CN106620841A - Low-temperature injectable acrylic resin bone cement and preparation method thereof - Google Patents
Low-temperature injectable acrylic resin bone cement and preparation method thereof Download PDFInfo
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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Abstract
The invention relates to low-temperature injectable acrylic resin bone cement and a preparation method thereof. The low-temperature injectable acrylic resin bone cement comprises a solid phase and a liquid phase, wherein the solid-to-liquid ratio of the solid phase and the liquid phase is 0.25mL/g to 0.5mL/g; the solid phase is prepared from the following components in percentage by mass: 25 weight percent to 80 weight percent of a component A and 20 weight percent to 75 weight percent of a component B, wherein the component A comprises 59.5 weight percent to 99.5 weight percent of a powdery acrylics resin polymer and 0.5 weight percent to 2 weight percent of a peroxide initiator; the liquid phase is prepared from the following components in percentage by volume: 95 volume percent to 99.9 volume percent of an acrylics monomer and 0.1 volume percent to 5 volume percent of an accelerant; the component B is granules prepared by mixing the component A and the liquid phase at the solid-to-liquid ratio of 0.25mL/g to 0.8mL/g. The low-temperature injectable acrylic resin bone cement provided by the invention is low in heat releasing temperature in a curing process; after the low-temperature injectable acrylic resin bone cement is cured, a new product is not introduced, the residual amount of the monomers is less and the biocompatibility is good.
Description
Technical field
The present invention relates to biomaterial for medical purpose field, and in particular to low temperature injectable acrylic resin bone cement and its preparation
Method.
Background technology
Osteoporosis is one of modal skeletal diseases of mid-aged population.China's sufferers of osteoporosis face number is close to
100000000, and have at least 2.1 hundred million people's bone amount less than normal value, it is the most country of sufferers of osteoporosis face quantity and potential quantity.State
One group of data display that border osteoporosis foundation is delivered, the whole world will occur osteoporotic fracture together per 3 seconds, and 1/3
Women and 1/5 male sex can meet with after 50 years old and once fracture, in 6 months that 20% patients with hip fracture can be after the fracture
Death, the patient of half can't take care of oneself.And bone cement is injected in the bone or vertebra being damaged, it is to treat sclerotin at present
Loose easier and effective method.
Polymethyl methacrylate (Polymethyl Methacrylate, PMMA) acts not only as bone alternate material
For filling bony defect, such as the packing material of balloon kyphoplasty (Kyphoplasty, KP)；Can be used for increasing
The hold of strong implant, such as injection screw or Periprosthetic reach the effect of stable inside-fixture.PMMA advantages are
For bone substitute, its good biocompatibility, mechanical strength is high；And used as hold enhancing thing, it not only can significantly increase
Plus the resisting pull out forces of axial direction, it is also possible to increase anti-shearing force and twisting resistance, this is not available for other materials, therefore PMMA is mesh
The most frequently used bone cement of front clinic.
But in clinical practice application, PMMA most prominent shortcoming is exactly highly exothermic in polymerization process, its highest temperature
Degree can be with tolerance range, so as to cause the necrosis of its surrounding tissue more than tissue.The fuel factor of non-physiologic can be brought very
Many deficiencies, and ultimately result in the failure for the treatment of：(1) during joint replacement surgery, cause bone tissue necrosis, the PMMA for making without
Method forms a stable strand lock construction with bone structure, there is fine motion between PMMA and event structure, produces a large amount of PMMA particles, long
Phase accumulation can form aseptic loosening；(2) when KP performs the operation, spongiosa osteonecrosis in centrum is caused, occurs an annular around PMMA
Downright bad band, the mechanical strength in this region is poor, not only easily causes caving in again after the reduction of the fracture, and sending out of fracturing again of same centrum
Raw rate also can accordingly increase；(3) the catastrophic complication of KP be exactly PMMA enter canalis spinalis injured nerve, and damage paathogenic factor
In addition to mechanics is extruded, thermal burn plays an important role；(4) when fracture operation Cement is reinforced, can cause outside cortex bone
The periosteum necrosis on surface, it is impossible to form external callus, ultimately cause fracture delayed union or disunion.Therefore it is clinically urgent at present
Need to solve the problems, such as the thermal necrosis that PMMA solidification process exothermic temperature height is caused.
In recent years, some scholars are to reducing the carrying out of bone cement polymerization temperature some researchs.For example, Deutsche Bundespatent
3245956A1 discloses one kind and is based on liquid monomer and powdery polymeric acrylate and/or methacrylate, catalyst and rush
Enter the bone cement of agent, a kind of surfactant fluid for being not involved in polymerisation is with the addition of in the bone cement liquor, can effectively drop
The heat that low bone cement discharges when being polymerized, but final product introduces surfactant fluid, limits clinical practice；Chinese patent
104784753A discloses a kind of with the composite bone cement for reducing thermal necrosis effect, and in the bone cement pulvis a kind of phase is with the addition of
Become microencapsulation material (PCM), maximum temperature when solidifying can be reduced so as to require significantly lower than clinical practice, although can
Thermal necrosis are reduced, but final product there occurs change, and clinical practice need further checking.
The content of the invention
In view of the drawbacks described above of prior art, it is an object of the invention to provide a kind of exothermic temperature substantially reduce, monomer
The low low temperature injectable acrylic resin bone cement of residual quantity.To realize this purpose, the low temperature injectable acrylic acid of the present invention
Component B that particle size range is 500-2000 μm is with the addition of in the solid phase of resin bone cement, total specific surface area of solid phase is reduced,
The timing of solid phase total amount one, in bone cement solidification process, the overall reaction amount of solid-liquid interface is reduced, therefore bone cement of the present invention is solid
During change, exothermic temperature is substantially reduced, and can be effectively improved during Clinical practice thermal burn, the thermal necrosis produced to tissue
Problem；In addition, in the timing of solid phase total amount one, because required overall reaction amount is reduced, liquid phase ratio is also low than current clinical prods, therefore solid
Level of residual monomers after change is reduced, it is possible to decrease because monomer residue causes the risk of complication, improve the bio-compatible of bone cement
Property.
Further object is that providing a kind of final product the low temperature injectable consistent with current clinical prods
Acrylic resin bone cement.To realize this purpose, the low temperature injectable acrylic resin bone cement of the present invention include solid phase and
Liquid phase, the solid phase includes component A and component B, and component B is mixed with and is formed by component A and the liquid phase, because
New product is not introduced after this bone cement solidification of the present invention, it is ensured that Clinical practice security, can be directly used for clinic.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of low temperature injectable acrylic resin bone cement, the low temperature injectable acrylic resin bone cement includes solid phase
And the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is 0.25-0.5mL/g, by percentage to the quality, the solid phase includes 25-
Component A of 80wt% and component B of 20-75wt%, wherein component A includes the Powdery propylene acid of 59.5-99.5wt%
The peroxide initiator of esters polymer and 0.5-2wt%, in terms of volume percent, the liquid phase includes 95-99.9vol%
Acrylic ester monomer and 0.1-5vol% accelerator, component B is with solid-to-liquid ratio by component A and the liquid phase
The particle that 0.25-0.8mL/g is mixed with.
Preferably, component A also including 10-40wt% developer, the developer selected from barium sulfate, zirconium oxide or
Strontium sulfate, the average grain diameter of the developer is 1-50 μm；The liquid phase is also including the polymerization inhibitor of 20-150ppm, the inhibition
Agent is selected from quinhydrones or hydroquinone monomethyl ether.
Preferably, the Powdery propylene esters of gallic acid polymer is selected from polymethyl methacrylate, styrene-methyl propylene
One or more in sour methyl terpolymer or methyl acrylate-methylmethacrylate copolymer, the Powdery propylene acid
The particle size range of esters polymer is 20-200 μm.
Preferably, the peroxide initiator includes benzoyl peroxide, the benzoyl peroxide tert-butyl ester or peroxidating
MEK, the acrylic ester monomer includes methyl methacrylate, methyl acrylate or butyl methacrylate, the rush
Enter agent including N-N- dimethyl-p-toluidines.
Preferably, the particle size range of the component B particle is 500-2000 μm.
The present invention solves another technical scheme for being adopted of its technical problem：
The preparation method of above-mentioned low temperature injectable acrylic resin bone cement, comprises the following steps：
(1) preparation of component A
A. Powdery propylene esters of gallic acid polymer is prepared using suspension polymerization：First prepare acrylic polymer suspended
Liquid, then suspension is cleaned and is dried, Powdery propylene esters of gallic acid polymer is obtained after screening；
B. by percentage to the quality, by Powdery propylene esters of gallic acid polymer obtained in 59.5-99.5wt% steps a and
The peroxide initiator of 0.5-2wt% obtains component A after being well mixed；
(2) preparation of liquid phase
C. in terms of volume percent, the accelerator of the acrylic ester monomer of 95-99.9vol% and 0.1-5vol% is mixed
Liquid phase is obtained after closing uniformly；
(3) preparation of component B
D. liquid phase obtained in adding step c in component A obtained in step b, and is well mixed, wherein component A and
The solid-to-liquid ratio of liquid phase is 0.25-0.8mL/g, crushes and screens after solidification and obtains component B particle；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by component A obtained in 25-80wt% steps b and group obtained in 20-75wt% steps d
B is divided to obtain solid phase after being well mixed；
F. the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is obtained in addition step c in solid phase obtained in step e
0.25-0.5mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Preferably, 10-40wt% developers are added in stepb, 20-150ppm polymerization inhibitors are added in step c, it is described
Developer is selected from barium sulfate, zirconium oxide or strontium sulfate, and the particle size range of the developer is 1-50 μm, and the polymerization inhibitor is selected from hydrogen
Quinone or hydroquinone monomethyl ether.
Preferably, the peroxide initiator includes benzoyl peroxide, the benzoyl peroxide tert-butyl ester or peroxidating
MEK, the acrylic ester monomer includes methyl methacrylate, methyl acrylate or butyl methacrylate, the rush
Enter agent including N-N- dimethyl-p-toluidines.
Preferably, the particle size range of the Powdery propylene esters of gallic acid polymer is 20-200 μm, the component B particle
Particle size range is 500-2000 μm.
Preferably, the Powdery propylene esters of gallic acid polymer is selected from polymethyl methacrylate, styrene-methyl propylene
One or more in sour methyl terpolymer or methyl acrylate-methylmethacrylate copolymer.
Compared with the existing technology, advantages of the present invention is as follows with progress：
1. the low temperature injectable acrylic resin bone cement of the present invention, the solid phase includes component A and component B, described group
The particle size range for dividing B particles is 500-2000 μm, is added after component B in solid phase, total specific surface area of solid phase is reduced, in solid phase
The timing of total amount one, in bone cement solidification process, the overall reaction amount of solid-liquid interface is reduced, therefore bone cement is in the curing process, puts
Hot temperature is greatly reduced, and can be effectively improved during Clinical practice thermal burn, the thermal necrosis problem produced to tissue；In addition,
In the timing of solid phase total amount one, liquid phase ratio is also low than current clinical prods, therefore the level of residual monomers after solidification is reduced, it is possible to decrease because
Monomer residue causes the risk of complication, improves the biocompatibility of bone cement.
2. the low temperature injectable acrylic resin bone cement of the present invention includes solid phase and liquid phase, and the solid phase includes component A
With component B, component B is mixed with and is formed by component A and the liquid phase, therefore is not had after bone cement of the present invention solidification
Have and introduce new product, it is ensured that Clinical practice security, can be directly used for clinic.
3. the low temperature injectable acrylic resin bone cement of the present invention, the particle size range of the component B particle is 500-
The maximum particle diameter of 2000 μm, i.e. solid phase is less than 2000 μm, after mixing, still with good mobility and injectable
Property, and setting time, mechanical property are close with current clinical prods, facilitate clinical manipulation and use.
Description of the drawings
Fig. 1 is the exothermic temperature curve of bone cement prepared by formula 2 in the embodiment of the present invention 1；
Fig. 2 is the highest heat release temperature of the bone cement of five kinds of formula preparations and Spineplex bone cements in the embodiment of the present invention 1
Degree comparison diagram；
Fig. 3 is the setting time pair of the bone cement of five kinds of formula preparations and Spineplex bone cements in the embodiment of the present invention 1
Than figure；
Fig. 4 is the compression strength pair of the bone cement of five kinds of formula preparations and Spineplex bone cements in the embodiment of the present invention 1
Than figure；
Fig. 5 is the level of residual monomers of the bone cement of five kinds of formula preparations and Simplex P bone cements in the embodiment of the present invention 1
Comparison diagram；
Fig. 6 is the SEM figures in the embodiment of the present invention 2 after bone cement solidification.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, develop simultaneously referring to the drawings embodiment
The present invention is described in detail.
In the present invention, the Powdery propylene esters of gallic acid polymer is prepared using suspension polymerization, including following step
Suddenly：
Under conditions of rotating speed is 100-200r/min, 5g polyvinyl alcohol is added in 500mL purified waters, treats polyethylene
After alcohol is completely dissolved, the monomer of 1-3g peroxide initiators and 100-300mL acrylic polymers is added, be warming up to 50
DEG C, 30-60min is incubated, it is continuously heating to 70 DEG C, it is incubated 1-3h, then it is warming up to 90 DEG C, and 30-60min is incubated, gained is suspended
Liquid is cleaned by ultrasonic and is dried, and the Powdery propylene esters of gallic acid polymer that particle size range is 20-200 μm is obtained after sieving.
Embodiment 1
The preparation method of low temperature injectable acrylic resin bone cement, including following step：
(1) preparation of component A
A. polymethyl methacrylate and particle diameter model that suspension polymerization prepares respectively particle size range for 60-120 μm are adopted
Enclose the styrene-methylmethacrylate copolymer for 80-150 μm；
B. by percentage to the quality, polymethyl methacrylate, 25wt% steps a obtained in 50wt% steps a are obtained
Styrene-methylmethacrylate copolymer, the benzoyl peroxide tert-butyl ester of 0.8wt% and the particle size range of 24.2wt%
Component A is obtained after being well mixed for 30-50 μm of barium sulfate；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidines of the methyl acrylate of 99vol% and 1vol% are mixed
Close uniform, to add and obtain liquid phase after 20ppm quinhydrones；
(3) preparation of component B
D. liquid phase obtained in adding step c in component A obtained in step b, and is well mixed, wherein component A and
The solid-to-liquid ratio of liquid phase is 0.38mL/g, crushes and screens after solidification and obtains particle size range for 800-1300 μm of component B particle；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by component A obtained in 25-80wt% steps b and group obtained in 20-75wt% steps d
B is divided to obtain solid phase after being well mixed；
F. the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is obtained in addition step c in solid phase obtained in step e
0.25-0.5mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Step e and f are from following five kinds formulas：
Component A, component B and liquid phase are prepared by the preparation method of embodiment 1, then solid phase and liquid is prepared by above-mentioned 5 kinds formulas
Phase, mixes 1-3min, reference under the conditions of 23 ± 1 DEG C《YY0459-2003 surgical implant acrylic resin bone water
Mud》Exothermic temperature, setting time and intensity test are carried out, and selects current clinical prods Spineplex bone cement conducts
Control group is contrasted.After bone cement solidification, detect the level of residual monomers of bone cement using gas chromatography, and with clinic
Product Simplex P bone cements are compared.
Fig. 1 is the exothermic temperature curve of bone cement prepared by formula 2 in the embodiment of the present invention 1, is also bone cement of the present invention
Typical exothermic temperature curve map, experimental result shows, low temperature injectable acrylic resin bone cement highest heat release of the invention
Temperature is 53.4 DEG C, and setting time is 12min15s.
Fig. 2 is the highest heat release temperature of the bone cement of five kinds of formula preparations and Spineplex bone cements in the embodiment of the present invention 1
Degree comparison diagram, experimental result shows, low temperature injectable acrylic resin bone cement highest exothermic temperature of the invention 60 DEG C with
Under, and the highest exothermic temperature of control group is 80 DEG C or so, test result indicate that, the low temperature injectable acrylic resin of the present invention
In the curing process exothermic temperature is significantly reduced bone cement, can be effectively improved Clinical practice process to tissue produce hot calcination,
Thermal necrosis problem, improves security of the bone cement during Clinical practice.
Fig. 3 is the setting time pair of the bone cement of five kinds of formula preparations and Spineplex bone cements in the embodiment of the present invention 1
Than figure, experimental result shows, the low temperature injectable acrylic resin bone cement setting time of the present invention is distributed in 11-15min, right
It is 14 ± 0.5min according to the setting time of group, test result indicate that, the low temperature injectable acrylic resin bone cement of the present invention
Setting time is basically identical with Spineplex bone cements, can meet clinician's operation.
Fig. 4 is the compression strength pair of the bone cement of five kinds of formula preparations and Spineplex bone cements in the embodiment of the present invention 1
Than figure, experimental result shows, the compression strength after the low temperature injectable acrylic resin bone cement solidification of the present invention is distributed in 69-
80MPa, the pressure resistance of control group for 73 ± 2MPa, test result indicate that, the low temperature injectable acrylic resin bone of the present invention
The compression strength of cement and Spineplex bone cement no significant differences, it is possible to provide enough mechanical supports, it is ensured that after product implantation
Biomechanical stability.
Fig. 5 is the level of residual monomers pair that the present invention implements the bone cement of five kinds of formula preparations and Simplex P bone cements in 1
Than figure, experimental result shows, the level of residual monomers of the low temperature injectable acrylic resin bone cement of the present invention is 3% or so,
The level of residual monomers of Simplex P bone cements is 4.3 ± 0.05wt%, test result indicate that, the low temperature injectable third of the present invention
The level of residual monomers of olefin(e) acid resin bone cement is less than Simplex P bone cements, it is possible to decrease because monomer residue causes the wind of complication
Danger, improves the biocompatibility of bone cement.
Embodiment 2
The preparation method of low temperature injectable acrylic resin bone cement, including following step：
(1) preparation of component A
A. polymethyl methacrylate and particle diameter model that suspension polymerization prepares respectively particle size range for 20-100 μm are adopted
Enclose the styrene-methylmethacrylate copolymer for 100-200 μm；
B. by percentage to the quality, by polymethyl methacrylate, 29.5wt% step a systems obtained in 30wt% steps a
Styrene-methylmethacrylate copolymer, the benzoyl peroxide tert-butyl ester of 2wt% and the particle size range of 38.5wt% for obtaining
Component A is obtained after being well mixed for 1-20 μm of barium sulfate；
(2) preparation of liquid phase
C. in terms of volume percent, by the N-N- dimethyl of the butyl methacrylate of 95vol% and 5vol% to toluene
Amine is well mixed, and to add and obtain liquid phase after 80ppm hydroquinone monomethyl ethers；
(3) preparation of component B
D. liquid phase obtained in adding step c in component A obtained in step b, and is well mixed, wherein component A and
The solid-to-liquid ratio of liquid phase is 0.5mL/g, and the component B particle for obtaining that particle size range is 1500-2000 μm is crushed and screened after solidification；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by component A obtained in 45wt% steps b and component B mixing obtained in 55wt% steps d
Solid phase is obtained after uniform；
F. the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is obtained in addition step c in solid phase obtained in step e
0.5mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Bone cement is prepared by the preparation method of embodiment 2 and carry out performance test, measure result and show, bone water after stirring 1min
Mud good fluidity, highest exothermic temperature is 55.2 DEG C, and setting time is 13min25s, and mean compressive strength is 73.5MPa, single
Body residual quantity is 2.95%.After bone cement solidification, the surface topography of bone cement is observed by SEM.
Fig. 6 be the present invention implement 2 in bone cement solidification after SEM figure, it can be seen that surface exist partial white particle and
It is evenly distributed, shows that bone cement uniform component of the present invention, Performance comparision are stable.
Embodiment 3
The preparation method of low temperature injectable acrylic resin bone cement, including following step：
The preparation of component A
A. suspension polymerization is adopted to prepare polymethyl methacrylate and particle size range of the particle size range for 20-80 μm respectively
For 80-150 μm of methyl acrylate-methylmethacrylate copolymer；
B. by percentage to the quality, polymethyl methacrylate, 44wt% steps a obtained in 45wt% steps a are obtained
Methyl acrylate-methylmethacrylate copolymer, the benzoyl peroxide tert-butyl ester of 1wt% and the particle size range of 10wt%
Component A is obtained after being well mixed for 10-30 μm of zirconium oxide；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidines of the methyl acrylate of 98vol% and 2vol% are mixed
Close uniform, to add and obtain liquid phase after 60ppm quinhydrones；
(3) preparation of component B
D. liquid phase obtained in adding step c in component A obtained in step b, and is well mixed, wherein component A and
The solid-to-liquid ratio of liquid phase is 0.6mL/g, crushes and screens after solidification and obtains particle size range for 1000-1500 μm of component B particle；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by component A obtained in 42wt% steps b and component B mixing obtained in 58wt% steps d
Solid phase is obtained after uniform；
F. the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is obtained in addition step c in solid phase obtained in step e
0.4mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Bone cement is prepared by the preparation method of embodiment 3 and carry out performance test, measure result and show, bone after stirring 1.5min
Cement fluidity is good, and highest exothermic temperature is 53.8 DEG C, and setting time is 12min50s, and mean compressive strength is 79MPa, single
Body residual quantity is 3.2%.
Embodiment 4
The preparation method of low temperature injectable acrylic resin bone cement, including following step：
(1) preparation of component A
A. suspension polymerization is adopted to prepare the polymethyl methacrylate that particle size range is for 20-100 μm；
B. by percentage to the quality, by the peroxide of polymethyl methacrylate and 0.5wt% obtained in 99.5wt% steps a
Change after benzoyl is well mixed and obtain component A；
(2) preparation of liquid phase
C. in terms of volume percent, by the methyl methacrylate of 99.9vol% and the N-N- dimethyl pair of 0.1vol%
Toluidines is well mixed, and adds after 50ppm oxygen quinones are well mixed and obtains liquid phase；
(3) preparation of component B
D. liquid phase obtained in adding step c in component A obtained in step b, and is well mixed, wherein component A and
The solid-to-liquid ratio of liquid phase is 0.25mL/g, and the component B particle for obtaining that particle size range is 500-1000 μm is crushed and screened after solidification；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by component A obtained in 63wt% steps b and component B mixing obtained in 37wt% steps d
Solid phase is obtained after uniform；
F. the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is obtained in addition step c in solid phase obtained in step e
0.48mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Bone cement is prepared by the preparation method of embodiment 4 and carry out performance test, measure result and show, bone water after stirring 1min
Mud good fluidity, highest exothermic temperature is 56.4 DEG C, and setting time is 14min25s, and mean compressive strength is 72MPa, monomer
Residual quantity is 3.0%.
Embodiment 5
The preparation method of low temperature injectable acrylic resin bone cement, including following step：
(1) preparation of component A
A. suspension polymerization is adopted to prepare polymethyl methacrylate, particle size range of the particle size range for 60-110 μm respectively
Styrene-methylmethacrylate copolymer and particle size range for 80-150 μm is 120-200 μm of methyl acrylate-methyl
Methyl acrylate copolymer；
B. by percentage to the quality, polymethyl methacrylate, 20wt% steps a obtained in 25wt% steps a are obtained
Styrene-methylmethacrylate copolymer, methyl acrylate-methyl methacrylate obtained in 13.5wt% steps a it is common
The particle size range of polymers, the methyl ethyl ketone peroxide of 1.5wt% and 40wt% is to obtain group after 5-30 μm of strontium sulfate is well mixed
Divide A；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidines of the methyl acrylate of 96vol% and 4vol% are mixed
Close uniform, to add and obtain liquid phase after 150ppm hydroquinone monomethyl ethers；
(3) preparation of component B
D. liquid phase obtained in adding step c in component A obtained in step b, and is well mixed, wherein component A and
The solid-to-liquid ratio of liquid phase is 0.8mL/g, crushes and screens after solidification and obtains particle size range for 900-1600 μm of component B particle；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by component A obtained in 50wt% steps b and component B mixing obtained in 50wt% steps d
Solid phase is obtained after uniform；
F. the solid-to-liquid ratio of liquid phase, the solid phase and liquid phase is obtained in addition step c in solid phase obtained in step e
0.43mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Bone cement is prepared by the preparation method of embodiment 5 and carry out performance test, measure result and show, bone after stirring 2mi n
Cement fluidity is good, and highest exothermic temperature is 52.4 DEG C, and setting time is 13min45s, and mean compressive strength is 75MPa, single
Body residual quantity is 3.1%.
The present invention with the addition of that particle size range is different to be prepared from by the key component of bone cement in the solid phase of bone cement
Component B, by adjust solid phase in each component particle size, that is, adjust solid phase specific surface area, and then regulate and control solid-liquid interface
Reacting dose and reaction speed, so as to reduce the purpose of exothermic heat of reaction temperature, during effectively improving Clinical practice
Thermal burn, the thermal necrosis problem that tissue is produced.Those skilled in the art can also equally utilize this principle, by adjusting
The particle diameter of each component of bone cement is prepared adjusting the specific surface area of solid phase, and then regulates and controls reacting dose and the reaction of solid-liquid interface
Speed, or by adjusting the degree of polymerization of each component to regulate and control the reaction speed of solid-liquid interface reducing exothermic heat of reaction temperature
The purpose of degree.Additionally, in the timing of solid phase total amount one, the present invention is reduced because of required overall reaction amount, liquid phase ratio is also than clinical at present
Product is low, therefore the level of residual monomers after solidifying is reduced, it is possible to decrease because monomer residue causes the risk of complication, improve bone water
The biocompatibility of mud.Importantly, component B of the present invention is by the key component and the liquid phase of the bone cement
It is mixed with and forms, therefore new product is not introduced after the bone cement solidification of the present invention, it is ensured that Clinical practice security, produces
Product can be directly used for clinic.
Finally it should be noted that the foregoing is only the preferred embodiment of the present invention, this is not limited to
Invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., should be included in this
Within bright protection domain.
Claims (10)
1. a kind of low temperature injectable acrylic resin bone cement, it is characterised in that：The low temperature injectable acrylic resin bone water
It is 0.25-0.5mL/g, by percentage to the quality, the solid phase that mud drum includes the solid-to-liquid ratio of solid phase and liquid phase, the solid phase and liquid phase
Component B of component A and 20-75wt% including 25-80wt%, wherein component A includes the powder of 59.5-99.5wt%
The peroxide initiator of acrylic polymer and 0.5-2wt%, in terms of volume percent, the liquid phase includes 95-
The acrylic ester monomer of 99.9vol% and the accelerator of 0.1-5vol%, component B is by component A and the liquid
The particle being mixed with solid-to-liquid ratio 0.25-0.8mL/g.
2. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：Component A is also wrapped
Developer is included, the developer is selected from barium sulfate, zirconium oxide or strontium sulfate, and the particle size range of the developer is 1-50 μm；Institute
Stating liquid phase also includes polymerization inhibitor, and the polymerization inhibitor is selected from quinhydrones or hydroquinone monomethyl ether.
3. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：The Powdery propylene
Esters of gallic acid polymer is selected from polymethyl methacrylate, styrene-methylmethacrylate copolymer or methyl acrylate-methyl
One or more in methyl acrylate copolymer, the particle size range of the Powdery propylene esters of gallic acid polymer is 20-200 μ
m。
4. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：The peroxide draws
Sending out agent includes benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide, and the acrylic ester monomer includes
Methyl methacrylate, methyl acrylate or butyl methacrylate, the accelerator includes N-N- dimethyl-p-toluidines.
5. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：The component B particle
Particle size range be 500-2000 μm.
6. a kind of preparation method of the low temperature injectable acrylic resin bone cement according to any one of claim 1-5,
Comprise the following steps：
(1) preparation of component A
A. Powdery propylene esters of gallic acid polymer is prepared using suspension polymerization：Acrylic polymer suspension is first prepared,
Again suspension is cleaned and is dried, Powdery propylene esters of gallic acid polymer is obtained after screening；
B. by percentage to the quality, by Powdery propylene esters of gallic acid polymer and 0.5- obtained in 59.5-99.5wt% steps a
The peroxide initiator of 2wt% obtains component A after being well mixed；
(2) preparation of liquid phase
C. it is in terms of volume percent, the accelerator mixing of the acrylic ester monomer of 95-99.9vol% and 0.1-5vol% is equal
Liquid phase is obtained after even；
(3) preparation of component B
D. liquid phase obtained in step c is added in component A obtained in step b, and is well mixed, wherein component A and liquid phase
Solid-to-liquid ratio be 0.25-0.8mL/g, crush and screen after solidification and obtain component B particle；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component A obtained in 25-80wt% steps b and component B obtained in 20-75wt% steps d are mixed
Solid phase is obtained after closing uniformly；
F. the solid-to-liquid ratio that liquid phase, the solid phase and liquid phase obtained in step c are added in solid phase obtained in step e is 0.25-
0.5mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
7. the preparation method of low temperature injectable acrylic resin bone cement according to claim 6, it is characterised in that：In step
Developer is added in rapid b, polymerization inhibitor is added in step c, the developer is selected from barium sulfate, zirconium oxide or strontium sulfate, described
The particle size range of developer is 1-50 μm, and the polymerization inhibitor is selected from quinhydrones or hydroquinone monomethyl ether.
8. the preparation method of low temperature injectable acrylic resin bone cement according to claim 6, it is characterised in that：It is described
Peroxide initiator includes benzoyl peroxide, the benzoyl peroxide tert-butyl ester or methyl ethyl ketone peroxide, the acrylate
Class monomer includes methyl methacrylate, methyl acrylate or butyl methacrylate, and the accelerator includes N-N- dimethyl
Para-totuidine.
9. the preparation method of low temperature injectable acrylic resin bone cement according to claim 6, it is characterised in that：It is described
The particle size range of Powdery propylene esters of gallic acid polymer is 20-200 μm, and the particle size range of the component B particle is 500-2000 μ
m。
10. the preparation method of low temperature injectable acrylic resin bone cement according to claim 6, it is characterised in that：Institute
Powdery propylene esters of gallic acid polymer is stated selected from polymethyl methacrylate, styrene-methylmethacrylate copolymer or third
One or more in e pioic acid methyl ester-methylmethacrylate copolymer.
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| CN201611195118.XA CN106620841B (en) | 2016-12-22 | 2016-12-22 | Low temperature injectable acrylic resin bone cement and preparation method thereof |
| PCT/CN2017/100780 WO2018113345A1 (en) | 2016-12-22 | 2017-09-06 | Cryogenically injectable acrylic bone cement and preparation method therefor |
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| CN201611195118.XA CN106620841B (en) | 2016-12-22 | 2016-12-22 | Low temperature injectable acrylic resin bone cement and preparation method thereof |
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| WO2018113345A1 (en) * | 2016-12-22 | 2018-06-28 | 宁波华科润生物科技有限公司 | Cryogenically injectable acrylic bone cement and preparation method therefor |
| CN109847100A (en) * | 2019-04-09 | 2019-06-07 | 浙江科惠医疗器械股份有限公司 | A kind of biologically active bone cement and preparation method thereof |
| CN114225108A (en) * | 2021-12-17 | 2022-03-25 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of high-viscosity anti-seepage PMMA bone cement, product and application thereof |
| CN114561030A (en) * | 2022-03-24 | 2022-05-31 | 大博医疗科技股份有限公司 | Methyl methacrylate copolymer microsphere with encapsulated initiator, preparation method thereof and injectable bone cement |
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| CN113855855B (en) * | 2021-11-05 | 2022-07-08 | 浙江科惠医疗器械股份有限公司 | Polymethyl methacrylate bone cement and preparation method thereof |
| CN114404658B (en) * | 2022-02-18 | 2023-01-31 | 中国科学技术大学先进技术研究院 | Bone cement, preparation method thereof and orthopedic implant material |
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| WO2018113345A1 (en) | 2018-06-28 |
| CN106620841B (en) | 2019-09-03 |
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