CN106729974A - A kind of low temperature injectable acrylic resin bone cement and preparation method thereof - Google Patents
A kind of low temperature injectable acrylic resin bone cement and preparation method thereof Download PDFInfo
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- CN106729974A CN106729974A CN201611195119.4A CN201611195119A CN106729974A CN 106729974 A CN106729974 A CN 106729974A CN 201611195119 A CN201611195119 A CN 201611195119A CN 106729974 A CN106729974 A CN 106729974A
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Abstract
The present invention relates to a kind of low temperature injectable acrylic resin bone cement and preparation method thereof, the low temperature injectable acrylic resin bone cement includes solid phase and liquid phase, the solid-to-liquid ratio of the solid phase and liquid phase is 0.25 0.5mL/g, by percentage to the quality, the solid phase includes the component B of the component A and 20 75wt% of 25 80wt%, wherein described component A includes the Powdery propylene esters of gallic acid polymer of 59.5 99.5wt% and the peroxide initiator of 0.5 2wt%, and the component B includes graininess acrylic polymer；In terms of volume percent, the liquid phase includes the acrylic ester monomer of 95 99.9vol% and the accelerator of 0.1 5vol%.Exothermic temperature is low in the curing process for low temperature injectable acrylic resin bone cement of the invention, is not introduced into that new product, level of residual monomers be few, biocompatibility is good after solidification.
Description
Technical field
The present invention relates to biomaterial for medical purpose field, and in particular to a kind of low temperature injectable acrylic resin bone cement and its
Preparation method.
Background technology
Osteoporosis is one of most common skeletal diseases of mid-aged population.China's sufferers of osteoporosis face number has been approached
100000000, and have at least 2.1 hundred million people's bone amount less than normal value, it is sufferers of osteoporosis face quantity and the most country of potential quantity.State
One group of data display that border osteoporosis foundation is delivered, the whole world will occur osteoporotic fracture together, 1/3 in every 3 seconds
Women and 1/5 male can be met with after 50 years old and once fractured, 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 be to treat sclerotin at present to bone cement is injected in the bone or vertebra being damaged
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 stabilization inside-fixture.PMMA advantages are
For bone substitute, its good biocompatibility, mechanical strength is high；And used as hold reinforcer, 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 preceding clinic.
But in clinical practice application, PMMA most prominent shortcoming is exactly highly exothermic, its highest temperature in polymerization process
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 strand lock construction for stabilization 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 the hair that same centrum fractures again
Raw rate also can accordingly increase；(3) the catastrophic complication of KP is exactly PMMA into canalis spinalis injured nerve, and the paathogenic factor damaged
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 PMMA solidification process exothermic temperatures thermal necrosis for causing high.
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 a kind of phase is with the addition of in the bone cement pulvis
Become microencapsulation material (PCM), maximum temperature during solidification can be reduced, it is significantly lower than clinical practice requirement, 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, substantially reduced it is an object of the invention to provide a kind of exothermic temperature, monomer
The low low temperature injectable acrylic resin bone cement of residual quantity.To realize this purpose, low temperature injectable acrylic acid of the invention
The 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 thermal burn, the thermal necrosis produced to tissue during Clinical practice
Problem；In addition, in the timing of solid phase total amount one, overall reaction amount is reduced because needed for, liquid phase ratio is also lower than current clinical prods, therefore solid
Level of residual monomers reduction after change, it is possible to decrease cause the risk of complication because of monomer residue, improve the bio-compatible of bone cement
Property.
It is another object of the present invention to provide the low temperature injectable that a kind of final product is consistent with current clinical prods
Acrylic resin bone cement.To realize this purpose, low temperature injectable acrylic resin bone cement of the invention include solid phase and
Liquid phase, the solid phase includes component A and component B, and the acrylic polymer of the component A and component B is selected from poly- methyl
Methyl acrylate, styrene-methylmethacrylate copolymer or methyl acrylate-methylmethacrylate copolymer, therefore
Do not have to introduce new product after 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 liquid phase, the solid-to-liquid ratio of the solid phase and liquid phase is 0.25-0.5mL/g, and by percentage to the quality, the solid phase includes 25-
The component B of the component A and 20-75wt% of 80wt%, wherein the component A includes the Powdery propylene acid of 59.5-99.5wt%
The peroxide initiator of esters polymer and 0.5-2wt%, the component B includes graininess acrylic polymer, with
Volume percent meter, the acrylic ester monomer of the 95-99.9vol% that the liquid phase includes and the accelerator of 0.1-5vol%.
Preferably, the component A also including 10-40wt% developer, the developer be selected from barium sulfate, zirconium oxide or
Strontium sulfate, the average grain diameter of the developer is 1-50 μm；The liquid phase also polymerization inhibitor including 20-150ppm, the inhibition
Agent is selected from quinhydrones or hydroquinone monomethyl ether.
Preferably, the Powdery propylene esters of gallic acid polymer and the graininess acrylic polymer are selected from poly- first
In base methyl acrylate, styrene-methylmethacrylate copolymer or methyl acrylate-methylmethacrylate copolymer
One or more, the Powdery propylene esters of gallic acid polymer and the graininess acrylic polymer are identical or different.
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
Entering agent includes N-N- dimethyl-p-toluidines.
Preferably, the particle size range of the Powdery propylene esters of gallic acid polymer is 20-200 μm, the graininess propylene
The particle size range of esters of gallic acid polymer is 500-2000 μm.
The present invention solves another technical scheme for being used of its technical problem：
A kind of preparation method of 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 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
Component A is obtained after the peroxide initiator of 0.5-2wt% is 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. graininess acrylic polymer is prepared using suspension polymerization：First prepare acrylic polymer suspended
Liquid, then suspension is cleaned and dried, graininess acrylic polymer, i.e. component B are obtained after screening；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by group obtained in component A and 20-75wt% step d obtained in 25-80wt% steps b
Solid phase is obtained after dividing B well mixed；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
0.25-0.5mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Preferably, 10-40wt% developers are added in stepb, and 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
Entering agent includes 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 and the graininess acrylic polymer are selected from poly- first
In base methyl acrylate, styrene-methylmethacrylate copolymer or methyl acrylate-methylmethacrylate copolymer
One or more, the Powdery propylene esters of gallic acid polymer and the graininess acrylic polymer are identical or different.
Compared with the existing technology, advantages of the present invention is as follows with progress：
1. low temperature injectable acrylic resin bone cement of the invention, the solid phase includes component A and component B, described group
The particle size range for dividing B particles is 500-2000 μm, after adding 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 thermal burn, the thermal necrosis problem produced to tissue during Clinical practice；In addition,
In the timing of solid phase total amount one, liquid phase ratio is also lower than current clinical prods, therefore the level of residual monomers reduction after solidification, it is possible to decrease because
Monomer residue causes the risk of complication, improves the biocompatibility of bone cement.
2. low temperature injectable acrylic resin bone cement of the invention includes solid phase and liquid phase, and the solid phase includes component A
With component B, the acrylic polymer of the component A and component B is selected from polymethyl methacrylate, styrene-methyl
Do not have after methyl acrylate copolymer or methyl acrylate-methylmethacrylate copolymer, therefore bone cement of the present invention solidification
Introduce new product, it is ensured that Clinical practice security, can be directly used for clinic.
3. low temperature injectable acrylic resin bone cement of the invention, the particle size range of the component B particle is 500-
The maximum particle diameter of 2000 μm, i.e. solid phase is no more 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.
Brief description of the drawings
Fig. 1 is the exothermic temperature curve of the bone cement of the preparation of formula 1 in the embodiment of the present invention 1；
Fig. 2 is the highest heat release temperature of five kinds of bone cements for being formulated preparation and Spineplex bone cements in the embodiment of the present invention 1
Degree comparison diagram；
Fig. 3 is the setting time pair of five kinds of bone cements for being formulated preparation and Spineplex bone cements in the embodiment of the present invention 1
Than figure；
Fig. 4 is the compression strength pair of five kinds of bone cements for being formulated preparation and Spineplex bone cements in the embodiment of the present invention 1
Than figure；
Fig. 5 is the level of residual monomers of five kinds of bone cements for being formulated preparation and Simplex P bone cements in the embodiment of the present invention 1
Comparison diagram；
Micro-CT after Fig. 6 is implanted into 1 month for the bone cements of the preparation of formula 3 in the embodiment of the present invention 1 schemes.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, develop simultaneously embodiment referring to the drawings
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 dries, and the Powdery propylene esters of gallic acid polymer that particle size range is 20-200 μm is obtained after sieving.
In the present invention, the graininess acrylic polymer is prepared using suspension polymerization, including following step
Suddenly：
Under conditions of rotating speed is 20-80r/min, 5g polyvinyl alcohol is added in 500mL purified waters, treats polyvinyl alcohol
After being completely dissolved, the monomer of 1-3g peroxide initiators and 100-300mL acrylic polymers is added, be warming up to 70
DEG C, 0.5-2h is incubated, then it is warming up to 95 DEG C, 30-60min is incubated, gained suspension is cleaned by ultrasonic and dried, obtained after sieving
Particle size range is 500-2000 μm of graininess acrylic polymer.
Embodiment 1
A kind of preparation method of low temperature injectable acrylic resin bone cement, including following steps：
(1) preparation of component A
A. suspension polymerization is used to prepare the polymethyl methacrylate and particle diameter model that particle size range is for 60-120 μm respectively
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, liquid phase is obtained after adding 20ppm quinhydrones；
(3) preparation of component B
D. suspension polymerization is used to prepare the polymethyl methacrylate that particle size range is for 800-1200 μm, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by group obtained in component A and 20-75wt% step d obtained in 25-80wt% steps b
Solid phase is obtained after dividing B well mixed；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
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 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 the bone cement of the preparation of formula 1 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 51.8 DEG C, and setting time is 12min35s.
Fig. 2 is the highest heat release temperature of five kinds of bone cements for being formulated preparation 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 58 DEG C with
Under, and the highest exothermic temperature of control group is 80 DEG C or so, test result indicate that, low temperature injectable acrylic resin of the invention
Exothermic temperature is significantly reduced bone cement in the curing process, 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 five kinds of bone cements for being formulated preparation and Spineplex bone cements in the embodiment of the present invention 1
Than figure, experimental result shows that low temperature injectable acrylic resin bone cement setting time of the invention is distributed in 10.5-16min,
The setting time of control group is 14 ± 0.5min, test result indicate that, low temperature injectable acrylic resin bone cement of the invention
Setting time it is basically identical with Spineplex bone cements, can meet clinician operation.
Fig. 4 is the compression strength pair of five kinds of bone cements for being formulated preparation and Spineplex bone cements in the embodiment of the present invention 1
Than figure, experimental result shows, the compression strength after low temperature injectable acrylic resin bone cement solidification of the invention is distributed in 72-
81MPa, the pressure resistance of control group is 73 ± 2MPa, test result indicate that, low temperature injectable acrylic resin bone of the 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 that the present invention implements five kinds of level of residual monomers pair for being formulated the bone cement and Simplex P bone cements for preparing in 1
Than figure, experimental result shows, the level of residual monomers of low temperature injectable acrylic resin bone cement of the invention is 2.9% or so,
The level of residual monomers of Simplex P bone cements is 4.3 ± 0.05wt%, test result indicate that, low temperature injectable third of the 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 cause the wind of complication because of monomer residue
Danger, improves the biocompatibility of bone cement.
Bone cement prepared by the present embodiment formula 3 is chosen, bone implantation experiment, selection are carried out with reference to GB16886.6
As a control group, experimental subjects is new zealand rabbit to Spinepiex bone cements.Result display test sample compares tissue with control group
Learning average integral is：1.05, illustrate that bone cement of the present invention compares no significant difference with control group, it is non-stimulated to organizing.
Micro-CT after Fig. 6 is implanted into 1 month for the bone cements of the preparation of formula 3 in the embodiment of the present invention 1 schemes.As schemed
Show, low temperature injectable acrylic resin bone cement development of the invention is obvious, and surrounding tissue does not occur infection or inflammatory reaction, says
The biocompatibility of bright low temperature injectable acrylic resin bone cement of the invention is good.
Embodiment 2
A kind of preparation method of low temperature injectable acrylic resin bone cement, including following steps：
(1) preparation of component A
A. suspension polymerization is used to prepare the polymethyl methacrylate and particle diameter model that particle size range is for 20-100 μm respectively
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 liquid phase is obtained after adding 80ppm hydroquinone monomethyl ethers；
(3) preparation of component B
D. suspension polymerization is used to prepare the styrene methyl methacrylate copolymerization that particle size range is for 1500-2000 μm
Thing, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B obtained in component A and 75wt% step d obtained in 35wt% steps b is mixed
Solid phase is obtained after uniform；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
0.32mL/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 after stirring 1.5min
Cement fluidity is good, and highest exothermic temperature is 56.3 DEG C, and setting time is 13min50s, and mean compressive strength is 75.5MPa,
Level of residual monomers is 2.83%.
Embodiment 3
A kind of preparation method of low temperature injectable acrylic resin bone cement, including following steps：
The preparation of component A
A. suspension polymerization is used to prepare polymethyl methacrylate and particle size range of the particle size range for 20-80 μm respectively
It is 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, liquid phase is obtained after adding 60ppm quinhydrones；
(3) preparation of component B
D. suspension polymerization is used to prepare the polymethyl methacrylate that particle size range is for 1000-1500 μm, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B obtained in component A and 58wt% step d obtained in 42wt% steps b is mixed
Solid phase is obtained after uniform；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
0.42mL/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 water after stirring 1min
Mud good fluidity, highest exothermic temperature is 52.8 DEG C, and setting time is 11min45s, and mean compressive strength is 78.3MPa, single
Body residual quantity is 3.15%.
Embodiment 4
A kind of preparation method of low temperature injectable acrylic resin bone cement, including following steps：
(1) preparation of component A
A. suspension polymerization is used 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 quinhydrones is well mixed and obtains liquid phase；
(3) preparation of component B
D. suspension polymerization is used to prepare particle size range for 500-1000 μm of methyl acrylate-methyl methacrylate is common
Polymers, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B obtained in component A and 38wt% step d obtained in 62wt% steps b is mixed
Solid phase is obtained after uniform；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
0.45mL/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 2min
Mud good fluidity, highest exothermic temperature is 58.4 DEG C, and setting time is 13min25s, and mean compressive strength is 74.7MPa, single
Body residual quantity is 2.95%.
Embodiment 5
A kind of preparation method of low temperature injectable acrylic resin bone cement, including following steps：
(1) preparation of component A
A. suspension polymerization is used to prepare polymethyl methacrylate, particle size range of the particle size range for 60-110 μm respectively
For 80-150 μm of styrene-methylmethacrylate copolymer and particle size range are 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% for 5-30 μm of strontium sulfate it is well mixed after obtain group
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, liquid phase is obtained after adding 150ppm hydroquinone monomethyl ethers；
(3) preparation of component B
D. suspension polymerization is used to prepare the polymethyl methacrylate that particle size range is for 600-1200 μm, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B obtained in component A and 55wt% step d obtained in 45wt% steps b is mixed
Solid phase is obtained after uniform；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
0.35mL/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 2.5min
Cement fluidity is good, and highest exothermic temperature is 50.9 DEG C, and setting time is 15min10s, and mean compressive strength is 78.4MPa,
Level of residual monomers is 3.16%.
Embodiment 6
A kind of preparation method of low temperature injectable acrylic resin bone cement, including following steps：
(1) preparation of component A
A. suspension polymerization is used to prepare the polymethyl methacrylate that particle size range is for 60-110 μm respectively；
B. by percentage to the quality, by the peroxidating first of polymethyl methacrylate, 1wt% obtained in 72wt% steps a
The particle size range of ethyl ketone and 27wt% for 5-30 μm of strontium sulfate it is well mixed after obtain component A；
(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, liquid phase is obtained after adding 80ppm hydroquinone monomethyl ethers；
(3) preparation of component B
D. suspension polymerization is used to prepare the polymethyl methacrylate that particle size range is for 600-1200 μm, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B obtained in component A and 52wt% step d obtained in 48wt% steps b is mixed
Solid phase is obtained after uniform；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase is
0.37mL/g, obtains the low temperature injectable acrylic resin bone cement after stirring.
Bone cement is prepared by the preparation method of embodiment 6 and carry out performance test, measure result and show, bone water after stirring 2min
Mud good fluidity, highest exothermic temperature is 52.4 DEG C, and setting time is 13min25s, and mean compressive strength is 75.6MPa, single
Body residual quantity is 3.09%.
Particle size by adjusting each component in solid phase of the invention, the i.e. specific surface area of regulation solid phase, and then regulate and control to consolidate-
The reacting dose and reaction speed at liquid interface, the purpose of exothermic heat of reaction temperature is reduced so as to reach, and effectively improves Clinical practice
During to tissue produce thermal burn, thermal necrosis problem.Those skilled in the art can also equally utilize this principle, lead to
Overregulate the particle diameter of each component for preparing bone cement to adjust the specific surface area of solid phase, and then regulate and control the reacting dose of solid-liquid interface
And reaction speed, or regulate and control the reaction speed of solid-liquid interface by adjusting the degree of polymerization of each component reach reduce reaction
The purpose of exothermic temperature.Additionally, in the timing of solid phase total amount one, present invention overall reaction amount because needed for is reduced, and liquid phase ratio also compares mesh
Preceding clinical prods are low, therefore the level of residual monomers reduction after solidification, it is possible to decrease cause the risk of complication because of monomer residue, improve
The biocompatibility of bone cement.Importantly, the present invention with the addition of by main group of bone cement in the solid phase of bone cement
Divide the component B being prepared from, bone cement of the invention is mixed with by the key component and liquid phase of bone cement in the prior art
Form, therefore do not have to introduce new product after bone cement of the invention solidification, it is ensured that Clinical practice security, product can be direct
For clinic.
Finally it should be noted that the foregoing is only preferred embodiment of the 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 hair
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
Mud drum includes solid phase and liquid phase, and the solid-to-liquid ratio of the solid phase and liquid phase is 0.25-0.5mL/g, by percentage to the quality, the solid phase
The component B of component A and 20-75wt% including 25-80wt%, wherein the component A includes that 59.5-99.5wt%'s is powdered
The peroxide initiator of acrylic polymer and 0.5-2wt%, the component B is polymerized including graininess esters of acrylic acid
Thing, in terms of volume percent, the acrylic ester monomer of the 95-99.9vol% that the liquid phase includes and the rush of 0.1-5vol%
Enter agent.
2. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：The component A is also wrapped
Developer is included, the developer is selected from barium sulfate, zirconium oxide or strontium sulfate, and the average grain diameter 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 and the graininess acrylic polymer are selected from polymethyl methacrylate, styrene-methyl propylene
One or more in sour methyl terpolymer or methyl acrylate-methylmethacrylate copolymer, the Powdery propylene acid
Esters polymer and the graininess acrylic polymer are identical or different.
4. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：The peroxide draws
Hair 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 include N-N- dimethyl-p-toluidines.
5. low temperature injectable acrylic resin bone cement according to claim 1, it is characterised in that：The Powdery propylene
The particle size range of esters of gallic acid polymer is 20-200 μm, and the particle size range of the graininess acrylic polymer is 500-
2000μm。
6. the preparation method of the low temperature injectable acrylic resin bone cement according to any one of claim 1-5, including
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,
Suspension is cleaned and dried again, 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
Component A is obtained after the peroxide initiator of 2wt% is 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 equal
Liquid phase is obtained after even；
(3) preparation of component B
D. graininess acrylic polymer is prepared using suspension polymerization：Acrylic polymer suspension is first prepared,
Suspension is cleaned and dried again, graininess acrylic polymer, i.e. component B are obtained after screening；
(4) a kind of preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B obtained in component A and 20-75wt% step d obtained in 25-80wt% steps b is mixed
Solid phase is obtained after closing uniformly；
F. liquid phase obtained in step c is added in the solid phase obtained in step e, the solid-to-liquid ratio of the solid phase and liquid phase 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
State Powdery propylene esters of gallic acid polymer and the graininess acrylic polymer is selected from polymethyl methacrylate, benzene second
One or more in alkene-methylmethacrylate copolymer or methyl acrylate-methylmethacrylate copolymer, the powder
Last shape acrylic polymer and the graininess acrylic polymer are identical or different.
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| CN108096629A (en) * | 2018-01-29 | 2018-06-01 | 北京奥精医药科技有限公司 | A kind of polymethyl methacrylate bone cement and preparation method thereof |
| CN109025108A (en) * | 2018-08-07 | 2018-12-18 | 苏州金螳螂文化发展股份有限公司 | A kind of acrylic crystal resin artificial water surface construction method |
| CN109053939A (en) * | 2018-07-04 | 2018-12-21 | 许昌学院 | A kind of nano combined bone cement and preparation method thereof |
| TWI733564B (en) * | 2020-08-18 | 2021-07-11 | 中央醫療器材股份有限公司 | Bone cement composition |
| 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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