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 PDF

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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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bone cement
component
low temperature
acrylic resin
preparation
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CN106729974A (en
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卓清山
张鹏云
汪宇
吕世文
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NINGBO HUAKERUN BIOTECHNOLOGY CO Ltd
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NINGBO HUAKERUN BIOTECHNOLOGY CO Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/16Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/025Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00Materials characterised by their function or physical properties
    • A61L2400/06Flowable or injectable implant compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

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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

A kind of low temperature injectable acrylic resin bone cement and preparation method thereof
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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