CN1475280A - Method of establishing nano organic silane dressing layer on hydroxy apatite surfac - Google Patents
Method of establishing nano organic silane dressing layer on hydroxy apatite surfac Download PDFInfo
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- CN1475280A CN1475280A CNA031281664A CN03128166A CN1475280A CN 1475280 A CN1475280 A CN 1475280A CN A031281664 A CNA031281664 A CN A031281664A CN 03128166 A CN03128166 A CN 03128166A CN 1475280 A CN1475280 A CN 1475280A
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Abstract
A process for preparing a nano-class decorative organic silane layer on the surface of hydroxyphosphorite features use of non-protonic system as solvent and includes reflux in solvent, reaction, centrifugal separation, washing and drying. Its advantages are high decorative effect and controllable thickness (1.5-2.7 nm).
Description
Technical field
The invention belongs to biomedical materials field, relate to specifically and a kind of hydroxyapatite surface is carried out modification, thereby in the method for its surface creation nanoscale organosilan decorative layer.
Technical background
Hydroxyapatite (HA) owing to have excellent biological compatibility, the synosteosis ability is widely used in the synthetic bone alternate material.But the pure ha material fragility is bigger, is mainly used in nonbearing small-sized implantation body in the past, as artificial dental root, otica, coating and the damaged filler of bone etc.At present, new important application direction of hydroxyapatite is to strengthen the toughness reinforcing macromolecule that absorbs with hydroxylapatite powder or granule, formation hydroxyapatite/can absorb macromolecule (as gathering 'alpha '-hydroxy acids etc.) composite bone substitution material, but its polymer moiety bio-absorbable, nontoxic, be easy to drain, the hydroxyapatite in the component then assimilates in vivo and provides calcium phosphorus source for the reparation of bone defect.Such composite bone substitution material has both the advantage of above-mentioned two kinds of materials, need not take out by second operation behind the internal fixation prothesis that is used to fracture, thereby has represented the developing direction of internal fixation material.Weak point is that this class composite loss of strength in physiological environment is very fast, and the position that at first takes place to degrade often is positioned at hydroxyapatite and macromolecule two-phase interface.
Can overcome above-mentioned defective to a certain extent by hydroxyapatite surface being carried out modification.The modifier of having advised comprises: inorganic zirconates, isocyanates, poly-acid and silane coupler etc., wherein silane coupler is considered to tool exploitation and is worth.Main cause is: one, some silane derivatives have been applied to tooth and filling material of bone in the past, show excellent biological compatibility; Its two, tentatively demonstrate certain effect.Discover that further being used for hydroxyapatite surface, to carry out the hydride modified layer of modification blocked up or cross the thin effective modification effect that all do not reach, the thickness of hydride modified layer generally should be in 1～3 nanometer (being equivalent to 1～2 silane monolayer roughly).Existing silane-modified method is to carry out in water or water-ethanol system at proton system, majority, and hydrolysis formation polysiloxanes clad very easily takes place silane in such system, and response speed is very fast, and coating thickness is difficult to control.
Summary of the invention
At above deficiency, the purpose of this invention is to provide and a kind ofly create the method for nano-organosilicon alkane decorative layer in hydroxyapatite surface, this decorative layer controllable thickness, modification effect are good.
To achieve these goals, technical scheme of the present invention is: a kind of method of creating nano-organosilicon alkane decorative layer in hydroxyapatite surface, make decorating molecule with silane derivative, the finishing of hydroxyapatite is carried out in non-proton kind solvent, prepared nanometer silane decorative layer in hydroxyapatite surface through backflow, reaction, centrifugalize, washing, drying at room temperature, vacuum drying process step.
Implementing concrete grammar of the present invention is:
(1) select for use silane derivative to make decorating molecule, its consumption is 1.0～2.0% (mass percents) of hydroxyapatite amount;
(2) under magnetic agitation hydroxylapatite powder is added in the non-proton kind solvent, nitrogen protection refluxed 0.5 hour,
Drip silane derivative then, continued back flow reaction 6～24 hours;
(3) cooling, centrifugalize;
(4) use chloroform and absolute ethanol washing precipitate successively;
(5) drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.
Described non-proton kind solvent is benzene,toluene,xylene or N, a kind of in the dinethylformamide.
Described silane derivative is a kind of in gamma-aminopropyl-triethoxy-silane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
The present invention adopts non-proton system to make solvent, and the hydride modified layer thickness of gained can be controlled in the 1.5-2.7 nanometer, and modification effect is good.
Description of drawings
Fig. 1 is the infrared spectrogram (IR) that silane derivative (gamma-aminopropyl-triethoxy-silane) is modified hydroxyapatite
Fig. 2 is X-photoelectron spectroscopy (XPS) figure that silane derivative (gamma-aminopropyl-triethoxy-silane) is modified hydroxyapatite
The specific embodiment
Example 1. adds 100 parts of hydroxyapatite micropowders (15～25 μ m) in the exsiccant toluene under magnetic agitation, and nitrogen protection refluxed 0.5 hour, dripped 2 parts of gamma-aminopropyl-triethoxy-silanes then, continues back flow reaction 12 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, obtaining hydride modified layer thickness is 1.8nm..
Computational methods are as follows:
Unmodified hydroxyapatite surface calcium atom percentage ratio (Ca Atom%): 18.6%, hydroxyapatite layer (maximum) the thickness T h that this moment, XPS scanned
Max=10nm; And XPS scans gamma-aminopropyl-triethoxy-silane to modify the calcium atom percentage ratio Ca Atom% of hydroxyapatite surface is 15.2%, the hydroxyapatite layer thickness T h that this moment, XPS scanned
HA=8.2nm; Then, the actual (real) thickness Th of hydride modified layer
Silane=Th
Max-Th
HA=10-8.2=1.8 (nm).
Example 2. adds exsiccant N with 100 parts of hydroxyapatite micropowders (15～25 μ m) under magnetic agitation, in the dinethylformamide, nitrogen protection refluxed 0.5 hour, dripped 2 parts of γ-(methacryloxypropyl) propyl trimethoxy silicane then, continued back flow reaction 13 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 2.7nm that the same method obtains hydride modified layer thickness.
Example 3. adds exsiccant N with 100 parts of hydroxyapatite micropowders (15～25 μ m) under magnetic agitation, in the dinethylformamide, nitrogen protection refluxed 0.5 hour, dripped 1 part of γ-(methacryloxypropyl) propyl trimethoxy silicane then, continued back flow reaction 14 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 1.6nm that the same method obtains hydride modified layer thickness.
Example 4. adds 100 parts of hydroxyapatite micropowders (15～25 μ m) in the exsiccant dimethylbenzene under magnetic agitation, and nitrogen protection refluxed 0.5 hour, dripped 1 part of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane then, continues back flow reaction 22 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 1.7nm that the same method obtains hydride modified layer thickness.
Example 5. adds exsiccant N with 100 parts of hydroxyapatite micropowders (15～25 μ m) under magnetic agitation, in the dinethylformamide, nitrogen protection refluxed 0.5 hour, dripped 1.5 parts of γ-(methacryloxypropyl) propyl trimethoxy silicane then, continued back flow reaction 18 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 2.2nm that the same method obtains hydride modified layer thickness.
Example 6. adds 100 parts of hydroxyapatite micropowders (15～25 μ m) in the exsiccant benzene under magnetic agitation, and nitrogen protection refluxed 0.5 hour, dripped 1.5 parts of gamma-aminopropyl-triethoxy-silanes then, continues back flow reaction 24 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 1.6nm that the same method obtains hydride modified layer thickness.
Example 7. adds exsiccant N with 100 parts of hydroxyapatite micropowders (15～25 μ m) under magnetic agitation, in the dinethylformamide, nitrogen protection refluxed 0.5 hour, dripped 1.5 parts of γ-(2 then, 3-epoxy third oxygen) propyl trimethoxy silicane continued back flow reaction 6 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 1.5nm that the same method obtains hydride modified layer thickness.
Example 8. adds exsiccant N with 100 parts of hydroxyapatite micropowders (15～25 μ m) under magnetic agitation, in the dinethylformamide, nitrogen protection refluxed 0.5 hour, dripped 2 parts of gamma-aminopropyl-triethoxy-silanes then, continued back flow reaction 16 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 1.7nm that the same method obtains hydride modified layer thickness.
Example 9. adds 100 parts of hydroxyapatite micropowders (15～25 μ m) in the exsiccant dimethylbenzene under magnetic agitation, and nitrogen protection refluxed 0.5 hour, dripped 2 parts of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane then, continues back flow reaction 16 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 2.3nm that the same method obtains hydride modified layer thickness.
Example 10. adds exsiccant N with 100 parts of hydroxyapatite micropowders (15～25 μ m) under magnetic agitation, in the dinethylformamide, nitrogen protection refluxed 0.5 hour, dripped 1 part of gamma-aminopropyl-triethoxy-silane then, continued back flow reaction 24 hours; Cooling, centrifugalize reactant mixture, precipitation is used chloroform and absolute ethanol washing 3 times successively, and drying at room temperature is after 8 hours, again in 50 ℃ of vacuum dryings 24 hours.According to X-photoelectron spectroscopy (XPS) result, it is 1.5nm that the same method obtains hydride modified layer thickness.
As shown in Figure 1, silane derivative (gamma-aminopropyl-triethoxy-silane) is modified the infrared spectrogram (IR) of hydroxyapatite: (CH
2-) C-H asymmetrical stretching vibration (2935cm
-1), amino (NH
2) bending vibration (1628cm of N-H
-1) and stretching vibration (3422cm
-1), and the stretching vibration (1136cm of C-N
-1) etc.Above-mentioned all peaks all are not present in the IR spectrum of hydroxyapatite, and this shows in the product after hydroxyapatite is modified and contains silane derivative (gamma-aminopropyl-triethoxy-silane) molecular structure.
As shown in Figure 2, silane derivative (gamma-aminopropyl-triethoxy-silane) is modified X-photoelectron spectroscopy (XPS) figure of hydroxyapatite except that the spectrum peak of the Ca that demonstrates hydroxyapatite, P and O, also show Si2p, Si2s and C1s power spectrum peak, show that further hydroxyapatite modified by silane derivative (gamma-aminopropyl-triethoxy-silane).Can calculate its atom percentage content (Atom%) and decorative layer thickness (as example 1) according to Ca spectrum peak relative area.
Claims (5)
1, a kind of method of creating nano-organosilicon alkane decorative layer in hydroxyapatite surface, make decorating molecule with silane derivative, it is characterized in that making the finishing of hydroxyapatite in non-proton kind solvent, to carry out, form nano-organosilicon alkane decorative layer in hydroxyapatite surface through backflow, reaction, centrifugalize, washing, dry back.
2, a kind of method at hydroxyapatite surface establishment nano-organosilicon alkane decorative layer as claimed in claim 1 is characterized in that carrying out as follows:
1) select for use silane derivative to make decorating molecule, its consumption is 1.0～2.0% of a hydroxyapatite mass percent;
2) under magnetic agitation hydroxylapatite powder is added in the non-proton kind solvent, nitrogen protection refluxed 0.5 hour, then
Drip silane derivative, continued back flow reaction 6～24 hours;
3) cooling, centrifugalize;
4) use chloroform and absolute ethanol washing precipitate successively;
5) drying at room temperature is after 8 hours, in 50 ℃ of vacuum dryings 24 hours, forms the hydroxyapatite surface decorative layer again.
3, as claimed in claim 1 or 2ly a kind ofly create the method for nano-organosilicon alkane decorative layer, it is characterized in that described non-proton kind solvent is benzene,toluene,xylene or N, a kind of in the dinethylformamide in hydroxyapatite surface.
4, a kind of method of creating nano-organosilicon alkane decorative layer in hydroxyapatite surface as claimed in claim 1 or 2, it is characterized in that described silane derivative is a kind of in gamma-aminopropyl-triethoxy-silane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-(methacryloxypropyl) propyl trimethoxy silicane.
5, a kind of method at hydroxyapatite surface establishment nano-organosilicon alkane decorative layer as claimed in claim 1 or 2 is characterized in that described hydroxyapatite surface decorative layer thickness is the 1.5-2.7 nanometer.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100545084C (en) * | 2007-11-29 | 2009-09-30 | 同济大学 | The preparation method of ordered porous hydroxyapatite material |
| CN101954119A (en) * | 2010-09-10 | 2011-01-26 | 北京化工大学 | Method for preparing light-cured bone repair material from double bond-containing siloxane coated and modified hydroxyapatite |
| CN101966349A (en) * | 2010-09-10 | 2011-02-09 | 北京化工大学 | Method for preparing photo-curable bone repairing material from epoxy group-containing siloxane-clad modified hydroxyapatite |
| CN102357261A (en) * | 2011-06-28 | 2012-02-22 | 东华大学 | Surface modification method of nanometer hydroxyapatite mediated by APTS |
| CN103316381A (en) * | 2013-07-07 | 2013-09-25 | 中国人民解放军成都军区总医院 | Preparation method of nanoscale compound type bone repair material |
| CN103816855A (en) * | 2014-03-06 | 2014-05-28 | 东华大学 | Preparation method for modified hydroxyapatite with grafted amino acid on surface |
| CN105255853A (en) * | 2015-11-10 | 2016-01-20 | 河南工业大学 | Preparation method of magnetic hydroxyapatite immobilized lipase and application in edible fat and oil processing |
| CN105999401A (en) * | 2016-07-22 | 2016-10-12 | 武汉理工大学 | Hydroxyapatite-based bacteriostatic repair material used in department of dentistry and preparation method thereof |
| CN107585750A (en) * | 2017-08-30 | 2018-01-16 | 浙江美加华医疗技术有限公司 | A kind of hydroxyapatite material of surface modification and preparation method thereof |
| CN110755625A (en) * | 2019-10-10 | 2020-02-07 | 广东药科大学 | Targeting type drug carrier based on nano-hydroxyapatite and construction method of nano-drug delivery system |
| CN111792634A (en) * | 2020-07-27 | 2020-10-20 | 刘小雄 | Preparation method of modified hydroxyapatite shaping material |
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2003
- 2003-06-17 CN CN 03128166 patent/CN1194773C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100545084C (en) * | 2007-11-29 | 2009-09-30 | 同济大学 | The preparation method of ordered porous hydroxyapatite material |
| CN101954119A (en) * | 2010-09-10 | 2011-01-26 | 北京化工大学 | Method for preparing light-cured bone repair material from double bond-containing siloxane coated and modified hydroxyapatite |
| CN101966349A (en) * | 2010-09-10 | 2011-02-09 | 北京化工大学 | Method for preparing photo-curable bone repairing material from epoxy group-containing siloxane-clad modified hydroxyapatite |
| CN101954119B (en) * | 2010-09-10 | 2013-08-21 | 北京化工大学 | Method for preparing light-cured bone repair material from double bond-containing siloxane coated and modified hydroxyapatite |
| CN101966349B (en) * | 2010-09-10 | 2013-09-18 | 北京化工大学 | Method for preparing photo-curable bone repairing material from epoxy group-containing siloxane-clad modified hydroxyapatite |
| CN102357261A (en) * | 2011-06-28 | 2012-02-22 | 东华大学 | Surface modification method of nanometer hydroxyapatite mediated by APTS |
| CN102357261B (en) * | 2011-06-28 | 2014-01-08 | 东华大学 | Surface modification method of nanometer hydroxyapatite mediated by APTS |
| CN103316381B (en) * | 2013-07-07 | 2014-06-25 | 中国人民解放军成都军区总医院 | Preparation method of nanoscale compound type bone repair material |
| CN103316381A (en) * | 2013-07-07 | 2013-09-25 | 中国人民解放军成都军区总医院 | Preparation method of nanoscale compound type bone repair material |
| CN103816855A (en) * | 2014-03-06 | 2014-05-28 | 东华大学 | Preparation method for modified hydroxyapatite with grafted amino acid on surface |
| CN105255853A (en) * | 2015-11-10 | 2016-01-20 | 河南工业大学 | Preparation method of magnetic hydroxyapatite immobilized lipase and application in edible fat and oil processing |
| CN105999401A (en) * | 2016-07-22 | 2016-10-12 | 武汉理工大学 | Hydroxyapatite-based bacteriostatic repair material used in department of dentistry and preparation method thereof |
| CN105999401B (en) * | 2016-07-22 | 2019-03-08 | 武汉理工大学 | Antibacterial repair materials of a kind of dentistry based on hydroxyapatite and preparation method thereof |
| CN107585750A (en) * | 2017-08-30 | 2018-01-16 | 浙江美加华医疗技术有限公司 | A kind of hydroxyapatite material of surface modification and preparation method thereof |
| CN110755625A (en) * | 2019-10-10 | 2020-02-07 | 广东药科大学 | Targeting type drug carrier based on nano-hydroxyapatite and construction method of nano-drug delivery system |
| CN111792634A (en) * | 2020-07-27 | 2020-10-20 | 刘小雄 | Preparation method of modified hydroxyapatite shaping material |
| CN111792634B (en) * | 2020-07-27 | 2023-06-13 | 青岛蓝皓生物技术有限公司 | Preparation method of modified hydroxyapatite shaping material |
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