CN107585750A - A kind of hydroxyapatite material of surface modification and preparation method thereof - Google Patents
A kind of hydroxyapatite material of surface modification and preparation method thereof Download PDFInfo
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- CN107585750A CN107585750A CN201710764274.1A CN201710764274A CN107585750A CN 107585750 A CN107585750 A CN 107585750A CN 201710764274 A CN201710764274 A CN 201710764274A CN 107585750 A CN107585750 A CN 107585750A
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- hydroxyapatite
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Abstract
The present invention relates to artificial bone and dental material field, provide a kind of hydroxyapatite material of surface modification and preparation method thereof, coupling agent is a kind of material with two kinds of different chemical property functional groups, one be close inorganic matter group, easily with mineral surfaces chemically reactive；Another is organophilic group, chemical reaction can occur with synthetic resin or other high molecular polymers or generation hydrogen bond is dissolved in wherein.By the active group adsorbing metal ions of its close inorganic matter, so as to the template and fairlead as crystal growth.The interface bond strength between hydroxyapatite mineral material and high-molecular organic material is 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 material 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.
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, hydroxyapatite surface is modified by coupling agent, will not only can be significantly
Improve the mechanical strength and toughness of hydroxyapatite；And the hydroxyapatite material modified by coupling agent, enhance the hydroxyl
Interface bond strength between base apatite inorganic material and high-molecular organic material, so as to further improve hydroxyapatite
The mechanical property of material, and improve the biocompatibility of high polymer material/hydroxyapatite composite material, ion exchangeable
With the characteristic such as adsorptivity.
The content of the invention
Object of the present invention is to provide a kind of hydroxyapatite material of surface modification and preparation method thereof.Specifically
Say, hydroxyapatite powder is dispersed in coupling agent, hydroxyapatite powder is attenuated by grinding and make coupling agent and its
Surface combine, formed coupling agent surface modification hydroxyapatite material, can greatly improve hydroxyapatite mineral material with
Interface bond strength between high-molecular organic material, so as to improve the life of high polymer material/hydroxyapatite composite material
The characteristics such as thing compatibility, ion exchangeable and adsorptivity.
To achieve the above object, the technical solution adopted by the present invention for a kind of surface modification hydroxyapatite material and
The preparation method of this material.
A kind of technical scheme of the hydroxyapatite material of surface modification of the present invention its be characterized in that, the hydroxyl phosphorus
Grey stone material includes following raw material：Ca10(PO4)6(OH)2:Rn, wherein R is coupling agent, n institutes inside whole material for coupling agent
The weight ratio accounted for.
Preferably, described R includes organic chromium complex coupling agent, silane coupler, titante coupling agent and aluminium
Acid compound coupling agent.
Preferably, described silane coupler includes KH550, KH560, KH570, KH792, DL602 and DL171.
Preferably, described n is the weight ratio of coupling agent in the material, n=0.5-50.
Preferably, the hydroxyapatite material also includes the auxiliary agent for accounting for hydroxyapatite gross weight 0.02-0.05%.
Preferably, it is 2 that the auxiliary agent, which is mass ratio,:1:2 dopamine, poly D, L-lactic acid and three [2.4- di-t-butyls
Phenyl] phosphite ester.
A kind of technical scheme of the preparation method of the hydroxyapatite material of surface modification of the present invention its be characterized in that
Using ground and mixed method, i.e., the hydroxyapatite powder of bulky grain is distributed in coupling agent solution, is then transferred to circular grinding
Machine, in grinding, adjusting body based environment makes it that fully coupling occur with hydroxyapatite, and final dusty material is obtained after drying.
Preferably, the particle diameter of the hydroxyapatite powder of bulky grain is 200-300 microns.
Preferably, by the hydroxyapatite powder of bulky grain, it is added to while stirring in coupling agent aqueous solution, 2000-
4000W is transferred to circular grinding machine after ultrasonic disperse 3-8 minutes.
Preferably, it is 9-10 that ammoniacal liquor adjustment pH value is added in circular grinding machine.
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 crystal 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 material of surface modification, hydroxyl is improved
Interface bond strength between base apatite inorganic material and high-molecular organic material, so as to improve high polymer material/hydroxyl
The characteristics such as biocompatibility, ion exchangeable and the adsorptivity of apatite composite material.
Brief description of the drawings
The hydroxyapatite material XRD spectrum of Fig. 1 surface modifications
The grain size distribution of the hydroxyapatite material of Fig. 2 surface modifications
Embodiment
The hydroxyapatite powder of bulky grain is distributed in coupling agent solution, is then transferred to circular grinding machine, side grinding
Side adjusting body based environment makes it that fully coupling occur with hydroxyapatite, and final dusty material is obtained after drying.Its material is examined
Survey is identified that Fig. 1 is that the XRD spectrum for the hydroxyapatite material for carrying out surface modification using silane coupler shows by XRD
Show, (a), (b), the part by weight of (c) KH550 silane couplers are respectively 1%, 20%, 50%, wherein the peak value of mark asterisk
The embodiment combined for silane coupler with hydroxyapatite.Accompanying drawing 2 is the hydroxy-apatite stone material of the silane coupler surface modification
Expect grain size distribution, show that it is uniformly dispersed, average grain diameter is 2 microns.
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:Hydroxyapatite material of 20% weight than KH550 silane coupler surface modifications
By the hydroxyapatite powder that 400g initial sizes are 200 microns, it is 5% to be added to 2kg solid contents while stirring
In the KH550 aqueous solution, 3600W ultrasonic disperses are transferred to circular grinding machine and (include the zirconium oxide abrasive pearl of 3 mm dias after 5 minutes
Son, rotating speed 2500rpm), it is 9 that ammoniacal liquor adjustment system pH is added in grinding, is taken out after continuing grinding 1 hour, passes through spray
Mist is dried to obtain final dusty material.
Embodiment 2:Hydroxyapatite material of 5% weight than KH550 silane coupler surface modifications
By the hydroxyapatite powder that 800g initial sizes are 200 microns, it is 2.5% to be added to 2kg solid contents while stirring
In the KH550 aqueous solution, 2200W ultrasonic disperses are transferred to circular grinding machine and (include the zirconium oxide abrasive pearl of 3 mm dias after 5 minutes
Son, rotating speed 2500rpm), it is 9 that ammoniacal liquor adjustment system pH is added in grinding, is taken out after continuing grinding 1 hour, passes through spray
Mist is dried to obtain final dusty material.
Embodiment 3:Hydroxyapatite material of 20% weight than organochromium complexes coupling agent surface modification
It is 200 microns of hydroxyapatite powder by 400g initial sizes, it is 5% to have to be added to 2kg solid contents while stirring
In the machine chromium complex coupling agent aqueous solution, 2300w ultrasonic disperses are transferred to circular grinding machine and (include the oxygen of 3 mm dias after 5 minutes
Change zirconium grinding pearl, rotating speed 2500rpm), it is 10 that ammoniacal liquor adjustment system pH is added in grinding, after continuing grinding 1 hour
Take out, final dusty material is obtained by spray drying.
Embodiment 4:Hydroxyapatite material of 0.5% weight than titante coupling agent surface modification
By the hydroxyapatite powder that 400g initial sizes are 300 microns, it is 0.94% to be added to 2kg solid contents while stirring
In the aqueous solution of titante coupling agent and 0.08g auxiliary agents, 3000W ultrasonic disperses are transferred to circular grinding machine and (include 3 after 3 minutes
The zirconium oxide abrasive pearl of mm dia, rotating speed 2500rpm), it is 10 that ammoniacal liquor adjustment system pH is added in grinding, is continued
Grinding is taken out after 1 hour, and final dusty material is obtained by spray drying.Auxiliary agent is that mass ratio is 2:1:2 dopamine, gather
D, Pfansteihl and three [2.4- di-tert-butyl-phenyls] phosphite esters.
Embodiment 5:Hydroxyapatite material of 50% weight than titante coupling agent surface modification
By the hydroxyapatite powder that 400g initial sizes are 300 microns, the titanium that 2kg solid contents are 20% is added to while stirring
In the aqueous solution of esters of gallic acid coupling agent and 0.2g auxiliary agents, 2000W ultrasonic disperses are transferred to circular grinding machine and (include 3 millimeters after 8 minutes
The zirconium oxide abrasive pearl of diameter, rotating speed 2500rpm), it is 10 that ammoniacal liquor adjustment system pH is added in grinding, continues to grind
Taken out after 1 hour, final dusty material is obtained by spray drying.Auxiliary agent is that mass ratio is 2:1:2 dopamine, poly- D, L-
Lactic acid and three [2.4- di-tert-butyl-phenyls] phosphite esters.
Claims (10)
1. a kind of hydroxyapatite material of surface modification, it is characterised in that the hydroxyapatite material includes following raw material：
Ca10(PO4)6(OH)2:Rn, wherein R is coupling agent, and n is coupling agent weight ratio shared inside whole material.
2. the hydroxyapatite material of a kind of surface modification according to claim 1, it is characterised in that described R is to have
At least one of machine chromium complex coupling agent, silane coupler, titante coupling agent or aluminic acid compound coupling agent.
3. the hydroxyapatite material of a kind of surface modification according to claim 1, it is characterised in that described n is even
Join the weight ratio of agent in the material, n=0.5-50.
A kind of 4. hydroxyapatite material of surface modification according to claim 2, it is characterised in that described silane
Coupling agent is KH550, KH560, KH570, KH792, DL602 or DL171.
A kind of 5. hydroxyapatite material of surface modification according to claim 1, it is characterised in that the hydroxy-apatite
Stone material also includes the auxiliary agent for accounting for hydroxyapatite gross weight 0.02-0.05%.
6. the hydroxyapatite material of a kind of surface modification according to claim 5, it is characterised in that the auxiliary agent is matter
Amount is than being 2:1:2 dopamine, poly D, L-lactic acid and three [2.4- di-tert-butyl-phenyls] phosphite esters.
7. the preparation method of the hydroxyapatite material of a kind of surface modification as described in claim 1-6, it is characterised in that adopt
With ground and mixed method, i.e., the hydroxyapatite powder of bulky grain is distributed in coupling agent solution, is then transferred to circular grinding machine,
In grinding, adjusting body based environment makes it that fully coupling occur with hydroxyapatite, and final hydroxy-apatite stone material is obtained after drying
Material.
8. the preparation method of the hydroxyapatite material of a kind of surface modification according to claim 7, it is characterised in that big
The particle diameter of the hydroxyapatite powder of particle is 200-300 microns.
9. the preparation method of the hydroxyapatite material of a kind of surface modification according to claim 7, it is characterised in that will
The hydroxyapatite powder of bulky grain, is added in coupling agent aqueous solution while stirring, 2000-4000W ultrasonic disperse 3-8 minutes
After be transferred to circular grinding machine.
A kind of 10. preparation method of the hydroxyapatite material of surface modification according to claim 7, it is characterised in that
It is 9-10 that ammoniacal liquor adjustment pH value is added in circular grinding machine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108721702A (en) * | 2018-06-29 | 2018-11-02 | 江西理工大学 | A kind of preparation method of magnesium/l-lactic acid Composite Bone holder |
| CN108786713A (en) * | 2018-06-08 | 2018-11-13 | 南京师范大学 | A kind of nano hydroxyapatite adsorbent and its preparation method and application that parents' absorbent-type is sulfhydryl modified |
| CN111388752A (en) * | 2020-05-20 | 2020-07-10 | 中鼎凯瑞科技成都有限公司 | PVA fiber/polyamino acid/hydroxyapatite bone supporting material and preparation thereof |
| CN116003941A (en) * | 2023-01-13 | 2023-04-25 | 湖北合聚高分子材料有限公司 | PMMA composite material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475280A (en) * | 2003-06-17 | 2004-02-18 | 武汉理工大学 | Method of establishing nano organic silane dressing layer on hydroxy apatite surfac |
| CN104524627A (en) * | 2014-12-23 | 2015-04-22 | 南京航空航天大学 | Method for preparing high-strength novel hydroxyapatite bone cement |
| CN105412983A (en) * | 2016-01-12 | 2016-03-23 | 河南工程学院 | Preparation method and application of nano-hydroxyapatite with surface grafted with RGD peptide |
-
2017
- 2017-08-30 CN CN201710764274.1A patent/CN107585750A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1475280A (en) * | 2003-06-17 | 2004-02-18 | 武汉理工大学 | Method of establishing nano organic silane dressing layer on hydroxy apatite surfac |
| CN104524627A (en) * | 2014-12-23 | 2015-04-22 | 南京航空航天大学 | Method for preparing high-strength novel hydroxyapatite bone cement |
| CN105412983A (en) * | 2016-01-12 | 2016-03-23 | 河南工程学院 | Preparation method and application of nano-hydroxyapatite with surface grafted with RGD peptide |
Non-Patent Citations (2)
| Title |
|---|
| 廖建国等: "硅烷偶联剂对纳米羟基磷灰石表面改性的研究", 《无机材料学报》 * |
| 王晓等: "硅烷偶联剂KH570表面修饰羟基磷灰石的结构与吸附性能研究", 《材料导报B：研究篇》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786713A (en) * | 2018-06-08 | 2018-11-13 | 南京师范大学 | A kind of nano hydroxyapatite adsorbent and its preparation method and application that parents' absorbent-type is sulfhydryl modified |
| CN108786713B (en) * | 2018-06-08 | 2021-04-27 | 南京师范大学 | Amphiphilic adsorption type sulfhydryl modified nano hydroxyapatite adsorbent and preparation method and application thereof |
| CN108721702A (en) * | 2018-06-29 | 2018-11-02 | 江西理工大学 | A kind of preparation method of magnesium/l-lactic acid Composite Bone holder |
| CN108721702B (en) * | 2018-06-29 | 2021-06-29 | 江西理工大学 | Preparation method of magnesium/L-polylactic acid composite bone scaffold |
| CN111388752A (en) * | 2020-05-20 | 2020-07-10 | 中鼎凯瑞科技成都有限公司 | PVA fiber/polyamino acid/hydroxyapatite bone supporting material and preparation thereof |
| CN116003941A (en) * | 2023-01-13 | 2023-04-25 | 湖北合聚高分子材料有限公司 | PMMA composite material and preparation method thereof |
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Application publication date: 20180116 |