A kind of preparation method of bone cement microballoon
Technical field
The invention belongs to inorganic bio preparation technical fields, and in particular to a kind of preparation method of bone cement microballoon.
Background technique
Bone is the bracket of human body, is responsible for the critical functions such as load-bearing, hematopoiesis and limb motion.However, with population old-age group
Aggravation, traffic accident, the appearance of bone tumour and the congenital disorders of change result in serious bone defect problem, because
This, it is significant for repairing bone defect to develop novel bone renovating material.
Inorganic bone cement is a kind of common bone renovating material, and this kind of material, which has, meets water or other water soluble solid agent
Can self-curing carry out the bone tissue of repair deficiency at block materials.Bone cement, which is processed into microballoon, to be had many advantages, such as, it can be with
Closely packed mode is filled in bone defect position, especially highly effective to the bone defect of some irregular, difficult fillings;Microballoon
Between gap be conducive to growing into for cambium and new vessels, and then the formation of new bone tissue can be accelerated;In addition, bone cement
Microballoon has excellent anti-disintegration after the molding of self-curing process in water, thus can give full play to its filling and mechanics branch
Support effect.Ye Jiandong etc. using by antiphase emulsifiable method prepare calcium phosphate bone cement microballoon (" a kind of self-setting calcium phosphate micro spheres and
Preparation method and application ", application number 201010188511.2), specific method is by gelatin/polysaccharide gum solidify liquid and calcium phosphate
Bone cement is deployed into slurry, then slurry is stirred in soybean oil and forms lotion, and is removed by the way of acetone and ethyl alcohol cleaning
Soybean oil is removed, and obtains wet calcium phosphate microsphere;It is then conserved aquation 2-7 days in climatic chamber, finally obtains calcium phosphate bone
Cement microballoon.This preparation method is extremely complex, long preparation period, in addition also introduces that soybean oil, acetone, ethyl alcohol etc. are toxic to be had
Harmful chemical substance;Bone cement huge number, in addition to calcium phosphate bone cement, there are also calcium sulfate bone cement, calcium silicon substrate bone cement, phosphorus
Sour magnesium bone cement etc., these bone cements all have potential application in Bone Defect Repari method, however this preparation method is only fitted
It is used to prepare calcium phosphate bone cement, the universality of this method is lower, and applicable surface is relatively narrow.These exactly above-mentioned disadvantages, limit
Application of this method in bio-medical field.
Summary of the invention
To overcome above-mentioned the deficiencies in the prior art, the purpose of the present invention is to provide a kind of sides of bone cement microballoon preparation
Method, there is raw material to utilize at the deficiencies of overcoming traditional preparation method complicated, poor using poisonous and harmful organic solvent and universality
The characteristics of rate is high, microballoon good fluidity simple and easy to operate and prepared.
To achieve the above object, the technical solution that the present invention just has is: a kind of method of bone cement microballoon preparation, including with
Lower step:
1) fluoropolymer solutions are configured using solvent, recycles electron spray that low-surface-energy macromolecule fluoropolymer sinks
Product forms super-hydrophobic coat in metallic conduction plate surface;
2) bone cement and deionized water or solidify liquid are mixed well, configures bone cement slurry;
3) the bone cement slurry quantitatively pipetted using liquid-transfering gun, and drip in super hydrophobic base, it stands at room temperature, to bone cement
After complete self-curing, bone cement microballoon is obtained;Bone cement slurry by pipetting different volumes may be implemented to prepare different sizes
Bone cement microballoon.
The concentration of fluoropolymer solutions described in step 1) be 0.010~0.100g/mL, solvent using dehydrated alcohol,
N,N-dimethylformamide or tetrahydrofuran.
The solvent is dehydrated alcohol.
Electron spray described in step 1) uses electrostatic spray, relevant parameter are as follows: flow velocity is 0.8~1.5mL/h, and voltage is
6.00~16.00 kV, collecting distance is 4~8cm, and acquisition time is 10~60min.
Metallic conduction plate described in step 1) is as receiver, using copper sheet, iron plate, aluminium sheet or stainless steel plate.
Bone cement described in step 2 uses half-H 2 O calcium sulphate, magnesium phosphate cement, calcium phosphorus base bone cement or calcium silicon substrate bone
Cement, preferred bone cement are half-H 2 O calcium sulphate.
Solidify liquid described in step 2 is ten water dobell's solutions or sodium radio-phosphate,P-32 solution.
The liquid-solid ratio of bone cement slurry described in step 2 is 0.1~3mL/g.
The volume that bone cement slurry is pipetted described in step 3) is 1~100 μ L.
The curing time at room temperature of bone cement slurry described in step 3) is 5~60min.
The beneficial effects of the present invention are:
Advantage is the present invention compared with prior art: 1) strong to water and aqueous solidify liquid using super hydrophobic surface
Repulsive interaction makes bone cement slurry be solidified into the microballoon of almost spherical in super hydrophobic surface in conjunction with bone cement self-curing characteristic,
Raw material availability can be effectively improved;2) preparation condition is mild, easy to operate, simple and easy to do, reproducible, and universality is strong;3)
Thus obtained microsphere morphological rules, size is uniform, and size is controllable, good fluidity, can better filling bone defects position.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram of calcium sulfate microballoon of the present invention.
Fig. 2 is the stereoscan photograph and contact angle photo on super-hydrophobic coat surface obtained by electrostatic spray of the present invention.
Fig. 3 is the digital photograph figure of 1 calcium sulfate microballoon of the embodiment of the present invention.
Fig. 4 is the pure half-H 2 O calcium sulphate powder of the embodiment of the present invention 1 and calcium sulfate microballoon X ray diffracting spectrum.A: pure half water
Calcium sulfate powder, b: calcium sulfate microballoon.
Specific embodiment
Technical solution of the present invention will be clearly and completely described below.The embodiment described is only the present invention
A part of the embodiment, instead of all the embodiments.
Embodiment 1
A kind of bone cement method for preparing microsphere, comprising the following steps:
1) fluoropolymer being dissolved in dehydrated alcohol, configuration concentration is the solution of 0.044g/mL, 4h is stirred at room temperature, to
After polymer is completely dissolved, stop stirring, it is stand-by in implantation glass syringe after static 15min;Glass syringe is fixed on
On syringe pump, syringe needle connects the anode of high-voltage power supply;Using aluminium sheet as receiver, and connect cathode;Start to carry out electrostatic spray, obtain
To super-hydrophobic coat;Parameter during electrostatic spray is as follows: flow velocity 1.0mL/h, voltage 10.00kV, collects distance and is
5cm, acquisition time 30min;
2) it weighs 0.3g half-H 2 O calcium sulphate powder and is placed in perfluoroethylene-propylene beaker bottom, add the deionization of 0.45mL
Water is uniformly mixed immediately, forms uniform slurry, is configured to the half-H 2 O calcium sulphate slurry that liquid-solid ratio is 1.5mL/g;
3) it is dripped on the super-hydrophobic coat prepared by step 1) using the slurry that liquid-transfering gun pipettes 10 μ L, due to super-hydrophobic
Strong repulsive interaction of the surface to half-H 2 O calcium sulphate slurry, to form the microballoon of almost spherical;Then because of half-H 2 O calcium sulphate
The calcium sulfate microballoon of curing molding can be obtained after 30min for self-curing characteristic, collects, saves at room temperature.The calcium sulfate being prepared
Microballoon is by X-ray powder diffraction it is found that the ingredient for including in calcium sulfate microballoon has dead plaster, half-H 2 O calcium sulphate and two water
Calcium sulfate.
Fig. 1 is the preparation process schematic diagram of calcium sulfate microballoon, can understand from figure and get information about preparation process.
Fig. 2 is the stereoscan photograph and contact angle photo on super-hydrophobic coat surface obtained by electrostatic spray, it can be seen that institute
Prepares coating has ultra-hydrophobicity.
Fig. 3 is the digital photograph of calcium sulfate microballoon, and as can be seen from the figure prepared calcium sulfate microballoon size is uniform, closely
Like spherical shape.
Fig. 4 is the X-ray powder diffraction pattern of pure half-H 2 O calcium sulphate powder and calcium sulfate microballoon, it can be seen from the figure that
It include dead plaster, half-H 2 O calcium sulphate and calcium sulphate dihydrate in calcium sulfate microballoon.
Embodiment 2
A kind of bone cement method for preparing microsphere, comprising the following steps:
1) fluoropolymer is dissolved in dehydrated alcohol, configuration concentration is the solution of 0.015g/mL, stirs 4h at room temperature;To
After polymer is completely dissolved, stop stirring, static 15min will be stand-by in solution implantation glass syringe;By glass syringe
It is fixed on syringe pump, syringe needle connects the anode of high-voltage power supply;Using iron plate as receiver, and connect cathode;Start to carry out electrostatic
It is spraying, obtain super-hydrophobic coat;Parameter during electrostatic spray is as follows: flow velocity 0.8mL/h, voltage 6.00kV, collects
Distance is 4cm, acquisition time 60min;
2) it weighs 0.3g half-H 2 O calcium sulphate powder and is placed in perfluoroethylene-propylene beaker bottom, add the deionization of 0.15mL
Water is uniformly mixed immediately, forms uniform slurry, is configured to the half-H 2 O calcium sulphate slurry that liquid-solid ratio is 0.5mL/g;
3) it is dripped on the super-hydrophobic coat prepared by step 1) using the slurry that liquid-transfering gun pipettes 5 μ L, then because of half water sulphur
The self-curing characteristic of sour calcium can obtain the calcium sulfate microballoon for being solidified into almost spherical after 15 min, collect, save at room temperature.
Embodiment 3
A kind of bone cement method for preparing microsphere, comprising the following steps:
1) fluoropolymer is dissolved in dehydrated alcohol, configuration concentration is the solution of 0.09g/mL, stirs 4h at room temperature;To poly-
After conjunction object is completely dissolved, stop stirring, static 15min will be stand-by in solution implantation glass syringe;Glass syringe is fixed
On syringe pump, syringe needle connects the anode of high-voltage power supply;Using copper sheet as receiver, and cathode is connected, carries out electrostatic spray, obtain
Super-hydrophobic coat;Parameter during electrostatic spray is as follows: flow velocity 1.5mL/h, voltage 16.00kV, collects distance and is
8cm, acquisition time 10min;
2) it weighs 0.3g half-H 2 O calcium sulphate powder and is placed in perfluoroethylene-propylene beaker bottom, add the deionization of 0.9mL
Water is uniformly mixed immediately, forms uniform slurry, is configured to the half-H 2 O calcium sulphate slurry that liquid-solid ratio is 3mL/g;
3) it is dripped on the super-hydrophobic coat prepared by step 1) using the slurry that liquid-transfering gun pipettes 90 μ L, then because of half water
The calcium sulfate microballoon of curing molding can be obtained after 60min for the self-curing characteristic of calcium sulfate, collects, saves at room temperature.
Embodiment 4
A kind of bone cement method for preparing microsphere, comprising the following steps:
1) fluoropolymer is dissolved in n,N-Dimethylformamide, configuration concentration is the solution of 0.04 g/mL, at room temperature
Stir 4h;After object to be polymerized is completely dissolved, stop stirring, static 15 min will be stand-by in solution implantation glass syringe;By glass
Glass syringe is fixed on syringe pump, and syringe needle connects the anode of high-voltage power supply;Using stainless steel plate as receiver, and connect cathode;
Start to carry out electrostatic spray, obtains super-hydrophobic coat;Parameter during electrostatic spray is as follows: flow velocity 1.0mL/h, voltage
For 10.00kV, collecting distance is 5 cm, acquisition time 30min;
2) it weighs 0.5g magnesium phosphate cement and is placed in perfluoroethylene-propylene beaker bottom, add the ten water boron of 0.075mL
Acid sodium solution is uniformly mixed immediately, forms uniform slurry, is configured to the magnesium phosphate cement that liquid-solid ratio is 0.15mL/g
Slurry;
3) it is dripped on the super-hydrophobic coat prepared by step 1) using the slurry that liquid-transfering gun pipettes 10 μ L, then because of magnesium phosphate
The self-curing characteristic of bone cement can obtain the magnesium phosphate cement microballoon for being solidified into almost spherical after 8min, collect, protect at room temperature
It deposits.
Embodiment 5
A kind of bone cement method for preparing microsphere, comprising the following steps:
1) fluoropolymer is dissolved in tetrahydrofuran, configuration concentration is the solution of 0.04g/mL, stirs 4h at room temperature;To
After polymer is completely dissolved, stop stirring, static 15min will be stand-by in solution implantation glass syringe;By glass syringe
It is fixed on syringe pump, syringe needle connects the anode of high-voltage power supply;Using aluminium sheet as receiver, and connect cathode;Start just electrostatic
It is spraying, obtain super-hydrophobic coat;Parameter during electrostatic spray is as follows: flow velocity 1.0mL/h, voltage 10.00kV, receives
Integrate distance as 5cm, acquisition time 30min;
2) it weighs 0.5g calcium phosphorus base bone cement and is placed in perfluoroethylene-propylene beaker bottom, the sodium phosphate for adding 0.2mL is molten
Liquid is uniformly mixed immediately, forms uniform slurry, is configured to the calcium phosphorus base bone cement slurry that liquid-solid ratio is 0.4mL/g;
3) it is dripped on the super-hydrophobic coat prepared by step 1) using the slurry that liquid-transfering gun pipettes 10 μ L, then because of calcium phosphorus
The self-curing characteristic of base bone cement can obtain the calcium phosphorus base bone cement microballoon for being solidified into almost spherical after 25min, collect, room temperature
Lower preservation.
Embodiment 6
A kind of bone cement method for preparing microsphere, comprising the following steps:
1) fluoropolymer is dissolved in dehydrated alcohol, configuration concentration is the solution of 0.04g/mL, stirs 4h at room temperature;To poly-
After conjunction object is completely dissolved, stop stirring, static 15min will be stand-by in solution implantation glass syringe;Glass syringe is consolidated
It is scheduled on syringe pump, syringe needle connects the anode of high-voltage power supply;Using aluminium sheet as receiver, and connect cathode.Start to carry out electrostatic
Mist obtains super-hydrophobic coat;Parameter during electrostatic spray is as follows: flow velocity 1.0mL/h, voltage 10.00kV, collects
Distance is 5cm, acquisition time 30min;
2) it weighs 0.3g calcium silicon substrate bone cement and is placed in perfluoroethylene-propylene beaker bottom, add the deionized water of 0.3mL,
It is uniformly mixed immediately, forms uniform slurry, be configured to the calcium silicon substrate bone cement slurry that liquid-solid ratio is 1.0mL/g;
3) it is dripped on the super-hydrophobic coat prepared by step 1) using the slurry that liquid-transfering gun pipettes 10 μ L, then because of calcium silicon
The self-curing characteristic of base bone cement can obtain the calcium silicon substrate bone cement microballoon for being solidified into almost spherical after 60min, collect, room temperature
Lower preservation.