CN104225660B - Bioactive glass fiber-polycaprolactone composite membrane and preparation method and application - Google Patents
Bioactive glass fiber-polycaprolactone composite membrane and preparation method and application Download PDFInfo
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Abstract
The invention belongs to bio-medical composition field, disclose a kind of bioactive glass fiber polycaprolactone composite membrane and preparation method and application.Described bioactive glass fiber polycaprolactone composite membrane is mainly combined with sol-gal process by electrostatic spinning technique and prepares the bioactive glass fiber with nano-pore, again this bioactive glass fiber is dispersed in the solution containing polycaprolactone, spread on glass dish, be dried and both obtained.Described bioactive glass fiber polycaprolactone composite membrane has graded porous structure, and on film, macropore is 20～100um, and aperture is less than 2um.Described bioactive glass fiber polycaprolactone composite membrane has good medicine carrying and carries the potential of gene, and graded porous structure makes it have preferable application prospect in terms of hard tissue repair and skin adjuvant simultaneously.
Description
Technical field
The invention belongs to bio-medical composition field, be specifically related to a kind of bioactive glass fiber-poly-oneself
Lactone composite membrane and preparation method and application.
Background technology
1969, prosperous strange (Hench) professor's first passage fusion method prepared 45S5
(45%SiO2-24.5%Na2O-24.5%CaO-6%P2O5) bio-vitric, and use it for the implantation of Mus femur
Model measurement, finds that under fluid environment, its surface can quickly form hydroxyapatite crystal, this crystal and phase
The adjacent oozy collagen fiber of osteocyte combine, and form the interface cohesion suitable with host bone intensity.After and
Phase finds, adjusts bio-vitric composition and itself and soft tissue can be made to form reasonable interface cohesion.20th century 80
Age has been used for reparation and the periodontal disease injury repairing of otica in clinic.
The preferable biological activity of bioactivity glass, biocompatibility etc. make it develop in recent years more to grow,
1991, Heng Qi seminar used sol-gel process to be prepared for stable bioactivity glass, and this method is spread out subsequently
Give birth to serial of methods, such as template, method of electrostatic spinning etc., obtain the life of a lot of different component and pattern
Thing activity glass.
Kim et al. utilizes method of electrostatic spinning to prepare biological activity glass nano-fibre (Adv.Funct. first
Mater.2006,16,1529), it can not only play the effect of fibrous template in Bone Defect Repari, also has superior
Biological activity and Osteoblast Differentiation potential.Hong et al. utilizes the separated characteristic (Adv.Funct. of electro-spinning process
Mater.2010,20,1503), prepare hollow bioactive glass fiber, there is preferable medicine and carry and slow-releasing
Energy.
The biological activity that bioactive glass fiber is excellent is attributed to quick plasma diffusing W,Mo, but can make material week
Enclose calcium, phosphate radical plasma concentration too high, relatively big to the toxicity of cell, it is unfavorable for being directly used in bone or skin
Reparation in tissue.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the primary and foremost purpose of the present invention is to provide a kind of biological alive
Property glass fibre-polycaprolactone composite membrane preparation method, bioactivity glass that described preparation method obtains is fine
Dimension-polycaprolactone composite membrane has graded porous structure；
Another object of the present invention is to the bioactive glass fiber that provides above-mentioned preparation method to obtain-poly-in oneself
Ester composite membrane, described bioactive glass fiber-polycaprolactone composite membrane has good biocompatibility, life
Thing activity and medicine carrying thing/load gene ability, and the release of contained medicine or gene can be controlled；
It is still another object of the present invention to provide answering of above-mentioned bioactive glass fiber-polycaprolactone composite membrane
With, it has the potential repaired as dressing for skin wound, and repaiies for bone as bioactivity coatings
Multiple.
The purpose of the present invention is achieved through the following technical solutions:
The preparation method of a kind of bioactive glass fiber-polycaprolactone composite membrane, comprises the steps:
(1) 50～150mg bioactive glass fiber being joined 10mL mass volume ratio is 8%～12%
Polycaprolactone-acetic acid solution in, stirring or ultrasonic wave concussion make bioactive glass fiber polycaprolactone-
Acetic acid solution is uniformly dispersed, then carries out magnetic agitation 30min, obtain bioactive glass fiber-poly-in oneself
Ester mixed solution；
(2) take bioactive glass fiber described in 4～10mL-polycaprolactone mixed solution and join a diameter of
In the glass dish of 10cm, it is vacuum dried 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, addition template, magnetic agitation mix homogeneously,
Sequentially add tetraethyl orthosilicate (TEOS), triethyl phosphate (TEP) and calcium nitrate, be uniformly mixing to 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, described ethanol is (6～14) with the consumption volume ratio of water: 1；
Preferably, water described in step (I) is (2.5～3.5) with the mol ratio of described tetraethyl orthosilicate: 1；
Preferably, step (I) described tetraethyl orthosilicate, triethyl phosphate and calcium nitrate mol ratio are: positive silicon
Acetoacetic ester: calcium nitrate: triethyl phosphate=(60～90): (36～6): 8；
According to described tetraethyl orthosilicate, triethyl phosphate and calcium nitrate mol ratio, the biological activity finally given
In glass fibre, the mol ratio of silicon oxide, calcium oxide and phosphorus pentoxide is: silicon oxide: calcium oxide: five oxygen
Change two phosphorus=(60～90): (36～6): 4；
Preferably, described template is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer
(P123), the consumption of described template is 0～2g；
(II) described bio-vitric precursor solution is sealed at ambient temperature ageing 0.5～4 day, obtain old
Bio-vitric precursor solution after change；
(III) take the bio-vitric precursor solution after ageing described in 5mL to mix with isopyknic ethanol, then
The binding agent of addition 300～500mg mixes to obtain clear solution；
Preferably, step (III) described bonding agent is polyvinyl butyral resin (PVB)；
(IV) take 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, and applying electric field is 1.4～2KV/cm, receives Static Spinning with aluminium-foil paper
The thick product of bioactive glass fiber that silk is formed, obtains being loaded with the thick product film of bioactive glass fiber
Aluminium-foil paper, is then placed in the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber in vacuum drying oven
It is dried 3 days；
(V) after being dried, thick for the bioactive glass fiber on aluminium-foil paper product film is taken off, by described
The thick product film of bioactive glass fiber is placed in heat treatment 3 hours in 650 DEG C of environment, obtains described biological alive
Property glass fibre.
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, described biological activity
Glass fibre is dispersed in surface and the inside of described polycaprolactone film；
Preferably, described bioactive glass fiber-polycaprolactone composite membrane has three class aperture specifications, its
A diameter of 20～100 μm of middle first kind hole, the diameter of Equations of The Second Kind hole is less than 2 μm, the 3rd class hole
The nano-pore being had by bioactive glass fiber itself；
Preferably, the thickness of described bioactive glass fiber-polycaprolactone composite membrane is 100 μm～400 μ
m；
Preferably, a diameter of 500nm of described bioactive glass fiber～2 μm；
Preferably, described bioactive glass fiber is that uniform nano-porous bioactive glass fiber, hollow are received
More than one in metre hole bioactive glass fiber or classifying nano hole bioactive glass fiber；
It is furthermore preferred that the aperture of described uniform nano-porous bioactive glass fiber is 7～13nm；Described hollow
The internal hollow channel a diameter of 50～200nm of nano-pore bioactive glass fiber, on surrounding wall, aperture is straight
Footpath is 7～20nm；On described classifying nano hole bioactive glass fiber, hole diameter is 5～300nm, internal
Aperture reduces from inside to outside.
Above-mentioned bioactive glass fiber-polycaprolactone composite membrane is preparing skin adjuvant, biologically inert substrate table
Face material and prepare medicine carrying thing or carry gene tissue repair film in application.
The principle of the present invention:
In preparation method of the present invention, employing acetic acid is as the solvent of polycaprolactone, compared to other organic solvents poison
Property little, and due in concentration range used, solution viscosity is relatively big, stablizes some the most in the solution more stingy
Bubble, it has certain pore effect in film forming procedure.The freezing point of glacial acetic acid is 16.7 DEG C, film forming procedure
In take away a large amount of heat due to surface solvent volatilization, the internal glacial acetic acid of film may be made to reach freezing point and solidify, from
And play the effect of porogen, it is many to make that described bioactive glass fiber-polycaprolactone composite membrane can form classification
Pore structure.
In the preparation technology of bioactive glass fiber, by without P123, or add after P123 with not
Solution viscosity, the bioactive glass fiber of available different pore space structures is regulated with content polyvinyl butyral；
Add P123 and there is considerable influence in the hole within bioactive glass fiber, with the increase of its P123 content,
Bioactive glass fiber internal holes increases.
The bioactive glass fiber of gained of the present invention-polycaprolactone composite membrane, wherein bioactivity glass has
Good promotion union of wounded skin, rush Bone Defect Repari characteristic and the performance of mediated gene transfection, good with having
The polycaprolactone combination of biocompatibility and mechanical property, is preparing skin adjuvant, biologically inert substrate surface
Material and the huge applications prospect that has in preparing medicine carrying thing or carrying the tissue repair film of gene.
The present invention has such advantages as relative to prior art and effect:
(1) acetic acid that the present invention uses is as solvent, and toxicity is little.
(2) bioactive glass fiber of the present invention-polycaprolactone composite membrane has graded porous structure, no
Only be conducive to the cell adhesion on its surface, in terms of skin adjuvant, also have preferable application prospect；
(3) bioactive glass fiber of the present invention-polycaprolactone composite membrane can be coated on biology as coating
The surface of inert base material, improves biocompatibility and the biological activity of base material；
(4) bioactivity glass that bioactive glass fiber of the present invention-polycaprolactone composite membrane has is fine
Dimension, is the good carrier of medicine or gene, and owing to described bioactive glass fiber-polycaprolactone is combined
Film has graded porous structure, beneficially medicine or the release of gene, therefore can be prepared as having superperformance
Medicine carrying thing or the tissue repair film of load 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, wherein white
Arrow indication is bioactive glass fiber, and black arrow indication is that described bioactive glass fiber-poly-is in oneself
The graded porous structure of ester 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
It is not limited to this.
Embodiment 1
A kind of bioactive glass fiber-polycaprolactone composite membrane, its preparation method is:
(1) in beaker, add, with pipettor, 1mL concentration is 2mol/L hydrochloric acid solution and 1mL go from
Sub-water, adds 8mL ethanol solution, 2.0gP123, mixed at room temperature stirring 30min；Then holding
It is sequentially added into 6.43mL tetraethyl orthosilicate, 0.65mL triethyl phosphate and 4.07g nitric acid under continuous stirring condition
Calcium, the time interval that described tetraethyl orthosilicate, triethyl phosphate and calcium nitrate add is 3h, adds calcium nitrate
Rear continuation stirs 12h, obtains bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, the biological glass after being aged
Glass precursor solution.
(3) take the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.5g polyethylene
Butyral, magnetic agitation is to forming clear solution.
(4) taking described clear solution 5mL with syringe, for electrostatic spinning, clear solution extruded velocity is
1mL/h, collecting board is from Wire outlet head 12cm, and two pole tensions are 21KV, receives electrostatic spinning with aluminium-foil paper and is formed
The thick product of bioactive glass fiber, obtain being loaded with the aluminium-foil paper of 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 the vacuum drying oven of 40 DEG C dry
Dry 3 days, to remove solvent.
(5) after being dried, thick for the bioactive glass fiber on aluminium-foil paper product film is taken off and be transferred to oxygen
Change in aluminum crucible, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber；
The bioactive glass fiber of gained is scanned Electronic Speculum and transmission electron microscope analysis, scanning electron microscope pattern
Figure as it is shown in figure 1, transmission electron microscope shape appearance figure as shown in Figure 2.
From Fig. 1 and Fig. 2 analysis, described bioactive glass fiber is classifying nano hole bioactive glass
Glass fiber.
(6) take 50mg step (5) described bioactive glass fiber and join 10ml mass volume ratio and be
In the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, then carry out magnetic agitation 30min, obtain biological living
Property glass fibre-polycaprolactone mixed solution.
(7) take the bioactive glass fiber described in 4mL-polycaprolactone mixed solution and join a diameter of
In the glass dish of 10cm, it is vacuum dried 2 days, obtains described bioactive glass fiber-polycaprolactone composite membrane.
Bioactive glass fiber-polycaprolactone the composite membrane of gained is carried out detection analysis, its optical microscope
Shape appearance figure as it is shown on figure 3, its scanning electron microscope shape appearance figure as shown in Figure 4, in the diagram, white arrow indication is institute
The bioactive glass fiber stated, black arrow indication is that described bioactive glass fiber-polycaprolactone is combined
The graded porous structure of film.From Fig. 3 and Fig. 4, described bioactive glass fiber-polycaprolactone composite membrane
There is the intensive hole varied in size, form graded porous structure.
Embodiment 2
A kind of bioactive glass fiber-polycaprolactone composite membrane, its preparation method is:
(1) in beaker, add, with pipettor, 1mL concentration is 2mol/L hydrochloric acid solution and 1mL go from
Sub-water, adds 8mL ethanol solution, 2.0gP123, mixed at room temperature stirring 30min；Then holding
It is sequentially added into 6.43mL tetraethyl orthosilicate, 0.65mL triethyl phosphate and 4.07g nitric acid under continuous stirring condition
Calcium, the time interval that described tetraethyl orthosilicate, triethyl phosphate and calcium nitrate add is 3h, adds calcium nitrate
Rear continuation stirs 12h, obtains bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, the biological glass after being aged
Glass precursor solution.
(3) take the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.3g polyethylene
Butyral, magnetic agitation is to forming clear solution.
(4) taking described clear solution 5mL with 10mL syringe, for electrostatic spinning, clear solution is extruded
Speed is 1mL/h, and collecting board is from Wire outlet head 12cm, and two pole tensions are 20KV, receive electrostatic with aluminium-foil paper
The thick product of bioactive glass fiber that spinning is formed, obtains being loaded with the thick product film of bioactive glass fiber
Aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in the vacuum of 40 DEG C
Drying baker is dried 3 days, to remove solvent.
(5) after being dried, thick for the bioactive glass fiber on aluminium-foil paper product film is taken off and be transferred to oxygen
Change in aluminum crucible, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber；
The bioactive glass fiber of gained is carried out the scanning electron microscope such as embodiment 1 and transmission electron microscope analysis,
Show that described bioactive glass fiber is hollow nano-pore bioactive glass fiber.
(6) take 100mg step (5) described bioactive glass fiber and join 10ml mass volume ratio and be
In the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, then carry out magnetic agitation 30min, obtain biological living
Property glass fibre-polycaprolactone mixed solution.
(7) take the bioactive glass fiber described in 10mL-polycaprolactone mixed solution and join a diameter of
In the glass dish of 10cm, it is vacuum dried 2 days, obtains described bioactive glass fiber-polycaprolactone composite membrane.
Take described bioactive glass fiber-polycaprolactone composite membrane and carry out the detection analysis such as embodiment 1, detection
Analysis result is 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, 1mL concentration is 2mol/L hydrochloric acid solution and 1mL go from
Sub-water, adds 8mL ethanol solution, mixed at room temperature stirring 10min；Then in continuously stirred condition
Under be sequentially added into 6.43mL tetraethyl orthosilicate, 0.65mL triethyl phosphate and 4.07g calcium nitrate, described just
The time interval that silester, triethyl phosphate and calcium nitrate add is 3h, continues stirring after adding calcium nitrate
12h, obtains bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, the biological glass after being aged
Glass precursor solution.
(3) take the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.5g polyethylene
Butyral, magnetic agitation is to forming clear solution.
(4) taking described clear solution 5mL with 10mL syringe, for electrostatic spinning, clear solution is extruded
Speed is 1mL/h, and collecting board is from Wire outlet head 12cm, and two pole tensions are 21KV, receive electrostatic with aluminium-foil paper
The thick product of bioactive glass fiber that spinning is formed, obtains being loaded with the thick product film of bioactive glass fiber
Aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in the vacuum of 40 DEG C
Drying baker is dried 3 days, to remove solvent.
(5) after being dried, thick for the bioactive glass fiber on aluminium-foil paper product film is taken off and be transferred to oxygen
Change in aluminum crucible, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber；
The bioactive glass fiber of gained is carried out the scanning electron microscope such as embodiment 1 and transmission electron microscope analysis,
Show that described bioactive glass fiber is uniform nano-porous bioactive glass fiber.
(6) take 100mg step (5) described bioactive glass fiber and join 10ml mass volume ratio and be
In the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, then carry out magnetic agitation 30min, obtain biological living
Property glass fibre-polycaprolactone mixed solution.
(7) take the bioactive glass fiber described in 6mL-polycaprolactone mixed solution and join a diameter of 10cm
Glass dish in, be vacuum dried 2 days, obtain described bioactive glass fiber-polycaprolactone composite membrane.
Take described bioactive glass fiber-polycaprolactone composite membrane and carry out the detection analysis such as embodiment 1, detection
Analysis result is 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, 1mL concentration is 2mol/L hydrochloric acid solution and 1mL go from
Sub-water, adds 8mL ethanol solution, mixed at room temperature stirring 10min；Then in continuously stirred condition
Under be sequentially added into 6.43mL tetraethyl orthosilicate, 0.433mL triethyl phosphate and 0.452g calcium nitrate, described
The time interval that tetraethyl orthosilicate, triethyl phosphate and calcium nitrate add is 3h, continues to stir after adding calcium nitrate
Mix 12h, obtain bio-vitric precursor solution.
(2) by described bio-vitric precursor solution in the still aging 1d of room temperature, the biological glass after being aged
Glass precursor solution.
(3) take the bio-vitric precursor solution 5mL after ageing, add 5mL ethanol and 0.5g polyethylene
Butyral, magnetic agitation is to forming clear solution.
(4) taking described clear solution 5mL with 10mL syringe, for electrostatic spinning, clear solution is extruded
Speed is 1mL/h, and collecting board is from Wire outlet head 12cm, and two pole tensions are 18KV, receive electrostatic with aluminium-foil paper
The thick product of bioactive glass fiber that spinning is formed, obtains being loaded with the thick product film of bioactive glass fiber
Aluminium-foil paper, then the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber is placed in the vacuum of 40 DEG C
Drying baker is dried 3 days, to remove solvent.
(5) after being dried, thick for the bioactive glass fiber on aluminium-foil paper product film is taken off and be transferred to oxygen
Change in aluminum crucible, then in high temperature furnace in 650 DEG C heat treatment 3 hours, obtain bioactive glass fiber；
The bioactive glass fiber of gained is carried out the scanning electron microscope such as embodiment 1 and transmission electron microscope analysis,
Show that described bioactive glass fiber is uniform nano-porous bioactive glass fiber.
(6) take 150mg step (5) described bioactive glass fiber and join 10ml mass volume ratio and be
In the polycaprolactone-acetic acid solution of 10%, ultrasonic disperse, then carry out magnetic agitation 30min, obtain biological living
Property glass fibre-polycaprolactone mixed solution.
(7) take the bioactive glass fiber described in 6mL-polycaprolactone mixed solution and join a diameter of 10cm
Glass dish in, be vacuum dried 2 days, obtain described bioactive glass fiber-polycaprolactone composite membrane.
Take described bioactive glass fiber-polycaprolactone composite membrane and carry out the detection analysis such as embodiment 1, detection
Analysis result is substantially the same manner as Example 1.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-mentioned enforcement
The restriction of example, the change made, modifies, replaces under other any spirit without departing from the present invention and principle
In generation, combine, simplify, all should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (9)
1. the preparation method of bioactive glass fiber-polycaprolactone composite membrane, it is characterised in that include as
Lower step:
(1) 50～150mg bioactive glass fiber being joined 10mL mass volume ratio is 8%～12%
Polycaprolactone-acetic acid solution in, stirring or ultrasonic wave concussion make bioactive glass fiber polycaprolactone-
Acetic acid solution is uniformly dispersed, then carries out magnetic agitation 30min, obtain bioactive glass fiber-poly-in oneself
Ester mixed solution；
(2) take bioactive glass fiber described in 4～10mL-polycaprolactone mixed solution and join a diameter of
In the glass dish of 10cm, it is vacuum dried 2 days, obtains described bioactive glass fiber-polycaprolactone composite membrane；
The preparation method of step (1) described bioactive glass fiber is:
(I) ethanol, water and 2mol/L hydrochloric acid solution are mixed, addition template, magnetic agitation mix homogeneously,
Sequentially add tetraethyl orthosilicate, triethyl phosphate and calcium nitrate, be uniformly mixing to obtain bio-vitric presoma
Solution；
(II) described bio-vitric precursor solution is sealed at ambient temperature ageing 0.5～4 day, obtain old
Bio-vitric precursor solution after change；
(III) take the bio-vitric precursor solution after ageing described in 5mL to mix with isopyknic ethanol, then
The binding agent of addition 300～500mg mixes to obtain clear solution；
(IV) take 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, and applying electric field is 1.4～2KV/cm, receives Static Spinning with aluminium-foil paper
The thick product of bioactive glass fiber that silk is formed, obtains being loaded with the thick product film of bioactive glass fiber
Aluminium-foil paper, is then placed in the aluminium-foil paper being loaded with the thick product film of bioactive glass fiber in vacuum drying oven
It is dried 3 days；
(V) after being dried, thick for the bioactive glass fiber on aluminium-foil paper product film is taken off, by described
The thick product film of bioactive glass fiber is placed in heat treatment 3 hours in 650 DEG C of environment, obtains described biological alive
Property glass fibre；Step (III) described binding agent is polyvinyl butyral resin；Template described in step (I)
Agent is poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer.
The preparation side of a kind of bioactive glass fiber-polycaprolactone composite membrane the most according to claim 1
Method, it is characterised in that: in the described polycaprolactone-acetic acid solution of step (1), the molecular weight of polycaprolactone is
40000～80000.
The preparation of a kind of bioactive glass fiber-polycaprolactone composite membrane the most according to claim 1
Method, it is characterised in that: in the preparation method of described bioactive glass fiber, step (I) described water
Consumption be 1mL, the consumption of described 2mol/L hydrochloric acid solution is 1mL, the consumption volume of described ethanol and water
Than being (6～14): 1；Water described in step (I) is (2.5～3.5) with the mol ratio of described tetraethyl orthosilicate:
1；Step (I) described tetraethyl orthosilicate, triethyl phosphate and calcium nitrate mol ratio be: tetraethyl orthosilicate: nitre
Acid calcium: triethyl phosphate=(60～90): (36～6): 8.
The preparation side of a kind of bioactive glass fiber-polycaprolactone composite membrane the most according to claim 1
Method, it is characterised in that: in the preparation method of described bioactive glass fiber, mould described in step (I)
The consumption of plate agent is 0～2g.
5. one kind according to the bioactive glass fiber described in any one of Claims 1 to 4-polycaprolactone composite membrane
Bioactive glass fiber-polycaprolactone composite membrane of obtaining of preparation method, described bioactive glass fiber-
Polycaprolactone composite membrane has graded porous structure, and described bioactive glass fiber is dispersed in described poly-
The surface of caprolactone film and inside.
Bioactive glass fiber the most according to claim 5-polycaprolactone composite membrane, it is characterised in that:
Described bioactive glass fiber-polycaprolactone composite membrane has three class aperture specifications, wherein first kind hole
A diameter of 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 thing activity glass
The nano-pore that glass fiber itself is had；The thickness of described bioactive glass fiber-polycaprolactone composite membrane is
100 μm～400 μm；A diameter of 500nm of described bioactive glass fiber～2 μm.
Bioactive glass fiber the most according to claim 6-polycaprolactone composite membrane, it is characterised in that:
Described bioactive glass fiber is uniform nano-porous bioactive glass fiber, hollow nano-pore biological activity
More than one in glass fibre or classifying nano hole bioactive glass fiber.
Bioactive glass fiber the most according to claim 7-polycaprolactone composite membrane, it is characterised in that:
The aperture of described uniform nano-porous bioactive glass fiber is 7～13nm；Described hollow nano-pore biological activity
The internal hollow channel a diameter of 50～200nm of glass fibre, on surrounding wall a diameter of the 7～20nm of aperture；
On described classifying nano hole bioactive glass fiber, hole diameter is 5～300nm, and internal aperture is from inside to outside
Reduce.
Bioactive glass fiber the most according to claim 5-polycaprolactone composite membrane is to prepare skin auxiliary
Material, biologically inert substrate surface material and prepare medicine carrying thing or carry gene tissue repair film in application.
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| CN107362388B (en) * | 2017-07-11 | 2020-04-03 | 同济大学 | Biological glass fiber-modified polyester composite dressing and preparation method thereof |
| CN107715174B (en) * | 2017-09-30 | 2020-01-14 | 清华大学 | Bionic tissue engineering scaffold containing micro-pores and nano-fiber composite structure and preparation method thereof |
| CN108420804A (en) * | 2018-05-09 | 2018-08-21 | 温州医科大学附属第二医院、温州医科大学附属育英儿童医院 | A kind of load Astragaloside IV pla-pcl film and its preparation method and application |
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