CN111115600A - Method for synthesizing hydroxyapatite concave-convex nano rod with assistance of ethyl acetate - Google Patents
Method for synthesizing hydroxyapatite concave-convex nano rod with assistance of ethyl acetate Download PDFInfo
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- CN111115600A CN111115600A CN201811273749.8A CN201811273749A CN111115600A CN 111115600 A CN111115600 A CN 111115600A CN 201811273749 A CN201811273749 A CN 201811273749A CN 111115600 A CN111115600 A CN 111115600A
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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Abstract
The invention relates to a method for synthesizing hydroxyapatite concave-convex nano-rods with the assistance of ethyl acetate, which comprises the following steps: (1) taking 20 parts of a mixed solution of calcium salt, water and ethyl acetate; (2) taking 20 parts of a mixed solution of a phosphorus source-sodium hydroxide-water-ethyl acetate; (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 110-160 ℃, and carrying out hydrothermal reaction under autogenous pressure for 12-36 hours; (5) standing the stock solution at room temperature, then washing, centrifuging and drying in vacuum to obtain the white powder which is the hydroxyapatite concave-convex nanorod. The nano hydroxyapatite obtained by the method has high purity and good crystallinity, does not need a template agent such as a surfactant, a polymer and the like, and has simple preparation process and low cost.
Description
Technical Field
The technical scheme of the invention belongs to the technical field of porous nanostructure material synthesis, and particularly relates to a method for synthesizing hydroxyapatite concave-convex nanorods with the aid of ethyl acetate.
Background
The emergence of the nano technology and the rapid development of the nano technology mark that the capability of human for improving the nature reaches an unprecedented new height, and indicate that the human material science creates a brand-new era, namely the nano technology era. Nanotechnology has a wide range of applications in many fields such as physics, chemistry, materials, biology, etc. Nanotechnology has allowed the development of materials research from experience and fumbling traditional methods toward the preparation of new materials with properties predetermined for humans.
Hydroxyapatite, abbreviated as HA or HAP, of the formula Ca10(PO4)6(OH)2Is an important chemical component in natural bone and teeth. The nano-hydroxyapatite has larger specific surface area, excellent biocompatibility, bioactivity, adsorbability and the like, and is widely applied to bone repair materials, gene carriers, separation and purification, heavy metal particle adsorption and the like.
The preparation method of hydroxyapatite has many methods, such as a main template method, a precipitation method, a micro-emulsion method, a sol-gel method and the like. Different synthesis methods and conditions can affect the properties of the nanoparticles. The synthesis of nano-hydroxyapatite by using template method has become a common method (Tari N E, Motlag M K, Sohrabi B. Synthesis of hydroxpayate composites in cationic mixed surfactants template [ J ]. Materials Chemistry & Physics, 2011, 131 (1): 132. 135.) the document reports that the mixture of cationic surfactant Cetyl Trimethyl Ammonium Bromide (CTAB) and anionic Sodium Dodecyl Sulfate (SDS) is used as template agent to synthesize nano-hydroxyapatite, the template agent adopted by the technology has high cost and toxicity, can cause harm to environment, and is not beneficial to the development of national economy. Although the nano-hydroxyapatite can be obtained by the method reported in the literature, the concave-convex rod-shaped nano-hydroxyapatite cannot be obtained. The ethyl acetate used in the method is an important organic solvent, is low in cost and has good dissolving capacity, but the synthesis of the concave-convex rod-shaped nano-hydroxyapatite by taking the ethyl acetate as a template agent is not reported, the synthesis of the concave-convex rod-shaped nano-hydroxyapatite by implementing the ethyl acetate template without the surfactant is a new method, the increase of the cost caused by the fact that the surfactant and the block polymer are used as templates in the traditional method can be overcome, and the concave-convex rod-shaped nano-hydroxyapatite can be obtained by the simple and convenient method.
Ethyl acetate is an important organic solvent and has good dissolving capacity, but the synthesis of the concave-convex rod-shaped nano hydroxyapatite by using the ethyl acetate as a template agent is not reported.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a method for synthesizing hydroxyapatite concave-convex nano-rods with the assistance of ethyl acetate, which adopts a novel method of combining reflux and mixed solvent heat to prepare concave-convex rod-shaped nano-hydroxyapatite in an ethyl acetate-water system. The defects that the rod-shaped nano hydroxyapatite can be synthesized only by taking a surfactant or an organic polymer and the like as a template, the preparation process is complex, the cost is high and the like are overcome; so as to overcome the defect that the hydroxyapatite nano rod does not contain concave-convex hole shape or less holes.
The technical scheme adopted by the invention for solving the technical problem is as follows: the method for synthesizing the hydroxyapatite concave-convex nanorod with the assistance of ethyl acetate comprises the following steps:
1. the method for synthesizing the hydroxyapatite concave-convex nanorod with the assistance of ethyl acetate is characterized by comprising the following steps of:
(1) taking 20 parts of calcium salt solution with the concentration of 0.00015 mol/ml of water, and then adding 10-40 parts of ethyl acetate to prepare a mixed solution of calcium salt-water-ethyl acetate for later use;
(2) taking 20 parts of sodium hydroxide solution with the concentration of 0.0003 mol of sodium hydroxide/ml of water, adding 0.00009 mol of phosphorus source into each ml of sodium hydroxide solution, and then adding 10-40 parts of ethyl acetate to prepare a mixed solution of the phosphorus source-sodium hydroxide-water-ethyl acetate 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 110-160 ℃, and carrying out mixed solvent thermal reaction for 12-36 hours under autogenous pressure;
(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 concave-convex rod-shaped 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 synthesizing hydroxyapatite nanorods assisted by ethyl acetate according to claim 1, wherein the calcium salt in the step (1) is calcium nitrate, calcium chloride or calcium acetate.
3. The method for synthesizing hydroxyapatite nanorods assisted by ethyl acetate 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.
4. The method for synthesizing hydroxyapatite concave-convex nano-rods with the assistance of ethyl acetate according to claim 1, wherein the overall ethyl acetate/water ratio in the steps (1) and (2) is 1/2-2/1.
The invention has the beneficial effects that:
1. the hydroxyapatite obtained by the method of the present invention has a concave-convex rod-shaped nano hydroxyapatite (as shown in fig. 2). As shown in figure 1, only one product is hydroxyapatite, and the diffraction peak is clear and sharp, the hydroxyapatite crystal has high purity and good crystallinity. The defects that the rod-shaped nano hydroxyapatite can be synthesized only by taking a surfactant or an organic polymer and the like as a template, the preparation process is complex, the cost is high and the like are overcome; so as to overcome the defect that the nano-hydroxyapatite does not present a concavo-convex rod shape.
2. In the method, an ethyl acetate-water preparation system is adopted, a surfactant, an organic polymer and other template agents are not needed, the ethyl acetate can be recycled, the production cost is reduced, and the method is beneficial to environmental protection.
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 a hydroxyapatite concave-convex nanorod in example 1.
FIG. 2 is a TEM photograph of hydroxyapatite nanorods in example 1.
Detailed Description
Example 1
(1) Dissolving 0.003mol of calcium nitrate in a flask containing 20mL of water, and then adding 20mL of ethyl acetate into the flask to prepare a calcium nitrate-ethyl acetate-water 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, and then adding 20mL of ethyl acetate to prepare a phosphoric acid-sodium hydroxide-ethyl acetate-water 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 thermal reaction on the mixed solvent for 12 hours under autogenous pressure;
(5) standing the stock solution at room temperature for 3 days, then washing with water for 3 times, then performing centrifugal separation, and performing vacuum drying on the obtained precipitate at 60 ℃ for 5 hours to obtain white powder which is porous nano-hydroxyapatite;
the X-ray diffraction spectrum analysis of the concave-convex rod-shaped nano hydroxyapatite 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 mixed phases. Three main diffraction peaks have certain broadening phenomena, which indicates that hydroxyapatite crystal grains are nano-crystals, and the diffraction peaks are clear and sharp, which indicates that the crystallinity of the nano-hydroxyapatite is good. The nano rod-shaped hydroxyapatite is uniformly distributed, has uniform length and width and has a concave-convex pit-shaped structure through the observation of a transmission electron microscope (as shown in figure 2).
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 mixed solvent of the step (4) in the example 1 was heated to 140 ℃ in the same manner as in the example 1. The product was obtained as in example 1.
Example 5
The mixed solvent of the step (4) in the example 1 was heated to 110 ℃ in the same manner as in the example 1. The product was obtained as in example 1.
Example 6
The mixed solvent thermal reaction time in the 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) in example 1 was replaced with diammonium phosphate, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 10
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 11
The phosphoric acid in step (2) of example 1 was replaced with sodium superphosphate, and the other steps were the same as in example 1. The product was obtained as in example 1.
Example 12
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 13
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.
Claims (4)
1. The method for synthesizing the hydroxyapatite concave-convex nanorod with the assistance of ethyl acetate is characterized by comprising the following steps of:
(1) taking 20 parts of calcium salt solution with the concentration of 0.00015 mol/ml of water, and then adding 10-40 parts of ethyl acetate to prepare a mixed solution of calcium salt-water-ethyl acetate for later use;
(2) taking 20 parts of sodium hydroxide solution with the concentration of 0.0003 mol of sodium hydroxide/ml of water, adding 0.00009 mol of phosphorus source into each ml of sodium hydroxide solution, and then adding 10-40 parts of ethyl acetate to prepare a mixed solution of the phosphorus source-sodium hydroxide-water-ethyl acetate 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 110-160 ℃, and carrying out mixed solvent thermal reaction for 12-36 hours under autogenous pressure;
(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 concave-convex rod-shaped 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 synthesizing hydroxyapatite nanorods assisted by ethyl acetate according to claim 1, wherein the calcium salt in the step (1) is calcium nitrate, calcium chloride or calcium acetate.
3. The method for synthesizing hydroxyapatite nanorods assisted by ethyl acetate 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.
4. The method for synthesizing hydroxyapatite concave-convex nano-rods with the assistance of ethyl acetate according to claim 1, wherein the overall ethyl acetate/water ratio in the steps (1) and (2) is 1/2-2/1.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101297978A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Preparation method of hydroxyapatite nano pole |
| WO2011035573A1 (en) * | 2009-09-28 | 2011-03-31 | 暨南大学 | Nanometer hydroxyapatite / natural polymer composite material, preparation method and use thereof |
| CN102464307A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院上海硅酸盐研究所 | Preparation method of hydroxyapatite nano grain |
| CN103641096A (en) * | 2013-12-19 | 2014-03-19 | 天津工业大学 | Hydroxyapatite porous nanorod and preparation method thereof |
| CN105600828A (en) * | 2016-01-04 | 2016-05-25 | 南京林业大学 | Preparation method of porous nano CuFe2O4 |
| CN107746046A (en) * | 2017-11-14 | 2018-03-02 | 湖北工业大学 | A kind of method that Oil soluble hydroxy apatite nano particle is prepared based on non-aqueous system |
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2018
- 2018-10-30 CN CN201811273749.8A patent/CN111115600B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101297978A (en) * | 2008-06-17 | 2008-11-05 | 东南大学 | Preparation method of hydroxyapatite nano pole |
| WO2011035573A1 (en) * | 2009-09-28 | 2011-03-31 | 暨南大学 | Nanometer hydroxyapatite / natural polymer composite material, preparation method and use thereof |
| CN102464307A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院上海硅酸盐研究所 | Preparation method of hydroxyapatite nano grain |
| CN103641096A (en) * | 2013-12-19 | 2014-03-19 | 天津工业大学 | Hydroxyapatite porous nanorod and preparation method thereof |
| CN105600828A (en) * | 2016-01-04 | 2016-05-25 | 南京林业大学 | Preparation method of porous nano CuFe2O4 |
| CN107746046A (en) * | 2017-11-14 | 2018-03-02 | 湖北工业大学 | A kind of method that Oil soluble hydroxy apatite nano particle is prepared based on non-aqueous system |
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