CN101391116A - Absorption-rate adjustable calcium sulphate group bone-grafting material and preparation method thereof - Google Patents
Absorption-rate adjustable calcium sulphate group bone-grafting material and preparation method thereof Download PDFInfo
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- CN101391116A CN101391116A CNA2008100543394A CN200810054339A CN101391116A CN 101391116 A CN101391116 A CN 101391116A CN A2008100543394 A CNA2008100543394 A CN A2008100543394A CN 200810054339 A CN200810054339 A CN 200810054339A CN 101391116 A CN101391116 A CN 101391116A
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Abstract
The invention belongs to calcium sulphate base bone grafting material with adjustable absorption rate and the preparing method thereof. The bone grafting material of the invention comprises calcium sulphate and degradable polymer; the calcium sulphate layer is a kernel, and the polymer layer and the calcium sulphate solid layer are alternately arranged. The thickness of the degradable polymer layer is 0.01-0.5 mm. The calcium sulphate and water are evenly mixed with the parts by weight of 9:1-5:4, and are injected into a mould, after forming, a sample is taken out and is aged for 5-24 h in 40-60 DEG C so as to form the sample with a column shape or other shapes; and surface coating is performed by adopting spraying process or immerging method, so the calcium sulphate material with a polymer coat is obtained. The steps are repeated to manufacture the multi-layer calcium sulphate base bone grafting material with adjustable absorption rate. The calcium sulphate base bone grafting material with adjustable absorption rate of the invention can be used as bone renovating material, not only can play the role of bone conduction of the calcium sulphate, but also can avoid the problem that the degrading speed of the calcium sulphate is too fast, and is a novel bone grafting material.
Description
Technical field
The invention belongs to biological technical field, particularly a kind of absorption-rate adjustable calcium sulphate group bone-grafting material and preparation method.
Background technology
Damaged and the bone injury patient more than 300 ten thousand of the annual bone in the whole nation needs a large amount of bone renovating materials.The home and abroad bone renovating material adopts the biologic inorganic material for example as calcium phosphate bone cement or hydroxyapatite series more at present, and degradable polymer for example polylactic acid and copolymer thereof, polycaprolactone and various natural macromolecular, wherein calcium phosphate bone cement has entered clinical practice.The research report of the timbering material that hydroxyapatite or calcium phosphate and polymer constitute is also a lot, and wherein the collagen/hydroxyapatite compound system has also entered the clinical practice stage in the U.S..Domestic bone renovating material is based on hydroxyapatite and calcium phosphate two big series, the subject matter that the calcium phosphate bone repair materials exists is that absorption rate is slow, and hydroxyapatite absorbs in vivo hardly, and this can delay the formation of new bone, and may cause some diseases.And there are problems such as infiltration rate instability, excessive velocities in calcium sulfate as bone-grafting material.Early stage clinical research shows, the outstanding advantage of calcined gypsum is can degraded and absorbed in the body, and catabolite does not disturb the formation of new bone, absorbs too fast problem but exist, and degradation time only had about 3 weeks.U.S. Wright company utilizes the Osteoset series bone sub of half-H 2 O calcium sulphate preparation, only costs an arm and a leg, and degradation time only was 6～8 weeks, compared with the degradation time of clinical requirement, and also there is a big difference.
Summary of the invention
For solving the problem that existing bone implant material exists, the present invention proposes a kind of new absorption-rate adjustable calcium sulphate group bone-grafting material and preparation method thereof.Concrete technology is as follows:
Absorption-rate adjustable calcium sulphate group bone-grafting material of the present invention comprises calcium sulfate and degradable polymer; It is characterized in that calcium sulphate layer is a kernel, polymeric layer and calcium sulphate solid layer are alternately arranged.Biodegradable polymer layer thickness is 0.01-0.5mm.
Described biodegradable polymer layer is with a kind of polymer or the blended mixture of two or more degradable polymer.The different layers of biodegradable polymer layer is identical degradable polymer or different degradable polymers.
The preparation method of absorption-rate adjustable calcium sulphate group bone-grafting material of the present invention is characterized in that step is as follows:
The A step: calcium sulfate is mixed with water, and the weight ratio of calcium sulfate and water is 9:1～5:4, and placed 1～5 minute the back that stirs, be injected into mould then, treat that sample condenses to take out after the molding, at 40-60 ℃ of following ageing 5-24 hour, dry in vacuum drying oven then, make sample;
B step: sample is placed on the turntable, polymer solution evenly is coated in specimen surface, be placed in the vacuum drying oven dry then; Perhaps sample is immersed in the polymer solution, taking-up places on the turntable then, makes solvent evaporates, is placed on drying in the vacuum drying oven, promptly gets the calcium sulfate material of polymer surface coating;
C step: calcium sulfate is fully mixed with water, the weight ratio of calcium sulfate and water is 9:1～5:4, back placement 1～5 minute stirs, a part of taking out wherein evenly is layered on mold bottom, and above the above-mentioned coating calcium sulfate block material that obtains is placed on, at last remaining calcium sulfate is inserted in the mould, take out after the molding, at 40-60 ℃ of following ageing 5-24 hour, dry in vacuum drying oven then, make double-deck calcium sulphate-based bone-grafting material.
Above-mentioned step B and step C repeated configuration make the calcium sulphate-based bone-grafting material of the adjustable multilamellar of infiltration rate.
Described calcium sulfate is half-H 2 O calcium sulphate.The weight ratio of described calcium sulfate and water is preferably 7:3～4:3.Described water comprises distilled water, deionized water or normal saline.
Described degradable polymer concentration is weight percentage 1%～10%.
Described degradability polymer is natural biological degradable polymer or synthesized degradable polymer.The natural biological degradable polymer comprises polysaccharide macro-molecular such as chitosan, alginate, carrageenan, starch and derivant thereof, cellulose and derivant thereof, and one or more composite uses of protein macromolecule such as collagen or gelatin.Synthetic degradable polymer material comprises one or more composite uses of poly-anhydride, Polyethylene Glycol, polylactic acid and copolymer thereof (as: polylactic acid/ethanol copolymer), polycaprolactone and copolymer thereof or poly butyric ester and copolymer thereof.
Described polymer concentration is weight percentage 1%～10%.
Wherein calcium sulfate is key component, is preferably half-H 2 O calcium sulphate, and its consumption is adjustable according to actual needs.
The present invention mainly controls infiltration rate by the kind of polymer and the number of plies of polymer, because the degradation speed of various materials is different, can reach our requirement according to the degradation speed of known material.Calcium sulfate surface coating polymerization thing material is the biodegradability polymer, and face coat thickness is by polymer concentration and apply the number of times decision, is made into certain density solution during use and applies.Can also on the not coplanar of same sample, apply the polymer coating of different-thickness, to adapt to different degraded requirements.The outermost layer of calcium sulphate-based bone-grafting material can be polymer or calcium sulphate layer.According to the requirement of degradation time, repeating step B and step C can make the calcium sulphate-based bone-grafting material of the adjustable multilamellar of infiltration rate.After calcium sulphate-based bone-grafting material carried out disinfection, can directly insert the damaged or bone injury position of bone, reach the purpose of repairing bone defect.
Absorption-rate adjustable calcium sulphate group bone-grafting material of the present invention, as bone renovating material, it can bring into play the bone conduction effect of calcium sulfate, can avoid the too fast problem of calcium sulfate degradation speed again, is a kind of novel bone-grafting material.
Description of drawings
The structural representation of Fig. 1: embodiment 1;
The structural representation of Fig. 2: embodiment 2;
The structural representation of Fig. 3: embodiment 5.
The specific embodiment
Example 1
Get 2g half-H 2 O calcium sulphate powder body, add the 0.5ml normal saline, mix homogeneously injected mould with calcium sulfate after 5 minutes, treated to take out after the sample molding, and is dry in vacuum drying oven 40 ℃ of following ageings 24 hours, makes the cuboid sample.
Get the 0.1g polylactic acid, be dissolved in the 10.0ml chloroformic solution, sample is placed on the turntable, the polylactic acid solution for preparing evenly is sprayed on specimen surface, dry in vacuum drying oven, can apply repeatedly, make that the polylactic acid shell thickness is 0.05mm～0.2mm, dry in vacuum drying oven, obtain the calcium sulfate sample of polylactic acid coating.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 11 months.
Said sample also can further apply, get the 0.2g chitosan, be dissolved in the acetum (10g) of 10.0ml 1M, add glutaraldehyde (chitosan amount 0.5%), obtain chitosan solution, will have the calcium sulfate sample of polylactic acid coating to immerse in this chitosan solution, take out then and place on the turntable, make solvent evaporates, be placed on drying in the vacuum drying oven, promptly get the calcium sulfate block material that polylactic acid and chitosan apply.The structure of material as shown in Figure 1, wherein 1 is calcium sulphate solid layer, the 2nd, the polymeric layer of polylactic acid (with gelatin).
Example 2
Get 1.8g half-H 2 O calcium sulphate powder body, add the 0.2ml distilled water, mix homogeneously injected mould with calcium sulfate after 1 minute, treated to take out after the sample molding, and is dry in vacuum drying oven 40 ℃ of following ageings 18 hours, makes the column sample.
Get the 0.1g polylactic acid, be dissolved in the 9.0ml chloroformic solution, sample is placed on the turntable, the polylactic acid solution for preparing evenly is sprayed on specimen surface, dry in vacuum drying oven, can apply repeatedly, make that the polylactic acid coating layer thickness is 0.08mm～0.25mm, promptly get the calcium sulfate block material that polylactic acid applies after the drying.
Get 4g half-H 2 O calcium sulphate powder body, add the 2.0ml distilled water, mix homogeneously, get part of sulfuric acid calcium after 3 minutes and evenly be layered on mold bottom, and the above-mentioned polylactic acid that obtains is applied above calcium sulfate block material is placed on, at last remaining calcium sulfate is put into mould, take out after the molding, 50 ℃ of following ageings 12 hours, dry in vacuum drying oven, make the double-deck calcium sulfate material of column.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 12 months.
The poly-lactic acid material of above-mentioned face coat is replaceable to be PLGA (being polylactic acid/ethanol copolymer).
The structure of material as shown in Figure 2, wherein 1 is calcium sulphate solid layer, the 2nd, the polymeric layer of polylactic acid or PLGA.Example 3
Get 2g half-H 2 O calcium sulphate powder body, add the 1.5ml distilled water, mix homogeneously injected mould with calcium sulfate after 3 minutes, treated to take out after the sample molding, and is dry in vacuum drying oven 60 ℃ of following ageings 5 hours, makes the column sample.
Get the 0.3g sodium alginate, be dissolved in the 3.0ml distilled water solution, calcium sulfate column sample is placed on the turntable, the sodium alginate soln for preparing evenly is sprayed on specimen surface, place vacuum drying oven dry, can apply repeatedly, make that the polylactic acid shell thickness is 0.10mm～0.30mm, promptly get the calcium sulfate block material that sodium alginate applies after the drying.
Get the 0.2g chitosan, be dissolved in the acetum (10g) of 10.0ml1M, add glutaraldehyde (chitosan amount 0.5%), obtain chitosan solution, the calcium sulfate block material that applies sodium alginate is immersed in this chitosan solution, take out then and place on the turntable, make solvent evaporates, be placed on drying in the vacuum drying oven, apply repeatedly, make that the chitosan shell thickness is 0.3mm～0.5mm, promptly get the calcium sulfate block material of sodium alginate and chitosan coat after the drying.
Get 4g half-H 2 O calcium sulphate powder body, add the 3.0ml distilled water, mix homogeneously, get part of sulfuric acid calcium after 3 minutes and evenly be layered on mold bottom, above then the above-mentioned coating calcium sulfate block material that obtains being placed on, at last remaining calcium sulfate is inserted in the mould, take out after the molding, 50 ℃ of following ageings 12 hours, place vacuum drying oven dry, make column double-decker calcium sulfate material.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 3 months.
The chitosan of above-mentioned face coat is replaceable to be collagen, gelatin or starch and derivant thereof, and sodium alginate is replaceable to be carrageenan.
Example 4
Get the 1g half-H 2 O calcium sulphate, add the 0.3ml normal saline, mix homogeneously injected mould with calcium sulfate after 4 minutes, treated to take out after the sample molding, and is dry in vacuum drying oven 50 ℃ of following ageings 16 hours, makes the column sample.
Get 0.1g PLGA (polylactic acid/ethanol copolymer), be dissolved in the 5.0ml chloroformic solution, above-mentioned column sample is placed on the turntable, polylactic acid solution evenly is sprayed on specimen surface, dry in vacuum drying oven, can apply repeatedly, make that the PLGA shell thickness is 0.05mm～0.20mm, promptly get the calcium sulfate block material of PLGA coating after the drying.
Get the 2g half-H 2 O calcium sulphate, add the 1.5ml normal saline, mix homogeneously, get part of sulfuric acid calcium after 5 minutes and evenly be layered on mold bottom, above the calcium sulfate block material that above-mentioned PLGA is applied is placed on then, at last remaining calcium sulfate is inserted in the mould, take out after the molding, 60 ℃ of following ageings 6 hours, place vacuum drying oven dry, make the column sample.
Get the 0.4g hypromellose, be scattered in the 10.0ml distilled water, above-mentioned column sample is immersed in this solution, take out then and place on the turntable, make solvent evaporates, be placed on drying in the vacuum drying oven, can apply repeatedly, make that the hypromellose shell thickness is 0.10mm～0.30mm, promptly get the double-decker calcium sulfate block material of hypromellose external coating after the drying.
Get the 4g half-H 2 O calcium sulphate, add the 2.0ml normal saline, mix homogeneously, get part of sulfuric acid calcium after 3 minutes and evenly be layered on mold bottom, and with above-mentioned obtain above calcium sulfate block material is placed on, at last remaining calcium sulfate is inserted in the mould, take out after the molding, 40 ℃ of following ageings 18 hours, place vacuum drying oven dry, make cylindricality three-decker calcium sulfate material.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 8 months.
Above-mentioned coating reversed order can be changed the PLGA coating into the hypromellose coating, and changes the hypromellose coating into the PLGA coating.
The PLGA material of above-mentioned coating is replaceable to be polylactic acid, poly sebacic polyanhydride or poly butyric ester and copolymer thereof.
The hypromellose of above-mentioned coating is replaceable to be PLGA, sodium alginate or gelatin.
Example 5
Get the 1g half-H 2 O calcium sulphate, add the 0.6ml distilled water, mix homogeneously injected mould with calcium sulfate after 3 minutes, treated to take out after the sample molding, and is dry in vacuum drying oven 50 ℃ of following ageings 18 hours, makes the cuboid sample.
Get 0.2g polycaprolactone-ethylene glycol copolymer and 0.08g Polyethylene Glycol, be dissolved in the 5.0ml chloroformic solution, said sample is immersed in this polymer solution, take out then and place on the turntable, make solvent evaporates, be placed on drying in the vacuum drying oven, can apply repeatedly, make that the polymer shell layer thickness is 0.01mm～0.05mm, promptly get the calcium sulfate block material of polycaprolactone-polyethylene glycol coating after the drying.
Get the 2.1g half-H 2 O calcium sulphate, add the 0.9ml distilled water, mix homogeneously, get part of sulfuric acid calcium after 3 minutes and evenly be layered on mold bottom, above the calcium sulfate block material that above-mentioned polycaprolactone-polyethylene glycol is applied is placed on then, at last remaining calcium sulfate is inserted in the mould, take out after the molding, 60 ℃ of following ageings 10 hours, dry in vacuum drying oven, make the cuboid sample.
Get 0.6g chitosan and gelatin (weight ratio is 1:1), be dissolved in the acetum (10g) of 10.0ml1M, add glutaraldehyde (chitosan amount 0.5%), sample is immersed in this polymer solution, and taking-up places on the turntable then, makes solvent evaporates, be placed in the vacuum drying oven dry, can apply repeatedly, make that the polymer shell layer thickness is 0.10mm～0.25mm, promptly get the double-decker calcium sulfate block material of chitosan and gelatin external coating after the drying.
Get the 4g half-H 2 O calcium sulphate, add the 3.2ml distilled water, mix homogeneously, get part of sulfuric acid calcium after 5 minutes and evenly be layered on mold bottom, above then the above-mentioned coating calcium sulfate block material that obtains being placed on, at last remaining calcium sulfate is inserted in the mould, take out after the molding, 60 ℃ of following ageings 8 hours, dry in vacuum drying oven, make cuboid three-decker calcium sulfate material.The structure of material as shown in Figure 3, wherein 1 is the calcium sulfate polymeric layer, the 2nd, the polymeric layer of polycaprolactone-polyethylene glycol, the 3rd, the polymeric layer of chitosan and gelatin
Repeat above step, can prepare structure calcium sulfate material more than three layers.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 10 months.
Above-mentioned coating reversed order can be changed the polycaprolactone-polyethylene glycol coating into chitosan and gelatin coating, and changes chitosan and gelatin coating into the polycaprolactone-polyethylene glycol coating.
The polycaprolactone material of above-mentioned face coat is replaceable to be polylactic acid or PLGA (polylactic acid/ethanol copolymer).
The chitosan-gelatin of above-mentioned face coat is replaceable to be collagen or sodium alginate.
Case of comparative examples 1
Get 2g half-H 2 O calcium sulphate powder body, add the 0.5ml normal saline, mix homogeneously injected mould with calcium sulfate after 5 minutes, treated to take out after the sample molding, and is dry in vacuum drying oven 40 ℃ of following ageings 24 hours, makes cylindricality calcium sulfate sample.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 30 days.
Case of comparative examples 2
Get 6g half-H 2 O calcium sulphate powder body, add the 3.0ml normal saline, mix homogeneously injected mould with calcium sulfate after 3 minutes, treated to take out after the sample molding, and is dry in vacuum drying oven 60 ℃ of following ageings 12 hours, makes cuboid calcium sulfate sample.
The PBS solution of this style is placed 37 ℃ of baking ovens, and its degradation time is about 35 days.
From Comparative Examples as can be seen, degradation time of the present invention is long, and infiltration rate is adjustable simultaneously.
The present invention proposes absorption-rate adjustable calcium sulphate group bone-grafting material and preparation method, be described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to product as herein described with technical method is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (10)
1. an absorption-rate adjustable calcium sulphate group bone-grafting material comprises calcium sulfate and degradable polymer; It is characterized in that calcium sulphate layer is a kernel, polymeric layer and calcium sulphate solid layer are alternately arranged.
2. absorption-rate adjustable calcium sulphate group bone-grafting material as claimed in claim 1 is characterized in that described biodegradable polymer layer thickness is 0.01-0.5mm.
3. absorption-rate adjustable calcium sulphate group bone-grafting material as claimed in claim 1 is characterized in that described biodegradable polymer layer is with a kind of polymer or the blended mixture of two or more degradable polymer.
4. absorption-rate adjustable calcium sulphate group bone-grafting material as claimed in claim 1, the different layers that it is characterized in that described biodegradable polymer layer are identical degradable polymer or different degradable polymers.
5. the preparation method of the absorption-rate adjustable calcium sulphate group bone-grafting material of claim 1 is characterized in that step is as follows:
The A step: calcium sulfate is mixed with water, and the weight ratio of calcium sulfate and water is 9:1～5:4, and placed 1～5 minute the back that stirs, be injected into mould then, treat that sample condenses to take out after the molding, at 40-60 ℃ of following ageing 5-24 hour, dry in vacuum drying oven then, make sample;
B step: sample is placed on the turntable, polymer solution evenly is coated in specimen surface, be placed in the vacuum drying oven dry then; Perhaps sample is immersed in the polymer solution, taking-up places on the turntable then, makes solvent evaporates, is placed on drying in the vacuum drying oven, promptly gets the calcium sulfate material of polymer surface coating;
C step: calcium sulfate is fully mixed with water, the weight ratio of calcium sulfate and water is 9:1～5:4, back placement 1～5 minute stirs, a part of taking out wherein evenly is layered on mold bottom, and above the above-mentioned coating calcium sulfate block material that obtains is placed on, at last remaining calcium sulfate is inserted in the mould, take out after the molding, at 40-60 ℃ of following ageing 5-24 hour, dry in vacuum drying oven then, make double-deck calcium sulphate-based bone-grafting material.
6. preparation method as claimed in claim 5 is characterized in that described step B and step C repeated configuration, makes the calcium sulphate-based bone-grafting material of the adjustable multilamellar of infiltration rate.
7. preparation method as claimed in claim 5 is characterized in that described water comprises distilled water, deionized water or normal saline.
8. preparation method as claimed in claim 5 is characterized in that described calcium sulfate is half-H 2 O calcium sulphate.The weight ratio of described calcium sulfate and water is 7:3～4:3.
9. preparation method as claimed in claim 5 is characterized in that described polymer concentration is weight percentage 1%～10%.
10. preparation method as claimed in claim 5 is characterized in that described degradability polymer is natural biological degradable polymer or synthesized degradable polymer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150250593A1 (en) * | 2011-03-29 | 2015-09-10 | Smith & Nephew, Inc. | Fracture fixation systems having intramedullary support |
| CN112552035A (en) * | 2020-12-11 | 2021-03-26 | 湖北联结生物材料有限公司 | Inducible bioactive 3D printing ceramic and preparation method thereof |
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2008
- 2008-08-28 CN CNA2008100543394A patent/CN101391116A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150250593A1 (en) * | 2011-03-29 | 2015-09-10 | Smith & Nephew, Inc. | Fracture fixation systems having intramedullary support |
| US9585755B2 (en) * | 2011-03-29 | 2017-03-07 | Smith & Nephew, Inc. | Fracture fixation systems having intramedullary support |
| CN107260293A (en) * | 2011-03-29 | 2017-10-20 | 史密夫和内修有限公司 | Bone fracture fixation system with marrow inner support thing |
| CN112552035A (en) * | 2020-12-11 | 2021-03-26 | 湖北联结生物材料有限公司 | Inducible bioactive 3D printing ceramic and preparation method thereof |
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