CN104368041A - Preparation method of composite bone repair support with oriented channel structure - Google Patents
Preparation method of composite bone repair support with oriented channel structure Download PDFInfo
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- CN104368041A CN104368041A CN201410552007.4A CN201410552007A CN104368041A CN 104368041 A CN104368041 A CN 104368041A CN 201410552007 A CN201410552007 A CN 201410552007A CN 104368041 A CN104368041 A CN 104368041A
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Abstract
The invention discloses a preparation method of a composite bone repair support with an oriented channel structure. The preparation method comprises the following steps: after a viscous calcium phosphate and polyurethane composite material is prepared into a membrane with the thickness of 0.02-3mm and preferably 1-2mm, arranging wires with diameters matched with a required channel at intervals on the surface of the channel, curling the wires into massive column shaped solids, aging for 1-48 hours under the condition that the temperature is 90-120 DEG C (the maximum allowable range is 75-150 DEG C and preferably 90-120 DEG C), preferably aging for 2-12 hours for solidifying the solids, and removing the wires in an electrolyte solution containing electrolyte components in an electrolysis manner that each oriented arranged wire therein is used as an anode and an inert electrode is used as a cathode, thereby obtaining the composite bone repair support with the oriented channel structure. The preparation method is simple and feasible and can be used for preparing a high-aperture penetrating calcium phosphate and polyurethane composite bone repair support with an oriented channel structure, and the composite bone repair support is favorable for cells and tissues to grow inwards and can promote regeneration and repair of bone tissues.
Description
Technical field
The present invention relates to a kind of preparation method with the Composite Bone recovery support of oriented channels structure.
Background technology
Porous support as material in bone tissue engineer and architecture basics greatly affects the reconstruction of cell behavior and tissue, and suitable pore passage structure is the key that can porous support play optimum skeletonization usefulness in bone tissue engineer.There is less " bottleneck " problem of interface channel between macropore (aperture often by means of only several microns to tens microns between macropore is communicated with) in the bone tissue engineering scaffold of traditional " spongy " isotropism pore structure, make biological cells and tissues be difficult to infiltration to grow into internal stent, ubiquitous problem is that freshman bone tissue is often only formed in the outer rim of support, have impact on effect.The tissue engineering bracket hole connectivity with " lotus-like " oriented channels structure is good, is beneficial to biological cells and tissues and grows into internal stent infiltration.
Existing preparation in recent years has the report of oriented channels structural bone recovery support, as Chinese patent CN102641523A reports the method that a kind of high temperature sintering (1250 ~ 1350 DEG C) removes the cellular hydroxylapatite ceramic support of orientations Template preparation, although the inorganic constituents in osseous tissue is also nano-apatite, but wherein still containing organic principle, what there were significant differences between the single hydroxylapatite ceramic therefore after its microstructure and mechanical property and sintering, Apatite Ceramic hardness after sintering is large, behind implantable bone defective region, mechanical property is not mated with autologous bone, easy generation stress shielding effect, affect osteanagenesis reparation.Chinese patent CN103263692A reports and adopts the method for physics extraction or chemolysis method removing template to prepare nanometer hydroxyapatite-polyamide orientation pore structure support that duct becomes tubular arrangement, although the class natural bone orientation structure stand of comparative study display preparation shows excellent at biological cells and tissues in internal stent infiltration and the reconstruction of promotion osseous tissue, but nanometer hydroxyapatite-polyamide support is not biodegradable, will retain in vivo as " foreign body " for a long time.Polyurethane be a kind of can the medical high polymer composition of degradation in vivo, but be characterized in that viscosity is very large.Cellosilks such as comprising tinsel is embedded in the composite bodies containing polyurethane-base, and/or be difficult to be extracted out by physics or it removes by the mode such as simple chemical attack from the stake body after solidification, the method that therefore Chinese patent CN103263692A reports is difficult to use in containing the composite of polyurethane-base.Therefore, develop that a kind of preparation method is more easy, the regulatable bionical Composite Bone recovery support of degraded that quality and effect have high hole connectivity more reliably, to meet the demand to high-performance tissue engineering bracket.
Summary of the invention
For above-mentioned situation, the invention provides a kind of more simple and easy to do new method preparing the Composite Bone recovery support with oriented channels structure.
The present invention has the basic process of the Composite Bone recovery support preparation method of oriented channels structure, that thick calcium phosphate-compound polyurethane material is made thickness 0.02 ~ 3mm, preferred thickness is after the film of 1 ~ 2mm, the tinsel with the diameter that to adapt with required passage footpath to be intervally arranged in its surface and after being curled into the block entity of post, in 90 ~ 120 DEG C of (the permitted maximum ranges 75 ~ 150 DEG C, preferably 90 ~ 120 DEG C) ripening 1 ~ 48 hour under condition, the preferred curing time is 2 ~ 12 hours, makes it solidify.In maturing process, improve the temperature of ripening, the time of ripening can correspondingly reduce; When temperature during maturing process is lower, then need the longer curing time just can make the complete curing molding of material.Such as contrast experiment's display, when curing temperature is 90 DEG C, ripening solidification process can complete for about 24 hours; When curing temperature is 110 DEG C, then within about 2 hours, can ripening be completed and realize solidification.Timbering material after ripening is placed in containing electrolytical acidic electrolysis bath, be anode with the tinsel of wherein each orientations, take inert electrode as the electrolysis mode of negative electrode removing tinsel, namely obtain the described Composite Bone recovery support with oriented channels structure.In obtained bone repairing support structure, can have by removing " lotus-like " oriented channels structure formed after tinsel, conduit wall also has can be mutually through pore structure.
In above-mentioned preparation method, when electrolytically removing tinsel, described inert electrode can adopt the electrode as the common used material such as carbon electrode, platinum electrode, wherein can preferred carbon electrode.
The sweller adapted with the polyurethane compositions in described composite can also be contained in described electrolyte, after making the polyurethane in composite suitably swelling by the effect of sweller in electrolyte, more can be conducive to the inside that electrolyte enters composite, improve electrolytic efficiency.Described sweller generally can select the most frequently used to be easy to get and medically acceptable includes but not limited to as at least one in the common solvent such as acetone, ethanol, propanol, isopropyl alcohol, oxolane and chloroform, and wherein more preferred sweller is low, the nontoxic or hypotoxic acetone of price and/or ethanol.
Electrolyte ingredient in described electrolyte, the hydrochlorate of alkali metal or the alkaline-earth metal commonly used in the electrolytic solution, nitrate, sulfate, phosphate, formates or acetate can be selected, as the conventional sodium chloride be easy to get, potassium chloride, calcium chloride, Chile saltpeter, at least one in potassium nitrate, lime nitrate, magnesium chloride, magnesium sulfate etc.Usually most preferably stable performance, cheap sodium chloride.Electrolytical use is the electric conductivity ensureing and increase electrolyte, and therefore electrolytical use amount reaches capacity as good to make it in electrolyte system.
Increase the H in electrolyte
+concentration is also be conducive to one of conventional measure improving the described tinsel electrolytic efficiency of removal.Therefore, suitably H can be increased equally in the electrolyte that the present invention is above-mentioned
+concentration.Experiment display, preferred H in electrolyte
+concentration can be 0.1 ~ 3 mol/L, better H
+concentration may be selected to be 0.5 ~ 1.5 mol/L.To described electrolyte H
+the adjustment of concentration, can adopt at least one in conventional hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid, formic acid and acetic acid.H in electrolyte
+concentration is unsuitable too high, to avoid causing a large amount of losses of calcium phosphate composition in composite.
Tinsel used during for forming above-mentioned oriented channels structure, the one in the tinsels such as the stainless steel silk of suitable diameter, titanium silk, titanium alloy wire, aluminium wire or Magnesium-aluminum alloy wire can be selected as required, its diameter generally can be selected in 100 ~ 1000 micrometer ranges, the channel design of respective diameters can be obtained after tinsel is removed, the preferred diameter of wherein said tinsel can be 300 ~ 700 microns, makes it be more conducive to osseous tissue and to grow into internal stent.
Experiment display, current intensity during above-mentioned electrolytically removing tinsel, can be preferably 0.01 ~ 0.3mA, better current intensity is 0.05 ~ 0.15mA.The too little efficiency that can affect electrolysis undoubtedly of electric current, but electric current crosses the local temperature mistake that conference makes material internal, also may have adverse effect to the internal structure of material.
For being more conducive to forming the hole that is interconnected between the oriented channels structure in formed bone repairing support, 0.01 ~ 0.5wt% can also be contained in described calcium phosphate-polymer composite material, the preferably foaming agent of 0.05 ~ 0.3wt%.Wherein, described foaming agent is preferably water, and the carbon dioxide utilizing water and the corresponding composition of polyurethane to generate in course of reaction realizes foaming, and has the advantage that non-toxic substance is residual especially.Added the height of temperature in the consumption and/or maturing process comprising the foaming agent of water by adjustment, the regulation and control to pore size in the porosity in support and/or oriented channels hole wall can be realized easily.The irregular through hole that passage hole wall distributes, can connect oriented adjacent passage, is beneficial to tissue fluid between adjacency channel, the exchange of nutrient substance and metabolite and eliminating.Wherein, increase the interpolation consumption of foaming agent, both corresponding increase can obtain the porosity of support, the diameter of irregular through hole on oriented channels hole wall also can be made larger.Such as, show using water as the test of foaming agent, when the addition of water is 0.2wt%, the porosity of the support obtained can >=85%.Curing temperature also can be used as the key factor affecting brace aperture rate and irregular hole pore size, improve curing temperature, in material system, bubble is more easily grown up, and the porosity in the support obtained is corresponding also higher, and can increase irregular through aperture on conduit wall.
As the calcium phosphate of one of main in above-mentioned calcium phosphate-compound polyurethane material bone repairing support and basis, the at least one in hydroxyapatite that is currently reported and/or that use, tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate and OCP can be comprised, the main inorganic composition of to be wherein the calcium phosphate inanimate matter of representative with hydroxyapatite be skeleton, when particularly making the mass ratio of described synthos in described composite be 10 ~ 65wt% scope, good biocompatibility and biological activity can be provided for composite.
Another polyurethane (Polyurethane that is main and basis in described bone repairing support, PU), can have good biocompatibility, blood compatibility and performance can the advantage such as flexible modulation, obtain extensive concern in field of tissue engineering technology, the multiple polyurethane compositions of acceptable in current medical domain can be comprised, the block polymer wherein preferably formed by polyether polyol or PEPA and isocyanates polymerization.
Such as, the composite bone repairing material of the present invention's above-mentioned hydroxyapatite-polyurethane (nHA/PU) form, " interfacial structure of alcoholization modified castor oil based polyurethanes/n-HA compound support frame material and mechanical property " (Journal of Inorganic Materials such as comprising Li Limei can be adopted, 2013,28 (8): 811-817) the nHA-PU composite of existing bibliographical information such as.
The method that above-mentioned preparation of the present invention has the high hole connectivity calcium phosphate-polyurethane Composite Bone recovery support of oriented channels structure is simple, particularly can adapt to the tough feature of polyurethane based-polymer, cellosilks such as comprising tinsel can be overcome and be difficult to orientation and insert problem in calcium phosphate-compound polyurethane material, also the cellosilks such as tinsel that comprise be buried in intermediary material after hardening can be avoided to be difficult to the problem that physics mode is extracted out or simple chemical attack mode is removed, make to be easy in the timbering material structure of preparation to be formed can mutually through needed for " lotus-like " oriented channels, and can easily to the porosity in timbering material, and the diameter of described oriented channels and/or the pore size of mutual through hole are regulated and controled, and material has suitable degradability, make the biology performance of material high, the high hole connectivity of degradation property and support high porosity and oriented channels structure obtains perfect adaptation, the clinical requirement to high-performance tissue engineering bracket can be met, have a extensive future.
Below in conjunction with the detailed description of the invention of accompanying drawing illustrated embodiment, foregoing of the present invention is described in further detail again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following example.Without departing from the idea case in the present invention described above, the various replacement made according to ordinary skill knowledge and customary means or change, all should comprise within the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the present invention prepares the calcium phosphate/polyurethane Composite Bone recovery support process with oriented channels structure.
Fig. 2 is scanning electron microscope (SEM) photo of the high hole connectivity calcium phosphate/polyurethane Composite Bone recovery support cross section of the oriented channels structure prepared by the inventive method.
Fig. 3 is the SEM photo in the vertical section of the support oriented channels structure of Fig. 2.
Fig. 4 be MG63 cell and oriented channels structure high hole connectivity calcium phosphate/polyurethane Composite Bone recovery support 4 days afterwards a large amount of cell to grow into the SEM photo in material vertical section of internal stent.
Fig. 5 be MG63 cell and oriented channels structure high hole connectivity calcium phosphate/polyurethane Composite Bone recovery support 4 days afterwards a large amount of cell to grow into the fluorescence staining photo in material vertical section of internal stent.
Detailed description of the invention
embodiment 1
By " interfacial structure of alcoholization modified castor oil based polyurethanes/n-HA compound support frame material and mechanical property " (Journal of Inorganic Materials such as Li Limei, 2013, 28 (8): 811-817) method reported prepares hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 40wt%), then chain extender 1 is added, after 4-butanediol continues reaction, be incorporated as the water of hydroxyapatite-polyurethane quality 0.2wt% as foaming agent, thick hydroxyapatite-compound polyurethane material is suppressed into about the thick film 1 of 1mm after discharging, spread in the Magnesium-aluminum alloy wire 2 of diameter arranged in a uniform about 600 microns, cylinder is curled into from side, then mould is put into, ripening 2 hours under 110 DEG C of conditions.After solidification, be placed in electrolyte, with tinsel to be removed for anode, taking carbon-point as negative electrode, is under the condition of 0.1mA in current intensity, after removing tinsel by electrolysis, cleaning, obtains the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure 3.Electrolyte is for regulate final H with aqueous hydrochloric acid solution
+concentration is the 85%(v/v of 1.2 mol/L) sodium chloride saturated solution of acetone.
Preparation process schematic diagram as in Fig. 1 by shown in a to e, in obtained Composite Bone recovery support product, have " lotus-like " oriented channels structure that the tinsel that removed by electrolysis is formed.
What Fig. 2 and Fig. 3 showed respectively is the obtained cross section of support product and the SEM photo in vertical section, " lotus-like " oriented channels structure that the circular macroscopic void on cross section is formed after removing with the parallel groove display tinsel electrolysis on vertical section.
Shown in Fig. 4 and Fig. 5 is that cell was cultivated after 4 days on this stake body, and a large amount of cell to be grown into stake body inside along oriented channels.Becoming the cell of fusiformis to be linked to be lamella in Fig. 4 is as seen covered with in orientation support aperture; White bright spot in Fig. 5 is the cell of growing in oriented channels.
embodiment 2
Hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 40wt%) is prepared by the mode executing document described in example 1, then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.2wt% water as foaming agent, hydroxyapatite-compound polyurethane material is suppressed into about the thick film of 1mm after discharging, spread on the stainless steel silk of diameter arranged in a uniform about 300 microns, cylinder is curled into from side, then mould is put into, ripening 12 hours under 100 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.1mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous hydrochloric acid solution makes final H
+concentration is about 1.2 mol/L, adds sodium chloride to saturated.
embodiment 3
Hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 40wt%) is prepared by the method executing document described in example 1, then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.2wt% water as foaming agent, hydroxyapatite-compound polyurethane material is suppressed into about the thick film of 2mm after discharging, spread on the titanium silk of diameter arranged in a uniform about 500 microns, cylinder is curled into from side, then mould is put into, ripening 48 hours under 90 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.01mA; (3) electrolyte is containing 85%(v/v) chloroform, aqueous formic acid makes final H
+concentration is about 1.2 mol/L, adds potassium sulfate to saturated.
embodiment 4
Hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 20wt%) is prepared by the method executing document described in example 1, then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.15wt% water as foaming agent, hydroxyapatite-compound polyurethane material is suppressed into about the thick film of 1mm after discharging, spread in the Magnesium-aluminum alloy wire of diameter arranged in a uniform about 600 microns, cylinder is curled into from side, then mould is put into, ripening 2 hours under 110 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.15mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous sulfuric acid makes final H
+concentration is about 1 mol/L, adds sodium sulfate to saturated.
embodiment 5
Hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 20wt%) is prepared by the method executing document described in example 1, then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.15wt% water as foaming agent, hydroxyapatite-compound polyurethane material is suppressed into about the thick film of 1mm after discharging, spread in the Magnesium-aluminum alloy wire of diameter arranged in a uniform about 600 microns, cylinder is curled into from side, then mould is put into, ripening 2 hours under 140 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and platinum electrode is negative electrode; (2) electric current is 0.05mA; (3) electrolyte is containing 85%(v/v) propanol, aqueous sulfuric acid makes final H
+concentration is about 1 mol/L, adds sodium acetate to saturated.
embodiment 6
Hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 60wt%) is prepared by the method executing document described in example 1, then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.3wt% water as foaming agent, hydroxyapatite-compound polyurethane material is suppressed into about the thick film of 1mm after discharging, spread in the Magnesium-aluminum alloy wire of diameter arranged in a uniform about 600 microns, cylinder is curled into from side, then mould is put into, ripening 48 hours under 80 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.25mA; (3) electrolyte is containing 85%(v/v) oxolane, phosphate aqueous solution makes final H
+concentration is about 2 mol/L, adds sodium phosphate to saturated.
embodiment 7
By the method executing document described in example 1, hydroxyapatite is wherein used instead tricalcium phosphate powder and prepares tricalcium phosphate-compound polyurethane material prepolymer (content of tricalcium phosphate is about 40wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for tricalcium phosphate-polyurethane quality 0.2wt% water as foaming agent, after discharging by the compacting of tricalcium phosphate-compound polyurethane material into about the thick film of 2mm, spread on the titanium silk of diameter arranged in a uniform about 1000 microns, cylinder is curled into from side, then mould is put into, ripening 24 hours under 90 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity tricalcium phosphate-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and platinum electrode is negative electrode; (2) electric current is 0.3mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous hydrochloric acid solution makes final H
+concentration is about 1.2 mol/L, adds calcium chloride to saturated.
embodiment 8
By the method executing document described in example 1, hydroxyapatite is wherein used instead tricalcium phosphate powder and prepares tricalcium phosphate-compound polyurethane material prepolymer (content of tricalcium phosphate is about 20wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for tricalcium phosphate-polyurethane quality 0.1wt% water as foaming agent, tricalcium phosphate-compound polyurethane material is suppressed into about the thick film of 2mm after discharging, spread on the aluminium wire of diameter arranged in a uniform about 600 microns, cylinder is curled into from side, then mould is put into, ripening 6 hours under 110 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity tricalcium phosphate-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.2mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous hydrochloric acid solution makes final H
+concentration is about 1.2 mol/L, adds magnesium chloride to saturated.
embodiment 9
By the method executing document described in example 1, hydroxyapatite is wherein used instead tricalcium phosphate powder and prepares tricalcium phosphate-compound polyurethane material prepolymer (content of tricalcium phosphate is about 50wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for tricalcium phosphate-polyurethane quality 0.1wt% water as foaming agent, tricalcium phosphate-compound polyurethane material is suppressed into about the thick film of 1.5mm after discharging, spread on the titanium alloy wire of diameter arranged in a uniform about 500 microns, cylinder is curled into from side, then mould is put into, ripening 6 hours under 130 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity tricalcium phosphate-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.1mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous solution of nitric acid makes final H
+concentration is about 1.5 mol/L, adds potassium chloride to saturated.
embodiment 10
By the method executing document described in example 1, hydroxyapatite is wherein used instead Dicalcium Phosphate and prepares calcium hydrogen phosphate-compound polyurethane material prepolymer (content of calcium hydrogen phosphate is about 40wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for calcium hydrogen phosphate-polyurethane quality 0.1wt% water as foaming agent, calcium hydrogen phosphate-compound polyurethane material is suppressed into about the thick film of 1.5mm after discharging, spread on the titanium alloy wire of diameter arranged in a uniform about 500 microns, cylinder is curled into from side, then mould is put into, ripening 6 hours under 110 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity calcium hydrogen phosphate-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.1mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous solution of nitric acid makes final H
+concentration is about 1.5 mol/L, adds lime nitrate to saturated.
embodiment 11
By the method executing document described in example 1, hydroxyapatite is wherein used instead Dicalcium Phosphate and prepares calcium hydrogen phosphate-compound polyurethane material prepolymer (content of calcium hydrogen phosphate is about 30wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for calcium hydrogen phosphate-polyurethane quality 0.1wt% water as foaming agent, calcium hydrogen phosphate-compound polyurethane material is suppressed into about the thick film of 1.5mm after discharging, spread on the titanium alloy wire of diameter arranged in a uniform about 500 microns, cylinder is curled into from side, then mould is put into, ripening 8 hours under 100 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity calcium hydrogen phosphate-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0. 05mA; (3) electrolyte is containing 85%(v/v) propanol, acetic acid aqueous solution makes final H
+concentration is about 0.5 mol/L, adds sodium acetate to saturated.
embodiment 12
By the method executing document described in example 1, hydroxyapatite is wherein used instead Dicalcium Phosphate and prepares calcium hydrogen phosphate-compound polyurethane material prepolymer (content of calcium hydrogen phosphate is about 30wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for calcium hydrogen phosphate-polyurethane quality 0.2wt% water as foaming agent, calcium hydrogen phosphate after discharging-compound polyurethane material is suppressed into about the thick film of 1.5mm, spread in the Magnesium-aluminum alloy wire of diameter arranged in a uniform about 600 microns, cylinder is curled into from side, then mould is put into, ripening 10 hours under 100 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity calcium hydrogen phosphate-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.2mA; (3) electrolyte is containing 85%(v/v) propanol, aqueous hydrochloric acid solution makes final H
+concentration is about 0.5 mol/L, adds magnesium sulfate to saturated.
embodiment 13
By (the composite journal such as Liu Haohuai " mechanical property of nano HA/PU composite and hot property ", 2010, 27 (3): 61-66) method reported prepares hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 40wt%), then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.2wt% water as foaming agent, hydroxyapatite-compound polyurethane material is suppressed into about the thick film of 1mm after discharging, spread on the stainless steel silk of diameter arranged in a uniform about 300 microns, cylinder is curled into from side, then mould is put into, ripening 12 hours under 100 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.1mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous hydrochloric acid solution makes final H
+concentration is about 1.2 mol/L, adds sodium chloride to saturated.
embodiment 14
Hydroxyapatite-compound polyurethane material prepolymer (content of hydroxyapatite is about 50wt%) is prepared by the literature method described in embodiment 13, then chain extender 1 is added, after 4-butanediol continues reaction, add account for hydroxyapatite-polyurethane quality 0.15wt% water as foaming agent, hydroxyapatite-polyurethane quality composite is suppressed into about the thick film of 1.5mm after discharging, spread on the stainless steel silk of diameter arranged in a uniform about 300 microns, cylinder is curled into from side, then mould is put into, ripening 4 hours under 120 DEG C of conditions, tinsel is removed by electrolysis after solidification, cleaning, obtain the high hole connectivity hydroxyapatite-polyurethane Composite Bone recovery support of oriented channels structure.Electrolytic condition is: (1) tinsel to be removed is anode, and carbon-point is negative electrode; (2) electric current is 0.1mA; (3) electrolyte is containing 85%(v/v) acetone, aqueous solution of nitric acid makes final H
+concentration is about 1.2 mol/L, adds potassium nitrate to saturated.
Claims (10)
1. there is the preparation method of the Composite Bone recovery support of oriented channels structure, thick calcium phosphate-compound polyurethane material is it is characterized in that to make thickness 0.02 ~ 3mm, preferred thickness is after the film of 1 ~ 2mm, the tinsel with the diameter that to adapt with required passage footpath to be intervally arranged in its surface and after being curled into the block entity of post, in 90 ~ 120 DEG C of (the permitted maximum ranges 75 ~ 150 DEG C, preferably 90 ~ 120 DEG C) ripening 1 ~ 48 hour under condition, preferred ripening 2 ~ 12 hours, make it solidify, then in containing the electrolyte of electrolyte ingredient with the tinsel of wherein each orientations for anode, take inert electrode as the electrolysis mode removing tinsel of negative electrode, obtain the described Composite Bone recovery support with oriented channels structure.
2. preparation method as claimed in claim 1, the inert electrode described in when it is characterized in that electrolytically removing tinsel is carbon electrode.
3. preparation method as claimed in claim 1, it is characterized in that in described electrolyte, also containing the sweller adapted with the polyurethane compositions in described composite, comprise at least one in acetone, ethanol, propanol, isopropyl alcohol, oxolane and chloroform, preferred sweller is acetone, ethanol.
4. preparation method as claimed in claim 1, it is characterized in that the electrolyte ingredient described in electrolyte is at least one in the hydrochlorate of alkali metal or alkaline-earth metal, nitrate, sulfate, phosphate, formates or acetate, preferred electrolyte ingredient is sodium chloride, potassium chloride, calcium chloride, Chile saltpeter, magnesium chloride, potassium nitrate, lime nitrate, magnesium sulfate.
5. preparation method as claimed in claim 1, is characterized in that electrolyte is described electrolytical saturated solution.
6. preparation method as claimed in claim 1, is characterized in that described electrolyte is for containing H
+concentration is the acid solution of 0.1 ~ 3 mol/L, preferred H
+concentration is 0.5 ~ 1.5 mol/L.
7. preparation method as claimed in claim 1, is characterized in that, containing 0.01 ~ 0.5wt% in described calcium phosphate-compound polyurethane material, be preferably the foaming agent of 0.05 ~ 0.3wt%, preferred foaming agent is water.
8. the preparation method as described in one of claim 1 to 7, is characterized in that described tinsel to be diameter is 100 ~ 1000 microns, the one be preferably in the stainless steel silk of 300 ~ 700 microns, titanium silk, titanium alloy wire, aluminium wire or Magnesium-aluminum alloy wire; Current intensity during electrolysis removing tinsel is preferably 0.01 ~ 0.3mA, and better current intensity is 0.05 ~ 0.15mA.
9. the preparation method as described in one of claim 1 to 7, the calcium phosphate that it is characterized in that in described calcium phosphate-compound polyurethane material is at least one in hydroxyapatite, tricalcium phosphate, calcium hydrogen phosphate, calcium pyrophosphate and OCP, and the mass ratio of described synthos is preferably 10 ~ 65wt%.
10. preparation method as claimed in claim 9, the polyurethane compositions that it is characterized in that in described calcium phosphate-polymer composite material is the block polymer formed by polyether polyol or PEPA and isocyanates polymerization.
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| CN108478879A (en) * | 2018-03-30 | 2018-09-04 | 华南理工大学 | A kind of porous calcium phosphate/natural polymer compound rest and the preparation method and application thereof |
| CN112107722A (en) * | 2020-09-04 | 2020-12-22 | 杭州俊为科技有限责任公司 | Film and preparation technology thereof |
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