Method for preparing nano-hydroxyapatite by using white latex as a template agent and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SICHUAN NORMAL UNIV
- Filing Date
- 2023-07-10
- Publication Date
- 2026-08-07
AI Technical Summary
[0027] Compared with existing technologies, the preparation method of nano-sized hydroxyapatite powder described in this invention has the following advantages:
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Figure CN116812891B_ABST
Abstract
Description
Technical Field
[0001] This invention discloses a method for preparing nano-hydroxyapatite using white latex as a template agent and its application, relating to the technical field of nano-hydroxyapatite preparation and application. Background Technology
[0002] Hydroxyapatite (HA or HAP) is a calcium phosphate-based inorganic material, a major mineral component of human bones and teeth, and possesses high biocompatibility. After implantation, calcium and phosphorus are released from the material's surface and absorbed by body tissues, leading to the growth of new tissue.
[0003] The finer the grains of hydroxyapatite, the higher its bioactivity. It is often used in the biomedical field, and with the development of technology, it has good application prospects in biomaterials, optics, cultural relic protection, environmental protection and catalysis engineering.
[0004] Hydroxyapatite nanostructured materials possess high surface energy, which can improve sintering performance and thus enhance mechanical properties. However, sintering behavior depends not only on particle size but also on the particle size distribution and morphology of the powder. In existing technologies, nano-HAP particles tend to agglomerate severely, making it difficult to control grain size during formation, resulting in uneven particle size distribution and long synthesis times. This affects their performance and limits their applications.
[0005] In the existing technology, only the paper "Dispersion of hydroxyapatite nanoparticles in natural rubber latex and polylactic acid based matrices" has studied the dispersion performance of hydroxyapatite nanoparticles in natural rubber latex, and the patent (CN108439360A) introduces a template agent to improve the flowability of the product during the preparation of hydroxyapatite nanoparticles.
[0006] However, overall, existing technologies have not yielded satisfactory results in addressing HAP particle agglomeration to improve dispersibility and flowability; furthermore, they have not solved the problems of difficulty in controlling grain size, uneven particle size distribution, and long synthesis time.
[0007] Content of this invention
[0008] The purpose of this invention is to provide a method for preparing nano-hydroxyapatite using white latex as a template agent and its application, thereby obtaining a well-dispersed and stable nano-HAP dispersion; resulting in uniform particle size distribution and shortening the synthesis time. Furthermore, this method is applied to cultural relic restoration, producing excellent results in the reinforcement of fragile cultural relics.
[0009] To achieve the above-mentioned technical objectives and effects, the invention is implemented through the following technical solution:
[0010] A method for preparing nano-hydroxyapatite using white latex as a template agent includes the following specific steps:
[0011] S1. First, dilute the white glue with deionized water and stir thoroughly until homogeneous. Then, mix it thoroughly with the calcium source solution and adjust the pH to 8-10 with ammonia water to obtain mixed solution A. In mixed solution A, the white glue and calcium... 2+ The molar ratio is 1:1, and the purity of ammonia water is 25-28%.
[0012] S2. Dilute the white glue with deionized water and stir thoroughly. Then, mix it thoroughly with the phosphate solution and adjust the pH to 8-10 with ammonia water to obtain mixed solution B. The white glue in mixed solution B... The molar ratio is 1:1, and the purity of ammonia water is 25-28%.
[0013] S3. The phosphate solution is slowly added dropwise to the calcium source solution, and hydroxyapatite precipitate is obtained after the reaction is complete.
[0014] S4. The hydroxyapatite precipitate is aged, washed, centrifuged, and then dried in an oven to obtain nano-sized hydroxyapatite powder.
[0015] Furthermore, in step S1, the main components of the white latex are one or more of polyvinyl acetate, polyvinyl alcohol formaldehyde, polyvinyl alcohol, dibutyl phthalate, octanol, and ammonium persulfate.
[0016] Furthermore, the concentration of the calcium salt solution in step S1 is 0.25–0.5 mol / L;
[0017] In step S2, the concentration of the phosphate salt solution is 0.075–0.3 mol / L, and the calcium-to-phosphorus ratio of the calcium salt solution to the phosphate salt solution is 1.67.
[0018] Furthermore, the soluble calcium salt in the calcium salt solution is one of anhydrous calcium chloride or calcium nitrate tetrahydrate.
[0019] Furthermore, the soluble phosphate in the phosphate solution is one of phosphorus pentoxide, diammonium hydrogen phosphate, or disodium hydrogen phosphate dodecahydrate.
[0020] Furthermore, the stirring described in steps S1 and S2 is one or both of magnetic stirring and homogenizing stirring;
[0021] In step S3, the dropping rate is 0.05–3 ml / min;
[0022] The aging time in step S4 is 24-48 hours, the number of washing cycles is 5-8 times, the oven drying temperature is 50-80℃, the centrifugation rate is 6000-12000 r / min, and the centrifugation time is 8-12 min.
[0023] Furthermore, the concentration of anhydrous citric acid is 0.1–0.3 mol / L.
[0024] Another object of the present invention is to disclose a method for preparing nano-hydroxyapatite using white latex as a template agent, and to apply it to the reinforcement of fragile cultural relics or the repair of bones in biomedical applications.
[0025] Furthermore, white latex was used as a structure-directing agent for the synthesis of nano-hydroxyapatite to repair the matrix.
[0026] Beneficial effects:
[0027] Compared with existing technologies, the preparation method of nano-sized hydroxyapatite powder described in this invention has the following advantages:
[0028] 1. The preparation method of nano-sized hydroxyapatite powder modified with white latex as a template agent of the present invention is carried out at room temperature and pressure, which can provide an application solution for the subsequent reinforcement of fragile cultural relics, and maximize the protection of cultural relics under non-destructive / minimally damaged conditions, and carry out simulation operation of cultural relic restoration and reinforcement.
[0029] 2. The method of the present invention is simple and easy to operate, with a short synthesis time, low energy consumption, and the reagents used are inexpensive and readily available.
[0030] 3. Anhydrous citric acid is used as a stabilizer in this invention. Citrate not only reduces the binding rate of calcium ions and phosphate ions and promotes the formation of hydroxyapatite crystals, but also makes the generated hydroxyapatite crystals negatively charged to maintain sufficient electrostatic repulsion between crystals, thereby reducing the viscosity of the system and giving the synthesized hydroxyapatite colloid good fluidity and stability.
[0031] 4. This invention uses the colloidal particles of white latex as templates for the formation of hydroxyapatite, and synthesizes nanoscale irregular particles by adjusting pH, component concentration, reaction time, etc. during the preparation process.
[0032] Of course, any product implementing this invention does not necessarily need to achieve all of the advantages described above at the same time. Attached Figure Description
[0033] Figure 1 The XRD pattern of hydroxyapatite (HAP) prepared in Example 5;
[0034] Figure 2 The FT-IR spectrum of hydroxyapatite (HAP) prepared in Example 5; Detailed Implementation
[0035] To more clearly illustrate the technical solutions of the embodiments of the present invention, the present invention will be described in detail below with reference to the accompanying drawings.
[0036] This invention discloses a method for preparing nano-hydroxyapatite using white latex as a template agent, which specifically includes the following steps:
[0037] S1. First, dilute the white glue with deionized water and stir thoroughly until homogeneous. Then, mix it thoroughly with the calcium source solution and adjust the pH to 8-10 with ammonia water to obtain mixed solution A. In mixed solution A, the white glue and calcium... 2+ The molar ratio is 1:1, and the purity of ammonia water is 25-28%. In this step, white glue is thoroughly mixed with the calcium source solution by stirring to form mixed solution A.
[0038] This step provides a homogeneous medium environment, which facilitates the subsequent addition of phosphate solution and reaction.
[0039] S2. Dilute the white glue with deionized water and stir thoroughly. Then, mix it thoroughly with the phosphate solution and adjust the pH to 8-10 with ammonia water to obtain mixed solution B. The white glue in mixed solution B... The molar ratio is 1:1, and the purity of ammonia water is 25-28%.
[0040] Similarly, mixing the white glue with the phosphate solution in this step is to better ensure the reaction between calcium ions and phosphate ions in the subsequent reaction.
[0041] S3. The phosphate solution is slowly added dropwise to the calcium source solution, and hydroxyapatite precipitate is obtained after the reaction is complete.
[0042] In this step, the reaction rate can be controlled by slowly adding the phosphate solution dropwise to the calcium source solution, thereby reducing the particle size of the hydroxyapatite and improving its dispersibility.
[0043] S4. The hydroxyapatite precipitate is aged, washed, centrifuged, and then dried in an oven to obtain nano-sized hydroxyapatite powder.
[0044] The purpose of this step is to remove any impurities and deposits that may be present on the surface of the hydroxyapatite particles, thereby further improving the dispersibility and purity of the hydroxyapatite particles.
[0045] In summary, the key to this invention is the use of white latex as a template agent for synthesis under ambient temperature and pressure. This synthesis method primarily relies on the mixing and reaction of white latex with a calcium source solution and a phosphate solution. Through appropriate stirring and pH control, and under correct reaction conditions, nano-sized hydroxyapatite powder can be obtained.
[0046] Theoretically, this powder can achieve a uniform particle size distribution, shorten the synthesis time, avoid agglomeration, and exhibit good dispersibility. To further illustrate the effects of this invention, the applicant has provided a series of specific embodiments.
[0047] Example 1
[0048] Based on the preparation method of this invention, the applicant has provided a comparative experiment in this embodiment. All raw materials and equipment used in this invention are known products, obtained by purchasing commercially available products. It should be noted that, unless otherwise specified, the comparative examples and embodiments, as well as the features in the comparative examples and embodiments, can be combined with each other.
[0049] First comparative example
[0050] A control experiment on a method for preparing nano-sized hydroxyapatite powder by modifying white latex as a template agent includes the following steps:
[0051] (1) At room temperature, 1.1098 g of anhydrous calcium chloride was dissolved in 20 ml of deionized water and stirred thoroughly with a magnetic stirrer to obtain a calcium salt solution.
[0052] (2) At room temperature, 0.69012 g of diammonium hydrogen phosphate was dissolved in 20 ml of deionized water and stirred thoroughly with a magnetic stirrer to obtain a phosphate solution;
[0053] (3) At room temperature, place the calcium salt solution on a stirrer and slowly add the phosphate solution to the calcium source solution at a dropping rate of 2 ml / min. At the same time, add ammonia water to the solution and stir continuously, and keep the pH of the reaction system at 9. After the reaction is complete for 3 hours, stop stirring to obtain hydroxyapatite precipitate.
[0054] (4) The hydroxyapatite precipitate was aged for 24 hours, then washed with deionized water 5-8 times, then centrifuged at a centrifugation rate of 8000 r / min for 10 min, and finally dried in an oven at 80°C for 24 hours to obtain nano-sized hydroxyapatite powder.
[0055] Second comparative example
[0056] The difference between this embodiment and Comparative Example 1 is that the phosphate solution in Comparative Example 1 is replaced with phosphorus pentoxide, and the amount weighed is 0.4258g.
[0057] The other steps are the same as in Control Example 1.
[0058] Third Comparative Example
[0059] The difference between this specific embodiment and Comparative Example 1 or 2 is that the phosphate in step (2) of the comparative example is replaced with disodium hydrogen phosphate dodecahydrate, and the amount weighed is 2.14884g.
[0060] The other steps are the same as in Comparative Example 1 or 2.
[0061] Fourth comparative example
[0062] The difference between this comparative example and comparative examples 1-3 is that the calcium salt in step (1) of the comparative examples was replaced with calcium nitrate tetrahydrate, and the amount weighed was 2.3615g. The phosphate solution in step (2) was replaced with diammonium hydrogen phosphate, and the amount weighed was 0.79236g.
[0063] The other steps are the same as those in Comparative Examples 1-3.
[0064] Fifth comparative example
[0065] The difference between this specific embodiment and specific embodiments 1-4 is that the phosphate solution in step (2) of the comparative example is replaced with disodium hydrogen phosphate dodecahydrate, and the amount weighed is 2.14884g.
[0066] The other steps are the same as those in Comparative Examples 1-4.
[0067] Sixth Comparative Example
[0068] The difference between this specific embodiment and Comparative Examples 1-5 is that the phosphate solution in step (2) of the comparative examples is replaced with phosphorus pentoxide, and the amount weighed is 0.42582g.
[0069] The other steps are the same as those in Comparative Examples 1-5.
[0070] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.
[0071] First Specific Embodiment
[0072] A method for preparing nano-sized hydroxyapatite powder by modifying white latex as a template agent includes the following steps:
[0073] (1) At room temperature, 1.1098 g of anhydrous calcium chloride and 0.38424 g of anhydrous citric acid were dissolved in 20 ml of deionized water and stirred thoroughly with a magnetic stirrer to obtain a calcium salt solution.
[0074] (2) At room temperature, 0.69012 g of diammonium hydrogen phosphate was dissolved in 20 ml of deionized water and stirred thoroughly with a magnetic stirrer to obtain a phosphate solution;
[0075] (3) Dilute the white glue with deionized water to 8% and then use a digital display high-speed dispersion homogenizer to stir it evenly.
[0076] (4) At room temperature, 8% white glue dilution solution was mixed with phosphorus source and calcium source solution under magnetic stirrer and the pH was adjusted to 9 with ammonia water to obtain mixed solution A and solution B.
[0077] (5) At room temperature, place the calcium salt solution on a stirrer and slowly add the phosphate solution to the calcium source solution at a dropping rate of 2 ml / min. At the same time, add ammonia water to the solution and stir continuously, and keep the pH of the reaction system at 9. After the reaction is fully completed for 3 hours, stop stirring to obtain hydroxyapatite precipitate.
[0078] (6) The hydroxyapatite precipitate is aged for 24 hours, then washed with deionized water 5-8 times, then centrifuged at a centrifugation rate of 8000 r / min for 10 min, and finally dried in an oven at 80℃ for 24 hours to obtain nano-sized hydroxyapatite powder.
[0079] Second specific embodiment
[0080] The difference between this embodiment and Specific Example 1 is that the phosphate solution in Specific Example 1 is replaced with phosphorus pentoxide, and the amount weighed is 0.4258g.
[0081] The other steps are the same as in Specific Implementation Example 1.
[0082] Third specific embodiment
[0083] The difference between this specific embodiment and specific embodiment 1 or 2 is that the phosphate in step (2) is replaced with disodium hydrogen phosphate dodecahydrate, and the amount weighed is 2.14884g.
[0084] The other steps are the same as in specific embodiment 1 or 2.
[0085] Fourth Specific Embodiment
[0086] The difference between this specific embodiment and specific embodiments 1-3 is that the calcium salt in step (1) is replaced with calcium nitrate tetrahydrate, and the amount weighed is 2.3615g. The phosphate solution in step (2) is replaced with diammonium hydrogen phosphate, and the amount weighed is 0.79236g.
[0087] The other steps are the same as in specific embodiments 1-3.
[0088] Fifth Specific Embodiment
[0089] The difference between this specific embodiment and specific embodiments 1-4 is that the phosphate solution in step (2) is replaced with disodium hydrogen phosphate dodecahydrate, and the amount weighed is 2.14884g.
[0090] The other steps are the same as in specific embodiments 1-4.
[0091] Sixth Specific Embodiment
[0092] The difference between this specific embodiment and specific embodiments 1-5 is that the phosphate solution in step (2) is replaced with phosphorus pentoxide, and the amount weighed is 0.42582g.
[0093] The other steps are the same as in specific embodiments 1-5.
[0094] Seventh Specific Embodiment
[0095] A method for preparing nano-sized hydroxyapatite powder by modifying white latex as a template agent includes the following steps:
[0096] (1) At room temperature, 1.1098 g of anhydrous calcium chloride and 0.38424 g of anhydrous citric acid were dissolved in 20 ml of deionized water and stirred thoroughly with a magnetic stirrer to obtain a calcium salt solution.
[0097] (2) At room temperature, 0.69012 g of diammonium hydrogen phosphate was dissolved in 20 ml of deionized water and stirred thoroughly with a magnetic stirrer to obtain a phosphate solution;
[0098] (3) At room temperature, place the calcium salt solution on a stirrer and slowly add the phosphate solution to the calcium source solution at a dropping rate of 2 ml / min. At the same time, add ammonia water to the solution and stir continuously, and keep the pH of the reaction system at 9. After the reaction is complete for 3 hours, stop stirring to obtain hydroxyapatite precipitate.
[0099] (4) The hydroxyapatite precipitate was aged for 24 hours, then washed with deionized water 5-8 times, then centrifuged at a centrifugation rate of 8000 r / min for 10 min, and finally dried in an oven at 80°C for 24 hours to obtain nano-sized hydroxyapatite powder.
[0100] Eighth Specific Embodiment
[0101] The difference between this embodiment and specific embodiment 7 is that the phosphate solution in specific embodiment 7 is replaced with phosphorus pentoxide, and the amount weighed is 0.4258g.
[0102] The other steps are the same as in specific embodiment 7.
[0103] Ninth Specific Embodiment
[0104] The difference between this specific embodiment and specific embodiments 7 or 8 is that the phosphate in step (2) is replaced with disodium hydrogen phosphate dodecahydrate, and the amount weighed is 2.14884g.
[0105] The other steps are the same as in specific embodiment 7 or 8.
[0106] Tenth Specific Embodiment
[0107] The difference between this specific embodiment and specific embodiments 7-9 is that the calcium salt in step (1) is replaced with calcium nitrate tetrahydrate, and the amount weighed is 2.3615g. The phosphate solution in step (2) is replaced with diammonium hydrogen phosphate, and the amount weighed is 0.79236g.
[0108] The other steps are the same as in specific embodiments 7-9.
[0109] Eleventh Specific Embodiment
[0110] The difference between this specific embodiment and specific embodiments 7-10 is that the phosphate solution in step (2) is replaced with disodium hydrogen phosphate dodecahydrate, and the amount weighed is 2.14884g.
[0111] The other steps are the same as in specific embodiments 7-10.
[0112] Twelfth Specific Embodiment
[0113] The difference between this specific embodiment and specific embodiments 7-11 is that the phosphate solution in step (2) is replaced with phosphorus pentoxide, and the amount weighed is 0.42582g.
[0114] The other steps are the same as in specific embodiments 7-11.
[0115] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this specific embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.
[0116] Comparison of the appearance of samples from different control groups and various specific embodiments revealed that HA was more easily generated at low concentrations using CaCl2 and (NH4)2HPO4, and that HA was easily generated when white latex was added as a template agent, resulting in smaller particle sizes. CaCl2 and Na2HPO4·12H2O yielded a blocky precipitate; when the phosphate was P2O5, the product was a gel-like precipitate; and when Ca(NO3)2·4H2O and (NH4)2HPO4 were used, a fluffy precipitate was obtained.
[0117] As can be seen from the XRD patterns in the attached figure, when CaCl2 and Ca(NO3)2·4H2O are used as calcium sources, citric acid is added as a stabilizer. When white glue is used as a template agent, the peak positions of its XRD pattern are more consistent with the standard card of hydroxyapatite. The peak positions of the pattern of the product without the addition of citric acid and white glue as template agents are more biased towards other crystal phases.
[0118] From the FT-IR image in the attached diagram, we can see that 3500cm... -1 The absorption peaks at the left and right are due to the stretching vibration of the hydroxyl group. (960 cm⁻¹) -1 The band at 600 cm⁻¹ is an absorption peak due to the symmetric stretching vibration of phosphate, while the band at 600 cm⁻¹ is an absorption peak due to the symmetric stretching vibration of phosphate. -1 The left and right sides represent the absorption peaks of the in-plane bending vibration of phosphate. Additionally, there are absorption peaks located at 1020-1100 cm⁻¹. -1 The peak at 1400 cm⁻¹ is an absorption peak caused by the asymmetric stretching vibration of phosphate ions; the wider the peak, the lower the crystallinity. The infrared spectrum confirms the product as hydroxyapatite. Furthermore, the spectral lines in the image show that at 1400 cm⁻¹… -1 ~1500cm -1 There is a weak CO2 emission nearby. 2 3 - The peak likely originates from CO2 in the air.
[0119] Example 2
[0120] In conjunction with the foregoing embodiments, this invention can achieve good results in the fields of cultural relic restoration and bone restoration. By introducing phosphate and calcium sources into water-based white latex, the colloidal particles of the white latex can be controlled to act as templates for the formation of hydroxyapatite, and the white latex can be used as a structure guiding agent for the synthesis of nano-hydroxyapatite.
[0121] In one specific embodiment, compared with traditional cultural relic restoration materials, such as organic adhesives and plaster, these materials are often somewhat destructive and cannot fully restore the original material and structure of the cultural relic.
[0122] The hardness, stability, and biocompatibility of the nano-hydroxyapatite in this specific embodiment allow it to better integrate with the original material of the artifact, thereby achieving a more refined and natural restoration effect. Furthermore, the small particle size of the nano-hydroxyapatite allows it to penetrate into tiny cracks, achieving microscopic-level restoration.
[0123] In one specific embodiment, since the main component of bone is hydroxyapatite, this embodiment utilizes nano-hydroxyapatite for bone repair. This ensures both the mechanical properties of the repaired site and maintains biocompatibility and bioactivity, promoting new bone formation. Furthermore, using white glue as a template allows for control over the shape and size of the generated nano-hydroxyapatite, further optimizing the repair effect.
[0124] Compared with existing repair methods using metal materials and bioceramic materials, the method of this invention can better guarantee the function and structure of the repaired bone, showing significant advantages.
[0125] The above are merely some of the embodiments of this application and are not intended to limit the application in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments shall still fall within the scope of protection of the technical solution of this application.
Claims
1. A method for preparing nano-hydroxyapatite using white latex as a template agent, characterized in that, The specific steps include the following: S1. First, dilute the white glue with deionized water and stir thoroughly until homogeneous. Then, mix it thoroughly with the calcium source solution and adjust the pH to 8-10 with ammonia water to obtain mixed solution A. In mixed solution A, the white glue and calcium... 2+ The molar ratio is 1:1, and the purity of ammonia water is 25-28%. S2. Dilute the white glue with deionized water and stir thoroughly until homogeneous. Then, mix it thoroughly with the phosphate solution and adjust the pH to 8-10 with ammonia water to obtain mixed solution B. In mixed solution B, the white glue and PO4... 3- The molar ratio is 1:1, and the purity of ammonia water is 25-28%. S3. The phosphate solution is slowly added dropwise to the calcium source solution, and hydroxyapatite precipitate is obtained after the reaction is complete. S4. The hydroxyapatite precipitate is aged, washed, centrifuged, and then dried in an oven to obtain nano-sized hydroxyapatite powder. The main components of the white glue in step S1 are one or more of the following: polyvinyl acetate, polyvinyl alcohol formaldehyde, polyvinyl alcohol, dibutyl phthalate, octanol, and ammonium persulfate. In step S1, the concentration of the calcium salt solution is 0.25–0.5 mol / L; in step S2, the concentration of the phosphate salt solution is 0.075–0.3 mol / L, and the calcium-to-phosphorus ratio of the calcium salt solution to the phosphate salt solution is 1.
67. The soluble calcium salt in the calcium salt solution is one of anhydrous calcium chloride or calcium nitrate tetrahydrate. The soluble phosphate in the phosphate solution is one of phosphorus pentoxide, diammonium hydrogen phosphate, and disodium hydrogen phosphate dodecahydrate. The stirring described in steps S1 and S2 is one or both of magnetic stirring and homogenizing stirring; In step S3, the dropping rate is 0.05–3 ml / min; In step S4, the aging time is 24-48 hours, the number of washing cycles is 5-8 times, the oven drying temperature is 50-80℃, the centrifugation rate is 6000-12000 r / min, and the centrifugation time is 8-12 min.
2. An application method, the method for preparing nano-hydroxyapatite using white latex as a template agent according to claim 1, characterized in that, It can be applied to the reinforcement of fragile cultural relics or to the repair of bones in biomedicine.
3. The application method according to claim 2, characterized in that: White latex was used as a structure-directing agent for the synthesis of nano-hydroxyapatite to repair the matrix.
Citation Information
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Preparation method of spherical porous nano-hydroxyapatite
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