CN109053968B - Injectable water-absorbing expansion bone cement with high expansion ratio and preparation method thereof - Google Patents
Injectable water-absorbing expansion bone cement with high expansion ratio and preparation method thereof Download PDFInfo
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Abstract
The invention discloses high-expansion-ratio injectable water-absorbing expandable bone cement, which comprises a solid-phase component and a liquid-phase component in a mass-volume ratio of 1.5 g: 1 ml-2 g: 1ml of the solid phase raw materials are mixed, and the solid phase raw materials comprise the following components in percentage by mass: 43-64% of polymethyl methacrylate, 31-47% of polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer and 5-10% of barium sulfate; the liquid phase raw material comprises 26.4-51.5% of methyl methacrylate, 33.5-68.6% of hydroxyethyl methacrylate, 2.5-5% of accelerator N, N-dimethyl-p-toluidine and 2.5-10% of retarder hydroquinone. The invention also discloses a preparation method of the bone cement, which solves the problem that the existing polymethyl methacrylate bone cement causes different degrees of abrasion to joints in human bodies due to volume shrinkage, overlarge strength and high elastic modulus.
Description
Technical Field
The invention belongs to the technical field of preparation of medical biomaterials, and relates to high-expansion-ratio injectable water-absorbing expandable bone cement and a preparation method of the bone cement.
Background
The polymethyl methacrylate bone cement has been clinically applied in orthopedics and dentistry for as long as 50 years, gradually expands from dentistry and joint fixation to a plurality of fields such as bone defect filling, vertebral fracture treatment, local bone infection control and the like, and is an injectable biomaterial with the widest orthopedic application range, the largest quantity and the largest dosage. The researchers in the past developed an injectable water-swellable bone cement aiming at the problems of the bone cement, but the bone cement still has some problems, which limits the curative effect. Firstly, the expansion process mainly occurs on the surface layer which can be contacted with the external body fluid, and the inside of the water-swelling bone cement cannot be contacted with the external body fluid, so that the water-swelling bone cement cannot be expanded by water, and the expansion rate of the water-swelling bone cement is lower. And secondly, the bone cement has water absorption and expansion properties, and the mechanical properties of the bone cement are greatly reduced and lower than the minimum standard of 70MPa of bone cement implant materials, so that the bone cement cannot play a better supporting role. Therefore, the research focus in the field is to find an injectable water-swellable bone cement which can be wholly swelled and has the mechanical property between the lowest standard of the polymethyl methacrylate bone cement and the bone cement implant material.
Chinese patent application No. 201510014513.2, published Japanese 2015.05.20, published 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, but the swelling multiplying power is low due to the influence of the content of water-absorbing resin fibers, the water-absorbing resin fibers on the surface of the bone cement, which are in contact with water, can swell, and the water-absorbing resin fibers embedded in the bone cement cannot absorb water to swell, so the cement belongs to gradient swelling and has uneven swelling effect. 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 this patent has a good expansion ratio, the expansion is not uniform, and the expansion performance of the bone cement is limited by the phenomenon that the surface of the bone cement expands well and the inside does not expand.
Disclosure of Invention
The invention aims to provide high-expansion-ratio injectable water-absorption expansion bone cement, which solves the problem that the existing polymethyl methacrylate bone cement causes different degrees of abrasion to joints in a human body due to volume shrinkage, overlarge strength and high elastic modulus.
It is another object of the present invention to provide a method for preparing the bone cement.
The invention adopts the technical scheme that the high-expansion-ratio injectable water-absorbing expandable bone cement is characterized in that a solid-phase component and a liquid-phase component are mixed according to the mass-volume ratio of 1.5 g: 1 ml-2 g: 1ml of the raw materials are mixed, solid-liquid double phases are simultaneously modified, and the solid-phase raw materials comprise the following components in percentage by mass: 43-64% of polymethyl methacrylate, 31-47% of polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer and 5-10% of barium sulfate, wherein the sum of the components is 100%; the liquid phase raw material comprises 26.4-51.5% of methyl methacrylate, 33.5-68.6% of hydroxyethyl methacrylate, 2.5-5% of accelerator N, N-dimethyl-p-toluidine and 2.5-10% of retarder hydroquinone, and the sum of all the components is 100%.
The invention also provides a method for preparing the injectable water-absorbing expansive bone cement with high expansion rate, which is implemented according to the following steps:
step 1, preparing polyethylene glycol modified graphene oxide:
firstly, adding graphene oxide into dimethylformamide for ultrasonic dispersion to obtain a mixed solution a, then adding polyethylene glycol and the mixed solution a into a round-bottom flask for ultrasonic mixing, then adding a proper amount of N, N-dicycloethyl carbodiimide and 4-dimethylaminopyridine into the round-bottom flask for ultrasonic treatment for a period of time, reacting at a constant temperature to obtain a mixed solution b, putting the mixed solution b into a dialysis bag for dialysis, removing free polyethylene glycol and a catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving a dispersing agent in a solvent, putting the solvent into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating and introducing nitrogen, then slowly adding a proper amount of an initiator potassium persulfate, a cross-linking agent N-N methylene bisacrylamide, a monomer consisting of methyl methacrylate and acrylic acid and the polyethylene glycol modified graphene oxide copolymer obtained in the step (1), and reacting at constant temperature to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying to obtain polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate, and uniformly mixing to obtain an injectable water-absorbing expansion bone cement solid phase with high expansion ratio;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerant N, N-dimethyl-p-toluidine and a retarder hydroquinone, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) uniformly stirring and mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to a certain proportion, quickly injecting the bone cement into an injector and injecting the bone cement into an inner cavity with a certain shape, and self-curing to obtain the injection molding and self-curing of the high-expansion-ratio injectable expansion bone cement.
Yet another feature of the present invention is that,
the specific process for preparing the polyethylene glycol modified graphene oxide in the step 1 is as follows: the mass volume ratio of the graphene oxide to the dimethylformamide solvent is 0.1-0.3 g: performing ultrasonic dispersion on 100mL of the mixture to obtain a mixed solution a, and mixing polyethylene glycol and the mixed solution a according to a mass-volume ratio of 0.1 g-0.2 g: 50mL of the graphene oxide modified by polyethylene glycol is ultrasonically mixed, then dicyclohexylcarbodiimide with the mass fraction of 5% -10% of graphene oxide and 1% -2% of 4-dimethylaminopyridine are added into a round-bottom flask, the mixture is ultrasonically treated for 30min to 60min, the mixture is reacted for 12h at the temperature of 60 ℃ to 70 ℃, the mixture is placed into a dialysis bag for dialysis for 1 week, free polyethylene glycol and catalyst 4-dimethylaminopyridine are removed, and the mixture is washed and dried after centrifugation to obtain the graphene oxide modified by the polyethylene glycol;
in the step 2, the dispersant is polyvinylpyrrolidone, the solvent is water or ethanol or a mixed solution of water and ethanol, and the initiator can also be benzoyl peroxide.
In the step 2, the mass ratio of methyl methacrylate to acrylic acid in the monomer consisting of methyl methacrylate and acrylic acid is 1.38:1, the mass of the dispersing agent is 7-10% of the total mass of the monomer, the mass of the cross-linking agent is 1-10% of the total mass of the monomer, the mass of the initiating agent is 1-3% of the total mass of the monomer, and the mass of the polyethylene glycol modified graphene oxide is 1-5% of the total mass of the monomer.
The conditions for the reaction in the three-neck flask in the step 2 are as follows: heating to 50-55 ℃, and introducing nitrogen for 0.5-1 h to obtain an emulsion sample, wherein the constant-temperature reaction time is 6-12 h; the vacuum drying conditions were: the temperature is 50-70 ℃ and the time is 8-12 h.
The mass percentages of the polymethyl methacrylate in the step 3, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and the barium sulfate are respectively as follows: 43-64%, 31-47% and 5-10%.
In the step 4, the mass percentages of the methyl methacrylate, the hydroxyethyl methacrylate, the accelerator N, N-dimethyl-p-toluidine and the retarder hydroquinone are respectively 26.4-51.5%, 33.5-68.6%, 2.5-5% and 2.5-10%.
In the step 5, the mass volume ratio of the solid phase to the liquid phase is 1.5 g-2 g: 1ml, the self-curing condition is that the temperature is 35-40 ℃, the humidity is 100 percent, and the time is 10-30 min.
The invention has the beneficial effects that the high-expansion-ratio injectable water-absorbing expansion bone cement solves the problem that the existing polymethyl methacrylate bone cement causes different degrees of abrasion to joints in a human body due to volume shrinkage, overlarge strength and high elastic modulus. The polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer is introduced into the solid phase, and the hydroxyethyl methacrylate is introduced into the liquid phase, so that the solid-liquid dual phase can absorb water synergistically, the water-absorption expansion rate of the water-absorption expansion bone cement is improved, and the problem of uneven internal expansion of the material is solved; meanwhile, due to the fact that the graphene oxide with good elastic modulus is contained, the mechanical properties of the water-swelling bone cement before and after swelling are greatly improved, and therefore the water-swelling bone cement has good application prospects clinically.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention relates to high-expansion-ratio injectable water-absorbing expandable bone cement, which comprises a solid-phase component and a liquid-phase component in a mass-volume ratio of 1.5 g: 1 ml-2 g: 1ml of the raw materials are mixed, solid-liquid double phases are simultaneously modified, and the solid-phase raw materials comprise the following components in percentage by mass: 43-64% of polymethyl methacrylate, 31-47% of polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer and 5-10% of barium sulfate, wherein the sum of the components is 100%; the liquid phase raw material comprises 26.4-51.5% of methyl methacrylate, 33.5-68.6% of hydroxyethyl methacrylate, 2.5-5% of accelerator N, N-dimethyl-p-toluidine and 2.5-10% of retarder hydroquinone, and the sum of all the components is 100%.
The invention relates to a preparation method of high-expansion-ratio injectable water-absorbing expansion bone cement, which is implemented according to the following steps:
step 1, preparing polyethylene glycol modified graphene oxide:
firstly, adding graphene oxide into dimethylformamide for ultrasonic dispersion to obtain a mixed solution a, then adding polyethylene glycol and the mixed solution a into a round-bottom flask for ultrasonic mixing, then adding a proper amount of N, N-dicycloethyl carbodiimide and 4-dimethylaminopyridine into the round-bottom flask for ultrasonic treatment for a period of time, reacting at a constant temperature to obtain a mixed solution b, putting the mixed solution b into a dialysis bag for dialysis, removing free polyethylene glycol and a catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving a dispersing agent in a solvent, putting the solvent into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating and introducing nitrogen, then slowly adding a proper amount of an initiator potassium persulfate, a cross-linking agent N-N methylene bisacrylamide, a monomer consisting of methyl methacrylate and acrylic acid and the polyethylene glycol modified graphene oxide copolymer obtained in the step (1), and reacting at constant temperature to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying to obtain polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate, and uniformly mixing to obtain an injectable water-absorbing expansion bone cement solid phase with high expansion ratio;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerant N, N-dimethyl-p-toluidine and a retarder hydroquinone, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) uniformly stirring and mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to a certain proportion, quickly injecting the bone cement into an injector and injecting the bone cement into an inner cavity with a certain shape, and self-curing to obtain the injection molding and self-curing of the high-expansion-ratio injectable expansion bone cement.
The specific process for preparing the polyethylene glycol modified graphene oxide in the step 1 is as follows: the mass volume ratio of the graphene oxide to the dimethylformamide solvent is 0.1-0.3 g: performing ultrasonic dispersion on 100mL of the mixture to obtain a mixed solution a, and mixing polyethylene glycol and the mixed solution a according to a mass-volume ratio of 0.1 g-0.2 g: 50mL of the graphene oxide modified by polyethylene glycol is ultrasonically mixed, then dicyclohexylcarbodiimide with the mass fraction of 5% -10% of graphene oxide and 1% -2% of 4-dimethylaminopyridine are added into a round-bottom flask, the mixture is ultrasonically treated for 30min to 60min, the mixture is reacted for 12h at the temperature of 60 ℃ to 70 ℃, the mixture is placed into a dialysis bag for dialysis for 1 week, free polyethylene glycol and catalyst 4-dimethylaminopyridine are removed, and the mixture is washed and dried after centrifugation to obtain the graphene oxide modified by the polyethylene glycol;
in the step 2, the dispersant is polyvinylpyrrolidone, the solvent is water or ethanol or a mixed solution of water and ethanol, and the initiator can also be benzoyl peroxide.
In the step 2, the mass ratio of methyl methacrylate to acrylic acid in the monomer consisting of methyl methacrylate and acrylic acid is 1.38:1, the mass of the dispersing agent is 7-10% of the total mass of the monomer, the mass of the cross-linking agent is 1-10% of the total mass of the monomer, the mass of the initiating agent is 1-3% of the total mass of the monomer, and the mass of the polyethylene glycol modified graphene oxide is 1-5% of the total mass of the monomer.
The conditions for the reaction in the three-neck flask in the step 2 are as follows: heating to 50-55 ℃, and introducing nitrogen for 0.5-1 h to obtain an emulsion sample, wherein the constant-temperature reaction time is 6-12 h; the vacuum drying conditions were: the temperature is 50-70 ℃ and the time is 8-12 h.
The mass percentages of the polymethyl methacrylate in the step 3, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and the barium sulfate are respectively as follows: 43-64%, 31-47% and 5-10%.
In the step 4, the mass percentages of the methyl methacrylate, the hydroxyethyl methacrylate, the accelerator N, N-dimethyl-p-toluidine and the retarder hydroquinone are respectively 26.4-51.5%, 33.5-68.6%, 2.5-5% and 2.5-10%.
In the step 5, the mass volume ratio of the solid phase to the liquid phase is 1.5 g-2 g: 1ml, the self-curing condition is that the temperature is 35-40 ℃, the humidity is 100 percent, and the time is 10-30 min.
The reason for selecting the Graphene Oxide in the invention is that the Graphene Oxide (Graphene Oxide) is a derivative of Graphene, and is a product obtained by chemically oxidizing and stripping graphite powder, after oxidation treatment, the Graphene Oxide still maintains the layered structure of graphite, but a large number of oxygen-containing functional groups are introduced to each layer of Graphene single sheet, wherein hydroxyl and epoxy are mainly distributed in the interior of the layered structure, and carboxyl and carbonyl are mainly distributed at the edge of the layered structure, so that the Graphene Oxide has better hydrophilic performance. In addition, the graphene oxide has strong adsorption force and good biocompatibility, and can perform various covalent reactions and non-covalent reactions, so that the graphene oxide has wide application in the field of biomedicine. The graphene oxide has good dispersibility in water due to more hydrophilic groups, but has poor dispersibility in PMMA bone cement, and is easy to agglomerate to influence the performance of the bone cement. Aiming at the problem, the graphene oxide is modified, and the polyethylene glycol which is proved to be stably dispersed in a physiological environment is used for modifying the graphene oxide, so that the graphene oxide can be uniformly dispersed in bone cement. In addition, the selected hydroxyethyl methacrylate (HEMA) is a common polymer material for biomedicine, and the monomer and the polymer of the hydroxyethyl methacrylate have better biocompatibility and are widely applied to the aspects of tooth repair, drug slow release, burn coating, organ transplantation, contact lens manufacturing, cell culture, biomolecule and enzyme immobilization and the like. The HEMA structure has a carbon-carbon double bond structure, and double bond opening can be copolymerized with MMA under certain conditions. Due to the existence of a HEMA long-chain structure, the main chain length can be increased after copolymerization with MMA monomers, so that the copolymer has better strength and hardness. Meanwhile, the long-chain end of the HEMA has hydrophilic group hydroxyl, which is beneficial to the material to play a water absorption role, so that the HEMA replaces or partially replaces MMA to serve as a liquid phase, the bone cement can be ensured to have rapid polymerization, the characteristics of water absorption and water retention are given to the bone cement, and the uniform degree of water absorption expansion of the water absorption expansion bone cement is improved.
The invention relates to high-expansion-ratio injectable water-swelling bone cement, which is prepared by a solution polymerization method under the action of a cross-linking agent and an initiator through a polymethyl methacrylate-acrylic acid copolymer with water-swelling characteristics and polyethylene glycol modified graphene oxide (PEG-GO) containing a large number of hydrophilic groups in a solid phase of the bone cement in a creativity manner, wherein the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide (PMMA-PAA-PEG-GO) can be uniformly distributed in the solid phase of the bone cement due to better dispersibility in the bone cement, and the excellent hydrophilic characteristics enable the water outside the bone cement to be combined with the polyethylene glycol modified graphene oxide through hydrogen bonds so as to transmit water molecules to the inside to play a certain role of bridging channels, therefore, the polymethyl methacrylate-acrylic acid copolymer with the three-dimensional network structure containing hydrophilic groups in the copolymer can absorb water and expand, and the overall expansion performance of the water-absorbing expansion bone cement is improved; meanwhile, the lamellar graphene oxide has better mechanical property, and the elastic modulus of the lamellar graphene oxide is 200-300GPa, so that the mechanical property of the bone cement before and after water absorption expansion can be improved by adding the graphene oxide. MMA is partially replaced by HEMA in a liquid phase of the bone cement, hydroxyethyl methacrylate (HEMA) belongs to a derivative of methacrylic acid, wherein double bonds exist to enable the cement to be polymerized with the MMA under the action of an initiator, the HEMA is a water-soluble monomer, straight branch chains exist in a molecular structure of the HEMA, hydroxyl groups on the branch chains can form strong hydrogen bonds, and the straight branch chain structures can be intertwined with each other and can form hydrogen bonds to form a physical crosslinking structure and a chemical crosslinking structure in the polymerization or copolymerization process. HEMA can be evenly distributed in a bone cement block in the solid-liquid mixing process, plays a role in transferring moisture, and can better connect polymer polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide (PMMA-PAA-PEG-GO) playing a role in water absorption and expansion in a solid phase, so that the overall water absorption and expansion capacity of the bone cement is improved. The introduction of the hydrophilic group can improve the water molecule migration efficiency and promote the water absorption expansion effect of the three-dimensional rigid network structure in the bone cement, and the solid phase and the liquid phase of the bone cement can absorb water and expand cooperatively, so that the expansion performance of the water absorption expansion bone cement is further improved.
Specific examples are as follows:
example 1
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.1 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.1 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding N, N-dicycloethyl carbodiimide with the mass fraction of graphene oxide being 5% and 1% of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic mixing for 30min, carrying out constant temperature reaction at 60 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, carrying out dialysis for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, carrying out centrifugation, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving 10% of polyvinylpyrrolidone in monomer mass fraction in water, putting the solution into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the solution to 50 ℃ and introducing nitrogen for 1h, then slowly adding a monomer consisting of Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring the solution, adding 1% of initiator potassium persulfate in mass fraction, 5% of cross-linking agent N-N methylene bisacrylamide in mass fraction and 1% of polyethylene glycol modified graphene oxide copolymer obtained in the step 1 in mass fraction, and reacting the mixture at constant temperature of 50 ℃ for 6h to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 50 ℃ for 8h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate respectively according to the mass percentages of 43%, 47% and 10%, and uniformly mixing to obtain an injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerator N, N-dimethyl-p-toluidine and a retarder hydroquinone in sequence according to the mass percentages of 26.4%, 68.6%, 2.5% and 2.5% to be uniformly mixed to obtain a liquid phase of the injectable water-absorbing expansion bone cement with high expansion ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step 3 and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step 4 according to the mass-volume ratio of 1.5 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the self-curing is carried out for 10min under the conditions that the temperature is 35 ℃ and the humidity is 100 percent, so that the injection molding and the self-curing of the high-expansion-ratio injectable expandable bone cement are obtained.
Example 2
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.3 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.1 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding 10 mass percent of N, N-dicycloethyl carbodiimide and 2 mass percent of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic mixing for 60min, carrying out constant temperature reaction at 70 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, carrying out dialysis for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving polyvinylpyrrolidone with the mass fraction of 7% of monomer in water, putting the polyvinylpyrrolidone into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the polyvinylpyrrolidone to 55 ℃ and introducing nitrogen for 0.5h, then slowly adding monomer Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring, adding initiator potassium persulfate with the mass fraction of 3%, cross-linking agent N-N methylene bisacrylamide with the mass fraction of 8% and polyethylene glycol modified graphene oxide copolymer obtained in the step 1 with the mass fraction of 3%, and reacting for 8h at the constant temperature of 55 ℃ to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 60 ℃ for 10h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate respectively according to the mass percentages of 64%, 31% and 5%, and uniformly mixing to obtain the injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing 51.5 percent, 33.5 percent, 5 percent and 10 percent of methyl methacrylate, hydroxyethyl methacrylate, N-dimethyl-p-toluidine as an accelerant and hydroquinone as a retarder in sequence by mass percent, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to the mass-volume ratio of 1.8 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the self-curing is carried out for 20min under the conditions that the temperature is 40 ℃ and the humidity is 100 percent, so that the injection molding and the self-curing of the high-expansion-ratio injectable expandable bone cement are obtained.
Example 3
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, according to the mass volume of 0.2 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.2 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding 8 mass percent of N, N-dicycloethyl carbodiimide and 1 mass percent of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic reaction for 45min, reacting at a constant temperature of 60 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, dialyzing for 1 week, removing free polyethylene glycol and a catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving polyvinylpyrrolidone with the mass fraction of 8% of monomer in water, putting the monomer into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the monomer to 50 ℃ and introducing nitrogen for 0.5h, then slowly adding monomer Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring, adding 2% of initiator potassium persulfate with the mass fraction, 6% of cross-linking agent N-N methylene bisacrylamide with the mass fraction of 6% and 5% of polyethylene glycol modified graphene oxide copolymer obtained in the step 1, and reacting for 10h at the constant temperature of 55 ℃ to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 70 ℃ for 8h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate respectively according to the mass percentages of 51%, 42% and 7%, and uniformly mixing to obtain the injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerator N, N-dimethyl-p-toluidine and a retarder hydroquinone in sequence according to the mass percentages of 32.3%, 60.1%, 5% and 2.6%, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step 3 and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step 4 according to the mass-volume ratio of 1.6 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and self-curing is carried out for 30min under the conditions that the temperature is 35 ℃ and the humidity is 100 percent, so that the injection molding and self-curing of the high-expansion-ratio injectable expandable bone cement are obtained.
Example 4
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.25 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.1 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding N, N-dicycloethyl carbodiimide with the mass fraction of graphene oxide being 5% and 1% of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic reaction for 35min, carrying out constant temperature reaction at 70 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, carrying out dialysis for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, carrying out centrifugation, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving 9% of monomer mass fraction polyvinylpyrrolidone in water, putting the dissolved polyvinylpyrrolidone into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the polyvinylpyrrolidone to 55 ℃ and introducing nitrogen for 1h, then slowly adding monomer Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring the mixture, adding 3% of initiator potassium persulfate, 3% of cross-linking agent N-N methylene bisacrylamide and 4% of polyethylene glycol modified graphene oxide copolymer obtained in the step 1, and reacting the mixture at the constant temperature of 55 ℃ for 12h to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 50 ℃ for 12h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing the polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate according to the mass percentages of 45%, 47% and 8%, and uniformly mixing to obtain the injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerator N, N-dimethyl-p-toluidine and a retarder hydroquinone in sequence according to the mass percentages of 42.1%, 48.9%, 3% and 6% respectively, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to the mass-volume ratio of 2 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the injection molding and self-curing of the injectable expandable bone cement with high expansion ratio can be obtained after the self-curing is carried out for 25min under the conditions that the temperature is 35 ℃ and the humidity is 100%.
Example 5
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.15 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.12 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding 10 mass percent of N, N-dicycloethyl carbodiimide and 1.5 mass percent of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic reaction for 40min, reacting at a constant temperature of 60 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, dialyzing for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving polyvinylpyrrolidone with the mass fraction of 10% in water, putting the dissolved polyvinylpyrrolidone into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the mixture to 53 ℃ and introducing nitrogen for 0.6h, then slowly adding monomers of Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring the mixture, adding 2.5% of initiator potassium persulfate with the mass fraction, 1% of cross-linking agent N-N methylene bisacrylamide with the mass fraction of 1% and polyethylene glycol modified graphene oxide copolymer obtained in the step 1, and reacting the mixture at the constant temperature of 50 ℃ for 9h to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 65 ℃ for 10h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing the polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate according to the mass percentages of 45%, 45% and 10%, and uniformly mixing to obtain the injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerator N, N-dimethyl-p-toluidine and a retarder hydroquinone in sequence according to the mass percentages of 46.6%, 40.4%, 4% and 9%, and uniformly mixing to obtain a liquid phase of the injectable water-swellable bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to the mass-volume ratio of 2 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the self-curing is carried out for 15min under the conditions that the temperature is 40 ℃ and the humidity is 100 percent, so that the injection molding and the self-curing of the high-expansion-ratio injectable expandable bone cement are obtained.
Example 6
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.3 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.2 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding N, N-dicycloethyl carbodiimide with the mass fraction of graphene oxide being 6% and 1% of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic mixing for 50min, carrying out constant-temperature reaction at 70 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, carrying out dialysis for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, carrying out centrifugation, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving polyvinylpyrrolidone with the mass fraction of 8.5% in water, putting the dissolved polyvinylpyrrolidone into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the mixture to 54 ℃ and introducing nitrogen for 0.5h, then slowly adding monomers of Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring the mixture, adding 1.5% of initiator potassium persulfate with mass fraction, 2% of cross-linking agent N-N methylene bisacrylamide with mass fraction and 4% of polyethylene glycol modified graphene oxide copolymer obtained in the step 1, and reacting the mixture at the constant temperature of 52 ℃ for 7h to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 70 ℃ for 9h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate respectively according to the mass percentages of 52%, 42% and 6%, and uniformly mixing to obtain an injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing 35%, 50%, 5% and 10% of methyl methacrylate, hydroxyethyl methacrylate, N-dimethyl-p-toluidine as an accelerant and hydroquinone as a retarder in sequence by mass percent, and uniformly mixing to obtain a liquid phase of the injectable water-absorbing expansive bone cement with high expansion ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step 3 and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step 4 according to the mass-volume ratio of 1.5 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the self-curing is carried out for 10min under the conditions that the temperature is 40 ℃ and the humidity is 100 percent, so that the injection molding and the self-curing of the high-expansion-ratio injectable expandable bone cement are obtained.
Example 7
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.1 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.15 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding N, N-dicycloethyl carbodiimide with the mass fraction of graphene oxide being 7.5% and 2% of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic mixing for 40min, carrying out constant temperature reaction at 60 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, carrying out dialysis for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, carrying out centrifugation, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving polyvinylpyrrolidone with the mass fraction of 7% of monomer in water, putting the polyvinylpyrrolidone into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the polyvinylpyrrolidone to 52 ℃ and introducing nitrogen for 0.8h, then slowly adding monomer Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring, adding 1% of initiator potassium persulfate with mass fraction, 5.5% of cross-linking agent N-N methylene bisacrylamide with mass fraction and 1.5% of polyethylene glycol modified graphene oxide copolymer obtained in the step 1, and reacting at constant temperature of 54 ℃ for 6h to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 50 ℃ for 12h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate respectively according to the mass percentages of 53%, 40% and 7%, and uniformly mixing to obtain the injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing methyl methacrylate, hydroxyethyl methacrylate, N-dimethyl-p-toluidine as an accelerator and hydroquinone as a retarder in sequence according to the mass percentages of 38%, 52%, 2.5% and 7.5% respectively, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to the mass-volume ratio of 1.7 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the injection molding and the self-curing of the injectable expandable bone cement with high expansion ratio are obtained after the self-curing is carried out for 20min under the conditions that the temperature is 36 ℃ and the humidity is 100%.
Example 8
Step 1, preparing polyethylene glycol modified graphene oxide:
firstly, the mass volume is 0.3 g: adding 100mL of graphene oxide into dimethylformamide, performing ultrasonic dispersion to obtain a mixed solution a, and mixing the mixed solution a with the mass volume of 0.18 g: adding 50mL of polyethylene glycol and the mixed solution a into a round-bottom flask, carrying out ultrasonic mixing, adding N, N-dicycloethyl carbodiimide with the mass fraction of graphene oxide being 5.5% and 1.2% of 4-dimethylaminopyridine into the round-bottom flask, carrying out ultrasonic mixing for 60min, carrying out constant-temperature reaction at 60 ℃ for 12h to obtain a mixed solution b, putting the mixed solution b into a dialysis bag, carrying out dialysis for 1 week, removing free polyethylene glycol and catalyst 4-dimethylaminopyridine, carrying out centrifugation, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving 9.5% of monomer mass fraction polyvinylpyrrolidone in water, putting the mixture into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating the mixture to 55 ℃ and introducing nitrogen for 0.7h, then slowly adding the monomers of Methyl Methacrylate (MMA) and Acrylic Acid (AA) according to the mass ratio (1.38:1), uniformly stirring the mixture, adding 3% of initiator potassium persulfate, 10% of cross-linking agent N-N methylene bisacrylamide and 5% of polyethylene glycol modified graphene oxide copolymer obtained in the step 1, and reacting the mixture at the constant temperature of 50 ℃ for 11h to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying at 55 ℃ for 11h to obtain a polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate respectively according to the mass percentages of 58%, 37% and 5%, and uniformly mixing to obtain the injectable water-absorbing expansion bone cement solid phase with high expansion rate;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
respectively weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerator N, N-dimethyl-p-toluidine and a retarder hydroquinone in sequence according to the mass percentages of 49.5%, 37.5%, 5% and 8%, and uniformly mixing to obtain a liquid phase of the injectable water-swellable bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to the mass-volume ratio of 2 g: after 1mL of the mixture is stirred and mixed uniformly, the bone cement is quickly injected into an injector and is injected into an inner cavity with a certain shape, and the self-curing is carried out for 25min under the conditions that the temperature is 38 ℃ and the humidity is 100 percent, so that the injection molding and the self-curing of the high-expansion-ratio injectable expandable bone cement are obtained.
The following is a comparison between the injectable water-absorption expansion bone cement with high expansion ratio prepared in the embodiment of the invention and the traditional PMMA bone cement:
as can be seen from the above table, compared with the traditional PMMA bone cement, the high-expansion-rate injectable water-swellable bone cement prepared by the invention has better water absorption rate and expansion rate due to dual-phase synergistic water absorption after solid-liquid phase modification, and meanwhile, the mechanical property of the high-expansion-rate injectable water-swellable bone cement is obviously reduced compared with that of the PMMA bone cement, but the compressive strength of the water-swellable bone cement is not greatly reduced due to the existence of graphene oxide, so that the low-pressure-resistant water-swellable bone cement meets the minimum standard of 70MPa for bone cement implant materials.
Claims (7)
1. The high-expansion-ratio water-swellable injectable bone cement is characterized in that a solid-phase component and a liquid-phase component are mixed according to a mass-volume ratio of 1.5 g: 1 ml-2 g: 1ml of the raw materials are mixed, solid-liquid double phases are simultaneously modified, and the solid-phase raw materials comprise the following components in percentage by mass: 43-64% of polymethyl methacrylate, 31-47% of polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer and 5-10% of barium sulfate, wherein the sum of the components is 100%; the liquid phase raw material comprises 26.4-51.5% of methyl methacrylate, 33.5-68.6% of hydroxyethyl methacrylate, 2.5-5% of accelerator N, N-dimethyl-p-toluidine and 2.5-10% of retarder hydroquinone, and the sum of all the components is 100%.
2. A method for preparing the injectable water-swellable bone cement with high swelling ratio according to claim 1, which comprises the following steps:
step 1, preparing polyethylene glycol modified graphene oxide:
firstly, adding graphene oxide into dimethylformamide for ultrasonic dispersion to obtain a mixed solution a, then adding polyethylene glycol and the mixed solution a into a round-bottom flask for ultrasonic mixing, then adding a proper amount of N, N-dicycloethyl carbodiimide and 4-dimethylaminopyridine into the round-bottom flask for ultrasonic treatment for a period of time, reacting at a constant temperature to obtain a mixed solution b, putting the mixed solution b into a dialysis bag for dialysis, removing free polyethylene glycol and a catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving a dispersing agent in a solvent, putting the solvent into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating and introducing nitrogen, then slowly adding a proper amount of an initiator potassium persulfate, a cross-linking agent N-N methylene bisacrylamide, a monomer consisting of methyl methacrylate and acrylic acid and the polyethylene glycol modified graphene oxide copolymer obtained in the step (1), and reacting at constant temperature to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying to obtain polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate, and uniformly mixing to obtain an injectable water-absorbing expansion bone cement solid phase with high expansion ratio;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerant N, N-dimethyl-p-toluidine and a retarder hydroquinone, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) uniformly stirring and mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to a certain proportion, quickly injecting the bone cement into an injector and injecting the bone cement into an inner cavity with a certain shape, and self-curing to obtain the injection molding and self-curing of the high-expansion-ratio injectable expansion bone cement.
3. The preparation method of the bone cement capable of being injected, absorbed and expanded with high expansion ratio according to claim 2, wherein the specific process for preparing the polyethylene glycol modified graphene oxide in the step 1 is as follows: the mass volume ratio of the graphene oxide to the dimethylformamide solvent is 0.1-0.3 g: performing ultrasonic dispersion on 100mL of the mixture to obtain a mixed solution a, and mixing polyethylene glycol and the mixed solution a according to a mass-volume ratio of 0.1 g-0.2 g: 50mL of the graphene oxide modified by polyethylene glycol is ultrasonically mixed, then dicyclohexylcarbodiimide with the mass fraction of 5% -10% of graphene oxide and 1% -2% of 4-dimethylaminopyridine are added into a round-bottom flask, the mixture is ultrasonically treated for 30min to 60min, the mixture is reacted for 12h at the temperature of 60 ℃ to 70 ℃, the mixture is placed into a dialysis bag for dialysis for 1 week, free polyethylene glycol and catalyst 4-dimethylaminopyridine are removed, and the mixture is washed and dried after centrifugation to obtain the graphene oxide modified by the polyethylene glycol;
4. a method for preparing the injectable water-swellable bone cement with high swelling ratio according to claim 1, which comprises the following steps:
step 1, preparing polyethylene glycol modified graphene oxide:
firstly, adding graphene oxide into dimethylformamide for ultrasonic dispersion to obtain a mixed solution a, then adding polyethylene glycol and the mixed solution a into a round-bottom flask for ultrasonic mixing, then adding a proper amount of N, N-dicycloethyl carbodiimide and 4-dimethylaminopyridine into the round-bottom flask for ultrasonic treatment for a period of time, reacting at a constant temperature to obtain a mixed solution b, putting the mixed solution b into a dialysis bag for dialysis, removing free polyethylene glycol and a catalyst 4-dimethylaminopyridine, centrifuging, washing and drying to obtain polyethylene glycol modified graphene oxide;
step 2, preparing the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer:
dissolving a dispersant polyvinylpyrrolidone in water or ethanol or a mixed solution of water and ethanol, putting the mixture into a three-neck flask provided with a condenser pipe, a mechanical stirrer and a nitrogen guide pipe, heating and introducing nitrogen, slowly adding a proper amount of monomer consisting of initiator benzoyl peroxide, cross-linking agent N-N methylene bisacrylamide, methyl methacrylate and acrylic acid and the polyethylene glycol modified graphene oxide copolymer obtained in the step (1), and reacting at constant temperature to obtain an emulsion sample; centrifuging the emulsion sample, removing supernatant, adding ethanol, repeatedly washing, and vacuum drying to obtain polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer;
step 3, preparing a solid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing polymethyl methacrylate, the polymethyl methacrylate-acrylic acid-polyethylene glycol modified graphene oxide copolymer prepared in the step 2 and barium sulfate, and uniformly mixing to obtain an injectable water-absorbing expansion bone cement solid phase with high expansion ratio;
step 4, preparing a liquid phase of the injectable water-swelling bone cement with high swelling ratio:
weighing methyl methacrylate, hydroxyethyl methacrylate, an accelerant N, N-dimethyl-p-toluidine and a retarder hydroquinone, and uniformly mixing to obtain a liquid phase of the injectable water-swelling bone cement with high swelling ratio;
step 5, preparing the high-expansion-ratio injectable water-absorption expansion bone cement:
and (3) uniformly stirring and mixing the solid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (3) and the liquid phase of the high-expansion-ratio injectable water-absorption expansion bone cement prepared in the step (4) according to a certain proportion, quickly injecting the bone cement into an injector and injecting the bone cement into an inner cavity with a certain shape, and self-curing to obtain the injection molding and self-curing of the high-expansion-ratio injectable expansion bone cement.
5. The method for preparing the bone cement capable of being injected, absorbed and expanded with high expansion ratio according to claim 2, wherein the mass ratio of the methyl methacrylate to the acrylic acid in the monomer composed of the methyl methacrylate and the acrylic acid in the step 2 is 1.38:1, the mass of the dispersing agent is 7-10% of the total mass of the monomer, the mass of the cross-linking agent is 1-10% of the total mass of the monomer, the mass of the initiator is 1-3% of the total mass of the monomer, and the mass of the polyethylene glycol modified graphene oxide is 1-5% of the total mass of the monomer.
6. The method for preparing the high-expansion-ratio injectable water-swellable bone cement according to claim 2, wherein the conditions for the reaction in the three-necked flask in the step 2 are as follows: heating to 50-55 ℃, and introducing nitrogen for 0.5-1 h to obtain an emulsion sample, wherein the constant-temperature reaction time is 6-12 h; the vacuum drying conditions were: the temperature is 50-70 ℃ and the time is 8-12 h.
7. The method for preparing the bone cement capable of being injected, absorbed and expanded with high expansion ratio according to claim 2, wherein the mass-to-volume ratio of the solid phase component to the liquid phase component in the step 5 is 1.5 g-2 g: 1ml, the self-curing condition is that the temperature is 35-40 ℃, the humidity is 100 percent, and the time is 10-30 min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8557916B1 (en) * | 2013-04-30 | 2013-10-15 | Alfaisal University | Composition and method of making nanocomposite containing graphene sheets |
| CN104623726A (en) * | 2015-01-12 | 2015-05-20 | 西安理工大学 | Injectable water-absorbing and swelling bone cement and preparation method thereof |
| CN104922733A (en) * | 2015-06-19 | 2015-09-23 | 西安理工大学 | Injectable expansion type bone cement and preparation method thereof |
| CN105536050A (en) * | 2016-02-05 | 2016-05-04 | 山东明德生物医学工程有限公司 | Graphene oxide modified bone cement as well as preparation method and application thereof |
| WO2016128933A1 (en) * | 2015-02-12 | 2016-08-18 | Tecres S.P.A. | Ternary mixture for a bone cement and method for its realisation |
| CN106344963A (en) * | 2016-10-19 | 2017-01-25 | 天津大学 | Graphene oxide modified bone cement and preparation method |
| CN107982576A (en) * | 2017-11-27 | 2018-05-04 | 山东明德生物医学工程有限公司 | A kind of bone cement and preparation method |
-
2018
- 2018-07-06 CN CN201810735161.3A patent/CN109053968B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8557916B1 (en) * | 2013-04-30 | 2013-10-15 | Alfaisal University | Composition and method of making nanocomposite containing graphene sheets |
| CN104623726A (en) * | 2015-01-12 | 2015-05-20 | 西安理工大学 | Injectable water-absorbing and swelling bone cement and preparation method thereof |
| WO2016128933A1 (en) * | 2015-02-12 | 2016-08-18 | Tecres S.P.A. | Ternary mixture for a bone cement and method for its realisation |
| CN104922733A (en) * | 2015-06-19 | 2015-09-23 | 西安理工大学 | Injectable expansion type bone cement and preparation method thereof |
| CN105536050A (en) * | 2016-02-05 | 2016-05-04 | 山东明德生物医学工程有限公司 | Graphene oxide modified bone cement as well as preparation method and application thereof |
| CN106344963A (en) * | 2016-10-19 | 2017-01-25 | 天津大学 | Graphene oxide modified bone cement and preparation method |
| CN107982576A (en) * | 2017-11-27 | 2018-05-04 | 山东明德生物医学工程有限公司 | A kind of bone cement and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Graphene oxide versus functionalized carbon nanotubes as a reinforcing agent in a PMMA/HA bone cement;Gil Goncalves et al.;《nanoscale》;20120229;第2937-2945页 * |
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