CN109172873A - A kind of medical artificial bone material and preparation method thereof - Google Patents
A kind of medical artificial bone material and preparation method thereof Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention discloses a kind of preparation methods of medical artificial bone material, include the following steps: the preparation of (one) titaniferous polymerization type monomer, (2) polydactyl acid nanofiber, (3) titaniferous polymerization type monomer, polydactyl acid nanofiber, methyl methacrylate copolymer, (four) ion exchange.The invention also discloses the medical artificial bone materials being prepared according to the preparation method.Preparation method is simple for medical artificial bone material disclosed by the invention, and raw material is easy to get, cheap, is suitble to large-scale production；The medical artificial bone being prepared material has the advantages that good biocompatibility, bioactivity height, intensity, elasticity, chemical stability, weatherability and excellent tenacity.
Description
Technical field
The present invention relates to medical material tech field more particularly to a kind of medical artificial bone material and its preparation sides
Method.
Background technique
In recent years, with social senilization, athletic injury and traffic accident the increase of the problems such as, world wide are interior to artificial
The demand of bone material is growing day by day.China human mortality is numerous, the Kaschin-Beck disease caused by rheumatism and rheumatoid, aged with population
The osteoporosis of change, patient's number of the bone defect as caused by disease, traffic accident and athletic injury etc., fracture and bone lacks
Amount is in trend is risen year by year, and increasing to the performance requirement of bone tissue reparation and reconstruction biomaterials, demand increasingly increases, to people
The research and development for making bone material have become one of project the most popular in the industry.
Currently, medical artificial bone material mainly have Titanium, ceramics, calcium phosphate and ossein composite material, sea grass,
Organic glass etc..Although Titanium has high-intensitive and good toughness, its biocompatibility is bad, lacks bioactivity,
Only simple mechanical-physical combines, and internal rejection is obvious, and its cost is very high, is not suitable for large-scale use.Though ceramics
Right comparatively robust, but quality is more crisp, is unable to stand collision.Although calcium phosphate and ossein composite material intensity and elasticity all close to
Real bone, but its preparation technology parameter is complicated.Polymethyl methacrylate has good chemistry because of its asepsis environment-protecting
Stability and weatherability, it is considered to be more wide one of the artificial bone material of medical prospect at present, but its biocompatibility
Still need to be further increased with antithrombotic.
Therefore, a kind of good biocompatibility, bioactivity height, intensity, elasticity, chemical stability, weatherability and tough are developed
Property excellent medical artificial bone accorded with the demands of the market with material, there is extensive market value and application prospect.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind of medical artificial bone material and its preparation side
Method, preparation method is simple for this, and not high to device dependence, raw material is easy to get, cheap, is suitble to large-scale production；Preparation
Obtained medical artificial bone material has good biocompatibility, bioactivity height, intensity, elasticity, chemical stability, weather-proof
The advantages of property and excellent tenacity.
To achieve the above object of the invention, the technical solution adopted by the present invention is that: a kind of system of medical artificial bone material
Preparation Method includes the following steps:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes, acrylic acid chlorine
Ethyl ester is added in organic solvent, then basic catalyst is added thereto, 8-10 hours is stirred to react at 30-40 DEG C, back spin
Solvent is evaporated off, adds methylene chloride and water extracting and demixing, takes organic phase, removed water with anhydrous magnesium sulfate, filters, revolving removes
Methylene chloride obtains titaniferous polymerization type monomer；
II polydactyl acid nanofiber: polylactic acid nano fiber is added in ethyl alcohol, then 3- phenyl is added thereto
Acryloyl chloride, fire retardant and catalyst react 6-8 hours at 90-110 DEG C, and ethyl alcohol is evaporated off in back spin, then is produced with acetone washing
Acetone is evaporated off in object 3-5 times, back spin, obtains polydactyl acid nanofiber；
The preparation of III polymer: it is prepared by the titaniferous polymerization type monomer being prepared by step I, by step II
Polydactyl acid nanofiber, methyl methacrylate be added in high boiling solvent, initiator is added, in nitrogen or lazy
Be stirred to react 8-10 hours at 85-95 DEG C of atmosphere of property, after be precipitated in ethanol, the polymer of precipitation is produced with acetone washing
Object 4-6 times, then be placed at 80-90 DEG C of vacuum oven and dry 15-20 hours, obtain medical artificial bone material；
IV ion exchange: the medical artificial bone being prepared by step III is immersed at 50-69 DEG C with material
Mass fraction is 20-30 hours in the aqueous solution of the calcium acid sodium of 5-10%, and rear taking-up is washed with water 4-6 times, then be placed in vacuum drying
It is dried 15-20 hours at 80-90 DEG C of case.
Preferably, (1- (2,4- difluorophenyl) -3- pyrrole radicals) titanocenes bis- described in step I, have acrylic acid chloroethene ester
Solvent, basic catalyst mass ratio be 2:1:(10-15): (0.2-0.4).
Preferably, the organic solvent is selected from one or more of tetrahydrofuran, acetonitrile, chloroform.
Preferably, the basic catalyst is selected from one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or several
Kind.
Preferably, polylactic acid nano fiber described in step II, ethyl alcohol, 3- phenylacrylyl chloride, fire retardant, catalyst
Mass ratio is (3-5): (10-15): 1:(0.1-0.2): (0.3-0.5).
Preferably, the fire retardant is selected from tetrachloroquinone, l, at least one of 4- naphthoquinones.
Preferably, the catalyst is selected from one or more of triethylamine, anhydrous pyridine, 4-dimethylaminopyridine.
Further, titaniferous polymerization type monomer described in step III, polydactyl acid nanofiber, methyl methacrylate
Ester, high boiling solvent, initiator mass ratio be 1:2:4:(20-25): (0.04-0.08).
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of.
Preferably, the initiator be selected from cyclohexanone peroxide, azodiisobutyronitrile, di-isopropyl peroxydicarbonate,
One or more of di-cyclohexylperoxy di-carbonate.
Preferably, the inert gas is selected from one of helium, neon, argon gas.
Preferably, the material of artificial skelecton described in step IV, calcium acid sodium the mass ratio of aqueous solution be 1:(10-20).
A kind of medical artificial bone material is prepared using the preparation method of above-mentioned medical artificial bone material.
The beneficial effects of adopting the technical scheme are that
1) medical artificial bone material provided by the invention, preparation method is simple, not high to device dependence, former
Material is easy to get, cheap, is suitble to large-scale production.
2) anticoagulation hemodialysis membrane provided by the invention overcomes conventional artificial's bone material more or less existing biology
Compatibility is bad, lacks bioactivity, and cost is very high, and preparation technology parameter is complicated, chemical stability and the bad skill of weatherability
Art problem, with the excellent of good biocompatibility, bioactivity height, intensity, elasticity, chemical stability, weatherability and excellent tenacity
Point.
3) medical artificial bone material provided by the invention introduces polylactic acid nano fiber structure in the molecular structure,
On the one hand the mechanical property of material is improved, on the other hand, due to the good biocompatibility of polylactic acid, and it is good to assign material
Biocompatibility；By being modified introducing vinyl to polylactic acid nano fiber, then directly it is copolymerized into other polymerized monomers
Film, so that material structure is more compact, mechanical property, chemical stability and weatherability are more preferable, avoid in the prior art directly
The generation of problem of phase separation caused by being added is blended.
4) medical artificial bone material provided by the invention, introduces the chemical stabilization that material is improved containing fluorine structure
Property and weatherability, introduce titanocenes structure, while ensure that the intensity and toughness of material；Calcium is introduced by ion exchange, is removed
Chlorine so that materials'use is more environment-friendly and safer, and is conducive to supplement the necessary calcium constituent of human body.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
A kind of preparation method of medical artificial bone material, includes the following steps:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes 20g, acrylic acid
Chloroethene ester 10g is added in tetrahydrofuran 100g, then sodium carbonate 2g is added thereto, 8 hours is stirred to react at 30 DEG C, back spin
Solvent is evaporated off, adds methylene chloride and water extracting and demixing, takes organic phase, removed water with anhydrous magnesium sulfate, filters, revolving removes
Methylene chloride obtains titaniferous polymerization type monomer；
II polydactyl acid nanofiber: polylactic acid nano fiber 30g is added in ethyl alcohol 100g, then is added thereto
3- phenylacrylyl chloride 10g, tetrachloroquinone 1g and triethylamine 3g react 6 hours at 90 DEG C, and ethyl alcohol is evaporated off in back spin, then uses
Acetone washing product 3 times, acetone is evaporated off in back spin, obtains polydactyl acid nanofiber；
The preparation of III polymer: it is prepared by the titaniferous polymerization type monomer 10g being prepared by step I, by step II
Obtained polydactyl acid nanofiber 20g, methyl methacrylate 40g is added in dimethyl sulfoxide 200g, adds peroxide
Change cyclohexanone 0.4g, be stirred to react at 85 DEG C of nitrogen atmosphere 8 hours, after be precipitated in ethanol, by the polymer of precipitation with third
Ketone washed product 4 times, then be placed at 80 DEG C of vacuum oven and dry 15 hours, obtain medical artificial bone material；
IV ion exchange: the medical artificial bone being prepared by step III is immersed at 50 DEG C with material 10g
It is rear to take out 20 hours in the aqueous solution 100g for the calcium acid sodium that mass fraction is 5%, it is washed with water 4 times, then be placed in vacuum oven 80
It is dried 15 hours at DEG C.
A kind of medical artificial bone material is prepared using the preparation method of above-mentioned medical artificial bone material.
Embodiment 2
A kind of preparation method of medical artificial bone material, includes the following steps:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes 20g, acrylic acid
Chloroethene ester 10g is added in acetonitrile 110g, then potassium carbonate 2.5g is added thereto, 8.5 hours is stirred to react at 32 DEG C, back spin
Solvent is evaporated off, adds methylene chloride and water extracting and demixing, takes organic phase, removed water with anhydrous magnesium sulfate, filters, revolving removes
Methylene chloride obtains titaniferous polymerization type monomer；
II polydactyl acid nanofiber: polylactic acid nano fiber 35g is added in ethyl alcohol 115g, then is added thereto
3- phenylacrylyl chloride 10g, l, 4- naphthoquinones 1.3g and anhydrous pyridine 3.5g, react 6.5 hours, second is evaporated off in back spin at 95 DEG C
Alcohol, then with acetone washing product 4 times, acetone is evaporated off in back spin, obtains polydactyl acid nanofiber；
The preparation of III polymer: it is prepared by the titaniferous polymerization type monomer 10g being prepared by step I, by step II
Obtained polydactyl acid nanofiber 20g, methyl methacrylate 40g is added in n,N-Dimethylformamide 215g, then
Azodiisobutyronitrile 0.5g is added, is stirred to react at 88 DEG C of helium atmosphere 9 hours, after be precipitated in ethanol, by the poly- of precipitation
Object is closed with acetone washing product 5 times, then is placed at 83 DEG C of vacuum oven and dries 16 hours, obtains medical artificial bone material；
IV ion exchange: the medical artificial bone being prepared by step III is immersed at 54 DEG C with material 10g
It is rear to take out 23 hours in the aqueous solution 130g for the calcium acid sodium that mass fraction is 6%, it is washed with water 5 times, then be placed in vacuum oven 83
It is dried 15-20 hours at DEG C.
A kind of medical artificial bone material is prepared using the preparation method of above-mentioned medical artificial bone material.
Embodiment 3
A kind of preparation method of medical artificial bone material, includes the following steps:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes 20g, acrylic acid
Chloroethene ester 10g is added in chloroform 130g, then sodium hydroxide 3g is added thereto, is stirred to react at 35 DEG C 9 hours, rear to rotate
Solvent is removed, methylene chloride and water extracting and demixing is added, takes organic phase, removed water with anhydrous magnesium sulfate, is filtered, revolving removes two
Chloromethanes obtains titaniferous polymerization type monomer；
II polydactyl acid nanofiber: polylactic acid nano fiber 40g is added in ethyl alcohol 132g, then is added thereto
3- phenylacrylyl chloride 10g, tetrachloroquinone 1.5g and 4-dimethylaminopyridine 4g react 7 hours at 100 DEG C, and back spin is evaporated off
Ethyl alcohol is removed, then with acetone washing product 5 times, acetone is evaporated off in back spin, obtains polydactyl acid nanofiber；
The preparation of III polymer: it is prepared by the titaniferous polymerization type monomer 10g being prepared by step I, by step II
Obtained polydactyl acid nanofiber 20g, methyl methacrylate 40g is added in N-Methyl pyrrolidone 230g, then plus
Enter di-isopropyl peroxydicarbonate 0.65g, be stirred to react at 90 DEG C of neon atmosphere 9.2 hours, after be precipitated in ethanol, will
The polymer of precipitation is with acetone washing product 6 times, then is placed at 86 DEG C of vacuum oven and dries 17 hours, obtains medical artificial bone
Use material；
IV ion exchange: the medical artificial bone being prepared by step III is immersed at 58 DEG C with material 10g
It is rear to take out 26 hours in the aqueous solution 160g for the calcium acid sodium that mass fraction is 7.5%, it is washed with water 6 times, then be placed in vacuum oven
It is dried 17.5 hours at 86 DEG C.
A kind of medical artificial bone material is prepared using the preparation method of above-mentioned medical artificial bone material.
Embodiment 4
A kind of preparation method of medical artificial bone material, includes the following steps:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes 20g, acrylic acid
Chloroethene ester 10g is added in organic solvent 145g, then basic catalyst 3.5g is added thereto, is stirred to react 9.5 at 38 DEG C
Hour, back spin is evaporated off solvent, adds methylene chloride and water extracting and demixing, take organic phase, removed water with anhydrous magnesium sulfate, mistake
Filter, revolving remove methylene chloride, obtain titaniferous polymerization type monomer；The organic solvent is tetrahydrofuran, acetonitrile, chloroform by quality
The mixture mixed than 2:1:1；The basic catalyst is sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide by quality
The mixture mixed than 1:2:1:1；
II polydactyl acid nanofiber: polylactic acid nano fiber 45g is added in ethyl alcohol 145g, then is added thereto
3- phenylacrylyl chloride 10g, fire retardant 1.8g and catalyst 4.5g react 7.5 hours at 106 DEG C, and ethyl alcohol is evaporated off in back spin,
It uses acetone washing product 5 times again, acetone is evaporated off in back spin, obtains polydactyl acid nanofiber；The fire retardant is tetrachlorobenzene
Quinone, l, the mixture that 4- naphthoquinones 3:5 in mass ratio is mixed；The catalyst is triethylamine, anhydrous pyridine, 4- dimethylamino
The mixture that pyridine 1:2:1 in mass ratio is mixed；
The preparation of III polymer: it is prepared by the titaniferous polymerization type monomer 10g being prepared by step I, by step II
Obtained polydactyl acid nanofiber 20g, methyl methacrylate 40g is added in high boiling solvent 240g, is added and is drawn
Send out agent 0.75g, be stirred to react at 94 DEG C of argon atmosphere 9.5 hours, after be precipitated in ethanol, by the polymer acetone of precipitation
Washed product 5 times, then be placed at 88 DEG C of vacuum oven and dry 19 hours, obtain medical artificial bone material；The higher boiling
Solvent is the mixture that dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone 1:3:2 in mass ratio are mixed；
The initiator is cyclohexanone peroxide, azodiisobutyronitrile, di-isopropyl peroxydicarbonate, two hexamethylene of dicetyl peroxydicarbonate
The mixture that ester 1:1:2:1 in mass ratio is mixed；
IV ion exchange: the medical artificial bone being prepared by step III is immersed at 65 DEG C with material 10g
It is rear to take out 28 hours in the aqueous solution 189g for the calcium acid sodium that mass fraction is 8.5%, it is washed with water 6 times, then be placed in vacuum oven
It is dried 19 hours at 89 DEG C.
A kind of medical artificial bone material is prepared using the preparation method of above-mentioned medical artificial bone material.
Embodiment 5
A kind of preparation method of medical artificial bone material, includes the following steps:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes 20g, acrylic acid
Chloroethene ester 10g is added in tetrahydrofuran 150g, then potassium hydroxide 4g is added thereto, is stirred to react at 40 DEG C 10 hours,
Solvent is evaporated off in back spin, adds methylene chloride and water extracting and demixing, takes organic phase, is removed water with anhydrous magnesium sulfate, filters, revolving
Methylene chloride is removed, titaniferous polymerization type monomer is obtained；
II polydactyl acid nanofiber: polylactic acid nano fiber 50g is added in ethyl alcohol 150g, then is added thereto
3- phenylacrylyl chloride 10g, tetrachloroquinone 2g and 4-dimethylaminopyridine 5g react 8 hours at 110 DEG C, and back spin is evaporated off
Ethyl alcohol, then with acetone washing product 5 times, acetone is evaporated off in back spin, obtains polydactyl acid nanofiber；
The preparation of III polymer: it is prepared by the titaniferous polymerization type monomer 10g being prepared by step I, by step II
Obtained polydactyl acid nanofiber 20g, methyl methacrylate 40g is added in n,N-Dimethylformamide 250g, then
Be added di-cyclohexylperoxy di-carbonate 0.8g, be stirred to react at 95 DEG C of nitrogen atmosphere 10 hours, after be precipitated in ethanol, will
The polymer of precipitation is with acetone washing product 6 times, then is placed at 90 DEG C of vacuum oven and dries 20 hours, obtains medical artificial bone
Use material.
IV ion exchange: the medical artificial bone being prepared by step III is immersed at 69 DEG C with material 10g
It is rear to take out 30 hours in the aqueous solution 200g for the calcium acid sodium that mass fraction is 10%, it is washed with water 6 times, then be placed in vacuum oven
It is dried 20 hours at 90 DEG C.
A kind of medical artificial bone material is prepared using the preparation method of above-mentioned medical artificial bone material.
Comparative example
A kind of medical artificial bone material, according to the preparation method of Chinese invention patent CN102492082B embodiment 1
And formula is prepared.
1-5 of the embodiment of the present invention and the comparative example medical artificial bone being prepared are tested for the property with material, surveyed
Method for testing and test result are shown in Table 1.
Table 1
| Performance detection | Deflection Modulus of Elasticity (GPa) | Pressure-proof elasticity modulus (GPa) | Hemolysis rate (%) |
| Testing standard | ISO/TR4137-1978 | GB/T14694-1993 | ISOTR7405 |
| Embodiment 1 | 18.5 | 16.1 | 0.15 |
| Embodiment 2 | 18.7 | 16.3 | 0.14 |
| Embodiment 3 | 18.8 | 16.4 | 0.12 |
| Embodiment 4 | 18.9 | 16.6 | 0.12 |
| Embodiment 5 | 19.1 | 16.8 | 0.10 |
| Comparative example | 15.8 | 12.5 | 0.41 |
As it can be seen from table 1 medical artificial bone disclosed by the invention material have more excellent mechanical property and
Biocompatibility.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of preparation method of medical artificial bone material, which comprises the steps of:
The preparation of I titaniferous polymerization type monomer: will be bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes, acrylic acid chloroethene ester
It is added in organic solvent, then basic catalyst is added thereto, be stirred to react at 30-40 DEG C 8-10 hours, back spin is evaporated off
Solvent is removed, methylene chloride and water extracting and demixing is added, takes organic phase, removed water with anhydrous magnesium sulfate, is filtered, revolving removes dichloro
Methane obtains titaniferous polymerization type monomer；
II polydactyl acid nanofiber: polylactic acid nano fiber is added in ethyl alcohol, then 3- phenylpropen is added thereto
Acyl chlorides, fire retardant and catalyst react 6-8 hours at 90-110 DEG C, and back spin is evaporated off ethyl alcohol, then with acetone washing product 3-
5 times, acetone is evaporated off in back spin, obtains polydactyl acid nanofiber；
The preparation of III polymer: change by the titaniferous polymerization type monomer being prepared by step I, by what step II was prepared
Property polylactic acid nano fiber, methyl methacrylate are added in high boiling solvent, initiator are added, in nitrogen or indifferent gas
Be stirred to react at 85-95 DEG C of body atmosphere 8-10 hours, after be precipitated in ethanol, by the polymer of precipitation acetone washing product 4-
6 times, then be placed at 80-90 DEG C of vacuum oven and dry 15-20 hours, obtain medical artificial bone material；
IV ion exchange: the quality medical artificial bone being prepared by step III being immersed in material at 50-69 DEG C
Score is 20-30 hours in the aqueous solution of the calcium acid sodium of 5-10%, and rear taking-up is washed with water 4-6 times, then be placed in vacuum oven
It is dried 15-20 hours at 80-90 DEG C.
2. the preparation method of medical artificial bone material according to claim 1, which is characterized in that described in step I
Bis- (1- (2,4 difluorobenzene base) -3- pyrrole radicals) titanocenes, acrylic acid chloroethene ester, organic solvent, basic catalyst mass ratio
For 2:1:(10-15): (0.2-0.4).
3. the preparation method of medical artificial bone material according to claim 1, which is characterized in that the organic solvent
Selected from one or more of tetrahydrofuran, acetonitrile, chloroform；The basic catalyst is selected from sodium carbonate, potassium carbonate, hydroxide
One or more of sodium, potassium hydroxide.
4. the preparation method of medical artificial bone material according to claim 1, which is characterized in that described in step II
Polylactic acid nano fiber, ethyl alcohol, 3- phenylacrylyl chloride, fire retardant, catalyst mass ratio be (3-5): (10-15): 1:
(0.1-0.2):(0.3-0.5)。
5. the preparation method of medical artificial bone material according to claim 1, which is characterized in that the fire retardant choosing
From tetrachloroquinone, l, at least one of 4- naphthoquinones；The catalyst is selected from triethylamine, anhydrous pyridine, 4-dimethylaminopyridine
One or more of.
6. the preparation method of medical artificial bone material according to claim 1, which is characterized in that described in step III
Titaniferous polymerization type monomer, polydactyl acid nanofiber, methyl methacrylate, high boiling solvent, initiator mass ratio be
1:2:4:(20-25):(0.04-0.08)。
7. the preparation method of medical artificial bone material according to claim 1, which is characterized in that the higher boiling is molten
Agent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone；The initiator was selected from
One of peroxyester, azodiisobutyronitrile, di-isopropyl peroxydicarbonate, di-cyclohexylperoxy di-carbonate are several
Kind.
8. the preparation method of medical artificial bone material according to claim 1, which is characterized in that the inert gas
Selected from one of helium, neon, argon gas.
9. the preparation method of medical artificial bone material according to claim 1, which is characterized in that described in step IV
Artificial skelecton material, calcium acid sodium the mass ratio of aqueous solution be 1:(10-20).
10. a kind of doctor that the preparation method using any one of claim 1-9 medical artificial bone material is prepared
With artificial skelecton material.
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