CN105148326A - Preparation method of self-foaming porous composite bone repair bracket - Google Patents
Preparation method of self-foaming porous composite bone repair bracket Download PDFInfo
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- CN105148326A CN105148326A CN201510645828.7A CN201510645828A CN105148326A CN 105148326 A CN105148326 A CN 105148326A CN 201510645828 A CN201510645828 A CN 201510645828A CN 105148326 A CN105148326 A CN 105148326A
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- Prior art keywords
- preparation
- calcium
- composite bone
- porous composite
- recovery support
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/12—Phosphorus-containing materials, e.g. apatite
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention relates to a preparation method of a treatment material, in particular to a preparation method of a self-foaming porous composite bone repair bracket. The preparation method comprises the following steps: during the synthesis process of a phosphomycin calcium-polyurethane composite, foaming agent water is uniformly compounded in the material in a phosphomycin calcium crystal water form; crystal water is released under a certain condition to react with isocyanato in polyurethane system, so as to generate CO2 gas, achieve self-foaming formation of the composite system, and prepare a phosphomycin calcium-polyurethane composite bone repair bracket with porosity and uniform pores. The in situ self-foaming method is easy and feasible.
Description
Technical field
The present invention relates to a kind of preparation method for the treatment of material, be specially the preparation method from foamed porous Composite Bone recovery support.
Background technology
Porous support materials, as material and stay in place form, plays an important role in bone tissue engineer.Suitable bionical pore structure is the key that can porous support play optimum skeletonization usefulness.Although porous support materials obtains greater advance in the investigation and application of bone tissue engineer, but ubiquity timbering material mechanical property, degradation property regenerate with natural bone and do not mate, hole is uneven, the problems such as poor connectivity, make biological cells and tissues be difficult to infiltration to grow into internal stent, only grow in the periphery of support, while matter transportation hindered, be unfavorable for the renewal of local organization, make the clinical practice of timbering material distance also have larger gap.
Polyurethane is by hard section and the soft section of block polymer formed, select different soft or hard sections or adjustment soft or hard section ratio can obtain different physicochemical property and degradation property according to different demands, because its good biocompatibility, blood compatibility and performance the advantage such as flexible modulation can obtain extensive concern in field of tissue engineering technology.Chinese patent CN103495203A reports a kind of preparation method utilizing biological rattan template synthesis to contain the cellular polyurethane support of disulfide bond, but complex stephanoporate bracket prepared by the polyurethane-base composite containing inorganic filler that the method is difficult to be applied to employing viscosity larger.Good biological activity and biocompatibility has been demonstrated with porous support prepared by calcium phosphate-polyurethane bionic composite material.CO is generated because the isocyano existed in polyurethane-based material system can react with water
2gas, often uses water as foaming agent in polyurethanes porous support preparation process.Li Limei etc. " interfacial structure of alcoholization modified castor oil based polyurethanes/n-HA compound support frame material and mechanical property " (Journal of Inorganic Materials, 2013,28 (8): 811-817) etc. existing bibliographical information has prepared nano-apatite/polyurethane cellular compound rest using water as foaming agent.Although foaming agent water is safe without toxic side effect, to carry out viscosity comparatively large along with reaction for synthos-polyurethane composite system, and foaming agent water is difficult to evenly be mixed into wherein, thus affects the uniformity of brace aperture structure.
Summary of the invention
For above-mentioned situation, the invention provides and a kind ofly prepare the simple and easy to do method with the controlled Composite Bone recovery support of porous nickel.
From the preparation method of foamed porous Composite Bone recovery support, comprise the following steps:
Using the calcium phosphate material containing calcium hydrophosphate crystal hydrate and/or dalcium biphosphate crystalline hydrate as inorganic filler, evenly be compound in polyurethane system in polyurethane building-up process and form composite, losing ripening 1-48 hour under the temperature conditions of water of crystallization higher than calcium hydrophosphate crystal hydrate and/or the decomposition of dalcium biphosphate crystalline hydrate.
Calcium phosphate material also comprises hydroxyapatite, tricalcium phosphate, calcium pyrophosphate and OCP.
In composite, the mass ratio of calcium phosphate material is preferably 10 ~ 65wt%.
In calcium phosphate material water of crystallization in the composite mass ratio be 0.05 ~ 10%, be preferably 0.2 ~ 2%.
Polyurethane is the block polymer formed by polyether polyol or PEPA and isocyanates polymerization.
In order to prepare have antibacterial functions from foamed porous Composite Bone recovery support, mix nanometer silver, silver phosphate, silver nitrate, silver sulfadiazine, copper sulfate, copper nitrate, copper chloride, zinc sulfate, zinc nitrate and zinc chloride at least one in calcium phosphate material.
Ripening the permitted maximum range 75 ~ 150 DEG C, preferably 85 ~ 125 DEG C, ripening 1-48 hour, the preferred curing time is 2-24 hour.The hydrone that crystalline hydrate decomposition produces can react with the isocyano in synthesis of polyurethane system and generate CO
2as the excellent foaming agent had no side effect, along with solidification and the ripening of composite system, obtain a kind of Novel phosphoric acid calcium-polyurethane from foaming composite bone repair stent material.
In above-mentioned preparation method, because of calcium hydrophosphate crystal hydrate CaHPO
42H
2o loses water of crystallization in temperature gradually higher than when 75 DEG C, if calcium phosphate material is selected containing calcium hydrophosphate crystal hydrate, preferred ripening blowing temperature is 85 ~ 100 DEG C.In maturing process, improve the temperature of ripening, the corresponding increase of hole of ripening product.When curing temperature is lower than 85 DEG C, in composite system, the water of crystallization of calcium hydrogen phosphate can not fully discharge, and is difficult to the porous support obtaining higher porosity and hole connectivity; When curing temperature is 90 DEG C, ripening solidification foaming uniform pore diameter, is about 300 ~ 500 μm; When curing temperature is higher than 100 DEG C, the reaction that decomposition loses water of crystallization is too fast, and gained brace aperture is excessive, uneven, and mechanical strength is poor.
When calcium phosphate material selects dalcium biphosphate crystalline hydrate to originate as foaming agent water, because of dalcium biphosphate crystalline hydrate Ca (H
2pO
4)
2h
2o loses water of crystallization in temperature gradually higher than when 100 DEG C, and preferred foaming and curing temperature are 105 ~ 130 DEG C.
If curing temperature is less than 100 DEG C, in composite, the polyreaction of polyurethane is insufficient, and the support mechanical property of preparation is lower.After compound rest molding, then maturation process a period of time at a higher temperature, the mechanical property of compound rest can be improved.As added calcium hydrophosphate crystal hydrate (CaHPO
42H
2o) composite was 90 DEG C of ripenings 24 hours, and after obtained molding, porous support continues 110 DEG C of ripenings 24 hours, and its mechanical property can improve more than 1 times.
Calcium phosphate material can be calcium hydrophosphate crystal hydrate and/or the phosphate conbined usage such as dalcium biphosphate crystalline hydrate and hydroxyapatite, tricalcium phosphate, calcium pyrophosphate and OCP.In synthos, the content of contained water of crystallization directly affects the pore structure of prepared support.The content of water of crystallization realizes by the consumption adjusting calcium hydrophosphate crystal hydrate and/or dalcium biphosphate crystalline hydrate.Water of crystallization accounting in composite system is higher, and the brace aperture rate of preparation and aperture are relatively high, and mechanical property reduces, and in experimentation display composite system, crystal water content is 0.05 ~ 10%, is preferably 0.2 ~ 2%.
Provided by the invention from foamed porous Composite Bone recovery support preparation method, in synthos-compound polyurethane material building-up process by foaming agent water with the even compound of the form of synthos water of crystallization in the material, allow its isocyano discharged in water of crystallization and polyurethane system react under certain condition and generate CO
2gas, realize composite system from foaming, preparation has the synthos-polyurethane Composite Bone recovery support of porous, porous nickel.Original position is simple from foaming method, particularly can foam as even polyurethane based-polymer, can overcome and comprise water etc. and be difficult to evenly to add to the problem such as the expanded material hole caused in viscosity larger polymeric material system is uneven as foaming agent, also impurity can be avoided the impact of material property, make to be easy to be formed evenly in the timbering material structure of preparation, mutually through pore structure, and can realize the porosity in timbering material, and pore size is regulated and controled; And material has suitable degradability, make the biology performance of material high, degradation property and support high porosity and high hole connectivity obtain perfect adaptation, the clinical requirement to high-performance tissue engineering bracket can be met, have a extensive future.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 gained is from foamed porous Composite Bone recovery support electron scanning micrograph.
Fig. 2 is that embodiment 4 gained is from foamed porous Composite Bone recovery support electron scanning micrograph.
Fig. 3 is that embodiment 10 gained is from foamed porous Composite Bone recovery support electron scanning micrograph.
Detailed description of the invention
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.
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, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, prepare calcium hydrogen phosphate-compound polyurethane material prepolymer, then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in calcium hydrogen phosphate-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 30wt%, corresponding about containing the Bound moisture of 6wt% as foaming agent, thick calcium hydrogen phosphate-compound polyurethane material is put into mould, under 90 DEG C of conditions, ripening is foamed 24 hours.After solidification, obtain from foamed porous Composite Bone recovery support.The structure of porous support as shown in Figure 1.
Embodiment 2
By the method for bibliographical information described in embodiment 1, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, prepare calcium hydrogen phosphate-compound polyurethane material prepolymer, then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in calcium hydrogen phosphate-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 40wt%, corresponding about containing the Bound moisture of 8wt% as foaming agent, thick calcium hydrogen phosphate-compound polyurethane material is put into mould, and under 110 DEG C of conditions, ripening is foamed 4 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 3
By the method for bibliographical information described in embodiment 1, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, prepare calcium hydrogen phosphate-compound polyurethane material prepolymer, then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in calcium hydrogen phosphate-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 10wt%, corresponding about containing the Bound moisture of 2wt% as foaming agent, thick calcium hydrogen phosphate-compound polyurethane material is put into mould, and under 100 DEG C of conditions, ripening is foamed 12 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 4
By the method for bibliographical information described in embodiment 1, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, hydroxyapatite mixture, calcium hydrogen phosphate: hydroxyapatite weight ratio is 1:2, prepare calcium hydrogen phosphate-hydroxyapatite-compound polyurethane material prepolymer, then chain extender 1 is added, continue reaction a period of time after 4-butanediol, obtain the composite of thickness; In calcium hydrogen phosphate-hydroxyapatite-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 10wt%, corresponding about containing the Bound moisture of 2wt% as foaming agent; Thick calcium hydrogen phosphate-hydroxyapatite-compound polyurethane material is put into mould, and under 90 DEG C of conditions, ripening is foamed 24 hours.After solidification, obtain from foamed porous Composite Bone recovery support.The structure of porous support as shown in Figure 2.
Embodiment 5
By the method for bibliographical information described in embodiment 1, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, tricalcium phosphate mixture, prepare calcium hydrogen phosphate-tricalcium phosphate-compound polyurethane material prepolymer, calcium hydrogen phosphate: tricalcium phosphate weight ratio is 1:1; Then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in calcium hydrogen phosphate-tricalcium phosphate-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 10wt%, corresponding about containing the Bound moisture of 2wt% as foaming agent; Thick calcium hydrogen phosphate-tricalcium phosphate-compound polyurethane material is put into mould, and under 90 DEG C of conditions, ripening is foamed 24 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 6
By the method for bibliographical information described in embodiment 1, the nanometer hydroxyapatite in document is replaced with dalcium biphosphate crystalline hydrate, hydroxyapatite mixture, prepare dalcium biphosphate-hydroxyapatite-compound polyurethane material prepolymer, dalcium biphosphate: hydroxyapatite weight ratio is 1:2; Then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in dalcium biphosphate-hydroxyapatite-compound polyurethane material, dalcium biphosphate crystalline hydrate is about 10wt%, corresponding about containing the Bound moisture of 0.7wt% as foaming agent; Thick dalcium biphosphate-hydroxyapatite-compound polyurethane material is put into mould, and under 120 DEG C of conditions, ripening is foamed 24 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 7
By the method for bibliographical information described in embodiment 1, the nanometer hydroxyapatite in document is replaced with dalcium biphosphate crystalline hydrate, tricalcium phosphate mixture, prepare dalcium biphosphate-hydroxyapatite-compound polyurethane material prepolymer, dalcium biphosphate: tricalcium phosphate weight ratio is 1:7; Then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in dalcium biphosphate-tricalcium phosphate-compound polyurethane material, synthos are about 40wt%, dalcium biphosphate crystalline hydrate is about 5wt%, corresponding about containing the Bound moisture of 0.36wt% as foaming agent; Thick dalcium biphosphate-tricalcium phosphate-compound polyurethane material is put into mould, and under 150 DEG C of conditions, ripening is foamed 2 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 8
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, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, prepare calcium hydrogen phosphate-compound polyurethane material prepolymer, then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in calcium hydrogen phosphate-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 40wt%, corresponding about containing the Bound moisture of 8wt% as foaming agent; Thick calcium hydrogen phosphate-compound polyurethane material is put into mould, and under 85 DEG C of conditions, ripening is foamed 24 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 9
By the method for bibliographical information described in embodiment 8, the nanometer hydroxyapatite in document is replaced with calcium hydrophosphate crystal hydrate, hydroxyapatite mixture, prepare calcium hydrogen phosphate-hydroxyapatite-compound polyurethane material prepolymer, calcium hydrogen phosphate: hydroxyapatite weight ratio is 1:2; Then chain extender 1 is added, reaction a period of time is continued after 4-butanediol, obtain the composite of thickness, in calcium hydrogen phosphate-hydroxyapatite-compound polyurethane material, calcium hydrophosphate crystal hydrate is about 20wt%, corresponding about containing the Bound moisture of 4wt% as foaming agent; Thick calcium hydrogen phosphate-hydroxyapatite-compound polyurethane material is put into mould, and under 90 DEG C of conditions, ripening is foamed 48 hours.After solidification, obtain from foamed porous Composite Bone recovery support.
Embodiment 10
By the method for bibliographical information described in embodiment 8, the nanometer hydroxyapatite in document is replaced with dalcium biphosphate crystalline hydrate, hydroxyapatite mixture, prepare dalcium biphosphate-hydroxyapatite-compound polyurethane material prepolymer, dalcium biphosphate: hydroxyapatite weight ratio is 1:2; Then continue reaction a period of time after adding chain extender BDO, obtain the composite of thickness; In dalcium biphosphate-hydroxy-apatite-compound polyurethane material, dalcium biphosphate crystalline hydrate is about 20wt%, corresponding about containing the Bound moisture of 1.5wt% as foaming agent; Thick dalcium biphosphate-hydroxyapatite-compound polyurethane material is put into mould, and under 125 DEG C of conditions, ripening is foamed 24 hours.After solidification, obtain from foamed porous Composite Bone recovery support.The structure of porous support as shown in Figure 3.
Claims (6)
1. from the preparation method of foamed porous Composite Bone recovery support, it is characterized in that, comprise the following steps:
Using the calcium phosphate material containing calcium hydrophosphate crystal hydrate and/or dalcium biphosphate crystalline hydrate as inorganic filler, evenly be compound in polyurethane system in polyurethane building-up process and form composite, losing ripening 1-48 hour under the temperature conditions of water of crystallization higher than calcium hydrophosphate crystal hydrate and/or the decomposition of dalcium biphosphate crystalline hydrate.
2. the preparation method from foamed porous Composite Bone recovery support according to claim 1, is characterized in that, described calcium phosphate material also to comprise in hydroxyapatite, tricalcium phosphate, calcium pyrophosphate and OCP one or more.
3. the preparation method from foamed porous Composite Bone recovery support according to claim 1, is characterized in that, in described composite, the mass ratio of calcium phosphate material is 10 ~ 65wt%.
4. the preparation method from foamed porous Composite Bone recovery support according to any one of Claim 1-3, is characterized in that, in described calcium phosphate material water of crystallization in the composite mass ratio be 0.05 ~ 10%.
5. the preparation method from foamed porous Composite Bone recovery support according to any one of Claim 1-3, is characterized in that, described polyurethane is the block polymer formed by polyether polyol or PEPA and isocyanates polymerization.
6. the preparation method from foamed porous Composite Bone recovery support according to any one of Claim 1-3, it is characterized in that, in described calcium phosphate material, mix nanometer silver, silver phosphate, silver nitrate, silver sulfadiazine, copper sulfate, copper nitrate, copper chloride, zinc sulfate, zinc nitrate and zinc chloride at least one.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510645828.7A CN105148326A (en) | 2015-10-08 | 2015-10-08 | Preparation method of self-foaming porous composite bone repair bracket |
| PCT/CN2016/075332 WO2017059654A1 (en) | 2015-10-08 | 2016-03-02 | Method for preparing self-foaming porous composite bone repair scaffold |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510645828.7A CN105148326A (en) | 2015-10-08 | 2015-10-08 | Preparation method of self-foaming porous composite bone repair bracket |
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| WO (1) | WO2017059654A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017059654A1 (en) * | 2015-10-08 | 2017-04-13 | 四川大学 | Method for preparing self-foaming porous composite bone repair scaffold |
| CN107982578A (en) * | 2017-12-15 | 2018-05-04 | 太原理工大学 | The preparation method of nanometer hydroxyapatite/compound porous bone tissue engineering stent material of Beta-cyclodextrin-based polyurethane |
| CN109260511A (en) * | 2018-09-14 | 2019-01-25 | 广州润虹医药科技股份有限公司 | A kind of Injectable porous calcium phosphate bone cement and preparation method thereof |
| CN111346255A (en) * | 2020-04-21 | 2020-06-30 | 四川大学 | Wound dressing with antibacterial and bacteria-carrying warning functions and preparation method thereof |
| CN114984328A (en) * | 2022-06-29 | 2022-09-02 | 海南大学 | Composite bone repair material and preparation method thereof |
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| CN113262326A (en) * | 2021-04-21 | 2021-08-17 | 成都理工大学 | Shape memory polyurethane bone scaffold prepared by gas foaming method and application thereof |
| CN116832223B (en) * | 2023-07-27 | 2024-01-30 | 重庆生物智能制造研究院 | Medical absorbable calcium phosphate salt/polyester composite material and preparation method thereof |
| CN117534956B (en) * | 2024-01-09 | 2024-04-16 | 乐陵思盛聚合物材料有限公司 | High-solid-content aqueous polyurethane emulsion easy to self-foam and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2017059654A1 (en) * | 2015-10-08 | 2017-04-13 | 四川大学 | Method for preparing self-foaming porous composite bone repair scaffold |
| CN107982578A (en) * | 2017-12-15 | 2018-05-04 | 太原理工大学 | The preparation method of nanometer hydroxyapatite/compound porous bone tissue engineering stent material of Beta-cyclodextrin-based polyurethane |
| CN107982578B (en) * | 2017-12-15 | 2021-04-13 | 太原理工大学 | Preparation method of nano hydroxyapatite/cyclodextrin-based polyurethane composite porous bone tissue engineering scaffold material |
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| CN114984328A (en) * | 2022-06-29 | 2022-09-02 | 海南大学 | Composite bone repair material and preparation method thereof |
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| Publication number | Publication date |
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| WO2017059654A1 (en) | 2017-04-13 |
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Application publication date: 20151216 |