CN104740687B - Carbonate form hydroxylapatite and chitosan three-dimensional is composite porous and preparation method - Google Patents
Carbonate form hydroxylapatite and chitosan three-dimensional is composite porous and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional is composite porous and preparation method thereof, this material comprises shitosan, carbonate form hydroxyapatite, carbonate form hydroxyapatite is uniformly attached to the porous scaffold surface of shitosan, form the macroporous structure with three-dimensional insertion, its aperture is 5～500 μm, and porosity is 10%～95%.During preparation, Chitosan powder is dissolved in solvent, is configured to chitosan solution, Calcium Carbonate is placed in chitosan solution, stirs；Then, mixed slurry is proceeded in mould, Calcium Carbonate/chitosan three-dimensional porous material is made in lyophilization molding；Finally, soak through aqueous slkali and phosphate solution, obtain carbonate form hydroxylapatite and chitosan three-dimensional composite porous.Compared with prior art, the inventive method is simple, easy to operate, environmentally friendly, the carbonate form hydroxylapatite and chitosan three-dimensional of synthesis is composite porous to have higher porosity, big specific surface area and good Adsorption of Heavy Metal Ions ability, has broad application prospects in 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 compoundses (VOC) place
Reason field, specially a kind of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional is composite porous and its prepares
Method.
Background technology
The water pollution causing containing heavy metal ion industrial wastewater is the ring of the most serious that our times various countries generally face
One of border problem, heavy metal ion not only can disturb the normal metabolism of human body, also indirectly leads to central nervous system's damage
Wound, DNA repairs and Cognitive inhibition.Heavy metals in industrial wastewater ion reaches 200 500mg/L, in order that it will not have to human body
Evil is it is necessary to heavy-metal ion removal is to relatively low level.At present, the various skills processing heavy metal ion have been researched and developed
Art, absorption method is unanimously considered that one kind is cost-effective and is gone removing heavy metals method.Ideal adsorption agent material needs satisfaction following
Require：() has heavy metal ion and has good absorbability, the particularly absorption to low-concentration heavy metal ions；(ⅱ)
There is the macroporous structure of three-dimensional insertion, high-specific surface area, pore volume and easily realize separating with water body；() has nontoxic to environment
Feature friendly, that raw material is cheap and easy to get；() suitable mechanical performance and good can processing type energy, in order in Industry Waste
Extensively apply in water.The more heavy metal ion adsorbing material of research is activated carbon, kieselguhr, hydroxyapatite, oxidation at present
The natural macromolecular material such as the inorganic material such as Graphene and shitosan, cellulose.
Hydroxyapatite is the main inorganic composition of vertebrate skeletal and tooth, and its corresponding synthetic material has environment
Friendly feature.Hydroxyapatite is high due to its adsorption capacity, and low aqueous solubility and low cost are widely used as effectively adsorbing
The long-term disposal of heavy metal.Ca in hydroxyapatite crystal2+Ion can be by ion-exchange reactionss by other metal ions
Replace (as Cu2+, Cr2+, Ni2+, Pb2+, Hg2+, Fe2+Deng).Shitosan is as the linear natural macromolecular material of poly-glucosamine
One kind, there is significant absorbability and nonpoisonous and tasteless corrosion resistant feature, be widely used in heavy metal wastewater thereby.Grind
Study carefully the amino proving to contain in the molecule segment of shitosan and hydroxyl isoreactivity group can be coordinated with heavy metal ion and form network
Compound, is a kind of efficient chelate medium.The size of the absorbability of shitosan depends on its deacetylation.Deacetylation is got over
Greatly, absorbability is stronger.However, due to hydroxy apatite powder granule be difficult in water process solid-liquid separation shortcoming and
The poor shortcoming of shitosan mechanical property, is restricted in the practical application of Industrial Wastewater Treatment.
In order to overcome the defect in performance of homogenous material, the mode that researcher employs organic or inorganic is prepared for hydroxyl
Base apatite composite material is to improve separating property, absorption property etc..The research worker such as Xiao Wang, by hydroxyapatite
The Ice-storing ball being formed with polyvinyl alcohol, is supported on obtained composite on polyvinyl alcohol foam, to Cd2+There is preferable absorption
Effect, saturated adsorption capacity is 53.1mg/g, and the stalling characteristic (J.Sol- improving hydroxyapatite to a great extent
Gel.Sci Technol.(2007)43:99 104) research worker such as .Suk Hyun Jang, hydroxyapatite and polyacrylamide
The composite aquogel that amine is formed can be used for the absorption to Pb2+ in water body, when the quality of hydroxyapatite contained in composite is divided
Number, in 70% and 50%, is respectively 209,150mg/g to the saturated extent of adsorption of Pb2+, and the actual operability of material obtains
Arrive raising (J.Hazard.Mater. (2008) 159:294-299)；The research worker such as Xiaoli Li, by by shitosan,
The mixture of polyvinyl alcohol and Paris white is dipped to formation complex microsphere in calcium chloride saturation boric acid solution.When polyvinyl alcohol,
Calcium Carbonate and chitosan mass are than for 6:10:When 7.5, microsphere is to Cu2+,Pb2+,Zn2+And Cd2+Adsorbance be respectively 238.45,
166.44,74.18 with 126.06mg/g (Chem.Eng.J. (2011) 178:60-68).But, above-mentioned composite is generally deposited
It is impossible to meet simultaneously, there is macroporous structure and the requirement of high absorption property in the problem of the macroporous structure lacking three-dimensional communication.
Based on this, the present invention prepares a kind of multistage hole composite material of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional,
This material is environmentally friendly and reusable edible.
Content of the invention
The purpose of the present invention is exactly to overcome the defect of above-mentioned prior art presence to provide one kind to have three-dimensional order
Macroporous structure, big specific surface area and good absorption property, can be applicable to remove the heavy metal ion in industrial wastewater
High absorption property carbonate form hydroxylapatite and chitosan three-dimensional is composite porous and preparation method thereof.
It is a further object to provide a kind of high absorption property carbonate form hydroxylapatite and chitosan three-dimensional is many
The preparation method of hole composite material.This preparation technology is not only simple but also short preparation period, low production cost.
The purpose of the present invention can be achieved through the following technical solutions：A kind of carbonate form hydroxyapatite/chitosan
Three-dimensional porous composite is it is characterised in that this material comprises shitosan, carbonate form hydroxyapatite, carbonate form hydroxyl
Apatite is uniformly attached to the porous scaffold surface of shitosan, forms the macroporous structure with three-dimensional insertion, and its aperture is 5～
500 μm, porosity is 10%～95%.
The weight of described shitosan and carbonate form hydroxyapatite powder is than for 1：1～1：50.
The present invention is with calcium carbonate powder as template, high molecular polymer chitosan porous rack, soaks through phosphate solution
Converted in-situ is prepared from.Its preparation process comprises the following steps：(1) turn after calcium carbonate powder and the uniform mixing of chitosan solution
Enter in mould, using lyophilization molding；(2) it is placed in phosphate by composite porous for the Calcium Carbonate/chitosan three-dimensional of molding
Inverted in solution becomes carbonate form hydroxylapatite and chitosan three-dimensional composite porous.
A kind of composite porous preparation method of carbonate form hydroxylapatite and chitosan three-dimensional is it is characterised in that wrap
Include following steps：
(1) dissolve the chitosan in solvent and be configured to chitosan solution, then calcium carbonate powder is dispersed in shell and gather
In sugar juice, the ultrasonic bubble removing that goes down, obtain Calcium Carbonate/shitosan mixed slurry, be placed in mould, using lyophilization molding
Prepared Calcium Carbonate/chitosan three-dimensional is composite porous；
(2) composite porous for the Calcium Carbonate/chitosan three-dimensional being obtained in step (1) being placed in alkaline solution is soaked,
Deionized water is washed till neutrality, is subsequently placed in phosphate solution, converted in-situ, takes out and deionized water is rinsed to neutrality, cold
Carbonate form hydroxylapatite and chitosan three-dimensional is obtained final product composite porous after lyophilizing is dry.
The concentration of the chitosan solution described in step (1) is 0.005g/L～saturated solution；Shitosan is dissolved in solvent institute
The solvent using is the mixture of organic solvent, deionized water or organic solvent and deionized water；Described organic solvent is selected from
Hydro carbons, acids, esters or alcohols.Solvent preferred volume fraction 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) be soluble phosphoric acid saline solution, selected from disodium hydrogen phosphate, sodium dihydrogen phosphate,
Sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium phosphate, ammonium dihydrogen phosphate 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, it is an advantage of the current invention that：
(1) present invention preparation carbonate form hydroxylapatite and chitosan three-dimensional composite porous, using shitosan,
Calcium Carbonate, phosphate are as raw material, not only cheap and easy to get, draw materials extensively, and environmentally friendly harmless, and process is simple, in room
Can carry out under temperature.
(2) the carbonate form hydroxylapatite and chitosan three-dimensional of present invention preparation is composite porous, and porosity is high, hole
Footpath is big, and pore size can adjust according to the concentration of shitosan, and macroporous structure is conducive to the conversion of hydroxyapatite and increase to compare table
Area, and then may advantageously facilitate the absorption of heavy metal ion.
(3) the carbonate form hydroxylapatite and chitosan three-dimensional of present invention preparation is composite porous, has suitable machine
Tool performance and good can processing type energy, be easy to separate with water body when processing heavy metal wastewater thereby, environment do not resulted in secondary dirt
Dye, in order to extensively apply in industrial wastewater.
Brief description
Fig. 1 is the composite porous SEM image of the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 preparation；
Fig. 2 is the composite porous XRD spectrum of the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 preparation；
Fig. 3 is the composite porous FTIR figure of the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 preparation
Spectrum；
Fig. 4 is the composite porous Adsorption of Heavy Metals of carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 preparation
The SEM image of resulting materials after ion；
Fig. 5 be embodiment 1 preparation carbonate form hydroxylapatite and chitosan three-dimensional composite porous carry out absorption weight
Lead ion adsorbance curve after metal ion experiment；
Fig. 6 be embodiment 1 preparation carbonate form hydroxylapatite and chitosan three-dimensional composite porous carry out absorption weight
Lead ion adsorption efficiency curve after metal ion experiment.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
(1) accurately weigh 10.00g shitosan to be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, stir to shell
Polysaccharide is dissolved completely in acetic acid solution, ultrasonic removes bubble removing.Accurately weigh again 10.00g calcium carbonate powder be placed in 10.00g shell gather
In sugar juice, stir and uniformly mix with chitosan solution to spherical calcium carbonate, ultrasonic remove bubble removing, then by Calcium Carbonate/shitosan
Mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, is transferred in freeze dryer, -80 DEG C, under 1～2Pa
Lyophilization 48h, you can obtain Calcium Carbonate/chitosan three-dimensional porous material.
(2), under room temperature, the Calcium Carbonate/chitosan three-dimensional porous material being obtained in step (1) is placed in sodium hydroxide solution
Middle immersion, deionized water are washed till neutrality, are placed in 0.2M disodium hydrogen phosphate and the mixed solution (pH=7.40) of sodium dihydrogen phosphate,
Converted in-situ 168h at 37 DEG C, takes out three-dimensional porous material and deionized water is cleaned to neutrality, obtains final product carbonate form hydroxyl
Apatite/chitosan three-dimensional is composite porous.
The pattern composite porous to the carbonate form hydroxylapatite and chitosan three-dimensional obtained by embodiment 1 with become
Divide and characterized, the scanning electron microscope image (SEM) obtaining, Radix Rumiciss x ray diffraction collection of illustrative plates (XRD) and the infrared conversion spectrum of Fourier
(FTIR), respectively by.
Schemed from Fig. 1 SEM, obtained support is the loose structure being mutually communicated, section pore size for 30～
200μm.The carbonate form hydroxyapatite generating is uniform in the surface distributed of porous material；Carbonic acid in the visible formation of high power lenses
Root type hydroxyapatite is laminated structure, and sheet thickness is～100nm.From Fig. 2 XRD spectra, carbonate form hydroxy-apatite
The composite porous middle hydroxyapatite of stone/chitosan three-dimensional has relatively low degree of crystallinity, converts 7 days in phosphate solution
Afterwards, substantially completely it is converted into hydroxyapatite.From Fig. 3 FTIR spectrogram, carbonate form hydroxylapatite and chitosan three-dimensional
Composite porous middle wave number is 563,603,1034cm-1 etc. shows and defined hydroxyapatite in material.
Composite porous porosity is carried out to the carbonate form hydroxylapatite and chitosan three-dimensional being obtained in the present embodiment
Test, the porosity of three-dimensional porous composite is 80%.
Adsorption test：
Composite porous to the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 1 gained carry out heavy metal lead
Ionic adsorption is tested：
(1) prepare leaded simulated wastewater solution：Accurately weigh 6.4586g plumbi nitrass (purity 99.0%), be configured to
The lead ion solution of 4000mg/L；Again the lead ion solution of 4000mg/L is added deionized water to be diluted to 400mg/L, use
Lead ion solution is adjusted to pH=5.5 by 0.1M sodium hydroxide solution and 0.1M dilute nitric acid solution, standby.
(2) lead ion adsorption experiment under constant current conditions：It is 25 DEG C using thermostat water bath Control release temperature, peristaltic pump control
Flow velocity processed is 0.8mL/min, and solution is all by the composite porous space of carbonate form hydroxylapatite and chitosan three-dimensional
Portion is flow through, and to ensure lead ion in the quick active adsorption solution of material energy, setting sampling interval time, lead ion is measured by sampling dense
Degree, carries out lyophilization by composite porous for the carbonate form hydroxylapatite and chitosan three-dimensional after absorption.
After the experiment of above-mentioned heavy metal lead ionic adsorption, obtained carbonate form hydroxylapatite and chitosan three-dimensional is many
The morphology analysis of hole composite material, the scanning electron microscope image obtaining (SEM) is as shown in Figure 4.
Schemed from Fig. 4 SEM, after adsorbing 7 days, composite porous in carbonate form hydroxylapatite and chitosan three-dimensional
Surface is uniform-distribution with the lead apatite [Pb10 (PO of size hexagonal club shaped structure4)3(OH)2], bar-shaped lead apatite a diameter of
20～300nm, length is～1 μm.
Above-mentioned heavy metal lead ionic adsorption experiment the data obtained is carried out drawing and has analyzed, lead ion adsorbance curve,
Adsorption efficiency curve respectively as shown in Figure 5, Figure 6, carbonate form hydroxylapatite and chitosan three-dimensional composite porous to solution
The maximal absorptive capacity of middle lead ion is 609.76mg/g, and adsorption efficiency drops to 3.67% from 99.48%,
Embodiment 2
(1) accurately weigh 20.00g shitosan to be placed in the acetic acid solution that 250mL volume fraction is 4vt.%, stir to shell
Polysaccharide is dissolved completely in acetic acid solution, ultrasonic removes bubble removing.Accurately weigh again 10.00g calcium carbonate powder be placed in 10.00g shell gather
In sugar juice, stir and uniformly mix with chitosan solution to spherical calcium carbonate, ultrasonic remove bubble removing, then by Calcium Carbonate/shitosan
Mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, is transferred in freeze dryer, -80 DEG C, under 1～2Pa
Lyophilization 48h, you can obtain Calcium Carbonate/chitosan three-dimensional porous material.
(2), under room temperature, the Calcium Carbonate/chitosan three-dimensional porous material being obtained in step (1) is placed in sodium hydroxide solution
Middle immersion, deionized water are washed till neutrality, are placed in 0.2M disodium hydrogen phosphate and the mixed solution (pH=7.40) of sodium dihydrogen phosphate,
Converted in-situ 168h at 37 DEG C, takes out three-dimensional porous material and deionized water is cleaned to neutrality, obtains final product carbonate form hydroxyl
Apatite/chitosan three-dimensional is composite porous.
Embodiment 3
(1) accurately weigh 10.00g shitosan to be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, stir to shell
Polysaccharide is dissolved completely in acetic acid solution, ultrasonic removes bubble removing.Accurately weigh again 20.00g calcium carbonate powder be placed in 10.00g shell gather
In sugar juice, stir and uniformly mix with chitosan solution to spherical calcium carbonate, ultrasonic remove bubble removing, then by Calcium Carbonate/shitosan
Mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, is transferred in freeze dryer, -80 DEG C, under 1～2Pa
Lyophilization 48h, you can obtain Calcium Carbonate/chitosan three-dimensional porous material.
(2), under room temperature, the Calcium Carbonate/chitosan three-dimensional porous material being obtained in step (1) is placed in sodium hydroxide solution
Middle immersion, deionized water are washed till neutrality, are placed in 0.2M disodium hydrogen phosphate and the mixed solution (pH=7.40) of sodium dihydrogen phosphate,
Converted in-situ 168h at 37 DEG C, takes out three-dimensional porous material and deionized water is cleaned to neutrality, obtains final product carbonate form hydroxyl
Apatite/chitosan three-dimensional is composite porous.
Embodiment 4
(1) accurately weigh 10.00g shitosan to be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, stir to shell
Polysaccharide is dissolved completely in acetic acid solution, ultrasonic removes bubble removing.Accurately weigh again 10.00g calcium carbonate powder be placed in 10.00g shell gather
In sugar juice, stir and uniformly mix with chitosan solution to spherical calcium carbonate, ultrasonic remove bubble removing, then by Calcium Carbonate/shitosan
Mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, is transferred in freeze dryer, -80 DEG C, under 1～2Pa
Lyophilization 48h, you can obtain Calcium Carbonate/chitosan three-dimensional porous material.
(2), under room temperature, the Calcium Carbonate/chitosan three-dimensional porous material being obtained in step (1) is placed in sodium hydroxide solution
Middle immersion, deionized water are washed till neutrality, are placed in 1M disodium hydrogen phosphate and the mixed solution of sodium dihydrogen phosphate, at 37 DEG C in situ
Conversion 168h, takes out three-dimensional porous material and deionized water is cleaned to neutrality, obtains final product carbonate form hydroxyapatite/chitosan
Three-dimensional porous composite.
Embodiment 5
(1) accurately weigh 10.00g shitosan to be placed in the acetic acid solution that 250mL volume fraction is 2vt.%, stir to shell
Polysaccharide is dissolved completely in acetic acid solution, ultrasonic removes bubble removing.Accurately weigh again 10.00g calcium carbonate powder be placed in 10.00g shell gather
In sugar juice, stir and uniformly mix with chitosan solution to spherical calcium carbonate, ultrasonic remove bubble removing, then by Calcium Carbonate/shitosan
Mixed slurry is transferred in 12mm × 18mm (diameter × highly) mould, is transferred in freeze dryer, -80 DEG C, under 1～2Pa
Lyophilization 48h, you can obtain Calcium Carbonate/chitosan three-dimensional porous material.
(2), under room temperature, the Calcium Carbonate/chitosan three-dimensional porous material being obtained in step (1) is placed in sodium hydroxide solution
Middle immersion, deionized water are washed till neutrality, are placed in 0.2M disodium hydrogen phosphate and the mixed solution (pH=7.40) of sodium dihydrogen phosphate,
Converted in-situ 168h at 50 DEG C, takes out three-dimensional porous material and deionized water is cleaned to neutrality, obtains final product carbonate form hydroxyl
Apatite/chitosan three-dimensional is composite porous.
Composite porous to the carbonate form hydroxylapatite and chitosan three-dimensional of embodiment 2～5 gained carry out heavy metal
Lead ion adsorption experiment：
(1) prepare leaded simulated wastewater solution：Accurately weigh 6.4586g plumbi nitrass (purity 99.0%), be configured to
The lead ion solution of 4000mg/L；Again the lead ion solution of 4000mg/L is added deionized water to be diluted to 400mg/L, use
Lead ion solution is adjusted to PH=3.0 by 0.1M sodium hydroxide solution and 0.1M dilute nitric acid solution, standby.
(2) lead ion adsorption experiment under constant current conditions：It is 25 DEG C using thermostat water bath Control release temperature, peristaltic pump control
Flow velocity processed is 0.8mL/min, and solution is all by the composite porous space of carbonate form hydroxylapatite and chitosan three-dimensional
Portion is flow through, and to ensure lead ion in the quick active adsorption solution of material energy, setting sampling interval time, lead ion is measured by sampling dense
Degree, 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 to be obtained in above-described embodiment 2-5
The composite porous adsorption rate to lead ion of each carbonate form hydroxylapatite and chitosan three-dimensional is all more than 99%.
Embodiment 6
A kind of composite porous preparation method of carbonate form hydroxylapatite and chitosan three-dimensional, comprises the following steps：
(1) chitosan solution being configured in solvent that concentration is 0.005g/L, the solvent being used are dissolved the chitosan in
For the acetic acid solution for 0.1vt.% for the volume fraction.Again calcium carbonate powder is dispersed in chitosan solution, ultrasonic
Bubble removing, obtains Calcium Carbonate/shitosan mixed slurry, is placed in mould, Calcium Carbonate/shitosan is obtained using lyophilization molding
Three-dimensional porous composite；The lyophilization temperature of described lyophilization molding is -80～-60 DEG C, and sublimation drying is
1min～1h.
(2) composite porous for the Calcium Carbonate/chitosan three-dimensional being obtained in step (1) being placed in alkaline solution is soaked,
Deionized water is washed till neutrality, is subsequently placed in phosphate solution, converted in-situ, takes out and deionized water is rinsed to neutrality, cold
Carbonate form hydroxylapatite and chitosan three-dimensional is obtained final product composite porous after lyophilizing is dry.Described phosphate solution is concentration
Disodium phosphate soln for 0.001M, described converted in-situ temperature is 0-10 DEG C, and the time is 700-720h.
The composite porous middle shitosan of gained carbonate form hydroxylapatite and chitosan three-dimensional and carbonate form hydroxyl phosphorus
The weight of lime stone is than for 1：50, there is the macroporous structure of three-dimensional insertion, its aperture is 5～10 μm, porosity is 80%～95%.
Embodiment 7
A kind of composite porous preparation method of carbonate form hydroxylapatite and chitosan three-dimensional, comprises the following steps：
(1) dissolving the chitosan in solvent and being configured to concentration is shitosan saturated solution, and the solvent being used is volume
Fraction is the acetic acid solution of 50vt.%.Again calcium carbonate powder is dispersed in chitosan solution, the ultrasonic bubble removing that goes down,
Obtain Calcium Carbonate/shitosan mixed slurry, be placed in mould, Calcium Carbonate/chitosan three-dimensional is obtained using lyophilization molding many
Hole composite material；The lyophilization temperature of described lyophilization molding be -10～0 DEG C, sublimation drying be 700～
720h.
(2) composite porous for the Calcium Carbonate/chitosan three-dimensional being obtained in step (1) being placed in alkaline solution is soaked,
Deionized water is washed till neutrality, is subsequently placed in phosphate solution, converted in-situ, takes out and deionized water is rinsed to neutrality, cold
Carbonate form hydroxylapatite and chitosan three-dimensional is obtained final product composite porous after lyophilizing is dry.Described phosphate solution is saturation
Potassium phosphate solution, described converted in-situ temperature is 180-200 DEG C, and the time is 1min-1h.
The composite porous middle shitosan of gained carbonate form hydroxylapatite and chitosan three-dimensional and carbonate form hydroxyl phosphorus
The weight of lime stone is than for 1：1, there is the macroporous structure of three-dimensional insertion, its aperture is 5～500 μm, porosity is 10%～30%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not subject to above-described embodiment
Limit, other any spirit without departing from the present invention and the change made under principle, modification, replacement, combine, simplify,
All should be equivalent substitute mode, be included within protection scope of the present invention.The term occurring in the present invention is used for this
The elaboration of inventive technique scheme and understanding, are not construed as limiting the invention.
Claims (7)
1. a kind of carbonate form hydroxylapatite and chitosan three-dimensional composite porous it is characterised in that this material comprise shell gather
Sugar, carbonate form hydroxyapatite, carbonate form hydroxyapatite is uniformly attached to the porous scaffold surface of shitosan, forms tool
There is the macroporous structure of three-dimensional insertion, its aperture is 5～500 μm, porosity is 10%～95%；
The preparation method of described three-dimensional porous composite comprises the steps of：
(1) dissolve the chitosan in solvent and be configured to chitosan solution, then it is molten that calcium carbonate powder is dispersed in shitosan
In liquid, the ultrasonic bubble removing that goes down, obtain Calcium Carbonate/shitosan mixed slurry, be placed in mould, be obtained using lyophilization molding
Calcium Carbonate/chitosan three-dimensional is composite porous；
(2) by step (1) be obtained Calcium Carbonate/chitosan three-dimensional composite porous be placed in alkaline solution soak, go from
Son is washed to neutrality, is subsequently placed in phosphate solution, converted in-situ, takes out and deionized water is rinsed to neutrality, freezing is dry
Carbonate form hydroxylapatite and chitosan three-dimensional is obtained final product composite porous after dry.
2. carbonate form hydroxylapatite and chitosan three-dimensional according to claim 1 is composite porous, and its feature exists
In, described shitosan and carbonate form hydroxyapatite powder weight than for 1：1～1：50.
3. the composite porous preparation side of a kind of carbonate form hydroxylapatite and chitosan three-dimensional as claimed in claim 1
Method is it is characterised in that the method comprises the steps of：
(1) dissolve the chitosan in solvent and be configured to chitosan solution, then it is molten that calcium carbonate powder is dispersed in shitosan
In liquid, the ultrasonic bubble removing that goes down, obtain Calcium Carbonate/shitosan mixed slurry, be placed in mould, be obtained using lyophilization molding
Calcium Carbonate/chitosan three-dimensional is composite porous；
(2) by step (1) be obtained Calcium Carbonate/chitosan three-dimensional composite porous be placed in alkaline solution soak, go from
Son is washed to neutrality, is subsequently placed in phosphate solution, converted in-situ, takes out and deionized water is rinsed to neutrality, freezing is dry
Carbonate form hydroxylapatite and chitosan three-dimensional is obtained final product composite porous after dry.
4. the composite porous preparation method of carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3,
It is characterized in that, the concentration of the chitosan solution described in step (1) is 0.005g/L～saturated solution；Shitosan is dissolved in solvent
The solvent being used is the mixture of organic solvent, deionized water or organic solvent and deionized water；Described organic solvent choosing
From hydro carbons, acids, esters or alcohols.
5. the composite porous preparation method of carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3,
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 composite porous preparation of a kind of carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3
Method is it is characterised in that the phosphate solution described in step (2) is soluble phosphoric acid saline solution, selected from disodium hydrogen phosphate, phosphoric acid
Sodium dihydrogen, sodium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, diammonium phosphate, ammonium dihydrogen phosphate or ammonium phosphate, concentration
For 0.001M～saturated concentration.
7. the composite porous preparation method of carbonate form hydroxylapatite and chitosan three-dimensional according to claim 3,
It 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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| CN108404217B (en) * | 2018-06-06 | 2021-01-26 | 浙江大学 | Method for rapidly preparing large-size calcium phosphate/chitosan organic-inorganic hybrid material by one-step method |
| CN109455720B (en) * | 2018-11-30 | 2021-09-07 | 中国科学院上海硅酸盐研究所 | Calcium silicophosphate nano powder, preparation method and application |
| CN111718519A (en) * | 2019-03-22 | 2020-09-29 | 东北林业大学 | Preparation method of composition |
| CN110575821B (en) * | 2019-10-30 | 2022-09-06 | 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 |
| CN112007619B (en) * | 2020-08-28 | 2023-03-31 | 玉林师范学院 | Chitosan calcium carbonate composite adsorbent for adsorption and preparation method thereof |
| CN113976084A (en) * | 2021-11-03 | 2022-01-28 | 玉林师范学院 | Used for adsorbing Pb in water2+Composite adsorbent and preparation method thereof |
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| US3929971A (en) * | 1973-03-30 | 1975-12-30 | Research Corp | Porous biomaterials and method of making same |
| US7514248B2 (en) * | 2002-04-18 | 2009-04-07 | University Of Florida Research Foundation, Inc. | Process for making organic/inorganic composites |
| EP1744793A2 (en) * | 2003-10-22 | 2007-01-24 | University of Florida | Biomimetic organic/inorganic composites, processes for their production, and methods of use |
| CN102302804B (en) * | 2011-09-05 | 2014-04-16 | 济宁学院 | Hydroxyapatite-based biological composite scaffold and tissue engineered bone |
| CN102674285A (en) * | 2012-05-14 | 2012-09-19 | 上海师范大学 | Preparation method of hollow carbonate radical type hydroxyapatite |
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