CN113633816A - Preparation method of injectable self-expanding bone cement - Google Patents
Preparation method of injectable self-expanding bone cement Download PDFInfo
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Abstract
The invention discloses a preparation method of injectable self-expansion bone cement, which comprises the steps of firstly preparing low-temperature expansion microspheres by adopting a suspension polymerization method, selecting polyvinyl acetate with low softening temperature as a shell structure, and wrapping n-pentane with low boiling point to form the low-temperature expansion microspheres with a core-shell structure; then uniformly mixing the low-temperature expansion microspheres and PMMA bone cement powder with a liquid phase, stirring and injecting to obtain the injectable self-expansion bone cement. The self-expanding bone cement has no toxic reaction to human body and high biocompatibility, and the prepared bone cement has excellent expansion performance without depending on the body fluid content and through softening vaporization and expansion solidification with the heat the low temperature expanding microsphere produces in the bone cement solidifying process.
Description
Technical Field
The invention belongs to the technical field of preparation methods of biomedical materials, and particularly relates to a preparation method of injectable self-expanding bone cement.
Background
Polymethylmethacrylate (PMMA) bone cement has been used clinically in orthopedics for decades and has become the first choice for adhesive support materials for orthopedics clinical treatments, such as vertebroplasty and joint replacement. However, the traditional bone cement has the defect of volume shrinkage of 3.82-7.08% in the solidification process, so that aseptic loosening is caused, and the subsequent treatment effect is caused. Therefore, solving the problem of volume shrinkage of the bone cement during the setting process becomes one of the key points in the research of the bone cement. The researchers in the prior period developed an injectable water-swellable bone cement aiming at the problems of the bone cement, but the bone cement still has some problems, the researchers compound the polymer microspheres with water swelling with PMMA bone cement, and test the water swelling performance in vitro simulated body fluid, the bone cement mixed with the polymer microspheres shows good water swelling performance in vitro, theoretically solves the defect of volume shrinkage of the bone cement, but the swelling performance mainly depends on the body fluid absorption of the polymer microspheres. If the bone cement is implanted into a human body, the bone cement is solidified only on the superficial layer of the surface of the bone cement after being implanted into the human body after absorbing water, considering that the body fluid content of the implanted part is not as much as or even far lower than the in-vitro simulation condition, the in-vivo expansion rate is far lower than the in-vitro measurement value, even the in-vivo expansion rate cannot play an additional supporting role, the treatment effect is the same as that of the traditional bone cement, even if other researchers construct a rapid water absorption channel to realize rapid water absorption expansion, but under the condition that the body fluid content of the filled part is low, the defect that the expansion rate is far lower than the in-vitro measurement value is inevitable. Therefore, the development of a bone cement which is not dependent on absorption of body fluid and can spontaneously expand during setting to solve the expansion problem of the existing water-swellable bone cement after being implanted into the body is another research focus for solving the volume shrinkage of the bone cement.
Chinese patent application No. 201510014513.2, published on 2015.05.20, published on No. CN104623726A discloses an injectable water-swelling acrylic acid bone cement and a preparation method thereof, the disclosed swelling bone cement has certain swelling performance, the swelling effect still depends on the water absorption performance of water-absorbing resin fibers, when the cement is implanted into a human body, the cement can be solidified only after water absorption is carried out on the superficial layer of the surface of the cement after the cement is implanted into the human body, the swelling multiplying power is far lower than the measured value in vitro, even the cement can not play an additional supporting role, and the treatment effect is the same as that of the traditional bone cement by considering that the body fluid content of the implanted part is not even far lower than the simulation condition in vitro.
Chinese patent 'an injectable expansive type bone cement and a preparation method thereof' (application number: 201510344651.7, published Japanese 2015.09.23, published No. CN104922733A) discloses an injectable expansive type bone cement and a preparation method thereof. Although the bone cement disclosed in the patent has a certain expansion rate, the expansion effect still depends on the water absorption performance of the water absorption microspheres, when the bone cement is implanted into a human body, the bone cement can be solidified only on the superficial layer of the surface of the bone cement after being implanted into the human body after absorbing water by considering that the body fluid content of the implanted part is not lower than or even far lower than the in-vitro simulation condition, the expansion rate is far lower than the in-vitro measurement value, and even the bone cement cannot play an additional supporting role, and the treatment effect is the same as that of the traditional bone cement.
Therefore, the development of a bone cement which is not dependent on absorption of body fluid and can spontaneously expand during setting to solve the expansion problem of the existing water-swellable bone cement after being implanted into the body is another research focus for solving the volume shrinkage of the bone cement.
Disclosure of Invention
The invention aims to provide a preparation method of injectable self-expandable bone cement, which can solve the expansion problem of the existing water-absorbing expandable bone cement implanted in a body.
The technical scheme adopted by the invention is as follows: a preparation method of injectable self-expanding bone cement comprises the following specific operation steps:
step 1, taking a polyvinyl alcohol solution as a dispersed phase for preparing the low-temperature expanded microspheres; uniformly mixing vinyl acetate monomer, ethanol solution of initiator azobisisobutyronitrile and n-pentane solution to obtain an oil phase for preparing the low-temperature expanded microspheres; then, sequentially adding the dispersed phase and the oil phase into a beaker, and fully stirring to obtain a stable dispersed suspension; transferring the stable dispersion suspension into a flask, heating under the protection of nitrogen, reacting for a certain time, cooling to room temperature after the reaction is finished, discharging, filtering, washing, and drying in vacuum to finally obtain low-temperature expanded microspheres;
step 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, polymethyl methacrylate, barium sulfate and dibenzoyl peroxide to obtain an injectable self-expansion bone cement solid phase;
step 3, uniformly mixing methyl methacrylate, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase;
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3, stirring and injecting to obtain the injectable self-expansion bone cement.
The present invention is also characterized in that,
in the step 1, the concentration of the polyvinyl alcohol solution is 0.05-0.15g/ml, the mass of the initiator AIBN is 0.1-1% of the mass of the vinyl acetate monomer, the mass of the n-pentane is 15-35% of the mass of the vinyl acetate monomer, the stirring time is 3-10 min, the polymerization temperature is 70-90 ℃, the reaction time is 2-6 h, and the washing is performed for 2-4 times.
In the step 2, the injectable self-expandable bone cement solid phase comprises, by mass, 20-48% of low-temperature expandable microspheres, 50.4-77.25% of methyl methacrylate, 1.5-2.5% of barium sulfate and 0.1-0.25% of dibenzoyl peroxide, and the sum of the mass percentages of the components is 100%.
In the step 3, the mass ratio of methyl methacrylate to N, N-dimethyl-p-toluidine to hydroquinone is 96.5-99.5: 0.4-3: 0.1 to 0.5.
In the step 4, the solid-to-liquid ratio of the injectable self-expandable bone cement solid phase to the liquid phase is 1: 0.5 to 1.5 g/ml.
The invention has the beneficial effects that: the invention relates to a preparation method of injectable self-expanding bone cement. The self-expanding bone cement prepared by the invention overcomes the defect that the expansion performance in vivo is limited because the traditional expanding bone cement mainly depends on the absorption and dispersion phase for water absorption and expansion. The low-temperature expansion microspheres and the bone cement are subjected to composite treatment, so that the bone cement has spontaneous expansion performance. The low-temperature expansion microspheres expand depending on the change of the cement solidification temperature in the cement solidification process. The temperature of the bone cement rises in the solidification process, the thermoplastic shell of the low-temperature expansion microsphere is softened under the temperature change, the liquid in the shell boils and vaporizes, and the internal gas pressure is increased, so that the volume of the expansion microsphere is obviously increased. When the bone cement is solidified and cooled, the shell of the expansion microsphere is hardened again, and the volume is fixed, so that the bone cement is increased in volume and has expansion performance. After the bone cement prepared by the method is implanted into a human body, the expansion performance of the bone cement does not depend on the content of body fluid, so that the bone cement still has good expansion performance after being implanted into the human body. And secondly, the prepared bone cement has good biocompatibility and does not influence normal bone tissues.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to a preparation method of injectable self-expanding bone cement, which is implemented according to the following steps:
step 1, taking a polyvinyl alcohol solution with the concentration of 0.05-0.15g/ml as a dispersion phase for preparing the low-temperature expanded microspheres, uniformly mixing a Vinyl Acetate (VAC) monomer, an ethanol solution of an initiator AIBN and an n-Pentane (n-Pentane) solution, wherein the mass of the initiator AIBN is 0.1-1% of that of the vinyl acetate monomer, and the mass of the n-Pentane solution is 15-35% of that of the vinyl acetate monomer to obtain an oil phase for preparing the low-temperature expanded microspheres, then sequentially adding the dispersion phase and the oil phase into a beaker, and fully stirring for 3-10 min to obtain a stable dispersion suspension. And transferring the stable dispersion suspension into a flask, heating to 70-90 ℃ under the protection of nitrogen, and reacting for 2-6 h. And cooling to room temperature after the reaction is finished, discharging, filtering, washing for 2-4 times, and drying in vacuum to finally obtain the low-temperature expanded microspheres. The average diameter of the microspheres is 10-50 μm.
And 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, PMMA, barium sulfate and BPO to obtain the injectable self-expansion bone cement solid phase. The injectable self-expandable bone cement solid phase consists of 20-48% of low-temperature expandable microspheres, 50.4-77.25% of methyl methacrylate, 1.5-2.5% of barium sulfate and 0.1-0.25% of dibenzoyl peroxide in percentage by mass, and the sum of the mass percentages of the components is 100%.
Step 3, uniformly mixing MMA, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase; the mass ratio of MMA to N, N-dimethyl-p-toluidine to hydroquinone is 96.5-99.5: 0.4-3: 0.1 to 0.5.
And 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3 according to a solid-liquid ratio of 1: and mixing 0.5-1.5 g/ml, stirring and injecting to obtain the injectable self-expanding bone cement.
The invention relates to a preparation method of injectable self-expansion bone cement, which comprises the steps of firstly preparing low-temperature expansion microspheres by adopting a suspension polymerization method, selecting polyvinyl acetate with low softening temperature (38 ℃) as a shell structure, wrapping n-pentane with low boiling point (36 ℃) to form the low-temperature expansion microspheres with the shell structure; then uniformly mixing the low-temperature expansion microspheres and PMMA bone cement powder with a liquid phase, stirring and injecting to obtain the injectable self-expansion bone cement.
The advantages are that: 1. the low-temperature expansion microsphere with the core-shell structure prepared from the polyvinyl acetate and the n-pentane is non-toxic to a human body, so that the self-expansion bone cement has no toxic reaction to the human body after being implanted into the human body, and has good biocompatibility; 2. the self-expanding bone cement overcomes the defect of the in vivo expansion performance of the traditional expanding bone cement which expands depending on the absorption and dispersion phases, and the low-temperature expanding microspheres and the bone cement are compounded to ensure that the bone cement has the self-expanding performance. The low-temperature expansion microspheres expand depending on the change of the cement solidification temperature in the cement solidification process. The temperature of the bone cement rises in the solidification process, the thermoplastic shell of the low-temperature expansion microsphere is softened under the temperature change, the liquid in the shell boils and vaporizes, and the internal gas pressure is increased, so that the volume of the expansion microsphere is obviously increased. When the bone cement is solidified and cooled, the shell of the expansion microsphere is hardened again, and the volume is fixed, so that the bone cement is increased in volume and has expansion performance. After the bone cement prepared by the method is implanted into a human body, the expansion performance of the bone cement does not depend on the content of body fluid, and the bone cement still has good expansion performance after being implanted into the human body; 3. the added low-temperature expansion microspheres can not greatly reduce the mechanical property of the bone cement, so that the bone cement still has certain mechanical support property after being implanted into a human body and expanded.
Example 1
The invention relates to a preparation method of injectable self-expanding bone cement, which specifically comprises the following steps:
step 1, taking a polyvinyl alcohol solution with the concentration of 0.05g/ml as a dispersion phase for preparing the low-temperature expanded microspheres to obtain the dispersion phase for preparing the low-temperature expanded microspheres, uniformly mixing a Vinyl Acetate (VAC) monomer, an ethanol solution of an initiator AIBN and an n-Pentane (n-Pentane) solution to obtain an oil phase for preparing the low-temperature expanded microspheres, wherein the mass of the initiator AIBN is 0.1 percent of that of the vinyl acetate monomer, dissolving the initiator AIBN in 50ml of the ethanol solution to form an AIBN ethanol solution, the mass of the n-Pentane solution is 15 percent of that of the vinyl acetate monomer, then sequentially adding the dispersion phase and the oil phase into a beaker, and fully stirring for 3min to obtain a stable dispersed suspension. Transferring the stable dispersion suspension into a flask, heating to 70 ℃ under the protection of nitrogen, and reacting for 2 h. And cooling to room temperature after the reaction is finished, discharging, filtering, washing for 2 times, and drying in vacuum to finally obtain the low-temperature expanded microspheres. The microspheres had an average diameter of 45.2. mu.m.
And 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, PMMA, barium sulfate and BPO to obtain the injectable self-expansion bone cement solid phase. The injectable self-expandable bone cement solid phase consists of 20 percent of low-temperature expandable microspheres, 77.25 percent of PMMA, 2.5 percent of barium sulfate and 0.25 percent of BPO by mass percent, and the sum of the mass percent of the components is 100 percent.
Step 3, uniformly mixing MMA, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase; the mass ratio of MMA to N, N-dimethyl-p-toluidine to hydroquinone is 96.5: 3: 0.5.
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3 according to a solid-liquid ratio of 1: mixing at 0.5g/ml, stirring, and injecting to obtain injectable self-expandable bone cement.
Example 2
Step 1, taking a polyvinyl alcohol solution with the concentration of 0.07g/ml as a dispersion phase for preparing the low-temperature expanded microspheres to obtain the dispersion phase for preparing the low-temperature expanded microspheres, uniformly mixing a Vinyl Acetate (VAC) monomer, an ethanol solution of an initiator AIBN and an n-Pentane (n-Pentane) solution to obtain an oil phase for preparing the low-temperature expanded microspheres, wherein the mass of the initiator AIBN is 0.2 percent of that of the vinyl acetate monomer, dissolving the initiator AIBN in 50ml of the ethanol solution to form an AIBN ethanol solution, the mass of the n-Pentane solution is 18 percent of that of the vinyl acetate monomer, then sequentially adding the dispersion phase and the oil phase into a beaker, and fully stirring for 5min to obtain a stable dispersed suspension. The stable dispersion suspension is transferred into a flask, and the temperature is raised to 75 ℃ under the protection of nitrogen, and the reaction lasts for 2.5 h. And cooling to room temperature after the reaction is finished, discharging, filtering, washing for 4 times, and drying in vacuum to finally obtain the low-temperature expanded microspheres. The microspheres had an average diameter of 31.2. mu.m.
And 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, PMMA, barium sulfate and BPO to obtain the injectable self-expansion bone cement solid phase. The injectable self-expandable bone cement solid phase consists of 25% of low-temperature expandable microspheres, 73% of PMMA, 1.8% of barium sulfate and 0.2% of BPO by mass percent, and the sum of the mass percentages of the components is 100%.
Step 3, uniformly mixing MMA, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase; the mass ratio of MMA to N, N-dimethyl-p-toluidine to hydroquinone is 97.5: 2: 0.5.
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3 according to a solid-liquid ratio of 1: 0.8g/ml, stirring and injecting to obtain the injectable self-expanding bone cement.
Example 3
Step 1, taking a polyvinyl alcohol solution with the concentration of 0.09g/ml as a dispersion phase for preparing the low-temperature expanded microspheres to obtain the dispersion phase for preparing the low-temperature expanded microspheres, uniformly mixing a Vinyl Acetate (VAC) monomer, an ethanol solution of an initiator AIBN and an n-Pentane (n-Pentane) solution to obtain an oil phase for preparing the low-temperature expanded microspheres, wherein the mass of the initiator AIBN is 0.4 percent of that of the vinyl acetate monomer, dissolving the initiator AIBN in 50ml of the ethanol solution to form an AIBN ethanol solution, the mass of the n-Pentane solution is 25 percent of that of the vinyl acetate monomer, then sequentially adding the dispersion phase and the oil phase into a beaker, and fully stirring for 7min to obtain a stable dispersed suspension. Transferring the stable dispersion suspension into a flask, heating to 80 ℃ under the protection of nitrogen, and reacting for 3 hours. And cooling to room temperature after the reaction is finished, discharging, filtering, washing for 4 times, and drying in vacuum to finally obtain the low-temperature expanded microspheres. The microspheres had an average diameter of 24.3. mu.m.
And 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, PMMA, barium sulfate and BPO to obtain the injectable self-expansion bone cement solid phase. The injectable self-expandable bone cement solid phase consists of 30 mass percent of low-temperature expandable microspheres, 67.75 mass percent of PMMA, 2.1 mass percent of barium sulfate and 0.15 mass percent of BPO, wherein the sum of the mass percent of the components is 100 percent.
Step 3, uniformly mixing MMA, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase; the mass ratio of MMA to N, N-dimethyl-p-toluidine to hydroquinone is 98.5: 1: 0.5.
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3 according to a solid-liquid ratio of 1: mixing at a ratio of 1.0g/ml, stirring, and injecting to obtain injectable self-expandable bone cement.
Example 4
Step 1, taking polyvinyl alcohol solution with the concentration of 0.12g/ml as dispersed phase for preparing the low-temperature expanded microspheres to obtain the dispersed phase for preparing the low-temperature expanded microspheres, uniformly mixing Vinyl Acetate (VAC) monomer, ethanol solution of initiator AIBN and n-Pentane (n-Pentane) solution to obtain oil phase for preparing the low-temperature expanded microspheres, wherein the mass of the initiator AIBN is 0.8 percent of that of the vinyl acetate monomer, dissolving the initiator AIBN in 50ml of ethanol solution to form AIBN ethanol solution, the mass of the n-Pentane solution is 30 percent of that of the vinyl acetate monomer, then sequentially adding the dispersed phase and the oil phase into a beaker, and fully stirring for 8min to obtain stable dispersed suspension. Transferring the stable dispersion suspension into a flask, heating to 85 ℃ under the protection of nitrogen, and reacting for 4 hours. And cooling to room temperature after the reaction is finished, discharging, filtering, washing for 4 times, and drying in vacuum to finally obtain the low-temperature expanded microspheres. The microspheres had an average diameter of 19.8. mu.m.
And 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, PMMA, barium sulfate and BPO to obtain the injectable self-expansion bone cement solid phase. The injectable self-expandable bone cement solid phase consists of 40 percent of low-temperature expandable microspheres, 58.25 percent of PMMA, 1.5 percent of barium sulfate and 0.25 percent of BPO by mass percentage, and the sum of the mass percentages of the components is 100 percent.
Step 3, uniformly mixing MMA, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase; the mass ratio of MMA to N, N-dimethyl-p-toluidine to hydroquinone is 99: 0.5: 0.5.
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3 according to a solid-liquid ratio of 1: mixing at a ratio of 1.2g/ml, stirring, and injecting to obtain injectable self-expandable bone cement.
Example 5
Step 1, taking a polyvinyl alcohol solution with the concentration of 0.15g/ml as a dispersion phase for preparing the low-temperature expanded microspheres to obtain the dispersion phase for preparing the low-temperature expanded microspheres, uniformly mixing a Vinyl Acetate (VAC) monomer, an ethanol solution of an initiator AIBN and an n-Pentane (n-Pentane) solution to obtain an oil phase for preparing the low-temperature expanded microspheres, dissolving the initiator AIBN with the mass of 1% of the vinyl acetate monomer in 50ml of the ethanol solution to form the AIBN ethanol solution, adding the dispersion phase and the oil phase into a beaker in sequence, and fully stirring for 10min to obtain the stable dispersion suspension. Transferring the stable dispersion suspension into a flask, heating to 90 ℃ under the protection of nitrogen, and reacting for 6 hours. And cooling to room temperature after the reaction is finished, discharging, filtering, washing for 4 times, and drying in vacuum to finally obtain the low-temperature expanded microspheres. The microspheres had an average diameter of 12.1. mu.m.
And 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, PMMA, barium sulfate and BPO to obtain the injectable self-expansion bone cement solid phase. The injectable self-expandable bone cement solid phase consists of 48 percent of low-temperature expandable microspheres, 50.4 percent of PMMA, 1.5 percent of barium sulfate and 0.1 percent of BPO by mass percentage, and the sum of the mass percentages of the components is 100 percent.
Step 3, uniformly mixing MMA, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase; the mass ratio of MMA to N, N-dimethyl-p-toluidine to hydroquinone is 99.5: 0.4: 0.1.
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3 according to a solid-liquid ratio of 1: mixing at a ratio of 1.5g/ml, stirring, and injecting to obtain injectable self-expandable bone cement.
The self-expanding bone cements prepared in examples 1, 2, 3, 4, and 5 were compared with conventional bone cements in vitro, as shown in table 1,
TABLE 1 injectable self-expandable bone cement compared with conventional PMMA bone cement
As can be seen from table 1, compared with the conventional PMMA bone cement, the injectable self-expandable bone cement prepared in examples 1, 2, 3, 4, 5 shows good expansion performance in vitro depending on the softening vaporization, expansion solidification process of the low temperature expandable microspheres, and the volume change rate of the bone cement prepared by the present invention also shows an increasing trend as the content of the expandable microspheres in the bone cement increases; because the added expansion microspheres belong to a hard phase, the bone cement doped with the expansion microspheres still has good compressive strength after expansion, and can generate additional supporting effect on surrounding tissues after in vivo expansion although the bone cement has a certain tendency of reduction compared with the traditional bone water.
Claims (5)
1. The preparation method of the injectable self-expanding bone cement is characterized by comprising the following specific operation steps:
step 1, taking a polyvinyl alcohol solution as a dispersed phase for preparing the low-temperature expanded microspheres; uniformly mixing vinyl acetate monomer, ethanol solution of initiator azobisisobutyronitrile and n-pentane solution to obtain an oil phase for preparing the low-temperature expanded microspheres; then, sequentially adding the dispersed phase and the oil phase into a beaker, and fully stirring to obtain a stable dispersed suspension; transferring the stable dispersion suspension into a flask, heating under the protection of nitrogen, reacting for a certain time, cooling to room temperature after the reaction is finished, discharging, filtering, washing, and drying in vacuum to finally obtain low-temperature expanded microspheres;
step 2, uniformly mixing the low-temperature expansion microspheres obtained in the step 1, polymethyl methacrylate, barium sulfate and dibenzoyl peroxide to obtain an injectable self-expansion bone cement solid phase;
step 3, uniformly mixing methyl methacrylate, N-dimethyl-p-toluidine and hydroquinone to obtain an injectable self-expanding bone cement liquid phase;
and 4, mixing the injectable self-expansion bone cement solid phase obtained in the step 2 and the injectable self-expansion bone cement liquid phase obtained in the step 3, stirring and injecting to obtain the injectable self-expansion bone cement.
2. The method for preparing injectable self-expandable bone cement according to claim 1, wherein in the step 1, the concentration of the polyvinyl alcohol solution is 0.05-0.15g/ml, the mass of the initiator azobisisobutyronitrile is 0.1-1% of the mass of the vinyl acetate monomer, and the mass of the n-pentane is 15-35% of the mass of the vinyl acetate monomer; the stirring time is 3-10 min, the polymerization temperature is 70-90 ℃, the reaction time is 2-6 h, and the washing is performed for 2-4 times.
3. The method for preparing the injectable self-expandable bone cement according to claim 2, wherein in the step 2, the injectable self-expandable bone cement solid phase comprises, by mass, 20 to 48% of low-temperature expandable microspheres, 50.4 to 77.25% of methyl methacrylate, 1.5 to 2.5% of barium sulfate and 0.1 to 0.25% of dibenzoyl peroxide, and the sum of the mass percentages of the components is 100%.
4. The method for preparing injectable self-expandable bone cement according to claim 1, wherein in the step 3, the mass ratio of methyl methacrylate, N-dimethyl-p-toluidine and hydroquinone is 96.5-99.5: 0.4-3: 0.1 to 0.5.
5. The method for preparing injectable self-expandable bone cement according to claim 3, wherein in the step 4, the solid-to-liquid ratio of the solid phase to the liquid phase of the injectable self-expandable bone cement is 1: 0.5 to 1.5 g/ml.
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