CN106362204A - High-strength artificial bone material and preparation method thereof - Google Patents

High-strength artificial bone material and preparation method thereof Download PDF

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CN106362204A
CN106362204A CN201610760868.0A CN201610760868A CN106362204A CN 106362204 A CN106362204 A CN 106362204A CN 201610760868 A CN201610760868 A CN 201610760868A CN 106362204 A CN106362204 A CN 106362204A
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artificial bone
bone material
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何仁英
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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
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • 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
    • A61L27/18Macromolecular materials obtained otherwise than 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
    • A61L27/14Macromolecular materials
    • A61L27/20Polysaccharides
    • 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • 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
    • A61L2430/40Preparation and treatment of biological tissue for implantation, e.g. decellularisation, cross-linking

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  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
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  • Oral & Maxillofacial Surgery (AREA)
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  • Materials For Medical Uses (AREA)
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Abstract

The invention discloses a high-strength artificial bone material, which is prepared from the following raw materials in parts by weight: 50-60 parts of polyethylene, 45-55 parts of a urethane dimethacrylate matrix, 40-50 parts of methacrylate, 35-45 parts of di-tert-butyl peroxide, 25-35 parts of polyvinylpyrrolidone, 20-25 parts of acetyl tributyl citrate, 18-22 parts of vinyl silicone oil, 15-20 parts of glycerol, 10-12 parts of glacial acetic acid, 9-12 parts of bis-maleamic acid, 6-8 parts of wollastonite powder, 6-8 parts of nano titanium dioxide, 5-7 parts of protonated chitosan, 3-5 parts of a stabilizer and 3-5 parts of a coupling agent. The high-strength artificial bone material prepared by the invention is excellent in mechanical strength and good in biocompatibility, and the high-strength artificial bone material is capable of meeting industry demands. Meanwhile, the invention also discloses a preparation method of the high-strength artificial bone material.

Description

High intensity Artificial bone material and preparation method thereof
Technical field
The present invention relates to biological material field, particularly to a kind of high intensity Artificial bone material and preparation method thereof.
Background technology
Bone is a kind of natural composite material.It is mainly by the collagen fiber with hierarchy and nanometer hydroxyapatite structure Become.The weight bearing area Cranial defect clinically being caused due to wound, infection, bone tumor etc. is very common, for repairing of this kind of defect Multiple, develop the medical embedded material matching with people's bone rigidity and be always the target that bio-medical circle is seek assiduously.At present, The bone implant material being related to has (1) bio-inert material: such as metal, inactive ceramic, material with carbon element, medical high polymer;(2) biological alive Property material: as bio-vitric, glass ceramics, calcium phosphate etc..(3) bioactive composite material: such as bioactivity coatings composite wood Material, whisker, granule or fiber reinforcement biologic active ceramic composite material.But these materials are in mechanical performance and biological activity side All there is respective defect in face.The elastic modelling quantity of titanium alloy material is 4~10 times of human body bone, there is stress and hide in clinical practice Gear phenomenon, is unfavorable for Bone Defect Repari.Carbon fibre material easily produces abrasive dust on surface, causes the tissue inflammation reaction repairing position, shadow Ring repairing effect.Additionally, the biology that the biocompatibility of the material such as titanium alloy, polyether-ether-ketone, carbon fiber each depends on them is lazy Property, they do not have and form synosteotic biological activity with human body natural bone tissue, but use as Permanent implantation body, It is not involved in the metabolism of human body, eventually serve as foreign body and be present in vivo, thus long-term repair effect is undesirable.
Bio-medical material, also known as biological material, is for diagnosing, treating, repair or replace tissue or organ Or promote a class hi tech and new material of its function, can be natural or synthesis, or theirs is compound.Should Class material is mainly used in that human body is soft, hard tissue repair body, artificial organ, artificial blood vessel, contact lenss, membrane material, bonding agent and tube chamber The aspects such as product.There is research that bio-medical material is used for manufacture of intraocular skeleton in recent years, and achieved certain effect. But it also has many defects in mechanical strength, to aspects such as human body sensitization, zests.Therefore, develop one kind can gram The Artificial bone material taking drawbacks described above is just particularly important.
Content of the invention
For solving above-mentioned technical problem, the present invention provides a kind of high intensity Artificial bone material and preparation method thereof, by adopting Specified raw material is combined, the corresponding production technology of cooperation, the high intensity Artificial bone material obtaining, its mechanical strength, Good biocompatibility, disclosure satisfy that the requirement of industry, has preferable application prospect.
The purpose of the present invention can be achieved through the following technical solutions:
High intensity Artificial bone material it is characterised in that: be prepared by the raw materials in: polyethylene 50-60 part, dimethyl Propenoic methyl carbamate substrate 45-55 part, methacrylate 40-50 part, di-tert-butyl peroxide 35-45 part, poly- second Alkene pyrrolidone 25-35 part, tributyl 2-acetylcitrate 20-25 part, vinyl silicone oil 18-22 part, glycerol 15-20 part, ice Acetic acid 10-12 part, double maleamic acid 9-12 part, wollastonite in powder 6-8 part, nano titanium oxide 6-8 part, protonation shitosan 5- 7 parts, stabilizer 3-5 part, coupling agent 3-5 part.
Preferably, described stabilizer is selected from one or more of zinc stearate, calcium stearate, calcium oxide.
Preferably, described coupling agent is selected from one of silane coupler, Aluminum zirconium coupling agent and titanate coupling agent Or it is several.
The preparation method of described high intensity Artificial bone material, comprises the following steps:
(1) weigh each raw material according to weight portion;
(2) by methacrylate, di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, the mixing of double maleamic acid, are passed through co2 and fumigate 3-7min, then will add through stifling material In ultrasonic emulsification disperser, the concentration adding material twice quality is 3% naoh solution, is 20- in supersonic frequency Ultrasonic disperse 20min under conditions of 35khz, obtains supersound process mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 3-4h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, stabilizer, coupling agent, are heated to 350-400 DEG C while stirring, react 35- 45 minutes, reaction terminated rear spray injection drying tower and is dried process, obtains granular material;
(5) granular material obtaining is injected in double screw extruder, extrusion, pressing mold are moulding, after cooling after irradiation sterilization Pack and obtain finished product.
Preferably, described drying tower inlet temperature is 820-960 DEG C, and outlet temperature is 180-220 DEG C.
Preferably, the screw speed of described double screw extruder is 380-400r/min, and extrusion temperature is 260-280 DEG C.
Compared with prior art, its advantage is the present invention:
(1) the high intensity Artificial bone material of the present invention is with polyethylene, urethane dimethacrylate substrate, metering system Acid esters, di-tert-butyl peroxide, Polyvinylpyrrolidone are main component, by adding tributyl 2-acetylcitrate, ethylene Base silicone oil, glycerol, glacial acetic acid, double maleamic acid, wollastonite in powder, nano titanium oxide, protonation shitosan, stabilizer, Coupling agent, is aided with that co2 fumigates, ultrasonic emulsification dispersion, grinding, ball milling, banburying, the technique such as Screw Extrusion is so that be prepared from High intensity Artificial bone material, its mechanical strength, good biocompatibility, disclosure satisfy that the requirement of industry, have preferably Application prospect.
(2) the high intensity Artificial bone material raw material of the present invention is cheap, process is simple, is suitable to heavy industrialization and uses, Practical.
Specific embodiment
With reference to specific embodiment, the technical scheme of invention is described in detail.
Embodiment 1
(1) 50 parts of polyethylene, 45 parts of urethane dimethacrylate substrate, methacrylate 40 are weighed according to weight portion Part, 35 parts of di-tert-butyl peroxide, 25 parts of Polyvinylpyrrolidone, 20 parts of tributyl 2-acetylcitrate, vinyl silicone oil 18 Part, 15 parts of glycerol, 10 parts of glacial acetic acid, 9 parts of double maleamic acid, 6 parts of wollastonite in powder, 6 parts of nano titanium oxide, protonation shell 5 parts of polysaccharide, 3 parts of zinc stearate, 3 parts of silane coupler;
(2) by methacrylate, di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, the mixing of double maleamic acid, are passed through co2 and fumigate 3min, then super by adding through stifling material In sound wave emulsion dispersion device, the concentration adding material twice quality is 3% naoh solution, in the bar for 20khz for the supersonic frequency Ultrasonic disperse 20min under part, obtains supersound process mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 3h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, zinc stearate, silane coupler, are heated to 350 DEG C while stirring, reaction 35 minutes, reaction terminated rear spray injection drying tower and is dried process, and drying tower inlet temperature is 820 DEG C, and outlet temperature is 180 DEG C, obtain granular material;
(5) granular material obtaining is injected in double screw extruder, the screw speed of double screw extruder is 380r/ Min, extrusion temperature is 260 DEG C, and extrusion, pressing mold are moulding, pack and obtain finished product after cooling after irradiation sterilization.
The performance test results of prepared high intensity Artificial bone material are as shown in table 1.
Embodiment 2
(1) 55 parts of polyethylene, 50 parts of urethane dimethacrylate substrate, methacrylate 45 are weighed according to weight portion Part, 40 parts of di-tert-butyl peroxide, PVPK30 part, 22 parts of tributyl 2-acetylcitrate, vinyl silicone oil 20 Part, 18 parts of glycerol, 11 parts of glacial acetic acid, 10 parts of double maleamic acid, 7 parts of wollastonite in powder, 7 parts of nano titanium oxide, protonation 6 parts of shitosan, 4 parts of calcium stearate, 4 parts of Aluminum zirconium coupling agent;
(2) by methacrylate, di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, the mixing of double maleamic acid, are passed through co2 and fumigate 5min, then super by adding through stifling material In sound wave emulsion dispersion device, the concentration adding material twice quality is 3% naoh solution, in the bar for 30khz for the supersonic frequency Ultrasonic disperse 20min under part, obtains supersound process mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 3.5h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, calcium stearate, Aluminum zirconium coupling agent, are heated to 380 DEG C while stirring, Reaction 40 minutes, reaction terminates rear spray injection drying tower and is dried process, and drying tower inlet temperature is 890 DEG C, outlet temperature Spend for 200 DEG C, obtain granular material;
(5) granular material obtaining is injected in double screw extruder, the screw speed of double screw extruder is 390r/ Min, extrusion temperature is 270 DEG C, and extrusion, pressing mold are moulding, pack and obtain finished product after cooling after irradiation sterilization.
The performance test results of prepared high intensity Artificial bone material are as shown in table 1.
Embodiment 3
(1) 60 parts of polyethylene, 55 parts of urethane dimethacrylate substrate, methacrylate 50 are weighed according to weight portion Part, 45 parts of di-tert-butyl peroxide, 35 parts of Polyvinylpyrrolidone, 25 parts of tributyl 2-acetylcitrate, vinyl silicone oil 22 Part, 20 parts of glycerol, 12 parts of glacial acetic acid, 12 parts of double maleamic acid, 8 parts of wollastonite in powder, 8 parts of nano titanium oxide, protonation 7 parts of shitosan, 5 parts of calcium oxide, 5 parts of titanate coupling agent;
(2) by methacrylate, di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, the mixing of double maleamic acid, are passed through co2 and fumigate 7min, then super by adding through stifling material In sound wave emulsion dispersion device, the concentration adding material twice quality is 3% naoh solution, in the bar for 35khz for the supersonic frequency Ultrasonic disperse 20min under part, obtains supersound process mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 4h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, calcium oxide, titanate coupling agent, are heated to 400 DEG C while stirring, reaction 45 minutes, reaction terminated rear spray injection drying tower and is dried process, and drying tower inlet temperature is 960 DEG C, and outlet temperature is 220 DEG C, obtain granular material;
(5) granular material obtaining is injected in double screw extruder, the screw speed of double screw extruder is 400r/ Min, extrusion temperature is 280 DEG C, and extrusion, pressing mold are moulding, pack and obtain finished product after cooling after irradiation sterilization.
The performance test results of prepared high intensity Artificial bone material are as shown in table 1.
Embodiment 4
(1) 50 parts of polyethylene, 55 parts of urethane dimethacrylate substrate, methacrylate 40 are weighed according to weight portion Part, 45 parts of di-tert-butyl peroxide, 25 parts of Polyvinylpyrrolidone, 25 parts of tributyl 2-acetylcitrate, vinyl silicone oil 18 Part, 20 parts of glycerol, 10 parts of glacial acetic acid, 12 parts of double maleamic acid, 6 parts of wollastonite in powder, 8 parts of nano titanium oxide, protonation 5 parts of shitosan, 5 parts of zinc stearate, titanate coupling agent 3-5 part;
(2) by methacrylate, di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, the mixing of double maleamic acid, are passed through co2 and fumigate 3min, then super by adding through stifling material In sound wave emulsion dispersion device, the concentration adding material twice quality is 3% naoh solution, in the bar for 35khz for the supersonic frequency Ultrasonic disperse 20min under part, obtains supersound process mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 3h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, zinc stearate, titanate coupling agent, are heated to 400 DEG C, instead while stirring Answer 35 minutes, reaction terminates rear spray injection drying tower and is dried process, drying tower inlet temperature is 960 DEG C, outlet temperature For 180 DEG C, obtain granular material;
(5) granular material obtaining is injected in double screw extruder, the screw speed of double screw extruder is 400r/ Min, extrusion temperature is 260 DEG C, and extrusion, pressing mold are moulding, pack and obtain finished product after cooling after irradiation sterilization.
The performance test results of prepared high intensity Artificial bone material are as shown in table 1.
Comparative example 1
(1) 50 parts of polyethylene, 45 parts of urethane dimethacrylate substrate, methacrylate 40 are weighed according to weight portion Part, 25 parts of Polyvinylpyrrolidone, 20 parts of tributyl 2-acetylcitrate, 18 parts of vinyl silicone oil, 15 parts of glycerol, glacial acetic acid 10 Part, 9 parts of double maleamic acid, 6 parts of wollastonite in powder, 5 parts of shitosan of protonation, 3 parts of zinc stearate, 3 parts of silane coupler;
(2) by methacrylate, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl silicone oil, glycerol, ice vinegar Sour, double maleamic acid mixing, are passed through co2 and fumigate 3min, then will add in ultrasonic emulsification disperser through stifling material, The concentration adding material twice quality is 3% naoh solution, ultrasonic disperse under conditions of supersonic frequency is for 20khz 20min, obtains supersound process mixed liquor;
(3) wollastonite in powder, protonation shitosan are poured in mortar into ground and mixed uniformly, then this mixed-powder is added to ball mill In, 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, and Ball-milling Time is 3h, subsequently will Mixed powder is put in vacuum drying oven and is dried under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, zinc stearate, silane coupler, are heated to 350 DEG C while stirring, reaction 35 minutes, reaction terminated rear spray injection drying tower and is dried process, and drying tower inlet temperature is 820 DEG C, and outlet temperature is 180 DEG C, obtain granular material;
(5) granular material obtaining is injected in double screw extruder, the screw speed of double screw extruder is 380r/ Min, extrusion temperature is 260 DEG C, and extrusion, pressing mold are moulding, pack and obtain finished product after cooling after irradiation sterilization.
The performance test results of prepared high intensity Artificial bone material are as shown in table 1.
Comparative example 2
(1) 60 parts of polyethylene, 55 parts of urethane dimethacrylate substrate, di-tert-butyl peroxide are weighed according to weight portion 45 parts of thing, 35 parts of Polyvinylpyrrolidone, 25 parts of tributyl 2-acetylcitrate, 22 parts of vinyl silicone oil, 20 parts of glycerol, ice vinegar 12 parts of acid, 8 parts of wollastonite in powder, 8 parts of nano titanium oxide, 7 parts of shitosan of protonation, 5 parts of calcium oxide, 5 parts of titanate coupling agent;
(2) by di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl silicone oil, glycerol, Glacial acetic acid mixes, and is passed through co2 and fumigates 7min, then will add in ultrasonic emulsification disperser through stifling material, adds thing The concentration of material twice quality is 3% naoh solution, and under conditions of supersonic frequency is for 35khz, ultrasonic disperse 20min, is surpassed Sonication mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 4h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, calcium oxide, titanate coupling agent, are heated to 400 DEG C while stirring, reaction 45 minutes, reaction terminated rear spray injection drying tower and is dried process, and drying tower inlet temperature is 960 DEG C, and outlet temperature is 220 DEG C, obtain granular material;
(5) granular material obtaining is injected in double screw extruder, the screw speed of double screw extruder is 400r/ Min, extrusion temperature is 280 DEG C, and extrusion, pressing mold are moulding, pack and obtain finished product after cooling after irradiation sterilization.
The performance test results of prepared high intensity Artificial bone material are as shown in table 1.
The prepared high intensity Artificial bone material of embodiment 1-4 and comparative example 1-2 is carried out tensile strength, tear respectively Intensity, sensitization test, zest test this several performance tests.
Table 1
  Tensile strength (mpa) Tearing strength (kn/m) Sensitization test gb/t16886.10-2005) Zest tests (gb/t16886.1-2011)
Embodiment 1 15.7 38.8 No anaphylaxiss Nonirritant is reacted
Embodiment 2 14.9 36.4 No anaphylaxiss Nonirritant is reacted
Embodiment 3 15.6 37.5 No anaphylaxiss Nonirritant is reacted
Embodiment 4 14.4 35.9 No anaphylaxiss Nonirritant is reacted
Comparative example 1 8.3 22.7 Slight anaphylaxiss Minimal irritation is reacted
Comparative example 2 8.1 21.2 Slight anaphylaxiss Minimal irritation is reacted
The high intensity Artificial bone material of the present invention is with polyethylene, urethane dimethacrylate substrate, methacrylic acid Ester, di-tert-butyl peroxide, Polyvinylpyrrolidone are main component, by adding tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, double maleamic acid, wollastonite in powder, nano titanium oxide, protonation shitosan, stabilizer, idol Connection agent, is aided with that co2 fumigates, ultrasonic emulsification dispersion, grinding, ball milling, banburying, the technique such as Screw Extrusion is so that the height that is prepared from Intensity artificial's bone material, its mechanical strength, good biocompatibility, disclosure satisfy that the requirement of industry, preferably should have Use prospect.Meanwhile, the high intensity Artificial bone material raw material of the present invention is cheap, process is simple, is suitable to heavy industrialization and uses, Practical.
The foregoing is only embodiments of the invention, not thereby limit the scope of the claims of the present invention, every said using the present invention Equivalent structure or equivalent flow conversion that bright book content is made, or directly or indirectly it is used in other related technical fields, all It is included within the scope of the present invention in the same manner.

Claims (6)

1. high intensity Artificial bone material it is characterised in that: be prepared by the raw materials in: polyethylene 50-60 part, diformazan Base propenoic methyl carbamate substrate 45-55 part, methacrylate 40-50 part, di-tert-butyl peroxide 35-45 part, poly- Vinylpyrrolidone 25-35 part, tributyl 2-acetylcitrate 20-25 part, vinyl silicone oil 18-22 part, glycerol 15-20 part, Glacial acetic acid 10-12 part, double maleamic acid 9-12 part, wollastonite in powder 6-8 part, nano titanium oxide 6-8 part, protonation shitosan 5-7 part, stabilizer 3-5 part, coupling agent 3-5 part.
2. high intensity Artificial bone material according to claim 1 it is characterised in that: described stabilizer be selected from stearic acid One or more of zinc, calcium stearate, calcium oxide.
3. high intensity Artificial bone material according to claim 1 it is characterised in that: described coupling agent be selected from silane coupled One or more of agent, Aluminum zirconium coupling agent and titanate coupling agent.
4. the preparation method according to the arbitrary described high intensity Artificial bone material of claims 1 to 3 is it is characterised in that include Following steps:
(1) weigh each raw material according to weight portion;
(2) by methacrylate, di-tert-butyl peroxide, Polyvinylpyrrolidone, tributyl 2-acetylcitrate, vinyl Silicone oil, glycerol, glacial acetic acid, the mixing of double maleamic acid, are passed through co2 and fumigate 3-7min, then will add through stifling material In ultrasonic emulsification disperser, the concentration adding material twice quality is 3% naoh solution, is 20- in supersonic frequency Ultrasonic disperse 20min under conditions of 35khz, obtains supersound process mixed liquor;
(3) wollastonite in powder, nano titanium oxide, protonation shitosan are poured in mortar into ground and mixed uniformly, then this is mixed Powder is added in ball mill, and 80% ethanol solution of the quality such as addition carries out wet ball grinding, and ball milling speed is 350 revolutions per seconds, ball milling Time is 3-4h, subsequently puts into mixed powder in vacuum drying oven and dries under the conditions of 80 DEG C, obtains powder dry-blend;
(4) by the powder dry-blend injection banburying stove of the supersound process mixed liquor of step (2) and step (3), add poly- Ethylene, urethane dimethacrylate substrate, stabilizer, coupling agent, are heated to 350-400 DEG C while stirring, react 35- 45 minutes, reaction terminated rear spray injection drying tower and is dried process, obtains granular material;
(5) granular material obtaining is injected in double screw extruder, extrusion, pressing mold are moulding, after cooling after irradiation sterilization Pack and obtain finished product.
5. high intensity Artificial bone material according to claim 4 preparation method it is characterised in that: described drying tower enters Mouth temperature is 820-960 DEG C, and outlet temperature is 180-220 DEG C.
6. high intensity Artificial bone material according to claim 4 preparation method it is characterised in that: described twin screw squeeze The screw speed going out machine is 380-400r/min, and extrusion temperature is 260-280 DEG C.
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