CN103691000B - The preparation method of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support - Google Patents
The preparation method of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include: A, by the mixing of the catechol based polyalcohol of the calcium phosphate of 100 parts heavy, the pore creating material of 1 ~ 40 part heavy and 0.1 ~ 45 part of weight, then add tris-HCI buffer and obtain paste mixture; Wherein, calcium phosphate is micron calcium phosphate and/or nano-calcium phosphate; Catechol based polyalcohol is poly-dopamine or dopamine graft copolymer; The mode molding that B, the paste mixture walked by A print with mold pressing, cast or 3D, molding is placed in 35-40 DEG C of water-bath solidifies 20-30h, to obtain final product.The bone renovating material support that the method obtains has good biological activity, bone conductibility, degradation capability and biocompatibility, and meanwhile, its mechanical property is good.Both by mold pressing, cast also by the molding of 3D Method of printing, the bone renovating material support of any shape and structure can be made.
Description
Technical field
The present invention relates to bio-medical material, particularly relate to a kind of preparation method of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support
Background technology
Bone impairment renovation material is one of biomaterial had the call clinically (Al-Aql Z S; et al.Molecular mechanisms controlling bone formation during fracture healing anddistraction osteogenesis.J Dent Res, 2008; 87 (2): 107-118), bone holder material is then the Bone Defect Repari and alternate material that are comparatively suitable for.Desirable bone holder material needs to possess following performance: (1) is biocompatibility, biological activity and bone conductibility preferably; (2) degradability; (3) similar with bone photo mechanical property, i.e. mechanical compatibility; (4) suitable porosity; (5) easily (Wagoner JohnsonA J such as moulding grade is processed; et al.A review of the mechanical behavior of CaP and CaP/polymer compositesfor applications in bone replacement and repair.Acta Biomater, 2011; 7 (1): 16-30).
Similar and the catabolite of inorganic constituents in calcium orthophosphate base biomaterial (calcium orthophosphate base bioceramic and calcium phosphate bone cement) and natural bone is the Ca of needed by human body
2+with
ion; therefore there is good biocompatibility and biological activity; be widely used in the field such as orthopaedics and dentistry (Bose s; et al.Calciumphosphate ceramic system in growth factor and drug delivery for bone tissueengineering:A review.Acta Biomater, 2012; 8 (4): 1401-1421).Calcium orthophosphate base bioceramic and calcium phosphate bone cement are usually assembled by micron order or nano level calcium phosphate and are made, because the binding ability between micron order or nano level calcium phosphate granules is more weak, the biomaterial scaffolds prepared often shows the deficiency that fragility is large and intensity is low.And desirable bone holder material should have suitable porosity is beneficial to growing into of cell and osseous tissue, higher porosity reduce further again the mechanical property of timbering material.
The method of existing raising calcium phosphate cement bracket mechanical property mainly adds tension, the fiber of bending resistance or the CNT of high strength in the powder of calcium phosphate granules, and then compression molding; Thus improve toughness or the intensity of support.But owing to being mix in the solid state, fiber and CNT are difficult to be evenly distributed, the mechanical property of material is caused to improve limited.And because fiber or CNT itself do not have viscosity, support can only be formed by mold pressing or pouring type, and the molding of 3D printing type cannot be adopted, the support of band inner chamber or meticulous special shape, structure cannot be made.
Summary of the invention
The object of this invention is to provide a kind of preparation method of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the bone renovating material support that the method obtains has good biological activity, bone conductibility, degradation capability and biocompatibility, meanwhile, its mechanical property is good.Both by mold pressing, cast also by the molding of 3D Method of printing, the bone renovating material support of any shape and structure can be made.
It is that the preparation method of Yi Zhongwei, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include: that the present invention realizes the technical scheme that its goal of the invention adopts
A, by the mixing of the catechol based polyalcohol of the calcium phosphate of 100 parts heavy, the pore creating material of 1 ~ 40 part heavy and 0.1 ~ 45 part of weight, then add tris-HCI buffer and obtain paste mixture; Wherein, calcium phosphate is micron calcium phosphate and/or nano-calcium phosphate; Catechol based polyalcohol is poly-dopamine or dopamine graft copolymer;
The mode molding that B, the paste mixture immediately walked by A print with mold pressing, cast or 3D, molding is placed in 35-40 DEG C of water-bath solidifies 20-30h, to obtain final product.
Compared with prior art, the invention has the beneficial effects as follows:
One, the mechanical property of catechol based polyalcohol (poly-dopamine or dopamine graft copolymer) itself is good, mixes, is evenly distributed, play good supporting role, be conducive to the mechanical property improving compound rest under liquid environment with calcium phosphate.Contain a large amount of catechol functional groups in catechol based polyalcohol simultaneously, can be formed with calcium phosphate material and covalently or non-covalently be combined, thus to calcium phosphate material, there is superpower adhesion property, under its adhesive attraction, calcium phosphate material is strong bonded in forming process, improves the mechanical property of support.And catechol functional group can lose H in the basic conditions
+and negatively charged, form benzene negative oxygen ion, to the Ca in calcium phosphate
2+also there is stronger affinity, be conducive to calcium ion enrichment, thus form compact hydroxyapatite, also further increase the mechanical property of support.Thus ensure that compound rest of the present invention still has good mechanical property when high hole.The adhesion property of catechol based polyalcohol still can keep in wet environment, thus under the wet environment implanted, timbering material can not occur defeated and dispersed, avoids the harmful effect of free calcium phosphate granules to surrounding tissue.
Experiment shows, the comprcssive strength of composite bone repairing support of the present invention is 2 times of calcium phosphate bone recovery support.
Two, catechol based polyalcohol (poly-dopamine or dopamine graft copolymer) has good biocompatibility, can improve cell in the adhesion of material surface, stretching, extension and propagation.On the other hand, after implanting, dispersed poly-dopamine is in the bracket to Ca
2+stronger absorption affinity, the Ca in Absorbable rod body fluid
2+, impel the quick mineralising of calcium phosphate rack surface, improve the biocompatibility of support, protein adsorption ability and cellular affinity further, to reach the object of the biological activity combination of support and implant site.Therefore compound rest of the present invention compared with the biocompatibility of calcium phosphate cement bracket and biological activity better.
Experiment shows, composite bone repairing support of the present invention soaks and can form obvious mineralized layer on its surface in 1 day in simulated body fluid, shows that its biological activity is good.
Three, because poly-dopamine or dopamine graft copolymer have Ultrastrength adhesive power, the slurry energy molding rapidly that itself and calcium phosphate, pore creating material are mixed to form, thus both by mold pressing, cast, more by the molding of 3D Method of printing, the bone renovating material support of any shape and structure can be made, the bone defect healing of various shape and the needs for the treatment of can be met.
Be placed in 35-40 DEG C of water-bath in above-mentioned B step when solidifying, also carry out irradiation under ultraviolet ray simultaneously.
Like this, the poly-dopamine that when can impel molding, material internal is uncrosslinked or dopamine graft copolymer continue crosslinked, to improve crosslinking degree, the adhesion of each phase in timbering material are improved further.
The mean diameter of above-mentioned micron calcium phosphate is 1 ~ 500 μm, be specially in dicalcium phosphate dehydrate, calcium hydrogen phosphate, tetracalcium phosphate, α tricalcium phosphate, β tricalcium phosphate, hydroxyapatite a kind of or a kind of with mixture;
The mean diameter of above-mentioned nano-calcium phosphate is 10 ~ 990nm, be specially in hydroxyapatite, unformed calcium phosphate, OCP a kind of or a kind of with mixture;
The micron calcium phosphate of these kinds or nano-calcium phosphate are ripe calcium phosphate bone cement raw material, all have good biocompatibility and biological activity.
Above-mentioned pore creating material is hydrogen peroxide, degradable macromolecule, mannitol, sodium chloride or glucose powder.
Hydrogen peroxide decomposes in molding and solidification process, thus prepares in the process of compound rest and form a lot of hole; And mannitol, sodium chloride or glucose powder are after implanting, can be dissolved very soon by body fluid, and form concrete dynamic modulus support; Degradable macromolecule is then degraded gradually after implanting, and forms concrete dynamic modulus support.They can form concrete dynamic modulus support by different way, meet different instructions for uses.
Above-mentioned poly-dopamine is obtained by following methods:
In the alkaline solution of pH7.4-10, add dopamine, when passing into oxygen or ultraviolet light irradiation, stirring 24h, or stir 24h after adding sodium metaperiodate or hydrogen peroxide; Then by solution centrifugal, lyophilization and get final product.
Poly-dopamine crosslinking degree prepared by this method is high, and self-force is learnt well, and adhesion property is good, and the mechanical property of compound rest is improved further.
Above-mentioned dopamine graft copolymer is obtained by following methods: be dissolved in by dopamine in sodium bicarbonate solution, add Polyethylene Glycol, polystyrene, polyurethane, polyacrylate or polyamide again, then reducing agent sodium tetraborate or sodium borohydride is added, pass into argon 10-20h again, filter, precipitation is cleaned, to obtain final product.
Dopamine graft copolymer crosslinking degree prepared by this method is high, and self-force is learnt well, and adhesion property is good, and the mechanical property of compound rest is improved further.
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is 5000 times of surface topography maps after simple calcium phosphate cement bracket soaks 24h in simulated body fluid.
Fig. 2 is 20000 times of surface topography maps after simple calcium phosphate cement bracket soaks 24h in simulated body fluid.
Fig. 3 is 5000 times of surface topography maps after the composite bone repairing support of embodiment 1 soaks 24h in simulated body fluid.
Fig. 4 is 20000 times of surface topography maps after the composite bone repairing support of embodiment 1 soaks 24h in simulated body fluid.
Detailed description of the invention
Embodiment 1
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
The hydroxyapatite that A, the dicalcium phosphate dehydrate that be α tricalcium phosphate, the mean diameter of 500 μm 85 parts heavy by mean diameter is 500 μm 10 parts heavy, mean diameter are 5 parts of weights of 500 μm, the poly-dopamine mixing of the pore creating material-mannitol of 20 parts of weights and 20 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 37 DEG C of water-baths solidifies 24h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the potassium hydroxide solution of pH8.5, adding dopamine, when passing into oxygen, stirring 24h, then by solution centrifugal, lyophilization and get final product.
Test shows that the comprcssive strength of the composite bone repairing support that this example is obtained is 24.5MPa; And with the same method of this example, but the comprcssive strength not adding the calcium phosphate support that poly-dopamine obtains in A step is only 12.5MPa, and the comprcssive strength of composite bone repairing support is about 2 times of calcium phosphate support.
Fig. 1,2 is respectively the same method by this example, but in A step, do not add poly-dopamine and the calcium phosphate cement bracket that obtains in simulated body fluid, soak 24h after 5000 times, 20000 times surface topography maps.Fig. 3,4 composite bone repairing supports being respectively this example soak 5000 times, 20000 times surface topography maps after 24h in simulated body fluid.Fig. 1-4 shows, the calcium phosphate cement bracket not adding poly-dopamine does not occur obvious mineralized layer after immersion 24h, and obvious mineralized layer has then appearred in the bone repairing support of this example, illustrates that the biological activity of the bone repairing support of this example is better.
Embodiment 2
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the α type tricalcium phosphate of 100 parts heavy of 1 μm, the poly-dopamine mixing of the pore creating material-hydrogen peroxide of 40 parts of weights and 0.1 part of weight by mean diameter, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with cast mode molding, molding is placed in 35 DEG C of water-baths solidifies 20h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the sodium hydroxide solution of pH10, add dopamine, when ultraviolet irradiation, stir 24h, then by solution centrifugal, lyophilization and get final product.
Embodiment 3
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the β tricalcium phosphate of 100 parts heavy of 500 μm, the poly-dopamine mixing of the pore creating material-degradable macromolecule of 1 part of weight and 45 parts of weights by mean diameter, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 40 DEG C of water-baths solidifies 30h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the sodium hydroxide solution of pH7.4, add dopamine, add sodium metaperiodate, stir 24h, then by solution centrifugal, lyophilization and get final product.
Embodiment 4
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the dicalcium phosphate dehydrate of 100 parts heavy of 250 μm, the poly-dopamine mixing of the pore creating material-sodium chloride of 20 parts of weights and 22 parts of weights by mean diameter, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, the mode molding printed with 3D by the paste mixture that A walks, molding is placed in 38 DEG C of water-baths solidifies 25h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the sodium hydroxide solution of pH7.4, add dopamine, add hydrogen peroxide, stir 24h, then by solution centrifugal, lyophilization and get final product.
Embodiment 5
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the calcium hydrogen phosphate of 100 parts heavy of 500 μm, the dopamine graft copolymer mixing of the pore creating material-glucose of 1 part of weight and 0.1 part of weight by mean diameter, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 37 DEG C of water-baths solidifies 24h, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds Polyethylene Glycol, then add reducing agent sodium tetraborate, then pass into argon 10h, filter, precipitation is cleaned, to obtain final product.
Embodiment 6
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the tetracalcium phosphate of 100 parts heavy of 1 μm, the dopamine graft copolymer mixing of the pore creating material-glucose of 40 parts of weights and 0.1 part of weight by mean diameter, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with cast mode molding, molding is placed in 37 DEG C of water-baths carries out ultraviolet radiation-curable 24h simultaneously, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds polystyrene, then add borane reducing agent sodium hydride, then pass into argon 20h, filter, precipitation is cleaned, to obtain final product.
Embodiment 7
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the hydroxyapatite of 100 parts heavy of 250 μm, the dopamine graft copolymer mixing of the pore creating material-glucose of 1 part of weight and 45 parts of weights by mean diameter, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, the mode molding printed with 3D by the paste mixture that A walks, molding is placed in 37 DEG C of water-baths carries out ultraviolet radiation-curable 24h simultaneously, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds polyurethane, then add reducing agent sodium tetraborate, then pass into argon 15h, filter, precipitation is cleaned, to obtain final product.
Embodiment 8
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
The tetracalcium phosphate of A, to be hydroxyapatite, the mean diameter of 1 μm 50 parts heavy by mean diameter be 50 parts of weights of 500 μm, the dopamine graft copolymer mixing of the pore creating material-glucose of 40 parts of weights and 0.1 part of weight, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 37 DEG C of water-baths solidifies 24h, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds polyacrylate, then add reducing agent sodium tetraborate, then pass into argon 20h, filter, precipitation is cleaned, to obtain final product.
Embodiment 9
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
The dicalcium phosphate dehydrate of A, to be hydroxyapatite, the mean diameter of 250 μm 50 parts heavy by mean diameter be 50 parts of weights of 250 μm, the dopamine graft copolymer mixing of the pore creating material-glucose of 25 parts of weights and 25 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of 3D, molding is placed in 35 DEG C of water-baths solidifies 30h, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds polyamide, then add reducing agent sodium tetraborate, then pass into argon 15h, filter, precipitation is cleaned, to obtain final product.
Embodiment 10
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the hydroxyapatite of 100 parts of weights of 990nm by mean diameter, the dopamine graft copolymer mixing of the pore creating material-glucose of 1 part of weight and 45 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 37 DEG C of water-baths solidifies 24h, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds polyacrylate, then add borane reducing agent sodium hydride, then pass into argon 20h, filter, precipitation is cleaned, to obtain final product.
Embodiment 11
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the unformed calcium phosphate of 100 parts of weights of 10nm by mean diameter, the dopamine graft copolymer mixing of the pore creating material-sodium chloride of 40 parts of weights and 0.1 part of weight, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with cast mode molding, molding is placed in 35 DEG C of water-baths solidifies 25h, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds Polyethylene Glycol, then add borane reducing agent sodium hydride, then pass into argon 20h, filter, precipitation is cleaned, to obtain final product.
Embodiment 12
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the OCP of 100 parts of weights of 450nm by mean diameter, the poly-dopamine mixing of the pore creating material-hydrogen peroxide of 25 parts of weights and 25 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, the mode molding printed with 3D by the paste mixture that A walks, molding is placed in 35 DEG C of water-baths solidifies 25h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the sodium hydroxide solution of pH10, add dopamine, add sodium metaperiodate, stir 20h, then by solution centrifugal, lyophilization and get final product.
Embodiment 13
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the OCP of 50 parts of weights of 990nm by mean diameter, mean diameter is the hydroxyapatite of 50 parts of weights of 990nm, the poly-dopamine mixing of the pore creating material-degradable macromolecule of 15 parts of weights and 35 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 35 DEG C of water-baths solidifies 25h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the potassium hydroxide solution of pH8.5, add dopamine, pass into oxygen, stir 20h, then by solution centrifugal, lyophilization and get final product.
Embodiment 14
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the unformed calcium phosphate of 50 parts of weights of 1nm by mean diameter, mean diameter is the hydroxyapatite of 50 parts of weights of 1nm, the poly-dopamine mixing of the pore creating material-mannitol of 20 parts of weights and 20 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 37 DEG C of water-baths carries out ultraviolet radiation-curable 25h simultaneously, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the potassium hydroxide solution of pH8.5, add dopamine, add hydrogen peroxide, stir 20h, then by solution centrifugal, lyophilization and get final product.
Embodiment 15
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the unformed calcium phosphate of 20 parts of weights of 450nm by mean diameter, mean diameter is the hydroxyapatite of 50 parts of weights of 450nm, mean diameter is the unformed calcium phosphate of 30 parts of weights of 450nm, the poly-dopamine mixing of the pore creating material-glucose of 10 parts of weights and 40 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 35 DEG C of water-baths carries out ultraviolet radiation-curable 25h simultaneously, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the potassium hydroxide solution of pH8.5, add dopamine, when ultraviolet light irradiation, stir 20h, then by solution centrifugal, lyophilization and get final product.
Embodiment 16
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the 50 parts heavy β tricalcium phosphates of 500 μm by mean diameter, mean diameter is the hydroxyapatite of 50 parts of weights of 990nm, the poly-dopamine mixing of the pore creating material-hydrogen peroxide of 1 part of weight and 45 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with the mode molding of mold pressing, molding is placed in 35 DEG C of water-baths solidifies 24h, to obtain final product.
The poly-dopamine of this example is obtained by following methods:
In the sodium hydroxide solution of pH7.4, add dopamine, add sodium metaperiodate, stir 15h, then by solution centrifugal, lyophilization and get final product.
Embodiment 17
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the 50 parts heavy α tricalcium phosphates of 1 μm by mean diameter, mean diameter is the 30 parts heavy dicalcium phosphate dehydrate of 1 μm, mean diameter is the unformed calcium phosphate of 20 parts of weights of 10nm, the dopamine graft copolymer mixing of the pore creating material-glucose of 40 parts of weights and 0.1 part of weight, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, the mode molding printed with 3D by the paste mixture that A walks, molding is placed in 35 DEG C of water-baths carries out ultraviolet lighting solidification 24h simultaneously, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds poly-imines fat, then add reducing agent sodium tetraborate, then pass into argon 15h, filter, precipitation is cleaned, to obtain final product.
Embodiment 18
A preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, be the 50 parts heavy α tricalcium phosphates of 250 μm by mean diameter, mean diameter is the unformed calcium phosphate of 20 parts of weights of 450nm, mean diameter is the OCP of 30 parts of weights of 450nm, the dopamine graft copolymer mixing of the pore creating material-degradable macromolecule of 25 parts of weights and 20 parts of weights, then add trihydroxy aminomethane-hydrochloride buffer and obtain paste mixture;
B, by A walk paste mixture with cast mode molding, molding is placed in 37 DEG C of water-baths solidifies 20h, to obtain final product.
The dopamine graft copolymer of this example is obtained by following methods:
Dopamine is dissolved in sodium bicarbonate solution, then adds ethylene glycol, then add reducing agent sodium tetraborate, then pass into argon 15h, filter, precipitation is cleaned, to obtain final product.
Claims (6)
1. a preparation method for micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support, the steps include:
A, by the mixing of the catechol based polyalcohol of the calcium phosphate of 100 parts heavy, the pore creating material of 1 ~ 40 part heavy and 0.1 ~ 45 part of weight, then add tris-HCI buffer and obtain paste mixture; Wherein, calcium phosphate is micron calcium phosphate and/or nano-calcium phosphate; Catechol based polyalcohol is poly-dopamine or dopamine graft copolymer;
The mode molding that B, the paste mixture walked by A print with mold pressing, cast or 3D, molding is placed in 35-40 DEG C of water-bath solidifies 20-30h, to obtain final product.
2. the preparation method of a kind of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support according to claim 1, is characterized in that: be placed in 35-40 DEG C of water-bath in described B step when solidifying, also carry out irradiation under ultraviolet ray simultaneously.
3. the preparation method of a kind of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support according to claim 1, is characterized in that:
The mean diameter of described micron calcium phosphate is 1 ~ 500 μm, is specially one or more the mixture in dicalcium phosphate dehydrate, calcium hydrogen phosphate, tetracalcium phosphate, α tricalcium phosphate, β tricalcium phosphate, hydroxyapatite;
The mean diameter of described nano-calcium phosphate is 10 ~ 990nm, is specially one or more the mixture in hydroxyapatite, unformed calcium phosphate, OCP.
4. the preparation method of a kind of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support according to claim 1, is characterized in that: described pore creating material is hydrogen peroxide, degradable macromolecule, mannitol, sodium chloride or glucose powder.
5. the preparation method of a kind of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support according to claim 1, is characterized in that: described poly-dopamine is obtained by following methods:
In the alkaline solution of pH7.4-10, add dopamine, when passing into oxygen or ultraviolet light irradiation, stirring 24h, or stir 24h after adding sodium metaperiodate or hydrogen peroxide; Then by solution centrifugal, lyophilization and get final product.
6. the preparation method of a kind of micro-, nano-calcium phosphate/catechol based polyalcohol bone repairing support according to claim 1, is characterized in that:
Described dopamine graft copolymer is obtained by following methods: be dissolved in by dopamine in sodium bicarbonate solution, add Polyethylene Glycol, polystyrene, polyurethane, polyacrylate or polyamide again, then reducing agent sodium tetraborate or sodium borohydride is added, pass into argon 10-20h again, filter, precipitation is cleaned, to obtain final product.
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| CN103877611A (en) * | 2014-04-08 | 2014-06-25 | 中山职业技术学院 | 3D printing preparation method of calcium phosphate-based medical bone tissue scaffold |
| CN105816918A (en) * | 2015-01-08 | 2016-08-03 | 北京化工大学 | Aliphatic polyester-nano hydroxyapatite composite material and preparation method thereof |
| EP3359594A4 (en) * | 2015-10-09 | 2019-07-03 | Hewlett-Packard Development Company, L.P. | Particulate mixtures |
| CN107050508B (en) * | 2017-01-19 | 2020-12-18 | 深圳清华大学研究院 | Injectable bone repair material and preparation method thereof |
| CN107320155A (en) * | 2017-06-30 | 2017-11-07 | 深圳市倍康美医疗电子商务有限公司 | A kind of digitlization forming method of intraoral tumor resection and repairing accessory |
| CN107150436A (en) * | 2017-06-30 | 2017-09-12 | 深圳市倍康美医疗电子商务有限公司 | A kind of digitlization shaping implementation method of positive gnatho-guide plate |
| CN108744055B (en) * | 2018-06-15 | 2021-04-27 | 福州大学 | Silk fibroin bone cement biological adhesive and preparation method thereof |
| CN109498844B (en) * | 2018-11-22 | 2020-12-22 | 北京科技大学 | Method for preparing bone tissue scaffold material with high composite porosity at low cost |
| CN110772430A (en) * | 2019-12-11 | 2020-02-11 | 广州润虹医药科技股份有限公司 | Calcium phosphate root canal filler with stable preservation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446109A (en) * | 2000-08-04 | 2003-10-01 | 欧健有限公司 | Porous synthetic bone graft and method of manufacture thereof |
| CN1488602A (en) * | 2003-08-12 | 2004-04-14 | 四川大学 | Porous calcium phosphate bioceramic material and preparing method thereof |
| CN103330960A (en) * | 2013-06-26 | 2013-10-02 | 西南交通大学 | Preparation method of coating having endothelium bionic function |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE525236C2 (en) * | 2002-10-31 | 2005-01-11 | Cerbio Tech Ab | Process for making structured ceramic coatings and coated devices made with this process |
| AU2009255648A1 (en) * | 2008-05-30 | 2009-12-10 | Warsaw Orthopedic, Inc. | Bioceramic and biopolymer composite |
-
2013
- 2013-12-12 CN CN201310682213.2A patent/CN103691000B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446109A (en) * | 2000-08-04 | 2003-10-01 | 欧健有限公司 | Porous synthetic bone graft and method of manufacture thereof |
| CN1488602A (en) * | 2003-08-12 | 2004-04-14 | 四川大学 | Porous calcium phosphate bioceramic material and preparing method thereof |
| CN103330960A (en) * | 2013-06-26 | 2013-10-02 | 西南交通大学 | Preparation method of coating having endothelium bionic function |
Non-Patent Citations (3)
| Title |
|---|
| 傅荣等.多孔磷酸钙生物材料的制备及表征.《成都医学院学报》.2008,第3卷(第4期),第259-262页. * |
| 刘宗光等.多巴胺对磷酸钙骨水泥性能影响的研究.《无机化学学报》.2013,第29卷(第3期),摘要、第508页左栏第3段至第514页右栏第5段以及表1、图6. * |
| 游晓波等.组织工程多孔生物材料的制备及表征.《实用医院临床杂志》.2008,第5卷(第1期),第23-25页. * |
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