CN100345600C - Biomedical sustained-releasing metal ion-containing calcium phosphate composite powder and preparation method thereof - Google Patents
Biomedical sustained-releasing metal ion-containing calcium phosphate composite powder and preparation method thereof Download PDFInfo
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- CN100345600C CN100345600C CNB2005100615261A CN200510061526A CN100345600C CN 100345600 C CN100345600 C CN 100345600C CN B2005100615261 A CNB2005100615261 A CN B2005100615261A CN 200510061526 A CN200510061526 A CN 200510061526A CN 100345600 C CN100345600 C CN 100345600C
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Abstract
The present invention discloses biomedical calcium phosphate composite powder which can slowly release metallic ions, and also discloses a preparation method thereof. A wet chemical method is used, compositions and ratio which are obtained through heat treatment can be adjusted, and each powder particle is composite powder which is composed of a nanometer structured hydroxyapatite which comprises metallic ions, and any one or two phases of alpha phase tricalcium phosphate which comprises metallic ions and beta phase tricalcium phosphate which comprises metallic ions. The two phase composition and the release rate of metallic ions of the calcium phosphate composite powder which comprises metallic ions and is prepared by the present invention are controllable; the powder has the advantages of uniform particle distribution and small particle size, and can be widely used for the field of biomedical materials, such as bone filling materials, bone cement, etc.
Description
Technical field
The present invention relates to calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing and preparation method thereof.
Background technology
Calcium phosphate material is the pottery that hard tissue substituting material is made in a kind of extensive use.Calcium phosphate material mainly contains α phase tricalcium phosphate (α-Ca
3(PO
4)
2, α-TCP), β phase tricalcium phosphate (β-Ca
3(PO
4)
2, β-TCP), hydroxyapatite (Ca
10(PO
4)
6(OH)
2, HA).Hydroxyapatite has superior bioactive and bone conductibility; α phase tricalcium phosphate and β be tricalcium phosphate biologically active and good biodegradation rate mutually.Behind the hydroxyapatite implant into body,, can not obtain best implantation effect because its dissolubility is very low; And the degradation rate of tricalcium phosphate will influence the synosteosis ability of implant too greatly.Generally speaking, implant requires calcium phosphate to have good bone conductibility and biodegradation rate simultaneously, and this just need mix the calcium phosphate of different crystalline phases compound use.Chinese patent CN1488680 adopts wet chemical method synthetic different by process conditions, obtains hydroxyapatite and/or α phase tricalcium phosphate composite powder, hydroxyapatite and/or β phase tricalcium phosphate composite powder or α phase tricalcium phosphate composite powder and/or the β phase tricalcium phosphate composite powder that ratio can be regulated arbitrarily through heat treatment.Chinese patent CN1079401 floods skeletal growth factor solution by the phosphate tricalcium artificial bone and the cmposite artificial bone that forms, skeletal growth factor is slowly discharged and induces new bone formation.And the calcium phosphate composite material of metal ion also can be used as bioactive materials stimulatory protein(SP) activity after implanting, and promotes the growth of bone or the absorption of inhibition bone, enlarges its further application.By new preparation method and chemical modification, be expected to study and prepare calcium phosphate composite powder with the active controllable sustained-release metal ion of good biological.
Summary of the invention
The object of the present invention is to provide calcium phosphate composite powder of a kind of nano-structured biomedical sustained-releasing metal ion-containing and preparation method thereof.
The calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing of the present invention, any one in the tricalcium phosphate be mutually or biphase compound formation mutually by the β of the α phase tricalcium phosphate of the hydroxyapatite of nano-structured metal ion, metal ion and metal ion for its each powder particle, Ca/P mol ratio in the composite powder is 1.50～1.67, the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metal ion zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium.
The particle diameter of above-mentioned composite powder is 40nm～500nm, and the single-phase crystallite dimension in every powder is 5nm-40nm.
The method of the calcium phosphate composite powder of preparation biomedical sustained-releasing metal ion-containing of the present invention has following three kinds of schemes:
Scheme 1
May further comprise the steps:
1) calcium containing compound, phosphorus-containing compound and metal ion chemical compound is soluble in water, be mixed with solution respectively, place under 0～20 ℃;
2) calcium solution that step 1) is made, metal ion solution and polymer mixed form mixed solution, place under 0～20 ℃, wherein the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metallic zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium ion; The mol ratio of polymer and calcium ion is 1: 10～10: 1, and polymer calculates with the molal quantity of construction unit;
3) phosphorus solution that step 1) is made is added dropwise to step 2) solution in, the Ca/P mol ratio is 1.50, drip alkaline solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, reaction temperature is 0 ℃～20 ℃, response time is 5 minutes～48 hours, and reaction back separation, washing, lyophilization obtain metal ion amorphous calcium phosphate precursor;
4) with the heating rate of metal ion amorphous calcium phosphate precursor with 5 ℃/min～50 ℃/min, 700 ℃～900 ℃ following heat treatments 10 minutes～5 hours, last furnace cooling obtains the α phase tricalcium phosphate and/or the β phase tricalcium phosphate composite powder of metal ion.
By the control heat treatment temperature, the biphase mol ratio that can make composite powder is in 0～100% range regulation.Heat treatment temperature obtains α phase tricalcium phosphate powder at 700～800 ℃; Heat treatment temperature obtains β phase tricalcium phosphate powder at 900 ℃; Heat treatment temperature obtains α phase tricalcium phosphate/β phase tricalcium phosphate composite powder being higher than 800 ℃ and be lower than between 900 ℃.
Scheme 2
May further comprise the steps:
1) calcium containing compound, phosphorus-containing compound, metal ion chemical compound and carbanion chemical compound is soluble in water, be mixed with solution respectively, place under 0～20 ℃;
2) calcium solution that step 1) is made, metal ion solution and polymer mixed form mixed solution, place under 0～20 ℃, wherein the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metallic zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium ion; The mol ratio of polymer and calcium ion is 1: 10～10: 1, and polymer calculates with the molal quantity of construction unit;
3) be added dropwise to step 2 after phosphorus solution that step 1) is made and carbanion solution mix) mixed solution in, the Ca/P mol ratio is 1.50～1.67, carbonate and phosphate radical mol ratio are 15%～70%, drip alkaline solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, reaction temperature is 0～20 ℃, and the response time is 5 minutes～48 hours, reaction back separation, washing, lyophilization obtain metal ion amorphous calcium phosphate precursor;
4),, obtain the hydroxyapatite and/or the α phase tricalcium phosphate composite powder of metal ion at 800 ℃ of following heat treatments 10 minutes～5 hours, last furnace cooling with the heating rate of metal ion amorphous calcium phosphate precursor with 5 ℃/min～50 ℃/min.
Under 800 ℃ of heat-treat conditions, by the addition of control carbonate, thus control powder Ca/P mol ratio, the biphase mol ratio that can make composite powder is in 0～100% range regulation.Carbonate and phosphate radical mol ratio are 15%, obtain α phase tricalcium phosphate powder; Carbonate and phosphate radical mol ratio are 70%, obtain hydroxyapatite; Carbonate and phosphate radical mol ratio obtain hydroxyapatite/α phase tricalcium phosphate composite powder between 15%～70%.
Scheme 3
May further comprise the steps:
1) calcium containing compound, phosphorus-containing compound, metal ion chemical compound and carbanion chemical compound is soluble in water, be mixed with solution respectively, place under 0～20 ℃;
2) calcium solution that step 1) is made, metal ion solution and polymer mixed form mixed solution, place under 0～20 ℃; Wherein the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metallic zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium ion; The mol ratio of polymer and calcium ion is 1: 10～10: 1, and polymer calculates with the molal quantity of construction unit;
3) be added dropwise to step 2 after phosphorus solution that step 1) is made and carbanion solution mix) mixed solution in, the Ca/P mol ratio is 1.50～1.67, carbonate and phosphate radical mol ratio are 15%～70%, drip alkaline solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, reaction temperature is 0～20 ℃, and the response time is 5 minutes～48 hours, reaction back separation, washing, lyophilization obtain metal ion amorphous calcium phosphate precursor;
4),, obtain the hydroxyapatite and/or the β phase tricalcium phosphate composite powder of metal ion at 900 ℃ of following heat treatments 10 minutes～5 hours, last furnace cooling with the heating rate of metal ion amorphous calcium phosphate precursor with 5 ℃/min～50 ℃/min.
Under 900 ℃ of heat-treat conditions, by the addition of control carbonate, thus control powder Ca/P mol ratio, the biphase mol ratio that can make composite powder is in 0～100% range regulation.Carbonate and phosphate radical mol ratio are 15%, obtain β phase tricalcium phosphate powder; Carbonate and phosphate radical mol ratio are 70%, obtain hydroxyapatite; Carbonate and phosphate radical mol ratio obtain hydroxyapatite/β phase tricalcium phosphate composite powder between 15%～70%.
In above-mentioned three kinds of preparation methoies, described calcium containing compound is lime nitrate, calcium chloride or calcium hydroxide; Described phosphorus-containing compound is ammonium hydrogen phosphate, sodium phosphate, phosphoric acid or potassium phosphate; Nitrate that described metal ion chemical compound is zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon or zirconium ion or chloride soluble compounds; Described carbanion chemical compound is the carbonate of zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, sodium or potassium ion; Described polymer is Polyethylene Glycol, polyvinyl alcohol or polyacrylic acid; The alkaline solution of described adjusting pH value is ammonia, sodium hydroxide or potassium hydroxide solution.
Multiple phase calcium phosphate calcium powder of the present invention can make in the granule biphase mol ratio regulate from 0～100% by the control process conditions, thus the biological activity and the biodegradation rate of control calcium phosphate composite powder.Composite powder biphase evenly, particle size distribution is even, size is between 40～500nm.The metal ion that mixes among the present invention can suppress crystal grows up, thereby reduces the particles of powder size, and can regulate the content of metal in the complex calcium phosphate by the mol ratio of M/ (M+Ca) in the conditioned reaction thing, to reach the purpose that controlled metal ion discharges.Can promote the osteocyte differentiation by metal ion, growth, thereby the healing of quickening osseous tissue.The calcium phosphate composite powder granule of the slow release metal ion of the present invention's preparation is not reunited, and easily disperses, and crystal property is good, and is simple to operate, is easy to industrialization, can be applicable to field of biomedical materials such as hard tissue substituting material, filling material of bone, bone cement and coating.
The specific embodiment
Embodiment 1
With a certain proportion of Zn (NO
3)
24H
2O, CaCl
26H
2O and Polyethylene Glycol (PEG) are dissolved in the distilled water, and wherein Zn/ (Zn+Ca) mol ratio is 0.03, PEG: CaCl
2=5: 1 (polymer calculates with the molal quantity of construction unit, down together); Na
3PO
412H
2O is dissolved in distilled water, and the Ca/P mol ratio is 1.50, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 9, drip the end back and under magnetic agitation, react 30min with sodium hydroxide.Precipitate is through sucking filtration, washing, lyophilization 72 hours, the amorphous zinc ion calcium phosphate that contains, with this precursor with 10 ℃/minute be warmed up to 700 ℃ down insulation obtain the α phase tricalcium phosphate powder of nano-structured slow release zinc ion after 3 hours.
Embodiment 2
With a certain proportion of Zn (NO
3)
24H
2O, Mg (NO
3)
26H
2O, CaCl
26H
2O and Polyethylene Glycol (PEG) are dissolved in the distilled water, and wherein (Zn+Mg)/(Zn+Mg+Ca) mol ratio is 0.09, PEG: CaCl
2=5: 1; (NH
4)
2HPO
4Be dissolved in distilled water, the Ca/P mol ratio is 1.50, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 30min with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, get amorphous zinc and the magnesium ion calcium phosphate of containing, with the be warmed up to 850 ℃ down insulations 3 hour after of this precursor with 10 ℃/minute, what obtain nano-structured slow release zinc and magnesium ion contains the 50% β calcium phosphate composite powder of tricalcium phosphate, 50% α phase tricalcium phosphate mutually.
Embodiment 3
With a certain proportion of Mg (NO
3)
26H
2O, CaCl
26H
2O and Polyethylene Glycol (PEG) are dissolved in the distilled water, and wherein Mg/ (Mg+Ca) mol ratio is 0.06, PEG: CaCl
2=3: 1; (NH
4)
2HPO
4Be dissolved in distilled water, the Ca/P mol ratio is 1.50, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 30min with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, the amorphous magnesium ion calcium phosphate that contains, with this precursor with 10 ℃/minute be warmed up to 900 ℃ down insulation obtain the β phase tricalcium phosphate powder of nano-structured slow release magnesium ion after 3 hours.
Embodiment 4
With a certain proportion of Sr (NO
3)
2, Ca (NO
3)
26H
2O and Polyethylene Glycol (PEG) are dissolved in the distilled water, and wherein Sr/ (Sr+Ca) mol ratio is 0.09, PEG: Ca (NO
3)
2=5: 1; (NH
4)
2CO
3(NH
4)
2HPO
4Be dissolved in distilled water, the Ca/P mol ratio is 1.67, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 30min with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, amorphous phosphate cement containing strontium, with this precursor with 10 ℃/minute be warmed up to 800 ℃ down insulation obtain the hydroxyapatite powder of nano-structured slow release strontium ion after 3 hours.
Embodiment 5
With a certain proportion of Mn (NO
3)
26H
2O, Ca (NO
3)
26H
2O and Polyethylene Glycol (PEG) are dissolved in the distilled water, and wherein Mn/ (Mn+Ca) mol ratio is 0.06, PEG: Ca (NO
3)
2=3: 1; (NH
4)
2CO
3(NH
4)
2HPO
4Be dissolved in distilled water, the Ca/P mol ratio is 1.60, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 30min with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, the amorphous manganese calcium phosphate that contains, with this precursor with 10 ℃/minute be warmed up to 800 ℃ down insulation obtain the calcium phosphate composite powder that contains 60% hydroxyapatite, 40% α phase tricalcium phosphate of nano-structured slow release manganese ion after 3 hours.
Embodiment 6
With a certain proportion of MgCl
26H
2O, CaCl
2And Polyethylene Glycol (PEG) is dissolved in distilled water, and wherein Mg/ (Mg+Ca) mol ratio is 0.03, PEG: CaCl
2=4: 1; (NH
4)
2CO
3(NH
4)
2HPO
4Be dissolved in distilled water, the Ca/P mol ratio is 1.54, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 30min with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, the amorphous magnesium calcium phosphate that contains, with this precursor with 10 ℃/minute be warmed up to 800 ℃ down insulation obtain the α phase tricalcium phosphate powder of nano-structured slow release magnesium ion after 3 hours.
Embodiment 7
With a certain proportion of MnCl
24H
2O, CaCl
26H
2O and Polyethylene Glycol (PEG) are dissolved in the distilled water, and wherein Mn/ (Mn+Ca) mol ratio is 0.04, PEG: Ca (NO
3)
2=4: 1; (NH
4)
2CO
3And Na
2HPO
4Be dissolved in distilled water, the Ca/P mol ratio is 1.67, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 30min with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, the amorphous manganese calcium phosphate that contains, with this precursor with 10 ℃/minute be warmed up to 900 ℃ down insulation obtain the hydroxyapatite powder of nano-structured slow release manganese ion after 3 hours.
Embodiment 8
With a certain proportion of La (NO
3)
3, Ca (NO
3)
26H
2O and polyvinyl alcohol (PVA) are dissolved in the distilled water, and wherein La/ (La+Ca) mol ratio is 0.0005, PVA: Ca (NO
3)
2=5: 1; Na
3PO
412H
2O and (NH
4)
2CO
3Be dissolved in distilled water, the Ca/P mol ratio is 1.60, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 1h with ammonia.Precipitate is through sucking filtration, washing, lyophilization 48 hours, the amorphous lanthanum calcium phosphate that contains, with this precursor with 5 ℃/minute be warmed up to 900 ℃ down insulation obtain the calcium phosphate composite powder that contains 60% hydroxyapatite, 40% β phase tricalcium phosphate of nano-structured slow release lanthanum ion after 4 hours.
Embodiment 9
With a certain proportion of Sr (NO
3)
2, La (NO
3)
3, Ca (NO
3)
26H
2O and polyvinyl alcohol (PVA) are dissolved in the distilled water, and wherein (La+Sr)/(La+Sr+Ca) mol ratio is 0.009, PVA: Ca (NO
3)
2=3: 1; K
3PO
4And K
2CO
3Be dissolved in distilled water, the Ca/P mol ratio is 1.54, is placed on 5 ℃ of following cold preservations after the stirring and dissolving.Treat temperature stabilization after 5 ℃, the speed of phosphorus solution with 2ml/min is added drop-wise in the calcium solution, regulate maintenance pH about 10, drip the end back and under magnetic agitation, react 1h with ammonia.Precipitate is through sucking filtration, washing, lyophilization 72 hours, amorphous strontium, the lanthanum calcium phosphate of containing, with this precursor with 5 ℃/minute be warmed up to 900 ℃ down insulation obtain the β phase tricalcium phosphate powder of nano-structured slow release strontium, lanthanum ion after 3 hours.
Claims (8)
1. the calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing, it is characterized in that the hydroxyapatite of each powder particle by nano-structured metal ion, any one in the tricalcium phosphate be mutually or biphase compound formation mutually for the α phase tricalcium phosphate of metal ion and the β of metal ion, single-phase crystallite dimension in every powder particle is 5nm-40nm, Ca/P mol ratio in the composite powder is 1.50～1.67, the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents metal ion zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, in the zirconium one or more.
2. the calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing according to claim 1, the particle diameter that it is characterized in that composite powder is 40nm～500nm.
3. the preparation method of the calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing according to claim 1, its feature may further comprise the steps:
1) calcium containing compound, phosphorus-containing compound and metal ion chemical compound is soluble in water, be mixed with solution respectively, place under 0～20 ℃, said calcium containing compound is lime nitrate, calcium chloride or calcium hydroxide; Said phosphorus-containing compound is ammonium hydrogen phosphate, sodium phosphate, phosphoric acid or potassium phosphate; Said metal ion chemical compound is a zinc, the nitrate of strontium, magnesium, lanthanum, europium, erbium, manganese, silicon or zirconium ion or chloride soluble compounds;
2) the calcium source solution that step 1) is made, metal ion solution and polymer mixed form mixed solution, place under 0～20 ℃, wherein the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metallic zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium ion; The mol ratio of polymer and calcium ion is 1: 10～10: 1, and polymer calculates with the molal quantity of construction unit, and said polymer is Polyethylene Glycol, polyvinyl alcohol or polyacrylic acid;
3) phosphorus solution that step 1) is made is added dropwise to step 2) solution in, the Ca/P mol ratio is 1.50, drip alkaline solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, reaction temperature is 0 ℃～20 ℃, response time is 5 minutes～48 hours, and reaction back separation, washing, lyophilization obtain metal ion amorphous calcium phosphate precursor;
4) with the heating rate of metal ion amorphous calcium phosphate precursor with 5 ℃/min～50 ℃/min, 700 ℃～900 ℃ following heat treatments 10 minutes～5 hours, last furnace cooling obtains the α phase tricalcium phosphate and/or the β phase tricalcium phosphate composite powder of metal ion.
4. press the preparation method of the calcium phosphate composite powder of the described biomedical sustained-releasing metal ion-containing of claim 3, the alkaline solution that it is characterized in that described adjusting pH value is ammonia, sodium hydroxide or potassium hydroxide solution.
5. the preparation method of the calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing according to claim 1, its feature may further comprise the steps:
1) calcium containing compound, phosphorus-containing compound, metal ion chemical compound and carbanion chemical compound is soluble in water, be mixed with solution respectively, place under 0～20 ℃, said calcium containing compound is lime nitrate, calcium chloride or calcium hydroxide; Said phosphorus-containing compound is ammonium hydrogen phosphate, sodium phosphate, phosphoric acid or potassium phosphate; Nitrate that said metal ion chemical compound is zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon or zirconium ion or chloride soluble compounds; Said carbanion chemical compound is the carbonate of zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, sodium or potassium ion;
2) calcium solution that step 1) is made, metal ion solution and polymer mixed form mixed solution, place under 0～20 ℃, wherein the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metallic zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium ion; The mol ratio of polymer and calcium ion is 1: 10～10: 1, and it is Polyethylene Glycol, polyvinyl alcohol or polyacrylic acid that polymer calculates said polymer with the molal quantity of construction unit;
3) be added dropwise to step 2 after phosphorus solution that step 1) is made and carbanion solution mix) mixed solution in, the Ca/P mol ratio is 1.50～1.67, carbonate and phosphate radical mol ratio are 15%～70%, drip alkaline solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, reaction temperature is 0～20 ℃, and the response time is 5 minutes～48 hours, reaction back separation, washing, lyophilization obtain metal ion amorphous calcium phosphate precursor;
4),, obtain the hydroxyapatite and/or the α phase tricalcium phosphate composite powder of metal ion at 800 ℃ of following heat treatments 10 minutes～5 hours, last furnace cooling with the heating rate of metal ion amorphous calcium phosphate precursor with 5 ℃/min～50 ℃/min.
6. press the preparation method of the calcium phosphate composite powder of the described biomedical sustained-releasing metal ion-containing of claim 5, the alkaline solution that it is characterized in that described adjusting pH value is ammonia, sodium hydroxide or potassium hydroxide solution.
7. the preparation method of the calcium phosphate composite powder of biomedical sustained-releasing metal ion-containing according to claim 1, its feature may further comprise the steps:
1) calcium containing compound, phosphorus-containing compound, metal ion chemical compound and carbanion chemical compound is soluble in water, be mixed with solution respectively, place under 0～20 ℃, said calcium containing compound is lime nitrate, calcium chloride or calcium hydroxide; Said phosphorus-containing compound is ammonium hydrogen phosphate, sodium phosphate, phosphoric acid or potassium phosphate; Nitrate that said metal ion chemical compound is zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon or zirconium ion or chloride soluble compounds; Said carbanion chemical compound is the carbonate of zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, zirconium, sodium or potassium ion;
2) calcium solution that step 1) is made, metal ion solution and polymer mixed form mixed solution, place under 0～20 ℃; Wherein the mol ratio of M/ (M+Ca) is 0.0001～0.1, and M represents one or more in metallic zinc, strontium, magnesium, lanthanum, europium, erbium, manganese, silicon, the zirconium ion; The mol ratio of polymer and calcium ion is 1: 10～10: 1, and polymer calculates with the molal quantity of construction unit, and said polymer is Polyethylene Glycol, polyvinyl alcohol or polyacrylic acid;
3) be added dropwise to step 2 after phosphorus solution that step 1) is made and carbanion solution mix) mixed solution in, the Ca/P mol ratio is 1.50～1.67, carbonate and phosphate radical mol ratio are 15%～70%, drip alkaline solution during reaction and regulate pH value 7～12, be reflected at constantly and carry out under the stirring, reaction temperature is 0～20 ℃, and the response time is 5 minutes～48 hours, reaction back separation, washing, lyophilization obtain metal ion amorphous calcium phosphate precursor;
4),, obtain the hydroxyapatite and/or the β phase tricalcium phosphate composite powder of metal ion at 900 ℃ of following heat treatments 10 minutes～5 hours, last furnace cooling with the heating rate of metal ion amorphous calcium phosphate precursor with 5 ℃/min～50 ℃/min.
8. press the preparation method of the calcium phosphate composite powder of the described biomedical sustained-releasing metal ion-containing of claim 7, the alkaline solution that it is characterized in that described adjusting pH value is ammonia, sodium hydroxide or potassium hydroxide solution.
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| CN108653804B (en) * | 2018-05-18 | 2020-05-08 | 山东大学 | Preparation method of silicon-doped calcium phosphate bone repair material |
| CN109091703B (en) * | 2018-08-08 | 2021-06-25 | 上海师范大学 | Rare earth element doped white phosphorus ore/gelatin three-dimensional porous composite material, and preparation method and application thereof |
| JP7281796B2 (en) * | 2019-01-09 | 2023-05-26 | 国立研究開発法人日本原子力研究開発機構 | Carbonate apatite with high carbonate group content |
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| JP2001198208A (en) * | 2000-01-19 | 2001-07-24 | Natl Inst For Res In Inorg Mater | Calcium phosphate type biocompatible ceramic sintered body and method of manufacturing the same |
| JP2004236895A (en) * | 2003-02-06 | 2004-08-26 | National Institute For Materials Science | Composite particle of calcium compound and glycosaminoglycane and manufacturing method |
| CN1213109C (en) * | 2003-07-28 | 2005-08-03 | 浙江大学 | Calcium phosphate composite powder and preparing method thereof |
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