CN116212117A - Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof - Google Patents

Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof Download PDF

Info

Publication number
CN116212117A
CN116212117A CN202211715375.7A CN202211715375A CN116212117A CN 116212117 A CN116212117 A CN 116212117A CN 202211715375 A CN202211715375 A CN 202211715375A CN 116212117 A CN116212117 A CN 116212117A
Authority
CN
China
Prior art keywords
strontium
magnesium
apatite
bone cement
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211715375.7A
Other languages
Chinese (zh)
Inventor
郭大刚
彭伟男
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Jiaotong University
Original Assignee
Xian Jiaotong University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Jiaotong University filed Critical Xian Jiaotong University
Priority to CN202211715375.7A priority Critical patent/CN116212117A/en
Publication of CN116212117A publication Critical patent/CN116212117A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
    • A61L27/425—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of phosphorus containing material, e.g. apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/602—Type of release, e.g. controlled, sustained, slow
    • A61L2300/604—Biodegradation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The invention discloses strontium magnesium slow-release apatite bioactive bone cement and a preparation process thereof, wherein the raw materials comprise solid phase powder and liquid phase, and the solid phase powder comprises tetra-calcium phosphate powder and beta tricalcium phosphate strontium magnesium powder; wherein, the molar ratio of the tetra-calcium phosphate to the beta tricalcium phosphate strontium magnesium is 1, (m+k), m is the ratio of the molar quantity of the beta tricalcium phosphate strontium magnesium which actually participates in the reaction to the molar quantity of the tetra-calcium phosphate, k is the ratio of the residual beta tricalcium phosphate strontium magnesium in the final solidified product after the reaction to the molar quantity of the tetra-calcium phosphate, x is the molar quantity of strontium doped in the tricalcium phosphate, and y is the molar quantity of magnesium doped in the tricalcium phosphate; the mass ratio of the solid phase powder to the liquid phase is 1.0-4.0. The strontium-magnesium slow-release apatite bioactive bone cement of the invention is only composed of two-phase powder, the strontium-magnesium doped amount and the calcium-strontium-magnesium/phosphorus ratio are adjustable, special pharmacological strontium and magnesium ions can be slowly released, and no toxic or side effect is caused.

Description

Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof
Technical Field
The invention belongs to the technical field of medical cement, and in particular relates to strontium-magnesium slow-release apatite bioactive bone cement and a preparation process thereof.
Background
Hydroxyapatite (HA) is one of the most commonly used calcium phosphates in bone tissue engineering, and artificial bone grafts composed of synthetic HA have been widely used as biological materials. Calcium phosphate cement (Calcium Phosphate Cement, abbreviated as CPC) is porous and the cured product is hydroxyapatite, however, this artificially synthesized hydroxyapatite is difficult to degrade in vivo, and this residue becomes a potential hazard for inducing inflammatory reactions. Therefore, it is very important to develop calcium phosphate bone cements with certain biodegradability.
Compared with the traditional calcium phosphate bone cement, the solubility of the magnesium phosphate bone cement is far higher than that of calcium phosphate, so that the magnesium ion release speed in vivo is higher, on the one hand, the strength of the cement is rapidly reduced, and on the other hand, the magnesium ion with too high concentration can obviously obstruct the activity of cells and cannot be used as a biological material well.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the strontium-magnesium slow-release apatite bioactive bone cement and the preparation process thereof.
The technical scheme adopted by the invention is as follows:
the strontium magnesium slow-release apatite bioactive bone cement comprises solid phase powder and liquid phase as raw materials, wherein the solid phase powder comprises Ca 4 (PO 4 ) 2 O powder and beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 A powder;
wherein Ca is 4 (PO 4 ) 2 O powder and beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The molar ratio of the powder is 1 (m+k), m is beta Ca actually participating in the reaction 3-x-y Sr x Mg y (PO 4 ) 2 Molar amount of (c) and Ca 4 (PO 4 ) 2 The ratio of the molar amount of O, k, is the beta Ca remaining in the final cured product after the reaction 3-x-y Sr x Mg y (PO 4 ) 2 Molar amount and Ca 4 (PO 4 ) 2 The ratio of the molar quantity of O, x is the molar quantity of strontium doped in tricalcium phosphate, and y is the molar quantity of magnesium doped in tricalcium phosphate;
the mass ratio of the solid phase powder to the liquid phase is 1.0-4.0.
Preferably, ca 4 (PO 4 ) 2 The particle size of the O powder is in the range of 0.8 μm to 200. Mu.m.
Preferably, beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The particle size of the powder is in the range of 0.8-200 μm.
Preferably, 0< m <50,0< k <50,0< x < 3.0,0< y < 3.0.
Preferably, the liquid phase is dilute phosphoric acid aqueous solution or deionized water.
Preferably, the concentration w of phosphoric acid in the dilute phosphoric acid aqueous solution satisfies 0mol/L < w.ltoreq.2.0 mol/L.
Preferably, the components of the strontium-magnesium slow-release apatite bioactive bone cement comprise strontium-magnesium-doped hydroxyapatite Ca 10-p-s-q Sr p Mg s (PO 4 ) 6 (OH) 2-2q And beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 Wherein p, s, q satisfy the following conditions: p=mx/n, s=my/n, q=10- (4+3m)/n, n=0.333 (m+1) + (0.069+0.052) w/z,0<p+s is less than or equal to 10, q is less than or equal to 0 and less than or equal to 1, w is the concentration of dilute phosphoric acid, and z is the mass ratio of solid phase powder to liquid phase.
Preferably, strontium-magnesium-doped hydroxyapatite Ca 10-p-s-q Sr p Mg s (PO 4 ) 6 (OH) 2-2q And beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The mass percentages of (a) and (b) are [100 na/(na+kb) respectively]% and [100 kb/(na+kb)]In%, a and b are intermediate parameters, a=87.62x+24.31y+1004.69-40.083 (p+s) -74.082q, and b= 47.54x-15.77y+310.2.
Preferably, the compression strength of the strontium-magnesium slow-release apatite bioactive bone cement solidified body is 15-50 MPa, the initial setting time is 3-8 min, the final setting time is 9-15 min, and the ratio of calcium, strontium, magnesium and phosphorus is 1.50-1.67.
The preparation method of the strontium-magnesium slow-release apatite bioactive bone cement comprises the following steps:
mixing the solid phase powder with a liquid phase to prepare the strontium-magnesium slow-release apatite bioactive bone cement.
The invention has the following beneficial effects:
the strontium-magnesium slow-release apatite bioactive bone cement is a degradable strontium-magnesium-doped biphasic calcium phosphate bioactive bone cement, the biodegradation rate of which can be regulated and controlled according to the relative content of two phases in a cured product, the strontium/magnesium-doped quantity and the strontium-magnesium/phosphorus molar ratio and is higher than the degradation rate of single-phase strontium-doped apatite bone cement. The strontium-magnesium-doped apatite bioactive bone cement has high and long-term stable mechanical property, proper setting time, adjustable strontium/magnesium-doped amount and calcium-strontium-magnesium/phosphorus ratio, controllable degradation rate, slow release of strontium magnesium ions for promoting bone tissue regeneration, and longer-term stable mechanical property and proper magnesium ion slow release speed compared with pure magnesium phosphate bone cement. Compared with the traditional calcium phosphate bone cement and other types of strontium-doped or magnesium-doped calcium phosphate bone cement, the material has remarkable advantages and is expected to be widely applied clinically.
Drawings
FIG. 1 SEM photograph of fracture morphology after fracturing a sample of example 1 of the present invention;
FIG. 2 is a graph of xrd of a sample of example 1 of the present invention after curing.
Detailed Description
The invention will be further described with reference to the drawings and examples.
The strontium-magnesium slow-release apatite bioactive bone cement consists of two-phase powder, the strontium/magnesium doping amount and the calcium-strontium-magnesium/phosphorus ratio are adjustable, and the novel strontium-magnesium co-doped apatite bone repair material which can slowly release special pharmacological strontium elements and magnesium elements and is degradable is prepared.
Specifically, the preparation method of the strontium magnesium sustained-release apatite bioactive bone cement comprises the following steps:
1) Composition of solid phase powder: tetracalcium phosphate Ca 4 (PO 4 ) 2 O, beta tricalcium phosphate strontium magnesium beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The powders are mixed according to a molar ratio of 1 (m+k), wherein m is beta Ca actually participating in the reaction in the reactants 3-x-y Sr x Mg y (PO 4 ) 2 Molar amount of (c) and Ca 4 (PO 4 ) 2 The ratio of the molar amount of O, k being beta Ca remaining in the final cured product 3-x-y Sr x Mg y (PO 4 ) 2 Molar amount and Ca 4 (PO 4 ) 2 Ratio of O molar quantity 0<x≤3.0，0<y≤3.0，0<m<50，0<k<50；
2) Preparation of a liquid phase: preparing dilute phosphoric acid H with concentration of w 3 PO 4 The water solution or deionized water is adopted as the cement curing liquid, wherein w is more than or equal to 0mol/L and less than or equal to 2.0mol/L;
3) Solid/liquid ratio selection: the mass ratio of the solid phase powder to the liquid phase is z, wherein z is more than or equal to 1.0 and less than or equal to 4.0.
The solid phase powder and the liquid phase are mixed according to the solid-liquid ratio range to prepare the strontium-magnesium slow-release apatite bioactive bone cement.
The final cured product of the novel strontium-magnesium slow-release apatite bioactive bone cement prepared by the preparation process is strontium-magnesium-doped hydroxyapatite Ca 10-p-s-q Sr p Mg s (PO 4 ) 6 (OH) 2-2q And the remaining beta tricalcium phosphate strontium magnesium beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 Wherein p, s, q satisfy p=mx/n, s=my/n, q=10- (4+3m)/n, n=0.333 (m+1) + (0.069+0.052) w/z,0<p+s is less than or equal to 10, q is less than or equal to 0 and less than or equal to 1, etc.; x, y are the same as beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 In the molecular formula, x, y and w are the concentration of dilute phosphoric acid, z is the mass ratio of solid phase powder to liquid phase in blending, the physical meanings of m and k are the same, and n, p and q are intermediate parameters convenient for expression; ca in the cured product 10-p-s-q Sr p Mg s (PO 4 ) 6 (OH) 2-2q And beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The mass percentages of (a) and (b) are [100 na/(na+kb) respectively]％、[100kb/(na+kb)]In%, a and b are only intermediate parameters, a=87.62x+24.31y+1004.69-40.083 (p+s) -74.082q, and b= 47.54x-15.77y+310.2. As long as the parameter x, y, s, w, z, m, k is given, n, p, s, q can be calculated to determine dopingThe specific molecular formula of the strontium-magnesium hydroxyapatite, the strontium/magnesium doping amount and the calcium-strontium-magnesium/phosphorus ratio.
The novel strontium-doped magnesium apatite bioactive bone cement prepared by the preparation process has the compression strength of a solidified body of 15-50 MPa, the initial setting time of 3-8 min, the final setting time of 9-15 min, the strontium/magnesium doped amount of 0-99%, and the calcium-strontium-magnesium/phosphorus ratio of 1.50-1.67, and is suitable for repairing and regenerating bones of non-bearing parts of human bodies.
The novel strontium-doped magnesium apatite bioactive bone cement prepared by the preparation process of the invention has solid phase powder of tetracalcium phosphate Ca 4 (PO 4 ) 2 O, tricalcium phosphate strontium magnesium beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The average particle size ranges of (2) are 0.8 μm to 200 μm and 0.8 μm to 200 μm, respectively.
Example 1
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 The molar ratio is 1 (2+0.5), i.e. m=2, k=0.5) to 0.33g of H with a concentration w of 0.75mol/L 3 PO 4 An aqueous solution (where x=0.25, y=0.25; solid/liquid mass ratio z is 1.8:1) was spoonalized for 30s to form a uniform cement paste, filled into a stainless steel cylinder mold having a diameter of 6mm and a height of 12mm and compacted under a pressure of 0.7MPa, the prepared cylinder sample was packed into a glass tube having a diameter of 6.5mm and a height of 13mm, then placed into an atmosphere having a temperature of 37 ℃ and a relative humidity of 100% for curing, pre-cured for 30min, the sample was taken out and rapidly immersed into a Simulated Body Fluid (SBF), and a final product composition of 86.35% strontium-doped magnesium hydroxyapatite (Ca) was formed after 3d 8.56 Sr 0.48 Mg 0.48 (PO 4 ) 6 (OH) 1.02 (ca+sr+mg)/p=1.59, strontium-doped Sr/(ca+sr+mg) =5.04%, magnesium-doped Mg/(ca+sr+mg) =5.04%) and 13.65% βca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 . The average compressive strength of the test specimen after 3 days of immersion in SBF was 25.90MPa. The initial setting time was 5min and the final setting time was 11.5min. From the fracture scanning electron microscope photograph of the cured product in FIG. 1It can be seen that particles with similar sizes and needle-like crystals attached to the surface exist on the section. In combination with the xrd spectrum analysis of FIG. 2, the solidified product is a biphasic mixture of hydroxyapatite and tricalcium phosphate, and the needle-like crystal in FIG. 1 is hydroxyapatite Ca in the reaction product 8.56 Sr 0.48 Mg 0.48 (PO 4 ) 6 (OH) 1.02 Crystals, particles are residual unreacted beta Ca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 。
Example 2
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 The molar ratio is 1 (2+1), i.e. m=2, k=1, to 0.33g of H with a concentration w of 0.75mol/L 3 PO 4 An aqueous solution (where x=0.25, y=0.25; solid/liquid mass ratio z is 1.8:1) was spooned and stirred for 30s to form a uniform cement paste, filled into a stainless steel cylinder mold having a diameter of 6mm and a height of 12mm and compacted under a pressure of 0.7MPa, the prepared cylinder sample was packed into a glass tube having a diameter of 6.5mm and a height of 13mm, then placed into an atmosphere having a temperature of 37 ℃ and a relative humidity of 100% for curing, pre-cured for 30min, the sample was taken out and rapidly immersed in an SBF simulated body fluid, and a final product composition of a cured body after 3d was 75.98% strontium-doped magnesium hydroxyapatite (Ca 8.56 Sr 0.48 Mg 0.48 (PO 4 ) 6 (OH) 1.02 (ca+sr+mg)/p=1.59, strontium-doped Sr/(ca+sr+mg) =5.04%, magnesium-doped Mg/(ca+sr+mg) =5.04%) and 24.02% βca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 . The average compressive strength of the test specimen after 3 days of soaking in SBF was 18.94MPa. The initial setting time was 6min and the final setting time was 13.5min.
Example 3
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.1 Mg 0.4 (PO 4 ) 2 The molar ratio is 1 (2+0.5), i.e. m=2, k=0.5) to 0.33g of H with a concentration w of 0.75mol/L 3 PO 4 Aqueous solution (whereinx=0.1, y=0.4; the solid/liquid mass ratio z is 1.8:1) is stirred with a medicine spoon for 30s to form uniform cement slurry, the cement slurry is filled into a stainless steel cylinder mould with the diameter of 6mm and the height of 12mm, the pressure of 0.7MPa is applied to compact the cement slurry, a prepared cylinder sample is plugged into a glass tube with the diameter of 6.5mm and the height of 13mm, the glass tube is placed into an environment with the temperature of 37 ℃ and the relative humidity of 100 percent to be solidified, after the pre-solidification for 30min, the sample is taken out and is quickly immersed into SBF simulated body fluid, and after 3d, the strontium-doped magnesium hydroxyapatite (Ca) with the final product component of 76.47 percent of a solidified body is formed 8.39 Sr 0.19 Mg 0.75 (PO 4 ) 6 (OH) 0.66 (ca+sr+mg)/p=1.56, strontium-doped Sr/(ca+sr+mg) =2.04%, magnesium-doped Mg/(ca+sr+mg) =8.15%) and 23.52% βca 2.5 Sr 0.1 Mg 0.4 (PO 4 ) 2 . The average compressive strength of the test specimen after 3 days of immersion in SBF was 19.36MPa. The initial setting time was 5.5min and the final setting time was 13.5min.
Example 4
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 The molar ratio is 1 (2+0.5), i.e. m=2, k=0.5) to 0.33g of H with a concentration w of 1.0mol/L 3 PO 4 An aqueous solution (where x=0.25, y=0.25; solid/liquid mass ratio z is 1.8:1) was spooned and stirred for 30s to form a uniform cement paste, filled into a stainless steel cylinder mold having a diameter of 6mm and a height of 12mm and compacted under a pressure of 0.7MPa, the prepared cylinder sample was packed into a glass tube having a diameter of 6.5mm and a height of 13mm, then placed into an atmosphere having a temperature of 37 ℃ and a relative humidity of 100% for curing, pre-cured for 30min, the sample was taken out and rapidly immersed in an SBF simulated body fluid, and a final product composition of a cured body after 3d was 86.50% strontium-doped magnesium hydroxyapatite (Ca 8.2 Sr 0.46 Mg 0.46 (PO 4 ) 6 (OH) 0.24 (ca+sr+mg)/p=1.52, strontium-doped amount Sr/(ca+sr+mg) =5.04%, magnesium-doped amount Mg/(ca+sr+mg) =5.04%) and 13.50% β -Ca 2.5 Sr 0.1 Mg 0.4 (PO 4 ) 2 . Average of samples soaked in SBF for 3 daysThe compressive strength was 27.43MPa. The initial setting time was 4.5min and the final setting time was 11.5min.
Example 5
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.4 Mg 0.1 (PO 4 ) 2 The molar ratio is 1 (2+0.5), i.e. m=2, k=0.5) to 0.30g of H with a concentration w of 0.75mol/L 3 PO 4 An aqueous solution (wherein x=0.40, y=0.10; solid/liquid mass ratio z is 2.0:1) was spooned and stirred for 30s to form a uniform cement paste, filled into a stainless steel cylinder mold having a diameter of 6mm and a height of 12mm and compacted by applying a pressure of 0.7MPa, the prepared cylinder sample was packed into a glass tube having a diameter of 6.5mm and a height of 13mm, and then placed into an atmosphere having a temperature of 37 ℃ and a relative humidity of 100% for curing, and after precuring for 30min, the sample was taken out and rapidly immersed into an SBF simulated body fluid, and after 3 days, a strontium-doped magnesium hydroxyapatite (Ca) having a product component of 85.55% was formed as a cured body 8.45 Sr 0.75 Mg 0.19 (PO 4 ) 6 (OH) 0.78 (ca+sr+mg)/p=1.57, strontium-doped amount Sr/(ca+sr+mg) =7.98%, magnesium-doped amount Mg/(ca+sr+mg) =2.02%) and β Ca of 14.45% 2.5 Sr 0.1 Mg 0.4 (PO 4 ) 2 . The average compressive strength of the test specimen after 3 days of immersion in SBF was 25.57MPa. The initial setting time was 6.5min and the final setting time was 14.5min.
Example 6
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 The molar ratio is 1 (2+2), i.e. m=2, k=2, to 0.33g of H with a concentration w of 0.75mol/L 3 PO 4 The aqueous solution (where x=0.25, y=0.25; solid/liquid mass ratio z is 1.8:1) was spooned and stirred for 30s to form a uniform cement paste, filled into a stainless steel cylinder mold with a diameter of 6mm and a height of 12mm and compacted under a pressure of 0.7MPa, the prepared cylinder sample was packed into a glass tube with a diameter of 6.5mm and a height of 13mm, then placed into an environment with a temperature of 37 ℃ and a relative humidity of 100% for curing, and after pre-curing for 30min, the sample was taken out and rapidly immersed in SBF in simulated body fluid, the product component forming a solidified body after 3 days was 61.43% strontium-magnesium-doped hydroxyapatite (Ca 8.39 Sr 0.47 Mg 0.47 (PO 4 ) 6 (OH) 0.66 (ca+sr+mg)/p=1.56, strontium-doped amount Sr/(ca+sr+mg) =5.19%, magnesium-doped amount Mg/(ca+sr+mg) =5.19%) and 38.57% βca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 . The average compressive strength of the test specimen after 3 days of soaking in SBF was 15.49MPa. The initial setting time was 5.5min and the final setting time was 13.5min.
Example 7
0.6g of cement mixed powder (Ca 4 (PO 4 ) 2 O and beta Ca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 The molar ratio is 1 (2+1.5), i.e. m=2, k=1.5, to 0.33g of H with a concentration w of 0.75mol/L 3 PO 4 The aqueous solution (where x=0.25, y=0.25; solid/liquid mass ratio z is 1.8:1) was spooned and stirred for 30s to form a uniform cement paste, filled into a stainless steel cylinder mold having a diameter of 6mm and a height of 12mm and compacted under a pressure of 0.7MPa, the prepared cylinder sample was packed into a glass tube having a diameter of 6.5mm and a height of 13mm, and then placed into an atmosphere having a temperature of 37 ℃ and a relative humidity of 100% for curing, and after precuring for 30min, the sample was taken out and rapidly immersed into an SBF simulated body fluid, and after 3 days, a strontium-doped magnesium hydroxyapatite (Ca) having a product composition of 67.97% was formed as a cured body 8.39 Sr 0.47 Mg 0.47 (PO 4 ) 6 (OH) 0.66 (ca+sr+mg)/p=1.56, strontium-doped amount Sr/(ca+sr+mg) =5.19%, magnesium-doped amount Mg/(ca+sr+mg) =5.19%) and 32.03% βca 2.5 Sr 0.25 Mg 0.25 (PO 4 ) 2 . The average compressive strength of the test specimen after 3 days of soaking in SBF was 18.45MPa. The initial setting time was 5.5min and the final setting time was 12.5min.
According to the above example, the compression strength of the strontium-magnesium co-doped biphasic calcium phosphate bone cement solidified body is 15-50 MPa, the initial setting time is 3-8 min, the final setting time is 9-15 min, and the ratio of calcium, strontium, magnesium and phosphorus is 1.50-1.67, so that the solidified body is suitable for repairing and regenerating bones of non-bearing parts of human bodies.
According to the scheme, the complex ion doped bone cement raw materials are reduced to two types through the solid phase sintering method, so that the raw material system is simpler. In addition, the invention transfers magnesium ions from a pure magnesium phosphate bone cement system to a strontium-doped biphasic calcium phosphate bone cement system, and overcomes the defect of excessively rapid degradation of the magnesium phosphate bone cement while retaining the biological characteristics of the magnesium phosphate bone cement system. Finally, the invention uses the high degradability of the strontium-doped biphase calcium phosphate bone cement, maintains the strength of the cement and certain degradability, and has wider clinical application space and wider industrialization prospect.

Claims (10)

1. The strontium magnesium slow-release apatite bioactive bone cement is characterized by comprising solid phase powder and liquid phase as raw materials, wherein the solid phase powder comprises Ca 4 (PO 4 ) 2 O powder and beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 A powder;
wherein Ca is 4 (PO 4 ) 2 O powder and beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The molar ratio of the powder is 1 (m+k), m is beta Ca actually participating in the reaction 3-x-y Sr x Mg y (PO 4 ) 2 Molar amount of (c) and Ca 4 (PO 4 ) 2 The ratio of the molar amount of O, k, is the beta Ca remaining in the final cured product after the reaction 3-x-y Sr x Mg y (PO 4 ) 2 Molar amount and Ca 4 (PO 4 ) 2 The ratio of the molar quantity of O, x is the molar quantity of strontium doped in tricalcium phosphate, and y is the molar quantity of magnesium doped in tricalcium phosphate;
the mass ratio of the solid phase powder to the liquid phase is 1.0-4.0.
2. The strontium magnesium extended release apatite bioactive bone cement of claim 1, wherein Ca 4 (PO 4 ) 2 The particle size of the O powder is in the range of 0.8 μm to 200. Mu.m.
3. The strontium magnesium sustained-release apatite bioactivity of claim 1Bone cement characterized by beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The particle size of the powder is in the range of 0.8-200 μm.
4. The strontium magnesium extended release apatite bioactive bone cement according to claim 1, wherein 0< m <50,0< k <50,0< x < 3.0,0< y < 3.0.
5. The strontium magnesium extended release apatite bioactive bone cement according to claim 1, wherein the liquid phase is dilute phosphoric acid aqueous solution or deionized water.
6. The strontium magnesium sustained-release apatite bioactive bone cement according to claim 1, wherein the concentration w of phosphoric acid in the diluted phosphoric acid aqueous solution satisfies 0mol/L < w.ltoreq.2.0 mol/L.
7. The strontium magnesium extended release apatite bioactive bone cement according to claim 1, wherein the strontium magnesium extended release apatite bioactive bone cement comprises strontium magnesium extended release hydroxyapatite Ca 10-p-s-q Sr p Mg s (PO 4 ) 6 (OH) 2-2q And beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 Wherein p, s, q satisfy the following conditions: p=mx/n, s=my/n, q=10- (4+3m)/n, n=0.333 (m+1) + (0.069+0.052) w/z,0<p+s is less than or equal to 10, q is less than or equal to 0 and less than or equal to 1, w is the concentration of dilute phosphoric acid, and z is the mass ratio of solid phase powder to liquid phase.
8. The strontium magnesium extended release apatite bioactive bone cement according to claim 7, wherein the strontium magnesium doped hydroxyapatite Ca 10-p-s-q Sr p Mg s (PO 4 ) 6 (OH) 2-2q And beta Ca 3-x-y Sr x Mg y (PO 4 ) 2 The mass percentages of (a) and (b) are [100 na/(na+kb) respectively]% and [100 kb/(na+kb)]In%, a and b are intermediate parameters, a=87.62x+24.31y+1004.69-40.083 (p+s) -74.082q, b= 47.54x-15.77y+310.2。
9. The strontium magnesium sustained-release apatite bioactive bone cement according to claim 1, wherein the compression strength of the strontium magnesium sustained-release apatite bioactive bone cement solidified body is 15-50 MPa, the initial setting time is 3-8 min, the final setting time is 9-15 min, and the calcium strontium magnesium/phosphorus ratio is 1.50-1.67.
10. The method for preparing the strontium magnesium sustained-release apatite bioactive bone cement according to claim 1, comprising the following steps:
mixing the solid phase powder with a liquid phase to prepare the strontium-magnesium slow-release apatite bioactive bone cement.
CN202211715375.7A 2022-12-29 2022-12-29 Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof Pending CN116212117A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211715375.7A CN116212117A (en) 2022-12-29 2022-12-29 Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211715375.7A CN116212117A (en) 2022-12-29 2022-12-29 Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof

Publications (1)

Publication Number Publication Date
CN116212117A true CN116212117A (en) 2023-06-06

Family

ID=86583497

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211715375.7A Pending CN116212117A (en) 2022-12-29 2022-12-29 Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof

Country Status (1)

Country Link
CN (1) CN116212117A (en)

Similar Documents

Publication Publication Date Title
US6521264B1 (en) Method for preparing a biomaterial based on hydroxyapatite, resulting biomaterial and surgical or dental use
EP1715829B1 (en) Rapid-hardening calcium phosphate cement compositions
Gbureck et al. Ionic modification of calcium phosphate cement viscosity. Part I: hypodermic injection and strength improvement of apatite cement
CN101157045B (en) Complex self-curing material, method and application of bioactivity calcium phosphate/tricalcium silicate
JPS6242625B2 (en)
Sun et al. Fast setting calcium phosphate cement-chitosan composite: mechanical properties and dissolution rates
CN104853783B (en) Form composition, monetite cement, implant and the method for correcting Cranial defect of cement
JPH09506588A (en) Reactive tricalcium phosphate compositions and uses
JP2004083410A (en) New calcium phosphate cement composition and method of preparing the same
CN108635624B (en) Anti-collapsibility injectable magnesium phosphate-based bone cement
CN100340526C (en) Preparation process of degradable foam-like strontium-doped calcium phosphate ceramic bone holder material
Haque et al. In vitro and in vivo research advancements on the magnesium phosphate cement biomaterials: A review
CN109395160B (en) Rapidly degradable injectable bone cement and application thereof
de Aza et al. α^ ′ _ H α′ H-Dicalcium silicate bone cement doped with tricalcium phosphate: characterization, bioactivity and biocompatibility
CN109331223B (en) Medicine-carrying bioactive glass composite calcium phosphate bone cement and application thereof
Jeong et al. Preparation, characterization, and in-vitro performance of novel injectable silanized-hydroxypropyl methylcellulose/phase-transformed calcium phosphate composite bone cements
JPS6272363A (en) Medical or dental cement composition
Sun et al. A novel fast-setting strontium-containing hydroxyapatite bone cement with a simple binary powder system
CN116212117A (en) Strontium magnesium slow-release apatite bioactive bone cement and preparation process thereof
DE102008010210A1 (en) Preparation for magnesium ammonium phosphate cements
RU2292868C1 (en) Material for filling maxillofacial and dental bone defects
CN107412874B (en) Injectable calcium sulfate hemihydrate/octacalcium phosphate/sodium hyaluronate sulfate composite artificial bone material and preparation method thereof
CN101444638B (en) Process for preparing degradable strontium-doped biphasic calcium phosphate bioactive bone cement
AU2011272740B2 (en) Fluorapatite-forming calcium phosphate cements
JPH0526503B2 (en)

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination