CN104383594A - Preparation method of polybutylene succinate/hydroxyapatite composite biological ceramic material - Google Patents
Preparation method of polybutylene succinate/hydroxyapatite composite biological ceramic material Download PDFInfo
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- CN104383594A CN104383594A CN201410626783.4A CN201410626783A CN104383594A CN 104383594 A CN104383594 A CN 104383594A CN 201410626783 A CN201410626783 A CN 201410626783A CN 104383594 A CN104383594 A CN 104383594A
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Abstract
The invention provides a preparation method of a polybutylene succinate/hydroxyapatite composite biological ceramic material. The preparation method comprises the following steps: (1) dissolving polybutylene succinate, surfactants and cosurfactants in organic solvents to prepare oil phase solutions of polybutylene succinate; (2) respectively adding calcium ion solutions and phosphate ion solutions to the oil phase solutions to prepare calcium ion emulsions and phosphate ion emulsions, mixing the calcium ion emulsions with the phosphate ion emulsions, and reacting at 20-50 DEG C for 24-48 hours to form a mixed emulsion of polybutylene succinate/hydroxyapatite; (3) volatilizing the organic solvents in the mixed emulsion, washing and drying the mixed emulsion, and putting the obtained powder in a spark plasma sintering cavity to be sintered. The prepared composite biological ceramic material has the beneficial effects that the composite biological ceramic material has good dispersibility and high mechanical strength; the reaction temperature is relatively low, and hydroxyapatite can not be degraded, so that the composite biological ceramic material has higher bioavailability and is safer in production.
Description
Technical field
The present invention relates to technical field of biological material, be specifically related to a kind of preparation method of polybutylene succinate/hydroxylapatite composite biological ceramic 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.
Polybutylene succinate, the outstanding person in biodegradable plastic material, excellent in mechanical performance, close to polypropylene (PP) and acrylonitrile-butadiene-styrene copolymer plastics, heat resistance is good, and heat distortion temperature is close to 100 DEG C, overcome the heat labile shortcoming of other biological degradative plastics, processing characteristics is very good, can carry out all kinds of formed machining on existing plastic processing common apparatus, is that in current degradative plastics, processing characteristics is best; But still come with some shortcomings, as fragility is high, heat distortion temperature is lower.
Therefore, take polybutylene succinate as substrate, hydroxyapatite is reinforcing agent, preparation polybutylene succinate/hydroxylapatite composite biological ceramic material is expected to obtain the good biological activity of existing hydroxyapatite and biocompatibility, has again the mechanical strength of polybutylene succinate 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, a kind of solution casting method that adopts is the object of the present invention is to provide to prepare ceramic powder, and in conjunction with the method for discharge plasma sintering, prepare good dispersion, polybutylene succinate/hydroxylapatite composite biological ceramic material that intensity is high.
The technical scheme of the preparation method of polybutylene succinate/hydroxylapatite composite biological ceramic material of the present invention is as follows:
A preparation method for polybutylene succinate/hydroxylapatite composite biological ceramic material, comprises the steps:
(1), polybutylene succinate, surfactant and cosurfactant are dissolved in organic solvent the oil-phase solution being mixed with polybutylene succinate;
(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 24 ~ 48 hours at 20 ~ 50 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite;
(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 70 ~ 90MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 80Pa, programming rate is 10 ~ 40 DEG C/min, when temperature is increased to 350 ~ 380 DEG C, start discharge plasma sintering and keep 2 ~ 10 minutes, sintering complete, stopping heating and removal pressure, cool to room temperature with the furnace, obtain polybutylene succinate/hydroxylapatite composite biological ceramic material.
In step (1), the mass ratio of described polybutylene succinate, surfactant and cosurfactant is 10 ~ 100: 5 ~ 15: 1.
The relative molecular mass of described polybutylene succinate is 10000 ~ 60000.
Described surfactant is one or more in glyceryl monostearate, sorbitan sesquioleate, methyl glycol fatty acid ester or dioctyl sodium sulfosuccinate.
Described cosurfactant is one or more in n-butyl alcohol, isoamyl alcohol, normal propyl alcohol or n-heptanol.
Described organic solvent is one or more in methanol, dichloromethane, dioxane or acetonitrile.
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), by polybutylene succinate 10g, glyceryl monostearate 5g and n-butyl alcohol 1g be dissolved into the oil-phase solution being mixed with polybutylene succinate in methanol 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 48 hours at 20 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite;
(3), the methanol 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 70MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 80Pa, programming rate is 10 DEG C/min, when temperature is increased to 350 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 polybutylene succinate/hydroxylapatite composite biological ceramic material, its Young's modulus is 54GPa, fracture toughness is 1.89MPam
1/2, density is 92%.
Embodiment 2
(1), by polybutylene succinate 30g, sorbitan sesquioleate 8g and isoamyl alcohol 1g be dissolved into the oil-phase solution being mixed with polybutylene succinate 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 36 hours at 30 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite;
(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 80MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 80Pa, programming rate is 20 DEG C/min, when temperature is increased to 360 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 polybutylene succinate/hydroxylapatite composite biological ceramic material, its Young's modulus is 58GPa, fracture toughness is 2.02MPam
1/2, density is 94%.
Embodiment 3
(1), by polybutylene succinate 60g, methyl glycol fatty acid ester 12g and normal propyl alcohol 1g be dissolved into the oil-phase solution being mixed with polybutylene succinate in dioxane 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 30 hours at 40 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite;
(3), the dioxane 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 80MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 80Pa, programming rate is 30 DEG C/min, when temperature is increased to 370 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 polybutylene succinate/hydroxylapatite composite biological ceramic material, its Young's modulus is 54GPa, fracture toughness is 2.11MPam
1/2, density is 96%.
Embodiment 4
(1), by polybutylene succinate 100g, dioctyl sodium sulfosuccinate 15g and hexanol 1g be dissolved into the oil-phase solution being mixed with polybutylene succinate in acetonitrile 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 50 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite;
(3), the acetonitrile 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 90MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 80Pa, programming rate is 40 DEG C/min, when temperature is increased to 380 DEG C, start discharge plasma sintering and keep 10 minutes, sinter complete, stop heating and removal pressure, cool to room temperature with the furnace, obtain polybutylene succinate/hydroxylapatite composite biological ceramic material, its Young's modulus is 56GPa, fracture toughness is 2.53MPam
1/2, density is 95%.
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 polybutylene succinate/hydroxylapatite composite biological ceramic material, is characterized in that, comprises the steps:
(1), polybutylene succinate, surfactant and cosurfactant are dissolved in organic solvent the oil-phase solution being mixed with polybutylene succinate;
(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 24 ~ 48 hours at 20 ~ 50 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite;
(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 70 ~ 90MPa is applied at two ends, evacuation, heating is started when agglomerating chamber's pressure reaches 80Pa, programming rate is 10 ~ 40 DEG C/min, when temperature is increased to 350 ~ 380 DEG C, start discharge plasma sintering and keep 2 ~ 10 minutes, sintering complete, stopping heating and removal pressure, cool to room temperature with the furnace, obtain polybutylene succinate/hydroxylapatite composite biological ceramic material.
2. the preparation method of a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material according to claim 1, it is characterized in that, in step (1), the mass ratio of described polybutylene succinate, surfactant and cosurfactant is 10 ~ 100:5 ~ 15:1.
3. the preparation method of a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material according to claim 2, is characterized in that, the relative molecular mass of described polybutylene succinate is 10000 ~ 60000.
4. the preparation method of a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material according to claim 2, it is characterized in that, described surfactant is one or more in glyceryl monostearate, sorbitan sesquioleate, methyl glycol fatty acid ester or dioctyl sodium sulfosuccinate.
5. the preparation method of a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material according to claim 2, is characterized in that, described cosurfactant is one or more in n-butyl alcohol, isoamyl alcohol, normal propyl alcohol or n-heptanol.
6. the preparation method of a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material according to claim 1, is characterized in that, described organic solvent is one or more in methanol, dichloromethane, dioxane or acetonitrile.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743886A (en) * | 2015-03-31 | 2015-07-01 | 苏州维泰生物技术有限公司 | Bioactive glass ceramic and preparation method thereof |
| CN104829217A (en) * | 2015-03-31 | 2015-08-12 | 苏州维泰生物技术有限公司 | Corrosion resistant alumina ceramic and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101052360A (en) * | 2003-09-23 | 2007-10-10 | 奥斯治疗有限公司 | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
| CN101756908A (en) * | 2010-01-25 | 2010-06-30 | 沈阳药科大学 | Hydroxyapatite micro-sphere with polyester coating and preparation method thereof |
| US8420774B2 (en) * | 2009-12-01 | 2013-04-16 | Wisconsin Alumni Research Foundation | Decorating hydroxyapatite biomaterials with modular biologically active molecules |
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2014
- 2014-11-10 CN CN201410626783.4A patent/CN104383594B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101052360A (en) * | 2003-09-23 | 2007-10-10 | 奥斯治疗有限公司 | Absorbable implants and methods for their use in hemostasis and in the treatment of osseous defects |
| 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 |
| US8420774B2 (en) * | 2009-12-01 | 2013-04-16 | Wisconsin Alumni Research Foundation | Decorating hydroxyapatite biomaterials with modular biologically active molecules |
| CN101756908A (en) * | 2010-01-25 | 2010-06-30 | 沈阳药科大学 | Hydroxyapatite micro-sphere with polyester coating and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743886A (en) * | 2015-03-31 | 2015-07-01 | 苏州维泰生物技术有限公司 | Bioactive glass ceramic and preparation method thereof |
| CN104829217A (en) * | 2015-03-31 | 2015-08-12 | 苏州维泰生物技术有限公司 | Corrosion resistant alumina ceramic and preparation method thereof |
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