CN102826529B - Biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and preparation method thereof - Google Patents
Biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and preparation method thereof Download PDFInfo
- Publication number
- CN102826529B CN102826529B CN201210328305.6A CN201210328305A CN102826529B CN 102826529 B CN102826529 B CN 102826529B CN 201210328305 A CN201210328305 A CN 201210328305A CN 102826529 B CN102826529 B CN 102826529B
- Authority
- CN
- China
- Prior art keywords
- hpo
- solid solution
- caso
- deionized water
- hpo4
- Prior art date
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- Expired - Fee Related
Links
- 239000006104 solid solution Substances 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 title abstract description 5
- 229910014480 Ca(HPO4) Inorganic materials 0.000 title abstract 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000011575 calcium Substances 0.000 claims description 36
- 239000008188 pellet Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- 150000003016 phosphoric acids Chemical class 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 18
- 210000000988 bone and bone Anatomy 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000002639 bone cement Substances 0.000 abstract description 2
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 abstract 1
- 229910052925 anhydrite Inorganic materials 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000001506 calcium phosphate Substances 0.000 description 6
- 229910000389 calcium phosphate Inorganic materials 0.000 description 6
- 235000011010 calcium phosphates Nutrition 0.000 description 6
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 6
- 239000007788 liquid Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000000278 osteoconductive effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and a preparation method thereof. The Ca(HPO4)x(SO4)1-x.2H2O solid solution particles which have regulable ingredients and proportion are obtained by adopting a wet chemical method and promoting a part of SO4<2-> in CaSO4 to be substituted by HPO4<2-> through thermal treatment. The Ca(HPO4)x(SO4)1-x.2H2O solid solution particles prepared by the invention can be widely used in the fields of biomedical materials such as bone filling materials, bone cement and the like.
Description
Technical field
The invention belongs to bio-medical material technical field, be specifically related to a kind of Ca (HPO
4)
x(SO
4)
1-x2H
2solid solution pellet of O and preparation method thereof.
Background technology
Calcium sulfate is as the existing century-old history of artificial bone repair materials, and with its good biocompatibility, osteoconductive, vivo degradation absorbability becomes the study hotspot of inorganic bone repair materials and is widely used in bone reparation.
Calcium sulfate mainly contains anhydrous CaSO
4, CaSO
41/2H
2o and CaSO
42H
2o.Three can transform under certain condition mutually.And medical calcium sulfate is mainly CaSO
41/2H
2caSO after O and its aquation
42H
2o.But, due to formed CaSO
42H
2the vivo degradation speed of O is still faster than the formation speed of new bone, and its bone repairing performance is subject to certain impact.
At present, be also widely used in bone reparation as the calcium phosphate of biological active materials equally.Investigator mainly utilizes calcium phosphate to have the moiety similar with human body hard tissue, be proved to be and there is good biocompatibility and osteoconductive, but, conventionally its degraded slowly, retention time is long in vivo, do not reach requirement degradable within the treatment phase, affected growing into of new bone, this also becomes investigator and enterprise problem in the urgent need to address.
The problem of and calcium phosphate hard degradation too fast for calcium sulfate degraded and the research carried out is a lot.Main research and patent are all that the degradation rate based on calcium sulfate and calcium phosphate is different, utilize the different adjustment degradation speed of two kinds of component proportionss, thereby make it to match with the body bone tissue speed of growth.But these matrix materials, just by calcium sulfate and calcium phosphate simple blend, utilize the degradation rate difference of the two to regulate the degradation rate of material, do not change material itself from structure, make it to have new characteristic to meet the demand of clinical application.
Summary of the invention
The object of the present invention is to provide a kind of bio-medical Ca (HPO with solid solution structure
4)
x(SO
4)
1-x2H
2particle of O and preparation method thereof.
Ca (HPO of the present invention
4)
x(SO
4)
1-x2H
2the solid solution pellet of O, is under hydrothermal condition, CaSO
4in part SO
4 2-by HPO
4 2-replace the Ca (HPO of formation
4)
x(SO
4)
1-x2H
2o solid solution pellet, particle size is 10～60 μ m, the span of x is 0.05～0.25.
Ca (HPO
4)
x(SO
4)
1-x2H
2the preparation method of the solid solution pellet of O, comprises the following steps:
1) water-soluble calcium containing compound and sulfocompound being dissolved in deionized water, being mixed with respectively solution, is that 1:1 mixes by the mol ratio of Ca/S at normal temperatures, stirs lower reaction after 2 hours, filters successively with deionized water and alcohol, dries, and obtains CaSO
42H
2o;
2) by phosphoric acid salt and step 1) CaSO that makes
42H
2o puts into reactor after mixing with deionized water and stirring, and the mol ratio that makes the P/S in mixed solution is 0.05～0.5, under the hydrothermal condition of 90～110 DEG C, reacts 6～10 hours, and reacted sample filters with alcohol, dries, and obtains Ca (HPO
4)
x(SO
4)
1-x2H
2the solid solution pellet of O.
In above-mentioned preparation method, described water-soluble calcium containing compound is CaNO
3, CaCl
2or Ca (OH)
2; Described water-soluble sulfocompound is H
2sO
4, Na
2sO
4, K
2sO
4or MgSO
4; Described phosphoric acid salt is Ca (H
2pO
4)
2h
2o, CaHPO
42H
2o, Ca
3(PO
4)
2, Ca
10(PO
4)
6(OH)
2, NaH
2pO
4, Na
2hPO
412H
2o, Na
3pO
4, KH
2pO
4, K
2hPO
43H
2o or K
3pO
4.
The present invention introduces phosphoric acid salt in water medium, and by hydrothermal treatment consists, makes CaSO
42H
2o dissolves and recrystallization under certain pressure and temperature, in the process of recrystallization, and the HPO in solution
4 2-replace part SO
4 2-form Ca (HPO
4)
x(SO
4)
1-x2H
2the solid solution pellet of O.
Compared with prior art, the present invention has following useful technique effect:
Ca (the HPO that the present invention is synthetic
4)
x(SO
4)
1-x2H
2o solid solution pellet is structurally with regard to the heterogeneous composite material of calcium sulfate different from the past and calcium phosphate.Than pure calcium sulfate, this solid solution pellet demonstrates different degradation characteristics, can improve its biodegradability, can be widely used in the biomedicine such as filling material of bone, bone cement Material Field, has good potential applicability in clinical practice.Preparation method of the present invention is simple, simple to operate, and cost is low, is easy to industrialization.
Brief description of the drawings
Fig. 1 is Ca (HPO
4)
x(SO
4)
1-x2H
2the SEM figure of the solid solution pellet of O.
Fig. 2 is Ca (HPO
4)
x(SO
4)
1-x2H
2the XRD figure of the solid solution pellet of O.
Fig. 3 is Ca (HPO
4)
x(SO
4)
1-x2H
2the EDS figure of the solid solution pellet of O.
Embodiment
Embodiment 1
1) by CaNO
3and K
2sO
4being dissolved in deionized water, being mixed with respectively solution, is that 1:1 mixes by the mol ratio of Ca/S at normal temperatures, and reaction is carried out under constantly stirring, temperature of reaction is room temperature, and the reaction times is 2 hours, inferior with deionized water filter 23 after reaction, alcohol filters once, then 60 DEG C of oven dry, obtains CaSO
42H
2o;
2) by the CaHPO of 1g
42H
2the step 1 of O and 10g) CaSO that makes
42H
2o mixes in the deionized water for stirring of 400ml, and mixed suspension liquid is put into reactor, under the hydrothermal condition of 90 DEG C, reacts 10 hours, and alcohol filter 23 for reacted sample, then 60 DEG C of oven dry obtain Ca (HPO
4)
0.08(SO
4)
0.922H
2the solid solution pellet of O, its particle size is 10-60 μ m.
Embodiment 2
1) by CaCl
2and Na
2sO
4being dissolved in deionized water, being mixed with respectively solution, is that 1:1 mixes by the mol ratio of Ca/S at normal temperatures, and reaction is carried out under constantly stirring, temperature of reaction is room temperature, and the reaction times is 2 hours, inferior with deionized water filter 23 after reaction, alcohol filters once, then 60 DEG C of oven dry, obtains CaSO
42H
2o;
2) by the Na of 4.16g
2hPO
412H
2the step 1 of O and 10g) CaSO that makes
42H
2o mixes in the deionized water for stirring of 400ml, and mixed suspension liquid is put into reactor, under the hydrothermal condition of 100 DEG C, reacts 8 hours, and alcohol filter 23 for reacted sample, then 60 DEG C of oven dry obtain Ca (HPO
4)
0.14(SO
4)
0.862H
2the solid solution pellet of O.
Its SEM schemes as shown in Figure 1: the size of particle is about 10 μ m～40 μ m as seen from the figure.
XRD figure is as shown in Figure 2: the standard card that curve 1 is terra alba, curve 2 is Ca (HPO
4)
0.14(SO
4)
0.862H
2the solid solution pellet of O; Curve 2 shows that particle is CaSO
42H
2o crystalline phase.
EDS schemes as shown in Figure 3, contains element sulphur and phosphoric in particle, and particle is Ca (HPO
4)
0.14(SO
4)
0.862H
2the solid solution pellet of O.
Embodiment 3
1) by CaNO
3and Na
2sO
4being dissolved in deionized water, being mixed with respectively solution, is that 1:1 mixes by the mol ratio of Ca/S at normal temperatures, and reaction is carried out under constantly stirring, temperature of reaction is room temperature, and the reaction times is 2 hours, inferior with deionized water filter 23 after reaction, alcohol filters once, then 60 DEG C of oven dry, obtains CaSO
42H
2o;
2) by the KH of 2.37g
2pO
4step 1 with 10g) CaSO that makes
42H
2o mixes in the deionized water for stirring of 400ml, and mixed suspension liquid is put into reactor, under the hydrothermal condition of 110 DEG C, reacts 6 hours, and alcohol filter 23 for reacted sample, then 60 DEG C of oven dry obtain Ca (HPO
4)
0.21(SO
4)
0.792H
2the solid solution pellet of O, its particle size is 10-60 μ m.
Claims (2)
1. Ca (the HPO of bio-medical
4)
x(SO
4)
1-x2H
2the solid solution pellet of O, is characterized in that it is under hydrothermal condition, CaSO
4in part SO
4 2-by HPO
4 2-replace the Ca (HPO of formation
4)
x(SO
4)
1-x2H
2the solid solution pellet of O, particle size is 10～60 μ m, the span of x is 0.05～0.25.
2. preparation Ca (HPO claimed in claim 1
4)
x(SO
4)
1-x2H
2the method of the solid solution pellet of O, its feature comprises the following steps:
1) water-soluble calcium containing compound and sulfocompound being dissolved in deionized water, being mixed with respectively solution, is that 1:1 mixes by the mol ratio of Ca/S at normal temperatures, stirs lower reaction after 2 hours, filters successively with deionized water and alcohol, dries, and obtains CaSO
42H
2o;
2) by phosphoric acid salt and step 1) CaSO that makes
42H
2o puts into reactor after mixing with deionized water and stirring, and the mol ratio that makes the P/S in mixed solution is 0.05～0.5, under the hydrothermal condition of 90～110 DEG C, reacts 6～10 hours, and reacted sample filters with alcohol, dries, and obtains Ca (HPO
4)
x(SO
4)
1-x2H
2the solid solution pellet of O;
Above-mentioned water-soluble calcium containing compound is Ca (NO
3)
2or CaCl
2; Described water-soluble sulfocompound is H
2sO
4, Na
2sO
4, K
2sO
4or MgSO
4; Described phosphoric acid salt is Ca (H
2pO
4)
2h
2o, CaHPO
42H
2o, Ca
3(PO
4)
2, Ca
10(PO
4)
6(OH)
2, NaH
2pO
4, Na
2hPO
412H
2o, Na
3pO
4, KH
2pO
4, K
2hPO
43H
2o or K
3pO
4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210328305.6A CN102826529B (en) | 2012-09-07 | 2012-09-07 | Biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210328305.6A CN102826529B (en) | 2012-09-07 | 2012-09-07 | Biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102826529A CN102826529A (en) | 2012-12-19 |
| CN102826529B true CN102826529B (en) | 2014-07-23 |
Family
ID=47329879
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|---|---|---|---|
| CN201210328305.6A Expired - Fee Related CN102826529B (en) | 2012-09-07 | 2012-09-07 | Biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102826529B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279806A (en) * | 1989-07-04 | 1994-01-18 | Office Togolais Des Phosphates | Process for eliminating heavy metals from phosphoric acid |
-
2012
- 2012-09-07 CN CN201210328305.6A patent/CN102826529B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5279806A (en) * | 1989-07-04 | 1994-01-18 | Office Togolais Des Phosphates | Process for eliminating heavy metals from phosphoric acid |
Non-Patent Citations (5)
| Title |
|---|
| P化工矿物与加工》.2010,(第7期),第8-10及26页. * |
| β-磷酸三钙/硫酸钙生物陶瓷的研究;邸利芝等;《天津工业大学学报》;20040430;第23卷(第2期);第40-43页 * |
| 王宇斌等.柠檬酸钠对半水硫酸钙晶须形貌的影响.《IM& * |
| 王宇斌等.柠檬酸钠对半水硫酸钙晶须形貌的影响.《IM&P化工矿物与加工》.2010,(第7期),第8-10及26页. |
| 邸利芝等.β-磷酸三钙/硫酸钙生物陶瓷的研究.《天津工业大学学报》.2004,第23卷(第2期),第40-43页. |
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| Publication number | Publication date |
|---|---|
| CN102826529A (en) | 2012-12-19 |
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