CN111202869A - Preparation method of ultralong fluorophosphates apatite whisker and anti-inflammation slurry - Google Patents

Preparation method of ultralong fluorophosphates apatite whisker and anti-inflammation slurry Download PDF

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CN111202869A
CN111202869A CN201911303333.0A CN201911303333A CN111202869A CN 111202869 A CN111202869 A CN 111202869A CN 201911303333 A CN201911303333 A CN 201911303333A CN 111202869 A CN111202869 A CN 111202869A
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calcium
ultralong
whisker
fluorophosphate
phosphate
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CN111202869B (en
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赵俊华
雷引林
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Quzhou University
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Abstract

The embodiment of the invention discloses an ultralong fluorapatite whisker, which comprises the following components: the preparation method of the rivet-group-containing coupling agent comprises the following steps: at normal temperature, in the water solution containing calcium salt and coupling agent containing rivet group, the expansion gas is blown in, reaction is carried out until the liquid drop distribution is not obviously changed by microscope observation, then phosphate is added, the solution is stirred until the pH value is stable, then villiaumite is added, and the ultralong fluorophosphoric acid apatite crystal whisker is prepared by heat treatment. The anti-inflammatory slurry is prepared by using the ultralong fluorophosphates as raw materials, has high size consistency, good biocompatibility, controllable release of fluorine ions and good safety and stability, and the fluorine hazard of the prepared anti-inflammatory slurry is controlled.

Description

Preparation method of ultralong fluorophosphates apatite whisker and anti-inflammation slurry
Technical Field
The invention relates to the technical field of inorganic nano material preparation, in particular to a preparation method of ultralong fluorophosphates apatite whiskers and anti-inflammatory slurry.
Background
Biological Apatite (BAp) has good biocompatibility and osteoconductivity, and is widely considered as a good inorganic substitute material in Biological tissue engineering. Hydroxyapatite (Ca)10(PO4)6(OH)2HAp) has been extensively studied for its chemical, crystallographic and biological similarities to human bone. However, as a bone substitute material, the rate of HAp degradation does not match the rate of new bone formation, and in addition, HAp as an implant coating material, its high solubility reduces the bonding strength of the coating.
Fluorine is considered as a necessary trace element of bone tissues, and fluorine ions can generate physicochemical action with bones, promote the proliferation and activity of osteoblasts and promote the mineralization of new bones. In addition, fluoride ions are not only widely used in the treatment of osteoporosis, to inhibit bacterial growth, to protect teeth from caries, but also to enhance BAp properties such as mechanical strength, chemical and thermal stability, biocompatibility and biodegradation period. Thus, fluorhydroxyapatite (Ca)10(PO4)6(OH)2-xFx) Or fluorapatite (Ca)5(PO4)3F) The preparation and performance research of (2) is always a hot spot. The hydroxide (OH-) of hydroxyapatite can be replaced by diffusion of fluoride ions at relatively low temperatures, even at room temperature, as disclosed in patent applications No. 200910310970.0, No. 201510956380.0, No. 201710081501.0, No. 201510605303.0. However, biomaterials prepared with such fluorinated hydroxyapatite or fluorapatite may undergo a faster and higher concentration of fluorine release in the living organism, which not only causes the organism to decrease the bone conductivity and causes undesirable bone mass effects such as fluorosis, accompanying osteoporosis, osteomalacia, osteopenia, but also the narrow therapeutic/toxic window greatly limits the biological application of fluorinated inorganics.
In addition, nano-hydroxyapatite is often used as an antibacterial disinfectant to improve the antimicrobial capability, such as patent applications 200980163322.5, 201710026418.3, 201780043519.X and the like. Studies in biomedical applications of nano-apatite written by lisipu et al show that biological cells can enter nano-hydroxyapatite into cells through phagocytosis, and then nanoparticles dissolve phagocytic vesicle membranes and surrounding cytoplasm and gradually move to the nucleus and even close to the nucleus, thereby inhibiting cell proliferation and growth. Meanwhile, in order to realize the dispersibility of the inflammation-eliminating nano functional material in the disinfectant, more additives are commonly used in the disinfectant, which is not beneficial to the effective control of the applicable risk and cost of organisms.
Disclosure of Invention
The technical problem to be solved by the embodiments of the present invention is to provide a method for preparing ultralong fluorapatite whiskers and anti-inflammatory slurry, which aims at the problem that a biological material prepared from fluorapatite or fluorapatite can release fluorine at a high speed and a high concentration in a biological organism, thereby not only reducing the bone conductivity of the organism and causing poor bone quality effect, but also greatly limiting the biological application of fluor inorganic substances through a narrow therapeutic/toxicity window, and the problem that nano-hydroxyapatite is frequently used as an antibacterial disinfectant to improve the antimicrobial capability.
In order to solve the above technical problems, according to one aspect of the present invention, there is provided an ultra-long fluoroapatite whisker, comprising: the ultra-long fluorophosphate whisker comprises a coupling agent containing a rivet group, a calcium salt, an expanding gas, phosphate and a villiaumite, and has the following structure: ca10(PO4)6-xF3x(OH)2。
The preparation method of the ultralong fluorophosphates apatite whisker comprises the following steps: blowing expanding gas into water solution containing calcium salt and coupling agent containing rivet group to react at normal temperature until the liquid drop distribution is observed with microscope and has no obvious change, adding phosphate, stirring until the pH value of the solution is stable and the change per minute is not greater than 0.3, adding fluoric salt, and heat treating to prepare the ultralong fluoro apatite crystal whisker.
Wherein the coupling agent containing rivet groups is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris- (2-methoxyethoxy) -silane, (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) -1-trichlorosilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, bis- [3- (trimethoxy silicon) -propyl ] -amine and 3-aminopropyltriethoxysilane; the calcium salt is at least one of calcium nitrate, calcium chloride, calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate, calcium gluconate, calcium lactate and calcium hypophosphite; the phosphate is at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium polymetaphosphate, potassium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium acid pyrophosphate, sodium phosphate, sodium pyrophosphate, sodium aluminum phosphate, sodium metaphosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium polyphosphate and sodium pyrophosphate; the fluoride salt may be at least one of sodium fluoride, potassium fluoride, ammonium bifluoride, tetrabutylammonium fluoride, stannous fluoride.
Wherein the calcium ion concentration of the calcium salt is 0.08-3.2 mol/L, preferably 0.1-1.5 mol/L; the phosphate has a phosphorus concentration of 0.1 to 4mol/L, preferably 0.2 to 2.0 mol/L.
Wherein the molar ratio of the coupling agent containing rivet groups to calcium ions is 0.001-1.4: 1, preferably 0.005-0.2: 1; the molar ratio of the calcium ions to the phosphorus in the phosphate is 0.5-3.2: 1; the molar ratio of the fluorine salt to the calcium ion is 0.005-1.6: 1, preferably 0.01-0.6: 1.
Wherein the expandable gas is steam carrying an organic solvent in a carbon dioxide bubbling mode, and the bubbling flow rate of the expandable gas is 10-2500 mL/min.
Wherein the organic solvent in the expanding gas is at least one of benzene, toluene, xylene, dichlorobenzene, carbon tetrachloride, cyclohexane, cyclopentane, dichloromethane, n-heptane, isooctane and n-pentane.
Wherein the heat treatment method is one of a water bath homogeneous precipitation method, a hydrothermal method, an ultrasonic auxiliary method or a pyrolysis method.
In order to solve the above technical problems, in another aspect, the present invention provides an anti-inflammatory slurry prepared using ultralong fluorophosphate whiskers as a raw material.
The preparation method of the anti-inflammation slurry comprises the following steps: ultrasonically dispersing the prepared ultralong fluorophosphate whiskers and nano silver in an ethanol solution for 15min to obtain anti-inflammatory slurry, wherein the mass ratio of the nano silver to the whiskers is 0.0001-1.3: 1, preferably 0.005-0.3: 1.
The embodiment of the invention has the following beneficial effects:
the ultralong fluorophosphate whisker of the present invention has Ca10(PO4)6-xF3x(OH)2The structure, the formation of F-Ca bond in the structure effectively regulates and controls the release speed of fluorinion; the polyhydroxy group on the surface is convenient for the rapid dispersion of the crystal whisker in a polar solvent; the ultra-long whisker structure effectively reduces the risk of phagocytosis by cells.
In the preparation method of the ultralong fluorophosphate whisker, the introduction of the rivet group improves the effect and the quality of the micelle formation of the expanding gas by bubbling, and simultaneously provides possibility for the formation of a micelle network, which is the premise of preparing the ultralong whisker; in addition, the rivet group can complex fluorine ions and phosphate ions, and an F-Ca bond is generated after heat treatment of the precursor, so that in-situ replacement of the fluorine ions and hydroxyl groups is avoided, and preparation of the fluorophosphates apatite crystal is realized; the expanding gas provides a mixed system required for micelle formation, and the swelling form of the expanding gas avoids the agglomeration of the ultra-long whiskers in the preparation process.
According to the preparation method of the anti-inflammation slurry, due to the use of the ultralong fluorophosphate whisker according to the first aspect of the invention, the anti-inflammation slurry has the advantages of high size consistency, good biocompatibility, controllable release of fluorine ions and good safety and stability, so that the fluorine harm of the anti-inflammation slurry is controlled; the overlong whisker structure provides a steric hindrance effect for the anti-inflammatory nano particles, and crystal dispersion is realized under the condition of no addition of a dispersing agent; in addition, the rivet group on the crystal fixes the anti-inflammatory nano particles on the crystal whisker, so that the secondary agglomeration of the anti-inflammatory nano particles is avoided, and the synergistic anti-inflammatory effect is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction (XRD) pattern of ultra-long fluorophosphate whiskers prepared in example 3 of the present invention;
FIG. 2 is a diagram of X-ray photoelectron spectroscopy (XPS) of Ca 2p of an ultra-long fluoroapatite apatite whisker prepared in example 3 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of an anti-inflammatory slurry containing ultra-long fluorophosphate whiskers, which is prepared in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an ultralong fluorapatite whisker, which comprises the following components: the ultra-long fluorophosphate whisker comprises a coupling agent containing a rivet group, a calcium salt, an expanding gas, phosphate and a villiaumite, and has the following structure: ca10(PO4)6-xF3x(OH)2。
The preparation method of the ultralong fluorophosphate whisker comprises the following steps:
at normal temperature, in the water solution containing calcium salt and coupling agent containing rivet group, the swelling gas is blown in to react until the liquid drop distribution is observed by microscope and does not change obviously. The expandable gas is steam carrying an organic solvent in a carbon dioxide bubbling mode, and the bubbling flow rate of the expandable gas is 10-2500 mL/min. The organic solvent in the expandable gas is at least one of benzene, toluene, xylene, dichlorobenzene, carbon tetrachloride, cyclohexane, cyclopentane, dichloromethane, n-heptane, isooctane and n-pentane. Introducing expandable gas to form a micelle structure containing calcium salt and provide a soft template prepared by the ultra-long crystal whisker; meanwhile, the existence of carbon dioxide finely adjusts the weak acid pH value in the solution, is convenient for compressing and forming long micelles, simultaneously regulates and controls the growth kinetics of crystals, is convenient for controllable nucleation and growth, and is more beneficial to the preparation of the ultra-long crystal whiskers.
And after the reaction is finished, adding phosphate, stirring until the pH value of the solution is stable and the change per minute is not more than 0.3, adding villiaumite to obtain a fluorapatite whisker precursor, and performing heat treatment on the fluorapatite whisker precursor to prepare the ultralong fluorapatite whisker.
Wherein the coupling agent containing rivet groups is at least one of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris- (2-methoxyethoxy) -silane, (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) -1-trichlorosilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, 3- (2, 3-epoxypropoxy) propyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, bis- [3- (trimethoxy silicon) -propyl ] -amine and 3-aminopropyltriethoxysilane; the calcium salt is at least one of calcium nitrate, calcium chloride, calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate, calcium gluconate, calcium lactate and calcium hypophosphite; the phosphate is at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium polymetaphosphate, potassium pyrophosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium acid pyrophosphate, sodium phosphate, sodium pyrophosphate, sodium aluminum phosphate, sodium metaphosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium polyphosphate and sodium pyrophosphate; the fluoride salt may be at least one of sodium fluoride, potassium fluoride, ammonium bifluoride, tetrabutylammonium fluoride, stannous fluoride.
The concentration of calcium ions in the calcium salt is 0.08-3.2 mol/L, preferably 0.1-1.5 mol/L; the phosphate has a phosphorus concentration of 0.1 to 4mol/L, preferably 0.2 to 2.0 mol/L. The molar ratio of the coupling agent containing a rivet group to calcium ions is 0.001-1.4: 1, preferably 0.005-0.2: 1. The molar ratio of the calcium ions to the phosphorus in the phosphate is 0.5-3.2: 1; the molar ratio of the fluorine salt to the calcium ion is 0.005-1.6: 1, preferably 0.01-0.6: 1.
The heat treatment method is one of a water bath homogeneous precipitation method, a hydrothermal method, an ultrasonic wave auxiliary method or a pyrolysis method.
Water bath homogeneous precipitation: and transferring the obtained fluorapatite whisker precursor into a three-neck flask, sealing and placing in a water bath at the temperature of 35-180 ℃, and reacting for 5-72 hours to obtain the ultralong fluorapatite whisker.
Hydrothermal method: and transferring the obtained fluorophosphates whisker precursor into a polytetrafluoroethylene reaction kettle lining, sealing the polytetrafluoroethylene reaction kettle in a steel high-pressure kettle, and placing the reaction kettle at the temperature of 120-280 ℃ for reaction for 5-48 hours to obtain the ultralong fluorophosphates whisker.
An ultrasonic wave assistance method: transferring the obtained fluorapatite whisker precursor into a polytetrafluoroethylene autoclave, sealing, heating by microwave to the temperature of 120-280 ℃, and reacting for 0.1-36 hours to obtain the ultralong fluorapatite whisker.
Pyrolysis method: the obtained precursor of the fluorapatite whisker is transferred into a pyrolysis furnace and reacts for 0.3 to 5 hours at the temperature of 200-.
The invention also provides an anti-inflammatory slurry which is prepared by taking the ultralong fluorophosphate whiskers as raw materials. The preparation method of the anti-inflammatory paste comprises the following steps: ultrasonically dispersing the prepared ultralong fluorophosphate whiskers and nano silver in an ethanol solution for 15min to obtain anti-inflammatory slurry, wherein the mass ratio of the nano silver to the whiskers is 0.0001-1.3: 1, preferably 0.005-0.3: 1.
In other embodiments, the anti-inflammatory slurry is prepared by all non-strong acid anti-inflammatory slurry systems and corresponding methods, and the anti-inflammatory slurry prepared by using the ultra-long fluorophosphate whiskers prepared by the method as raw materials is within the protection scope of the invention.
In the preparation process of the invention, deionized water is preferably used as a solvent, so that the reaction process has good environment and the production cost is reduced.
The following description will be made with reference to comparative examples and examples to describe the properties of the ultra-long fluorophosphate whiskers and anti-inflammatory slurry of the present invention:
comparative example
Adding 0.3mol/L sodium phosphate aqueous solution (added according to the molar ratio of calcium to phosphorus of 0.8: 1) and 0.03mol/L sodium fluoride aqueous solution (added according to the ratio of fluorine to calcium of 0.04: 1) into 0.2mol/L calcium chloride aqueous solution at room temperature, stirring for 30min, adding into a reaction kettle, reacting at 180 ℃ for 12 hours, taking out, washing for 3 times by deionized water, and drying at 60 ℃ to obtain the ultralong fluorophosphoric acid apatite whisker comparative example.
And (3) performing ultrasonic dispersion on the ultralong fluorophosphate whisker comparative example and nano silver (the mass ratio of the nano silver to the ultralong fluorophosphate whisker comparative example is 0.1: 1) in an ethanol solution for 15min to obtain an anti-inflammatory slurry comparative example.
Example 1
Adding 0.03mol/L of coupling agent containing rivet groups of vinyl triethoxysilane (added according to the molar ratio of the coupling agent to calcium of 0.16: 1) into 0.2mol/L of calcium chloride aqueous solution, stirring uniformly, then blowing expanding gas with toluene steam at the speed of 20mL/min, reacting until the toluene liquid drop distribution is not obviously changed by microscope observation, then adding 0.3mol/L of sodium phosphate according to the molar ratio of calcium to phosphorus of 0.8:1, stirring until the pH value of the solution is stable, namely, the change per minute is not more than 0.3, at the moment, 0.03mol/L sodium fluoride aqueous solution is added after stirring for 15min, the molar ratio of fluorine to calcium is 0.04:1, the mixture is added into a reaction kettle after stirring for 30min, the mixture is taken out after reacting for 12 hours at 180 ℃, and then washing for 3 times by deionized water, and drying at 60 ℃ to obtain the ultralong fluorophosphate whisker.
And ultrasonically dispersing the prepared ultralong fluorophosphate whisker and nano silver in an ethanol solution for 15min to obtain the anti-inflammatory slurry, wherein the nano silver and the ultralong fluorophosphate whisker are added according to the mass ratio of 0.1: 1.
Example 2
Adding 0.08mol/L (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) -1-trichlorosilane coupling agent containing rivet groups into 0.4mol/L calcium dihydrogen phosphate aqueous solution (the coupling agent is added according to the mol ratio of 0.09:1 of the coupling agent to calcium), stirring uniformly, blowing expanding gas with cyclohexane steam at the speed of 100mL/min, reacting until the cyclohexane droplet distribution is not obviously changed by microscope observation, adding 0.6mol/L ammonium dihydrogen phosphate, adding according to the mol ratio of 1.1:1 of calcium to phosphorus, stirring until the pH value of the solution is stable, namely the change per minute is not more than 0.3, stirring for 20min, adding 0.12mol/L ammonium fluoride aqueous solution, adding according to the mol ratio of 0.05:1 of fluorine to calcium, stirring for 40min, adding into a reaction kettle, reacting in a water bath with a three-neck at 90 ℃ for 24 hours, taking out, and then washing for 3 times by deionized water, and drying at 60 ℃ to obtain the ultralong fluorophosphate whisker.
And ultrasonically dispersing the prepared ultralong fluorophosphate whisker and nano silver in an ethanol solution for 15min to obtain the anti-inflammatory slurry, wherein the nano silver and the ultralong fluorophosphate whisker are added according to the mass ratio of 0.17: 1.
Example 3
Adding 0.14 mol/L2- (3, 4-epoxy cyclohexyl) ethyl triethoxysilane rivet group-containing coupling agent (added according to the molar ratio of the coupling agent to calcium of 0.2: 1) into 0.6mol/L calcium bicarbonate aqueous solution, stirring uniformly, blowing expanding gas with methylene dichloride steam at the speed of 500mL/min, reacting until the methylene dichloride droplet distribution is not obviously changed by microscope observation, adding 0.9mol/L sodium polyphosphate, adding according to the molar ratio of calcium to phosphorus of 1.6:1, stirring until the pH value of the solution is stable, namely the change per minute is not more than 0.3, stirring for 19min, adding 0.19mol/L ammonium bifluoride aqueous solution, adding according to the molar ratio of fluorine to calcium of 0.07:1, stirring for 40min, adding into a reaction kettle, reacting for 18 hours at 240 ℃, taking out, washing for 3 times by deionized water, drying at 60 ℃ to obtain the ultralong fluorophosphate crystal whisker.
And ultrasonically dispersing the prepared ultralong fluorophosphate whiskers and nano silver in an ethanol solution for 15min to obtain the anti-inflammatory slurry, wherein the nano silver and the ultralong fluorophosphate whiskers are added according to the mass ratio of 0.08: 1.
Example 4
Adding 0.16 mol/L3-aminopropyltriethoxysilane rivet-group-containing coupling agent (added according to the molar ratio of the coupling agent to calcium being 0.06: 1) into 0.8mol/L calcium nitrate aqueous solution, stirring uniformly, blowing expanding gas with carbon tetrachloride steam at the speed of 800 mL/min, reacting until the distribution of carbon tetrachloride droplets is not obviously changed by using a microscope, adding 1.3mol/L potassium metaphosphate according to the molar ratio of calcium to phosphorus being 2.4:1, stirring until the pH value of the solution is stable, namely the change per minute is not more than 0.3, stirring for 15min, adding 0.24mol/L potassium fluoride aqueous solution, adding according to the molar ratio of fluorine to calcium being 0.08:1, stirring for 40min, adding into a pyrolysis furnace, reacting for 0.5 hour at 810 ℃, taking out, washing with deionized water for 3 times, drying at 60 ℃, obtaining the ultra-long fluorophosphates apatite crystal whisker.
And ultrasonically dispersing the prepared ultralong fluorophosphate whiskers and nano silver in an ethanol solution for 15min to obtain the anti-inflammatory slurry, wherein the nano silver and the ultralong fluorophosphate whiskers are added according to the mass ratio of 0.21: 1.
TEM tests were carried out on the ultralong fluorophosphate whiskers obtained in examples 1 to 4, and the test results are shown in Table 1,
the length-diameter ratio is calculated according to a length-diameter ratio/width formula;
and (3) fluoride ion soaking release: adding 2 g of the prepared ultralong fluorophosphates apatite whisker into 100ml of SBF simulated body fluid at 37 ℃, and measuring the concentration of fluorine ions in the solution by using an ionization gauge after 30 days;
leaching silver concentration: adding 2 g of the prepared ultralong fluorophosphate whisker into 100ml of SBF simulated body fluid at 37 ℃ for 30 days, filtering out the whisker, adding the solution into a polytetrafluoroethylene digestion tank, adding 10ml of nitric acid, carrying out pre-digestion for 2h at 80 ℃ in a graphite digestion instrument, heating to 140 ℃ for digestion, continuing adding acid for digestion if the solution is brown until the digestive juice is colorless, adding a small amount of ultrapure water, heating to 180 ℃ to expel acid to 0.5 ml-1.0 ml, taking out the digestion tank, cooling, washing the digestion tank with a small amount of ultrapure water for 2-3 times, fixing the volume, and measuring the silver content by using a graphite atomic absorption spectrometry.
TABLE 1 EXAMPLES 1-4 TEM TEST OF ULTRA-LENGTH FLUOROPHOSPHATE ASTABLES
Figure RE-GDA0002451873070000091
As can be seen from table 1, the introduction of the micron-sized ultralong HAP whisker precursors of examples 1-4 greatly improved the aspect ratio of the micron-sized ultralong HAP whiskers.
Referring to FIGS. 1-3, FIG. 1 is an XRD pattern of ultra-long fluorophosphate whiskers prepared in example 3 of the present invention; FIG. 2 is an XPS plot of Ca 2p for ultra-long fluorophosphate whiskers produced in example 3 of the present invention; FIG. 3 is an SEM image of an anti-inflammatory slurry containing ultra-long fluorophosphate whiskers, prepared in example 3 of the present invention. As can be seen from FIG. 1, compared with HAP, the prepared ultralong fluorophosphates apatite whisker has no any impure phase, has pure phase and is suitable for the design and development of high-end products; as can be seen from FIG. 2, in the prepared ultralong fluorophosphate whisker, Ca-F bond is formed due to the substitution of phosphate radical, which is beneficial to the stability of F ion in the system and shows that the soaking release amount of fluorine ion is obviously reduced; as can be seen from figure 3, the dispersibility of the nano silver particles and the ultralong fluorophosphate whiskers is good, the agglomeration of the silver nano particles is effectively avoided, and meanwhile, the concentration of leached silver is remarkably reduced by the surface constraint of the ultralong fluorophosphate whiskers, the use effect of the anti-inflammatory slurry is improved, and the damage risk of nano dissociation on a biological matrix is reduced.
The embodiment of the invention has the following beneficial effects: the ultralong fluorophosphates apatite whisker of the present invention contains Ca10(PO4)6-xF3x(OH)2The structure, the formation of F-Ca bond in the structure effectively regulates and controls the release speed of fluorinion; surface polyhydroxy radicalsThe crystal whisker can be dispersed in polar solvent quickly; the ultra-long whisker structure effectively reduces the risk of phagocytosis by cells; the introduction of the rivet group improves the effect and quality of micelle formation by bubbling of the expandable gas; meanwhile, the possibility is provided for the formation of a micelle network; in addition, the rivet group can complex fluorine ions and phosphate ions, and an F-Ca bond is generated after heat treatment of the precursor, so that in-situ replacement of the fluorine ions and hydroxyl groups is avoided, and preparation of the fluorapatite phosphate crystal is realized; the expanding gas provides a mixed system required by micelle formation, and the agglomeration of the ultra-long whiskers in the preparation process is avoided in a form of the expanding gas bubbling; meanwhile, the existence of carbon dioxide finely adjusts the weak acid pH value in the solution, is convenient for compressing and forming long micelles, simultaneously regulates and controls the growth kinetics of crystals, is convenient for controllable nucleation and growth, and is more beneficial to the preparation of the ultra-long crystal whiskers.
In the preparation method of the anti-inflammatory slurry, the ultralong fluorophosphates apatite whiskers prepared by the invention are used as raw materials, so that the anti-inflammatory slurry has the characteristics of high size consistency, good biocompatibility, controllable release of fluorine ions and good safety and stability, and the fluorine hazard of the anti-inflammatory slurry is controlled; ca in the prepared ultralong fluorophosphate crystal whisker10(PO4)6- xF3x(OH)2The structure, the formation of F-Ca bond in the structure effectively regulates and controls the release speed of fluorinion; the polyhydroxy group on the surface is convenient for the rapid dispersion of the crystal whisker in a polar solvent; the ultra-long whisker structure effectively reduces the risk of phagocytosis by cells; the overlong whisker structure provides a steric hindrance effect for the anti-inflammatory nano particles, and crystal dispersion is realized under the condition of no addition of a dispersing agent; in addition, the rivet group on the crystal fixes the anti-inflammatory nano particles on the crystal whisker, so that the secondary agglomeration of the anti-inflammatory nano particles is avoided, and the synergistic anti-inflammatory effect is realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. An ultralong fluoroapatite whisker, characterized in that the ultralong fluoroapatite whisker comprises the following components: the ultra-long fluorophosphate whisker comprises a coupling agent containing a rivet group, a calcium salt, an expanding gas, phosphate and a villiaumite, and has the following structure: ca10(PO4)6-xF3x(OH)2。
2. The ultra-long fluorophosphate whisker according to claim 1, wherein the preparation method of the ultra-long fluorophosphate whisker comprises: blowing expanding gas into water solution containing calcium salt and coupling agent containing rivet group to react at normal temperature until the liquid drop distribution is observed with microscope and has no obvious change, adding phosphate, stirring until the pH value of the solution is stable and the change per minute is not greater than 0.3, adding fluoric salt, and heat treating to prepare the ultralong fluoro apatite crystal whisker.
3. The ultralong fluorophosphate whisker according to claim 1 or 2, characterized in that:
the coupling agent containing the rivet group is at least one of vinyl triethoxysilane, vinyl trimethoxysilane, vinyl tri- (2-methoxyethoxy) -silane, (tridecafluoro-1, 1,2, 2-tetrahydrooctyl) -1-trichlorosilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxysilane, 3- (2, 3-epoxypropoxy) propyl triethoxysilane, 3-aminopropyl methyl diethoxysilane, bis- [3- (trimethoxy silicon) -propyl ] -amine and 3-aminopropyl triethoxysilane;
the calcium salt is at least one of calcium nitrate, calcium chloride, calcium perchlorate, calcium bicarbonate, calcium dihydrogen phosphate, calcium gluconate, calcium lactate and calcium hypophosphite;
the phosphate is at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium polymetaphosphate, potassium pyrophosphate, monopotassium phosphate, dipotassium hydrogen phosphate, sodium acid pyrophosphate, sodium phosphate, sodium pyrophosphate, sodium aluminum phosphate, sodium metaphosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium polyphosphate and sodium pyrophosphate;
the fluoride salt may be at least one of sodium fluoride, potassium fluoride, ammonium bifluoride, tetrabutylammonium fluoride, stannous fluoride.
4. The ultra-long fluorophosphate apatite whisker according to claim 3, wherein the calcium salt has a calcium ion concentration of 0.08 to 3.2mol/L, preferably 0.1 to 1.5 mol/L; the phosphorus concentration of the phosphate is 0.1-4 mol/L, preferably 0.2-2.0 mol/L.
5. The ultra-long fluorophosphate apatite whisker according to claim 4, wherein the molar ratio of the rivet group-containing coupling agent to calcium ions is 0.001-1.4: 1, preferably 0.005-0.2: 1; the molar ratio of the calcium ions to the phosphorus in the phosphate is 0.5-3.2: 1; the molar ratio of the villiaumite to the calcium ion is 0.005-1.6: 1, preferably 0.01-0.6: 1.
6. The ultra-long fluorophosphate whisker according to claim 5, wherein the expanding gas is steam in which an organic solvent is entrained by bubbling carbon dioxide, and the blowing flow rate of the expanding gas is 10 to 2500 mL/min.
7. The apatite ultralong fluorophosphate whisker according to claim 6, wherein the organic solvent in the expanding gas is at least one of benzene, toluene, xylene, dichlorobenzene, carbon tetrachloride, cyclohexane, cyclopentane, dichloromethane, n-heptane, isooctane, n-pentane.
8. The ultra-long fluorophosphate whisker according to claim 2, wherein the heat treatment method is one of a water bath homogeneous precipitation method, a hydrothermal method, an ultrasonic-assisted method, or a pyrolysis method.
9. An anti-inflammatory paste, which is prepared from the ultralong fluorophosphate apatite whisker according to any one of claims 1 to 8.
10. The anti-inflammatory paste according to claim 9, prepared by a method comprising: ultrasonically dispersing the prepared ultralong fluorophosphate whiskers and nano silver in an ethanol solution for 15min to obtain anti-inflammatory slurry, wherein the mass ratio of the nano silver to the whiskers is 0.0001-1.3: 1, preferably 0.005-0.3: 1.
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