CN106139252B - A kind of hydroxyapatite of titania additive and preparation method thereof - Google Patents
A kind of hydroxyapatite of titania additive and preparation method thereof Download PDFInfo
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- CN106139252B CN106139252B CN201510177081.7A CN201510177081A CN106139252B CN 106139252 B CN106139252 B CN 106139252B CN 201510177081 A CN201510177081 A CN 201510177081A CN 106139252 B CN106139252 B CN 106139252B
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Abstract
The present invention relates to hydroxyapatites of a kind of titania additive and preparation method thereof, its specific solution are as follows: (1) prepare hydroxyapatite: containing in certain density calcium salt and phosphate aqueous solution, precipitating reagent is added, homogeneous reaction occurs, obtains hydroxyapatite after filtration, washing and drying.Wherein precipitating reagent is urea or hexamethylenetetramine；(2) it prepares titania hydrosol: first hydrolyzing to obtain metatitanic acid precipitating for titanium salt, hydrogen peroxide is then added and carries out ultrasound, then adds stabilizer and carries out reflow treatment, obtains stable titania hydrosol；(3) titania additive: hydroxyapatite is soaked in titania hydrosol, then by filtering, dry, calcining, obtains the hydroxyapatite of titania additive.The hydroxyapatite partial size that the present invention obtains is at 76 ~ 150 microns, size narrow distribution, and size is controllable.Process flow is simple, at low cost, and the chemical substance being related to is few, and resulting hydroxylapatite biology compatibility is good, has significant bactericidal effect.
Description
Technical field
The present invention relates to hydroxyapatites of a kind of titania additive and preparation method thereof.
Background technique
Hydroxyapatite is the main inorganic composition for constituting human body hard tissue, accounts for the 77% of people's bone inorganic constituents, in dentary more
Up to 97%.It and other biomaterial significant differences are that it contains calcium and P elements necessary to tissue, and not
Containing other harmful elements.After implanting, under the action of body fluid, calcium and phosphorus can dissociate material surface out, by body tissue institute
It absorbs, and chemical bonds can be organized the formation of with skeleton, grow new tissue.Therefore, hydroxyapatite is current public affairs
Recognize the biomaterial with superperformance.With the development of modern medical techniques and material science, there is biocompatibility and life
The active artificial substituting material of object is widely used in the reparation of human body hard and soft tissue and organ.Many research tables in recent years
It is bright, in the infection caused by biomaterial, when 45% the reason of is due to biomaterial and human contact, shape on the surface of the material
At one layer of protein film, and bacterium is easy to adhere on this layer of protein film, then growth and breeding, using traditional antibacterial therapy without
Method is eradicated.
Nano-TiO2There is very strong bactericidal effect to staphylococcus aureus, Escherichia coli, Candida albicans etc..Its machine
Reason is TiO2Under illumination condition, the oxygen radical of generation can destroy cell wall structure, make cell wall fracture, damaged, plasma membrane solution
Body.Subsequently into cell space internal sabotage inner membrance and cellular component, make cytoplasmic condensation, cellular content is caused to overflow, may occur in which
Thallus cavitation phenomenon.High Jinhua master thesis " titanium dioxide nano-particle to the osteoblastic proliferation of originally culture, point
Change and the influence of mineralization function " think, TiO2Nano particle is while promoting Primary osteoblast cells proliferation, it is suppressed that it is to rouge
Fat cell transdifferentiationof and its mineralization function, the influence for alkaline phosphatase activities then have promotion and inhibiting effect concurrently.QiJian
It is grade doping diamond-like rock layers and Ag, TiO that big patent of invention (201410139015.6), which reports a kind of,2Adulterate hydroxyl phosphorus
The preparation method of grey rock layers polynary nanometer composite coating, wherein the method for using magnetron sputtering.Yu Qifeng et al. will be averaged grain
Degree is the anatase nano-TiO of 5 nm2Mix hydroxylapatite powder in powder, be put into dehydrated alcohol, through ultrasonic grind and mixing,
TiO is made by isostatic cool pressing base, sintering in low temperature drying2Hydroxyapatite composite ceramics reach automatically cleaning and sterilization
Effect improves materials microstructure compatibility and bioactivity." titanium dioxide and hydroxyapatite nano are multiple in paper by Xu Kan et al.
Condensation material preparation and representation " in, using solution chemistry synthetic method, by Coated With Hydroxyapatite nano-titanium dioxide table
Face prepares titanium dioxide and Hydroxyapatite Nanocomposites, achievees the purpose that bacterium is inhibited to improve material safety.Zhang Hang
State et al. is in paper " hydroxyapatite/TiO2The biocompatibility of nanotube complex " in, by titania nanotube with receive
Rice hydroxyapatite is compound, shows good biocompatibility.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of hydroxyapatite of titania additive and
Preparation method.This method process equipment is simple, particle is uniform, particle size is controllable, low in cost, the chemical substance being related to
It is few.To achieve the purpose of the present invention, it adopts the following technical scheme that.
A kind of preparation method of the hydroxyapatite for the titania additive can be used for biological tissue's reparation, including walk as follows
Suddenly.
1, the preparation of hydroxyapatite
(1) compound concentration is the calcium saline solution of 0.5-0.7 mol/L, the HNO for being 32% by mass fraction3Solution is added dropwise
To wherein, until the pH value of solution is 1.5 ~ 3.5；
The calcium salt is Ca (NO3)2、CaCl2、CaCO3Or Ca (CH3COO)2；
(2) compound concentration is the phosphate aqueous solution of 0.1-0.2 mol/L；
The phosphate is KH2PO4、K2HPO4、(NH4)2HPO4Or Na2HPO4；
(3) phosphate aqueous solution that step (2) are prepared is added dropwise to the calcium salt that step (1) obtains in mechanical stirring
It in acid solution, is vigorously stirred after adding, is uniformly mixed it, then adds organic silicon surfactant；
The calcium salt and phosphatic molar ratio are 1.67, and the surfactant is to step figure CoatOSil 1211,
CoatOSil 7602, CoatOSil 7604, CoatOSil 3573, CoatOSil 7500, CoatOSil 3509,
CoatOSil 47, CoatOSil 77, CoatOSil 2400, CoatOSil 2812, CoatOSil 3500 or Silwet
408,HR-3408；
(4) a certain amount of precipitating reagent is slowly added in the mixed solution that step (3) obtains, is warming up to 70 ~ 95 DEG C, does not stop
Ground mechanical stirring reacts it 36-72 hours；
The precipitating reagent is or mixtures thereof urea, hexamethylenetetramine, and the molar ratio of calcium salt and precipitating reagent is 1.1-
1.5；
(5) reaction solution that step (4) obtains is filtered, washed and is dried afterwards for several times, required hydroxyapatite can be obtained.
2, the preparation of titania hydrosol
(1) a certain amount of titanium salt is dissolved in deionized water, by sufficient hydrolysis, the metatitanic acid for obtaining yellow is heavy
It forms sediment；
The titanium salt be titanyl sulfate, titanium tetrachloride, tetraisopropyl titanate, four n-propyl of metatitanic acid, tetraethyl titanate or
Butyl titanate；
(2) a certain amount of hydrogen peroxide is added into above-mentioned metatitanic acid precipitating again, faint yellow colloidal sol is then obtained by ultrasound；
A small amount of isopropanol or acetylacetone,2,4-pentanedione are added simultaneously, carries out reflow treatment, obtains the stable anatase titania hydrosol.
3, the preparation of the hydroxyapatite of titania additive
(1) hydroxyapatite is soaked in the titania hydrosol of above-mentioned preparation, the time is 4 ~ 8 hours；
(2) then obtained white product is filtered, is dry, then 600 degree are calcined 10 ~ 60 minutes.
The present invention is by changing the ginseng such as reactant concentration, reaction time, temperature, system pH, mixing speed, doping concentration
Count the control, it can be achieved that hydroapatite particles partial size, particle diameter distribution, doping concentration, biocompatibility.Obtained hydroxyl phosphorus
Lime stone partial size is at 76-150 microns, as shown in Figure 1.Hydroxyapatite particle diameter distribution is uniform, have good biocompatibility and
Bactericidal effect can be used for the reparation of biological tissue.
Compared with prior art, of the invention to be advantageous in that:
1, using homogeneous precipitation method one-pass molding, product can be directly obtained, preparation process is simple, low in cost.It is not necessarily to
Carry out secondary granulation and the high-temperature calcination in later period processing, preparation process without be added any complexing agent, oxidant, template and
Other metal ions are adulterated, advantageously ensure that the purity and performance of hydroxyapatite；
2, the simple process for preparing titanium dioxide, the chemical substance being related to is less, can be to avoid the introducing of harmful substance.It mixes
Miscellaneous simple process, controllable, prepared hydroxyapatite has good biocompatibility and bactericidal effect.
Detailed description of the invention
Fig. 1 is the hydroxyapatite scanning electron microscope (SEM) photograph of titania addition prepared by embodiment 1.
Specific implementation method
Below with reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to down
The embodiment stated.
Embodiment 1.
By HNO3Solution is slowly added into the KH of 99.8 ml, 0.15 mol/L2PO4In solution, until the pH value of solution is
2.4, under mechanical agitation, by 50 ml, 0.5 mol/L CaCl2Solution is added dropwise to KH2PO4It is acute in acid solution
Strong stirring is uniformly mixed it, and 1.08 g urea, 10 drop Silwet 408 are added in mixed solution, is warming up to 80 DEG C, makes it
48h is reacted, reaction solution is filtered, washed and is dried afterwards for several times, required hydroxyapatite can be obtained.
2ml titanium tetrachloride is dissolved in 50ml deionized water, by sufficient hydrolysis, the metatitanic acid for obtaining yellow is heavy
It forms sediment.The hydrogen peroxide of 5ml is added into above-mentioned metatitanic acid precipitating again, the concentration of hydrogen peroxide is 65%.Then super for 50W by power
Sound wave carries out ultrasound 30 minutes, obtains faint yellow colloidal sol.Simultaneously 1ml isopropanol is added, 70 degree reflow treatment 50 minutes, obtain
The stable anatase titania hydrosol.
Hydroxyapatite is soaked in the titania hydrosol of above-mentioned preparation, the time is 4 hours.It then will be acquired
White product filtering, dry, then 600 degree calcining 40 minutes.
Embodiment 2.
By HNO3Solution is slowly added into the KH of 50 ml, 0.3 mol/L2PO4In solution, until the pH value of solution is 2.4,
Under mechanical agitation, by 100 ml, 0.25 mol/L CaCl2Solution is added dropwise to KH2PO4In acid solution, acutely
Stirring is uniformly mixed it, and 1.2 g urea, 15 drop HR-3408 are added in mixed solution, is warming up to 90 DEG C, makes its reaction
Reaction solution is filtered, washed and dries afterwards for several times by 48h, and required hydroxyapatite can be obtained.
2ml butyl titanate is dissolved in 50ml deionized water, by sufficient hydrolysis, obtains the metatitanic acid of yellow
Precipitating.The hydrogen peroxide of 8ml is added into above-mentioned metatitanic acid precipitating again, the concentration of hydrogen peroxide is 65%.It then is 80W by power
Ultrasonic wave carries out ultrasound 10 minutes, obtains faint yellow colloidal sol.Simultaneously 1ml acetylacetone,2,4-pentanedione is added, 90 degree reflow treatment 20 minutes,
Obtain the stable anatase titania hydrosol.
Hydroxyapatite is soaked in the titania hydrosol of above-mentioned preparation, the time is 4 hours.It then will be acquired
White product filtering, dry, then 600 degree calcining 40 minutes.
Embodiment 3.
By HNO3Solution is slowly added into the NaH of 50 ml 0.3mol/L2PO4In solution, until the pH value of solution is 2.6,
Under mechanical agitation, by 50 ml, 0.5 mol/L Ca (CH3COO)2Solution is added dropwise to NaH2PO4In acid solution,
Being vigorously stirred is uniformly mixed it, and 1.08 g urea, 10 drop CoatOSil 77 are added in mixed solution, is warming up to 85 DEG C, makes
It reacts 50h, and reaction solution is filtered, washed and is dried afterwards for several times, required hydroxyapatite can be obtained.
Four n-propyl of 1.5ml metatitanic acid is dissolved in 40ml deionized water, by sufficient hydrolysis, obtains the inclined of yellow
Metatitanic acid precipitating.The hydrogen peroxide of 4ml is added into above-mentioned metatitanic acid precipitating again, the concentration of hydrogen peroxide is 65%.Then it is by power
90W ultrasonic wave carries out ultrasound 30 minutes, obtains faint yellow colloidal sol.1ml isopropanol is added simultaneously, divides in 70 degree of reflow treatments 50
Clock obtains the stable anatase titania hydrosol.
Hydroxyapatite is soaked in the titania hydrosol of above-mentioned preparation, the time is 4 hours.It then will be acquired
White product filtering, dry, then 600 degree calcining 40 minutes.
Embodiment 4.
By HNO3Solution is slowly added into the (NH of 99.8 ml, 0.15 mol/L4)2HPO4In solution, until the pH of solution
Value is 2.4, under mechanical agitation, by 50 ml, 0.5 mol/L Ca (NO3)2Solution is added dropwise to (NH4)2HPO4It is acid
In solution, being vigorously stirred is uniformly mixed it, and 1.08 g urea, 10 drop Silwet 408 are added in mixed solution, are warming up to
80 DEG C, so that it is reacted 48h, reaction solution is filtered, washed and is dried afterwards for several times, required hydroxyapatite can be obtained.
2ml titanium tetrachloride is dissolved in 50ml deionized water, by sufficient hydrolysis, the metatitanic acid for obtaining yellow is heavy
It forms sediment.The hydrogen peroxide of 5ml is added into above-mentioned metatitanic acid precipitating again, the concentration of hydrogen peroxide is 65%.Then super for 30W by power
Sound wave carries out ultrasound 100 minutes, obtains faint yellow colloidal sol.Simultaneously 1ml isopropanol is added, 70 degree reflow treatment 50 minutes, obtain
To the stable anatase titania hydrosol.
Hydroxyapatite is soaked in the titania hydrosol of above-mentioned preparation, the time is 4 hours.It then will be acquired
White product filtering, dry, then 600 degree calcining 40 minutes.
Claims (6)
1. a kind of preparation method of the hydroxyapatite of titania additive, it is characterised in that specific step is as follows:
(1) hydroxyapatite is prepared
Compound concentration is the calcium saline solution of 0.1 ~ 0.8 mol/L, by HNO3Solution is added dropwise to wherein, until the pH value of solution is
1.5~3.5；Compound concentration is the phosphate aqueous solution of 0.1 ~ 0.5 mol/L；Then phosphate aqueous solution is added dropwise to calcium salt acid
Property solution in, be vigorously stirred after adding, make its be uniformly mixed；Add organic silicon surfactant；It finally again will be a certain amount of
Precipitating reagent is slowly added in this mixed solution, is warming up to 70 ~ 95 DEG C, while carrying out mechanical stirring, controls the reaction time 24 ~ 72
Hour；Obtained white product is filtered, washed after completion of the reaction and is dried afterwards for several times, required hydroxyapatite can be obtained；
(2) titania hydrosol is prepared
A certain amount of titanium salt is dissolved in deionized water, by sufficient hydrolysis, obtains the metatitanic acid precipitating of yellow；Again to
The hydrogen peroxide that a certain amount of concentration is 65% is added in above-mentioned metatitanic acid precipitating, faint yellow colloidal sol is then obtained by ultrasound；Add simultaneously
Enter a small amount of stabilizer, carries out reflow treatment, obtain the stable anatase titania hydrosol；
(3) titania additive hydroxyapatite is prepared
Hydroxyapatite prepared by step (1) is soaked in the titania hydrosol of step (2) preparation, the time is 4 ~ 8 small
When；Then it is filtered, dries, then calcined 10 ~ 60 minutes at 400 ~ 800 degree.
2. a kind of preparation method of the hydroxyapatite of titania additive according to claim 1, it is characterised in that: institute
The calcium salt stated is Ca (NO3)2、CaCl2、CaCO3、Ca(CH3COO)2；The phosphate is KH2PO4、K2HPO4、(NH4)2HPO4、Na2HPO4；The calcium salt and phosphatic molar ratio are 1.67.
3. a kind of preparation method of the hydroxyapatite of titania additive according to claim 1, it is characterised in that: institute
The precipitating reagent stated is or mixtures thereof urea, hexamethylenetetramine；The organic silicon surfactant is to step figure CoatOSil
1211, CoatOSil 7602, CoatOSil 7604, CoatOSil 3573, CoatOSil 7500, CoatOSil 3509,
CoatOSil 47, CoatOSil 77, CoatOSil 2400, CoatOSil 2812, CoatOSil 3500, Silwet 408
Or one or more of HR-3408, additive amount are 0.01 ~ 0.5 weight %.
4. a kind of preparation method of the hydroxyapatite of titania additive according to claim 1, it is characterised in that step
Suddenly titanium salt described in (2) is titanyl sulfate, titanium tetrachloride, tetraisopropyl titanate, four n-propyl of metatitanic acid, tetraethyl titanate or titanium
One of sour four butyl esters are several, and concentration is 0.01 ~ 1 mol/L；The additive amount of 65% hydrogen peroxide is 1 ~ 25 weight
Measure %；The stabilizer is one or more of isopropanol or acetylacetone,2,4-pentanedione, and additive amount is 0.01 ~ 0.5 weight %；It is described
Ultrasonic power be 10 ~ 100W, the time is 10 ~ 600 minutes, and the temperature of reflux is 40 ~ 90 degree, and the time is 4 ~ 8 hours.
5. a kind of preparation method of the hydroxyapatite of titania additive according to claim 1, it is characterised in that step
Suddenly the time that (3) are impregnated is 4 ~ 8 hours, and the solid content of titania hydrosol used is 0.01 ~ 5 weight %.
6. a kind of preparation method of the hydroxyapatite of titania additive according to claim 1, it is characterised in that step
Suddenly calcination temperature used in (3) is 400 ~ 800 degree, and calcination time is 10 ~ 60 minutes.
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| CN108424138B (en) * | 2018-03-28 | 2021-01-19 | 华南理工大学 | Silicon-containing grain boundary phase modified hydroxyapatite ceramic, bone injury repair material and preparation method thereof |
| CN108456016A (en) * | 2018-04-13 | 2018-08-28 | 日正九安科技（北京）有限公司 | A kind of water solubility organic titanium fertilizer and preparation method thereof |
| CN109023366A (en) * | 2018-09-02 | 2018-12-18 | 张家港市六福新材料科技有限公司 | A kind of preparation method of hydroxyapatite-composite titania material |
| CN109701082B (en) * | 2019-02-22 | 2021-10-08 | 九江学院 | Preparation method and application of hydroxyapatite-titanium hydroxide composite powder |
| CN115553302B (en) * | 2022-01-14 | 2023-11-03 | 华升科技集团有限公司 | Disinfecting composition containing nanoscale titanium dioxide and preparation method thereof |
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| CN101491693A (en) * | 2008-09-23 | 2009-07-29 | 西北有色金属研究院 | Preparation method of hydroxylapatite/titanic oxide composite biological coatings |
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