CN102102242B - Method for preparing polylactic acid-amorphous calcium phosphate nano composite fiber material - Google Patents
Method for preparing polylactic acid-amorphous calcium phosphate nano composite fiber material Download PDFInfo
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- CN102102242B CN102102242B CN2010106194182A CN201010619418A CN102102242B CN 102102242 B CN102102242 B CN 102102242B CN 2010106194182 A CN2010106194182 A CN 2010106194182A CN 201010619418 A CN201010619418 A CN 201010619418A CN 102102242 B CN102102242 B CN 102102242B
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- calcium phosphate
- amorphous calcium
- fiber material
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Abstract
The invention discloses a method for preparing a polylactic acid-amorphous calcium phosphate nano composite fiber material, which comprises the following steps of: preparing aqueous solution A and aqueous solution B by using water-soluble calcium salt, water-soluble phosphate and polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer (P123) as raw materials, and then performing precipitation reaction under the alkali condition to obtain amorphous calcium phosphate nano granules; and then dispersing the amorphous calcium phosphate nano granules into mixed solution of nitrogen-nitrogen-dimethyl formamide and tetrahydrofuran, adding polylactic acid, stirring till full dissolution, and performing electrostatic spinning to obtain the material. The preparation method has the advantages of simple process, quickness, low cost and the like, and is suitable for large-scale production. The prepared polylactic acid-amorphous calcium phosphate nano composite fiber material has good biocompatibility, high specific surface and internal through porous structure; and the composite material can be widely applied in the field of biomedical engineering.
Description
Technical field
The present invention relates to the preparation method of a kind of PLA-amorphous calcium phosphate composite nano-fiber material; Specifically; Relate to a kind of method of utilizing electrostatic spinning technique to prepare PLA-amorphous calcium phosphate composite nano-fiber material, belong to the nano-fiber material preparing technical field.
Background technology
PLA (PLA) is because of having many outstanding performances; Comprise favorable mechanical performance, heat resistance, resistance to chemical corrosion; The good transparency, fibre forming property and thermoplasticity etc.; Particularly have favorable biological degradability and biocompatibility, thereby can be widely used in field of biomedical materials owing to it.Yet the greatest problem that poly-lactic acid material exists when human use is can produce a large amount of lactic acid in its degradation process to cause local sour environment, thereby causes the inflammatory reaction of partial musculature.
Amorphous calcium phosphate as utilizing a kind of middle phase that exists in the wet chemistry method synthesizing hydroxylapatite process, have excellent bone conductibility and Gegenbaur's cell adhesion, and biodegradation rate is higher, is widely used in the interpolation material of biomaterial.At orthopaedics, because it is similar to composition natural among the human skeletal, and be used as the packing material of bone material, such as the cement bone, dentistry is filled material etc.Because it is solubility property preferably, in degradation process, can form the Ca that contains of a flexibility around
2+Ion, PO
4 3-The ion district, this ion district can in the sour environment that brings with PLA, delay the speed of bio-absorbable, thereby remove the inflammatory reaction that causes by acidic materials.But the quality of calcium phosphate is too crisp, and the material of processing is cracked easily, and mechanical performance is not good, and the adding of PLA can improve the performance of material.PLA and calcium phosphate are made engineering material of bone tissue with appropriate preparation method, can improve mechanical property and induced osteogenesis characteristic, can control the biodegradation rate of material again.Therefore, PLA-calcium phosphate complex stephanoporate bracket is adopted by most scholars.
The tissue engineering bracket material that is used for biomedical engineering field can influence tissue construction on three levels: the 1. composition structure of timbering material, the basic physical and mechanical properties of decision material; 2. the morphosis of brace aperture and size are regulated the migration and the growth of cell; 3. the surface chemical property of timbering material (like hydrophily and surface charge) is regulated the sticking of cell contacted with it, stretching, extension and gene expression process.The structure of desirable tissue engineering bracket is wanted comprehensive above each factor, makes timbering material at aspect simulation living organism tissues such as the physics and chemistry on three-D space structure, surface and biological properties.Therefore, the morphosis of the composition of timbering material and brace aperture is two key factors of tissue engineering bracket material.Present tissue engineering bracket material; Biocompatibility is poor, degradation rate is unreasonable; Mechanical property is not high, the gas permeability difference that also has or be unfavorable for cell growth, nutrition supply and waste discharge because hole does not connect, and common netted material hole footpath is too big; Pair cell does not have barrier action, thereby is difficult to satisfy the clinical practice requirement.
Nanofiber has the special nature that much is different from the stock size material, mainly is because it has great specific area.For nanoparticle material, nanofiber keeps the nanoscale pattern more easily, and can directly be used for practical uses such as industry.Strictness, nanofiber generally are meant the fiber of diameter less than 100nm.Usually, the fiber of diameter below the hundreds of nanometer is called superfine fibre, also has property.The superfine fibre porous material of method of electrostatic spinning preparation has excellent properties such as high-specific surface area, high porosity; Bionic extracellular matrix preferably on form, thereby comprise that in biomedicine aspects such as tissue engineering bracket, surface coating, medicament slow release have broad application prospects.
Electrostatic spinning technique is a kind of Polymer Processing technology that under the high voltage electric field effect, forms superfine fibre.Can prepare the polymer superfine fibre of diameter easily through this technology in tens nanometers to hundreds of nanometer.In the electrostatic spinning process, adopt the static resulting fiber of ground connection receiving system generally can be deposited as fibrofelt, microscopic pattern is similar to nonwoven fabric.An important use direction of electrostatic spinning material is a biomedical sector.The material that will have good biocompatibility spins through electricity and is processed into the focus that the tissue engineering bracket with special ultra-fine fiber construction is present Tissue Engineering Study.Compare other support technologies of preparing, electrospinning has following characteristics: (1) superfine fibre can be simulated the mesh nanometer structure of n cell epimatrix.A lot of results of study think, the adhesion of the micro-structural pair cell of support and grow significant.(2) polymer support of preparation can be the composite of multiple polymers, can fully utilize the characteristic of different materials.(3) support of preparation has internal run-through property.
But utilize electrostatic spinning technique to prepare PLA-amorphous calcium phosphate composite nano-fiber material, do not see relevant report so far.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing electrostatic spinning technique to prepare PLA-amorphous calcium phosphate composite nano-fiber material, to realize the extensive use of such composite in biomedical engineering field and the purpose of large-scale production.
For realizing the foregoing invention purpose, the technical scheme that the present invention adopts is following:
The preparation method of PLA provided by the invention-amorphous calcium phosphate composite nano-fiber material comprises following concrete steps:
A) water-soluble Ca salt and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer P123 are added in the deionized water, be mixed with mixed aqueous solution A;
B) water-soluble phosphate and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer P123 are added in the deionized water, be mixed with mixed aqueous solution B;
The pH value of c) regulating mixed aqueous solution B is added dropwise to mixed aqueous solution A then and wherein carries out precipitation reaction to alkalescence;
D) drip and finish, obtain the oyster white turbid liquid, centrifugation gets milky white precipitate, and this deposition is the amorphous calcium phosphate nano particle;
E) carry out ultrasonic dispersion in the mixed solvent with amorphous calcium phosphate nano particle adding nitrogen-nitrogen-dimethyl formamide that obtains and oxolane;
F) in the dispersion that adding PLA to step e) obtains, stirring is dissolved it fully;
G) carry out electrostatic spinning, promptly get PLA-amorphous calcium phosphate composite nano-fiber material.
Said water-soluble Ca salt is recommended as any one in calcium chloride, calcium nitrate, the calcium acetate.
Among the said mixed aqueous solution A: the concentration of water-soluble Ca salt is recommended as 0.03～0.05mol/L, and the concentration of P123 is recommended as 0.00006～0.0001mol/L.
Said water-soluble phosphate is recommended as any one in sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, the ammonium dihydrogen phosphate (ADP).
Among the said mixed aqueous solution B: the concentration of water-soluble phosphate is recommended as 0.05～0.08mol/L, and the concentration of P123 is recommended as 0.00006～0.0001mol/L.
The pH value of recommending in the step c) to regulate mixed aqueous solution B with ammoniacal liquor is to alkalescence.
PH value in the step c) is recommended as 10～12.
The precipitation reaction time in the step c) is recommended as 1～30 minute.
The volume ratio of said nitrogen-nitrogen-dimethyl formamide and oxolane is recommended as (0.1～10): 1.
The concentration of said PLA in dispersion is recommended as 0.004～0.007mol/L.
The syringe specification that said electrostatic spinning uses is recommended as 5～20 milliliters, injects speed and is recommended as 1～5 milliliter/hour, and DC voltage is recommended as 10～20 kilovolts, and receiving range is recommended as 10～20 centimetres, and receiving system is recommended as aluminium foil.
Compared with prior art, the present invention has following beneficial effect:
1) preparation method of the present invention has simple, the quick and low cost and other advantages of technology, is fit to large-scale production.
2) PLA that makes by preparation method of the present invention-amorphous calcium phosphate composite nano-fiber material; Has excellent biological compatibility; Certain bond strength is arranged; And have the loose structure of high-ratio surface and internal run-through, and can facilitate for cell growth, nutrition supply and waste discharge, can realize the extensive use of such composite in biomedical engineering field.
Description of drawings
Fig. 1 is the X-ray powder diffraction spectrogram of the amorphous calcium phosphate nano particle that makes of embodiment 1.
Fig. 2 is the transmission electron microscope photo of the amorphous calcium phosphate nano particle that makes of embodiment 1.
Fig. 3 is the electron scanning micrograph of PLA-amorphous calcium phosphate composite nano-fiber material of making of embodiment 1.
Fig. 4 is the transmission electron microscope photo of PLA-amorphous calcium phosphate composite nano-fiber material of making of embodiment 1.
The practical implementation method
Below in conjunction with embodiment the present invention is done further in detail, intactly explains, but do not limit content of the present invention.
Embodiment 1
The concrete steps that present embodiment prepares PLA-amorphous calcium phosphate composite nano-fiber material are:
A) with 0.0017mol CaCl
2With 3.4 * 10
-6Mol polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer P123 is dissolved in the 40ml deionized water, is mixed with mixed aqueous solution A;
B) with 0.0028mol Na
2HPO
412H
2O and 3.4 * 10
-6Mol P123 is dissolved in the 40ml deionized water, is mixed with mixed aqueous solution B;
C) the pH value of using ammoniacal liquor to regulate mixed aqueous solution B is 10～10.5, mixed aqueous solution A is added dropwise to the speed of 10 ml/min with electronic peristaltic pump then and wherein carries out precipitation reaction, and the pH value in the use ammoniacal liquor adjusting entire reaction course is 10～10.5;
D) drip and finish, obtain the oyster white turbid liquid, centrifugation gets the oyster white calcium phosphate precipitation;
E) calcium phosphate precipitation that obtains is added in the mixed solvent of 2ml nitrogen-nitrogen-dimethyl formamide and 2ml oxolane, ultrasonic dispersion is dispersed in the mixed solvent milky white precipitate;
F) add 2.1 * 10
-5In the dispersion that mol PLA to step e) obtains, stirring is dissolved it fully;
G) carry out electrostatic spinning: the suspension that step f) is obtained joins in 10 milliliters of syringes; Add 15 kilovolts voltage at the syringe needle place; The speed of injecting with 1 milliliter/hour is injected, and utilizes aluminium foil receiving apart from syringe needle 15 centimeters, promptly gets PLA-amorphous calcium phosphate composite.
Fig. 1 is the X-ray powder diffraction spectrogram of the oyster white calcium phosphate precipitation that makes of present embodiment; Fig. 2 is the transmission electron microscope photo of the oyster white calcium phosphate precipitation that makes of present embodiment, and complex chart 1 can be known with Fig. 2: the oyster white calcium phosphate precipitation that makes is the amorphous calcium phosphate nano particle.
Fig. 3 is the electron scanning micrograph of PLA-amorphous calcium phosphate composite of making of present embodiment; Fig. 4 is the transmission electron microscope photo of PLA-amorphous calcium phosphate composite of making of present embodiment; Complex chart 3 can be known with Fig. 4: the PLA that present embodiment makes-amorphous calcium phosphate composite is a nanofiber, has the loose structure of internal run-through.
Embodiment 2
The difference of present embodiment and embodiment 1 only is:
A) with 0.0012mol CaCl
2With 3.4 * 10
-6Mol polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer P123 is dissolved in the 40ml deionized water, is mixed with mixed aqueous solution A;
B) with 0.002mol Na
2HPO
412H
2O and 3.4 * 10
-6Mol is dissolved in the 40ml deionized water, is mixed with mixed aqueous solution B;
All the other contents are all with identical described in the embodiment 1.
Embodiment 3
The difference of present embodiment and embodiment 1 only is:
A) with 0.002mol CaCl
2With 4 * 10
-6Mol polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer (P123) is dissolved in the 40ml deionized water, is mixed with mixed aqueous solution A;
B) with 0.0032mol Na
2HPO
412H
2O and 4 * 10
-6Mol P123 is dissolved in the 40ml deionized water, is mixed with mixed aqueous solution B;
All the other contents are all with identical described in the embodiment 1.
Embodiment 4
The difference of present embodiment and embodiment 1 only is:
C) using the pH value of the sodium hydrate aqueous solution adjusting mixed aqueous solution B of 2mol/L is 11.5～12; Mixed aqueous solution A is added dropwise to the speed of 10 ml/min with electronic peristaltic pump then and wherein carries out precipitation reaction, and the pH value of using the sodium hydrate aqueous solution of 2mol/L to regulate in the entire reaction course is 11.5～12;
All the other contents are all with identical described in the embodiment 1.
Embodiment 5
The difference of present embodiment and embodiment 1 only is:
F) add 1.6 * 10
-5In the dispersion that mol PLA to step e) obtains, stirring is dissolved it fully;
All the other contents are all with identical described in the embodiment 1.
Embodiment 6
The difference of present embodiment and embodiment 1 only is:
F) add 2.8 * 10
-5In the dispersion that mol PLA to step e) obtains, stirring is dissolved it fully;
All the other contents are all with identical described in the embodiment 1.
Embodiment 7
The difference of present embodiment and embodiment 1 only is:
G) carry out electrostatic spinning: the suspension that step f) is obtained joins in 20 milliliters of syringes, adds 20 kilovolts voltage at the syringe needle place, injects with 5 milliliters/hour the speed of injecting, and utilizes aluminium foil receiving apart from syringe needle 20 centimeters.
All the other contents are all with identical described in the embodiment 1.
Embodiment 8
The difference of present embodiment and embodiment 1 only is:
G) carry out electrostatic spinning: the suspension that step f) is obtained joins in 5 milliliters of syringes, adds 10 kilovolts voltage at the syringe needle place, injects with 1 milliliter/hour the speed of injecting, and utilizes aluminium foil receiving apart from syringe needle 10 centimeters.
All the other contents are all with identical described in the embodiment 1.
Embodiment 9
The difference of present embodiment and embodiment 1 only is:
Utilize the stainless steel bar of rotation receiving apart from syringe needle 15 centimeters, obtaining product is the tubular material that PLA-amorphous calcium phosphate composite nano fiber forms.
In addition, experiment proof: the CaCl among the embodiment 1
2Can be equal to alternative by any one water-soluble Ca salts such as calcium nitrate, calcium acetates; Na among the embodiment 1
2HPO
412H
2O can be equal to alternative by any one water-soluble phosphates such as sodium phosphate, dibastic sodium phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP)s.
Claims (15)
1. the preparation method of PLA-amorphous calcium phosphate composite nano-fiber material is characterized in that, comprises following concrete steps:
A) water-soluble Ca salt and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer P123 are added in the deionized water, be mixed with mixed aqueous solution A;
B) water-soluble phosphate and polyoxyethylene-poly-oxypropylene polyoxyethylene triblock polymer P123 are added in the deionized water, be mixed with mixed aqueous solution B;
The pH value of c) regulating mixed aqueous solution B is added dropwise to mixed aqueous solution A then and wherein carries out precipitation reaction to alkalescence;
D) drip and finish, obtain the oyster white turbid liquid, centrifugation gets milky white precipitate, and this deposition is the amorphous calcium phosphate nano particle;
E) the amorphous calcium phosphate nano particle that obtains is added in the mixed solvent of nitrogen-nitrogen-dimethyl formamide and oxolane, carry out ultrasonic dispersion;
F) in the dispersion that adding PLA to step e) obtains, stirring is dissolved it fully;
G) polymer solution that uses step f) to obtain carries out electrostatic spinning, promptly gets PLA-amorphous calcium phosphate composite nano-fiber material.
2. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: said water-soluble Ca salt is any one in calcium chloride, calcium nitrate, the calcium acetate.
3. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material; It is characterized in that: the concentration of the water-soluble Ca salt among the mixed aqueous solution A is 0.03～0.05mol/L, and the concentration of P123 is 0.00006～0.0001mol/L.
4. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: said water-soluble phosphate is any one in sodium phosphate, dibastic sodium phosphate, sodium dihydrogen phosphate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, ammonium phosphate, ammonium hydrogen phosphate, the ammonium dihydrogen phosphate (ADP).
5. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material; It is characterized in that: the concentration of the water-soluble phosphate among the mixed aqueous solution B is 0.05～0.08mol/L, and the concentration of P123 is 0.00006～0.0001mol/L.
6. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the pH value of regulating mixed aqueous solution B with ammoniacal liquor in the step c) is to alkalescence.
7. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the pH value in the step c) is 10～12.
8. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the precipitation reaction time in the step c) is 1～30 minute.
9. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the volume ratio of said nitrogen-nitrogen-dimethyl formamide and oxolane is (0.1～10): 1.
10. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the concentration of said PLA in dispersion is 0.004～0.007mol/L.
11. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the syringe specification of using in the electrostatic spinning is 5～20 milliliters.
12. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: it is 1～5 milliliter/hour that the syringe in the electrostatic spinning is injected speed.
13. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the DC voltage in the electrostatic spinning is 10～20 kilovolts.
14. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the receiving range in the electrostatic spinning is 10～20 centimetres.
15. the preparation method of PLA according to claim 1-amorphous calcium phosphate composite nano-fiber material is characterized in that: the receiving system in the electrostatic spinning is an aluminium foil.
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| US9896782B2 (en) | 2012-06-20 | 2018-02-20 | Jnc Corporation | Method for producing porous calcium phosphate body |
| CN107126582A (en) * | 2017-06-02 | 2017-09-05 | 北京航空航天大学 | The preparation of amorphous calcium phosphate/PLA electrospun scaffolds |
| CN107875455A (en) * | 2017-10-23 | 2018-04-06 | 广州润虹医药科技股份有限公司 | A kind of organic-inorganic blending electrospun fibers and preparation method thereof |
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| CN1217855C (en) * | 2003-07-28 | 2005-09-07 | 浙江大学 | Method for preparing biomedical amorphous nano calcium phosphate |
| CN100445201C (en) * | 2006-10-16 | 2008-12-24 | 南京工业大学 | Method for preparing nano amorphous calcium phosphate powder |
| CN101613524B (en) * | 2009-07-14 | 2011-03-16 | 中国科学院上海硅酸盐研究所 | Triblock copolymer PEO-PPO-PEO/calcium phosphate nanometer composite material and preparation method thereof |
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