CN1546180A - Degradable composite support frame and its preparing process - Google Patents
Degradable composite support frame and its preparing process Download PDFInfo
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- CN1546180A CN1546180A CNA2003101115339A CN200310111533A CN1546180A CN 1546180 A CN1546180 A CN 1546180A CN A2003101115339 A CNA2003101115339 A CN A2003101115339A CN 200310111533 A CN200310111533 A CN 200310111533A CN 1546180 A CN1546180 A CN 1546180A
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- degradable
- nanometer hydroxyapatite
- article shaped
- support frame
- tricalcium phosphate
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Abstract
The invention relates to an inorganic / organic degradable composite porous support material and its preparing process, wherein the mass percent content of each constituent in the materials are, degradable polymer 40-90%, beta-tricalcium phosphate 9.5-45%, nano hydroxyapatite 0.5-15%. The invention also provides the process for preparing the materials.
Description
Technical field
The invention belongs to field of biomedical materials, be specifically related to osseous tissue substitution material and preparation thereof.
Background technology
Utilizing the tissue engineering technique repairing bone defect is a major progress of orthopaedics and biomedical engineering field, degradable stephanoporate stent material is one of three big key elements that realize tissue engineering technique, it is in vivo except that playing the support structure effect, also play a part to be cell adhesion, growth, breeding and tissue regeneration and moulding place and the border of providing, as bone tissue engineering stent material, it should possess following condition: (1) excellent biological compatibility and synosteosis ability; (2) suitable aperture and porosity; (3) surface of suitable cell adhesion growth and breeding; (4) degradable absorption and degraded and absorbed speed are controlled; Be easy to machine-shaping and have certain mechanical strength.At present, the more bone tissue engineering stent material of domestic and international application mainly comprises following several big class: the polymer of (1) degradable hydroxy carboxylic acid and derivant thereof; (2) inorganic calcium phosphate material such as calcium phosphate and compositions thereof; (3) phosphate/degradable macromolecule; (4) phosphate/collagen/degradable macromolecule; (5) hydroxyapatite (HA) pottery/degradable polymer etc.There is limitation separately in actual applications in above-mentioned a few class material, and wherein (1) class material hydrophilic is not, the cell adhesion ability a little less than, lack the synosteosis ability; (2) class material is owing to only contain inorganic composition, and very difficult acquisition comprises the excellent comprehensive performance of degradation property, mechanical property and processing characteristics etc.; Collagen and inorganic salt part degradation speed are too fast in (3) class and (4) the class material, and new bone is not grown up as yet and just formed new hole, and wherein might there be the immunogenicity problem in the collagen component; Used hydroxyapatite is a sintering HA pottery in (5) the class material, does not degrade substantially in vivo.
Nanometer hydroxyapatite and ordinary sinter hydroxylapatite ceramic are having in nature than big difference, and its The Nomenclature Composition and Structure of Complexes size is inorganic mutually similar with mankind itself's bone, thereby show excellent biological compatibility and cell adhesion characteristic.Non-sintering nanometer hydroxyapatite is a kind of low-crystallinity hydroxyapatite, its ion concentration in solution is long-pending to exceed about 14～16 orders of magnitude than ordinary sinter hydroxylapatite ceramic, so can dissolve gradually after non-sintering nanometer hydroxyapatite implants, its mechanism of degradation in vivo is mainly being dissolved as the master, but its degradation rate is slow than tricalcium phosphate.Utilize the too fast degradation speed of this characteristic scalable tricalcium phosphate of nanometer hydroxyapatite.The preparation technology commonly used of non-sintering nanometer hydroxyapatite is, earlier by wet method synthesis of nano hydroxyapatite colloidal sols (nano-HA-sol), and obtained by freeze drying nano hydroxyapatite powder again, particle diameter 40～100nm.(AoKi?H.Science?andMedical?Application?of?Hydroxyapatite.Tokyo：Jpn.Asso.ApatiteSci.，1991，P179；Kano?S.Bio-Med.Mater.Eng.，1994，4(4)：283；Linyun?F.Biomed.Mater.Res.in?the?Far?East(III)，Jpn：KobunshiKankokai?Press，1997，P158)
Summary of the invention
The present invention proposes a kind of degradable compound support frame material and preparation method thereof, purpose is to overcome the deficiency of existing bone tissue engineering stent material, regulate and control the too fast degradation speed of calcium phosphate by the nanometer hydroxyapatite that adds and human natural bone inorganic composition is similar, make that the degraded and absorbed speed of inorganic composition and organic polymer composition all has controllability in the above-mentioned compound system, to satisfy different clinical case requirements.
A kind of degradable compound support frame material of the present invention comprises degradable polymer and calcium phosphate, it is characterized in that it is added with non-sintering, low-crystallinity nanometer hydroxyapatite, granularity is 40-100nm; Described calcium phosphate is that bata-tricalcium phosphate, granularity are 1-10 μ m; The degree of described each ingredients constitute gross mass is: degradable polymer 40-90%, bata-tricalcium phosphate 9.5-45%, nanometer hydroxyapatite 0.5-15%.
Described degradable compound support frame material, it is further characterized in that described degradable polymer is any one or the blend or the copolymer of composition more than two kinds and two kinds among the poly-D of degradable aliphatic polyester material, L-lactic acid PDLLA, poly (l-lactic acid) PLLA, polyglycolic acid PGA, the poly-epsilon-caprolactone PCL, and its molecular weight is 70,000-350,000.
The present invention makes the method for degradable compound support frame material, and step is:
(1) by mass ratio 5～25: 95～75 mill nanometer hydroxyapatite and bata-tricalcium phosphate raw material, mix homogeneously, make nanometer hydroxyapatite/tricalcium phosphate composition, wherein nanometer hydroxyapatite is that non-sintering, low-crystallinity nanometer hydroxyapatite, granularity are 40-100nm, and described bata-tricalcium phosphate granularity is 1-10 μ m;
(2) with any one or the blend or the copolymer of composition more than two kinds and two kinds among the poly-D of degradable polymer degradable aliphatic polyester material, L-lactic acid PDLLA, poly (l-lactic acid) PLLA, polyglycolic acid PGA, the poly-epsilon-caprolactone PCL, its molecular weight is 70,000-350,000, be dissolved in ethyl acetate or chloroform or acetone or the oxolane, stir, make 10～25% degradable polymer solution;
(3) in above-mentioned degradable polymer solution, nanometer hydroxyapatite/tricalcium phosphate composition that adding is made by (1), addition is by weight: said composition: degradable polymer solution=10-60: 90-40, and the back supersound process that stirs gets mixed liquor;
(4) the sodium chloride nacl granule of adding particle diameter 50～150 μ m in mixed liquor, addition is sodium chloride by weight: mixture=8～92: 20～8 controls stir, then cast molding;
(5) with after the article shaped ventilation volatilization, the demoulding, evacuation drying again;
(6) dried article shaped is fixed in the distilled water soaks, change distilled water and in the distilled water that was soaking, can not detect chloride ion Cl
-
(7) take out article shaped, after the drying, the evacuation drying promptly gets composite porous support material again.
The manufacture method of described degradable compound support frame material, it is further characterized in that the volatilization of ventilating of described article shaped carries out in ventilated chamber, 35～38 ℃ of volatilizations after 24～48 hours down, the demoulding, dry 12-24 hour of evacuation in vacuum desiccator again;
The manufacture method of described degradable compound support frame material, dried article shaped are fixed in when soaking in the distilled water, can change first water in per 5～6 hours, can not detect chloride ion Cl in the distilled water that was soaking
-
The manufacture method of described degradable compound support frame material, after it was characterised in that further the article shaped of soaking places the dry 12-24 of exsiccator hour, evacuation drying 24～48 hours in vacuum desiccator promptly got composite porous support material again.
The adding of non-sintering nanometer hydroxyapatite among the present invention, not only can improve the cell adhesion characteristic (because the surface of nanoparticle lacks the special affinity that pair cells such as limit, high-ratio surface, high surface energy produce) of compound system and regulate the too fast degradation speed of tricalcium phosphate in the compound system, but also can in and the acidic materials that produce in the polymer degradation processes, thereby reduce the generation of implanting the back aseptic inflammation, therefore material aperture porosity 89～92.5% is a kind of widely used composite porous support material.The degradation rate of inorganic composition can realize that the degradation speed of organic polymer is then regulated and control by molecular weight, kind and the ratio thereof of polymer in the material by the ratio of regulating nanometer hydroxyapatite and tricalcium phosphate in this compound support frame material.
The specific embodiment
Below by instantiation the present invention is done further explaination.
Embodiment 1
With 1 part of (in mass, down with) nanometer hydroxyapatite (mean diameter 40～100nm,, down with) with 9 parts of bata-tricalcium phosphates (particle diameter 1～10 μ m) are milled together, mix homogeneously, get the inorganic composite of nanometer hydroxyapatite/bata-tricalcium phosphate.The inorganic composite that makes is joined in 450 parts of chloroform solns that contain 20%PDLLA (molecular weight 70,000) that prepare in advance, after being stirred to evenly, ultra-sonic dispersion is 2 minutes again, add the NaCl granule that 500 parts of particle diameters are 130～150 μ m immediately, stir the back and continued ultrasonic 1 minute, then moulding by casting.
Article shaped is inserted in the ventilated chamber,, inserted evacuation in the vacuum desiccator (100mmHg) again 24 hours 35 ℃ of volatilization demouldings after 30 hours down.Dried article shaped is fixed in the redistilled water soaks, changed first water, and in the distilled water that soaked in article shaped, can not detect chloride ion [Cl in per 5～6 hours
-].Take out article shaped, inserted earlier in the exsiccator dry 24 hours, evacuation (100mmHg) is dry 28 hours again, promptly gets composite porous support material, its porosity 89%.
The degree of each ingredients constitute gross mass is described in this material: degradable polymer 90%, bata-tricalcium phosphate 9%, nanometer hydroxyapatite 1%.
Embodiment 2
With 1 part of nanometer hydroxyapatite (40～100nm) and 3 parts of bata-tricalcium phosphates (1～10 μ m) are milled together, mix homogeneously, the inorganic composite of nanometer hydroxyapatite/bata-tricalcium phosphate.It is joined in 160 parts of tetrahydrofuran solutions that contain 10%L-lactic acid/ethanol copolymer (molecular weight 350,000) that prepare in advance, after being stirred to evenly, ultra-sonic dispersion is 2 minutes again, the NaCl granule that adds 180 parts of particle diameters, 90～120 μ m immediately, stir the back and continued ultrasonic 1 minute, then moulding by casting.
Article shaped is placed ventilated chamber,, inserted evacuation in the vacuum desiccator (100mmHg) again 24 hours 34 ℃ of volatilization demouldings after 48 hours down.Dried article shaped is fixed in the redistilled water soaks, changed first water, and in the distilled water that soaked in article shaped, can not detect chloride ion [Cl in per 5～6 hours
-].Take out article shaped, inserted earlier in the exsiccator dry 24 hours, evacuation (100mmHg) is dry 40 hours again.Promptly get composite porous support material, its porosity 90.2%.
The degree of each ingredients constitute gross mass is described in this material: degradable polymer 80%, bata-tricalcium phosphate 15%, nanometer hydroxyapatite 5%.
Embodiment 3
With 1 part of nanometer hydroxyapatite (40～100nm) and 19 parts of bata-tricalcium phosphates (1～10 μ m) are milled together, mix homogeneously, the inorganic composite of nanometer hydroxyapatite/bata-tricalcium phosphate.It is joined in 80 parts of ethyl acetate solutions that contain 25%PCL (molecular weight 110,000) that prepare in advance, after being stirred to substantially evenly, ultra-sonic dispersion is 2 minutes again, adds the NaCl granule of 360 parts of particle diameters, 50～83 μ m immediately, stir the back and continued ultrasonic 1 minute, then moulding by casting.
Article shaped is placed ventilated chamber,, inserted evacuation in the vacuum desiccator (100mmHg) again 24 hours 38 ℃ of volatilization demouldings after 24 hours down.Dried article shaped is fixed in the redistilled water soaks, changed first water, and in the distilled water that soaked in article shaped, can not detect chloride ion [Cl in per 5～6 hours
-].Take out article shaped, inserted earlier in the exsiccator dry 24 hours, evacuation (100mmHg) is dry 38 hours again, i.e. gained composite porous support material, porosity 91.5%.
The degree of each ingredients constitute gross mass is described in this material: degradable polymer 80%, bata-tricalcium phosphate 19%, nanometer hydroxyapatite 1%.
Embodiment 4
With 1 part of nanometer hydroxyapatite (40～100nm) and 5 parts of bata-tricalcium phosphates (1～10 μ m) are milled together, mix homogeneously, the inorganic composite of nanometer hydroxyapatite/bata-tricalcium phosphate.It is joined in 40 parts of chloroform solns that contain 10%PLLA (molecular weight 150,000) that prepare in advance, after being stirred to substantially evenly, ultra-sonic dispersion is 2 minutes again, adds 50 parts of particle diameters, 90～120 μ mNaCl granules immediately, stir the back and continued ultrasonic 1 minute, then moulding by casting.
Article shaped is placed ventilated chamber,, inserted evacuation in the vacuum desiccator (100mmHg) again 24 hours 38 ℃ of volatilization demouldings after 26 hours down.Dried article shaped is fixed in the redistilled water soaks, changed first water, and in the distilled water that soaked in article shaped, can not detect chloride ion [Cl in per 5～6 hours
-].Take out article shaped, inserted earlier in the exsiccator dry 24 hours, evacuation (100mmHg) is dry 28 hours again, promptly gets composite porous support material, porosity 89.6%.
The degree of each ingredients constitute gross mass is described in this material: degradable polymer 40%, bata-tricalcium phosphate 45%, nanometer hydroxyapatite 10%.
Embodiment 5
With 1 part of nanometer hydroxyapatite (40～100nm) and 11 parts of bata-tricalcium phosphates (1～10 μ m) are milled together, mix homogeneously, the inorganic composite of nanometer hydroxyapatite/type alpha tricalcium phosphate.With its join 360 parts prepare in advance contain 20%D, in the chloroform soln of L-lactic acid/L-lactic acid copolymer (molecular weight 200,000), after being stirred to substantially evenly, ultra-sonic dispersion is 2 minutes again, add 924 parts of particle diameters, 83～90 μ mNaCl granules immediately, stir the back and continued ultrasonic 1 minute, then moulding by casting.
Article shaped is placed ventilated chamber,, inserted evacuation in the vacuum desiccator (100mmHg) again 24 hours 35～38 ℃ of volatilization demouldings after 24～48 hours down.Dried article shaped is fixed in the redistilled water soaks, changed first water, and in the distilled water that soaked in article shaped, can not detect chloride ion [Cl in per 5～6 hours
-].Take out article shaped, inserted earlier in the exsiccator dry 24 hours, evacuation (100mmHg) is dry 24～48 hours again, promptly gets composite porous support material, porosity 92.5%.
The degree of each ingredients constitute gross mass is described in this material: degradable polymer 90%, bata-tricalcium phosphate 9.5%, nanometer hydroxyapatite 0.5%.
Embodiment 6
With 1 part of nanometer hydroxyapatite (40～100nm) and 14 parts of bata-tricalcium phosphates (1～10 μ m) are milled together, mix homogeneously, the inorganic composite of nanometer hydroxyapatite/bata-tricalcium phosphate.It is joined in 100 parts of chloroform solns that contain 15%PDLLA (molecular weight 350,000) that prepare in advance, after being stirred to substantially evenly, ultra-sonic dispersion is 2 minutes again, adds 300 parts of particle diameters, 90～120 μ mNaCl granules immediately, stir the back and continued ultrasonic 1 minute, then moulding by casting.
Article shaped is placed ventilated chamber,, inserted evacuation in the vacuum desiccator (100mmHg) again 24 hours 35～38 ℃ of volatilization demouldings after 24～48 hours down.Dried article shaped is fixed in the redistilled water soaks, changed first water, and in the distilled water that soaked in article shaped, can not detect chloride ion [Cl in per 5～6 hours
-].Take out article shaped, inserted earlier in the exsiccator dry 24 hours, evacuation (100mmHg) is dry 24～48 hours again, promptly gets composite porous support material, porosity 92.1%.
The degree of each ingredients constitute gross mass is described in this material: degradable polymer 40%, bata-tricalcium phosphate 45%, nanometer hydroxyapatite 15%.
Claims (6)
1, a kind of degradable compound support frame material comprises degradable polymer and calcium phosphate, it is characterized in that it is added with non-sintering, low-crystallinity nanometer hydroxyapatite, granularity is 40-100nm; Described calcium phosphate is that bata-tricalcium phosphate, granularity are 1-10 μ m; The degree of described each ingredients constitute gross mass is: degradable polymer 40-90%, bata-tricalcium phosphate 9.5-45%, nanometer hydroxyapatite 0.5-15%.
2, degradable compound support frame material as claimed in claim 1, it is characterized in that described degradable polymer is any one or the blend or the copolymer of composition more than two kinds and two kinds among the poly-D of degradable aliphatic polyester material, L-lactic acid PDLLA, poly (l-lactic acid) PLLA, polyglycolic acid PGA, poly-ε-caprolactone PCL, its molecular weight is 70,000-350,000.
3, the manufacture method of claim 1 or 2 described degradable compound support frame materials the steps include:
(1) by mass ratio 5～25: 95～75 mill nanometer hydroxyapatite and bata-tricalcium phosphate raw material, mix homogeneously, make nanometer hydroxyapatite/tricalcium phosphate composition, wherein nanometer hydroxyapatite is that non-sintering, low-crystallinity nanometer hydroxyapatite, granularity are 40-100nm, and described bata-tricalcium phosphate granularity is 1-10 μ m;
(2) with any one or the blend or the copolymer of composition more than two kinds and two kinds among the poly-D of degradable polymer degradable aliphatic polyester material, L-lactic acid PDLLA, poly (l-lactic acid) PLLA, polyglycolic acid PGA, poly-ε-caprolactone PCL, its molecular weight is 70,000-350,000, be dissolved in ethyl acetate or chloroform or acetone or the oxolane, stir, make 10～25% degradable polymer solution;
(3) in degradable polymer solution, add the nanometer hydroxyapatite/tricalcium phosphate composition that makes by (1), addition is by weight: said composition: degradable polymer solution=10-60: 90-40, the back supersound process that stirs gets mixed liquor;
(4) the sodium chloride nacl granule of adding particle diameter 50～150 μ m in mixed liquor, addition is sodium chloride by weight: mixture=8～92: 20～8 controls stir, then cast molding;
(5) with after the article shaped ventilation volatilization, the demoulding, evacuation drying again;
(6) dried article shaped is fixed in the distilled water soaks, change distilled water and in the distilled water that was soaking, can not detect chloride ion Cl
-
(7) take out article shaped, after the drying, the evacuation drying promptly gets composite porous support material again.
4, the manufacture method of degradable compound support frame material as claimed in claim 3, it is characterized in that the volatilization of ventilating of described article shaped carries out in ventilated chamber, 35～38 ℃ of down volatilizations after 24～48 hours, the demoulding, dry 12-24 hour of evacuation in vacuum desiccator again;
5, the manufacture method of degradable compound support frame material as claimed in claim 4, it is characterized in that dried article shaped is fixed in the distilled water soaks, and changed first water, and can not detect chloride ion Cl in the distilled water that was soaking in per 5～6 hours
-
6, the manufacture method of degradable compound support frame material as claimed in claim 5, after it is characterized in that the article shaped of soaking places the dry 12-24 of exsiccator hour, evacuation drying 24～48 hours in vacuum desiccator promptly gets composite porous support material again.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100338118C (en) * | 2005-12-16 | 2007-09-19 | 西南交通大学 | Preparation method of biodegradable calcium phosphorus inorganic bioparticlel polymer composite material |
| CN100356989C (en) * | 2005-11-03 | 2007-12-26 | 同济大学 | Method for preparing organic and inorganic nanometer composite organization engineering stent material by using thermal phase separation |
| CN101947332A (en) * | 2010-09-09 | 2011-01-19 | 曹宏 | Porous biodegradable composite-type bone repairing material and preparation method thereof |
| CN102335461A (en) * | 2011-09-13 | 2012-02-01 | 东华大学 | Controllable safe human body pipeline bracket made of PLA (Poly Lactic Acid)/PCLA (Polycaprolactone Lactide) degradable composite material and production method thereof |
| CN104127270A (en) * | 2007-01-19 | 2014-11-05 | 万能医药公司 | Biodegradable endoprostheses and methods for their fabrication |
| CN106433056A (en) * | 2016-10-19 | 2017-02-22 | 深圳市艾科赛龙科技股份有限公司 | 3D printing biological material as well as preparation method and printing method thereof |
| CN108578787A (en) * | 2018-08-07 | 2018-09-28 | 宁波宝亭生物科技有限公司 | A kind of absorbable bone anchoring device and preparation method thereof |
-
2003
- 2003-12-08 CN CN 200310111533 patent/CN1242818C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100356989C (en) * | 2005-11-03 | 2007-12-26 | 同济大学 | Method for preparing organic and inorganic nanometer composite organization engineering stent material by using thermal phase separation |
| CN100338118C (en) * | 2005-12-16 | 2007-09-19 | 西南交通大学 | Preparation method of biodegradable calcium phosphorus inorganic bioparticlel polymer composite material |
| CN104127270A (en) * | 2007-01-19 | 2014-11-05 | 万能医药公司 | Biodegradable endoprostheses and methods for their fabrication |
| CN101947332A (en) * | 2010-09-09 | 2011-01-19 | 曹宏 | Porous biodegradable composite-type bone repairing material and preparation method thereof |
| CN102335461A (en) * | 2011-09-13 | 2012-02-01 | 东华大学 | Controllable safe human body pipeline bracket made of PLA (Poly Lactic Acid)/PCLA (Polycaprolactone Lactide) degradable composite material and production method thereof |
| CN106433056A (en) * | 2016-10-19 | 2017-02-22 | 深圳市艾科赛龙科技股份有限公司 | 3D printing biological material as well as preparation method and printing method thereof |
| CN108578787A (en) * | 2018-08-07 | 2018-09-28 | 宁波宝亭生物科技有限公司 | A kind of absorbable bone anchoring device and preparation method thereof |
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