CN102815683B - Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof - Google Patents

Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof Download PDF

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CN102815683B
CN102815683B CN201210327974.1A CN201210327974A CN102815683B CN 102815683 B CN102815683 B CN 102815683B CN 201210327974 A CN201210327974 A CN 201210327974A CN 102815683 B CN102815683 B CN 102815683B
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hpo
solid solution
caso
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pellet
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CN102815683A (en
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程逵
章华勇
翁文剑
黄海生
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Zhejiang University ZJU
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Abstract

The invention discloses a biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and a preparation method thereof. By means of a wet-chemical method and heat treatment, parts of SO4 <2-> in CaSO4 are promoted to be replaced by HPO4<2-> to obtain the alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle, and compositions and proportions of the alpha- Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle can be adjusted. The prepared alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle can be widely used in the filed of biomedical materials of bone filling materials, bone cement and the like.

Description

α-Ca (HPO of bio-medical 4) x(SO 4) 1-x1/2H 2solid solution pellet of O and preparation method thereof
Technical field
The invention belongs to bio-medical material technical field, be specifically related to a kind of α-Ca (HPO 4) x(SO 4) 1-x1/2H 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, bone conductibility, the characteristics such as vivo degradation absorbability and high comprcssive strength become the study hotspot of inorganic bone repair materials and are widely used in during bone repairs.
Calcium sulfate mainly contains anhydrous CaSO 4, CaSO 41/2H 2o and CaSO 42H 2o.Three can transform under certain condition mutually.Anhydrous CaSO 4be used as plaster bandage, artware and construction material more.And medical calcium sulfate is mainly CaSO 41/2H 2caSO after O and its aquation 42H 2o, and CaSO 42H 2o is often used as crystal seed and makes an addition to CaSO 41/2H 2in O, accelerate CaSO 41/2H 2the aquation of O becomes CaSO 42H 2o.Wherein CaSO 41/2H 2o is divided into again α-CaSO 41/2H 2o and β-CaSO 41/2H 2o.According to Thomas, M. V. (Journal of Biomedical Materials Research Part B, 2009,88B (2): P. 597-610), Chen, H. (Journal of Craniofacial Surgery, 2010,21 (1): P. 188-197) and Guan, B. H. (J. Chem. Eng. Data, 2009,54 (3): P. 719-725.) report, α-CaSO 41/2H 2o and β-CaSO 41/2H 2both architectural differences of O are very little, but α-CaSO 41/2H 2the crystal grain of O is larger, has hexagonal prism structure; And in DTA analyzes, α-CaSO 41/2H 2o has a very little exothermic peak after endothermic peak, and β-CaSO 41/2H 2o does not but have this exothermic peak; And under the condition of the identical ratio of mud, α-CaSO 41/2H 2caSO after O aquation 42H 2o have higher intensity and less can absorption rate, this has alleviated to a certain extent traditional calcium sulfate material and has absorbed in vivo too fast problem.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 bioactive materials equally.Researcher mainly utilizes calcium phosphate to have the constituent similar with human body hard tissue, be proved to be and there is good biocompatibility and bone conductibility, 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 researcher 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 ratios, thereby make it to match with the body bone tissue speed of growth.The Chinese invention patent that is CN200710063903.4 as the patent No. discloses a kind of new-type of inorganic bone grafting material, by β-Ca 3(PO 4) 2and α-CaSO 41/2H 2o is by certain mass fraction proportioning composition; Application number is the preparation method that 201010201897.6 Chinese invention patent application discloses a kind of self pore-forming calcium phosphate cement bracket, and certain calcium sulfate is joined to injectable calcium phosphate bone cement, prepares novel composite bone cement; It is a kind of based on nanometer Ca that application number is that 201010185090.8 Chinese invention patent application discloses 10(PO 4) 6(OH) 2and CaSO 41/2H 2composite bone repairing material of O and preparation method thereof, by α-CaSO 41/2H 2o, Ca 10(PO 4) 6(OH) 2form composite bone repairing material with additive.But these composites, 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 practice.
Summary of the invention
The object of the present invention is to provide a kind of bio-medical α-Ca (HPO with solid solution structure 4) x(SO 4) 1-x1/2H 2solid solution pellet of O and preparation method thereof.
α-Ca (HPO of the present invention 4) x(SO 4) 1-x1/2H 2the solid solution pellet of O, is under hydrothermal condition, CaSO 4in part SO 4 2-by HPO 4 2-replace α-Ca (HPO of formation 4) x(SO 4) 1-x1/2H 2o solid solution pellet, particle size is 30～100 μ m, the span of x is 0.03～0.25.
α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the preparation method of the solid solution pellet of O, comprises the following steps:
1) water-soluble calcium containing compound and sulfur-containing compound 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 ethanol, dries, and obtains CaSO 42H 2o;
2) monohydrate potassium is dissolved in deionized water, makes electrolyte solution;
3) by step 1) CaSO that makes 42H 2o and step 2) electrolyte solution that makes mixes, and makes suspension;
4) after the suspension of phosphate and step 3) being made is uniformly mixed, put into reactor, the mol ratio that makes the P/S in mixed liquor is 0.05～0.5, under the hydrothermal condition of 130～150 DEG C, react 6～10 hours, then ethanol filters, and dries, and obtains α-Ca (HPO 4) x(SO 4) 1-x1/2H 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 sulfur-containing compound is H 2sO 4, Na 2sO 4, K 2sO 4or MgSO 4; Described phosphate 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 phosphate in aqueous 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 α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the solid solution pellet of O.
Compared with prior art, the present invention has following useful technique effect:
α-Ca (HPO that the present invention is synthetic 4) x(SO 4) 1-x1/2H 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 α-CaSO 41/2H 2o, HPO 4 2-existence can hinder α-Ca (HPO 4) x(SO 4) 1-x1/2H 2o is to Ca (HPO 4) x(SO 4) 1-x2H 2the transformation of O and Ca (HPO 4) x(SO 4) 1-x2H 2the structure of O network, therefore, extends α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the hydration time of O, meanwhile, the Ca (HPO of generation 4) x(SO 4) 1-x2H 2o also demonstrates slower degradation characteristic.This solid solution pellet demonstrates different aquations and degradation characteristic, can improve its injection property and 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 α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the SEM figure of the solid solution pellet of O.
Fig. 2 is α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the XRD figure of the solid solution pellet of O;
Fig. 3 is α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the DTA-TG figure of the solid solution pellet of O.
Fig. 4 is α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the EDS figure of the solid solution pellet of O.
Detailed description of the invention
Embodiment 1
1) by CaCl 2and 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, reaction temperature is room temperature, and the response time is 2 hours, inferior with deionized water filter 23 after reaction, ethanol filters once, then 60 DEG C of oven dry, obtains CaSO 42H 2o;
2) monohydrate potassium of 0.4g is dissolved in the deionized water of 400ml, makes electrolyte solution;
3) by 10g step 1) CaSO that makes 42H 2o and step 2) electrolyte solution that makes mixes, and makes suspension;
4) by the CaHPO of 1g 42H 2after the suspension that O and step 3) are made is uniformly mixed, put into reactor, the mol ratio that makes the P/S in mixed liquor is 0.1, and reaction is carried out under the hydrothermal condition of 130 DEG C, response time is 10 hours, ethanol filter 23 for reacted sample, then 60 DEG C of oven dry, obtain α-Ca (HPO 4) 0.07(SO 4) 0.931/2H 2the solid solution pellet of O, its particle size is 30～60 μ m.
Embodiment 2
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, reaction temperature is room temperature, and the response time is 2 hours, inferior with deionized water filter 23 after reaction, ethanol filters once, then 60 DEG C of oven dry, obtains CaSO 42H 2o;
2) monohydrate potassium of 0.4g is dissolved in the deionized water of 400ml, makes electrolyte solution;
3) by 10g step 1) CaSO that makes 42H 2o and step 2) electrolyte solution that makes mixes, and makes suspension;
4) by the Na of 4.16g 2hPO 412H 2after the suspension that O and step 3) are made is uniformly mixed, put into reactor, the mol ratio that makes the P/S in mixed liquor is 0.2, and reaction is carried out under the hydrothermal condition of 140 DEG C, response time is 8 hours, ethanol filter 23 for reacted sample, then 60 DEG C of oven dry, obtain α-Ca (HPO 4) 0.15(SO 4) 0.851/2H 2the solid solution pellet of O.
Its SEM schemes as shown in Figure 1: granule is hexagonal prism structure as seen from the figure, and particle size is about 30～50 μ m.
XRD figure is as shown in Figure 2: the standard card that curve 1 is half-H 2 O calcium sulphate, curve 2 is α-Ca (HPO 4) 0.15(SO 4) 0.851/2H 2the solid solution pellet of O; Curve 2 shows that granule is CaSO 41/2H 2o crystalline phase.
And further analyzed from the DTA-TG figure of Fig. 3: the weightlessness of the differential thermal of curve 1 and curve 2 all illustrates that granule is a-CaSO 41/2H 2o crystalline phase.
EDS schemes as shown in Figure 4, contains element sulphur and P elements in granule, and granule is α-Ca (HPO 4) 0.15(SO 4) 0.851/2H 2the solid solution pellet of O.
Embodiment 3
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, reaction temperature is room temperature, and the response time is 2 hours, inferior with deionized water filter 23 after reaction, ethanol filters once, then 60 DEG C of oven dry, obtains CaSO 42H 2o;
2) monohydrate potassium of 0.4g is dissolved in the deionized water of 400ml, makes electrolyte solution;
3) by 10g step 1) CaSO that makes 42H 2o and step 2) electrolyte solution that makes mixes, and makes suspension;
4) by the KH of 2.37g 2pO 4after the suspension made from step 3) is uniformly mixed, put into reactor, the mol ratio that makes the P/S in mixed liquor is 0.3, and reaction is carried out under the hydrothermal condition of 150 DEG C, response time is 6 hours, ethanol filter 23 for reacted sample, then 60 DEG C of oven dry, obtain α-Ca (HPO 4) 0.21(SO 4) 0.791/2H 2the solid solution pellet of O, its particle size is 40～100 μ m.

Claims (5)

1. α-Ca (HPO of bio-medical 4) x(SO 4) 1-x1/2H 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 α-Ca (HPO of formation 4) x(SO 4) 1-x1/2H 2o solid solution pellet, particle size is 30～100 μ m, the span of x is 0.03～0.25.
2. preparation α-Ca (HPO claimed in claim 1 4) x(SO 4) 1-x1/2H 2the method of the solid solution pellet of O, is characterized in that comprising the following steps:
1) water-soluble calcium containing compound and sulfur-containing compound 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 ethanol, dries, and obtains CaSO 42H 2o;
2) monohydrate potassium is dissolved in deionized water, makes electrolyte solution;
3) by step 1) CaSO that makes 42H 2o and step 2) electrolyte solution that makes mixes, and makes suspension;
4) after the suspension of phosphate and step 3) being made is uniformly mixed, put into reactor, the mol ratio that makes the P/S in mixed liquor is 0.05～0.5, under the hydrothermal condition of 130～150 DEG C, react 6～10 hours, then ethanol filters, and dries, and obtains α-Ca (HPO 4) x(SO 4) 1-x1/2H 2the solid solution pellet of O.
3. by α-Ca (HPO claimed in claim 2 4) x(SO 4) 1-x1/2H 2the preparation method of the solid solution pellet of O, is characterized in that described water-soluble calcium containing compound is Ca (NO 3) 2, CaCl 2or Ca (OH) 2.
4. by α-Ca (HPO claimed in claim 2 4) x(SO 4) 1-x1/2H 2the preparation method of the solid solution pellet of O, is characterized in that described water-soluble sulfur-containing compound is H 2sO 4, Na 2sO 4, K 2sO 4or MgSO 4.
5. by α-Ca (HPO claimed in claim 2 4) x(SO 4) 1-x1/2H 2the preparation method of the solid solution pellet of O, is characterized in that described phosphate 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.
CN201210327974.1A 2012-09-07 2012-09-07 Biomedical alpha-Ca (HPO4) x (SO4)1-x*1/2H2O solid solution particle and preparation method thereof Expired - Fee Related CN102815683B (en)

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Citations (3)

* 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
CN101596330A (en) * 2009-07-09 2009-12-09 毛克亚 α-half-H 2 O calcium sulphate/bata-tricalcium phosphate porous particle type cmposite artificial bone and preparation method thereof
CN102488920A (en) * 2011-12-14 2012-06-13 浙江大学 Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof

Patent Citations (3)

* 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
CN101596330A (en) * 2009-07-09 2009-12-09 毛克亚 α-half-H 2 O calcium sulphate/bata-tricalcium phosphate porous particle type cmposite artificial bone and preparation method thereof
CN102488920A (en) * 2011-12-14 2012-06-13 浙江大学 Alpha-calcium sulfate hemihydrate/hydroxyapatite composite granule with nuclear shell structure and preparation thereof

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