CN109053968A - A kind of high expansion multiplying power injectable water swelling bone cement and preparation method thereof - Google Patents
A kind of high expansion multiplying power injectable water swelling bone cement and preparation method thereof Download PDFInfo
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- CN109053968A CN109053968A CN201810735161.3A CN201810735161A CN109053968A CN 109053968 A CN109053968 A CN 109053968A CN 201810735161 A CN201810735161 A CN 201810735161A CN 109053968 A CN109053968 A CN 109053968A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
A kind of high expansion multiplying power injectable water swelling bone cement disclosed by the invention, solid-phase component and liquid phase ingredient are that 1.5g:1ml~2g:1ml is mixed according to mass volume ratio, and Solid raw materials composition includes: the polyethyleneglycol modified graphite oxide alkene copolymer 31%~47% of polymethyl methacrylate 43%~64%, polymethyl methacrylate-acrylic acid-, barium sulfate 5%~10% according to mass percent；Liquid phase feed composition includes methyl methacrylate 26.4%~51.5%, hydroxyethyl methacrylate 33.5%~68.6%, accelerant N, N- dimethyl-p-toluidine 2.5%~5%, retarding agent hydroquinone 2.5%~10%.The invention also discloses the preparation method of the bone cement, solve the problem of existing PMMA bone cement due to volume contraction, intensity is excessive, elasticity modulus is high causes to wear in various degree to joint in human body.
Description
Technical field
The invention belongs to biomaterial for medical purpose preparation technical fields, are related to a kind of high expansion multiplying power injectable water swelling bone
Cement further relates to the preparation method of above-mentioned bone cement.
Background technique
PMMA bone cement is up to 50 years as long as in the clinical application of orthopaedics, gear division, solid from dentistry, joint
It is fixed to be gradually extended to the multiple fields such as bone defect filling, vertebral fracture treatment and the control of localized bone infections, it is orthopaedics application
It is widest in area, quantity is most, the maximum Injectable biomaterials of dosage.Early-stage study personnel bone cement there are aiming at the problem that grind
A kind of injectable water swelling bone cement is sent out, but there are still some problems for the bone cement, limits its curative effect.It is expanded first
Journey occurs mainly in the surface layer that can be contacted with extraneous body fluid, and the inside of water swelling bone cement with extraneous body fluid due to that can not connect
Touching, thus can not water swelling, cause the expansion multiplying power of water swelling bone cement lower.Secondly, bone cement has water suction swollen
Its mechanical property is greatly reduced while swollen performance, lower than the minimum standard of bone cement implantation material 70MPa, can not play preferably
Supporting role.Bulk expansion while there can be mechanical property between polymethyl methacrylate bone water so finding one kind
Mud and the injectable water swelling bone cement of bone cement implantation material mechanical performance minimum standard are the research weights in the current field
One of point.
Chinese patent " a kind of injectable type water swelling bone cement and preparation method thereof " (application number:
201510014513.2, publication date: 2015.05.20, publication number: CN104623726A) to disclose a kind of injectable type water suction swollen
Swollen acrylic acid bone cement and preparation method thereof, disclosed expansion bone cement have certain expansion character, but due to being absorbed water
Its expansion multiplying power of the influence of resin fibre content is lower, and the water-absorbing resin fiber that bone cement surface is contacted with water can expand,
Be embedded in water-absorbing resin fiber inside bone cement then can not water swelling, be consequently belonging to gradient expansion, expansion effect is uneven.In
State's patent " a kind of injectable intumescent bone cement and preparation method thereof " (application number: 201510344651.7, publication date:
2015.09.23, publication number: CN104922733A) disclose a kind of injectable intumescent bone cement and preparation method thereof.Although
The bone cement of the patent disclosure has preferable expansion multiplying power, but expands unevenly, and it is good to show bone cement superficial expansion effect
Inside does not expand this phenomenon, limits the expansion character of bone cement.
Summary of the invention
The object of the present invention is to provide a kind of high expansion multiplying power injectable water swelling bone cements, solve existing poly- methyl-prop
E pioic acid methyl ester bone cement due to volume contraction, intensity is excessive, elasticity modulus is high, in human body joint is caused to wear in various degree
The problem of.
It is a further object of the present invention to provide a kind of methods for preparing the bone cement.
The technical scheme adopted by the invention is that a kind of high expansion multiplying power injectable water swelling bone cement, feature exist
In solid-phase component and liquid phase ingredient are mixed according to mass volume ratio for 1.5g:1ml~2g:1ml, and solid-liquid double-phase changes simultaneously
Property, Solid raw materials composition includes following components according to mass percent: polymethyl methacrylate 43%~64%, poly- methyl-prop
The polyethyleneglycol modified graphite oxide alkene copolymer 31%~47% of e pioic acid methyl ester-acrylic acid-, barium sulfate 5%~10%, each group
The summation divided is 100%；Liquid phase feed composition includes methyl methacrylate 26.4%~51.5%, hydroxyethyl methacrylate
33.5%~68.6%, accelerant N, N- dimethyl-p-toluidine 2.5%~5%, retarding agent hydroquinone 2.5%~10%,
The summation of each component is 100%.
Another technical solution of the invention is, a kind of to prepare a kind of above-mentioned high expansion multiplying power injectable water swelling bone cement
Method, specifically in accordance with the following steps implement:
Step 1. prepares polyethyleneglycol modified graphene oxide:
Ultrasonic disperse in dimethylformamide is added graphene oxide into first and obtains mixed solution a, then by poly- second two
Ultrasonic mixing in round-bottomed flask is added in alcohol and mixed solution a, and appropriate N, bis- ring ethyl carbon two of N- are then added into round-bottomed flask
After imines and 4-dimethylaminopyridine ultrasonic a period of time, isothermal reaction obtains mixed solution b, and mixed solution b is packed into and is dialysed
It dialyses in bag, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, washing is dried to obtain polyethylene glycol after centrifugation
Modify graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
Dispersing agent is dissolved in solvent, and is put into the three-necked flask equipped with condenser pipe, mechanical agitator and nitrogen conduit,
Nitrogen is heated and led to, then, is slowly added to appropriate initiator potassium peroxydisulfate, crosslinking agent N-N methylene-bisacrylamide, methyl-prop
The polyethyleneglycol modified graphite oxide alkene copolymer that the monomer and step 1 of e pioic acid methyl ester and acrylic acid composition obtain, constant temperature are anti-
It should obtain samples of latex；Samples of latex is centrifugated, supernatant liquor is removed, ethyl alcohol is added and washs repeatedly, after vacuum drying
To the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Weigh that polymethyl methacrylate, polymethyl methacrylate-acrylic acid-polyethylene glycol obtained is repaired in step 2
Decorations graphite oxide alkene copolymer and barium sulfate uniformly mix, and obtain high expansion multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Weigh methyl methacrylate, hydroxyethyl methacrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent pair
Benzenediol uniformly mixes, and obtains the liquid phase of high expansion multiplying power injectable type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
It is after the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to a certain percentage, bone cement is quick
It in injection syringe and is injected into the inner cavity of certain shapes, self-curing is to obtain high expansion multiplying power injectable expansion bone cement
Injection moulding and self-curing.
Other features of the invention also reside in,
Polyethyleneglycol modified graphene oxide is prepared in step 1, and detailed process is as follows: by graphene oxide and diformazan
The mass volume ratio of base formamide solvent be 0.1g~0.3g:100mL ultrasonic disperse obtain mixed solution a, by polyethylene glycol with
Mixed solution a is 0.1g~0.2g:50mL ultrasonic mixing according to mass volume ratio, and mass fraction is then added into round-bottomed flask
For graphene oxide 5%~10% dicyclohexylcarbodiimide and 1%~2% 4-dimethylaminopyridine ultrasound 30min~
After 60min, 12h mixed solution b is reacted at 60 DEG C~70 DEG C, mixed solution b is fitted into bag filter and is dialysed 1 week, remove trip
From polyethylene glycol and catalyst 4-dimethylaminopyridine, after centrifugation washing be dried to obtain polyethyleneglycol modified graphene oxide；
Dispersing agent is polyvinylpyrrolidone in step 2, and solvent is the mixed solution of water or ethyl alcohol or water and ethyl alcohol, is caused
Benzoyl peroxide also can be selected in agent.
The quality of methyl methacrylate and acrylic acid in the monomer that methyl methacrylate and acrylic acid form in step 2
Than for 1.38:1, the quality of dispersing agent is the 7%~10% of monomer gross mass, crosslinking agent quality be monomer gross mass 1%~
10%, initiator quality is the 1%~3% of monomer gross mass, and the quality of polyethyleneglycol modified graphene oxide is the total matter of monomer
The 1%~5% of amount.
The condition reacted in three-necked flask in step 2 is: 50 DEG C~55 DEG C of heating temperature, the time for leading to nitrogen is 0.5h
~1h, the time for obtaining samples of latex isothermal reaction is 6h~12h；Vacuum drying condition is: temperature is 50 DEG C~70 DEG C, when
Between be 8h~12h.
Polymethyl methacrylate in step 3, polymethyl methacrylate-acrylic acid-polyethylene glycol obtained in step 2
The mass percent of modification graphite oxide alkene copolymer and barium sulfate is respectively as follows: 43%~64%, 31%~47%, 5%~
10%.
Methyl methacrylate, hydroxyethyl methacrylate, accelerant N in step 4, N- dimethyl-p-toluidine, retardance
The mass percent of agent hydroquinone is respectively 26.4%~51.5%, 33.5%~68.6%, 2.5%~5%, 2.5%~
10%.
The mass volume ratio of solid phase and liquid phase ingredient is 1.5g~2g:1ml in step 5, and the condition of self-curing is that temperature is
35 DEG C~40 DEG C, humidity 100%, the time is 10min~30min.
The invention has the advantages that a kind of high expansion multiplying power injectable water swelling bone cement, solves existing poly- methyl
Methyl acrylate bone cement due to volume contraction, intensity is excessive, elasticity modulus is high, in human body joint is caused to grind in various degree
The problem of damage.The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-is introduced in solid phase,
Hydroxyethyl methacrylate is introduced in liquid phase, solid-liquid double-phase can cooperate with water suction, and the water suction for improving water swelling bone cement is swollen
Swollen multiplying power improves material internal and expands non-uniform problem；Simultaneously because containing the preferable graphene oxide of elasticity modulus, inhale
The mechanical property of water expansion bone cement expansion front and back has been greatly improved, therefore clinically with good application prospect.
Specific embodiment
The present invention is described in detail With reference to embodiment.
A kind of high expansion multiplying power injectable water swelling bone cement of the invention, solid-phase component and liquid phase ingredient are according to quality
Volume ratio is that 1.5g:1ml~2g:1ml is mixed, and solid-liquid double-phase is modified simultaneously, and Solid raw materials are formed according to mass percent
Including following components: polymethyl methacrylate 43%~64%, polymethyl methacrylate-acrylic acid-are polyethyleneglycol modified
Graphite oxide alkene copolymer 31%~47%, barium sulfate 5%~10%, the summation of each component is 100%；Liquid phase feed composition
Including methyl methacrylate 26.4%~51.5%, hydroxyethyl methacrylate 33.5%~68.6%, accelerant N, N- bis-
Methyl para-totuidine 2.5%~5%, retarding agent hydroquinone 2.5%~10%, the summation of each component are 100%.
A kind of preparation method of high expansion multiplying power injectable water swelling bone cement of the invention, specifically in accordance with the following steps
Implement:
Step 1. prepares polyethyleneglycol modified graphene oxide:
Ultrasonic disperse in dimethylformamide is added graphene oxide into first and obtains mixed solution a, then by poly- second two
Ultrasonic mixing in round-bottomed flask is added in alcohol and mixed solution a, and appropriate N, bis- ring ethyl carbon two of N- are then added into round-bottomed flask
After imines and 4-dimethylaminopyridine ultrasonic a period of time, isothermal reaction obtains mixed solution b, and mixed solution b is packed into and is dialysed
It dialyses in bag, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, washing is dried to obtain polyethylene glycol after centrifugation
Modify graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
Dispersing agent is dissolved in solvent, and is put into the three-necked flask equipped with condenser pipe, mechanical agitator and nitrogen conduit,
Nitrogen is heated and led to, then, is slowly added to appropriate initiator potassium peroxydisulfate, crosslinking agent N-N methylene-bisacrylamide, methyl-prop
The polyethyleneglycol modified graphite oxide alkene copolymer that the monomer and step 1 of e pioic acid methyl ester and acrylic acid composition obtain, constant temperature are anti-
It should obtain samples of latex；Samples of latex is centrifugated, supernatant liquor is removed, ethyl alcohol is added and washs repeatedly, after vacuum drying
To the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Weigh that polymethyl methacrylate, polymethyl methacrylate-acrylic acid-polyethylene glycol obtained is repaired in step 2
Decorations graphite oxide alkene copolymer and barium sulfate uniformly mix, and obtain high expansion multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Weigh methyl methacrylate, hydroxyethyl methacrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent pair
Benzenediol uniformly mixes, and obtains the liquid phase of high expansion multiplying power injectable type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
It is after the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to a certain percentage, bone cement is quick
It in injection syringe and is injected into the inner cavity of certain shapes, self-curing is to obtain high expansion multiplying power injectable expansion bone cement
Injection moulding and self-curing.
Polyethyleneglycol modified graphene oxide is prepared in step 1, and detailed process is as follows: by graphene oxide and diformazan
The mass volume ratio of base formamide solvent be 0.1g~0.3g:100mL ultrasonic disperse obtain mixed solution a, by polyethylene glycol with
Mixed solution a is 0.1g~0.2g:50mL ultrasonic mixing according to mass volume ratio, and mass fraction is then added into round-bottomed flask
For graphene oxide 5%~10% dicyclohexylcarbodiimide and 1%~2% 4-dimethylaminopyridine ultrasound 30min~
After 60min, 12h mixed solution b is reacted at 60 DEG C~70 DEG C, mixed solution b is fitted into bag filter and is dialysed 1 week, remove trip
From polyethylene glycol and catalyst 4-dimethylaminopyridine, after centrifugation washing be dried to obtain polyethyleneglycol modified graphene oxide；
Dispersing agent is polyvinylpyrrolidone in step 2, and solvent is the mixed solution of water or ethyl alcohol or water and ethyl alcohol, is caused
Benzoyl peroxide also can be selected in agent.
The quality of methyl methacrylate and acrylic acid in the monomer that methyl methacrylate and acrylic acid form in step 2
Than for 1.38:1, the quality of dispersing agent is the 7%~10% of monomer gross mass, crosslinking agent quality be monomer gross mass 1%~
10%, initiator quality is the 1%~3% of monomer gross mass, and the quality of polyethyleneglycol modified graphene oxide is the total matter of monomer
The 1%~5% of amount.
The condition reacted in three-necked flask in step 2 is: 50 DEG C~55 DEG C of heating temperature, the time for leading to nitrogen is 0.5h
~1h, the time for obtaining samples of latex isothermal reaction is 6h~12h；Vacuum drying condition is: temperature is 50 DEG C~70 DEG C, when
Between be 8h~12h.
Polymethyl methacrylate in step 3, polymethyl methacrylate-acrylic acid-polyethylene glycol obtained in step 2
The mass percent of modification graphite oxide alkene copolymer and barium sulfate is respectively as follows: 43%~64%, 31%~47%, 5%~
10%.
Methyl methacrylate, hydroxyethyl methacrylate, accelerant N in step 4, N- dimethyl-p-toluidine, retardance
The mass percent of agent hydroquinone is respectively 26.4%~51.5%, 33.5%~68.6%, 2.5%~5%, 2.5%~
10%.
The mass volume ratio of solid phase and liquid phase ingredient is 1.5g~2g:1ml in step 5, and the condition of self-curing is that temperature is
35 DEG C~40 DEG C, humidity 100%, the time is 10min~30min.
The reason of selective oxidation graphene of the present invention is that graphene oxide (Graphene Oxide) is the derivative of graphene
Object is product of the powdered graphite after chemical oxidation and removing, and after oxidation processes, graphite oxide still keeps the stratiform of graphite
Structure, but a large amount of oxygen-containing functional group is introduced on each layer of graphene monolithic, wherein hydroxyl and epoxy group are mainly distributed
Inside sheet, carboxyl and carbonyl are mainly distributed on lamella edge, therefore have preferable hydrophilicity.In addition, due to oxygen
Graphite alkene has stronger adsorption capacity and good biocompatibility, and a variety of covalent reactions and non-covalent reaction can occur, because
This has a wide range of applications in field of biomedicine.Graphene oxide is due to containing more hydrophilic radical, in water
Dispersibility preferably, but the dispersibility in PMMA bone cement is poor, is easy to reunite to influence the performance of bone cement.This hair
It is bright be directed to this problem, graphene oxide is modified, using have been found can in physiological environment stable dispersion poly- second
Glycol modifies graphene oxide, makes it that can be uniformly dispersed in bone cement.In addition, the hydroxyethyl methacrylate of selection
It (HEMA) is a kind of common high molecular material of biomedicine, monomer and polymer have preferable biocompatibility, extensively
Applied to dentures, medicament slow release, burn coating, organ transplant, contact lense manufacture, cell culture and biomolecule and enzyme immobilization
Etc..There is carbon-carbon double bond structure, double bond opening can be copolymerized with MMA under certain condition in HEMA structure.Due to
The presence of HEMA backbone, thus with MMA monomer copolymerization after can increase backbone length, make copolymer have preferable intensity and
Hardness.Meanwhile HEMA long chain end has hydrophilic radical hydroxyl, is conducive to materials serve water sorption, therefore substitute with HEMA
Or part substitution MMA can assign bone cement water suction, water conservation while guaranteeing that bone cement has rapid polymerization as liquid phase
Characteristic, promoted the water swelling of water swelling bone cement uniformity coefficient.
A kind of high expansion multiplying power injectable type water swelling bone cement that the present invention is, it is creative in the solid phase of bone cement
By polymethyl methacrylate-acrylic copolymer with water absorption behavior and contain the poly- second two of a large amount of hydrophilic radicals
Poly- methyl-prop has been made by solution polymerization process under the action of crosslinking agent and initiator in alcohol modification graphene oxide (PEG-GO)
The polyethyleneglycol modified graphene oxide of e pioic acid methyl ester-acrylic acid-(PMMA-PAA-PEG-GO), the polyethylene glycol of two-dimensional slice stratiform
Graphene oxide is modified due to having preferable dispersibility in bone cement, can be uniformly distributed in the solid phase of bone cement
In, it is in connection by hydrogen bond that excellent water-wet behavior makes the moisture outside bone cement, and then in hydrone is transmitted to
Certain bridged appearances are played the role of in portion, to make the polymethylacrylic acid of the internal tridimensional network containing hydrophilic radical
Methyl esters-acrylic copolymer can water swelling, improve water swelling bone cement bulk expansion performance；Meanwhile sheet
Graphene oxide has preferable mechanical property, and elasticity modulus is in 200-300GPa, therefore the addition of graphene oxide can mention
Mechanical property before and after high bone cement water swelling.With the part HEMA substitution MMA, hydroxyethyl methacrylate second in the liquid phase of bone cement
Ester (HEMA) belongs to the derivative of methacrylic acid, wherein the presence of double bond make its under the action of initiator can and MMA into
Row polymerization, HEMA is water-soluble monomer, and there is allotment chains in molecular structure, and the hydroxyl on branch be capable of forming it is relatively strong
Hydrogen bond, during polymerization or copolymerization, these allotment chain structures can mutually be wound, and be capable of forming hydrogen bond, formed
It is physical crosslinking structure and chemical crosslinking structure.HEMA is can be uniformly distributed in solid-liquid mixed process in bone cement block, right
Moisture plays the role of transmitting, while polymer poly methyl methacrylate-propylene of water swelling can will be played in solid phase
Acid-polyethyleneglycol modified graphene oxide (PMMA-PAA-PEG-GO) preferably links together, and improves the whole of bone cement and inhales
Water swelliong power.The introducing of hydrophilic radical can also promote bone cement interior three-dimensional rigid while improving hydrone transport efficiency
The water swelling effect of property network structure, the solid phase of bone cement will cooperate with water swelling with liquid phase, and further increase water swelling
The expansion character of bone cement.
Specific embodiment is as follows:
Embodiment 1
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.1g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.1g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Then the N of graphene oxide mass fraction 5%, N- bicyclic ethyl carbodiimide and 1% is added in sound mixing into round-bottomed flask
After 4-dimethylaminopyridine ultrasound 30min, 60 DEG C of isothermal reaction 12h obtain mixed solution b, and mixed solution b is packed into bag filter
Middle dialysis 1 week, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, and washing is dried to obtain polyethylene glycol after centrifugation
Modify graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 10% is soluble in water, and put into and condenser pipe, mechanical stirring are housed
In the three-necked flask of device and nitrogen conduit, it is heated to 50 DEG C and logical nitrogen 1h and is then slowly added to according to mass ratio (1.38:1)
The monomer of methyl methacrylate (MMA) and acrylic acid (AA) composition, is stirring evenly and then adding into the initiator mistake of 1% mass fraction
The poly- second two that potassium sulfate, the crosslinking agent N-N methylene-bisacrylamide of 5% mass fraction and 1% mass fraction step 1 obtain
Alcohol modifies graphite oxide alkene copolymer, and 50 DEG C of reaction 6h of constant temperature obtain samples of latex；Samples of latex is centrifugated, upper layer is removed
Clear liquid is added ethyl alcohol and washs repeatedly, obtains polymethyl methacrylate-acrylic acid-polyethylene glycol after 50 DEG C of vacuum drying 8h and repair
Adorn graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Polymethyl methacrylate is successively weighed for 43%, 47%, 10% by mass percentage respectively, is made in step 2
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, obtain height
Expansion multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate is successively weighed for 26.4%, 68.6%, 2.5%, 2.5% according to mass percent respectively,
Hydroxyethyl methacrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtain high expansion times
The liquid phase of rate injectable type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
After the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 1.5g:1mL,
Bone cement is rapidly injected in the inner cavity in syringe and being injected into certain shapes, is 35 DEG C in temperature, the item that humidity is 100%
Self-curing 10min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement under part.
Embodiment 2
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.3g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.1g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Sound mixing, is then added the N of graphene oxide mass fraction 10%, N- bicyclic ethyl carbodiimide and 2% into round-bottomed flask
4-dimethylaminopyridine ultrasound 60min after, 70 DEG C of isothermal reaction 12h obtain mixed solution b, by mixed solution b be packed into dialyse
It dialyses 1 week in bag, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, washing is dried to obtain poly- second two after centrifugation
Alcohol modifies graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 7% is soluble in water, and put into and condenser pipe, mechanical agitator are housed
In the three-necked flask of nitrogen conduit, it is heated to 55 DEG C and logical nitrogen 0.5h and is then slowly added to according to mass ratio (1.38:1)
Monomers methyl methacrylate (MMA) and acrylic acid (AA), are stirring evenly and then adding into the initiator persulfuric acid of 3% mass fraction
The polyethylene glycol that potassium, the crosslinking agent N-N methylene-bisacrylamide of 8% mass fraction and 3% mass fraction step 1 obtain is repaired
Graphite oxide alkene copolymer is adornd, 55 DEG C of reaction 8h of constant temperature obtain samples of latex；Samples of latex is centrifugated, it is clear to remove upper layer
Liquid is added ethyl alcohol and washs repeatedly, and it is polyethyleneglycol modified to obtain polymethyl methacrylate-acrylic acid-after 60 DEG C of vacuum drying 10h
Graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Respectively by mass percentage for 64%, 31%, 5% successively weigh polymethyl methacrylate, in step 2 it is obtained
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, and obtain high swollen
Swollen multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, methyl are successively weighed for 51.5%, 33.5%, 5%, 10% according to mass percent respectively
Hydroxy-ethyl acrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtaining high expansion multiplying power can
The liquid phase of injection-type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
After the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 1.8g:1mL,
Bone cement is rapidly injected in the inner cavity in syringe and being injected into certain shapes, is 40 DEG C in temperature, the item that humidity is 100%
Self-curing 20min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement under part.
Embodiment 3
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.2g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.2g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Then the N of graphene oxide mass fraction 8%, N- bicyclic ethyl carbodiimide and 1% is added in sound mixing into round-bottomed flask
After 4-dimethylaminopyridine ultrasound 45min, 60 DEG C of isothermal reaction 12h obtain mixed solution b, and mixed solution b is packed into bag filter
Middle dialysis 1 week, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, and washing is dried to obtain polyethylene glycol after centrifugation
Modify graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 8% is soluble in water, and put into and condenser pipe, mechanical agitator are housed
In the three-necked flask of nitrogen conduit, it is heated to 50 DEG C and logical nitrogen 0.5h and is then slowly added to according to mass ratio (1.38:1)
Monomers methyl methacrylate (MMA) and acrylic acid (AA), are stirring evenly and then adding into the initiator persulfuric acid of 2% mass fraction
The polyethylene glycol that potassium, the crosslinking agent N-N methylene-bisacrylamide of 6% mass fraction and 5% mass fraction step 1 obtain is repaired
Graphite oxide alkene copolymer is adornd, 55 DEG C of reaction 10h of constant temperature obtain samples of latex；Samples of latex is centrifugated, it is clear to remove upper layer
Liquid is added ethyl alcohol and washs repeatedly, and it is polyethyleneglycol modified to obtain polymethyl methacrylate-acrylic acid-after 70 DEG C of vacuum drying 8h
Graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Respectively by mass percentage for 51%, 42%, 7% successively weigh polymethyl methacrylate, in step 2 it is obtained
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, and obtain high swollen
Swollen multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, first are successively weighed for 32.3%, 60.1%, 5%, 2.6% according to mass percent respectively
Base hydroxy-ethyl acrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtain high expansion multiplying power
The liquid phase of injectable type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
After the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 1.6g:1mL,
Bone cement is rapidly injected in the inner cavity in syringe and being injected into certain shapes, is 35 DEG C in temperature, the item that humidity is 100%
Self-curing 30min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement under part.
Embodiment 4
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.25g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.1g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Then the N of graphene oxide mass fraction 5%, N- bicyclic ethyl carbodiimide and 1% is added in sound mixing into round-bottomed flask
After 4-dimethylaminopyridine ultrasound 35min, 70 DEG C of isothermal reaction 12h obtain mixed solution b, and mixed solution b is packed into bag filter
Middle dialysis 1 week, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, and washing is dried to obtain polyethylene glycol after centrifugation
Modify graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 9% is soluble in water, and put into and condenser pipe, mechanical agitator are housed
In the three-necked flask of nitrogen conduit, it is heated to 55 DEG C and logical nitrogen 1h and is then slowly added to list according to mass ratio (1.38:1)
Body methyl methacrylate (MMA) and acrylic acid (AA), be stirring evenly and then adding into 3% mass fraction initiator potassium persulfate,
The crosslinking agent N-N methylene-bisacrylamide of 3% mass fraction and 4% mass fraction step 1 obtain polyethyleneglycol modified
Graphite oxide alkene copolymer, 55 DEG C of reaction 12h of constant temperature obtain samples of latex；Samples of latex is centrifugated, supernatant liquor is removed,
Ethyl alcohol is added to wash repeatedly, obtains the polyethyleneglycol modified oxygen of polymethyl methacrylate-acrylic acid-after 50 DEG C of vacuum drying 12h
Graphite alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Respectively by mass percentage for 45%, 47%, 8% successively weigh polymethyl methacrylate, in step 2 it is obtained
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, and obtain high swollen
Swollen multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, methyl are successively weighed for 42.1%, 48.9%, 3%, 6% according to mass percent respectively
Hydroxy-ethyl acrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtaining high expansion multiplying power can
The liquid phase of injection-type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
It, will after the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 2g:1mL
Bone cement is rapidly injected in syringe and is injected into the inner cavity of certain shapes, is 35 DEG C in temperature, the condition that humidity is 100%
Lower self-curing 25min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement.
Embodiment 5
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.15g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.12g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Sound mixing, then into round-bottomed flask be added graphene oxide mass fraction 10% N, N- bicyclic ethyl carbodiimide and
After 1.5% 4-dimethylaminopyridine ultrasound 40min, 60 DEG C of isothermal reaction 12h obtain mixed solution b, and mixed solution b is packed into
It dialyses 1 week in bag filter, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, washing is dried to obtain poly- after centrifugation
Ethylene glycol modifies graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 10% is soluble in water, and put into and condenser pipe, mechanical stirring are housed
In the three-necked flask of device and nitrogen conduit, 53 DEG C and logical nitrogen 0.6h are heated to, then, is slowly added according to mass ratio (1.38:1)
Enter monomers methyl methacrylate (MMA) and acrylic acid (AA), is stirring evenly and then adding into the initiator over cure of 2.5% mass fraction
The polyethylene glycol that sour potassium, the crosslinking agent N-N methylene-bisacrylamide of 1% mass fraction and 1% mass fraction step 1 obtain
Graphite oxide alkene copolymer is modified, 50 DEG C of reaction 9h of constant temperature obtain samples of latex；Samples of latex is centrifugated, it is clear to remove upper layer
Liquid is added ethyl alcohol and washs repeatedly, and it is polyethyleneglycol modified to obtain polymethyl methacrylate-acrylic acid-after 65 DEG C of vacuum drying 10h
Graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Polymethyl methacrylate is successively weighed for 45%, 45%, 10% by mass percentage respectively, is made in step 2
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, obtain height
Expansion multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, methyl are successively weighed for 46.6%, 40.4%, 4%, 9% according to mass percent respectively
Hydroxy-ethyl acrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtaining high expansion multiplying power can
The liquid phase of injection-type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
It, will after the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 2g:1mL
Bone cement is rapidly injected in syringe and is injected into the inner cavity of certain shapes, is 40 DEG C in temperature, the condition that humidity is 100%
Lower self-curing 15min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement.
Embodiment 6
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.3g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.2g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Then the N of graphene oxide mass fraction 6%, N- bicyclic ethyl carbodiimide and 1% is added in sound mixing into round-bottomed flask
After 4-dimethylaminopyridine ultrasound 50min, 70 DEG C of isothermal reaction 12h obtain mixed solution b, and mixed solution b is packed into bag filter
Middle dialysis 1 week, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, and washing is dried to obtain polyethylene glycol after centrifugation
Modify graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 8.5% is soluble in water, and put into and condenser pipe, mechanical stirring are housed
In the three-necked flask of device and nitrogen conduit, 54 DEG C and logical nitrogen 0.5h are heated to, then, is slowly added according to mass ratio (1.38:1)
Enter monomers methyl methacrylate (MMA) and acrylic acid (AA), is stirring evenly and then adding into the initiator over cure of 1.5% mass fraction
The polyethylene glycol that sour potassium, the crosslinking agent N-N methylene-bisacrylamide of 2% mass fraction and 4% mass fraction step 1 obtain
Graphite oxide alkene copolymer is modified, 52 DEG C of reaction 7h of constant temperature obtain samples of latex；Samples of latex is centrifugated, it is clear to remove upper layer
Liquid is added ethyl alcohol and washs repeatedly, and it is polyethyleneglycol modified to obtain polymethyl methacrylate-acrylic acid-after 70 DEG C of vacuum drying 9h
Graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Respectively by mass percentage for 52%, 42%, 6% successively weigh polymethyl methacrylate, in step 2 it is obtained
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, and obtain high swollen
Swollen multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, metering system are successively weighed for 35%, 50%, 5%, 10% according to mass percent respectively
Sour hydroxyl ethyl ester, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtain high expansion multiplying power injectable
The liquid phase of type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
After the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 1.5g:1mL,
Bone cement is rapidly injected in the inner cavity in syringe and being injected into certain shapes, is 40 DEG C in temperature, the item that humidity is 100%
Self-curing 10min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement under part.
Embodiment 7
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.1g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.15g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Sound mixing, is then added the N of graphene oxide mass fraction 7.5%, N- bicyclic ethyl carbodiimide and 2% into round-bottomed flask
4-dimethylaminopyridine ultrasound 40min after, 60 DEG C of isothermal reaction 12h obtain mixed solution b, by mixed solution b be packed into dialyse
It dialyses 1 week in bag, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, washing is dried to obtain poly- second two after centrifugation
Alcohol modifies graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 7% is soluble in water, and put into and condenser pipe, mechanical agitator are housed
In the three-necked flask of nitrogen conduit, it is heated to 52 DEG C and logical nitrogen 0.8h and is then slowly added to according to mass ratio (1.38:1)
Monomers methyl methacrylate (MMA) and acrylic acid (AA), are stirring evenly and then adding into the initiator persulfuric acid of 1% mass fraction
The poly- second two that potassium, the crosslinking agent N-N methylene-bisacrylamide of 5.5% mass fraction and 1.5% mass fraction step 1 obtain
Alcohol modifies graphite oxide alkene copolymer, and 54 DEG C of reaction 6h of constant temperature obtain samples of latex；Samples of latex is centrifugated, upper layer is removed
Clear liquid is added ethyl alcohol and washs repeatedly, obtains polymethyl methacrylate-acrylic acid-polyethylene glycol after 50 DEG C of vacuum drying 12h and repair
Adorn graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Respectively by mass percentage for 53%, 40%, 7% successively weigh polymethyl methacrylate, in step 2 it is obtained
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, and obtain high swollen
Swollen multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, methyl are successively weighed for 38%, 52%, 2.5%, 7.5% according to mass percent respectively
Hydroxy-ethyl acrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtaining high expansion multiplying power can
The liquid phase of injection-type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
After the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 1.7g:1mL,
Bone cement is rapidly injected in the inner cavity in syringe and being injected into certain shapes, is 36 DEG C in temperature, the item that humidity is 100%
Self-curing 20min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement under part.
Embodiment 8
Step 1. prepares polyethyleneglycol modified graphene oxide:
It is that 0.3g:100mL adds graphene oxide into ultrasonic disperse in dimethylformamide first, in accordance with quality volume
Mixed solution a is obtained, is that 0.18g:50mL will surpass in polyethylene glycol and mixed solution a addition round-bottomed flask according still further to quality volume
Sound mixing, then into round-bottomed flask be added graphene oxide mass fraction 5.5% N, N- bicyclic ethyl carbodiimide and
After 1.2% 4-dimethylaminopyridine ultrasound 60min, 60 DEG C of isothermal reaction 12h obtain mixed solution b, and mixed solution b is packed into
It dialyses 1 week in bag filter, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, washing is dried to obtain poly- after centrifugation
Ethylene glycol modifies graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
The polyvinylpyrrolidone of monomer mass score 9.5% is soluble in water, and put into and condenser pipe, mechanical stirring are housed
In the three-necked flask of device and nitrogen conduit, 55 DEG C and logical nitrogen 0.7h are heated to, then, is slowly added according to mass ratio (1.38:1)
Enter monomers methyl methacrylate (MMA) and acrylic acid (AA), is stirring evenly and then adding into the initiator persulfuric acid of 3% mass fraction
The polyethylene glycol that potassium, the crosslinking agent N-N methylene-bisacrylamide of 10% mass fraction and 5% mass fraction step 1 obtain
Graphite oxide alkene copolymer is modified, 50 DEG C of reaction 11h of constant temperature obtain samples of latex；Samples of latex is centrifugated, upper layer is removed
Clear liquid is added ethyl alcohol and washs repeatedly, obtains polymethyl methacrylate-acrylic acid-polyethylene glycol after 55 DEG C of vacuum drying 11h and repair
Adorn graphite oxide alkene copolymer；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Respectively by mass percentage for 58%, 37%, 5% successively weigh polymethyl methacrylate, in step 2 it is obtained
The polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-and barium sulfate uniformly mix, and obtain high swollen
Swollen multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate, methyl are successively weighed for 49.5%, 37.5%, 5%, 8% according to mass percent respectively
Hydroxy-ethyl acrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent hydroquinone uniformly mix, and obtaining high expansion multiplying power can
The liquid phase of injection-type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
It will be obtained in the solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and step 4
It, will after the liquid phase of high expansion multiplying power injectable type water swelling bone cement is uniformly mixed according to mass volume ratio for 2g:1mL
Bone cement is rapidly injected in syringe and is injected into the inner cavity of certain shapes, is 38 DEG C in temperature, the condition that humidity is 100%
Lower self-curing 25min is to obtain injection moulding and the self-curing of high expansion multiplying power injectable expansion bone cement.
It is the high expansion multiplying power injectable type water swelling bone cement being prepared in the embodiment of the present invention and tradition below
The comparison of PMMA bone cement:
As can be seen from the above table, compared with traditional PMMA bone cement, since the high expansion multiplying power that the present invention is prepared can
The modified biphase cooperative water suction of injection-type water swelling bone cement solid liquid phase, therefore there is preferable water absorbent rate and expansion times
Rate, meanwhile, mechanical property is substantially reduced compared with PMMA bone cement, but the presence of graphene oxide makes water swelling bone cement
Compression strength is not greatly lowered, and meets the minimum standard of bone cement implantation material 70MPa.
Claims (9)
1. a kind of high expansion multiplying power injectable water swelling bone cement, which is characterized in that solid-phase component and liquid phase ingredient are according to matter
Amount volume ratio is that 1.5g:1ml~2g:1ml is mixed, and solid-liquid double-phase is modified simultaneously, and Solid raw materials are formed according to quality percentage
Than including following components: polymethyl methacrylate 43%~64%, polymethyl methacrylate-acrylic acid-polyethylene glycol are repaired
Graphite oxide alkene copolymer 31%~47%, the barium sulfate 5%~10% of decorations, the summation of each component is 100%；Liquid phase feed group
At including methyl methacrylate 26.4%~51.5%, hydroxyethyl methacrylate 33.5%~68.6%, accelerant N, N-
Dimethyl-p-toluidine 2.5%~5%, retarding agent hydroquinone 2.5%~10%, the summation of each component are 100%.
2. a kind of prepare a kind of method of high expansion multiplying power injectable water swelling bone cement as described in claim 1, specifically
Implement in accordance with the following steps:
Step 1. prepares polyethyleneglycol modified graphene oxide:
Add graphene oxide into ultrasonic disperse in dimethylformamide first and obtain mixed solution a, then by polyethylene glycol with
Ultrasonic mixing in round-bottomed flask is added in mixed solution a, and appropriate N, N- bicyclic ethyl carbodiimide are then added into round-bottomed flask
After 4-dimethylaminopyridine ultrasonic a period of time, isothermal reaction obtains mixed solution b, and mixed solution b is fitted into bag filter
Dialysis, removes free polyethylene glycol and catalyst 4-dimethylaminopyridine, and washing is dried to obtain polyethyleneglycol modified after centrifugation
Graphene oxide；
Step 2. prepares the polyethyleneglycol modified graphite oxide alkene copolymer of polymethyl methacrylate-acrylic acid-:
Dispersing agent is dissolved in solvent, and is put into the three-necked flask equipped with condenser pipe, mechanical agitator and nitrogen conduit, heating
And then logical nitrogen is slowly added to appropriate initiator potassium peroxydisulfate, crosslinking agent N-N methylene-bisacrylamide, methacrylic acid
The polyethyleneglycol modified graphite oxide alkene copolymer that the monomer and step 1 of methyl esters and acrylic acid composition obtain, isothermal reaction obtain
To samples of latex；Samples of latex is centrifugated, supernatant liquor is removed, ethyl alcohol is added and washs repeatedly, is gathered after vacuum drying
The polyethyleneglycol modified graphite oxide alkene copolymer of methyl methacrylate-acrylic acid-；
The solid phase of step 3. preparation high expansion multiplying power injectable type water swelling bone cement:
Weigh polymethyl methacrylate, the polyethyleneglycol modified oxygen of polymethyl methacrylate-acrylic acid-obtained in step 2
Graphite alkene copolymer and barium sulfate uniformly mix, and obtain high expansion multiplying power injectable type water swelling bone cement solid phase；
The liquid phase of step 4. preparation high expansion multiplying power injectable type water swelling bone cement:
Methyl methacrylate is weighed, hydroxyethyl methacrylate, accelerant N, N- dimethyl-p-toluidine, retarding agent is to benzene two
Phenol uniformly mixes, and obtains the liquid phase of high expansion multiplying power injectable type water swelling bone cement；
Step 5. prepares high expansion multiplying power injectable water swelling bone cement:
The solid phase of high expansion multiplying power injectable type water swelling bone cement obtained in step 3 and height obtained in step 4 is swollen
After the liquid phase of swollen multiplying power injectable type water swelling bone cement is uniformly mixed according to a certain percentage, bone cement is rapidly injected
It in syringe and is injected into the inner cavity of certain shapes, self-curing is to obtain the injection of high expansion multiplying power injectable expansion bone cement
Molding and self-curing.
3. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In preparing polyethyleneglycol modified graphene oxide in the step 1, detailed process is as follows: by graphene oxide and dimethyl
The mass volume ratio of formamide solvent is that 0.1g~0.3g:100mL ultrasonic disperse obtains mixed solution a, by polyethylene glycol and is mixed
It is 0.1g~0.2g:50mL ultrasonic mixing that solution a, which is closed, according to mass volume ratio, and mass fraction is then added into round-bottomed flask and is
The dicyclohexylcarbodiimide of graphene oxide 5%~10% and 1%~2% 4-dimethylaminopyridine ultrasound 30min~
After 60min, 12h mixed solution b is reacted at 60 DEG C~70 DEG C, mixed solution b is fitted into bag filter and is dialysed 1 week, remove trip
From polyethylene glycol and catalyst 4-dimethylaminopyridine, after centrifugation washing be dried to obtain polyethyleneglycol modified graphene oxide.
4. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In dispersing agent is polyvinylpyrrolidone in the step 2, and solvent is the mixed solution of water or ethyl alcohol or water and ethyl alcohol, is caused
Benzoyl peroxide also can be selected in agent.
5. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In the quality of methyl methacrylate and acrylic acid in the monomer that methyl methacrylate and acrylic acid form in the step 2
Than for 1.38:1, the quality of dispersing agent is the 7%~10% of monomer gross mass, crosslinking agent quality be monomer gross mass 1%~
10%, initiator quality is the 1%~3% of monomer gross mass, and the quality of polyethyleneglycol modified graphene oxide is the total matter of monomer
The 1%~5% of amount.
6. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In the condition reacted in three-necked flask in the step 2 is: 50 DEG C~55 DEG C of heating temperature, the time for leading to nitrogen is 0.5h
~1h, the time for obtaining samples of latex isothermal reaction is 6h~12h；Vacuum drying condition is: temperature is 50 DEG C~70 DEG C, when
Between be 8h~12h.
7. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In polymethyl methacrylate in the step 3, polymethyl methacrylate-acrylic acid-polyethylene glycol obtained in step 2
The mass percent of modification graphite oxide alkene copolymer and barium sulfate is respectively as follows: 43%~64%, 31%~47%, 5%~
10%.
8. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In, methyl methacrylate, hydroxyethyl methacrylate, accelerant N in the step 4, N- dimethyl-p-toluidine, retarding agent
The mass percent of hydroquinone is respectively 26.4%~51.5%, 33.5%~68.6%, 2.5%~5%, 2.5%~
10%.
9. a kind of preparation method of high expansion multiplying power injectable water swelling bone cement as claimed in claim 2, feature exist
In the mass volume ratio of solid phase and liquid phase ingredient is 1.5g~2g:1ml in the step 5, and the condition of self-curing is that temperature is 35
DEG C~40 DEG C, humidity 100%, the time is 10min~30min.
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| CN111317861A (en) * | 2020-03-20 | 2020-06-23 | 西安理工大学 | Expansion acrylic acid bone cement capable of controlling release of antibiotics and preparation method thereof |
| CN114984310A (en) * | 2022-06-30 | 2022-09-02 | 西安理工大学 | Anti-collapsibility water-swelling organic-inorganic composite bone cement and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111317861A (en) * | 2020-03-20 | 2020-06-23 | 西安理工大学 | Expansion acrylic acid bone cement capable of controlling release of antibiotics and preparation method thereof |
| CN111317861B (en) * | 2020-03-20 | 2022-02-18 | 西安理工大学 | Expansion acrylic acid bone cement capable of controlling release of antibiotics and preparation method thereof |
| CN114984310A (en) * | 2022-06-30 | 2022-09-02 | 西安理工大学 | Anti-collapsibility water-swelling organic-inorganic composite bone cement and preparation method thereof |
| CN114984310B (en) * | 2022-06-30 | 2023-09-08 | 西安理工大学 | Organic-inorganic composite bone cement capable of resisting collapse, absorbing water and expanding and preparation method thereof |
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