CN104740687A - Carbonated hydroxyapatite/chitosan three-dimensional porous composite material and preparation method - Google Patents
Carbonated hydroxyapatite/chitosan three-dimensional porous composite material and preparation method Download PDFInfo
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Abstract
The invention relates to a carbonated hydroxyapatite/chitosan three-dimensional porous composite material and a preparation method thereof. The material comprises chitosan and carbonated hydroxyapatite, wherein the carbonated hydroxyapatite is uniformly attached to the porous scaffold surface of the chitosan to form a three-dimensional through macroporous structure with an aperture of 5-500 mu m and a porosity of 10-95%. The preparation method comprises the steps of dissolving chitosan powder into a solvent to form a chitosan solution, putting calcium carbonate into the chitosan solution, and stirring uniformly; then, transferring the mixed slurry to a mold, and freeze-drying to form a calcium carbonate/chitosan three-dimensional porous material; and finally, soaking into an alkali solution and a phosphate solution to obtain the carbonated hydroxyapatite/ chitosan three-dimensional porous composite material. Compared with the prior art, the method has the advantages of simplicity, convenience in operation and environmental friendliness; and the synthesized carbonated hydroxyapatite/chitosan three-dimensional porous composite material has relatively high porosity, large specific surface area and good heavy metal ion adsorption capability, and has broad application prospect in the technical field of heavy metal wastewater treatment.
Description
Technical field
The present invention relates to polymeric material field, field of inorganic nonmetallic material, indoor volatile organic compounds (VOC) process field, be specially a kind of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional composite porous and preparation method thereof.
Background technology
The water pollution caused containing heavy metal ion industrial wastewater is one of the most serious environmental problem of generally facing of our times various countries, heavy metal ion not only can disturb the normal metabolism of human body, also indirectly cause central nervous system injury, DNA repairs and Cognitive inhibition.Heavy metals in industrial wastewater ion reaches 200 – 500mg/L, in order to make it can not be harmful, must heavy-metal ion removal to lower level.At present, researched and developed the technology of various process heavy metal ion, absorption method is unanimously thought a kind of cost-effective removal heavy metal method.Require below Ideal adsorption agent material demand fulfillment: (I) has heavy metal ion and have good absorbability, particularly to the absorption of low-concentration heavy metal ions; (II) has three-dimensional through macroporous structure, high-specific surface area, pore volume and easily realize being separated with water body; (III) has the nontoxic close friend of environment, raw material feature cheap and easy to get; The mechanical performance that (IV) is suitable and good can processing type energy so that extensive use in industrial wastewater.The more heavy metal ion adsorbing material of current research is inorganic material and the natural macromolecular materials such as chitosan, cellulose such as active carbon, kieselguhr, hydroxyapatite, graphene oxide.
Hydroxyapatite is the main inorganic composition of vertebrate skeletal and tooth, and its corresponding synthetic material has eco-friendly feature.Hydroxyapatite due to its adsorption capacity high, low aqueous solubility and low cost have been widely used as the long-term disposal of effective Adsorption of Heavy Metals.At the Ca of hydroxyapatite crystal
2+ion can be replaced (as Cu by other metal ion by ion-exchange reactions
2+, Cr
2+, Ni
2+, Pb
2+, Hg
2+, Fe
2+deng).Chitosan, as the one of the linear natural macromolecular material of poly-glucosamine, has significant absorbability and nonpoisonous and tasteless corrosion resistant feature, is widely used in heavy metal wastewater thereby.The amino contained in the molecule segment of research proof chitosan and hydroxyl isoreactivity group can form complex with heavy metal ion coordination, are a kind of chelate media efficiently.The size of the absorbability of chitosan depends on its deacetylation.Deacetylation is larger, and absorbability is stronger.But, because hydroxy apatite powder granule is difficult to realize solid-liquid separation shortcoming and the poor shortcoming of chitosan mechanical property in water treatment, be restricted in the practical application of Industrial Wastewater Treatment.
In order to overcome the defect in performance of homogenous material, the mode that researcher have employed organic or inorganic has prepared hydroxyapatite composite material to improve separating property, absorption property etc.The research worker such as Xiao Wang, the Ice-storing ball formed by hydroxyapatite and polyvinyl alcohol, the composite that load obtains on polyvinyl alcohol foam, to Cd
2+there is good adsorption effect, saturated adsorption capacity is 53.1mg/g, and the research worker such as stalling characteristic (J.Sol-Gel.Sci Technol. (2007) 43:99 – 104) .Suk Hyun Jang improving hydroxyapatite to a great extent, the composite aquogel that hydroxyapatite and polyacrylamide are formed can be used for the absorption to Pb2+ in water body, when the mass fraction of hydroxyapatite contained in composite is at 70% and 50%, 209 are respectively to the saturated extent of adsorption of Pb2+, 150mg/g, and the actual operability of material is improved (J.Hazard.Mater. (2008) 159:294-299), the research worker such as Xiaoli Li, form complex microsphere by being dipped in the saturated boric acid solution of calcium chloride by the mixture of chitosan, polyvinyl alcohol and Paris white.When polyvinyl alcohol, calcium carbonate and chitosan mass are than when being 6:10:7.5, microsphere is to Cu
2+, Pb
2+, Zn
2+and Cd
2+adsorbance be respectively 238.45,166.44,74.18 and 126.06mg/g (Chem.Eng.J. (2011) 178:60-68).But above-mentioned composite ubiquity lacks the problem of the macroporous structure of three-dimensional communication, the requirement with macroporous structure and high absorption property can not be met simultaneously.Based on this, the present invention prepares a kind of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional multi-stage porous composite, the environmentally friendly and reusable edible of this material.
Summary of the invention
Object of the present invention is exactly provide a kind of the have macroporous structure of three-dimensional order, large specific surface area and good absorption property to overcome defect that above-mentioned prior art exists, and it is composite porous and preparation method thereof to can be applicable to the high absorption property carbonate form hydroxylapatite and chitosan three-dimensional of the heavy metal ion removed in industrial wastewater.
Another object of the present invention is to provide the composite porous preparation method of a kind of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional.This preparation technology is not only simple but also manufacturing cycle is short, and production cost is low.
Object of the present invention can be achieved through the following technical solutions: a kind of carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, it is characterized in that, this material comprises chitosan, carbonate form hydroxyapatite, carbonate form hydroxyapatite is evenly attached to the porous scaffold surface of chitosan, formed and there is three-dimensional through macroporous structure, its aperture is 5 ~ 500 μm, and porosity is 10% ~ 95%.
The weight ratio of described chitosan and carbonate form hydroxyapatite powder is 1:1 ~ 1:50.
The present invention take calcium carbonate powder as template, high molecular polymer chitosan porous rack, soaks converted in-situ be prepared from through phosphate solution.Its preparation process comprises the following steps: proceed in mould after (1) calcium carbonate powder and chitosan solution Homogeneous phase mixing, adopts lyophilization molding; (2) be placed in phosphate solution by composite porous for the calcium carbonate/chitosan three-dimensional of molding to change into carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
The preparation method that carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, is characterized in that, comprise the following steps:
(1) chitosan is dissolved in solvent is mixed with chitosan solution, again calcium carbonate powder is dispersed in chitosan solution, the ultrasonic bubble removing that goes down, obtain calcium carbonate/chitosan mixed slurry, be placed in mould, adopt lyophilization molding to obtain calcium carbonate/chitosan three-dimensional composite porous;
(2) the composite porous alkaline solution that is placed in of calcium carbonate/chitosan three-dimensional obtained in step (1) is soaked, deionized water is washed till neutrality, then phosphate solution is placed in, converted in-situ, take out and with deionized water rinsing to neutral, namely obtain carbonate form hydroxylapatite and chitosan three-dimensional after lyophilization composite porous.
The concentration of the chitosan solution described in step (1) is 0.005g/L ~ saturated solution; Chitosan is dissolved in that the solvent that solvent uses is organic solvent, the mixture of deionization or organic solvent and deionized water; Described organic solvent is selected from hydro carbons, alcohols, acids, esters or alcohols.Solvent preferred volume mark is the acetic acid solution of 0.1-50vt.%.
The lyophilization temperature of the lyophilization molding described in step (1) is-80 ~ 0 DEG C, and sublimation drying is 1min ~ 720h.
Phosphate solution described in step (2) is soluble phosphoric acid saline solution, be selected from sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium phosphate, Ammonium biphosphate or ammonium phosphate, concentration is 0.001M ~ saturated concentration.
Converted in-situ temperature described in step (2) is 0-200 DEG C, and the time is 1min-720h.
Compared with prior art, the invention has the advantages that:
(1) the carbonate form hydroxylapatite and chitosan three-dimensional prepared of the present invention is composite porous, use chitosan, calcium carbonate, phosphate as raw material, not only cheap and easy to get, draw materials extensively, and environmentally friendly harmless, technique is simple, at room temperature can carry out.
(2) the carbonate form hydroxylapatite and chitosan three-dimensional prepared of the present invention is composite porous, porosity is high, aperture is large, pore size can adjust according to the concentration of chitosan, macroporous structure is conducive to the conversion of hydroxyapatite and increases specific surface area, and then is conducive to the absorption promoting heavy metal ion.
(3) the carbonate form hydroxylapatite and chitosan three-dimensional prepared of the present invention is composite porous, have suitable mechanical performance and good can processing type energy, be easy to be separated with water body during process heavy metal wastewater thereby, secondary pollution can not be caused, so that extensive use in industrial wastewater to environment.
Accompanying drawing explanation
Fig. 1 is the composite porous SEM image of carbonate form hydroxylapatite and chitosan three-dimensional prepared by embodiment 1;
Fig. 2 be embodiment 1 prepare carbonate form hydroxylapatite and chitosan three-dimensional composite porous XRD figure spectrum;
Fig. 3 is the composite porous FTIR collection of illustrative plates of carbonate form hydroxylapatite and chitosan three-dimensional prepared by embodiment 1;
Fig. 4 is the SEM image of resulting materials after the composite porous Adsorption of Heavy Metal Ions of carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 preparation;
To be that carbonate form hydroxylapatite and chitosan three-dimensional prepared by embodiment 1 is composite porous carry out the lead ion adsorbance curve after Adsorption of Heavy Metal Ions experiment to Fig. 5;
To be that carbonate form hydroxylapatite and chitosan three-dimensional prepared by embodiment 1 is composite porous carry out the lead ion adsorption efficiency curve after Adsorption of Heavy Metal Ions experiment to Fig. 6.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
(1) accurately take 10.00g chitosan and be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, be stirred to chitosan and be dissolved in acetic acid solution completely, ultrasonic removal bubble.Accurately take 10.00g calcium carbonate powder again and be placed in 10.00g chitosan solution, be stirred to spherical calcium carbonate and chitosan solution Homogeneous phase mixing, ultrasonic removal bubble, again calcium carbonate/chitosan mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, be transferred in freeze dryer,-80 DEG C, lyophilization 48h under 1 ~ 2Pa, can obtain calcium carbonate/chitosan three-dimensional porous material.
(2) under room temperature, calcium carbonate/chitosan three-dimensional porous material obtained in step (1) is placed in sodium hydroxide solution soaks, deionized water is washed till neutrality, be placed in the mixed solution (pH=7.40) of 0.2M sodium hydrogen phosphate and sodium dihydrogen phosphate, converted in-situ 168h at 37 DEG C, take out three-dimensional porous material and by washed with de-ionized water to neutral, obtain carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
The pattern composite porous to the carbonate form hydroxylapatite and chitosan three-dimensional obtained by embodiment 1 and composition characterize, the scanning electron microscope image (SEM) obtained, Radix Rumicis x ray diffraction collection of illustrative plates (XRD) and the infrared conversion spectrum of Fourier (FTIR), respectively by as shown in Figure 1, Figure 2 and Figure 3.
Schemed from Fig. 1 SEM, the support obtained is mutually through loose structure, and section pore size is 30 ~ 200 μm.The carbonate form hydroxyapatite generated is even in the surface distributed of porous material; The carbonate form hydroxyapatite formed as seen at high power lens is laminated structure, and sheet thickness is ~ 100nm.From Fig. 2 XRD spectra, the composite porous middle hydroxyapatite of carbonate form hydroxylapatite and chitosan three-dimensional has lower degree of crystallinity, after transforming 7 days, is converted into hydroxyapatite substantially completely in phosphate solution.From Fig. 3 FTIR spectrogram, the composite porous middle wave number of carbonate form hydroxylapatite and chitosan three-dimensional is 563,603,1034cm-1 etc. shows in material and defines hydroxyapatite.
To the composite porous test carrying out porosity of carbonate form hydroxylapatite and chitosan three-dimensional obtained in the present embodiment, the porosity of three-dimensional porous composite is 80%.
Adsorption test:
The experiment of heavy metal lead ionic adsorption is carried out to the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 gained is composite porous:
(1) leaded simulated wastewater solution is prepared: accurately take 6.4586g plumbi nitras (purity 99.0%), be mixed with the lead ion solution of 4000mg/L; Again the lead ion solution of 4000mg/L is added deionized water and be diluted to 400mg/L, use 0.1M sodium hydroxide solution and 0.1M dilute nitric acid solution that lead ion solution is adjusted to pH=5.5, for subsequent use.
(2) lead ion adsorption experiment under constant current conditions: adopt thermostat water bath Control release temperature to be 25 DEG C, peristaltic pump coutroi velocity is 0.8mL/min, solution is all flow through by the inside, space that carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, to ensure lead ion in the quick active adsorption solution of material energy, sampling interval time is set, sampling and measuring plumbum ion concentration, carries out lyophilization by composite porous for the carbonate form hydroxylapatite and chitosan three-dimensional after absorption.
After above-mentioned heavy metal lead ionic adsorption experiment, the morphology analysis that obtained carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, the scanning electron microscope image obtained (SEM) as shown in Figure 4.
Schemed from Fig. 4 SEM, adsorb after 7 days, be dispersed with the plumbous apatite [Pb10 (PO of size hexagonal club shaped structure at the composite porous surface uniform of carbonate form hydroxylapatite and chitosan three-dimensional
4)
3(OH)
2], the diameter of bar-shaped plumbous apatite is 20 ~ 300nm, and length is ~ 1 μm.
Carry out drawing and analyzing to above-mentioned heavy metal lead ionic adsorption experiment the data obtained, lead ion adsorbance curve, adsorption efficiency curve are respectively as shown in Figure 5, Figure 6, the composite porous maximal absorptive capacity to lead ion in solution of carbonate form hydroxylapatite and chitosan three-dimensional is 609.76mg/g, adsorption efficiency drops to 3.67% from 99.48%
Embodiment 2
(1) accurately take 20.00g chitosan and be placed in the acetic acid solution that 250mL volume fraction is 4vt.%, be stirred to chitosan and be dissolved in acetic acid solution completely, ultrasonic removal bubble.Accurately take 10.00g calcium carbonate powder again and be placed in 10.00g chitosan solution, be stirred to spherical calcium carbonate and chitosan solution Homogeneous phase mixing, ultrasonic removal bubble, again calcium carbonate/chitosan mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, be transferred in freeze dryer,-80 DEG C, lyophilization 48h under 1 ~ 2Pa, can obtain calcium carbonate/chitosan three-dimensional porous material.
(2) under room temperature, calcium carbonate/chitosan three-dimensional porous material obtained in step (1) is placed in sodium hydroxide solution soaks, deionized water is washed till neutrality, be placed in the mixed solution (pH=7.40) of 0.2M sodium hydrogen phosphate and sodium dihydrogen phosphate, converted in-situ 168h at 37 DEG C, take out three-dimensional porous material and by washed with de-ionized water to neutral, obtain carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
Embodiment 3
(1) accurately take 10.00g chitosan and be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, be stirred to chitosan and be dissolved in acetic acid solution completely, ultrasonic removal bubble.Accurately take 20.00g calcium carbonate powder again and be placed in 10.00g chitosan solution, be stirred to spherical calcium carbonate and chitosan solution Homogeneous phase mixing, ultrasonic removal bubble, again calcium carbonate/chitosan mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, be transferred in freeze dryer,-80 DEG C, lyophilization 48h under 1 ~ 2Pa, can obtain calcium carbonate/chitosan three-dimensional porous material.
(2) under room temperature, calcium carbonate/chitosan three-dimensional porous material obtained in step (1) is placed in sodium hydroxide solution soaks, deionized water is washed till neutrality, be placed in the mixed solution (pH=7.40) of 0.2M sodium hydrogen phosphate and sodium dihydrogen phosphate, converted in-situ 168h at 37 DEG C, take out three-dimensional porous material and by washed with de-ionized water to neutral, obtain carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
Embodiment 4
(1) accurately take 10.00g chitosan and be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, be stirred to chitosan and be dissolved in acetic acid solution completely, ultrasonic removal bubble.Accurately take 10.00g calcium carbonate powder again and be placed in 10.00g chitosan solution, be stirred to spherical calcium carbonate and chitosan solution Homogeneous phase mixing, ultrasonic removal bubble, again calcium carbonate/chitosan mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, be transferred in freeze dryer,-80 DEG C, lyophilization 48h under 1 ~ 2Pa, can obtain calcium carbonate/chitosan three-dimensional porous material.
(2) under room temperature, calcium carbonate/chitosan three-dimensional porous material obtained in step (1) is placed in sodium hydroxide solution soaks, deionized water is washed till neutrality, be placed in the mixed solution of 1M sodium hydrogen phosphate and sodium dihydrogen phosphate, converted in-situ 168h at 37 DEG C, take out three-dimensional porous material and by washed with de-ionized water to neutral, obtain carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
Embodiment 5
(1) accurately take 10.00g chitosan and be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, be stirred to chitosan and be dissolved in acetic acid solution completely, ultrasonic removal bubble.Accurately take 10.00g calcium carbonate powder again and be placed in 10.00g chitosan solution, be stirred to spherical calcium carbonate and chitosan solution Homogeneous phase mixing, ultrasonic removal bubble, again calcium carbonate/chitosan mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, be transferred in freeze dryer,-80 DEG C, lyophilization 48h under 1 ~ 2Pa, can obtain calcium carbonate/chitosan three-dimensional porous material.
(2) under room temperature, calcium carbonate/chitosan three-dimensional porous material obtained in step (1) is placed in sodium hydroxide solution soaks, deionized water is washed till neutrality, be placed in the mixed solution (pH=7.40) of 0.2M sodium hydrogen phosphate and sodium dihydrogen phosphate, converted in-situ 168h at 50 DEG C, take out three-dimensional porous material and by washed with de-ionized water to neutral, obtain carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
The experiment of heavy metal lead ionic adsorption is carried out to the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 2 ~ 5 gained is composite porous:
(1) leaded simulated wastewater solution is prepared: accurately take 6.4586g plumbi nitras (purity 99.0%), be mixed with the lead ion solution of 4000mg/L; Again the lead ion solution of 4000mg/L is added deionized water and be diluted to 400mg/L, use 0.1M sodium hydroxide solution and 0.1M dilute nitric acid solution that lead ion solution is adjusted to PH=3.0, for subsequent use.
(2) lead ion adsorption experiment under constant current conditions: adopt thermostat water bath Control release temperature to be 25 DEG C, peristaltic pump coutroi velocity is 0.8mL/min, solution is all flow through by the inside, space that carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, to ensure lead ion in the quick active adsorption solution of material energy, sampling interval time is set, sampling and measuring plumbum ion concentration, carries out lyophilization by composite porous for the carbonate form hydroxylapatite and chitosan three-dimensional after absorption.
The content of lead ion in leaded simulated wastewater solution before and after contrast absorption, finds that in above-described embodiment 2-5, the obtained composite porous adsorption rate to lead ion of each carbonate form hydroxylapatite and chitosan three-dimensional is all more than 99%.
Embodiment 6
The preparation method that carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, comprises the following steps:
(1) chitosan is dissolved in solvent is mixed with the chitosan solution that concentration is 0.005g/L, the acetic acid solution that the solvent used is 0.1vt.% for volume fraction.Again calcium carbonate powder is dispersed in chitosan solution, the ultrasonic bubble removing that goes down, obtains calcium carbonate/chitosan mixed slurry, be placed in mould, adopt lyophilization molding to obtain calcium carbonate/chitosan three-dimensional composite porous; The lyophilization temperature of described lyophilization molding is-80 ~-60 DEG C, and sublimation drying is 1min ~ 1h.
(2) the composite porous alkaline solution that is placed in of calcium carbonate/chitosan three-dimensional obtained in step (1) is soaked, deionized water is washed till neutrality, then phosphate solution is placed in, converted in-situ, take out and with deionized water rinsing to neutral, namely obtain carbonate form hydroxylapatite and chitosan three-dimensional after lyophilization composite porous.The disodium phosphate soln of described phosphate solution to be concentration be 0.001M, described converted in-situ temperature is 0-10 DEG C, and the time is 700-720h.
The weight ratio of the composite porous middle chitosan of gained carbonate form hydroxylapatite and chitosan three-dimensional and carbonate form hydroxyapatite is 1:50, and have three-dimensional through macroporous structure, its aperture is 5 ~ 10 μm, and porosity is 80% ~ 95%.
Embodiment 7
The preparation method that carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, comprises the following steps:
(1) chitosan is dissolved in solvent to be mixed with concentration be chitosan saturated solution, the acetic acid solution that the solvent used is 50vt.% for volume fraction.Again calcium carbonate powder is dispersed in chitosan solution, the ultrasonic bubble removing that goes down, obtains calcium carbonate/chitosan mixed slurry, be placed in mould, adopt lyophilization molding to obtain calcium carbonate/chitosan three-dimensional composite porous; The lyophilization temperature of described lyophilization molding is-10 ~ 0 DEG C, and sublimation drying is 700 ~ 720h.
(2) the composite porous alkaline solution that is placed in of calcium carbonate/chitosan three-dimensional obtained in step (1) is soaked, deionized water is washed till neutrality, then phosphate solution is placed in, converted in-situ, take out and with deionized water rinsing to neutral, namely obtain carbonate form hydroxylapatite and chitosan three-dimensional after lyophilization composite porous.Described phosphate solution is saturated potassium phosphate solution, and described converted in-situ temperature is 180-200 DEG C, and the time is 1min-1h.
The weight ratio of the composite porous middle chitosan of gained carbonate form hydroxylapatite and chitosan three-dimensional and carbonate form hydroxyapatite is 1:1, and have three-dimensional through macroporous structure, its aperture is 5 ~ 500 μm, and porosity is 10% ~ 30%.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.The term occurred in the present invention, for the elaboration of technical solution of the present invention and understanding, is not construed as limiting the invention.
Claims (7)
1. a carbonate form hydroxylapatite and chitosan three-dimensional is composite porous, it is characterized in that, this material comprises chitosan, carbonate form hydroxyapatite, carbonate form hydroxyapatite is evenly attached to the porous scaffold surface of chitosan, formed and there is three-dimensional through macroporous structure, its aperture is 5 ~ 500 μm, and porosity is 10% ~ 95%.
2. carbonate form hydroxylapatite and chitosan three-dimensional according to claim 1 is composite porous, it is characterized in that, the weight ratio of described chitosan and carbonate form hydroxyapatite powder is 1:1 ~ 1:50.
3. the preparation method that carbonate form hydroxylapatite and chitosan three-dimensional as claimed in claim 1 is composite porous, is characterized in that, comprise the following steps:
(1) chitosan is dissolved in solvent is mixed with chitosan solution, again calcium carbonate powder is dispersed in chitosan solution, obtain calcium carbonate/chitosan mixed slurry, adopt lyophilization molding to obtain calcium carbonate/chitosan three-dimensional composite porous;
(2) be placed in phosphate solution by composite porous for calcium carbonate/chitosan three-dimensional obtained in step (1), it is composite porous that in-situ transesterification changes into carbonate form hydroxylapatite and chitosan three-dimensional.
4. the preparation method that carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3 is composite porous, is characterized in that, the concentration of the chitosan solution described in step (1) is 0.005g/L ~ saturated solution; Chitosan is dissolved in that the solvent that solvent uses is organic solvent, the mixture of deionization or organic solvent and deionized water; Described organic solvent is selected from hydro carbons, alcohols, acids, esters or alcohols.
5. the preparation method that carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3 is composite porous, it is characterized in that, the lyophilization temperature of the lyophilization molding described in step (1) is-80 ~ 0 DEG C, and sublimation drying is 1min ~ 720h.
6. the preparation method that a kind of carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3 is composite porous, it is characterized in that, phosphate solution described in step (2) is soluble phosphoric acid saline solution, be selected from sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium phosphate, Ammonium biphosphate or ammonium phosphate, concentration is 0.001M ~ saturated concentration.
7. the preparation method that carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3 is composite porous, is characterized in that, the converted in-situ temperature described in step (2) is 0-200 DEG C, and the time is 1min-720h.
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| CN105727878A (en) * | 2016-01-28 | 2016-07-06 | 中国科学院合肥物质科学研究院 | Lead adsorbent and preparing method and application thereof |
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| CN108404217A (en) * | 2018-06-06 | 2018-08-17 | 浙江大学 | The method that one-step method quickly prepares large scale calcium phosphate/chitosan organic-inorganic hybrid material |
| CN109455720A (en) * | 2018-11-30 | 2019-03-12 | 中国科学院上海硅酸盐研究所 | A kind of silicon calcium phosphate nano powder, preparation method and application |
| CN110575821A (en) * | 2019-10-30 | 2019-12-17 | 上海师范大学 | Hydroxyapatite/chitosan composite material and preparation method and application thereof |
| CN111117636A (en) * | 2019-12-03 | 2020-05-08 | 广西师范大学 | Preparation method and application of phosphorus-based soil heavy metal passivator |
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