CN106729974B - 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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- CN106729974B CN106729974B CN201611195119.4A CN201611195119A CN106729974B CN 106729974 B CN106729974 B CN 106729974B CN 201611195119 A CN201611195119 A CN 201611195119A CN 106729974 B CN106729974 B CN 106729974B
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Abstract
The present invention relates to a kind of low temperature injectable acrylic resin bone cements 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 the component A includes the Powdery propylene acid esters quasi 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 promotor 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 are few, biocompatibility is good after solidification.
Description
Technical field
The present invention relates to biomaterial for medical purpose fields, and in particular to a kind of low temperature injectable acrylic resin bone cement and its
Preparation method.
Background technique
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 amounts lower than normal value, it is sufferers of osteoporosis face quantity and the most country of potential quantity.State
One group of data that border osteoporosis foundation is delivered show, osteoporotic fracture together will occur for every 3 seconds for the whole world, 1/3
Women and 1/5 male can meet with primary fracture after 50 years old, 20% patients with hip fracture can be in 6 months after the fracture
The patient of death, half can't take care of oneself.And bone cement is injected into the bone or vertebra being damaged, it is current treatment sclerotin
Loose easier and effective method.
Polymethyl methacrylate (Polymethyl Methacrylate, PMMA) acts not only as bone alternate material
For filling bony defect, it is such as used as the packing material of balloon kyphoplasty (Kyphoplasty, KP)；It can be used for increasing
The holding power of strong implant, such as injects screw or Periprosthetic has the function that stable inside-fixture.PMMA advantage is
For bone substitute, good biocompatibility, mechanical strength is high；And as holding power reinforcer, it not only can significantly increase
Add axial resisting pull out forces, anti-shearing force and twisting resistance can also be increased, this is not available for other materials, therefore PMMA is mesh
The preceding most common bone cement of clinic.
However in clinical practice application, PMMA most prominent disadvantage is exactly highly exothermic in polymerization process, the highest temperature
Degree is more than tissue can be with tolerance range, to cause the necrosis of its surrounding tissue.The fuel factor of non-physiologic can be brought very
More deficiency, and eventually lead to the failure for the treatment of: (1) when joint replacement surgery, causing bone tissue downright bad, the PMMA made without
Method and bone structure form a stable strand lock construction, and there are fine motions between PMMA and event structure, generate a large amount of PMMA particles, long
Phase accumulation will form aseptic loosening；(2) when KP performs the operation, spongiosa osteonecrosis in centrum is caused, an annular occurs around PMMA
The mechanical strength of downright bad band, this region is poor, the collapsing again after not only easily causing the reduction of the fracture, and the hair of same centrum refracture
Raw rate also can accordingly increase；(3) the catastrophic complication of KP is exactly that PMMA enters canalis spinalis injuring nerve, and the pathogenic factor damaged
Other than mechanics squeezes, thermal burn plays an important role；(4) it when fracture operation Cement is reinforced, will cause outside cortex bone
The periosteum necrosis on surface, can not form external callus, ultimately cause fracture delayed union or disunion.Therefore it is clinically urgent at present
Need to solve the problems, such as thermal necrosis caused by PMMA solidification process exothermic temperature height.
In recent years, some scholars have carried out some researchs to reduction bone cement polymerization temperature.For example, Deutsche Bundespatent
3245956A1 discloses a kind of based on liquid monomer and powdery polymeric acrylate and/or methacrylate, catalyst and rush
Into the bone cement of agent, it is added to a kind of surfactant fluid for being not involved in polymerization reaction in the bone cement liquor, can effectively be dropped
The heat that low bone cement discharges when polymerizeing, but final product introduces surfactant fluid, limits clinical application；Chinese patent
104784753A discloses a kind of composite bone cement with reduction thermal necrosis effect, is added to a kind of phase in the bone cement pulvis
Become microencapsulation material (PCM), maximum temperature when solidification can be reduced, makes it significantly lower than clinical application requirement, although can
Thermal necrosis is reduced, but final product is changed, clinical application need further to verify.
Summary of the invention
In view of the drawbacks described above of the prior art, the purpose of the present invention is to provide a kind of exothermic temperatures to be substantially reduced, monomer
The low low temperature injectable acrylic resin bone cement of residual quantity.For this purpose, low temperature injectable acrylic acid of the invention
It is added to the component B that particle size range is 500-2000 μm in the solid phase of resin bone cement, reduces total specific surface area of solid phase,
Periodically, in bone cement solidification process, the overall reaction amount of solid-liquid interface is reduced solid phase total amount one, 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 generated during clinical use to tissue
Problem；In addition, because required overall reaction amount is reduced, liquid phase ratio is also lower than current clinical prods, therefore solid in one timing of solid phase total amount
Level of residual monomers after change reduces, and can reduce because monomer residue causes the risk of complication, improve the bio-compatible of bone cement
Property.
It is another object of the present invention to provide a kind of final products and the consistent low temperature injectable of current clinical prods
Acrylic resin bone cement.For this purpose, low temperature injectable acrylic resin bone cement of the invention include solid phase and
Liquid phase, the solid phase include that the acrylic polymer of component A and component B, the component A and component B are selected from poly- methyl
Methyl acrylate, styrene-methylmethacrylate copolymer or methyl acrylate-methylmethacrylate copolymer, therefore
Bone cement of the present invention does not introduce new product after solidifying, guarantee clinical use safety, can be directly used for clinic.
The technical solution adopted by 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 include graininess acrylic polymer, with
Volume percent meter, the acrylic ester monomer for the 95-99.9vol% that the liquid phase includes and the promotor of 0.1-5vol%.
Preferably, the component A further includes the developer of 10-40wt%, the developer be selected from barium sulfate, zirconium oxide or
Strontium sulfate, the average grain diameter of the developer are 1-50 μm；The liquid phase further includes the polymerization inhibitor of 20-150ppm, the polymerization inhibitor
Agent is selected from quinhydrones or hydroquinone monomethyl ether.
Preferably, the Powdery propylene acid esters quasi 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 acid esters quasi polymer and the graininess acrylic polymer are identical or different.
Preferably, the peroxide initiator includes benzoyl peroxide, benzoyl peroxide or peroxidating
Methyl ethyl ketone, the acrylic ester monomer include methyl methacrylate, methyl acrylate or butyl methacrylate, the rush
It include N-N- dimethyl-p-toluidine into agent.
Preferably, the particle size range of the Powdery propylene acid esters quasi polymer is 20-200 μm, the graininess propylene
The particle size range of acid esters quasi polymer is 500-2000 μm.
The present invention solves another technical solution used by its technical problem:
A kind of preparation method of low temperature injectable acrylic resin bone cement, including the following steps:
(1) preparation of component A
A. Powdery propylene acid esters quasi polymer is prepared using suspension polymerization: it is suspended first prepares acrylic polymer
Liquid, then suspension is washed and dried, Powdery propylene acid esters quasi polymer is obtained after screening；
B. by percentage to the quality, by Powdery propylene acid esters quasi polymer made from 59.5-99.5wt% step a and
The peroxide initiator of 0.5-2wt% obtains component A after mixing；
(2) preparation of liquid phase
C. in terms of volume percent, the promotor 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: it is suspended first prepares acrylic polymer
Liquid, then suspension is washed 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 made from component A and 20-75wt% step d made from 25-80wt% step b
B is divided to obtain solid phase after mixing；
F. liquid phase made from step c is added in the solid phase made from 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% developer is added in stepb, 20-150ppm polymerization inhibitor is 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, benzoyl peroxide or peroxidating
Methyl ethyl ketone, the acrylic ester monomer include methyl methacrylate, methyl acrylate or butyl methacrylate, the rush
It include N-N- dimethyl-p-toluidine into agent.
Preferably, the particle size range of the Powdery propylene acid esters quasi polymer is 20-200 μm, the component B particle
Particle size range is 500-2000 μm.
Preferably, the Powdery propylene acid esters quasi 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 acid esters quasi polymer and the graininess acrylic polymer are identical or different.
Compared with the existing technology, advantages of the present invention and progress are as follows:
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 particle is 500-2000 μm, after component B is added in solid phase, total specific surface area of solid phase is reduced, in solid phase
Periodically, in bone cement solidification process, the overall reaction amount of solid-liquid interface is reduced total amount one, 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 generated during clinical use to tissue；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 solidify, can reduce 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, the solid phase includes component A
Polymethyl methacrylate, styrene-methyl are selected from the acrylic polymer of component B, the component A and component B
Methyl acrylate copolymer or methyl acrylate-methylmethacrylate copolymer, therefore do not have after bone cement of the present invention solidification
New product is introduced, guarantees clinical use safety, 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-
2000 μm, i.e. the maximum particle diameter of solid phase is no more than 2000 μm, after mixing, still has good mobility and injectable
Property, and setting time, mechanical property are close with current clinical prods, facilitate clinical manipulation and use.
Detailed description of the invention
Fig. 1 is the exothermic temperature curve of the bone cement of 1 preparation of formula in the embodiment of the present invention 1；
Fig. 2 is the highest heat release temperature of bone cement and Spineplex bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
Spend comparison diagram；
Fig. 3 is the setting time pair of bone cement and Spineplex bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
Than figure；
Fig. 4 is the compression strength pair of bone cement and Spineplex bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
Than figure；
Fig. 5 is the level of residual monomers of bone cement and Simplex P bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
Comparison diagram；
Fig. 6 is the micro-CT figure after the bone cement of 3 preparation of formula in the embodiment of the present invention 1 is implanted into 1 month.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, as follows in conjunction with drawings and embodiments
The present invention is described in detail.
In the present invention, the Powdery propylene acid esters quasi polymer is prepared using suspension polymerization, including following step
It is rapid:
Under conditions of revolving speed is 100-200r/min, 5g polyvinyl alcohol is added in 500mL purified water, to polyethylene
After alcohol is completely dissolved, the monomer of 1-3g peroxide initiator and 100-300mL acrylic polymer is added, is warming up to 50
DEG C, 30-60min is kept the temperature, is continuously heating to 70 DEG C, keeps the temperature 1-3h, then be warming up to 90 DEG C, keeps the temperature 30-60min, gained is suspended
Liquid is cleaned by ultrasonic and dries, and the Powdery propylene acid esters quasi 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
It is rapid:
Under conditions of revolving speed is 20-80r/min, 5g polyvinyl alcohol is added in 500mL purified water, to polyvinyl alcohol
After being completely dissolved, the monomer of 1-3g peroxide initiator and 100-300mL acrylic polymer is added, is warming up to 70
DEG C, 0.5-2h is kept the temperature, then be warming up to 95 DEG C, keeps the temperature 30-60min, gained suspension is cleaned by ultrasonic and is dried, is obtained after sieving
The graininess acrylic polymer that particle size range is 500-2000 μm.
Embodiment 1
A kind of preparation method of low temperature injectable acrylic resin bone cement, including the following steps:
(1) preparation of component A
A. suspension polymerization is used to prepare particle size range respectively as 60-120 μm of polymethyl methacrylate and partial size model
Enclose the styrene-methylmethacrylate copolymer for 80-150 μm；
B. by percentage to the quality, polymethyl methacrylate made from 50wt% step a, 25wt% step a are made
Styrene-methylmethacrylate copolymer, the benzoyl peroxide of 0.8wt% and the particle size range of 24.2wt%
Component A is obtained after mixing for 30-50 μm of barium sulfate；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidine of the methyl acrylate of 99vol% and 1vol% are mixed
It closes uniformly, obtains liquid phase after adding 20ppm quinhydrones；
(3) preparation of component B
D. use suspension polymerization preparation particle size range for 800-1200 μm of polymethyl methacrylate, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, by group made from component A and 20-75wt% step d made from 25-80wt% step b
B is divided to obtain solid phase after mixing；
F. liquid phase made from step c is added in the solid phase made from 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 select following five kinds of formulas:
By 1 preparation method of embodiment preparation component A, component B and liquid phase, then by above-mentioned 5 kinds of formulas preparation solid phase and liquid
1-3min is mixed in phase under the conditions of 23 ± 1 DEG C, referring to " YY0459-2003 surgical implant acrylic resin bone water
Mud " carry out exothermic temperature, setting time and intensity test, and select current clinical prods Spineplex bone cement as
Control group compares.After bone cement solidification, detect the level of residual monomers of bone cement using gas chromatography, and with clinic
Product Simplex P bone cement is compared.
Fig. 1 is the exothermic temperature curve of the bone cement of 1 preparation of formula in the embodiment of the present invention 1, and bone cement of the present invention
Typically exothermic temperature curve graph, experimental result are shown, low temperature injectable acrylic resin bone cement highest heat release of the invention
Temperature is 51.8 DEG C, setting time 12min35s.
Fig. 2 is the highest heat release temperature of bone cement and Spineplex bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
Spend 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, the experimental results showed that, low temperature injectable acrylic resin of the invention
Bone cement in the curing process exothermic temperature significantly reduce, can be effectively improved clinical use process to tissue generate hot calcination,
Thermal necrosis problem improves safety of bone cement during clinical use.
Fig. 3 is the setting time pair of bone cement and Spineplex bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
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, the experimental results showed that, low temperature injectable acrylic resin bone cement of the invention
Setting time and Spineplex bone cement it is almost the same, can meet clinician operation.
Fig. 4 is the compression strength pair of bone cement and Spineplex bone cement that in the embodiment of the present invention 1 prepared by five kinds of formulas
Than figure, experimental result shows that the compression strength after low temperature injectable acrylic resin bone cement of the invention solidifies is distributed in 72-
81MPa, the pressure resistance of control group are 73 ± 2MPa, the experimental results showed that, low temperature injectable acrylic resin bone of the invention
The compression strength and Spineplex bone cement no significant difference of cement, it is possible to provide enough mechanical supports, after guaranteeing product implantation
Biomechanical stability.
Fig. 5 is the level of residual monomers pair that the present invention implements bone cement and Simplex P bone cement that in 1 prepared by five kinds of formulas
Than figure, experimental result is shown, 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 cement is 4.3 ± 0.05wt%, the experimental results showed that, low temperature injectable third of the invention
The level of residual monomers of olefin(e) acid resin bone cement is lower than Simplex P bone cement, can reduce because monomer residue causes the wind of complication
Danger, improves the biocompatibility of bone cement.
The bone cement for choosing 3 preparation of the present embodiment formula carries out bone implant experiment, selection referring to GB16886.6
As a control group, experimental subjects is new zealand rabbit to Spinepiex bone cement.Test sample is organized compared with the control group as the result is shown
Learn average integral are as follows: 1.05, illustrate bone cement of the present invention no significant difference compared with the control group, it is non-stimulated to organizing.
Fig. 6 is the micro-CT figure after the bone cement of 3 preparation of formula in the embodiment of the present invention 1 is implanted into 1 month.As schemed
Show, low temperature injectable acrylic resin bone cement development of the invention is obvious, and infection or inflammatory reaction do not occur for surrounding tissue, say
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 the following steps:
(1) preparation of component A
A. suspension polymerization is used to prepare particle size range respectively as 20-100 μm of polymethyl methacrylate and partial size model
Enclose the styrene-methylmethacrylate copolymer for 100-200 μm；
B. by percentage to the quality, by polymethyl methacrylate made from 30wt% step a, 29.5wt% step a system
Styrene-methylmethacrylate copolymer, the benzoyl peroxide of 2wt% and the particle size range of 38.5wt% obtained
Component A is obtained after mixing 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 uniformly mixed, and obtains liquid phase after adding 80ppm hydroquinone monomethyl ether；
(3) preparation of component B
D. suspension polymerization preparation particle size range is used to be copolymerized for 1500-2000 μm of styrene methyl methacrylate
Object, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B made from component A and 75wt% step d made from 35wt% step b is mixed
Solid phase is obtained after uniformly；
F. liquid phase made from step c is added in the solid phase made from 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 2 preparation method of embodiment and is tested for the property, and is measured the results show that stirring bone after 1.5min
Cement fluidity is good, and highest exothermic temperature is 56.3 DEG C, setting time 13min50s, mean compressive strength 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 the 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
For 80-150 μm of methyl acrylate-methylmethacrylate copolymer；
B. by percentage to the quality, polymethyl methacrylate made from 45wt% step a, 44wt% step a are made
Methyl acrylate-methylmethacrylate copolymer, the benzoyl peroxide of 1wt% and the particle size range of 10wt%
Component A is obtained after mixing for 10-30 μm of zirconium oxide；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidine of the methyl acrylate of 98vol% and 2vol% are mixed
It closes uniformly, obtains liquid phase after adding 60ppm quinhydrones；
(3) preparation of component B
D. use suspension polymerization preparation particle size range for 1000-1500 μm of polymethyl methacrylate, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B made from component A and 58wt% step d made from 42wt% step b is mixed
Solid phase is obtained after uniformly；
F. liquid phase made from step c is added in the solid phase made from 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 3 preparation method of embodiment and is tested for the property, and is measured the results show that stirring bone water after 1min
Mud good fluidity, highest exothermic temperature is 52.8 DEG C, setting time 11min45s, mean compressive strength 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 the following steps:
(1) preparation of component A
A. suspension polymerization is used to prepare particle size range as 20-100 μm of polymethyl methacrylate；
B. by percentage to the quality, by the peroxide of polymethyl methacrylate and 0.5wt% made from 99.5wt% step a
Change benzoyl and obtains component A after mixing；
(2) preparation of liquid phase
C. in terms of volume percent, by the N-N- dimethyl pair of the methyl methacrylate of 99.9vol% and 0.1vol%
Toluidines is uniformly mixed, and is added 50ppm quinhydrones and is obtained liquid phase after mixing；
(3) preparation of component B
D. use suspension polymerization preparation particle size range total for 500-1000 μm of methyl acrylate-methyl methacrylate
Polymers, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B made from component A and 38wt% step d made from 62wt% step b is mixed
Solid phase is obtained after uniformly；
F. liquid phase made from step c is added in the solid phase made from 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 4 preparation method of embodiment and is tested for the property, and is measured the results show that stirring bone water after 2min
Mud good fluidity, highest exothermic temperature is 58.4 DEG C, setting time 13min25s, mean compressive strength 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 the following steps:
(1) preparation of component A
A. suspension polymerization is used to prepare polymethyl methacrylate of the particle size range for 60-110 μm, particle size range respectively
Methyl acrylate-the methyl for being 120-200 μm for 80-150 μm of styrene-methylmethacrylate copolymer and particle size range
Methyl acrylate copolymer；
B. by percentage to the quality, polymethyl methacrylate made from 25wt% step a, 20wt% step a are made
Styrene-methylmethacrylate copolymer, methyl acrylate-methyl methacrylate is total made from 13.5wt% step a
The particle size range of polymers, the methyl ethyl ketone peroxide of 1.5wt% and 40wt% is that 5-30 μm of strontium sulfate obtains group after mixing
Divide A；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidine of the methyl acrylate of 96vol% and 4vol% are mixed
It closes uniformly, obtains liquid phase after adding 150ppm hydroquinone monomethyl ether；
(3) preparation of component B
D. use suspension polymerization preparation particle size range for 600-1200 μm of polymethyl methacrylate, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B made from component A and 55wt% step d made from 45wt% step b is mixed
Solid phase is obtained after uniformly；
F. liquid phase made from step c is added in the solid phase made from 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 5 preparation method of embodiment and is tested for the property, and is measured the results show that stirring bone after 2.5min
Cement fluidity is good, and highest exothermic temperature is 50.9 DEG C, setting time 15min10s, mean compressive strength 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 the following steps:
(1) preparation of component A
A. suspension polymerization is used to prepare particle size range respectively as 60-110 μm of polymethyl methacrylate；
B. by percentage to the quality, by the peroxidating first of polymethyl methacrylate made from 72wt% step a, 1wt%
The particle size range of ethyl ketone and 27wt% are that 5-30 μm of strontium sulfate obtains component A after mixing；
(2) preparation of liquid phase
C. in terms of volume percent, the N-N- dimethyl-p-toluidine of the methyl acrylate of 98vol% and 2vol% are mixed
It closes uniformly, obtains liquid phase after adding 80ppm hydroquinone monomethyl ether；
(3) preparation of component B
D. use suspension polymerization preparation particle size range for 600-1200 μm of polymethyl methacrylate, i.e. component B；
(4) preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B made from component A and 52wt% step d made from 48wt% step b is mixed
Solid phase is obtained after uniformly；
F. liquid phase made from step c is added in the solid phase made from 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 6 preparation method of embodiment and is tested for the property, and is measured the results show that stirring bone water after 2min
Mud good fluidity, highest exothermic temperature is 52.4 DEG C, setting time 13min25s, mean compressive strength 75.6MPa, single
Body residual quantity is 3.09%.
The present invention adjusts the specific surface area of solid phase by adjusting the particle size of each component in solid phase, so regulate and control it is solid-
The reacting dose and reaction speed at liquid interface effectively improve clinical use to achieve the purpose that reduce exothermic heat of reaction temperature
Thermal burn, the thermal necrosis problem that tissue is generated in the process.Those skilled in the art equally also can use this principle, lead to
It overregulates and prepares the partial size of each component of 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 the degree of polymerization by adjusting each component regulates and controls the reaction speed of solid-liquid interface, to reach reduces reaction
The purpose of exothermic temperature.In addition, for the present invention because required overall reaction amount is reduced, liquid phase ratio also compares mesh in one timing of solid phase total amount
Preceding clinical prods are low, therefore the level of residual monomers after solidifying reduces, and can reduce because monomer residue causes the risk of complication, improve
The biocompatibility of bone cement.Importantly, the present invention is added to by main group of bone cement in the solid phase of bone cement
Divide the component B being prepared, bone cement of the invention is mixed with by the main component and liquid phase of bone cement in the prior art
Form, thus bone cement of the invention solidify after do not introduce new product, ensure that clinical use safety, product can be direct
For clinic.
Finally it should be noted that the foregoing is merely preferred embodiment of the invention, it is not limited to this
Invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in this hair
Within bright protection scope.
Claims (8)
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 the powdered of 59.5-99.5wt%
The peroxide initiator of acrylic polymer and 0.5-2wt%, the partial size of the Powdery propylene acid esters quasi polymer
Range is 20-200 μm, and the component B is graininess acrylic polymer, the graininess acrylic polymer
Particle size range is 500-2000 μm, and in terms of volume percent, the liquid phase includes the acrylic ester monomer of 95-99.9vol%
With the promotor of 0.1-5vol%.
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 further 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
Acid esters quasi polymer and the graininess acrylic polymer are selected from polymethyl methacrylate, styrene-methyl propylene
One of sour methyl terpolymer or methyl acrylate-methylmethacrylate copolymer are a variety of, 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
Sending out agent includes benzoyl peroxide, benzoyl peroxide or methyl ethyl ketone peroxide, and the acrylic ester monomer includes
Methyl methacrylate, methyl acrylate or butyl methacrylate, the promotor include N-N- dimethyl-p-toluidine.
5. the preparation method of low temperature injectable acrylic resin bone cement described in any one of -4 according to claim 1, including
The following steps:
(1) preparation of component A
A. Powdery propylene acid esters quasi polymer is prepared using suspension polymerization: first prepares acrylic polymer suspension,
Suspension is washed and dried again, Powdery propylene acid esters quasi polymer is obtained after screening, the Powdery propylene acid esters is birdsed of the same feather flock together
The particle size range for closing object is 20-200 μm；
B. by percentage to the quality, by Powdery propylene acid esters quasi polymer and 0.5- made from 59.5-99.5wt% step a
The peroxide initiator of 2wt% obtains component A after mixing；
(2) preparation of liquid phase
C. in terms of volume percent, the promotor of the acrylic ester monomer of 95-99.9vol% and 0.1-5vol% are mixed equal
Liquid phase is obtained after even；
(3) preparation of component B
D. graininess acrylic polymer is prepared using suspension polymerization: first prepares acrylic polymer suspension,
Suspension is washed and dried again, graininess acrylic polymer, i.e. component B are obtained after screening, the component B particle
Particle size range is 500-2000 μm；
(4) a kind of preparation of low temperature injectable acrylic resin bone cement
E. by percentage to the quality, component B made from component A and 20-75wt% step d made from 25-80wt% step b is mixed
Solid phase is obtained after closing uniformly；
F. the solid-to-liquid ratio of liquid phase made from addition step c in the solid phase made from step e, the solid phase and liquid phase is 0.25-
0.5mL/g obtains the low temperature injectable acrylic resin bone cement after stirring.
6. the preparation method of low temperature injectable acrylic resin bone cement according to claim 5, 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.
7. the preparation method of low temperature injectable acrylic resin bone cement according to claim 5, it is characterised in that: described
Peroxide initiator includes benzoyl peroxide, benzoyl peroxide or methyl ethyl ketone peroxide, the acrylate
Class monomer includes methyl methacrylate, methyl acrylate or butyl methacrylate, and the promotor includes N-N- dimethyl
Para-totuidine.
8. the preparation method of low temperature injectable acrylic resin bone cement according to claim 5, it is characterised in that: described
Powdery propylene acid esters quasi polymer and the graininess acrylic polymer are selected from polymethyl methacrylate, benzene second
One of alkene-methylmethacrylate copolymer or methyl acrylate-methylmethacrylate copolymer are a variety of, the powder
Last shape acrylic polymer and the graininess acrylic polymer are identical or different.
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| CN109053939B (en) * | 2018-07-04 | 2020-11-10 | 许昌学院 | Nano composite bone cement and preparation method thereof |
| CN109025108B (en) * | 2018-08-07 | 2020-07-28 | 苏州金螳螂文化发展股份有限公司 | Acrylic crystal resin simulation water surface construction method |
| 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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| CN104826170B (en) * | 2015-04-22 | 2017-12-22 | 山东明德生物医学工程有限公司 | A kind of developability bone cement and preparation method and purposes |
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