CN106145077B - A kind of preparation method of hydroxyapatite oriented growth structure - Google Patents

A kind of preparation method of hydroxyapatite oriented growth structure Download PDF

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Publication number
CN106145077B
CN106145077B CN201610489924.1A CN201610489924A CN106145077B CN 106145077 B CN106145077 B CN 106145077B CN 201610489924 A CN201610489924 A CN 201610489924A CN 106145077 B CN106145077 B CN 106145077B
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hydroxyapatite
preparation
oriented growth
growth structure
structure according
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CN106145077A (en
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赵火英
汤金华
张文凯
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Jiangsu Hongxin Construction Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/32Phosphates of magnesium, calcium, strontium, or barium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention provides a kind of preparation method of hydroxyapatite oriented growth structure, hydroxyapatite can be made to be grown according to assigned direction, comprised the following steps:1) according to mol ratio Ca:P=10:Soluble calcium salt and soluble phosphate are dissolved in water by 6, are configured to Ca2+Concentration is 0.01~1mol/L solution;2) carragheen and polyacrylic acid are added, the addition of carragheen is the 0.5~5% of solution quality, and the addition of polyacrylic acid is the 1~5% of solution quality, in 40~50 DEG C of stirrings to after being completely dissolved, continues 30~60min of stirring;3) room temperature is cooled to, is placed in open-top receptacle, to the ammonia that liquid level wind drift amount is 0.01~1ml/min at 5~20mm of ullage, is reacted 1~7 day;4) filter, be washed to PH as 7~8;5) alcohol is washed, and is heated 2~4h at 140~300 DEG C, is ground, obtain product.

Description

A kind of preparation method of hydroxyapatite oriented growth structure
【Technical field】
The present invention relates to artificial bone field, more particularly to a kind of preparation method of hydroxyapatite oriented growth structure.
【Background technology】
Phosphorus ash stone mineral are most common calcium phosphate mineral, wherein again with hydroxyapatite (HAP, Ca10(PO4)6 (OH)2For Typical Representative), bone and the most important inorganic constituents of tooth are HAP.HAP is in organism mainly with monoclinic system It is existence phase with hexagonal crystal system, both things mutually can be converted mutually under certain condition.In order to further explore life mistake Journey, promoting biology --- bionical development, it is always to study heat to form HAP physiology mineralization process and life regulatory mechanism Point.
Research finds that what is formed at first from solution in HAP forming processes is the unformed phosphoric acid of thermodynamic instability Calcium precursor (AmorpHous calcium pHospHate, ACP).ACP possesses good mobility and plasticity, using ACP as Interference and regulation and control of the HAP crystallization process of forerunner's phase by many factors such as temperature, pH value, solution degree of supersaturation, organic additives. The HAP orientation of growth has been largely fixed the performances such as HAP intensity, elasticity, therefore, finds new preparation method so that HAP is significantly for the applications of artificial HAP medically according to assigned direction oriented growth.
【The content of the invention】
For above mentioned problem of the prior art, the present invention provides a kind of preparation side of hydroxyapatite oriented growth structure Method, hydroxyapatite can be made to be grown according to assigned direction.
The technical scheme is that:
A kind of preparation method of hydroxyapatite oriented growth structure, it is characterised in that comprise the following steps:
(1) according to mol ratio Ca:P=10:6 ratio, soluble calcium salt and soluble phosphate are dissolved in water, are configured to Ca2+Concentration is 0.01~1mol/L solution;
(2) carragheen and polyacrylic acid (Polyacrylic acid, PAA), institute are added in the solution obtained by step (1) The addition for stating carragheen is the 0.5~5% of step (1) solution quality, and the addition of the polyacrylic acid is step (1) solution The 1~5% of quality, under the conditions of 40~50 DEG C, stir to after being completely dissolved, continue 30~60min of stirring;
(3) stop heating, the solution obtained by step (2) is cooled to room temperature, is placed in open-top receptacle, in ullage 5 To the ammonia that liquid level wind drift amount is 0.01~1mL/min at~20mm, react 1~7 day;
(4) mixture obtained by step (3) is filtered, filter cake is washed to pH as 7~8;
(5) the filter cake alcohol obtained by step (4) is washed, 2~4h is heated at 140~300 DEG C, is ground, obtained final Product.
Preferably, above-mentioned soluble calcium salt refers to the one or more in calcirm-fluoride, calcium chloride, calcium nitrate.
Preferably, above-mentioned soluble phosphate refers to sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate One or more.
Preferably, above-mentioned carragheen is lambda-carrageenan.
Preferably, the molecular weight of above-mentioned polyacrylic acid is 4000~5000.
Preferably, the addition of carragheen is the 0.5~2% of step (1) solution quality in above-mentioned steps (2).
Preferably, the addition of polyacrylic acid is the 3~5% of step (1) solution quality in above-mentioned steps (2).
Preferably, during above-mentioned steps (3), container and solution keep standing.
Preferably, the flow of ammonia is 0.05~0.1mL/min in above-mentioned steps (3).
Preferably, being provided with above above-mentioned steps (3) open-top receptacle prevents the dust cover of pollution.
The present invention has technique effect beneficial below:
1) present invention can prepare hydroxyapatite pure phase, and make hydroxyl phosphorus by appropriate formula, proportioning and step Lime stone is grown to the umbrella cylindricality to be grown centered on the site that ammonia enters solution system;2) present invention passes through polyacrylic acid molecule The carboxyl of carrying and the chelation of calcium ion, extend stabilization time of the ACP forerunner mutually in aqueous phase so that hydroxyapatite is given birth to It is grown to ordered structure;3) present invention limits life of the hydroxyapatite in radial direction by the double-spiral structure between carrageenan molecule Long spacing, its phase axial growth is limited, form specific structure, the size of radial direction can be carried out necessarily by the concentration of carragheen The regulation and control of scope;4) in whole course of reaction, the power of crystallization is from quiet with diffusion of the ammonia to liquid internal, holding container Other disturbances only can be reduced with appropriate ammonia flow, make structural integrity orderly.
【Brief description of the drawings】
Fig. 1 is the stereoscan photograph of embodiment one.
【Embodiment】
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment provided below is simultaneously not used to the scope that the limitation present invention is covered, described step nor with To limit its execution sequence.Those skilled in the art do conspicuously improved with reference to existing common knowledge to the present invention, also fall Enter within the protection domain of application claims.
Embodiment one
A kind of preparation method of hydroxyapatite oriented growth structure, it is characterised in that comprise the following steps:
(1) according to mol ratio Ca:P=10:6 ratio, calcirm-fluoride and sodium dihydrogen phosphate are dissolved in water, are configured to Ca2+It is dense Spend the solution for 0.01mol/L;
(2) lambda-carrageenan and molecular weight are added in the solution obtained by step (1) as 4000~5000 polyacrylic acid, institute The addition for stating carragheen is the 0.5% of step (1) solution quality, and the addition of the polyacrylic acid is step (1) solution matter The 1% of amount, under the conditions of 40~50 DEG C, stir to after being completely dissolved, continue 30~60min of stirring;
(3) stop heating, the solution obtained by step (2) is cooled to room temperature, takes and is placed in right amount in open glass container, should It is 0.01mL/min's to liquid level wind drift amount that the dust cover for preventing polluting is provided with above open-top receptacle at ullage 5mm Ammonia, stand reaction 7 days;
(4) mixture obtained by step (3) is filtered, filter cake is washed to pH as 7~8;
(5) the filter cake alcohol obtained by step (4) is washed, heats 2h at 300 DEG C, grind, obtain final products, such as schemed Shown in 1.Characterized by XRD, product is hydroxyapatite, and can be seen that product from Fig. 1 SEM photograph is using any as growth Center, radial direction is limited, prolongs the umbrella column construction of axial growth.
Embodiment two
A kind of preparation method of hydroxyapatite oriented growth structure, it is characterised in that comprise the following steps:
(1) according to mol ratio Ca:P=10:6 ratio, calcium chloride and disodium hydrogen phosphate are dissolved in water, are configured to Ca2+It is dense Spend the solution for 0.02mol/L;
(2) lambda-carrageenan and molecular weight are added in the solution obtained by step (1) as 4000~5000 polyacrylic acid, institute The addition for stating lambda-carrageenan is the 2% of step (1) solution quality, and the addition of the polyacrylic acid is step (1) solution matter The 3% of amount, under the conditions of 40~50 DEG C, stir to after being completely dissolved, continue 30~60min of stirring;
(3) stop heating, the solution obtained by step (2) is cooled to room temperature, takes and is placed in right amount in open glass container, should The dust cover that being provided with above open-top receptacle prevents from polluting is 0.05mL/min to liquid level wind drift amount at ullage 10mm Ammonia, stand reaction 5 days;
(4) mixture obtained by step (3) is filtered, filter cake is washed to pH as 7~8;
(5) the filter cake alcohol obtained by step (4) is washed, heats 3h at 250 DEG C, grind, obtain final products.
Embodiment three
A kind of preparation method of hydroxyapatite oriented growth structure, it is characterised in that comprise the following steps:
(1) according to mol ratio Ca:P=10:6 ratio, calcium nitrate and dipotassium hydrogen phosphate are dissolved in water, are configured to Ca2+It is dense Spend the solution for 0.5mol/L;
(2) lambda-carrageenan and molecular weight are added in the solution obtained by step (1) as 4000~5000 polyacrylic acid, institute The addition for stating lambda-carrageenan is the 5% of step (1) solution quality, and the addition of the polyacrylic acid is step (1) solution matter The 5% of amount, under the conditions of 40~50 DEG C, stir to after being completely dissolved, continue 30~60min of stirring;
(3) stop heating, the solution obtained by step (2) is cooled to room temperature, takes and is placed in right amount in open glass container, should It is 0.1mL/min's to liquid level wind drift amount that the dust cover for preventing polluting is provided with above open-top receptacle at ullage 15mm Ammonia, stand reaction 3 days;
(4) mixture obtained by step (3) is filtered, filter cake is washed to pH as 7~8;
(5) the filter cake alcohol obtained by step (4) is washed, heats 3h at 200 DEG C, grind, obtain final products.
Example IV
A kind of preparation method of hydroxyapatite oriented growth structure, it is characterised in that comprise the following steps:
(1) according to mol ratio Ca:P=10:6 ratio, calcium chloride, calcium nitrate and potassium dihydrogen phosphate are dissolved in water, configured Into Ca2+Concentration is 0.1mol/L solution;
(2) lambda-carrageenan and molecular weight are added in the solution obtained by step (1) as 4000~5000 polyacrylic acid, institute The addition for stating lambda-carrageenan is the 5% of step (1) solution quality, and the addition of the polyacrylic acid is step (1) solution matter The 3% of amount, under the conditions of 40~50 DEG C, stir to after being completely dissolved, continue 30~60min of stirring;
(3) stop heating, the solution obtained by step (2) is cooled to room temperature, takes and is placed in right amount in open glass container, should The dust cover for preventing polluting is provided with above open-top receptacle at ullage 20mm to the ammonia that liquid level wind drift amount is 1mL/min Gas, stand reaction 1 day;
(4) mixture obtained by step (3) is filtered, filter cake is washed to pH as 7~8;
(5) the filter cake alcohol obtained by step (4) is washed, heats 4h at 140 DEG C, grind, obtain final products.

Claims (10)

1. a kind of preparation method of hydroxyapatite oriented growth structure, it is characterised in that comprise the following steps:
(1) according to mol ratio Ca:P=10:6 ratio, soluble calcium salt and soluble phosphate are dissolved in water, are configured to Ca2+ Concentration is 0.01~1mol/L solution;
(2) carragheen and polyacrylic acid are added in the solution obtained by step (1), the addition of the carragheen is step (1) The 0.5~5% of solution quality, the addition of the polyacrylic acid is the 1~5% of step (1) solution quality, in 40~50 DEG C of bars Under part, stir to after being completely dissolved, continue 30~60min of stirring;
(3) stop heating, the solution obtained by step (2) is cooled to room temperature, takes and is placed in right amount in open-top receptacle, in ullage To the ammonia that liquid level wind drift amount is 0.01~1mL/min at 5~20mm, react 1~7 day;
(4) mixture obtained by step (3) is filtered, filter cake is washed to pH as 7~8;
(5) the filter cake alcohol obtained by step (4) is washed, 2~4h is heated at 140~300 DEG C, grinds, obtains final products.
2. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that described solvable Property calcium salt refers to the one or more in calcium chloride, calcium nitrate.
3. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that described solvable Acid phosphate refers to the one or more of sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate.
4. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that the OK a karaoke club Glue is lambda-carrageenan.
5. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that described poly- third The molecular weight of olefin(e) acid is 4000~5000.
6. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that the step (2) addition of carragheen is the 0.5~2% of step (1) solution quality in.
7. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that the step (2) addition of polyacrylic acid is the 3~5% of step (1) solution quality in.
8. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that the step (3) during, container and solution keep standing.
9. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that the step (3) flow of ammonia is 0.05~0.1mL/min in.
10. the preparation method of hydroxyapatite oriented growth structure according to claim 1, it is characterised in that the step Suddenly being provided with above (3) open-top receptacle prevents the dust cover of pollution.
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CN107522883B (en) * 2017-08-18 2020-10-13 深圳技术大学筹备办公室 Preparation method of hydroxyapatite composite film material
CN108926743B (en) * 2018-08-20 2020-07-14 北京恒泽博泰生物科技有限公司 Three-dimensional mineralized collagen scaffold material and bone regeneration application thereof
CN110236958B (en) * 2019-06-28 2020-12-29 武汉大学 Material for promoting repair of defective and missing tooth tissues and preparation method thereof
CN113603933B (en) * 2021-07-16 2023-04-11 佛山仙湖实验室 Method for regulating and controlling hydroxyapatite nanoparticle aggregate and application
CN114934389B (en) * 2022-06-30 2024-01-26 首都医科大学 Mineralization method of collagen fibers
CN118490715A (en) * 2024-05-14 2024-08-16 江苏海洋大学 Composite material for promoting bone and resisting tumor after osteosarcoma excision and preparation method thereof

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CN103553013A (en) * 2013-11-17 2014-02-05 北华航天工业学院 Preparation method of nano hydroxyapatite powder with controllable morphology
CN104709886A (en) * 2013-12-12 2015-06-17 江南大学 Dual-component template hydrothermal preparation method of nano hydroxyapatite
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