CN103641466A - Preparation method of porous calcium polyphosphate biological material - Google Patents
Preparation method of porous calcium polyphosphate biological material Download PDFInfo
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- CN103641466A CN103641466A CN201310727005.XA CN201310727005A CN103641466A CN 103641466 A CN103641466 A CN 103641466A CN 201310727005 A CN201310727005 A CN 201310727005A CN 103641466 A CN103641466 A CN 103641466A
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- monocalcium phosphate
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Abstract
The invention relates to a preparation method of a porous calcium polyphosphate biological material, belonging to the field of biomedical materials. The preparation method comprises the following steps: (1) calcining calcium dihydrogen phosphate; (2) uniformly mixing the calcined calcium dihydrogen phosphate with a proper amount of un-calcined calcium dihydrogen phosphate; and (3) sintering the mixture obtained in the step (2) at a high temperature. In the preparation method provided by the invention, based on the characteristic of high-temperature condensation polymerization, the calcium dihydrogen phosphate is poly-condensed to form pores, thus forming a porous calcium polyphosphate biological material for bone repair, thereby avoiding the introduction of other impurities and guaranteeing the purity of the material to the greatest extent.
Description
Technical field
The present invention relates to stephanoporate calcium polyphosphate biomaterial preparation method, belong to biomedical materials field.
Background technology
Damaged very common clinically because of joint cartilage and bone that all multi-pathogenesis such as wound, tumour, infection, congenital disorders cause, its reparation is one of difficult problem of international Osteopathic Medicine always.For a long time, bone defect repair is mainly taked autologous or allogenic bone transplantation, but autologous bone transplanting exists serious defect aspect material source, to patient, increases extra wound and cost, get bony site pathology may occur, and available autologous bone source is very limited.Heteroplastic transplantation aspect, quite difficult, expensive aspect material screening, processing, storage, also easily produce immunological rejection, and may cause the problems such as introducing of pathogeny, operative failure rate is higher.
Calcium orthophosphate base biomaterial has similar composition to the mineral in bone, and possesses good biological degradability, biological activity and osteoconductive, can by moulding, sintering process be prepared into and bone photo like the high strength support of functional structure, implant calcium phosphorus product after degraded and can be used as raw material and rebuild for new bone by scleroblast.Therefore, the calcium phosphate ceramic material that hydroxyapatite (HA), β tricalcium phosphate (β-TCP) be representative of take becomes the study hotspot of bio-medical material, and in recent years, has obtained part marketization development achievement.
After calcium orthophosphate base material is studied and is applied by biomedical boundary, calcium polyphosphate (CPP) is also studied and confirm it is a kind of new type bone tissue engineering material that has biological activity, controllable biodegradable and higher force to learn performance gradually, cause in recent years extensive concern both domestic and external, become engineering material of bone tissue of new generation.The preparation of porous C PP is mainly adopted at present the preparation technology of melting → wire drawing → shrend → oven dry → ethanol wet-milling → interpolation pore-forming material moulding → sintering both at home and abroad, the deficiency of this mode is: easily material is polluted, cause purity not reach medical rank; Sintering schedule is also because of influencing each other between uncontrollable polyreaction, crystal conversion temperature and material vesicular structure, and causes failing to obtain desirable material property, limited CPP material carrying out in clinical study and application aspect.
Summary of the invention
According to above the deficiencies in the prior art, the object of the invention is to: a kind of stephanoporate calcium polyphosphate biomaterial preparation method is provided, simple, fully meet pure, the stable medical requirement of material.
Stephanoporate calcium polyphosphate biomaterial preparation method of the present invention, comprises the steps:
(1) calcining monocalcium phosphate;
(2) by the monocalcium phosphate after calcining with do not calcine in right amount monocalcium phosphate and mix;
(3) mixture step 2 being obtained is sintering at high temperature.
In step 1, monocalcium phosphate calcining temperature is 300～500 ℃.
In step 1, monocalcium phosphate calcining temperature is 650～750 ℃.
Monocalcium phosphate in step 2 after calcining with not calcine monocalcium phosphate mass ratio be 1:(0～3).
Monocalcium phosphate in step 2 after calcining with not calcine monocalcium phosphate mass ratio be 1:(0.5～4).
Soaking time is 1～2 hour.
The mixture that step 2 is obtained grinds, and the powder after grinding sieves, and gets the powder that particle diameter is 100～500 μ m, puts into crucible compacting, is then heated to be incubated 1～2 hour under 950～970 ℃ of conditions.
Monocalcium phosphate molecular formula is Ca (H
2pO
4)
2, its chemical equation of at high temperature calcining is as follows:
Experimental data shows, monocalcium phosphate, after 300～500 ℃ or 650～750 ℃ of calcinings, has obvious weightlessness, and this is mainly due to monocalcium phosphate generation polycondensation, and the crystal water in it runs off and causes rapidly.After the crystal water loss in early stage, because whole reaction system is still solid-state, the water in it can not volatilize completely, makes calcium polyphosphate that DeR occur simultaneously, the inverse process that its reaction process is above-mentioned reaction:
After monocalcium phosphate calcining certain hour, reaction reaches balance, no longer has obvious weightlessness.The appropriate monocalcium phosphate of not calcining is mixed, grinds, sieved with the monocalcium phosphate after calcining, mixture is heated to be incubated 1～2 hour under 950～970 ℃ of conditions, monocalcium phosphate after calcining and do not calcine monocalcium phosphate and polycondensation occurs be simultaneously converted into calcium polyphosphate, because weightless degree is different, both mix and react after generate stephanoporate calcium polyphosphate, the porosity of calcium polyphosphate can be controlled by grinding the particle diameter of rear powder.
The present invention utilizes the characteristic of monocalcium phosphate high-temperature polycondensation, makes himself polycondensation pore-forming form bone reparation stephanoporate calcium polyphosphate biomaterial.Avoid like this introducing of other impurity, can guarantee to greatest extent the pure of material.Thereby make this material only contain the skeletonization elements such as calcium, phosphorus, can be used as He Lin source, calcium source stable in new osteogenesis, fully met medically pure, stable requirement.And the particle diameter that can grind powder by control is controlled the aperture, inside of final calcium polyphosphate biomaterial, can better meet various cells, the growth of blood vessel, thus it is damaged to repair better various bones.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
Calcining monocalcium phosphate:
Weigh in the balance and get Powdered monocalcium phosphate 300g, put into quartz crucible, put into electric furnace after adding a cover protection, with the speed of 4 ℃/m, be warming up to 350 ℃, be incubated naturally cooling after 1～2 hour, thereby obtain the calcining material of loose bulk.This calcining material, with after mortar or ball mill crushing, is put into loft drier standby.
By the monocalcium phosphate after calcining with do not calcine in right amount monocalcium phosphate and mix:
Take respectively calcining material 80g, Powdered monocalcium phosphate 20g, after mixing, is used ball mill dry ball milling 1 minute, and the powder making is crossed to 40 orders and 80 mesh sieves, gets the triage on 80 mesh sieves, and gained powder particle size is about 200～400 μ m.
Mixture is sintering at high temperature:
The powder preparing is put into crucible compacting, then crucible is put into electric furnace and carried out sintering.Temperature rise rate is: room temperature to 200 ℃ is 2 ℃/m, and 200 ℃～960 ℃ is 4 ℃/m, and heat preservation sintering 2 hours makes it fully sinter porcelain into.After naturally cooling, make the bone reparation stephanoporate calcium polyphosphate biomaterial that aperture is about 100～400 μ m.
Embodiment 2
Calcining monocalcium phosphate:
Weigh in the balance and get Powdered monocalcium phosphate 300g, put into quartz crucible, put into electric furnace after adding a cover protection, with the speed of 4 ℃/m, be warming up to 500 ℃, be incubated naturally cooling after 1～2 hour, thereby obtain the calcining material of loose bulk.This calcining material, with after mortar or ball mill crushing, is put into loft drier standby.
By the monocalcium phosphate after calcining with do not calcine in right amount monocalcium phosphate and mix:
Take respectively calcining material 80g, Powdered monocalcium phosphate 240g, after mixing, is used ball mill dry ball milling 1 minute, and the powder making is crossed to 40 orders and 120 mesh sieves, gets the triage on 120 mesh sieves, and gained powder particle size is about 100～400 μ m.
Mixture is sintering at high temperature:
The powder preparing is put into crucible compacting, then crucible is put into electric furnace and carried out sintering.Temperature rise rate is: room temperature to 200 ℃ is 2 ℃/m, and 200 ℃～950 ℃ is 4 ℃/m, and heat preservation sintering 2 hours makes it fully sinter porcelain into.After naturally cooling, make the bone reparation stephanoporate calcium polyphosphate biomaterial that aperture is about 100～400 μ m.
Embodiment 3
Calcining monocalcium phosphate:
Weigh in the balance and get Powdered monocalcium phosphate 300g, put into quartz crucible, put into electric furnace after adding a cover protection, with the speed of 4 ℃/m, be warming up to 300 ℃, be incubated naturally cooling after 1～2 hour, thereby obtain the calcining material of loose bulk.This calcining material, with after mortar or ball mill crushing, is put into loft drier standby.
Take calcining material 80g, use ball mill dry ball milling 1 minute, the powder making is crossed to 120 mesh sieves, gained powder particle size is about 100 μ m.
Mixture is sintering at high temperature:
The powder preparing is put into crucible compacting, then crucible is put into electric furnace and carried out sintering.Temperature rise rate is: room temperature to 200 ℃ is 2 ℃/m, and 200 ℃～970 ℃ is 4 ℃/m, and heat preservation sintering 2 hours makes it fully sinter porcelain into.After naturally cooling, make the bone reparation stephanoporate calcium polyphosphate biomaterial that aperture is about 50～300 μ m.
By after monocalcium phosphate preroasting, crystal water in it runs off, and its reaction reaches certain equilibrium state, and abrasive dust is sintering again, monocalcium phosphate is forming stephanoporate calcium polyphosphate under polycondensation, and its aperture can be controlled by the powder particle size that the abrasive dust stage screens.
Embodiment 4
Calcining monocalcium phosphate:
Weigh in the balance and get Powdered monocalcium phosphate 200g, put into quartz crucible, put into electric furnace after adding a cover protection, with the speed of 4 ℃/m, be warming up to 650 ℃, be incubated naturally cooling after 1 hour, thereby obtain block calcining material.By after the preliminary fragmentation of this calcining material, put into loft drier standby.
By the monocalcium phosphate after calcining with do not calcine in right amount monocalcium phosphate and mix:
Take respectively calcining material 50g, Powdered monocalcium phosphate 25g, after mixing, is used ball mill dry grinding 2 minutes, and the powder making is crossed to 60 mesh sieves, and the powder particle size obtaining is less than 250 μ m.
Mixture is sintering at high temperature:
The powder preparing is put into crucible compacting, then crucible is put into electric furnace and carried out sintering.Temperature rise rate is: room temperature to 200 ℃ is 2 ℃/m, and 200 ℃～960 ℃ is 4 ℃/m, and heat preservation sintering 2 hours makes it fully sinter porcelain into.After naturally cooling, make the bone reparation stephanoporate calcium polyphosphate biomaterial that aperture is about 100～400 μ m.
Embodiment 5
Calcining monocalcium phosphate:
Weigh in the balance and get Powdered monocalcium phosphate 200g, put into quartz crucible, put into electric furnace after adding a cover protection, with the speed of 4 ℃/m, be warming up to 750 ℃, be incubated naturally cooling after 1 hour, thereby obtain block calcining material.By after the preliminary fragmentation of this calcining material, put into loft drier standby.
By the monocalcium phosphate after calcining with do not calcine in right amount monocalcium phosphate and mix:
Take respectively calcining material 50g, Powdered monocalcium phosphate 200g, after mixing, is used ball mill dry grinding 1 minute, and the powder making is crossed to 40 mesh sieves, and the powder particle size obtaining is less than 400 μ m.
Mixture is sintering at high temperature:
The powder preparing is put into crucible compacting, then crucible is put into electric furnace and carried out sintering.Temperature rise rate is: room temperature to 200 ℃ is 2 ℃/m, and 200 ℃～960 ℃ is 4 ℃/m, and heat preservation sintering 2 hours makes it fully sinter porcelain into.After naturally cooling, make the bone reparation stephanoporate calcium polyphosphate biomaterial that aperture is about 100～500 μ m.
The stephanoporate calcium polyphosphate biomaterial being made by embodiment 1～5, pore diameter range is 50～500 μ m, utilize the characteristic of monocalcium phosphate high-temperature polycondensation, make himself polycondensation pore-forming form bone reparation stephanoporate calcium polyphosphate biomaterial, avoid the introducing of other impurity, can guarantee to greatest extent the pure of material.
Claims (7)
1. a stephanoporate calcium polyphosphate biomaterial preparation method, is characterized in that comprising the steps:
(1) calcining monocalcium phosphate;
(2) by the monocalcium phosphate after calcining with do not calcine in right amount monocalcium phosphate and mix;
(3) mixture step 2 being obtained is sintering at high temperature.
2. stephanoporate calcium polyphosphate biomaterial preparation method according to claim 1, is characterized in that: in step 1, monocalcium phosphate calcining temperature is 300～500 ℃.
3. stephanoporate calcium polyphosphate biomaterial preparation method according to claim 1, is characterized in that: in step 1, monocalcium phosphate calcining temperature is 650～750 ℃.
4. stephanoporate calcium polyphosphate biomaterial preparation method according to claim 2, is characterized in that: the monocalcium phosphate in step 2 after calcining with not calcine monocalcium phosphate mass ratio be 1:(0～3).
5. stephanoporate calcium polyphosphate biomaterial preparation method according to claim 3, is characterized in that: the monocalcium phosphate in step 2 after calcining with not calcine monocalcium phosphate mass ratio be 1:(0.5～4).
6. according to the stephanoporate calcium polyphosphate biomaterial preparation method described in claim 2 or 3, it is characterized in that: soaking time is 1～2 hour.
7. according to the arbitrary described stephanoporate calcium polyphosphate biomaterial preparation method of claim 1～5, it is characterized in that: the mixture that step 2 is obtained grinds, powder after grinding sieves, get the powder that particle diameter is 100～500 μ m, put into crucible compacting, be then heated to be incubated 1～2 hour under 950～970 ℃ of conditions.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607119A (en) * | 2018-03-20 | 2018-10-02 | 山东大学 | A kind of calcium polyphosphate surface poly-dopamine modified lithium composite boilogical ceramic and preparation method thereof |
| CN116283017A (en) * | 2023-03-16 | 2023-06-23 | 广西产研院新型功能材料研究所有限公司 | Modified calcium tripolyphosphate, preparation method and application thereof in producing high-strength corrosion-resistant ceramic-based-semi-metal friction lining |
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| CN101407414A (en) * | 2008-11-06 | 2009-04-15 | 上海交通大学 | Method for preparing calcium polyphosphate / tricalcium phosphate two-phase biological ceramic |
| WO2011072262A2 (en) * | 2009-12-11 | 2011-06-16 | Latitude 18, Inc. | Inorganic phosphate compositions and methods |
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| CN101352583A (en) * | 2007-07-29 | 2009-01-28 | 山东硅苑新材料科技股份有限公司 | Stephanoporate calcium polyphosphate biological ceramic and preparation method thereof |
| CN101407414A (en) * | 2008-11-06 | 2009-04-15 | 上海交通大学 | Method for preparing calcium polyphosphate / tricalcium phosphate two-phase biological ceramic |
| WO2011072262A2 (en) * | 2009-12-11 | 2011-06-16 | Latitude 18, Inc. | Inorganic phosphate compositions and methods |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108607119A (en) * | 2018-03-20 | 2018-10-02 | 山东大学 | A kind of calcium polyphosphate surface poly-dopamine modified lithium composite boilogical ceramic and preparation method thereof |
| CN108607119B (en) * | 2018-03-20 | 2020-06-23 | 山东大学 | Calcium polyphosphate surface polydopamine modified composite biological ceramic and preparation method thereof |
| CN116283017A (en) * | 2023-03-16 | 2023-06-23 | 广西产研院新型功能材料研究所有限公司 | Modified calcium tripolyphosphate, preparation method and application thereof in producing high-strength corrosion-resistant ceramic-based-semi-metal friction lining |
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