the diameter of Equations of The Second Kind hole is less than 2 μm, and the 3rd class hole is made a living the nano-pore that thing activity glass fiber itself has;
Preferably, the thickness of described bioactive glass fiber-polycaprolactone composite membrane is 100 μm ~ 400 μm;
Preferably, the diameter of described bioactive glass fiber is 500nm ~ 2 μm;
Preferably, described bioactive glass fiber is more than one in uniform nano-porous bioactive glass fiber, hollow nano-pore bioactive glass fiber or classifying nano hole bioactive glass fiber;
Preferred, the aperture of described uniform nano-porous bioactive glass fiber is 7 ~ 13nm; The internal hollow channel diameter of described hollow nano-pore bioactive glass fiber is 50 ~ 200nm, and on surrounding wall, the diameter of aperture is 7 ~ 20nm; On described classifying nano hole bioactive glass fiber, hole diameter is 5 ~ 300nm, and inner aperture reduces from inside to outside.
Above-mentioned bioactive glass fiber-polycaprolactone composite membrane is in the application preparing skin adjuvant, biologically inert substrate surface material and prepare medicine carrying thing or carry in the tissue repair film of gene.
Principle of the present invention:
Adopt acetic acid as the solvent of polycaprolactone in preparation method of the present invention, little compared to other organic solvent toxicities, and due in concentration range used, solution viscosity is larger, easily stablize some smaller bubbles in the solution, it has certain pore effect in film forming procedure.The freezing point of glacial acetic acid is 16.7 DEG C, because a large amount of heat is taken away in surface solvent volatilization in film forming procedure, the inner glacial acetic acid of film may be made to reach freezing point and solidify, thus play the effect of porogen, make described bioactive glass fiber-polycaprolactone composite membrane form graded porous structure.
In the preparation technology of bioactive glass fiber, by not adding P123, or regulating solution viscosity with different content polyvinyl butyral after adding P123, the bioactive glass fiber of different pore space structure can be obtained; Add the hole of P123 to bioactive glass fiber inside and have considerable influence, with the increase of its P123 content, bioactive glass fiber internal holes increases.
Bioactive glass fiber-polycaprolactone the composite membrane of gained of the present invention, wherein bioactivity glass has the performance of good promotion union of wounded skin, short Bone Defect Repari characteristic and mediated gene transfection, combine with the polycaprolactone with good biocompatibility and mechanical property, preparing skin adjuvant, biologically inert substrate surface material and preparing medicine carrying thing or carry the huge applications prospect had in the tissue repair film of gene.
The present invention has following advantage and effect relative to prior art:
(1) acetic acid of the present invention's employing is as solvent, and toxicity is little.
(2) bioactive glass fiber of the present invention-polycaprolactone composite membrane has graded porous structure, is not only conducive to the adhesion of cell on its surface, in skin adjuvant, also has good application prospect;
(3) bioactive glass fiber of the present invention-polycaprolactone composite membrane can be used as the surface that coating is coated on the base material of biologically inert, improves biocompatibility and the biological activity of base material;
(4) bioactive glass fiber that has of bioactive glass fiber of the present invention-polycaprolactone composite membrane, it is the good carrier of medicine or gene, and because described bioactive glass fiber-polycaprolactone composite membrane has graded porous structure, be beneficial to the release of medicine or gene, therefore can be prepared into the medicine carrying thing with superperformance or the tissue repair film carrying gene.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope shape appearance figure of described bioactive glass fiber.
Fig. 2 is the transmission electron microscope shape appearance figure of described bioactive glass fiber.
Fig. 3 is the inverted light microscope shape appearance figure of described bioactive glass fiber-polycaprolactone composite membrane.
Fig. 4 is the stereoscan photograph of described bioactive glass fiber-polycaprolactone composite membrane, and wherein white arrow indication is bioactive glass fiber, and black arrow indication is the graded porous structure of described bioactive glass fiber-polycaprolactone composite membrane.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of bioactive glass fiber-polycaprolactone composite membrane, its preparation method is:
(1) in beaker, add with pipettor the hydrochloric acid solution and 1mL deionized water that 1mL concentration is 2mol/L, then add 8mL ethanol solution, 2.0gP123, mixed at room temperature stirs 30min; Then under Keep agitation condition, 6.43mL ethyl orthosilicate, 0.65mL triethyl phosphate and 4.07g lime nitrate is added successively, the interval that described ethyl orthosilicate, triethyl phosphate and lime nitrate add is 3h, continue to stir 12h after adding lime nitrate, obtain bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, obtain the bio-vitric precursor solution after ageing.
(3) get the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.5g polyvinyl butyral resin, magnetic agitation is to forming clear solution.
(4) described clear solution 5mL is got with syringe, for electrostatic spinning, clear solution extruded velocity is 1mL/h, collecting board is from Wire outlet head 12cm, two pole tensions are 21KV, receive the thick product of bioactive glass fiber of electrostatic spinning formation, obtain the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber with aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in dry 3 days of the vacuum drying oven of 40 DEG C, with except desolventizing.
(5) thick for the bioactive glass fiber on aluminium-foil paper product film to be taken off after completing and is transferred in alumina crucible by drying, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber;
Carry out scanning electron microscope and transmission electron microscope analysis to the bioactive glass fiber of gained, as shown in Figure 1, transmission electron microscope shape appearance figure as shown in Figure 2 for scanning electron microscope shape appearance figure.
Analyzed from Fig. 1 and Fig. 2, described bioactive glass fiber is classifying nano hole bioactive glass fiber.
(6) getting 50mg step (5) described bioactive glass fiber, to join 10ml mass volume ratio be in the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, carry out magnetic agitation 30min again, obtain bioactive glass fiber-polycaprolactone mixed solution.
(7) it is in the glass dish of 10cm that the bioactive glass fiber-polycaprolactone mixed solution got described in 4mL joins diameter, and vacuum drying 2 days obtains described bioactive glass fiber-polycaprolactone composite membrane.
Carry out detection to the bioactive glass fiber-polycaprolactone composite membrane of gained to analyze, its optical microscope shape appearance figure as shown in Figure 3, its scanning electron microscope shape appearance figure as shown in Figure 4, in the diagram, white arrow indication is described bioactive glass fiber, and black arrow indication is the graded porous structure of described bioactive glass fiber-polycaprolactone composite membrane.From Fig. 3 and Fig. 4, described bioactive glass fiber-polycaprolactone composite membrane has the intensive hole varied in size, and forms graded porous structure.
Embodiment 2
A kind of bioactive glass fiber-polycaprolactone composite membrane, its preparation method is:
(1) in beaker, add with pipettor the hydrochloric acid solution and 1mL deionized water that 1mL concentration is 2mol/L, then add 8mL ethanol solution, 2.0gP123, mixed at room temperature stirs 30min; Then under Keep agitation condition, 6.43mL ethyl orthosilicate, 0.65mL triethyl phosphate and 4.07g lime nitrate is added successively, the interval that described ethyl orthosilicate, triethyl phosphate and lime nitrate add is 3h, continue to stir 12h after adding lime nitrate, obtain bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, obtain the bio-vitric precursor solution after ageing.
(3) get the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.3g polyvinyl butyral resin, magnetic agitation is to forming clear solution.
(4) described clear solution 5mL is got with 10mL syringe, for electrostatic spinning, clear solution extruded velocity is 1mL/h, collecting board is from Wire outlet head 12cm, two pole tensions are 20KV, receive the thick product of bioactive glass fiber of electrostatic spinning formation, obtain the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber with aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in dry 3 days of the vacuum drying oven of 40 DEG C, with except desolventizing.
(5) thick for the bioactive glass fiber on aluminium-foil paper product film to be taken off after completing and is transferred in alumina crucible by drying, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber;
Scanning electron microscope as embodiment 1 and transmission electron microscope analysis are carried out to the bioactive glass fiber of gained, show that described bioactive glass fiber is hollow nano-pore bioactive glass fiber.
(6) getting 100mg step (5) described bioactive glass fiber, to join 10ml mass volume ratio be in the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, carry out magnetic agitation 30min again, obtain bioactive glass fiber-polycaprolactone mixed solution.
(7) it is in the glass dish of 10cm that the bioactive glass fiber-polycaprolactone mixed solution got described in 10mL joins diameter, and vacuum drying 2 days obtains described bioactive glass fiber-polycaprolactone composite membrane.
Get the detection analysis that described bioactive glass fiber-polycaprolactone composite membrane carries out as embodiment 1, detect analysis result substantially the same manner as Example 1.
Embodiment 3
A kind of bioactive glass fiber-polycaprolactone composite membrane, its preparation method is:
(1) in beaker, add with pipettor the hydrochloric acid solution and 1mL deionized water that 1mL concentration is 2mol/L, then add 8mL ethanol solution, mixed at room temperature stirs 10min; Then under Keep agitation condition, 6.43mL ethyl orthosilicate, 0.65mL triethyl phosphate and 4.07g lime nitrate is added successively, the interval that described ethyl orthosilicate, triethyl phosphate and lime nitrate add is 3h, continue to stir 12h after adding lime nitrate, obtain bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, obtain the bio-vitric precursor solution after ageing.
(3) get the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.5g polyvinyl butyral resin, magnetic agitation is to forming clear solution.
(4) described clear solution 5mL is got with 10mL syringe, for electrostatic spinning, clear solution extruded velocity is 1mL/h, collecting board is from Wire outlet head 12cm, two pole tensions are 21KV, receive the thick product of bioactive glass fiber of electrostatic spinning formation, obtain the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber with aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in dry 3 days of the vacuum drying oven of 40 DEG C, with except desolventizing.
(5) thick for the bioactive glass fiber on aluminium-foil paper product film to be taken off after completing and is transferred in alumina crucible by drying, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber;
Scanning electron microscope as embodiment 1 and transmission electron microscope analysis are carried out to the bioactive glass fiber of gained, show that described bioactive glass fiber is uniform nano-porous bioactive glass fiber.
(6) getting 100mg step (5) described bioactive glass fiber, to join 10ml mass volume ratio be in the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, carry out magnetic agitation 30min again, obtain bioactive glass fiber-polycaprolactone mixed solution.
(7) it is in the glass dish of 10cm that the bioactive glass fiber-polycaprolactone mixed solution got described in 6mL joins diameter, and vacuum drying 2 days obtains described bioactive glass fiber-polycaprolactone composite membrane.
Get the detection analysis that described bioactive glass fiber-polycaprolactone composite membrane carries out as embodiment 1, detect analysis result substantially the same manner as Example 1.
Embodiment 4
A kind of bioactive glass fiber-polycaprolactone composite membrane, its preparation method is:
(1) in beaker, add with pipettor the hydrochloric acid solution and 1mL deionized water that 1mL concentration is 2mol/L, then add 8mL ethanol solution, mixed at room temperature stirs 10min; Then under Keep agitation condition, 6.43mL ethyl orthosilicate, 0.433mL triethyl phosphate and 0.452g lime nitrate is added successively, the interval that described ethyl orthosilicate, triethyl phosphate and lime nitrate add is 3h, continue to stir 12h after adding lime nitrate, obtain bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, obtain the bio-vitric precursor solution after ageing.
(3) get the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.5g polyvinyl butyral resin, magnetic agitation is to forming clear solution.
(4) described clear solution 5mL is got with 10mL syringe, for electrostatic spinning, clear solution extruded velocity is 1mL/h, collecting board is from Wire outlet head 12cm, two pole tensions are 18KV, receive the thick product of bioactive glass fiber of electrostatic spinning formation, obtain the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber with aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in dry 3 days of the vacuum drying oven of 40 DEG C, with except desolventizing.
(5) thick for the bioactive glass fiber on aluminium-foil paper product film to be taken off after completing and is transferred in alumina crucible by drying, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber;
Scanning electron microscope as embodiment 1 and transmission electron microscope analysis are carried out to the bioactive glass fiber of gained, show that described bioactive glass fiber is uniform nano-porous bioactive glass fiber.
(6) getting 150mg step (5) described bioactive glass fiber, to join 10ml mass volume ratio be in the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, carry out magnetic agitation 30min again, obtain bioactive glass fiber-polycaprolactone mixed solution.
(7) it is in the glass dish of 10cm that the bioactive glass fiber-polycaprolactone mixed solution got described in 6mL joins diameter, and vacuum drying 2 days obtains described bioactive glass fiber-polycaprolactone composite membrane.
Get the detection analysis that described bioactive glass fiber-polycaprolactone composite membrane carries out as embodiment 1, detect analysis result substantially the same manner as Example 1.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (10)

1. a preparation method for bioactive glass fiber-polycaprolactone composite membrane, is characterized in that comprising the steps:
(1) 50 ~ 150mg bioactive glass fiber being joined 10mL mass volume ratio is in the polycaprolactone-acetic acid solution of 8% ~ 12%, stirring or ultrasonic wave concussion make bioactive glass fiber be uniformly dispersed in polycaprolactone-acetic acid solution, carry out magnetic agitation 30min again, obtain bioactive glass fiber-polycaprolactone mixed solution;
(2) getting bioactive glass fiber described in 4 ~ 10mL-polycaprolactone mixed solution, to join diameter be in the glass dish of 10cm, and vacuum drying 2 days, obtains described bioactive glass fiber-polycaprolactone composite membrane.
2. the preparation method of a kind of bioactive glass fiber-polycaprolactone composite membrane according to claim 1, is characterized in that: in the described polycaprolactone-acetic acid solution of step (1), the molecular weight of polycaprolactone is 40000 ~ 80000.
3. the preparation method of a kind of bioactive glass fiber-polycaprolactone composite membrane according to claim 1, is characterized in that: the preparation method of step (1) described bioactive glass fiber is:
(I) ethanol, water and 2mol/L hydrochloric acid solution are mixed, add template, magnetic agitation mix homogeneously, then add ethyl orthosilicate, triethyl phosphate and lime nitrate successively, stir and obtain bio-vitric precursor solution;
(II) described bio-vitric precursor solution is sealed ageing 0.5 ~ 4 day at ambient temperature, obtain the bio-vitric precursor solution after ageing;
(III) get the bio-vitric precursor solution after ageing described in 5mL to mix with isopyknic ethanol, then the binding agent adding 300 ~ 500mg mixes to and obtains clear solution;
(IV) get 5mL step (III) described clear solution with syringe and carry out electrostatic spinning, clear solution extruded velocity is set as 0.5 ~ 1.0mL/h, applying electric field is 1.4 ~ 2KV/cm, the thick product of bioactive glass fiber of electrostatic spinning formation is received with aluminium-foil paper, obtain the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in vacuum drying oven dry 3 days;
(V) thick for the bioactive glass fiber on aluminium-foil paper product film is taken off after completing by drying, thick for described bioactive glass fiber product film is placed in 650 DEG C of environment heat treatments 3 hours, obtains described bioactive glass fiber.
4. the preparation method of a kind of bioactive glass fiber-polycaprolactone composite membrane according to claim 3, it is characterized in that: in the preparation method of described bioactive glass fiber, the consumption of step (I) described water is 1mL, the consumption of described 2mol/L hydrochloric acid solution is 1mL, and the consumption volume ratio of described ethanol and water is (6 ~ 14): 1; Described in step (I), the mol ratio of water and described ethyl orthosilicate is (2.5 ~ 3.5): 1; Step (I) described ethyl orthosilicate, triethyl phosphate and lime nitrate mol ratio are: ethyl orthosilicate: lime nitrate: triethyl phosphate=(60 ~ 90): (36 ~ 6): 8; Step (III) described bonding agent is polyvinyl butyral resin.
5. the preparation method of a kind of bioactive glass fiber-polycaprolactone composite membrane according to claim 3, it is characterized in that: in the preparation method of described bioactive glass fiber, template described in step (I) is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, and the consumption of described template is 0 ~ 2g.
6. bioactive glass fiber-polycaprolactone composite membrane of obtaining of the preparation method of the bioactive glass fiber-polycaprolactone composite membrane according to any one of Claims 1 to 5, described bioactive glass fiber-polycaprolactone composite membrane has graded porous structure, and described bioactive glass fiber is dispersed in surface and the inside of described polycaprolactone film.
7. bioactive glass fiber according to claim 6-polycaprolactone composite membrane, it is characterized in that: there are in described bioactive glass fiber-polycaprolactone composite membrane three class aperture specifications, wherein the diameter of first kind hole is 20 ~ 100 μm, the diameter of Equations of The Second Kind hole is less than 2 μm, and the 3rd class hole is made a living the nano-pore that thing activity glass fiber itself has; The thickness of described bioactive glass fiber-polycaprolactone composite membrane is 100 μm ~ 400 μm; The diameter of described bioactive glass fiber is 500nm ~ 2 μm.
8. bioactive glass fiber according to claim 7-polycaprolactone composite membrane, is characterized in that: described bioactive glass fiber is more than one in uniform nano-porous bioactive glass fiber, hollow nano-pore bioactive glass fiber or classifying nano hole bioactive glass fiber.
9. bioactive glass fiber according to claim 8-polycaprolactone composite membrane, is characterized in that: the aperture of described uniform nano-porous bioactive glass fiber is 7 ~ 13nm; The internal hollow channel diameter of described hollow nano-pore bioactive glass fiber is 50 ~ 200nm, and on surrounding wall, the diameter of aperture is 7 ~ 20nm; On described classifying nano hole bioactive glass fiber, hole diameter is 5 ~ 300nm, and inner aperture reduces from inside to outside.
10. bioactive glass fiber according to claim 6-polycaprolactone composite membrane is in the application preparing skin adjuvant, biologically inert substrate surface material and prepare medicine carrying thing or carry in the tissue repair film of gene.
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