CN107596450A - A kind of hydroxyapatite nanoparticle of surface modification and preparation method thereof - Google Patents
A kind of hydroxyapatite nanoparticle of surface modification and preparation method thereof Download PDFInfo
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- CN107596450A CN107596450A CN201710764240.2A CN201710764240A CN107596450A CN 107596450 A CN107596450 A CN 107596450A CN 201710764240 A CN201710764240 A CN 201710764240A CN 107596450 A CN107596450 A CN 107596450A
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- hydroxyapatite
- surface modification
- coupling agent
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Abstract
The present invention relates to artificial bone and dental material field, provide a kind of hydroxyapatite nanoparticle of surface modification, using in-situ synthesis, calcium ion, phosphate ion, coupling agent will be added with and adjust pH value into the premixed liquid addition reactor of alkalescence, the nanometer particle material that 150 DEG C of 10 hours of reaction are crystallized, it is washed with deionized after cooling, and final hydroxyapatite nanoparticle is obtained after 60 DEG C of drying.The invention provides a kind of hydroxyapatite nanoparticle of surface modification, it has good mechanical property, the interface bond strength between hydroxyapatite nano inorganic material and high-molecular organic material is especially improved, so as to improve the characteristics such as the biocompatibility of high polymer material/hydroxyapatite composite material, ion exchangeable and adsorptivity.
Description
Technical field
The present invention relates to artificial bone and dental material field, more particularly to one applied to bone repair and gear division reparation
Hydroxyapatite nanoparticle of kind surface modification and preparation method thereof.
Background technology
Hydroxyapatite (Hydroxyapatite, HAP) is the bone of vertebrate and the main component of tooth, in human body bone
HAP mass fraction accounts for 60% or so, and the enamel surface HAP mass fractions of people's tooth account for more than 95%.Human body bone master
To be made up of organic bone matrix structure and inorganic bone salts frame structure, the elementary cell of inorganic structure is needle-like and column
Phosphorite crystal, it is about 40~60nm, wide about 20nm, thickness about 3~5nm.Artificial synthesized hydroxyapatite has good life
Thing compatibility, biocompatibility, bioactivity and bone conduction effect, it is a kind of excellent hard tissue substituting material.But due to hydroxyl
The shortcomings such as fragility that base apatite has ceramic material intrinsic is big, toughness is low, cannot be used for the reparation of heavy burden position Cranial defect.And
And because hydroxyapatite also has a feature such as excellent ion exchangeable and adsorptivity, therefore composite reinforcing material, catalysis,
Separation and ion exchange etc. are widely used, it is particularly possible to effectively remove industrial wastewater (such as metal smelt and textile printing and dyeing
Process) in contain cadmium, chromium, copper, the heavy metal ion such as lead.
Nano ceramics has the advantages that high intensity, high tenacity, meanwhile, based on bionic angle, nanometer hydroxyapatite
Crystallization and collagen, bone growth factor etc. are compound to prepare composite bio-active bone renovating material, can have osteoacusis and self-bone grafting concurrently
Effect, the osteogenic ability of bone implant material is improved, and, nanoscale HAP functionally shows some specific performances, such as nanometer
Growth of the level HAP particles to some tumour cells is inhibited, and does not have negative effect substantially to normal cell.
HAP is compound with high polymer material, it can not only improve the toughness of HAP materials, and high polymer material can be assigned
Certain function, such as biocompatibility, excellent ion exchangeable and adsorptivity.But due to the boundary between HAP and polymer
Surface properties are different so that compatibility is poor between the two, therefore HAP is difficult to be uniformly dispersed in polymeric matrix, and HAP's is effective
Content is relatively low, so as to limit its application function.In addition, in inorganic/organic composite material, composite materials property is determined
Principal element be interface cohesion degree between organic phase and inorganic phase, it is excellent that good interface cohesion can assign composite
Mechanical property.Coupling agent is a kind of material with Liang Zhong heterogeneitys functional group, and a part of functional group in molecule can be with
Reactive organic molecule, another part can form good bond with mineral surfaces adsorption reaction.Using with parents (it is hydrophilic and
It is hydrophobic) coupling agent of group forms connection between polymer and HAP, can improve HAP dispersiveness and composite in two
Alternate interface bond strength.
From above-mentioned prior art, by chemical synthesis nanometer hydroxyapatite, and using coupling agent to nanometer hydroxyl
Base apatite surface is modified, and will can not only greatly improve the mechanical strength and toughness of hydroxyapatite；And pass through idol
Join the hydroxyapatite nanoparticle of agent modification, enhance between the hydroxyapatite mineral material and high-molecular organic material
Interface bond strength, so as to further improve the mechanical property of hydroxyapatite material, and improve high polymer material/hydroxyl
The characteristics such as biocompatibility, ion exchangeable and the adsorptivity of base apatite composite material.
The content of the invention
Object of the present invention is to provide a kind of hydroxyapatite nanoparticle of surface modification and preparation method thereof.Tool
Say body, synthesize the hydroxyapatite nanoparticle of surface modification by in-situ synthesis as template using coupling agent, its
With good mechanical property, the boundary between hydroxyapatite nano inorganic material and high-molecular organic material is especially improved
Face combination degree, so as to improve the biocompatibility of high polymer material/hydroxyapatite composite material, ion exchangeable and suction
The characteristics such as attached property.
To achieve the above object, the technical solution adopted by the present invention is a kind of hydroxyapatite nanoparticle of surface modification
And this material preparation method.
A kind of technical scheme of the hydroxyapatite nanoparticle of surface modification of the present invention its be characterized in that the hydroxyl
The chemical formula of base apatite nano material is Ca10(PO4)6(OH)2:Rn, wherein R is coupling agent, and n is coupling agent in whole material
Mol ratio shared by the inside.
Preferably, described R includes organic chromium complex coupling agent, silane coupler, titante coupling agent and aluminium
Acid compound coupling agent.
Preferably, described silane coupler is KH550, KH560, KH570, KH792, DL602 or DL171.
Preferably, described n is the mol ratio of coupling agent in the material, n=0.5-50.
A kind of its special character of the technical scheme of preparation method of the hydroxyapatite nanoparticle of surface modification of the present invention
Be to use in-situ synthesis, will be added with calcium ion, phosphate ion, coupling agent and adjust pH value to alkalescence premixed liquid add
Enter in reactor, the nanometer particle material that 150 DEG C of 10 hours of reaction are crystallized, be washed with deionized after cooling, and
Final hydroxyapatite nanoparticle is obtained after 60 DEG C of drying.
Preferably, the power that ultrasonic wave disperses is 500-800w.
Method of the present invention, in-situ synthesis, i.e., sent out under certain condition using between different elements or chemicals
Biochemical reaction, and one or more of reinforcements are generated in a kind of matrix, to reach the purpose for improving single substrate performance.It is logical
Cross composite prepared by this method, reinforcement be in matrix nucleation, it is spontaneous grow up, therefore, reinforcement surface no-pollution,
Matrix and the intermiscibility of reinforcement are good, and interface bond strength is higher.
In-situ synthesis of the present invention, matrix are coupling agent, and reinforcement is hydroxyapatite nanoparticle.
Coupling agent of the present invention, i.e., a kind of material with two kinds of different chemical property functional groups, one is close nothing
The group of machine thing, easily with mineral surfaces chemically reactive；Another is organophilic group, can be with synthetic resin or other
Chemical reaction occurs for high molecular polymer or generation hydrogen bond is dissolved in wherein.By the active group adsorbing metal of its close inorganic matter from
Son, so as to the template and fairlead as nanocrystal growth.
Coupling agent of the present invention, can be organochromium complexes coupling agent, silane coupler, titante coupling agent
Or aluminic acid compound coupling agent.
Silane coupler of the present invention, can be KH550, KH560, KH570, KH792, DL602 or DL171.
The solution have the advantages that:The invention provides a kind of hydroxyapatite nanoparticle of surface modification, and it has
There is good mechanical property, especially improve the interface between hydroxyapatite nano inorganic material and high-molecular organic material
Bond strength, so as to improve the biocompatibility of high polymer material/hydroxyapatite composite material, ion exchangeable and absorption
The characteristics such as property.
Brief description of the drawings
The hydroxyapatite nanoparticle XRD spectrum of Fig. 1 surface modifications
The hydroxyapatite nanoparticle TEM Electronic Speculum of Fig. 2 surface modifications
Embodiment
First calcium ion is mixed with coupling agent solution, 3 hours are stirred at room temperature after ultrasonic wave is scattered, then side is stirred
Side adds (NH4)2HPO4The aqueous solution, and pH value is adjusted to 10 with ammoniacal liquor, obtain surface modification and contain the pre- of hydroxyapatite nucleus
Mixed liquid, the premixed liquid is then transferred to autoclave, 150 DEG C of reactions, 10 hours nanometer particle materials crystallized, cooling
After be washed with deionized, and 60 DEG C drying after obtain final powder sample.Its material is detected and identified by XRD,
Fig. 1 is that the XRD spectrum for the hydroxyapatite nanoparticle for carrying out surface modification using silane coupler is shown, wherein marking asterisk
Peak value be the embodiment that is combined with hydroxyapatite of silane coupler.Accompanying drawing 2 is the hydroxyl phosphorus of the silane coupler surface modification
Lime stone nano material TEM electron microscopes, it is shown as being about the rod-like nano material of 20 nanometers of 60 nanometer diameter.
The following example is provided so that the present invention is further illustrated, but the embodiment should not solve in any way
It is interpreted as limiting the scope of the present invention.
Embodiment 1:The hydroxyapatite nanoparticle of 50% mol ratio KH550 silane coupler surface modifications
By the Ca (NO of 10mL 0.01mol/L concentration3)2The aqueous solution is added to 10mlKH550 silane couplers while stirring
The aqueous solution in (0.01mol/L), ultrasonic disperse after 5 minutes again room temperature continue stir 3 hours, then add while stirring
10mL(NH4)2HPO4(0.006mol/L) aqueous solution, pH value is adjusted to 10 with 0.05mol/L ammoniacal liquor, then by the mixed liquor
36mL autoclave is transferred to, 150 DEG C are reacted 10 hours, and crystal is taken out after cooling, is washed with deionized, last 60 DEG C of drying
Final sample is obtained afterwards.
Embodiment 2:The hydroxyapatite nanoparticle of 20% mol ratio KH550 silane coupler surface modifications
By the Ca (NO of 10mL 0.02mol/L concentration3)2The aqueous solution is added to 10mlKH550 silane couplers while stirring
The aqueous solution in (0.005mol/L), ultrasonic disperse after 5 minutes again room temperature continue stir 3 hours, then add while stirring
10mL(NH4)2HPO4(0.006mol/L) aqueous solution, pH value is adjusted to 10 with 0.05mol/L ammoniacal liquor, then by the mixed liquor
36mL autoclave is transferred to, 150 DEG C are reacted 10 hours, and crystal is taken out after cooling, is washed with deionized, last 60 DEG C of drying
Final sample is obtained afterwards.
Embodiment 3:The hydroxyapatite nanoparticle of 50% mol ratio KH570 silane coupler surface modifications
By the Ca (NO of 10mL 0.01mol/L concentration3)2The aqueous solution is added to 10mlKH570 silane couplers while stirring
The aqueous solution in (0.01mol/L), ultrasonic disperse after 5 minutes again room temperature continue stir 3 hours, then add while stirring
10mL(NH4)2HPO4(0.006mol/L) aqueous solution, pH value is adjusted to 10 with 0.05mol/L ammoniacal liquor, then by the mixed liquor
36mL autoclave is transferred to, 150 DEG C are reacted 10 hours, and crystal is taken out after cooling, is washed with deionized, last 60 DEG C of drying
Final sample is obtained afterwards.
Embodiment 4:The hydroxyapatite nanoparticle of 50% mol ratio organochromium complexes coupling agent surface modification
By the Ca (NO of 10mL 0.01mol/L concentration3)2The aqueous solution is added to the coupling of 10ml organochromium complexes while stirring
In the aqueous solution of agent (0.01mol/L), room temperature continues to stir 3 hours ultrasonic disperse again after 5 minutes, then adds while stirring
10mL(NH4)2HPO4(0.006mol/L) aqueous solution, pH value is adjusted to 10 with 0.05mol/L ammoniacal liquor, then by the mixed liquor
36mL autoclave is transferred to, 150 DEG C are reacted 10 hours, and crystal is taken out after cooling, is washed with deionized, last 60 DEG C of drying
Final sample is obtained afterwards.
Embodiment 5:The hydroxyapatite nanoparticle of 0.5% mol ratio organochromium complexes coupling agent surface modification
By the Ca (NO of 10mL 0.01mol/L concentration3)2The aqueous solution is added to the coupling of 10ml organochromium complexes while stirring
In the aqueous solution of agent (0.000125mol/L), room temperature continues to stir 3 hours ultrasonic disperse again after 5 minutes, then while stirring
Add 10mL (NH4)2HPO4(0.006mol/L) aqueous solution, pH value is adjusted to 10 with 0.05mol/L ammoniacal liquor, then mixes this
The autoclave that liquid is transferred to 36mL is closed, 150 DEG C are reacted 10 hours, and crystal is taken out after cooling, is washed with deionized, last 60 DEG C
Final sample is obtained after drying.
Claims (6)
- A kind of 1. hydroxyapatite nanoparticle of surface modification, it is characterised in that the change of the hydroxyapatite nanoparticle Formula is Ca10(PO4)6(OH)2:Rn, wherein R is coupling agent, and n is coupling agent mol ratio shared inside whole material.
- A kind of 2. hydroxyapatite nanoparticle of surface modification according to claim 1, it is characterised in that described R For at least one of organochromium complexes coupling agent, silane coupler, titante coupling agent or aluminic acid compound coupling agent.
- A kind of 3. hydroxyapatite nanoparticle of surface modification according to claim 1, it is characterised in that described n For the mol ratio of coupling agent in the material, n=0.5-50.
- 4. the hydroxyapatite nanoparticle of a kind of surface modification according to claim 2, it is characterised in that described Silane coupler is KH550, KH560, KH570, KH792, DL602 or DL171.
- A kind of 5. preparation method of the hydroxyapatite nanoparticle of surface modification as claimed in claim 1, it is characterised in that Using in-situ synthesis, calcium ion mixes with coupling agent solution, and 3 hours, Ran Houbian is stirred at room temperature after ultrasonic wave is scattered Stir side and add (NH4)2HPO4The aqueous solution, and pH value is adjusted to 10 with ammoniacal liquor, obtain surface modification and contain hydroxyapatite nucleus Premixed liquid, the premixed liquid is then transferred to autoclave, 150 DEG C of reactions, 10 hours nanometer particle materials crystallized, It is washed with deionized after cooling, and hydroxyapatite nanoparticle is obtained after 60 DEG C of drying.
- 6. a kind of preparation method of the hydroxyapatite nanoparticle of surface modification according to claim 5, its feature exist In the scattered power of ultrasonic wave is 500-800w.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114099775A (en) * | 2021-10-21 | 2022-03-01 | 华南理工大学 | HAp-SF artificial periosteum loading SDF-1 alpha/CGRP and preparation method thereof |
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| CN102745660A (en) * | 2011-04-18 | 2012-10-24 | 中国科学院大连化学物理研究所 | Microfluidic chip based method for synthesizing needle-like hydroxyapatite nanoparticle |
| CN103919686A (en) * | 2013-01-11 | 2014-07-16 | 王青山 | Tooth repair nanometer hydroxyapatite composite material and preparation method thereof |
| CN104548199A (en) * | 2015-01-14 | 2015-04-29 | 石家庄铁道大学 | Hard biotissue replacement and repair material and preparation method thereof |
| WO2017025359A1 (en) * | 2015-08-11 | 2017-02-16 | FECKL, Johann | Mesoporous calcium phosphate-citrate nanoparticles and uses thereof |
| CN106496600A (en) * | 2016-10-26 | 2017-03-15 | 河南工程学院 | A kind of preparation method of modifted-nano-hydroxyapatite/Polyethylene Glycol composite aquogel |
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- 2017-08-30 CN CN201710764240.2A patent/CN107596450A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102745660A (en) * | 2011-04-18 | 2012-10-24 | 中国科学院大连化学物理研究所 | Microfluidic chip based method for synthesizing needle-like hydroxyapatite nanoparticle |
| CN103919686A (en) * | 2013-01-11 | 2014-07-16 | 王青山 | Tooth repair nanometer hydroxyapatite composite material and preparation method thereof |
| CN104548199A (en) * | 2015-01-14 | 2015-04-29 | 石家庄铁道大学 | Hard biotissue replacement and repair material and preparation method thereof |
| WO2017025359A1 (en) * | 2015-08-11 | 2017-02-16 | FECKL, Johann | Mesoporous calcium phosphate-citrate nanoparticles and uses thereof |
| CN106496600A (en) * | 2016-10-26 | 2017-03-15 | 河南工程学院 | A kind of preparation method of modifted-nano-hydroxyapatite/Polyethylene Glycol composite aquogel |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114099775A (en) * | 2021-10-21 | 2022-03-01 | 华南理工大学 | HAp-SF artificial periosteum loading SDF-1 alpha/CGRP and preparation method thereof |
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