CN110025406A - A kind of preparation method of 3D printing bone defect filler - Google Patents

A kind of preparation method of 3D printing bone defect filler Download PDF

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Publication number
CN110025406A
CN110025406A CN201910308623.8A CN201910308623A CN110025406A CN 110025406 A CN110025406 A CN 110025406A CN 201910308623 A CN201910308623 A CN 201910308623A CN 110025406 A CN110025406 A CN 110025406A
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CN
China
Prior art keywords
printing
coral
bone
artificial bone
preparation
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Pending
Application number
CN201910308623.8A
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Chinese (zh)
Inventor
付昆
郑建超
胡天宙
张洪波
陆益栋
邢天龙
王子振彪
于鹏
殷瑞雪
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First Affiliated Hospital Of Hainan Medical College
Shanghai Heiyan Medical Technology Co ltd
Original Assignee
First Affiliated Hospital Of Hainan Medical College
Shanghai Heiyan Medical Technology Co ltd
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Application filed by First Affiliated Hospital Of Hainan Medical College, Shanghai Heiyan Medical Technology Co ltd filed Critical First Affiliated Hospital Of Hainan Medical College
Priority to CN201910308623.8A priority Critical patent/CN110025406A/en
Publication of CN110025406A publication Critical patent/CN110025406A/en
Pending legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02Prostheses implantable into the body
    • A61F2/28Bones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00Products made by additive manufacturing

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Vascular Medicine (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Transplantation (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Cardiology (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The present invention provides a kind of preparation method of 3D printing bone defect filler, it include: the artificial bone that coral structures are imitated in 3D printing, the hydrothermal synthesis of imitative artificial bone of coral and ammonium dihydrogen phosphate, the artificial bone that coral structures are imitated in the 3D printing includes printing slurry preparation, printer model slice, imitative artificial bone of coral printing, 3D printing obtained by the present invention is imitated artificial bone of coral and can be printed by patient's CT scan data, fitting bone defect position completely, 3D printing obtained by the present invention imitates artificial bone of coral after hydrothermal synthesis reaction, surface forms hydroxyapatite, it is consistent with skeleton ingredient, lot of documents shows, hydroxyapatite is conducive to Bone Defect Repari, artificial bone of coral is imitated in the obtained 3D printing of invention has good biocompatibility, calcium carbonate has faster degradation speed, without taking out after implantation.

Description

A kind of preparation method of 3D printing bone defect filler
Technical field
The present invention relates to medical science and technology technical field, specially a kind of preparation method of 3D printing bone defect filler.
Background technique
Bone defect is a kind of common clinical, and Chang Fasheng treats the big limbs of difficulty in wound, various wounds, explosion injury etc. Functional rehabilitation is difficult, and present treatment is using outer implant filling bone defects position as main means.But due to the bone of different parts Defect has significant difference, and the histocompatbility of filler, stress, cell adhesion have different degrees of limitation, make Restore obstacle at limb function.
Hassan Green has the pore structure similar with people's bone, and 20 for many years, and a variety of researchs through many scholars confirm, Artificial bone of coral is a kind of good bone substitute, and main component is calcium carbonate.It is currently known with good biofacies Capacitive and bone guided effect, and have biological degradability, porous structure is conducive to host bone tissue and blood, and fibr tissue is long Enter, has stronger compatibility, no rejection with bone tissue.But because coral is endangered species, harvesting and use are by tight Raw material, is unable to supply using the artificial bone that coral makes, just cannot be widely applied to clinic by lattice limitation.
Summary of the invention
Technical problem solved by the invention is to provide a kind of preparation method of 3D printing bone defect filler, to solve The problems mentioned above in the background art.
Technical problem solved by the invention is realized using following technical scheme: a kind of 3D printing bone defect filler Preparation method, comprising: the hydrothermal synthesis of the artificial bone of coral structures, imitative artificial bone of coral and ammonium dihydrogen phosphate, institute are imitated in 3D printing Stating 3D printing and imitating the artificial bone of coral structures includes printing slurry preparation, printer model slice, imitative artificial bone of coral printing,
The hydrothermal synthesis of the imitative artificial bone of coral and ammonium dihydrogen phosphate is the following steps are included: (a) putting dry completion Artificial bone of coral is weighed;(b) according to the equation of hydro-thermal reaction, it is molten that ammonium dihydrogen phosphate is prepared using 1.2 times of mol ratios Liquid;(c) the imitative artificial bone of coral that 3D printing goes out is put into reaction kettle, ammonium dihydrogen phosphate is added, reacts 12 in an oven Hour;Reaction equation is as follows: 10CaCO3+6(NH4)H2PO4+2H2O→Ca10(PO4)6(OH)2+3(NH4)2CO3+7H2O+7CO2 ↑。
The printing slurry preparation is the following steps are included: biocompatible polymer material is dissolved in methylene chloride by (a) In, uniform biocompatible polymer material solution is formed after stirring;(b) it is added after nanometer grade calcium carbonate being crossed 400 meshes Into biocompatible polymer material solution, calcium carbonate is set to be uniformly dispersed by stirring;(c) poloxamer F68 is added to In biocompatible polymer material solution, stir evenly;(d) dehydrated alcohol is eventually adding to be uniformly mixed.
The slice thickness 0.2-0.4mm, interior porosity 40%-90% of the printer model slice.
The printing type of the imitative artificial bone of coral printing is that material squeezes out sedimentation type.
The artificial bone of imitative coral structures score meter by weight is made of 20% polylactic acid and 80% nanometer grade calcium carbonate.
The biocompatible polymer material is polylactic acid and its derivative.
The imitative artificial bone of coral is porous structure, and porosity 40%-90%, line spacing is 0.3-1.0mm.
The print temperature of the imitative artificial bone of coral printing is 20 DEG C, print speed 13-18mm/s, force of impression 1.5- 4bar.It is printed using the dispensing needle head of 200 μm or 300 μm.The bracket that printing is completed is put into convection oven, at 40 DEG C Lower drying 8 hours.
The imitative artificial bone of coral reacts 12 with ammonium dihydrogen phosphate at 80 DEG C with the hydrothermal synthesis of ammonium dihydrogen phosphate Hour.Cooled to room temperature after the reaction was completed.It takes out bracket to be embathed 3 times with ultrapure water, 10 minutes every time, is then placed in 80 DEG C It is dried in baking oven.
The hydrothermal synthesis temperature of the imitative artificial bone of coral and ammonium dihydrogen phosphate is 60-100 DEG C.
Compared with prior art, the beneficial effects of the present invention are:
(1) 3D printing obtained by the present invention is imitated artificial bone of coral and can be printed by patient's CT scan data, pastes completely Close bone defect position.
(2) 3D printing obtained by the present invention imitates artificial bone of coral after hydrothermal synthesis reaction, and surface forms hydroxyl phosphorus Lime stone, consistent with skeleton ingredient, lot of documents shows that hydroxyapatite is conducive to Bone Defect Repari.
(3) artificial bone of coral is imitated in the 3D printing obtained by the present invention has good biocompatibility, and calcium carbonate has more Fast degradation speed, without taking out after implantation.
Detailed description of the invention
Fig. 1 is the final bone defect filler schematic diagram of invention.
Fig. 2 is the monoclinic system hydroxyapatite SEM result schematic diagram on filler surface after the hydrothermal synthesis reaction invented.
Fig. 3 is bracket EDS and the SEM result schematic diagram under different hydrothermal temperatures of the invention.
Specific embodiment
In order to make implement technical means of the invention, creation characteristic, reach purpose and effect is easy to understand, tie below Conjunction is specifically illustrating, and the present invention is further explained, in the description of the present invention, it should be noted that unless otherwise specific regulation And restriction, term " installation ", " company ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, be also possible to detachable Connection, or be integrally connected and can be mechanical connection, it is also possible to be electrically connected;It can be directly connected, centre can also be passed through Medium is indirectly connected, can connection inside two elements.
A kind of preparation method of 3D printing bone defect filler, comprising the following steps:
Step 1. prints slurry preparation:
Polylactic acid is pressed to the concentration adding into dichloromethane of 20% (w/v) at room temperature, closed container is stirred using magnetic force It mixes machine stirring and obtains uniform solution in 30 minutes.Nanometer grade calcium carbonate is crossed after 400 meshes and is added in the ratio of polylactic acid 1:4 Into aforementioned acquired solution, is stirred 30 minutes using magnetic stirrer and obtain evenly dispersed solution.By the pool Lip river of 3% (v/v) The dehydrated alcohol of husky nurse F68 and 22% (v/v) are added in aforementioned acquired solution, are mixed on turbula shaker with 3000rpm 90 seconds, resulting slurry is transferred in the barrel of 3D printer.
Step 2. printer model slice
The threedimensional model of bone defect position STL format is obtained according to the CT scan data of patient.It is opened using Slice Software It is placed on print platform at an appropriate angle according to the feature of model file and is sliced by stl file, slice thickness 0.2-0.4mm, interior porosity 40%-90%, saves after the completion.
Step 3. imitates artificial bone of coral printing
The printer that the present invention uses is pneumatic mode driving.Slice file is opened using 3D printer control software, if Setting print temperature is 20 DEG C, print speed 13-18mm/s, force of impression 1.5-4bar.Use 200 μm or 300 μm of dispensing Syringe needle is printed.The bracket that printing is completed is put into convection oven, is dried 8 hours at 40 DEG C.
Step 4. imitates artificial bone of coral hydrothermal synthesis
The quality of artificial bone of coral is imitated with electronic balance weighing, and according to needed for expansion incremental computations of the reaction equation with 1.2 times Ammonium dihydrogen phosphate content.Ammonium dihydrogen phosphate is configured to aqueous solution by mol ratio, is transferred to reaction kettle after mixing evenly In.The imitative artificial bone of coral of aforementioned drying is put into reaction kettle, is reacted with ammonium dihydrogen phosphate 12 hours at 80 DEG C.Instead Cooled to room temperature after the completion of answering.It takes out bracket to be embathed 3 times with ultrapure water, 10 minutes every time, be then placed in 80 DEG C of baking ovens Drying.
3D printing of the invention is one kind based on mathematical model, by the data of the acquisitions such as computer simulation, CT scan, Construct the technology of 3 D stereo fine structure by printed material according to the principle being successively superimposed under the control of the computer.Past It is often used for modeling in fields such as mold manufacture, industrial designs, is now increasingly used for the medical material of such as tooth, hip joint The manufacture of material.3D printing has the characteristics that flexible, quick, fine.Currently, multiple using calcium carbonate/hydroxyapatite and adhesive Cooperation is printed material, and the three-dimensional structure of similar human body bone trabecula is constructed using the fining feature of 3D printing technique, according to The characteristics of different bone defect positions, prepares the artificial bone with different performance, has a good application prospect.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.Claimed range of the invention by appended claims and Its equivalent thereof.

Claims (10)

1. a kind of preparation method of 3D printing bone defect filler, it is characterised in that: include: that the artificial of coral structures is imitated in 3D printing The hydrothermal synthesis of bone, imitative artificial bone of coral and ammonium dihydrogen phosphate, the artificial bone that coral structures are imitated in the 3D printing includes printing slurry Material is prepared, printer model slice, imitative artificial bone of coral print, the hydrothermal synthesis packet of the imitative artificial bone of coral and ammonium dihydrogen phosphate It includes following steps: (a) the dry artificial bone of coral of putting completed being weighed;(b) it according to the equation of hydro-thermal reaction, uses 1.2 times of mol ratios prepare ammonium dihydrogen phosphate;(c) the imitative artificial bone of coral that 3D printing goes out is put into reaction kettle, is added Ammonium dihydrogen phosphate reacts 12 hours in an oven;Reaction equation is as follows: 10CaCO3+6(NH4)H2PO4+2H2O→Ca10 (PO4)6(OH)2+3(NH4)2CO3+7H2O+7CO2↑。
2. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the printing Slurry preparation is the following steps are included: (a) dissolves biocompatible polymer material in methylene chloride, and formation is uniform after stirring Biocompatible polymer material solution;(b) biocompatibility macromolecule is added to after nanometer grade calcium carbonate being crossed 400 meshes In material solution, calcium carbonate is set to be uniformly dispersed by stirring;(c) poloxamer F68 is added to biocompatibility macromolecule material Expect to stir evenly in solution;(d) dehydrated alcohol is eventually adding to be uniformly mixed.
3. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the printing The slice thickness 0.2-0.4mm of model slice, interior porosity 40%-90%.
4. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the imitative coral The printing type of coral artificial bone printing is that material squeezes out sedimentation type.
5. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the imitative coral The artificial bone of coral structure score meter by weight is made of 20% polylactic acid and 80% nanometer grade calcium carbonate.
6. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the life Object compatible polymeric material is polylactic acid and its derivative.
7. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: described is imitative Artificial bone of coral is porous structure, and porosity 40%-90%, line spacing is 0.3-1.0mm.
8. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the imitative coral The print temperature of coral artificial bone printing is 20 DEG C, print speed 13-18mm/s, force of impression 1.5-4bar;Using 200 μm or 300 μm of dispensing needle head is printed;The bracket that printing is completed is put into convection oven, is dried 8 hours at 40 DEG C.
9. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: the imitative coral Coral artificial bone reacts 12 hours with the hydrothermal synthesis of ammonium dihydrogen phosphate at 80 DEG C with ammonium dihydrogen phosphate;After the reaction was completed certainly So it is cooled to room temperature;It takes out bracket to be embathed 3 times with ultrapure water, 10 minutes every time, is then placed in 80 DEG C of baking ovens and dries.
10. a kind of preparation method of 3D printing bone defect filler according to claim 1, it is characterised in that: described imitative The hydrothermal synthesis temperature of artificial bone of coral and ammonium dihydrogen phosphate is 60-100 DEG C.
CN201910308623.8A 2019-04-17 2019-04-17 A kind of preparation method of 3D printing bone defect filler Pending CN110025406A (en)

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CN113831110A (en) * 2021-09-17 2021-12-24 杭州电子科技大学 3D printing porous coral and preparation method thereof

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Application publication date: 20190719