CN101376567A - Composite bioactivity glass superfine fibre with nano hole and preparation thereof - Google Patents

Composite bioactivity glass superfine fibre with nano hole and preparation thereof Download PDF

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CN101376567A
CN101376567A CNA2008100512409A CN200810051240A CN101376567A CN 101376567 A CN101376567 A CN 101376567A CN A2008100512409 A CNA2008100512409 A CN A2008100512409A CN 200810051240 A CN200810051240 A CN 200810051240A CN 101376567 A CN101376567 A CN 101376567A
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nanoporous
electrostatic spinning
containing compound
superfine fibre
bioactivity glass
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CN101376567B (en
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庄秀丽
洪友良
陈学思
景遐斌
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to a composite bioactive superfine glass fiber with nanometer pores, and a preparation method thereof. The molar ratio of silicon compounds, calcium compounds, phosphorus compounds and magnesium compounds, all of which are adopted by the superfine glass fiber is (50-100):(0-40):(0-10):(0-10):(0-2). The preparation method comprises the following steps: the electrostatic spinning technology is adopted, and the superfine glass fiber is obtained by combining the self-assembly of a template agent with a sol-gel method. The diameter of the fiber can be controlled within the range from 20 nanometers to 0.1 millimeters, the diameter of the nanometer pores of the fiber can be adjusted within the range from 0.5-500 nanometers, the specific surface area can reach 300 m<2>/g, the pore volume can reach 0.8 cm<3>/g, and the fiber can be assembled into three-dimensional, flaky and non-woven fabric or milled into powder. The bioactive superfine glass fiber can be made into advanced bone repairing and filling materials and wound dressings.

Description

Has composite bioactivity glass superfine fibre of nanoporous and preparation method thereof
Technical field
The present invention relates to composite bioactivity glass superfine fibre that has nanoporous and preparation method thereof.The invention belongs to technical field of biological material.
Background technology
Since finding bio-vitric in 1971, people have carried out research extensively and profoundly to bio-vitric from Larry L.Hench.Bioactivity glass can promote very fast generation of osseous tissue and growth as the clinical use of bone renovating material more than ten years, and biocompatibility is good.Bio-vitric in vivo not only can with the firm bonding of osseous tissue, can also with the soft tissue bonding.The success of bio-vitric clinical application not only derives from it bone guided, and the biological activity that promotes the osseous tissue growth is arranged.Recently studies show that bioactivity glass not only has the ability of controllable release and degraded in the certain ingredients scope, and be present unique generation that can promote somatomedin, promote the inorganic materials of the synthetic of cells multiply, active cells genetic expression.
The biological activity of bioactivity glass is directly related with quality structure properties, chemical composition, chemical structure and the synthetic method of activity glass material.The initial density height that uses the bioactivity glass of scorification preparation does not have the space, and activity is low as a result.Use sol-gel process to prepare activity glass, the product that obtains has a large amount of spaces, and the result has improved the biological activity of product greatly.Recently, people such as Yan use the tensio-active agent assembling to have even mesoporous activity glass in conjunction with the sol-gel process preparation, have further improved the biologic activity (Angew.Chem.Int.Ed.2004,43,5980) of activity glass.
In practical clinical, it is vital that bioactivity glass is processed into structure specific, that be suitable for corresponding application.For example, be used for the timbering material that bone is repaired, require materials used to have the porous three-dimensional structure.And be used for the treatment of the surperficial dressing of dermatosis, then requiring material should be membranaceous structure.Recently, the existing bioactivity glass development is become has many empty three-dimensional blocky report (numbers of applying for a patent: 200410017240.9).Yet this support lacks the aperture that is situated between and sees, and does not have nano level structure formation to exist.This has just reduced the biological activity of product.
Recently, people such as Kim use the method for electrostatic spinning to prepare biological activity glass nano-fibre (Adv.Funct.Mater.2006,16,1529).This nanometer level bioactive glass fibre has shown huge biological activity and structural advantage: take the non-woven membrane of structure by fiber, both can be used as the bone supporting structure, also can be used as dressing for skin.Because activity glass is the form with nano-scale fiber, so show high biological activity.But also there is textural defect in people's synthetic products such as Kim, that is, lack mesoporous in the nanofiber substrates.This textural defect makes the nanofiber of people such as Kim preparation not reach the optimum structure and the activity of activity glass.
Summary of the invention
The objective of the invention is to develop the composite bioactivity glass superfine fibre with nanoporous, wherein, the nanoporous aperture in the fiber can be controlled to 500 nanometers from 0.5 nanometer; The diameter of fiber can be controlled at the 0.02-100 micrometer range; Specific surface area is 100-300m 2/ g, pore volume are 0.5-0.8cm 3/ g.
The used silicon-containing compound of composite bioactivity glass superfine fibre with nanoporous: calcium containing compound: P contained compound: compounds containing sodium: the mol ratio of magnesium-containing compound is (50-100): (0-40): (0-10): (0-10): (0-2); Be preferably (60-90): (10-40): (0-10): (0-10): 0; The best is (70-85): (10-30): (0-10): (0-5): 0;
Described silicon compound is tetraethoxy [Si (OC 2H 5) 4] or methyl silicate [Si (OCH 3) 4], preferred tetraethoxy;
Described calcium containing compound is nitrocalcite crystal [Ca (NO 3) 24H 2O] or calcium chloride, lime acetate crystal [Ca (OC 2H 5) 2H 2O] or organic calcium;
Described P contained compound is triethyl phosphate [(C 2H 5) 3PO 4] or other organophosphoruss;
Described magnesium-containing compound is magnesium nitrate [Mg (NO 3) 2] or sal epsom [MgSO 4], preferred magnesium nitrate;
Described compounds containing sodium is sodium chloride or SODIUMNITRATE, preferred sodium chloride.
In order to prepare this activity glass fiber, the present invention has adopted tensio-active agent as the nanoporous template, and polymer is as fibre guide reagent, and by method such as sol-gel and electrostatic spinning finish jointly.
Preparation method's the step and the condition of composite bioactivity glass superfine fibre with nanoporous is as follows:
A. prepare electrostatic spinning solution
Mol ratio silicon-dioxide by the composite bioactivity glass superfine fibre composition with nanoporous: calcium oxide: Vanadium Pentoxide in FLAKES: oxidation is received: magnesium oxide is (50-100): (0-40): (0-10): (0-10): (0-2); Be preferably (60-90): (10-40): (0-10): (0-10): 0; The best is (70-85): (10-30): (0-10): (0-5): 0.
Nanoporous template, fibrous texture guiding polymkeric substance and silicon-containing compound, calcium containing compound, P contained compound, compounds containing sodium and magnesium-containing compound by said ratio are dissolved in the solvent, under whipped state, mixed 10-40 hour the preparation electrostatic spinning solution;
The mass concentration of described nanoporous template in solution depends on structure and molecular weight with template molecule, in the 20-40% scope, and preferred 25-35%;
Described nanoporous template is an ionic surfactant reagent, and its chemical formula is C nH 2n+1X, n=10-20, R is-CH 3Or-C 2H 5, X is Cl -Or Br -Or
Poly-oxyethylene is as hydrophilic block, the long chain alkane nonionic surface active agent as hydrophobic group; Or
PEO is as hydrophilic block, and poly-propylene oxide or poly-epoxy butylene are as hydrophobic block, and its molecular formula is EO nPO mEO n, n=10-140, m=5-100; Or EO nBO mEO n, n=10-200, m=10-100; Or EO nBO m, n=10-100, m=5-60;
Described fibrous texture guiding polymer quality concentration depends on the molecular weight of polymkeric substance, in the 0.5-20% scope, and preferred 1-10%;
Fibrous texture guiding polymkeric substance is a Polyvinylpyrolidone (PVP), and weight-average molecular weight is 10,000-1,000,000; Or polyvinyl butyral acetal, weight-average molecular weight is 10,000-1,000,000; Or polyoxyethylene glycol, weight-average molecular weight is 5,000-1,000,000; Or polyoxyethylene, weight-average molecular weight is 10000-2,000,000; Preferred polyoxyethylene glycol or polyoxyethylene;
Also can not use fibrous texture guiding polymkeric substance.
Employed solvent is water, ethanol or their mixed solvent;
B. the polymers soln with preparation carries out electrostatic spinning, obtains micron or nanofiber
(1) equipment of the electrostatic spinning that adopts of the present invention, its structural representation as Figure 1-1, by 1 electrostatic spinning container, be loaded with spinning solution, 2 piston-type transferpumps, 3 electrostatic spinning mouths, 4 high-voltage power supplies and 5 electrode fiber dash receivers and constitute.The 7th, the electrostatic spinning jet; By 6 ground connection.
Fig. 1-2 is that 7 electrostatic spinning jet amplifies among Fig. 1-1.Wherein, the diameter of electrostatic spinning mouth is in 0.05-5 millimeter scope, preferred 0.1-2 millimeter, preferably 0.5-1 millimeter; The working voltage scope of high-voltage power supply 4 is 500-30,000 volt;
The basic structure of electrospinning device is that a HV generator is as high-voltage power supply 4, at device for spinning of high-voltage power supply 4 high pressure terminations, at an electrode fiber of high-voltage power supply 4 ground connection terminations dash receiver 5; Wherein electrostatic spinning apparatus is made up of electrostatic spinning liquid container 1 and electrostatic spinning mouth 3, the electricity spinning solution is evenly adjustable from electrostatic spinning mouth 3 take-off rate, electrostatic spinning mouth 3 between the dash receiver 5 apart from 3-50 centimetre, voltage 500-30 between them, 000 volt, from electrostatic spinning mouth 3 effusive solution, under the effect of high-voltage electric field, form jet 7, because the solution that penetrates carries highdensity like charges, can be mutually exclusive, jet solution begins to solidify to form fiber behind straightaway one segment distance (1-2 centimetre), along with moving to electrode fiber dash receiver 5, the fiber completely solidified becomes fiber and deposits to form the sheet-like fiber film on the collecting board.
(2) earlier the spinning solution of steps A preparation is transferred in the spinning container 1 by piston-type transferpump 2, apply a high static voltage by the liquid in 4 pairs of containers of high-voltage power supply then, because electrostatic effect, liquid penetrates from the electrostatic spinning mouth 3 of spinning solution container 1, and the liquid that the jet 7 of ejaculation can form in fiber and the fiber can very fast volatilization.After these fibers arrive electrode fiber dash receiver 5, can dryly form solid fiber.
C. the removal of organic composition
At 500-900 ℃, the fiber that electrostatic spinning is prepared carries out roasting in 6-10 hour, removes organic composition, obtains having the composite bioactivity glass superfine fibre of nanoporous.
Composite bioactivity glass superfine fibre with nanoporous of the present invention has the particular structure feature:
(1) owing to have abundant nanoporous in this fibre substrate, and fiber has the superfine diameter, makes product that high specific surface area (100-300m be arranged 2/ g) and high pore volume (0.5-0.8cm 3/ g).
(2) diameter with composite bioactivity glass superfine fibre of nanoporous is the 0.02-100 micron, preferred 0.1-10 micron, preferably 0.1-5 micron.
(2) has nanoporous in Zhi Bei the composite bioactivity glass superfine fibre with nanoporous.The even aperture distribution of nanoporous and adjustable, the diameter of nanoporous are the 0.5-500 nanometer, preferred 1-200 nanometer, preferably 1-100 nanometer.
(3) synthetic has the composite bioactivity glass superfine fibre of nanoporous, characteristics according to technology, such as, in the engineering of electrostatic spinning, the composite bioactivity glass superfine fibre with nanoporous can use collecting board to collect three-dimensional flaky non-woven fabrics of composition or fibrefelt.This sheet non-woven fabrics is taken by fiber and is configured to, and the result can produce the space with 50-300 micron between fiber.Simultaneously, the composite bioactivity glass superfine fibre that synthetic has a nanoporous also can grind into powder, forms the short activity glass rod with nanoporous.
Composite bioactivity glass superfine fibre with nanoporous of the present invention has good biological activity in human body simulation body fluid, can discharge silicon, calcium, phosphorus plasma in a few hours, and at surface deposition class bone hydroxyapatite crystallite.
What the bioactive evaluation of the composite bioactivity glass superfine fibre with nanoporous of preparation was used is human body simulation liquid.Human body simulation liquid contains ion identical with human plasma and ionic group concentration, the consisting of of human body simulation liquid:
Ion component volumetric molar concentration (mM)
Na + 142.0
HCO 3 - 4.2
Cl - 147.8
HPO 4 2- 1.0
Mg 2+ 1.5
K + 5.0
Ca 2+ 2.5
SO 4 2- 0.5
In concrete experiment, 0.1 gram nanoporous fiber is dipped in the 30mL human body simulation liquid, reaction is 24 hours in 37 degree thermostat containers.Take out sample and, use the test of surface sweeping Electronic Speculum then, the results are shown in Figure 4 with acetone and deionized water wash.
In sum, composite bioactivity glass superfine fibre with nanoporous of the present invention can use collecting board to collect becomes thin three-D non-woven cloth, both be suitable as sclerous tissues's bone defect repair timbering material, external osseous tissue and cultivated and use cytoskeleton, can be used as the skin medical dressing again.Nanoporous stub after the grinding can be used as sclerous tissues's packing material, treatment gastric duodenal ulcer medicine, and pharmaceutical carrier etc.
Description of drawings:
The structural formula synoptic diagram of the electrospinning device that Fig. 1-the 1st, the present invention adopt.It also is bright book extract accompanying drawing.Among the figure, 1 spinning solution container is loaded with spinning solution; 2 piston-type transferpumps; 3 electrostatic spinning mouths; 4 high-voltage power supplies; 5 receiving electrodes; The 7th, the spinning solution jet; 6 ground connection.
Fig. 1-2 is the enlarged view of spinning solution jet 7 among Fig. 1-1.
Fig. 2-the 1st, the SEM photo of the composite bioactivity glass superfine fibre with nanoporous of embodiment 1 preparation.
Fig. 2-the 2nd, the TEM photo of the composite bioactivity glass superfine fibre with nanoporous of embodiment 1 preparation.
Fig. 2-the 3rd, the nitrogen adsorption result of the composite bioactivity glass superfine fibre with nanoporous of embodiment 1 preparation.
Fig. 2-the 4th, the composite bioactivity glass superfine fibre median pore diameter distribution results with nanoporous of embodiment 1 preparation.
Fig. 3-the 1st, the SEM photo of the composite bioactivity glass superfine fibre with nanoporous of embodiment 2 preparations.
Fig. 3-the 2nd, the TEM photo of the composite bioactivity glass superfine fibre with nanoporous of embodiment 2 preparations.
Fig. 3-the 3rd, the nitrogen adsorption result of the composite bioactivity glass superfine fibre with nanoporous of embodiment 2 preparations.
Fig. 3-the 4th, the composite bioactivity glass superfine fibre median pore diameter distribution results with nanoporous of embodiment 2 preparations.
Fig. 4 is that the composite bioactivity glass superfine fibre with nanoporous of embodiment 10 preparations soaks the SEM photo after 24 hours in SBF solution.
Embodiment
Embodiment 1. please refer to Fig. 1.With 3 gram EO 20PO 70EO 20(P123), 1 gram molecular weight is 2,000,000 polyoxyethylene (PEO), 5 gram nitrocalcite crystal [Ca (NO 3) 24H 2O], 10 gram tetraethoxys (TEOS), 0.4 gram triethyl phosphate (TEP) and 0.5 gram 0.5M hydrochloric acid add ethanol to, the mixed solvent of water, and stirred 24 hours.Then solution is joined in the container 1 of electrostatic spinning apparatus, the container that present embodiment uses is to repack into 20 milliliters glass syringe, and the piston 2 of syringe be a transferpump, and adopting by diameter is 1.0 millimeters flat mouth spinning mouth 3.Spinning mouth 3 connects high pressure one end of high-voltage power supply 4, and the ground terminal of high-voltage power supply 4 is connected with the ground terminal 6 of ultra-fine fibre dash receiver 5.The flow velocity of solution at spinning mouth 3 places is 2.0 milliliters/hour, and the voltage that is applied is 10000 volts, and two interpolar distance is 30 centimetres.The solution at spinning mouth 3 places is subjected to the effect of high-voltage electric field, forms hydrofluidic 7, and jet is constantly refinement in electric field, the solvent in the jet volatilizees rapidly simultaneously, the ultra-fine fibre that finally on dash receiver, has obtained solidifying, its diameter in nanometer to micrometer range.The conjugated fibre of gained is further put into chamber type electric resistance furnace and is removed organic composition in 600 degree high-temperature roastings, and the result obtains having the composite bioactivity glass superfine fibre of nanoporous, sees Fig. 2.
Embodiment 2. other conditions with embodiment 1 the same terms under spinning prepare conjugated fibre.Put into baking oven from the conjugated fibre that collecting board is collected, under 120 degree, allow filament contraction 60%, then conjugated fibre is further put into chamber type electric resistance furnace and remove organic composition in 600 degree high-temperature roastings, the result obtains having the composite bioactivity glass superfine fibre of nanoporous, sees Fig. 3.
Embodiment 3. uses tensio-active agent to be EO 106PO 70EO 106(F127), other condition with embodiment 1 the same terms under prepare polymer particle.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 4. uses 4 gram nitrocalcite crystal [Ca (NO 3) 24H 2O] and 0.2 the gram triethyl phosphate (TEP), other condition with embodiment 1 the same terms under spinning prepare conjugated fibre, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 5. uses 3 gram nitrocalcite crystal [Ca (NO 3) 24H 2O] and 0.1 the gram triethyl phosphate (TEP), other condition with embodiment 1 the same terms under spinning prepare conjugated fibre, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 6. uses 8 gram tetraethoxys (TEOS), other condition with embodiment 1 the same terms under spinning prepare conjugated fibre, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 7. uses 8 gram tetraethoxys (TEOS), uses 4 gram nitrocalcite crystal [Ca (NO 3) 24H 2O] and 0.2 the gram triethyl phosphate (TEP), other condition with embodiment 1 the same terms under spinning prepare conjugated fibre, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 8. adds 0.4 gram magnesium nitrate and 0.2 gram sodium-chlor, other condition with embodiment 1 the same terms under spinning prepare conjugated fibre, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 9. adds 0.4 gram magnesium nitrate and 0.2 gram sodium-chlor, other condition with embodiment 7 the same terms under spinning prepare conjugated fibre, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 10. adds 0.4 gram magnesium nitrate and 0.2 gram sodium-chlor, other condition with embodiment 4 the same terms under spinning prepare conjugated fibre.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 11. adds 5 gram lime acetates, other condition with embodiment 4 the same terms under spinning prepare conjugated fibre.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 12. other conditions with embodiment 3 the same terms under spinning prepare conjugated fibre, put into baking oven from the conjugated fibre that collecting board is collected, under 120 degree, allow filament contraction 60%, then conjugated fibre is further put into chamber type electric resistance furnace and remove organic composition in 600 degree high-temperature roastings, the result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 13. uses tensio-active agent to be EO 132PO 50EO 132(F 108), other condition with embodiment 1 the same terms under prepare polymer particle.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 14. uses tensio-active agent to be EO 20PO 30EO 20(F 65), other condition with embodiment 1 the same terms under prepare polymer particle.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
It is 1,000,000 PEO that embodiment 15. uses 1.5 gram molecular weights, other condition with embodiment 1 the same terms under prepare polymer particle.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
It is 500,000 polyoxyethylene that embodiment 16. uses 3 gram molecular weights, other condition with embodiment 1 the same terms under prepare polymer particle.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
It is that 100,000 polymers are polyvinyl butyral acetal that embodiment 17. uses 3 gram molecular weights, other condition with embodiment 1 the same terms under prepare polymer particle.The result obtains having the composite bioactivity glass superfine fibre of nanoporous.
Embodiment 18. is dipped into the composite bioactivity glass superfine fibre that 0.1 gram of embodiment 1 preparation has nanoporous in the 30mL human body simulation liquid, and reaction is 24 hours in 37 degree thermostat containers.Take out sample and use acetone and deionized water wash, the result forms carbonated hydroxyapatite on the product surface, sees Fig. 4.
Embodiment 19. is dipped into the composite bioactivity glass superfine fibre that 0.1 gram of embodiment 2 preparations has nanoporous in the 30mL human body simulation liquid, and reaction is 24 hours in 37 degree thermostat containers.Take out sample and use acetone and deionized water wash, the result forms carbonated hydroxyapatite on the product surface.

Claims (13)

1, the composite bioactivity glass superfine fibre that has nanoporous, it is characterized in that used silicon-containing compound: calcium containing compound: P contained compound: compounds containing sodium: the mol ratio of magnesium-containing compound is (50-100): (0-40): (0-10): (0-10): (0-2);
Described silicon-containing compound is tetraethoxy [Si (OC 2H 5) 4] or methyl silicate [Si (OCH 3) 4], preferred tetraethoxy;
Described calcium containing compound is nitrocalcite crystal [Ca (NO 3) 24H 2O] or calcium chloride, lime acetate crystal [Ca (OC 2H 5) 2H 2O] or organic calcium;
Described P contained compound is triethyl phosphate [(C 2H5) 3PO 4] or other organophosphoruss;
Described magnesium-containing compound is magnesium nitrate [Mg (NO 3) 2] or sal epsom [MgSO 4];
Described compounds containing sodium is sodium chloride or SODIUMNITRATE.
2, the composite bioactivity glass superfine fibre with nanoporous as claimed in claim 1, it is characterized in that used silicon-containing compound: calcium containing compound: P contained compound: compounds containing sodium: the mol ratio of magnesium-containing compound is (60-90): (10-40): (0-10): (0-10): 0.
3, the composite bioactivity glass superfine fibre with nanoporous as claimed in claim 1, it is characterized in that used silicon-containing compound: calcium containing compound: P contained compound: compounds containing sodium: the mol ratio of magnesium-containing compound is ((70-85): (10-30): (0-10): (0-5): 0.
4, the composite bioactivity glass superfine fibre with nanoporous as claimed in claim 1 is characterized in that, described magnesium-containing compound is a magnesium nitrate.
5, the composite bioactivity glass superfine fibre with nanoporous as claimed in claim 1 is characterized in that, described compounds containing sodium is a sodium chloride.
6, the preparation method with composite bioactivity glass superfine fibre of nanoporous as claimed in claim 1 is characterized in that step and condition are as follows:
A. prepare electrostatic spinning solution
Silicon-containing compound, calcium containing compound, P contained compound, compounds containing sodium and the magnesium-containing compound of nanoporous template and described proportioning are dissolved in the solvent, under whipped state, mixed 10-40 hour, the preparation electrostatic spinning solution;
The mass concentration of described nanoporous template in solution is in the 20-40% scope;
Described nanoporous template is an ionic surfactant reagent, and its chemical formula is C nH 2n+1X, n=10-20, R is-CH 3Or-C 2H 5, X is Cl -Or Br -Or
Poly-oxyethylene is as hydrophilic block, the long chain alkane nonionic surface active agent as hydrophobic group; Or
PEO is as hydrophilic block, and poly-propylene oxide or poly-epoxy butylene are as hydrophobic block, and its molecular formula is EO nPO mEO n, n=10-140, m=5-100; Or EO nBO mEO n, n=10-200, m=10-100; Or EO nBO m, n=10-100, m=5-60;
Employed solvent is water, ethanol or their mixed solvent;
B. the polymers soln with preparation carries out electrostatic spinning, obtains micron or nanofiber
(1) structure of the equipment of the electrostatic spinning of Cai Yonging is constructed as follows: electrostatic spinning container (1), be loaded with spinning solution, piston-type transferpump (2), electrostatic spinning mouth (3), high-voltage power supply (4) and electrode fiber dash receiver (5); Wherein, the diameter of electrostatic spinning mouth (3) is in 0.05-5 millimeter scope;
At device for spinning of high pressure termination of high-voltage power supply (4), at high-voltage power supply (4) ground connection termination electrode fiber dash receiver (5); Wherein electrostatic spinning apparatus is made up of electrostatic spinning liquid container (1) and electrostatic spinning mouth (3), and electricity silk liquid flows out from electrostatic spinning mouth (3), and electrostatic spinning mouth (3) is 3-50 centimetre to the distance between the electrode fiber dash receiver (5);
(2) earlier the spinning solution of steps A preparation is transferred in the spinning container (1) by piston-type transferpump (2), by high-voltage power supply (4) liquid in the container being applied voltage then is 500-30,000 volt static voltage, because electrostatic effect, liquid penetrates from the spinning mouth (3) of spinning solution container (1), the liquid that the jet (7) that penetrates can form in fiber and the fiber can very fast volatilization, after these fibers arrive electrode fiber dash receivers (5), can dryly form solid fiber;
C. the removal of organic composition
At 500-900 ℃, the fiber that electrostatic spinning is prepared carries out roasting in 6-10 hour, removes organic composition, obtains having the composite bioactivity glass superfine fibre of nanoporous.
7, the preparation method with composite bioactivity glass superfine fibre of nanoporous as claimed in claim 6 is characterized in that described:
A. prepare electrostatic spinning solution
Silicon-containing compound, calcium containing compound, P contained compound, compounds containing sodium and the magnesium-containing compound of nanoporous template, fibrous texture guiding polymkeric substance and described proportioning be dissolved into prepare electrostatic spinning solution in the solvent;
Described fibrous texture guiding polymer quality concentration is in the 0.5-20% scope;
Fibrous texture guiding polymkeric substance is a Polyvinylpyrolidone (PVP), and weight-average molecular weight is 10,000-1,000,000; Or polyvinyl butyral acetal, weight-average molecular weight is 10,000-1,000,000; Or polyoxyethylene glycol, weight-average molecular weight is 5,000-1,000,000; Or polyoxyethylene, weight-average molecular weight is 10000-2,000,000;
Remaining condition is with claim 6.
8, as claim 6 or 7 described preparation methods, it is characterized in that described step with composite bioactivity glass superfine fibre of nanoporous
B. the polymers soln with preparation carries out electrostatic spinning, obtains in micron or the nanofiber, and the diameter of electrostatic spinning mouth (3) is the 0.1-2 millimeter.
9, the preparation method with composite bioactivity glass superfine fibre of nanoporous as claimed in claim 8 is characterized in that described step
B. the polymers soln with preparation carries out electrostatic spinning, obtains in micron or the nanofiber, and the diameter of electrostatic spinning mouth (3) is the 0.5-1 millimeter.
10, the preparation method with composite bioactivity glass superfine fibre of nanoporous as claimed in claim 7 is characterized in that, described fibrous texture guiding polymer quality concentration is 1-10%.
11, the preparation method with composite bioactivity glass superfine fibre of nanoporous as claimed in claim 7 is characterized in that, described fibrous texture guiding polymkeric substance is polyoxyethylene glycol or polyoxyethylene.
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