CN104383594B - A kind of preparation method of polybutylene succinate/hydroxylapatite composite biological ceramic material - Google Patents
A kind of preparation method of polybutylene succinate/hydroxylapatite composite biological ceramic material Download PDFInfo
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- CN104383594B CN104383594B CN201410626783.4A CN201410626783A CN104383594B CN 104383594 B CN104383594 B CN 104383594B CN 201410626783 A CN201410626783 A CN 201410626783A CN 104383594 B CN104383594 B CN 104383594B
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Abstract
The preparation method that the present invention provides a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material, comprises the steps: (1), is dissolved in organic solvent by polybutylene succinate, surfactant and cosurfactant to be configured to the oil-phase solution of polybutylene succinate；(2), ionic calcium soln and phosphate anion solution are added separately in oil-phase solution and prepare formation emulsion and phosphate anion emulsion, calcium ion emulsion and phosphate anion emulsion are mixed, react 24 ~ 48 hours at 20 ~ 50 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite；(3), the organic solvent vapored away in mixed emulsion, washing, dry, gained powder body is put into discharge plasma sintering intracavity and is sintered.Composite bioceramic material good dispersion, mechanical strength that the present invention prepares are high, and reaction temperature is relatively low, non-degradable hydroxyapatite, and bioavailability is higher, produces industry safer.
Description
Technical field
The present invention relates to technical field of biological material, the preparation method being specifically related to a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material.
Background technology
Cranial defect is always up a difficult problem medically.Method ideal at present is 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 bone tissue, but still suffer from some drawbacks, as limited in autologous bone transplanting donor, secondary insult occurs, increases operating difficulty, there is certain mortality etc..Allograph bone cannot stimulate skeletonization sometimes, and often brings out bad reaction, and studying novel bone substitute products becomes medical personnel and the problem of material supplier author institute facing.
Hydroxyapatite is people and the main inorganic composition of animal skeleton, tooth, it 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 implanting human body and combine closely, thus becoming wide variety of bone grafting succedaneum, 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 is increasingly subject to pay attention to.
Polybutylene succinate, it is 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 forming 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 relatively low.
Therefore, with polybutylene succinate be substrate, hydroxyapatite is for 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 has: melt-blending process, solution casting method and in-situ compositing etc..Melt-blending process is simple to operation, but owing to polymer has certain viscosity, filler particles is difficult at base internal fully dispersed, causes that distribution of particles is uneven, and boundary strength is low；In-situ compositing can improve boundary strength preferably, but easily remains reaction impurities, affects properties of product；Solution casting method is to select suitable solvent, adds nano inorganic granule in polymer body solution, removes solvent after fully dispersed, and 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, it is an object of the invention to provide and a kind of adopt solution casting method 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 the polybutylene succinate/hydroxylapatite composite biological ceramic material of the present invention is as follows:
The preparation method of a kind of polybutylene succinate/hydroxylapatite composite biological ceramic material, comprises the steps:
(1), it is dissolved in organic solvent by polybutylene succinate, surfactant and cosurfactant to be configured to the oil-phase solution of polybutylene succinate；
(2), ionic calcium soln and phosphate anion solution are added separately in the oil-phase solution that step (1) is prepared and prepare formation calcium ion emulsion and phosphate anion emulsion, calcium ion emulsion and phosphate anion emulsion are mixed, 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, begin to warm up when agglomerating chamber's pressure reaches 80Pa time, 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 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.
The invention have the benefit that the ceramic powder being prepared good dispersion by solution casting method, the method for recycling discharge plasma sintering, improve the mechanical strength of pottery, and reaction temperature is relatively low, non-degradable hydroxyapatite, bioavailability is higher, produces industry safer.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail.
Embodiment 1
(1), polybutylene succinate 10g, glyceryl monostearate 5g and n-butyl alcohol 1g are dissolved into the oil-phase solution being configured to polybutylene succinate in methanol 50mL, seal standby；
(2), will be added separately in the oil-phase solution that 25mL step (1) is prepared to prepare formation calcium ion emulsion and phosphate anion emulsion dissolved with the dipotassium hydrogen phosphate solution 2mL of calcium nitrate solution 2mL and the 3mol/L of the 6mol/L of 0.1gNaOH respectively, calcium ion emulsion and phosphate anion emulsion are mixed, react 48 hours at 20 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite；
(3), fume hood vapors away the methanol in mixed emulsion prepared by step (2), washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 70MPa is applied at two ends, evacuation, begin to warm up when agglomerating chamber's pressure reaches 80Pa time, 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 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 1.89MPa m1/2, consistency is 92%.
Embodiment 2
(1), polybutylene succinate 30g, sorbitan sesquioleate 8g and isoamyl alcohol 1g are dissolved into the oil-phase solution being configured to polybutylene succinate in dichloromethane 100mL, seal standby；
(2), will be added separately in the oil-phase solution that 50mL step (1) is prepared to prepare formation calcium ion emulsion and phosphate anion emulsion dissolved with the dipotassium hydrogen phosphate solution 6mL of calcium nitrate solution 6mL and the 3mol/L of the 6mol/L of 0.5gNaOH respectively, calcium ion emulsion and phosphate anion emulsion are mixed, react 36 hours at 30 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite；
(3), fume hood vapors away the dichloromethane in mixed emulsion prepared by step (2), washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 80MPa is applied at two ends, evacuation, begin to warm up when agglomerating chamber's pressure reaches 80Pa time, 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 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 2.02MPa m1/2, consistency is 94%.
Embodiment 3
(1), polybutylene succinate 60g, methyl glycol fatty acid ester 12g and normal propyl alcohol 1g are dissolved into the oil-phase solution being configured to polybutylene succinate in dioxane 200mL, seal standby；
(2), will be added separately in the oil-phase solution that 100mL step (1) is prepared to prepare formation calcium ion emulsion and phosphate anion emulsion dissolved with the dipotassium hydrogen phosphate solution 12mL of calcium nitrate solution 12mL and the 3mol/L of the 6mol/L of 1gNaOH respectively, calcium ion emulsion and phosphate anion emulsion are mixed, react 30 hours at 40 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite；
(3), fume hood vapors away the dioxane in mixed emulsion prepared by step (2), washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 80MPa is applied at two ends, evacuation, begin to warm up when agglomerating chamber's pressure reaches 80Pa time, 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 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 2.11MPa m1/2, consistency is 96%.
Embodiment 4
(1), polybutylene succinate 100g, dioctyl sodium sulfosuccinate 15g and hexanol 1g are dissolved into the oil-phase solution being configured to polybutylene succinate in acetonitrile 400mL, seal standby；
(2), will be added separately in the oil-phase solution that 200mL step (1) is prepared to prepare formation calcium ion emulsion and phosphate anion emulsion dissolved with the dipotassium hydrogen phosphate solution 25mL of calcium nitrate solution 25mL and the 3mol/L of the 6mol/L of 5gNaOH respectively, calcium ion emulsion and phosphate anion emulsion are mixed, react 24 hours at 50 DEG C, form the mixed emulsion of polybutylene succinate/hydroxyapatite；
(3), fume hood vapors away the acetonitrile in mixed emulsion prepared by step (2), washing, dry, gained powder body is put into discharge plasma sintering intracavity, the axial compressive force of 90MPa is applied at two ends, evacuation, begin to warm up when agglomerating chamber's pressure reaches 80Pa time, 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 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 2.53MPa m1/2, consistency is 95%.
Although embodiment of the present invention are disclosed as above, but listed utilization that it is not restricted in description and embodiment, it can be applied to various applicable the field of the invention completely, for those skilled in the art, it is easily achieved other amendment, therefore, under the general concept limited without departing substantially from claim and equivalency range, the present invention is not limited to specific details.
Claims (6)
1. the preparation method of polybutylene succinate/hydroxylapatite composite biological ceramic material, it is characterised in that comprise the steps:
(1), it is dissolved in organic solvent by polybutylene succinate, surfactant and cosurfactant to be configured to the oil-phase solution of polybutylene succinate；
(2), ionic calcium soln and phosphate anion solution are added separately in the oil-phase solution that step (1) is prepared and prepare formation calcium ion emulsion and phosphate anion emulsion, calcium ion emulsion and phosphate anion emulsion are mixed, 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, begin to warm up when agglomerating chamber's pressure reaches 80Pa time, 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 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, it is characterised 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, it is characterised 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, it is characterised in that described organic solvent is one or more in methanol, dichloromethane, dioxane or acetonitrile.
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| 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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| 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 |
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