CN111115597A - Preparation method of porous nano hydroxyapatite based on aromatic acid salt - Google Patents
Preparation method of porous nano hydroxyapatite based on aromatic acid salt Download PDFInfo
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- CN111115597A CN111115597A CN201811272362.0A CN201811272362A CN111115597A CN 111115597 A CN111115597 A CN 111115597A CN 201811272362 A CN201811272362 A CN 201811272362A CN 111115597 A CN111115597 A CN 111115597A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
Abstract
The invention relates to a preparation method of porous nano hydroxyapatite based on aromatic acid salt, which comprises the following steps: (1) taking 20 parts of calcium salt-water-aromatic acid salt mixed solution; (2) taking 20 parts of sodium hydroxide-water-phosphorus source mixed solution; (3) adding the mixed solution prepared in the step (2) into the reactor in the step (1), and carrying out reflux reaction for 1-4 hours; (4) then heating the mixture obtained in the step (3) to 100-160 ℃, and carrying out hydrothermal reaction under autogenous pressure for 12-36 hours; (5) standing the stock solution at room temperature for 0-3 days, then washing with water, centrifuging, and drying in vacuum to obtain white powder which is porous nano-hydroxyapatite. The method does not need template agents such as organic polymers, surfactants and the like, and the finally obtained product is the porous nano-hydroxyapatite with good crystallinity and high purity. The method has simple operation procedure and low required cost.
Description
Technical Field
The technical scheme of the invention belongs to the technical field of synthesis of porous nano-structure materials, and particularly relates to a preparation method of porous nano-hydroxyapatite based on aromatic acid salt.
Background
Hydroxyapatite is a natural apatite mineral with a chemical structure of Ca10(PO4)6(OH)2. Pure hydroxyapatite powder is white, but natural hydroxyapatite is mixed with brown and yellowOr green. Hydroxyapatite is the main inorganic component of bones and teeth of humans and vertebrates, and after being implanted into the body, calcium and phosphorus are liberated from the surface of the material and absorbed by body tissues, and new tissues grow out.
The porous nano-hydroxyapatite has the characteristics of the nano-hydroxyapatite, such as high specific surface area and high reaction activity; and the porous nano-hydroxyapatite has the characteristics of a nano-mesoporous structure, such as special optical, electrical and magnetic properties and good adsorption capacity, so that the porous nano-hydroxyapatite has wide application values in the aspects of bionic preparation, biomedical materials, nano-reinforcement and catalysis.
At present, many researches on porous nano-hydroxyapatite are carried out, but most of them adopt surfactant or polymer as template agent, (Guo X, Wang W, Wu G, et al. controlled synthesis of hydroxyapatite by novel surfactant surfactants and the same enhanced biological activity [ J ]. New journal of Chemistry, 2011, 35 (3): 663-) 671.) which reports 4-aminobenzenesulfonic acid (ABSA) and polyethylene glycol 4000(PEG-4000) as structure guiding template to prepare Hydroxyapatite (HAP) nanocrystals with different shapes and sizes, and the technology adopts surfactant with high price and high toxicity as template agent, thus causing adverse effects on human body and environment. (KAKhalil, AA Almajid, MS Soliman, Effect of Hydroxide Ion Concentration on the morphology of the Hydroxide nanoparticles Synthesized used electrophoretic deposition, Materials Sciences and Applications, 2011, 2, 105) this document reports a process for preparing Hydroxyapatite Using electrophoretic deposition, which process is not simple to operate. Although the hydroxyapatite can be obtained by the method, the porous nano-hydroxyapatite cannot be obtained by using the template agent, the cost and the environmental load are increased, the aromatic acid salt without the surfactant template is used for synthesizing the porous nano-hydroxyapatite, the problems of cost increase and environmental problems caused by using the surfactant, the block polymer and the like as the template in the traditional method can be solved, the method is simple to operate, environment-friendly and easy to implement, and the porous nano-hydroxyapatite with good crystallinity and high purity can be obtained.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: according to the preparation method, the aromatic acid salt is used as the template agent and a new method combining reflux and hydrothermal is adopted to prepare the porous nano-hydroxyapatite without the participation of the template agents such as a surfactant and a polymer in the preparation process. The defects that the porous nano-hydroxyapatite can be synthesized only by taking a surfactant or a polymer as a template, the operation is complex, the cost is high, the product crystallinity is low, the purity is low and the like are overcome; so as to overcome the defect that the existing hydroxyapatite does not contain pores.
The technical scheme adopted by the invention for solving the technical problem is as follows: the preparation method of the porous nano hydroxyapatite based on the aromatic acid salt comprises the following steps:
1. the preparation method of the porous nano hydroxyapatite based on the aromatic acid salt is characterized by comprising the following steps:
(1) taking 20 parts of calcium salt solution with the concentration of 0.00015 mol of calcium salt/ml of water, and adding 0.00003-0.0003 mol of aromatic acid salt into each ml of calcium salt solution to prepare calcium salt-water-aromatic acid salt mixed solution for later use;
(2) taking 20 parts of sodium hydroxide solution with the concentration of 0.0003 mol of sodium hydroxide/ml of water, and adding 0.00009 mol of phosphorus source into each ml of sodium hydroxide solution to prepare sodium hydroxide-water-phosphorus source mixed solution for later use;
(3) adding the mixed solution prepared in the step (2) into the reactor in the step (1) under the condition of stirring, heating, and carrying out reflux reaction for 1-4 hours;
(4) then transferring the mixture obtained in the step (3) to a reaction kettle, heating to 100-160 ℃, and carrying out hydrothermal reaction under autogenous pressure for 12-36 hours;
(5) standing the stock solution at room temperature for 0-3 days, then washing with water, performing centrifugal separation, and performing vacuum drying at 60 ℃ for 5 hours to obtain white powder which is porous nano-hydroxyapatite;
the parts of the components are parts by volume, and the volume units used in the steps are the same.
2. The method for preparing the porous nano-hydroxyapatite based on the aromatic acid salt according to claim 1, wherein the aromatic acid salt in the step (1) is sodium benzoate, potassium benzoate, calcium benzoate, zinc benzoate, sodium phenylacetate, potassium phenylacetate, calcium phenylacetate, zinc phenylacetate, sodium phenylalanine or potassium phenylalanine.
3. The method for preparing porous nano hydroxyapatite based on aromatic acid salt according to claim 1, wherein the calcium salt in the step (1) is calcium nitrate, calcium chloride or calcium acetate.
4. The method for preparing porous nano hydroxyapatite based on aromatic acid salt according to claim 1, wherein the phosphorus source in the step (2) is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate or sodium superphosphate.
5. The method for preparing the porous nano hydroxyapatite based on the aromatic acid salt according to claim 1, wherein the ratio of the whole aromatic acid salt to the calcium salt in the steps (1) and (2) is 1/5-2/1.
The invention has the beneficial effects that:
1. the porous nano-hydroxyapatite obtained by the method of the invention is the porous nano-hydroxyapatite (as shown in figure 2). As shown in figure 1, the product is pure hydroxyapatite, and the diffraction peak is very clear and sharp, which indicates that the crystallinity of the hydroxyapatite is very good. Overcomes the defects that the hydroxyapatite nanorod can be synthesized only by taking a surfactant or a polymer as a template, the process is complex, the condition is harsh, the addition amount is large, the cost is high, the crystallinity is low and the like; overcomes the defect that the existing hydroxyapatite nano rod contains no holes or less holes.
2. The method of the invention does not need template agents such as surfactant, polymer and the like, has small addition amount, can be repeatedly utilized, is beneficial to environmental protection and is beneficial to saving production cost.
3. The raw materials of calcium nitrate, phosphoric acid, sodium hydroxide and the like adopted by the invention belong to common chemical reagents, and are cheap and easy to obtain.
Drawings
The invention is further illustrated with reference to the following figures and examples.
Fig. 1 is an XRD spectrum of porous nano-hydroxyapatite in example 1.
Fig. 2 is a TEM photograph of the porous nano-hydroxyapatite in example 1.
Detailed Description
Example 1
(1) Dissolving 0.003mol of calcium nitrate in a flask containing 20mL of water, and then adding 0.0015mol of sodium benzoate into the flask to prepare a calcium salt-water-sodium benzoate mixed solution for later use;
(2) dissolving 0.006mol of sodium hydroxide in a beaker filled with 20mL of water, adding 0.0018mol of phosphoric acid to prepare a sodium hydroxide-water-phosphorus source mixed solution for later use;
(3) adding the mixed solution prepared in the step (2) into the flask in the step (1) under the condition of stirring, heating, and carrying out reflux reaction for 2 hours;
(4) then transferring the mixture obtained in the step (3) into a polytetrafluoroethylene container sleeved in a reaction kettle, sealing, putting the reaction kettle into an oven, heating to 160 ℃, and carrying out hydrothermal reaction under self-generated pressure for 12 hours;
(5) standing the stock solution at room temperature for 3 days, then washing with water for 3 times, then performing centrifugal separation, and vacuum-drying the obtained precipitate at 60 ℃ for 5 hours to obtain 0.22g of white powder which is porous nano-hydroxyapatite;
the X-ray diffraction spectrum analysis of the hydroxyapatite porous nanorod prepared by the invention is shown in figure 1, and the diffraction peak in the figure shows that the product is pure hydroxyapatite and does not contain other impure phases. The hydroxyapatite crystal grains are nano-crystals, and the diffraction peaks are clear and sharp, which shows that the crystallinity of the nano-hydroxyapatite is good. Through the observation of a transmission electron microscope (as shown in figure 2), the nano rod-shaped hydroxyapatite is uniformly distributed, and has uniform length and width, and the nano rod is of a porous structure.
Example 2
The reflux reaction time in step (3) in example 1 was set to 1 hour, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 3
The reflux reaction time in step (3) in example 1 was set to 4 hours, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 4
The hydrothermal temperature in step (4) in example 1 was adjusted to 140 ℃ and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 5
The hydrothermal temperature in step (4) in example 1 was adjusted to 120 ℃ and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 6
The hydrothermal reaction time in step (4) in example 1 was set to 36 hours, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 7
The stock solution in step (5) in example 1 was allowed to stand at room temperature for 0 day, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 8
The phosphoric acid in step (2) in example 1 was replaced with ammonium dihydrogen phosphate, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 9
The phosphoric acid in step (2) of example 1 was replaced with sodium phosphate, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 10
The calcium salt in step (1) of example 1 was replaced with calcium chloride, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 11
The calcium salt in step (1) of example 1 was replaced with calcium acetate, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 12
The sodium benzoate in step (1) of example 1 was replaced with potassium benzoate, and the other steps were the same as in example 1. The product was obtained as in example 1.
Claims (5)
1. The preparation method of the porous nano hydroxyapatite based on the aromatic acid salt is characterized by comprising the following steps:
(1) taking 20 parts of calcium salt solution with the concentration of 0.00015 mol of calcium salt/ml of water, and adding 0.00003-0.0003 mol of aromatic acid salt into each ml of calcium salt solution to prepare calcium salt-water-aromatic acid salt mixed solution for later use;
(2) taking 20 parts of sodium hydroxide solution with the concentration of 0.0003 mol of sodium hydroxide/ml of water, and adding 0.00009 mol of phosphorus source into each ml of sodium hydroxide solution to prepare sodium hydroxide-water-phosphorus source mixed solution for later use;
(3) adding the mixed solution prepared in the step (2) into the reactor in the step (1) under the condition of stirring, heating, and carrying out reflux reaction for 1-4 hours;
(4) then transferring the mixture obtained in the step (3) to a reaction kettle, heating to 100-160 ℃, and carrying out hydrothermal reaction under autogenous pressure for 12-36 hours;
(5) standing the stock solution at room temperature for 0-3 days, then washing with water, performing centrifugal separation, and performing vacuum drying at 60 ℃ for 5 hours to obtain white powder which is porous nano-hydroxyapatite;
the parts of the components are parts by volume, and the volume units used in the steps are the same.
2. The method for preparing the porous nano-hydroxyapatite based on the aromatic acid salt according to claim 1, wherein the aromatic acid salt in the step (1) is sodium benzoate, potassium benzoate, calcium benzoate, zinc benzoate, sodium phenylacetate, potassium phenylacetate, calcium phenylacetate, zinc phenylacetate, sodium phenylalanine or potassium phenylalanine.
3. The method for preparing porous nano hydroxyapatite based on aromatic acid salt according to claim 1, wherein the calcium salt in the step (1) is calcium nitrate, calcium chloride or calcium acetate.
4. The method for preparing porous nano hydroxyapatite based on aromatic acid salt according to claim 1, wherein the phosphorus source in the step (2) is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate or sodium superphosphate.
5. The method for preparing the porous nano hydroxyapatite based on the aromatic acid salt according to claim 1, wherein the ratio of the whole aromatic acid salt to the calcium salt in the steps (1) and (2) is 1/5-2/1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111115601A (en) * | 2018-10-30 | 2020-05-08 | 天津工业大学 | Synthetic method of aromatic acid assisted hydroxyapatite mesoporous nanorod |
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| JP2002080210A (en) * | 2000-09-05 | 2002-03-19 | Taihei Chemical Industrial Co Ltd | Hydroxyapatite for calcium enrichment and highly concentrated hydroxyapatite slurry using it |
| CN101058416A (en) * | 2007-01-30 | 2007-10-24 | 河北工业大学 | Method of preparing ordered nano hydroxyl apatite polycrystal powder |
| CN101585523A (en) * | 2008-07-31 | 2009-11-25 | 华南理工大学 | The preparation method of the nanometer hydroxyapatite that grain orientation is arranged |
| CN101880034A (en) * | 2010-07-08 | 2010-11-10 | 中国科学院上海硅酸盐研究所 | Preparation method and application of porous hydroxyapatite |
| CN102583288A (en) * | 2012-02-01 | 2012-07-18 | 福州大学 | Hydroxyapatite nanorod as well as preparation method and alignment controlling method thereof |
| CN104477867A (en) * | 2014-12-18 | 2015-04-01 | 福州大学 | Nano-hydroxyapatite synthesized and stably existing in weak acid environment |
| CN107440913A (en) * | 2017-07-27 | 2017-12-08 | 武汉大学 | A kind of preparation method of coloured hydroxyapatite available for the detection of dentistry bleaching agent effectiveness |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002080210A (en) * | 2000-09-05 | 2002-03-19 | Taihei Chemical Industrial Co Ltd | Hydroxyapatite for calcium enrichment and highly concentrated hydroxyapatite slurry using it |
| CN101058416A (en) * | 2007-01-30 | 2007-10-24 | 河北工业大学 | Method of preparing ordered nano hydroxyl apatite polycrystal powder |
| CN101585523A (en) * | 2008-07-31 | 2009-11-25 | 华南理工大学 | The preparation method of the nanometer hydroxyapatite that grain orientation is arranged |
| CN101880034A (en) * | 2010-07-08 | 2010-11-10 | 中国科学院上海硅酸盐研究所 | Preparation method and application of porous hydroxyapatite |
| CN102583288A (en) * | 2012-02-01 | 2012-07-18 | 福州大学 | Hydroxyapatite nanorod as well as preparation method and alignment controlling method thereof |
| CN104477867A (en) * | 2014-12-18 | 2015-04-01 | 福州大学 | Nano-hydroxyapatite synthesized and stably existing in weak acid environment |
| CN107440913A (en) * | 2017-07-27 | 2017-12-08 | 武汉大学 | A kind of preparation method of coloured hydroxyapatite available for the detection of dentistry bleaching agent effectiveness |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111115601A (en) * | 2018-10-30 | 2020-05-08 | 天津工业大学 | Synthetic method of aromatic acid assisted hydroxyapatite mesoporous nanorod |
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