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 PDF

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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
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hpo
solid solution
caso
deionized water
hpo4
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CN102826529A (en
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程逵
章华勇
翁文剑
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Zhejiang University ZJU
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Zhejiang University ZJU
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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

Ca (the HPO of bio-medical 4) x(SO 4) 1-xsolid solution pellet of 2H2O and preparation method thereof
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.
CN201210328305.6A 2012-09-07 2012-09-07 Biomedical Ca(HPO4)x(SO4)1-x.2H2O solid solution particles and preparation method thereof Expired - Fee Related CN102826529B (en)

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Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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&amp *
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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