CN1055061C - Method for preparing hydroxy phosphatic rock - Google Patents
Method for preparing hydroxy phosphatic rock Download PDFInfo
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- CN1055061C CN1055061C CN97103827A CN97103827A CN1055061C CN 1055061 C CN1055061 C CN 1055061C CN 97103827 A CN97103827 A CN 97103827A CN 97103827 A CN97103827 A CN 97103827A CN 1055061 C CN1055061 C CN 1055061C
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Abstract
The present invention relates to a preparation method for biological active material of hydroxyapatite converted by natural ore by an anion exchange reaction under the conditions of water and heating, which is characterized in that the reaction is carried out in a sealed stainless steel reaction kettle lined with polytetrafluoroethylene; the concentration of an exchange agent of diammonium hydrogen phosphate is from 0.88 to 6.8 mol/l; the temperature of the reaction is from 100 to 240 DEG C; the pressure of the reaction is less than or equal to 40 bar to be close to the normal pressure; the reaction proportion of coral reef to the diammonium hydrogen phosphate is from 1: 1 to 1: 5. When the method is used for producing hydroxyapatite, the conversion rate of the reaction can reach more than 95 %, the strength of the product can reach Mohs 6.5 DEG, and the volume of the single product can reach 15 cc or even more to satisfy various requirements of a bone transplantation operation. The present invention has the advantages of low technology requirements, easy realization of production conditions, simple equipment and low cost.
Description
The present invention relates to a kind of preparation method of hydroxyapatite, specifically, what the present invention relates to is that a kind of natural coral that utilizes carries out anion exchange reaction under hydrothermal condition, is converted to the preparation method of the block hydroxyapatite that is used for the skeleton reparation of biologically active.
The inorganic composition of skeleton is hydroxyapatite [Ca
10(PO
4)
6(OH)
2], long ago, people have just carried out bone injury tissue and bone substitution investigation.But the bone of animal or human's body is not suitable for the allosome displacement, because of it can cause the intensive rejection.For the displacement and the repairing in damage joint, required material will have certain mechanical strength, goods such as commonly used is cochrome, but use this material regular meeting to cause the damage of other tissue etc.Other available material also has vitreum, porous ceramics etc., but restive because of its aperture, has limited the application of this class material.The aperture that studies show that graft materials is necessary 100 to 200 microns development for hemotrophic nutrition supply and Haversian system.The uniform porous material of synthetic is difficult, recent decades, synthetic or obtain certain effect with the reparation that the hydroxyapatite that the animal bone sintering forms is applied to bony defect, but because material is widely different, hole is inhomogeneous, can not be unimpeded between hole, influenced bone tissue growth, thereby clinical application is restricted, yet quite general at this porous material of occurring in nature.For example: U.S. doctor Rog at first uses natural coral and is converted into hydroxyapatite.Karang has three-dimensional pore network structure.This karang is exchanged into alkali calcium phosphate, and its hardness improves (mineralising), and the pore structure of its pore structure and people's bone is approaching.And this material do not contain organism, can sterilize again, having a wide range of applications aspect the transplanting of people's bone.Through experimentation on animals and clinical application, effect is very good.This material is called CHA (Coralline Hydroxyapatite).At present, external medical circles are extensive use of the preferred material of CHA as the bone defect repair.The method of the CHA that doctor Rog produces is that high temperature, high pressure, its pressure are 105Mpa, belongs to ultra-high voltage.Its temperature range is 250-350 ℃, makes contact substance with precious metal.Reaction times is 12-48 hour because that Technology requires is high, the equipment preciousness, this method is produced CHA, the cost height, yield poorly, this material of domestic use can only rely on import, costs an arm and a leg, and supplies untimelyly, can not satisfy medical requirement.
Warm low-pressure process during purpose of the present invention is utilized exactly, under low-cost equipment and contact substance effect, finish natural coral and convert biological active materials to---the anion exchange reaction that the skeleton reparation is carried out with block hydroxyapatite.Prepare high quality, hydroxyapatite cheaply.
The technology that the present invention adopts is middle temperature low-pressure process, and reaction process is the anion exchange reaction under the hydrothermal condition.Temperature of reaction is 100-240 ℃, and reaction pressure is≤4Mpa that contact substance is a polytetrafluoroethylene (PTFE).Exchanger is Secondary ammonium phosphate [(NH
4)
2HPO
4(AR)], concentration is 0.88-6.8mol/l.With coral (CaCO
3) making material, the reaction ratio of coral and Secondary ammonium phosphate (weight ratio) Ca/P is 1: 1-1: 5.
Concrete reaction is carried out in a sealing stainless steel cauldron (1cr18NiTi).Reactor is made lining with tetrafluoroethylene, is placed on a temperature limitation and is in 350 ℃ the Electric heat oven.Use deionized water, phosphorus ammonium [(NH
4)
3PO
4(AR)], ammonium hypophosphite [(NH
4) H
2PO
4(AR)] ammonium hydrogen phosphate of preparation different concns.Chemical equation is as follows:
6 (NH
4)
2CO
3+ 4H
2CO
3The invention has the advantages that:
1. reaction conversion ratio height.Can reach more than 95%, and the U.S. has only 90%.
2. product hardness is the Mohs6.5 degree, and U.S.'s product hardness is the Mohs5 degree, and quality is better than U.S.'s product.The condition that should possess bone tissue growth as the material of bone repair, need certain mechanical strength again, the product of the U.S. can only be used for the damaged reparation of spongy bone at present, can't be used for the position that cortex bone or lumbar vertebra etc. bear gravity, thereby product clinical application range of the present invention is more wide.
3. the volume size of product is unrestricted, and single volume can reach 15cc or bigger, can satisfy the various requirement of orthopaedics transplantation fully, and the single maximum volume of the U.S. can only reach 10cc.
4. Technology of the present invention is less demanding, and the working condition ratio is easier to realize that production unit is simple relatively, low production cost.
Embodiment 1
The equipment that present embodiment adopts is the sealing stainless steel cauldron of inner liner polytetrafluoroethylene, and internal diameter is 25mm, and volume is 25ml, and temperature of reaction is 240 ℃, and the reaction times is 4 days, and Ca/P is 1: 1, changes exchanger concentration, with deionized water, (NH
4)
3PO
4(AR), (NH
4) H
2PO
4(AR) preparation exchanger (NH
4)
2HPO
4(AR) concentration 0.88-6.8mol/l.
The sample test method:
1.X ray powder diffraction analysis (XRD)-determine phase
2. Infrared spectroscopy (IR)-determine thing phase, component
3. scanning electron microscope pattern and pore size analysis-determine pore structure
4. chemical composition analysis (ICP) method-determine product important component and foreign matter content.
The results are shown in Table 1.
Table 1 conversion exchanger concentration and product facies analysis table [(NH
4)
2HPO
4] temperature of reaction reaction times XRD IR (mol/l) (℃) (my god) 0.88 240 4 CaP PO
41.68 240 4 CaP PO
42.00 240 4 CaP PO
46.8 240 4 CaP PO
4
By table 1 as seen, (NH
4)
2HPO
4Concentration all can be exchanged into hydroxyapatite between 0.88-6.8mol/l, no carbonate exists, and turnover ratio is more than 95%, and the aperture is even, all between the 100-200 micron.
Annotate: CaP=Ca
10(PO
4)
6(OH)
2
Ca/p＝CaCO
3/(NH
4)
2HPO
4(AR)
Embodiment 2
Present embodiment adopts the equipment of embodiment 1, and temperature of reaction and time, the ratio of change Ca/P is produced hydroxyapatite, and the product analysis method is with embodiment 1.
The results are shown in Table 2
Table 2 changes Ca/P ratio and product facies analysis table
Ca/P (mol) temperature (℃) time (my god) XRD IR
1∶1 240 2 CaP+CaCO
3 PO
4+CO
3
1∶1 240 4 CaP PO
4
1∶2 240 4 CaP PO
4
1∶3 240 4 CaP PO
4
1∶4 240 4 CaP PO
4
1∶5 240 4 CaP PO
4
1∶5 240 2 CaP PO
4+CO
3
As shown in Table 2, Ca/P all can exchange fully than between 1: 1 to 1: 5, and Ca/P ratio is low, and the swap time that needs is short; Time increases, and the dissolution phenomena of sample is fairly obvious.
Turnover ratio reaches more than 95%, and the aperture is even, all between the 100-200 micron.
Embodiment 3
Present embodiment adopts identical equipment and technology with embodiment 1, and temperature of reaction, Ca/P ratio are 1: 2, and exchanger Secondary ammonium phosphate concentration is 2mol/l, changes the reaction times.
Product is used with embodiment 1 identical method and is tested, and the results are shown in Table 3.
Table 3 change time and product are shown mutually
Time (my god) temperature (℃) XRD IR
1 240 CaP+CaCO
3 PO4+CO
3
2 240 CaP+CaCO
3 PO
4+CO
3
3 240 CaP PO
4+CO
3
4 240 CaP PO
4
By table 3 as seen, the reaction times can exchange in the time of 4 days fully.
Embodiment 4
Present embodiment adopts identical equipment and technology with embodiment 1, and the Ca/P ratio is 1: 3, and exchanger Secondary ammonium phosphate concentration is 6mol/l, changes temperature of reaction.
Product identical method test with embodiment the results are shown in Table 4.
Table 4 changes temperature and product is shown mutually
Temperature (℃) time (my god) XRD IR
100 4 CaP PO
4
150 4 CaP PO
4
200 4 CaP PO
4
240 4 CaP PO
4
By table 4 as seen, temperature is in 100-240 ℃ of scope, and the reaction times is can exchange fully in 4 days, and turnover ratio is more than 95%, inclusion-free.
Claims (3)
1. a skeleton reparation is with the preparation method of block hydroxyapatite, it is characterized in that: natural coral is placed on an inside is lined with tetrafluoroethylene as in the sealing stainless steel cauldron of contact substance, with concentration be the Secondary ammonium phosphate [(NH of 0.88-6.8mol/l
4)
2HPO
4(AR)] carry out anion exchange reaction, temperature of reaction is 100-240 ℃, and reaction pressure≤4MPa, the reaction ratio of coral and Secondary ammonium phosphate are 1: 1-1: 5 (weight ratios), the reaction times is 2-4 days.
2. according to claims 1 described preparation method, it is characterized in that natural coral generates block hydroxyapatite transformation rate 〉=95% through reaction.
3. preparation method according to claim 1, the hardness that it is characterized in that block hydroxyapatite are Mohs 6.5 degree.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103827A CN1055061C (en) | 1997-04-02 | 1997-04-02 | Method for preparing hydroxy phosphatic rock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103827A CN1055061C (en) | 1997-04-02 | 1997-04-02 | Method for preparing hydroxy phosphatic rock |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1161305A CN1161305A (en) | 1997-10-08 |
| CN1055061C true CN1055061C (en) | 2000-08-02 |
Family
ID=5166907
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97103827A Expired - Fee Related CN1055061C (en) | 1997-04-02 | 1997-04-02 | Method for preparing hydroxy phosphatic rock |
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| Country | Link |
|---|---|
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069614C (en) * | 1998-05-16 | 2001-08-15 | 冯守华 | Chemical hole-enlarging technology for natural coral hydroxyl apatite material |
| AUPR152100A0 (en) * | 2000-11-16 | 2000-12-14 | University Of Technology, Sydney | Method for treating coral |
| CN101306806B (en) * | 2008-06-30 | 2010-09-29 | 广西大学 | Process for synthesizing hydroxylapatite |
| CN104909347B (en) * | 2015-07-03 | 2017-11-24 | 厦门大学 | A kind of preparation method of hydroxyapatite |
| CN107474849A (en) * | 2017-08-11 | 2017-12-15 | 安徽理工大学 | A kind of original position prepares the method that hydroxyapatite reinforces sand |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107535A (en) * | 1985-09-23 | 1987-08-19 | 东亚燃料工业株式会社 | Calcium phosphate type hydroxyl (base) phosphatic rock and preparation method thereof |
| WO1988007498A1 (en) * | 1987-03-26 | 1988-10-06 | Rolf Ewers | Process for manufacturing a hydroxyapatite material |
| US5427754A (en) * | 1993-01-11 | 1995-06-27 | Agency Of Industrial Science & Technology | Method for production of platelike hydroxyapatite |
-
1997
- 1997-04-02 CN CN97103827A patent/CN1055061C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86107535A (en) * | 1985-09-23 | 1987-08-19 | 东亚燃料工业株式会社 | Calcium phosphate type hydroxyl (base) phosphatic rock and preparation method thereof |
| WO1988007498A1 (en) * | 1987-03-26 | 1988-10-06 | Rolf Ewers | Process for manufacturing a hydroxyapatite material |
| US5427754A (en) * | 1993-01-11 | 1995-06-27 | Agency Of Industrial Science & Technology | Method for production of platelike hydroxyapatite |
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|---|---|
| CN1161305A (en) | 1997-10-08 |
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Address after: Beijing City, Haidian District No. 1 Wanshou Road Hongji garden 13 Building 302 room Applicant after: Chuangyi Biological Engineering New Materials Co., Ltd., Beijing Inventor after: Song Zhengzhi Address before: No. 28 Fuxing Road, Beijing, 15 - 1102, Haidian District Applicant before: Chen Wenjing Inventor before: Chen Wenjing |
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