CN1485098A - Degradable nanometer composite material for biological and medical use - Google Patents
Degradable nanometer composite material for biological and medical use Download PDFInfo
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Abstract
A nanometer-grade medical decomposable composite material and its preparation method. By different Ca/P, different crystallizing states in the inorganic phase, the composite material adjusts decomposing rate, recombines with decomposable polymer, thus the biological decomoposing rate of the whole composite material is adjustable. The inorganic phase is selected from one or two of amorphous calcium phosphate, alpha-tricalcium phosphate, beta-tricalcium phosphate, phosphorite and calcium phosphate dibasic. The preparation method comprises selecting organic solvents for uniformly dispersing calcium phosphate powder in a decomposable polymer matrix, then obtaining nanometer-grade composite material.
Description
Technical field
The present invention relates to a kind of degradable biological medical nano composite material and preparation method thereof, belong to the technical field of bio-medical substitution material preparation.
Background technology
Owing to reasons such as disease or wounds, sclerous tissueses such as people's skeleton or tooth produce sclerous tissues's damage or disappearance, need a large amount of synthetic substitution material to repair and treat.Hard tissue substituting material mainly contains metal, pottery and polymer three class materials at present.They respectively have characteristics.
Strength of Metallic Materials height, processing easily.But cost an arm and a leg, do not match with bone stress, can produce osseous tissue and absorb, the metal ion that the physiology corrosion produces produces untoward reaction to tissue, and this class material require second operation takes out after the organization healing.
Calcium phosphate material because of its have with skeleton in inorganic mutually similar chemical composition, good biological activity and bone conductibility, be the ceramic material of using widely.But its relatively poor mechanical property has limited the range of application of calcium phosphate, is mainly used in nonweight-bearing field (as the filling of bone lacks and bone cement etc.).
Polymeric material mainly contains two kinds: biological non-degradable material and Biodegradable material.The former is as polyethylene, polypropylene, politef and polymethyl methacrylate etc.These materials have mechanical property and bio-compatible preferably, but they do not possess biological activity, and cannot degrade, and need second operation to take out.The latter such as α-polyester polymer have good mechanical performance and biocompatibility, and its maximum characteristics are can degrade behind the implant into body, along with the healing of tissue, implant is slowly degraded, after the organization healing, the implant degraded is complete, thereby does not want second operation.But this class degradation material also exists many deficiencies: X ray did not develop after material implanted, and can't effectively detect the implantation situation; This class material is along with the increase of degradation time, and mechanical properties decrease is too fast; The acidic materials that produce in degradation process can cause tissue to produce the aseptic inflammation reaction.
The biodegradation rate of calcium phosphate material can be regulated.The degradation rate of the calcium phosphate of Different Ca/P ratio and degree of crystallinity is different, and their descending orders are: α-TCP＞β-TCP＞HA, the calcium phosphate of the calcium phosphate＞high-crystallinity of amorphous calcium phosphate＞low-crystallinity.If the calcium phosphate of different crystalline phases is together compound, promptly can regulate the degradation rate of calcium phosphate.
Therefore, people join the degradable polymer preparation organic/inorganic composite material similar to bone structure from the structure angle of osseous tissue with calcium phosphate.Calcium phosphate is filled into polymer manufacture degradable biomedical Biocomposite material has the incomparable advantage of single constituent: (1) can improve the deficiency of the mechanical property of calcium phosphate own aspect the mechanical property, has improved the toughness of material; (2) aspect biological activity, add biological that not commensurability calcium phosphate can reinforced polymeric material; (3) aspect biodegradation, the acidic materials that add calcium phosphate post polymerization deposits yields can be suppressed effectively, the crystalline phase by regulating calcium phosphate and crystalline phase is formed or the proportion of composing of the monomer of polymer and each monomeric proportion of composing of copolymer or calcium phosphate and polymer can be regulated the biodegradation rate of composite; (3) in the medical science context of detection, behind the interpolation calcium phosphate, implant can develop by X ray, detects the implantation situation and is more prone to; In addition, the acidic materials that polymer produces can promote the degraded of calcium phosphate, help the healing of osseous tissue more.
Chinese patent (CN1403167) and United States Patent (USP) (US5981619) disclose calcium phosphate added and have obtained mechanical property composite preferably in the polymer.But these composite structures are compared with the structure of osseous tissue, also exist difference: the particle size that mainly is calcium phosphate is bigger, and (calcium phosphate in the skeleton is tens nm, and their calcium phosphate is 1～100 μ m), the degradation property of composite is good inadequately, goes back organic/inorganic substance and disperses even inadequately at polymeric matrix.Foregoing invention can not be regulated composite degradation speed effectively, to satisfy the requirement of different implant sites to the implant degradation rate.In addition, the appearance of bone tissue engineer and development need also to have proposed the adjustable requirement of biodegradation rate to porous support materials.
Summary of the invention
The object of the present invention is to provide a kind of calcium phosphate granules tiny, in polymeric matrix finely dispersed degradable biological medical nano composite material and preparation method thereof.
Laminated film that degradable biological medical nano composite material of the present invention is made up of calcium phosphate and degradable polymer or composite powder or for the composite of preparation bio-medical succedaneum, wherein the content of calcium phosphate (mass percent) is 5～50%, and the content of degradable polymer (mass percent) is 95～50%.
The preparation method of degradable biological medical nano composite material of the present invention has:
Scheme 1
Preparation method may further comprise the steps:
1) under the effect of ultrasound wave or machinery emulsification machine calcium phosphate is dispersed in the organic solvent, the content (by mass/volume percentage ratio) of calcium phosphate in organic solvent is 0.1%～10%;
2) under 10 ℃～60 ℃ degradable polymer is dissolved in calcium phosphate-organic solvent mixed solution, through the effect formation homogeneous mixture solotion of ultrasound wave or machinery emulsification machine, the mass/volume percent concentration of polymer solution is 1%～10%.
3) adopt conventional solution casting method to be cast into calcium phosphate/degradable polymer laminated film homogeneous mixture solotion, or adopt conventional non-solvent intermediate processing to be settled out calcium phosphate/degradable polymer composite powder, carry out drying again.
Further preparation, can adopt composite hot-forming or that injection mo(u)lding is made confession preparation bio-medical succedaneum with the laminated film or the composite powder of gained, its hot-forming step is as follows: above-mentioned laminated film or composite powder are put in the mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 0.5MPa～40MPa, be that 80～190 ℃, pressure are under the condition of 0.5～100MPa in temperature then, pressurize 5～30 minutes, goods are taken out in cooling;
The injection mo(u)lding step is as follows: with above-mentioned composite powder or laminated film pulverize at low temperature, add hot injection mo(u)lding in the injection machine to, condition of molding is: injection pressure is 0.1MPa～5Mpa, and temperature is 100 ℃～250 ℃.
The bending strength of the degradable biological medical nano composite material that scheme 1 makes is 80～250MPa, and bending modulus is 1～10Gpa.
Scheme 2
Preparation method may further comprise the steps:
1) under the effect of ultrasound wave or machinery emulsification machine calcium phosphate and pore creating material are joined in the organic solvent, the content (by mass/volume percentage ratio) of calcium phosphate in organic solvent is 0.1%～10%;
2) under 10 ℃～60 ℃ degradable polymer is dissolved in the above-mentioned mixed solution, through the effect formation homogeneous mixture solotion of ultrasound wave or machinery emulsification machine, the mass/volume percent concentration of polymer solution is 1%～10%.
3) homogeneous mixture solotion is adopted conventional solution casting method be cast into calcium phosphate/degradable polymer laminated film, or adopt conventional non-solvent intermediate processing to be settled out calcium phosphate/degradable polymer composite powder, to carry out drying again.
Further preparation, can adopt hot-forming laminated film or composite powder to make for the composite for preparing the bio-medical succedaneum with gained, hot-forming step is as follows: above-mentioned laminated film or composite powder are put in the mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 0.5～40MPa, it is 80～190 ℃ in temperature then, pressure is under the condition of 0.5～100MPa, pressurize 5～30 minutes, goods are taken out in cooling, it is immersed in 37 ℃ the thermostatic water bath, stripping pore creating material under the frequency of oscillation of 100 times/h obtains composite porous.
The aperture of the degradable biological medical nano composite material that scheme 2 makes is 10 μ m～200 μ m, and porosity is 75%～95%, and compressive strength is 0.5MPa～3MPa.
Among the present invention, described calcium phosphate comprises: amorphous calcium phosphate or α phase tricalcium phosphate or β phase tricalcium phosphate or apatite or calcium hydrogen phosphate or apatite/α phase tricalcium phosphate composite powder or apatite/β phase tricalcium phosphate composite powder or α phase tricalcium phosphate composite powder/β phase tricalcium phosphate composite powder, wherein apatite is fluoridated hydroxyapatite or contains carbonate apatite.These particles of powder are evenly distributed, size is generally about 40nm～500nm, wherein the content of each phase in the calcium phosphate composite powder is 0～100% scalable, and crystalline phase that the degradation rate of (promptly regulate Ca/P than) calcium phosphate can be by changing calcium phosphate or crystalline phase are formed and regulated.
Among the present invention, described degradable polymer comprises: polylactic acid or polyglycolic acid or poly butyric or poly-own lactone or poly-to dioxanone or poly-anhydride or poly-former ester or their monomeric copolymers, wherein polylactic acid is poly--L-lactic acid or poly--(D, L)-and lactic acid or poly--L-(D, L)-lactic acid.The degradation rate of polymer can be regulated by the monomer composition and the ratio that change in the polymer.
In the preparation process of the present invention, described organic solvent can be dichloromethane or chloroform or oxolane or dimethyl formamide or dimethyl sulfoxide or dioxane.Pore creating material can be with sodium chloride or sugar.Non-solvent is methanol or ethanol.
The preparation process condition that the present invention adopts is simple, simple to operate, and cost is low, is easy to industrialization.This preparation method adopts solvent solution-cast or solution-non-solvent to precipitate in the calcium phosphate powder homodisperse degradable polyalcohol group body by selecting organic solvent, thereby it is compound to make composite reach nanoscale, brings into play the usefulness of composite more fully.In addition, can obtain the porous nano composite by particle filtering method.Biological medical nano composite of the present invention, its biodegradation rate can be by changing calcium phosphate composition or the composition of polymer or the proportion of composing of calcium phosphate and polymer regulated effectively, thereby can satisfy the requirement of different tissues engineering.The acidic materials that this material polymers produces can promote the degraded of calcium phosphate, help the healing of osseous tissue more.The mechanical property of its mechanical property and bone is complementary.Can be widely used for biomedical materials field such as bone screw, bone fishplate bar and bone tissue engineer.
The specific embodiment
Degradable biological medical nano composite material of the present invention is made up of calcium phosphate and degradable polymer, and wherein the content of calcium phosphate (mass percent) is 5～50%, and the content of degradable polymer (mass percent) is 95～50%.
During employing scheme 1 preparation degradable biological medical nano composite material, earlier calcium phosphate is joined and under ultrasound wave or the effect of machinery emulsification machine, form uniform calcium phosphate aaerosol solution in the organic solvent, under 10 ℃～60 ℃, polymer is joined in the calcium phosphate aaerosol solution again, treat under the magnetic agitation that polymer dissolves back ultrasound wave or the effect of machinery emulsification machine 10～30 minutes fully, be cast into calcium phosphate/degradable polymer thin film again or add a large amount of ethanol or methanol extraction goes out calcium phosphate/degradable polymer composite powder.Again with powder or thin film 40～60 ℃ dry 24 hours down, again 40～60 ℃ of following vacuum dryings 48 hours, till the quality of dry thing no longer reduced, taking out calcium phosphate/degradable polymer thin film or powder, to put into 5 ℃ of cold preservations of exsiccator standby.
Calcium phosphate/degradable polymer thin film or powder thermoforming have dual mode: hot compression molding and hot injection mo(u)lding.Hot compression molding route: above-mentioned laminated film or composite powder are put in the special mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 0.5MPa～40MPa, be that 80～190 ℃, pressure are under the condition of 0.5～100MPa in temperature then, pressurize 5～30 minutes, goods are taken out in cooling, are processed into the samples such as bone screw, bone fishplate bar of required form then on lathe.It is standby to seal cold preservation after sample process oxireme or the gamma-radiation sterilization up for safekeeping.
Hot injection mo(u)lding route:, add hot injection mo(u)lding in the injection machine to above-mentioned composite powder or laminated film pulverize at low temperature.Condition of molding is: injection pressure is that 0.1MPa～5MPa temperature is 100 ℃～250 ℃.Injection mold is bone screw bone fishplate bar mould of required special shape etc.Can obtain required bone screw, bone fishplate bar etc. after sample process pruning that injection mo(u)lding obtains and oxireme or the gamma-radiation sterilization, it is standby that sample is sealed cold preservation up for safekeeping.
Employing scheme 2 can prepare porous, degradable biological medical nano composite, earlier calcium phosphate and pore creating material (sodium chloride or sugar) are joined and under the ultrasound wave or the situation of machinery emulsification machine effect, form uniform aaerosol solution in the organic solvent, polymer is joined in the calcium phosphate aaerosol solution again, magnetic agitation treats that polymer dissolves back ultrasound wave or the effect of machinery emulsification machine 10～30 minutes fully, again casting film or add a large amount of ethanol or methanol extraction goes out calcium phosphate/degradable polymer composite powder.Again with powder or thin film 40～60 ℃ dry 24 hours down, again 40～60 ℃ of following vacuum dryings 48 hours, till the quality of dry thing was not reducing, taking out calcium phosphate/degradable polymer thin film or powder, to put into 5 ℃ of cold preservations of exsiccator standby.
Above-mentioned thin film or powder are put in the special mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 0.5～40MPa, be that 80～190 ℃, pressure are under the condition of 0.5～100MPa in temperature then, pressurize 5～30 minutes, goods are taken out in cooling, be immersed in then in 37 ℃ the thermostatic water bath, stripping pore creating material under the frequency of oscillation of 100 times/h, soak time is 72 hours, per hour changed one time water in preceding 12 hours, changed water one time, changed once in later per 8 hours in back 36 hours 6 hours.The aperture that obtains behind the filtering pore creating material is calcium phosphate/degradable pollutant polyalcohol stephanoporate nano composite material of 10 μ m～200 μ m.
Further specify the present invention below in conjunction with embodiment
Embodiment 1
Apatite/β phase tricalcium phosphate composite powder of 0.4g is added in the oxolane of 200ml, after the supersonic oscillations 15 minutes, add the 3.6g polylactic acid, casting in film forming in the mould that diameter is 38mm after the ultrasonic Treatment after 50 ℃ of lower magnetic force stirring and dissolving, after under 40 ℃ dry 24 hours, putting in the vacuum drying oven vacuum drying till the constant mass of thin film, is that calcium phosphate/lactic acid composite material of 10wt% is put into exsiccator cold preservation with the apatite/β phase tricalcium phosphate composite powder content that obtains.
Embodiment 2
The α phase tricalcium phosphate powder of 0.2g is added in the dimethyl formamide of 200ml, after the supersonic oscillations 15 minutes, add the poly-own lactone of 3.8g, casting in film forming in the mould that diameter is 38mm after the ultrasonic Treatment after 50 ℃ of lower magnetic force stirring and dissolving, after under 160 ℃ dry 24 hours, putting in the vacuum drying oven vacuum drying till the constant mass of thin film, with the α phase tricalcium phosphate content that obtains be the calcium phosphate/poly-of 5wt% in oneself resin composite material put into exsiccator cold preservation.
Embodiment 3
α phase tricalcium phosphate composite powder/β phase tricalcium phosphate composite powder of 0.8g is added in the dimethyl sulfoxide of 200ml, after the supersonic oscillations 15 minutes, add the 3.2g polylactic acid, casting in film forming in the mould that diameter is 38mm after the ultrasonic Treatment after 50 ℃ of lower magnetic force stirring and dissolving, after under 160 ℃ dry 24 hours, putting in the vacuum drying oven vacuum drying till the constant mass of thin film, is that calcium phosphate/lactic acid composite material of 20wt% is put into exsiccator cold preservation with the α phase tricalcium phosphate composite powder/β phase tricalcium phosphate composite powder content that obtains.
Embodiment 4
The sodium chloride that apatite/α phase tricalcium phosphate composite powder and the granularity of 0.8g is 200～300 μ m adds in the oxolane of 200ml, after the supersonic oscillations 15 minutes, add the 3.2g polylactic acid, casting in film forming in the mould that diameter is 38mm after the ultrasonic Treatment after 50 ℃ of lower magnetic force stirring and dissolving, after under 40 ℃ dry 24 hours, vacuum drying is calcium phosphate/sodium chloride/lactic acid composite material of 20wt% with the calcium phosphate content that obtains till the constant mass of thin film in the vacuum drying oven putting into.At room temperature with the pressure precompressed of 30MPa, is 180 ℃, pressure be the condition of 40MPa under in temperature then with above-mentioned composite, and pressurize 5 minutes, is taken out goods at cooling.Goods are put into 37 ℃ thermostatic water bath and are soaked under the frequency of oscillation of 100 times/h, and soak time is 72 hours, per hour changes water one time, changes water one time, changed once in later per 8 hours in back 36 hours 6 hours in preceding 12 hours.The aperture that obtains behind the filtering sodium chloride is about 200 μ m, porosity is 90%, compressive strength is at porous, degradable calcium phosphate/degradable polymer composite material of 2MPa.
Embodiment 5
Composite with embodiment 1 acquisition, put in the special mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 30MPa, be that 180 ℃, pressure are under the condition of 40MPa in temperature then, pressurize 5 minutes, is taken out goods at cooling, is processed into the samples such as bone screw, bone fishplate bar of required form then on lathe.It is standby to seal cold preservation after sample process oxireme or the gamma-radiation sterilization up for safekeeping.
Embodiment 6
With the composite that embodiment 1 obtains, pulverize at low temperature is added hot injection mo(u)lding in the injection machine to.Condition of molding such as table 1.Injection mold is the bone screw bone fishplate bar mould of required special shape.Can obtain required bone screw, bone fishplate bar etc. after sample process pruning that injection mo(u)lding obtains and oxireme or the gamma-radiation sterilization, it is standby that sample is sealed cold preservation up for safekeeping.
The injection molding process condition of table 1 calcium phosphate/poly lactic acid nano composite material
First section second section the 3rd section discharging opening injection pressure mould in labor and materials district
The thermal treatment zone, temperature thermal treatment zone Heating Zone Temperature power temperature
45 ℃ of 200 ℃ of 215 ℃ of 220 ℃ of 200 ℃ of 0.15MPa room temperatures
Claims (10)
1. degradable biological medical nano composite material, it is characterized in that laminated film that it is made up of calcium phosphate and degradable polymer or composite powder or for the composite of preparation bio-medical succedaneum, wherein the content of calcium phosphate (mass percent) is 5～50%, and the content of degradable polymer (mass percent) is 95～50%.
2. according to the described degradable biological medical nano composite material of claim 1, it is characterized in that described calcium phosphate comprises: amorphous calcium phosphate or α phase tricalcium phosphate or β phase tricalcium phosphate or apatite or calcium hydrogen phosphate or apatite/α phase tricalcium phosphate composite powder or apatite/β phase tricalcium phosphate composite powder or α phase tricalcium phosphate composite powder/β phase tricalcium phosphate composite powder, wherein apatite is fluoridated hydroxyapatite or contains carbonate apatite.
3. according to the described degradable biological medical nano composite material of claim 1, it is characterized in that described degradable polymer comprises: polylactic acid or polyglycolic acid or poly butyric or poly-own lactone or poly-to dioxanone or poly-anhydride or poly-former ester or their monomeric copolymers, wherein polylactic acid is poly--L-lactic acid or poly--(D, L)-and lactic acid or poly--L-(D, L)-lactic acid.
4. according to the described degradable biological medical nano composite material of claim 1, it is characterized in that said bio-medical succedaneum is bone screw or bone fishplate bar.
5. according to the preparation method of the described degradable biological medical nano composite material of claim 1, it is characterized in that may further comprise the steps:
1) under the effect of ultrasound wave or machinery emulsification machine calcium phosphate is dispersed in the organic solvent, the content (by mass/volume percentage ratio) of calcium phosphate in organic solvent is 0.1%～10%;
2) under 10 ℃～60 ℃ degradable polymer is dissolved in calcium phosphate-organic solvent mixed solution, through the effect formation homogeneous mixture solotion of ultrasound wave or machinery emulsification machine, the mass/volume percent concentration of polymer solution is 1%～10%.
3) adopt conventional solution casting method to be cast into calcium phosphate/degradable polymer laminated film homogeneous mixture solotion, or adopt conventional non-solvent intermediate processing to be settled out calcium phosphate/degradable polymer composite powder, carry out drying again.
6. according to the described preparation method of claim 5, it is characterized in that organic solvent is dichloromethane or chloroform or oxolane or dimethyl formamide or dimethyl sulfoxide or dioxane.
7. according to the preparation method of the described degradable biological medical nano composite material of claim 5, it is characterized in that also comprising and adopt hot-forming or injection mo(u)lding to make composite the laminated film of gained or composite powder for preparation bio-medical succedaneum, its hot-forming step is as follows: above-mentioned laminated film or composite powder are put in the mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 0.5MPa～40MPa, it is 80～190 ℃ in temperature then, pressure is under the condition of 0.5～100MPa, pressurize 5～30 minutes, goods are taken out in cooling;
The injection mo(u)lding step is as follows: with above-mentioned composite powder or laminated film pulverize at low temperature, add hot injection mo(u)lding in the injection machine to, condition of molding is: injection pressure is 0.1MPa～5Mpa, and degree is 100 ℃～250 ℃.
8. the preparation method of the described degradable biological medical nano composite material of claim 1 is characterized in that may further comprise the steps:
1) calcium phosphate and pore creating material are joined in the organic solvent, the content (by mass/volume percentage ratio) of calcium phosphate in organic solvent is 0.1%～10%;
2) degradable polymer is dissolved in the above-mentioned mixed solution forms homogeneous mixture solotion, the mass/volume percent concentration of polymer solution is 1%～10%.
3) homogeneous mixture solotion is adopted conventional solution casting method be cast into calcium phosphate/degradable polymer laminated film, or adopt conventional non-solvent intermediate processing to be settled out calcium phosphate/degradable polymer composite powder, to carry out drying again.
9. according to the described preparation method of claim 8, it is characterized in that organic solvent is chloroform or oxolane or dimethyl formamide or dimethyl sulfoxide or dioxane; Pore creating material is sodium chloride or sugar.
10. according to the preparation method of the described degradable biological medical nano composite material of claim 8, it is characterized in that also comprising that laminated film or composite powder with gained adopt the hot-forming composite of making for preparation bio-medical succedaneum, hot-forming step is as follows: above-mentioned laminated film or composite powder are put in the mould, amount of filling is 70% of a mould, earlier at room temperature with the pressure precompressed of 0.5～40MPa, it is 80～190 ℃ in temperature then, pressure is under the condition of 0.5～100MPa, pressurize 5～30 minutes, goods are taken out in cooling, it is immersed in 37 ℃ the thermostatic water bath, stripping pore creating material under the frequency of oscillation of 100 times/h obtains composite porous.
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| CN1314462C (en) * | 2005-04-25 | 2007-05-09 | 浙江大学 | Degradable biomedicine composite material in nanometer structure and its prepn process |
| CN100356991C (en) * | 2005-09-28 | 2007-12-26 | 浙江大学 | Biological medical material with biological responding coating and preparing method |
| CN100428963C (en) * | 2005-11-30 | 2008-10-29 | 浙江大学 | Preparation method of non-sizing nano-calcium phosphate powder for medical slow release metal ion |
| CN101773690A (en) * | 2010-03-11 | 2010-07-14 | 浙江大学 | Polylactic acid based/20nm calcium phosphate composite stent material and preparation method thereof |
| CN102247624A (en) * | 2011-01-21 | 2011-11-23 | 北京中奥汇成生物材料科技有限公司 | Absorbable bone screw and preparation method thereof |
| CN101507841B (en) * | 2009-03-30 | 2012-11-07 | 西南交通大学 | Preparation method of inorganic calcium phosphate salt/biodegradable polymer fiber film composite material |
| CN104524637A (en) * | 2014-06-03 | 2015-04-22 | 东莞天天向上医疗科技有限公司 | High-molecular biological ceramic composite nanometer particle biodegradable stent and manufacturing method thereof |
| CN105013006A (en) * | 2015-06-24 | 2015-11-04 | 东莞天天向上医疗科技有限公司 | Bioabsorbable bone repair material and its use and manufacturing method |
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| CN108815579A (en) * | 2018-07-09 | 2018-11-16 | 苏州市贝克生物科技有限公司 | Nanocomposite and preparation method thereof |
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| CN1314462C (en) * | 2005-04-25 | 2007-05-09 | 浙江大学 | Degradable biomedicine composite material in nanometer structure and its prepn process |
| CN100356991C (en) * | 2005-09-28 | 2007-12-26 | 浙江大学 | Biological medical material with biological responding coating and preparing method |
| CN100428963C (en) * | 2005-11-30 | 2008-10-29 | 浙江大学 | Preparation method of non-sizing nano-calcium phosphate powder for medical slow release metal ion |
| CN101507841B (en) * | 2009-03-30 | 2012-11-07 | 西南交通大学 | Preparation method of inorganic calcium phosphate salt/biodegradable polymer fiber film composite material |
| CN101773690A (en) * | 2010-03-11 | 2010-07-14 | 浙江大学 | Polylactic acid based/20nm calcium phosphate composite stent material and preparation method thereof |
| CN102247624A (en) * | 2011-01-21 | 2011-11-23 | 北京中奥汇成生物材料科技有限公司 | Absorbable bone screw and preparation method thereof |
| CN104524637A (en) * | 2014-06-03 | 2015-04-22 | 东莞天天向上医疗科技有限公司 | High-molecular biological ceramic composite nanometer particle biodegradable stent and manufacturing method thereof |
| CN105013006A (en) * | 2015-06-24 | 2015-11-04 | 东莞天天向上医疗科技有限公司 | Bioabsorbable bone repair material and its use and manufacturing method |
| CN107126582A (en) * | 2017-06-02 | 2017-09-05 | 北京航空航天大学 | The preparation of amorphous calcium phosphate/PLA electrospun scaffolds |
| CN108815579A (en) * | 2018-07-09 | 2018-11-16 | 苏州市贝克生物科技有限公司 | Nanocomposite and preparation method thereof |
| CN111744058A (en) * | 2019-03-28 | 2020-10-09 | 施吉生技应材股份有限公司 | Method for producing bone plate |
| CN111643736A (en) * | 2020-05-28 | 2020-09-11 | 北京市春立正达医疗器械股份有限公司 | Composite material for interface screw and preparation method thereof |
| CN112546294A (en) * | 2020-12-03 | 2021-03-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of polyanhydride modified controllable biodegradable calcium phosphate bone cement, product and application thereof |
| CN112933300A (en) * | 2021-02-03 | 2021-06-11 | 北京天星博迈迪医疗器械有限公司 | Absorbable fixed graft and preparation method thereof |
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