CN104436296A - Preparation method of polylactic/hydroxyapatite composite biological ceramic material - Google Patents
Preparation method of polylactic/hydroxyapatite composite biological ceramic material Download PDFInfo
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- CN104436296A CN104436296A CN201410626618.9A CN201410626618A CN104436296A CN 104436296 A CN104436296 A CN 104436296A CN 201410626618 A CN201410626618 A CN 201410626618A CN 104436296 A CN104436296 A CN 104436296A
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- polylactic acid
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Abstract
The invention provides a preparation method of a polylactic/hydroxyapatite composite biological ceramic material. The preparation method comprises the following steps: (1) dissolving polylactic acid, a surfactant and a cosurfactant in an organic solvent to prepare an oil phase solution of polylactic acid; (2) respectively adding a calcium ion solution and a phosphate ion solution into the oil phase solution to prepare an emulsion and a phosphate ion emulsion, mixing the calcium ion emulsion with the phosphate ion emulsion and reacting for 12-24 hours at 25-40 DEG C to form a polylactic/hydroxyapatite mixed emulsion; and (3) volatilizing the organic solvent out of the mixed emulsion prepared in the step (2), washing, drying and sintering the obtained powder in a spark plasma sintering cavity. The composite biological ceramic material prepared by the invention is good in dispersibility, high in mechanical strength and relatively low in reaction temperature, and hydroxyapatite is not degraded, so that the composite biological ceramic material is high in bioavailability and safe to produce.
Description
Technical field
The present invention relates to technical field of biological material, be specifically related to a kind of preparation method of polylactic acid/hydroxy apatite composite bioceramic material.
Background technology
Cranial defect is a difficult problem medically always.Method ideal is at present autologous or homogeneous allogenic bone transplantation, and autologous bone transplanting is thought to weigh " goldstandard " of bone-graft fusion widely.Although autologous bone transplanting has many benefits, as adapted to the regeneration etc. of surrounding bone tissue, but still there are some drawbacks, as limited in autologous bone transplanting donor, there is secondary insult, increase operating difficulty, there is certain mortality etc.Allograph bone cannot stimulate skeletonization sometimes, and often brings out bad reaction, studies the problem that novel bone substitute products become medical personnel and material supplier author institute facing.
Hydroxyapatite is the main inorganic composition of people and animal skeleton, tooth, it is a kind of typical biomaterial, there is excellent biological activity and biocompatibility, can be formed with human body hard tissue at short notice after implant into body and combine closely, thus become the bone grafting succedaneum of extensive use, but in clinical practice simple using hydroxyapatite as hard tissue substituting and repair materials, its mechanical strength does not reach required intensity, and therefore the research of hydroxylapatite compound comes into one's own day by day.
Polylactic acid is a kind of novel high polymer material, because it has the advantages such as quality is light, plasticity is strong, anti-fatigue performance is good, therefore has wide market prospect, as can extruding, injection moulding, automobile, multiple fields application such as biological medicine.But polylactic acid also exists many deficiencies in mechanical property, as: modulus of compressibility is little, softening point is lower, degradation time is longer, and these deficiencies limit its application in many aspects.So the performance how improving polylactic acid just becomes large focus and a difficult point of current research.
Therefore, take polylactic acid as substrate, hydroxyapatite is reinforcing agent, prepare polylactic acid/hydroxy apatite composite bioceramic material to be expected to obtain the good biological activity of existing hydroxyapatite and biocompatibility, have again the mechanical strength of polylactic acid and the composite of degradability.
At present, the preparation method of the composite of the hydroxyapatite of report mainly contains: melt-blending process, solution casting method and in-situ compositing etc.Melt-blending process is simple to operation, but has certain viscosity due to polymer, and filler particles is difficult to fully disperse at base internal, and cause distribution of particles uneven, boundary strength is low; In-situ compositing can improve boundary strength preferably, but easily remains reaction impurities, affects properties of product; Solution casting method selects suitable solvent, adds nano inorganic granule in polymer body solution, and except desolventizing after fully disperseing, the composite dispersibility obtained is better, but relative density is low, and performance can not be guaranteed.
Summary of the invention
Based on above-mentioned information, the object of the present invention is to provide a kind of solution casting method that adopts to prepare ceramic powder, and in conjunction with the method for discharge plasma sintering, prepare good dispersion, polylactic acid/hydroxy apatite composite bioceramic material that intensity is high.
The technical scheme of the preparation method of polylactic acid/hydroxy apatite composite bioceramic material of the present invention is as follows:
A preparation method for polylactic acid/hydroxy apatite composite bioceramic material, comprises the steps:
(1), polylactic acid, surfactant and cosurfactant are dissolved in organic solvent the oil-phase solution being mixed with polylactic acid;
(2), ionic calcium soln and phosphate anion solution are joined respectively preparation in the oil-phase solution that step (1) prepares and form calcium ion emulsion and phosphate anion emulsion, by calcium ion emulsion and phosphate anion emulsion mixing, react 12 ~ 24 hours at 25 ~ 40 DEG C, form the mixed emulsion of polylactic acid/hydroxy apatite;
(3) organic solvent in mixed emulsion prepared by step (2), is vapored away, washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 10 ~ 30MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 50Pa, programming rate is 20 ~ 60 DEG C/min, when temperature is increased to 500 ~ 560 DEG C, start discharge plasma sintering and keep 2 ~ 8 minutes, sintering complete, stopping heating and removal pressure, cool to room temperature with the furnace, obtain polylactic acid/hydroxy apatite composite bioceramic material.
In step (1), the mass ratio of described polylactic acid, surfactant and cosurfactant is 55 ~ 85:11 ~ 14:1.
The relative molecular mass of described polylactic acid is 10000 ~ 80000.
Described surfactant is one or more in glyceryl monostearate, methyl glycol fatty acid ester, polysorbate60 or Tween 80.
Described cosurfactant is one or more in normal propyl alcohol, isopropyl alcohol, hexanol or n-heptanol.
Described organic solvent is one or more in 1,2-dichloroethanes, dichloromethane, oxolane or acetone.
Beneficial effect of the present invention is: the ceramic powder being prepared good dispersion by solution casting method, and the method for recycling discharge plasma sintering, improves the mechanical strength of pottery, and reaction temperature is relatively low, non-degradable hydroxyapatite, bioavailability is higher, and production industry is safer.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.
Embodiment 1
(1), polylactic acid 10g, glyceryl monostearate 5g and normal propyl alcohol 1g are dissolved into the oil-phase solution being mixed with polylactic acid in 1,2-dichloroethanes 50mL, seal for subsequent use;
(2), the dipotassium hydrogen phosphate solution 2mL of calcium nitrate solution 2mL and 3mol/L being dissolved with the 6mol/L of 0.1gNaOH is respectively joined respectively preparation in the oil-phase solution that 25mL step (1) prepares and form calcium ion emulsion and phosphate anion emulsion, by calcium ion emulsion and phosphate anion emulsion mixing, react 12 hours at 25 DEG C, form the mixed emulsion of polylactic acid/hydroxy apatite;
(3), 1 in mixed emulsion prepared by step (2) is vapored away in fume hood, 2-dichloroethanes, washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 10MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 50Pa, programming rate is 20 DEG C/min, when temperature is increased to 500 DEG C, start discharge plasma sintering and keep 2 minutes, sinter complete, stop heating and removal pressure, cool to room temperature with the furnace, obtain polylactic acid/hydroxy apatite composite bioceramic material, its Young's modulus is 58GPa, fracture toughness is 2.08MPam
1/2, density is 95%.
Embodiment 2
(1), by polylactic acid 30g, methyl glycol fatty acid ester 8g and isopropyl alcohol 1g be dissolved into the oil-phase solution being mixed with polylactic acid in dichloromethane 100mL, seal for subsequent use;
(2), the dipotassium hydrogen phosphate solution 6mL of calcium nitrate solution 6mL and 3mol/L being dissolved with the 6mol/L of 0.5gNaOH is respectively joined respectively preparation in the oil-phase solution that 50mL step (1) prepares and form calcium ion emulsion and phosphate anion emulsion, by calcium ion emulsion and phosphate anion emulsion mixing, react 16 hours at 30 DEG C, form the mixed emulsion of polylactic acid/hydroxy apatite;
(3), the dichloromethane in mixed emulsion prepared by step (2) is vapored away in fume hood, washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 20MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 50Pa, programming rate is 30 DEG C/min, when temperature is increased to 520 DEG C, start discharge plasma sintering and keep 4 minutes, sinter complete, stop heating and removal pressure, cool to room temperature with the furnace, obtain polylactic acid/hydroxy apatite composite bioceramic material, its Young's modulus is 62GPa, fracture toughness is 2.31MPam
1/2, density is 96%.
Embodiment 3
(1), by polylactic acid 60g, polysorbate60 12g and hexanol 1g be dissolved into the oil-phase solution being mixed with polylactic acid in oxolane 200mL, seal for subsequent use;
(2), the dipotassium hydrogen phosphate solution 12mL of calcium nitrate solution 12mL and 3mol/L being dissolved with the 6mol/L of 1gNaOH is respectively joined respectively preparation in the oil-phase solution that 100mL step (1) prepares and form calcium ion emulsion and phosphate anion emulsion, by calcium ion emulsion and phosphate anion emulsion mixing, react 20 hours at 35 DEG C, form the mixed emulsion of polylactic acid/hydroxy apatite;
(3), the oxolane in mixed emulsion prepared by step (2) is vapored away in fume hood, washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 20MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 50Pa, programming rate is 50 DEG C/min, when temperature is increased to 540 DEG C, start discharge plasma sintering and keep 6 minutes, sinter complete, stop heating and removal pressure, cool to room temperature with the furnace, obtain polylactic acid/hydroxy apatite composite bioceramic material, its Young's modulus is 63GPa, fracture toughness is 2.23MPam
1/2, density is 97%.
Embodiment 4
(1), by polylactic acid 100g, Tween 80 15g and n-heptanol 1g be dissolved into the oil-phase solution being mixed with polylactic acid in acetone 400mL, seal for subsequent use;
(2), the dipotassium hydrogen phosphate solution 25mL of calcium nitrate solution 25mL and 3mol/L being dissolved with the 6mol/L of 5gNaOH is respectively joined respectively preparation in the oil-phase solution that 200mL step (1) prepares and form calcium ion emulsion and phosphate anion emulsion, by calcium ion emulsion and phosphate anion emulsion mixing, react 24 hours at 40 DEG C, form the mixed emulsion of polylactic acid/hydroxy apatite;
(3), the acetone in mixed emulsion prepared by step (2) is vapored away in fume hood, washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 30MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 50Pa, programming rate is 60 DEG C/min, when temperature is increased to 560 DEG C, start discharge plasma sintering and keep 8 minutes, sinter complete, stop heating and removal pressure, cool to room temperature with the furnace, obtain polylactic acid/hydroxy apatite composite bioceramic material, its Young's modulus is 62GPa, fracture toughness is 2.40MPam
1/2, density is 98%.
Although embodiment of the present invention are open as above, but it is not restricted to listed in description and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the general concept that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (6)
1. a preparation method for polylactic acid/hydroxy apatite composite bioceramic material, is characterized in that, comprises the steps:
(1), polylactic acid, surfactant and cosurfactant are dissolved in organic solvent the oil-phase solution being mixed with polylactic acid;
(2), ionic calcium soln and phosphate anion solution are joined respectively preparation in the oil-phase solution that step (1) prepares and form calcium ion emulsion and phosphate anion emulsion, by calcium ion emulsion and phosphate anion emulsion mixing, react 12 ~ 24 hours at 25 ~ 40 DEG C, form the mixed emulsion of polylactic acid/hydroxy apatite;
(3) organic solvent in mixed emulsion prepared by step (2), is vapored away, washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 10 ~ 30MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 50Pa, programming rate is 20 ~ 60 DEG C/min, when temperature is increased to 500 ~ 560 DEG C, start discharge plasma sintering and keep 2 ~ 8 minutes, sintering complete, stopping heating and removal pressure, cool to room temperature with the furnace, obtain polylactic acid/hydroxy apatite composite bioceramic material.
2. the preparation method of a kind of polylactic acid/hydroxy apatite composite bioceramic material according to claim 1, is characterized in that, in step (1), the mass ratio of described polylactic acid, surfactant and cosurfactant is 55 ~ 85:11 ~ 14:1.
3. the preparation method of a kind of polylactic acid/hydroxy apatite composite bioceramic material according to claim 2, is characterized in that, the relative molecular mass of described polylactic acid is 10000 ~ 80000.
4. the preparation method of a kind of polylactic acid/hydroxy apatite composite bioceramic material according to claim 2, it is characterized in that, described surfactant is one or more in glyceryl monostearate, methyl glycol fatty acid ester, polysorbate60 or Tween 80.
5. the preparation method of a kind of polylactic acid/hydroxy apatite composite bioceramic material according to claim 2, is characterized in that, described cosurfactant is one or more in normal propyl alcohol, isopropyl alcohol, hexanol or n-heptanol.
6. the preparation method of a kind of polylactic acid/hydroxy apatite composite bioceramic material according to claim 1, is characterized in that, described organic solvent is one or more in 1,2-dichloroethanes, dichloromethane, oxolane or acetone.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382660A (en) * | 2002-06-19 | 2002-12-04 | 北京工业大学 | Composite Ti-HA material and its preparing process |
| CN1544524A (en) * | 2003-11-17 | 2004-11-10 | 中国科学院长春应用化学研究所 | Method for preparing hydroxyapatite biodegradable aliphatic polyester composite material |
| CN101249410A (en) * | 2008-04-10 | 2008-08-27 | 华东理工大学 | Preparation of organic-inorganic composite microballoons |
| US8420774B2 (en) * | 2009-12-01 | 2013-04-16 | Wisconsin Alumni Research Foundation | Decorating hydroxyapatite biomaterials with modular biologically active molecules |
| CN103087485A (en) * | 2013-01-28 | 2013-05-08 | 河南师范大学 | Preparation method of hydroxyapatite/polylactic acid composite material |
-
2014
- 2014-11-10 CN CN201410626618.9A patent/CN104436296A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382660A (en) * | 2002-06-19 | 2002-12-04 | 北京工业大学 | Composite Ti-HA material and its preparing process |
| CN1544524A (en) * | 2003-11-17 | 2004-11-10 | 中国科学院长春应用化学研究所 | Method for preparing hydroxyapatite biodegradable aliphatic polyester composite material |
| CN101249410A (en) * | 2008-04-10 | 2008-08-27 | 华东理工大学 | Preparation of organic-inorganic composite microballoons |
| US8420774B2 (en) * | 2009-12-01 | 2013-04-16 | Wisconsin Alumni Research Foundation | Decorating hydroxyapatite biomaterials with modular biologically active molecules |
| CN103087485A (en) * | 2013-01-28 | 2013-05-08 | 河南师范大学 | Preparation method of hydroxyapatite/polylactic acid composite material |
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