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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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Publication number
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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containing compound
electrospinning
nanopores
fiber
bioactive 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

本发明涉及一种具有纳米孔的复合生物活性玻璃超细纤维及制备方法。该玻璃超细纤维所用的含硅化合物∶含钙化合物∶含磷化合物∶含钠化合物∶含镁化合物的摩尔比为(50－100)∶(0－40)∶(0－10)∶(0－10)∶(0－2)。其制备方法是利用静电纺丝技术，结合模板剂自组装和溶胶－凝胶方法获得。所得纤维的直径可控制在20纳米至0.1毫米范围，纤维中的纳米孔的直径可在0.5至500纳米范围内调节，比表面积可达300m2/g，孔容可达0.8cm3/g，纤维可以组装成三维片状的无纺布或者研磨成粉末。这种活性玻璃纤维可以作为高级的骨修复、填充材料和伤口敷料。

Figure 200810051240

The invention relates to a composite bioactive glass superfine fiber with nano holes and a preparation method. The molar ratio of silicon-containing compound used in the glass ultrafine fiber: calcium-containing compound: phosphorus-containing compound: sodium-containing compound: magnesium-containing compound is (50-100): (0-40): (0-10): (0 -10): (0-2). Its preparation method is obtained by using electrospinning technology combined with self-assembly of template agent and sol-gel method. The diameter of the obtained fiber can be controlled in the range of 20 nanometers to 0.1 millimeters, the diameter of the nanopores in the fiber can be adjusted in the range of 0.5 to 500 nanometers, the specific surface area can reach 300m 2 /g, and the pore volume can reach 0.8cm 3 /g. Fibers can be assembled into three-dimensional sheets of nonwovens or ground into powders. This activated glass fiber can be used as an advanced bone repair, filling material and wound dressing.

Figure 200810051240

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、具有纳米孔的复合生物活性玻璃超细纤维，其特征在于，所用的含硅化合物：含钙化合物：含磷化合物：含钠化合物：含镁化合物的摩尔比为(50-100)：(0-40)：(0-10)：(0-10)：(0-2)；1. Composite bioactive glass microfibers with nanopores are characterized in that the silicon-containing compound used: the calcium-containing compound: the phosphorus-containing compound: the sodium-containing compound: the mol ratio of the magnesium-containing compound is (50-100): ( 0-40):(0-10):(0-10):(0-2); 所述的含硅化合物是正硅酸乙酯[Si(OC2H5)4]或正硅酸甲酯[Si(OCH3)4]，优选正硅酸乙酯；The silicon-containing compound is ethyl orthosilicate [Si(OC 2 H 5 ) 4 ] or methyl orthosilicate [Si(OCH 3 ) 4 ], preferably ethyl orthosilicate; 所述的含钙化合物是硝酸钙晶体[Ca(NO3)2·4H2O]、或氯化钙、乙酸钙晶体[Ca(OC2H5)2·H2O]或有机钙；The calcium-containing compound is calcium nitrate crystal [Ca(NO 3 ) 2 ·4H 2 O], or calcium chloride, calcium acetate crystal [Ca(OC 2 H 5 ) 2 ·H 2 O] or organic calcium; 所述的含磷化合物是磷酸三乙酯[(C2H5)3PO4]或其他有机磷；The phosphorus-containing compound is triethyl phosphate [(C 2 H5) 3 PO 4 ] or other organic phosphorus; 所述的含镁化合物是硝酸镁[Mg(NO3)2]或硫酸镁[MgSO4]；The magnesium-containing compound is magnesium nitrate [Mg(NO 3 ) 2 ] or magnesium sulfate [MgSO 4 ]; 所述的含钠化合物是氯化纳或硝酸钠。The sodium-containing compound is sodium chloride or sodium nitrate. 2、如权利要求1所述的具有纳米孔的复合生物活性玻璃超细纤维，其特征在于，所用的含硅化合物：含钙化合物：含磷化合物：含钠化合物：含镁化合物的摩尔比为(60-90)：(10-40)：(0-10)：(0-10)：0。2. The composite bioactive glass microfiber with nanopores as claimed in claim 1, characterized in that the molar ratio of silicon-containing compound: calcium-containing compound: phosphorus-containing compound: sodium-containing compound: magnesium-containing compound is (60-90):(10-40):(0-10):(0-10):0. 3、如权利要求1所述的具有纳米孔的复合生物活性玻璃超细纤维，其特征在于，所用的含硅化合物：含钙化合物：含磷化合物：含钠化合物：含镁化合物的摩尔比为((70-85)：(10-30)：(0-10)：(0-5)：0。3. The composite bioactive glass microfiber with nanopores as claimed in claim 1, characterized in that the molar ratio of silicon-containing compound: calcium-containing compound: phosphorus-containing compound: sodium-containing compound: magnesium-containing compound is ((70-85):(10-30):(0-10):(0-5):0. 4、如权利要求1所述的具有纳米孔的复合生物活性玻璃超细纤维，其特征在于，所述的含镁化合物是硝酸镁。4. The composite bioactive glass microfiber with nanopores as claimed in claim 1, wherein the magnesium-containing compound is magnesium nitrate. 5、如权利要求1所述的具有纳米孔的复合生物活性玻璃超细纤维，其特征在于，所述的所述的含钠化合物是氯化纳。5. The composite bioactive glass microfiber with nanopores as claimed in claim 1, wherein said sodium-containing compound is sodium chloride. 6、如权利要求1所述的具有纳米孔的复合生物活性玻璃超细纤维的制备方法，其特征在于步骤和条件如下：6. The method for preparing composite bioactive glass microfibers with nanopores as claimed in claim 1, characterized in that the steps and conditions are as follows: A.配制静电纺丝溶液A. Preparation of electrospinning solution 将纳米孔模板剂与所述配比的含硅化合物、含钙化合物、含磷化合物、含钠化合物和含镁化合物溶解到溶剂中，在搅拌状态下混合10-40小时，配制静电纺丝溶液；dissolving the nanopore template agent and the silicon-containing compound, calcium-containing compound, phosphorus-containing compound, sodium-containing compound and magnesium-containing compound in the solvent, and mixing them under stirring for 10-40 hours to prepare an electrospinning solution ; 所述的纳米孔模板剂在溶液中的质量浓度在20-40％范围；The mass concentration of the nanopore template in the solution is in the range of 20-40%; 所述的纳米孔模板剂是离子型表面活性试剂，其化学式为CnH2n+1X，n＝10-20，R为-CH3或-C2H5，X为Cl-或Br-；或者是The nanopore template agent is an ionic surface active agent, its chemical formula is C n H 2n+1 X, n=10-20, R is -CH 3 or -C 2 H 5 , X is Cl - or Br - ;or 聚环氧乙烯作为亲水嵌段、长链烷烃作为疏水基的非离子型表面活性剂；或者是Polyethylene oxide as a hydrophilic block, long-chain alkane as a non-ionic surfactant with a hydrophobic base; or PEO作为亲水嵌段，聚环氧丙烯或聚环氧丁烯作为疏水嵌段，其分子式为EOnPOmEOn，n＝10-140，m＝5-100；或EOnBOmEOn，n＝10-200，m＝10-100；或EOnBOm，n＝10-100，m＝5-60；PEO is used as a hydrophilic block, polypropylene oxide or polybutylene oxide is used as a hydrophobic block, and its molecular formula is EO n PO m EO n , n=10-140, m=5-100; or EO n BO m EO n , n=10-200, m=10-100; or EO n BO m , n=10-100, m=5-60; 所使用的溶剂是水、乙醇或它们的混合溶剂；The solvent used is water, ethanol or their mixed solvents; B.将配制的聚合物溶液进行静电纺丝，获得微米或纳米纤维B. Electrospinning the prepared polymer solution to obtain micro or nano fibers (1)采用的静电纺丝的设备的结构构成如下：静电纺丝容器(1)、载有纺丝溶液、活塞式输送泵(2)、静电纺丝口(3)、高压电源(4)和电极纤维接收板(5)；其中，静电纺丝口(3)的直径在0.05-5毫米范围；(1) The structure of the electrospinning equipment adopted is as follows: electrospinning container (1), carrying spinning solution, piston type delivery pump (2), electrospinning port (3), high voltage power supply (4) and electrode fiber receiving plate (5); wherein, the diameter of the electrospinning port (3) is in the range of 0.05-5 mm; 在高压电源(4)的高压端接一个纺丝装置，在高压电源(4)接地端接一个电极纤维接收板(5)；其中静电纺丝装置由静电纺丝液容器(1)和静电纺丝口(3)组成，电丝液从静电纺丝口(3)流出，静电纺丝口(3)到电极纤维接收板(5)之间的距离为3-50厘米；A spinning device is connected to the high-voltage terminal of the high-voltage power supply (4), and an electrode fiber receiving plate (5) is connected to the grounding terminal of the high-voltage power supply (4); Composed of a silk port (3), the electrofilament liquid flows out from the electrospinning port (3), and the distance between the electrospinning port (3) and the electrode fiber receiving plate (5) is 3-50 cm; (2)先将步骤A制备的纺丝溶液通过活塞式输送泵(2)转移到纺丝容器(1)中，然后通过高压电源(4)对容器中的液体施加电压为500-30,000伏的静电压，由于静电的作用，液体从纺丝液容器(1)的纺丝口(3)射出，射出的射流(7)会形成纤维并且纤维中的液体会很快挥发，当这些纤维到达电极纤维接收板(5)后，会干燥形成固体纤维；(2) First transfer the spinning solution prepared in step A to the spinning container (1) through the piston delivery pump (2), and then apply a voltage of 500-30,000 volts to the liquid in the container through a high-voltage power supply (4) Static voltage, due to the effect of static electricity, the liquid is ejected from the spinning port (3) of the spinning solution container (1), and the ejected jet (7) will form fibers and the liquid in the fibers will evaporate quickly. When these fibers reach the electrode After the fiber receiving plate (5), it will dry to form solid fibers; C.有机成分的去除C. Removal of organic components 在500-900℃，对静电纺丝制备的纤维进行6-10小时焙烧，除去有机成分，得到具有纳米孔的复合生物活性玻璃超细纤维。The fiber prepared by electrospinning is calcined at 500-900 DEG C for 6-10 hours to remove the organic component and obtain the composite bioactive glass superfine fiber with nanometer holes. 7、如权利要求6所述的具有纳米孔的复合生物活性玻璃超细纤维的制备方法，其特征在于所述的：7. The method for preparing composite bioactive glass microfibers with nanopores as claimed in claim 6, characterized in that: A.配制静电纺丝溶液A. Preparation of electrospinning solution 将纳米孔模板剂、纤维结构导向聚合物与所述配比的含硅化合物、含钙化合物、含磷化合物、含钠化合物和含镁化合物溶解到溶剂中配制静电纺丝溶液；Dissolving the nanopore template agent, the fiber structure-directing polymer and the silicon-containing compound, calcium-containing compound, phosphorus-containing compound, sodium-containing compound and magnesium-containing compound in a solvent to prepare an electrospinning solution; 所述的纤维结构导向聚合物质量浓度在0.5-20％范围；The mass concentration of the fiber structure-guiding polymer is in the range of 0.5-20%; 纤维结构导向聚合物是聚乙烯基吡咯烷酮，重均分子量为10,000-1,000,000；或聚乙烯醇缩丁醛，重均分子量为10,000-1,000,000；或聚乙二醇，重均分子量为5,000-1,000,000；或聚氧乙烯，重均分子量为10000-2,000,000；The fiber structure directing polymer is polyvinylpyrrolidone with a weight average molecular weight of 10,000-1,000,000; or polyvinyl butyral with a weight average molecular weight of 10,000-1,000,000; or polyethylene glycol with a weight average molecular weight of 5,000-1,000,000; or Polyoxyethylene, with a weight average molecular weight of 10,000-2,000,000; 其余的条件同权利要求6。All the other conditions are the same as claim 6. 8、如权利要求6或7所述的具有纳米孔的复合生物活性玻璃超细纤维的制备方法，其特征在于所述的步骤8. The method for preparing composite bioactive glass microfibers with nanopores as claimed in claim 6 or 7, characterized in that the steps B.将配制的聚合物溶液进行静电纺丝，获得微米或纳米纤维中，静电纺丝口(3)的直径为0.1-2毫米。B. Electrospinning the prepared polymer solution to obtain micron or nanofibers, the diameter of the electrospinning port (3) is 0.1-2 mm. 9、如权利要求8所述的具有纳米孔的复合生物活性玻璃超细纤维的制备方法，其特征在于所述的步骤9. The method for preparing composite bioactive glass microfibers with nanopores as claimed in claim 8, characterized in that the steps B.将配制的聚合物溶液进行静电纺丝，获得微米或纳米纤维中，静电纺丝口(3)的直径为0.5-1毫米。B. Electrospinning the prepared polymer solution to obtain micron or nanofibers, the diameter of the electrospinning port (3) is 0.5-1 mm. 10、如权利要求7所述的具有纳米孔的复合生物活性玻璃超细纤维的制备方法，其特征在于，所述的纤维结构导向聚合物质量浓度为1-10％。10. The method for preparing composite bioactive glass superfine fibers with nanopores according to claim 7, characterized in that the mass concentration of the fiber structure-directing polymer is 1-10%. 11、如权利要求7所述的具有纳米孔的复合生物活性玻璃超细纤维的制备方法，其特征在于，所述的纤维结构导向聚合物是聚乙二醇或聚氧乙烯。11. The method for preparing composite bioactive glass microfibers with nanopores according to claim 7, characterized in that the fiber structure-guiding polymer is polyethylene glycol or polyoxyethylene.
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