CN107837421A - A kind of high-strength bone reparation with bioactivity modified Nano particle composite thermoplastic polymer 3D printing material and preparation - Google Patents
A kind of high-strength bone reparation with bioactivity modified Nano particle composite thermoplastic polymer 3D printing material and preparation Download PDFInfo
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- CN107837421A CN107837421A CN201710834976.2A CN201710834976A CN107837421A CN 107837421 A CN107837421 A CN 107837421A CN 201710834976 A CN201710834976 A CN 201710834976A CN 107837421 A CN107837421 A CN 107837421A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
A kind of high-strength bone reparation with bioactivity modified Nano particle composite thermoplastic polymer 3D printing material and preparation, are related to 3D printing field.Include and with polymer matrix bluk recombination prepared by two parts to the surface modification of nano-particle and modified Nano particle.Present invention process is simple, and prepared composite has good mechanical property and biocompatibility, and the advantage customized with reference to 3D printing in micromodel structure, the composite has a good application prospect in Bone Defect Repari field.
Description
Technical field
The present invention relates to 3D printing field, is received more particularly to a kind of high-strength bone reparation with bioactivity with modification
Rice corpuscles composite thermoplastic polymer 3D printing material
Background technology
Bone is used for supporting body, protection internal organ, the histoorgan for completing motion as human body, carries the weight of vital movement
Want responsibility.But because disease, accident, congenital sexual factor etc. easily cause the defect of bone tissue, according to statistics, have every year millions of
Bone tissue defect patient need be treated surgically.In such a populous nation of China, it is estimated that every year because of traffic accident
With the orthopaedic disease such as trauma fracture caused by work safety accident, backbone degenerative disease and bone tumour, bone tuberculosis, Cranial defect is caused
Or dysfunction is more than 3,000,000 people.Bone collection turns into the graft having the call for being only second to blood transfusion.
Because the size and shape at Cranial defect position varies with each individual, it is therefore desirable to a kind of quick molding method, it is individual to realize
Propertyization is treated.To meet this demand, 3D printing technique is got the attention in the therapeutic process of Cranial defect.3D is beaten
Print, i.e., traditional increases material manufacturing technology, it is the technology that the method gradually to be added up using material manufactures entity component, relatively
It is the manufacture method of a kind of " from bottom to top " in traditional material removal-Machining Technology for Cutting.3D printing technique greatly drops
Low product innovation cost, shorten the innovation R＆D cycle；Simplify to make and improve product quality and performance；Traditional work can be produced
The parts that skill can not process, greatly enhance technique fulfillment capability；Difficult-to-machine material machinability is improved, has expanded engineering
Field；Promote green manufacturing mode；Conventionally manufactured pattern is changed, forms new manufacturing system.
For bone defect healing material, mechanical property and osteogenic induction ability are two crucial technical indicators, are
The performance of this respect is improved, the technology of organic/inorganic composite material can be taken.China Patent Publication No. CN100471912C is public
A kind of controlled degradation absorbability bioactive composite material and preparation method thereof is opened.The composite can be used as cancellous bone and portion
Divide the cortex bone even degradable resorbable bone inner fixing device of cortex bone, there is good biocompatibility, but its material sheet
For body because the simple physical for being inorganic matter and organic matter is compound, organic/inorganic interface lacks effective adhesion, causes its mechanical property
It is not very excellent, if in human body bone weight bearing area, its mechanical property can not meet to require as stent applications.
To solve the interfacial combined function of composite, surface modification can be carried out to inorganic filler, to strengthen itself and base
The binding ability of body.China Patent Publication No. CN1544524A discloses a kind of hydroxylapatite biology degrading aliphatic polyester and answered
The preparation method of condensation material.Polymeric chain is connected by the composite by chemical bond with hydroxyapatite, is made inorganic
Phase uniform particle stable dispersion, improve the mechanical property of material.But shortcoming is complex process, the dehydrating polycondensation that it is utilized is anti-
Condition is answered to require harsh, it is costly in actual industrial production, it is not easy to realize.
At present in 3D printing industry, most research is concentrated in the species of Biodegradable material, for work(
The research of energy property Biodegradable material is very deficient.In order to widen the application field of 3D printing Biodegradable material and more
The deficiency for stating other patents is filled, the present invention is intended to provide a kind of preparation technology is simple, excellent in mechanical performance, biocompatibility
It is good, and the thermoplastic polymer composite material with Bone Defect Repari application prospect.
The content of the invention
Beaten in view of the above-mentioned problems, the present invention proposes a kind of Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D
The preparation method of material is printed, surface modification is carried out to inorganic nano-particle by relatively simple technique, and by itself and thermoplasticity
Polyester is compound, and obtained composite can keep the good rapid shaping performance of thermoplastic polymer, but also with superior power
Performance and biocompatibility are learned, while there is Bone Defect Repari application prospect.
The technical solution adopted for the present invention to solve the technical problems is：A kind of Bone Defect Repari modified Nano particle compound thermal
Thermoplastic polymer 3D printing material, it is characterised in that including thermoplastic polymer and modified Nano particle, thermoplastic polymer is
60~95 mass parts, the mass parts of nano-particle 5~40, preferred thermoplastic polymer and nano-particle amount to 100 mass parts；
Above-mentioned thermoplastic polymer is the one or more in polyesters compound or poly- acid compounds；Such as selected from poly- breast
One or more in acid, polycaprolactone, Poly(D,L-lactide-co-glycolide, poly butylene succinate etc..
Above-mentioned nano-particle is hydroxyapatite, is shaped as needle-like, and particle diameter length is about 20~40nm.
Above-mentioned modification uses dopamine and alkyl diamine compound, and modified mode is solution modification, dopamine and alkyl
The mass concentration of diamine compound is respectively preferably 2~10mg/mL and 10~100mg/mL.
Abovementioned alkyl diamine compound is diamine compound of the C atom numbers of alkyl chain between 2~12, is preferably oneself
Diamines.
Above-mentioned solution modification system is Tris cushioning liquid, and its concentration is preferably 0.1mol/L.
Thermoplastic polymer a large amount of add in system also functions as polymeric matrix as modifying agent.
The preparation method of above-mentioned Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material, including with
Lower step：
(1) the Tris cushioning liquid prepared, preferred concentration 0.1mol/L add dopamine, and concentration is preferably maintained at 2~
10mg/mL, alkyl diamine compound is added, the concentration for keeping alkyl diamine compound is preferably 10~100mg/mL；
(2) the solution (1) nano-particle addition step prepared, concentration preferably remain in 5~10mg/mL, are ultrasonically treated 10
~60min, by the product handled centrifugation, washing, dry, obtain dopamine modified Nano particle of the surface containing a large amount of amino；
(3) the modified Nano particle and thermoplastic polymer that are obtained through step (2) are proportionally added into oil-based solvent,
Modified Nano particle concentration preferably remains in 5~10mg/mL, and aminolysis reaction is carried out at 20~60 DEG C and stirs 12~36h, will be anti-
Answered product revolving, dry, obtain surface modification polymer modified Nano particle and its be dispersed in polymeric matrix
Composite；
(4) will be added through the material that step (3) obtain in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：150~170 DEG C；2nd area：180~200 DEG C；3rd area：170~190 DEG C；Head temperature：160~180 DEG C；
Screw speed is controlled in 100~200r/min；After melting extrusion through traction, water cooling, air-dry, winding obtains the Bone Defect Repari with changing
Property Nanocomposites thermoplastic polymer 3D printing material；
Above-mentioned oil-based solvent is that the one or more mixing in dioxane, chloroform, dichloromethane, tetrahydrofuran is molten
Liquid.
The preparation method of the above-mentioned 3D printing material with Bone Defect Repari performance is also including the use of filament winding machine by the step
(5) the 3D printing material with Bone Defect Repari performance obtained from single screw rod nose towing wind the step of, the bracing wire hauling machine
Automatic hauling speed is arranged to 100~300r/min, so as to obtain the regular wire rod of diameter (a diameter of 1.75mm of wire rod or
3.00mm)。
The beneficial effects of the invention are as follows：The thermoplastic polymer composite material with Bone Defect Repari performance prepared by the present invention
Preparation technology it is simple, obtained product mechanical property is excellent, good biocompatibility, widened Biodegradable material should
Use field.
Embodiment
With reference to embodiment, the present invention is further explained and illustrated, but embodiments of the present invention are not limited to
This.
In embodiment, thermoplastic resin be Shandong Prov. Medical Apparatus ＆ Instrument Research Inst provide PLLA, molecular weight 100000；
Nano-particle selects hydroxyapatite, and its average grain diameter is 30nm；Dopamine, hexamethylene diamine, three (methylol) aminomethanes
(Tris) purchase from Sa En chemical technologies (Shanghai) Co., Ltd., dioxane and be purchased from Beijing Chemical Plant.
Embodiment 1
There is Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material in the present embodiment, by following
The component composition of mass fraction：PLLA is 90 parts；Hydroxyapatite is 10 parts；Tris buffer concentrations are 0.1mol/L；It is more
Bar amine concentration remains 7mg/mL；Hexamethylene diamine concentration is 70mg/mL；
The Bone Defect Repari is as follows with the preparation method of PLLA composites：
(1) the Tris cushioning liquid prepared, concentration 0.1mol/L, dopamine is added, concentration remains 7mg/mL, then adds
Enter hexamethylene diamine, the concentration for keeping hexamethylene diamine is 70mg/mL；
(2) the solution (1) nano-particle addition step prepared, concentration are maintained at 5mg/mL, are ultrasonically treated 15min, will locate
The product managed is centrifuged, washes, dried, and obtains dopamine modified Nano particle of the surface containing a large amount of amino；
(3) dioxane will be added by different proportion through the modified Nano particle that step (2) obtain and thermoplastic polymer
In, nanoparticle concentration is maintained at 5mg/mL, and aminolysis reaction stirring 24h is carried out at 37 DEG C, by the product reacted revolving, is done
It is dry, obtain surface modification polymer modified Nano particle and its be dispersed in the composite of polymeric matrix；
(4) will be added through the material that step (3) obtain in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：160℃；2nd area：190℃；3rd area：180℃；Head temperature：175℃；Screw speed is controlled in 125r/
min；Obtain the Bone Defect Repari modified Nano particle composite thermoplastic through traction, water cooling, air-dried, winding after melting extrusion and polymerize
Thing 3D printing material；
Material through step (5) melting extrusion by traction, water cooling, air-dry, wind to obtain by filament winding machine again and described there is bone
PLLA composites are used in reparation, and the hauling speed of filament winding machine is arranged to 180r/min, so as to obtain the regular of a diameter of 1.75mm
Wire rod.
A diameter of 1.75mm regular wire rod is sent into 3D printer, parameter is arranged to nozzle temperature in print procedure
230 DEG C, floor height 0.2mm, extruded velocity 90mm/s, translational speed 150mm/s, filling rate 15%.
Embodiment 2
There is Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material in the present embodiment, by following
The component composition of mass fraction：PLLA is 70 parts；Hydroxyapatite is 30 parts；Tris buffer concentrations are 0.1mol/L；It is more
Bar amine concentration remains 7mg/mL；Hexamethylene diamine concentration is 70mg/mL；
The Bone Defect Repari is as follows with the preparation method of PLLA composites：
(1) the Tris cushioning liquid prepared, concentration 0.1mol/L, dopamine is added, concentration remains 7mg/mL, then adds
Enter hexamethylene diamine, the concentration for keeping hexamethylene diamine is 70mg/mL；
(2) the solution (1) nano-particle addition step prepared, concentration are maintained at 5mg/mL, are ultrasonically treated 15min, will locate
The product managed is centrifuged, washes, dried, and obtains dopamine modified Nano particle of the surface containing a large amount of amino；
(3) dioxane will be added by different proportion through the modified Nano particle that step (2) obtain and thermoplastic polymer
In, nanoparticle concentration is maintained at 5mg/mL, and aminolysis reaction stirring 24h is carried out at 37 DEG C, by the product reacted revolving, is done
It is dry, obtain surface modification polymer modified Nano particle and its be dispersed in the composite of polymeric matrix；
(4) will be added through the material that step (3) obtain in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：160℃；2nd area：190℃；3rd area：180℃；Head temperature：175℃；Screw speed is controlled in 125r/
min；Obtain the Bone Defect Repari modified Nano particle composite thermoplastic through traction, water cooling, air-dried, winding after melting extrusion and polymerize
Thing 3D printing material；
Material through step (5) melting extrusion by traction, water cooling, air-dry, wind to obtain by filament winding machine again and described there is bone
PLLA composites are used in reparation, and the hauling speed of filament winding machine is arranged to 180r/min, so as to obtain the regular of a diameter of 1.75mm
Wire rod.
A diameter of 1.75mm regular wire rod is sent into 3D printer, parameter is arranged to nozzle temperature in print procedure
230 DEG C, floor height 0.2mm, extruded velocity 90mm/s, translational speed 150mm/s, filling rate 15%.
Comparative example 1
There is Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material in the present embodiment, by following
The component composition of mass fraction：PLLA is 90 parts；Hydroxyapatite is 10 parts；Tris buffer concentrations are 0.1mol/L；It is more
Bar amine concentration remains 7mg/mL.
The Bone Defect Repari is as follows with the preparation method of PLLA composites：
(1) the Tris cushioning liquid prepared, concentration 0.1mol/L add dopamine, and concentration remains 7 mg/mL；
(2) the solution (1) nano-particle addition step prepared, concentration are maintained at 5mg/mL, are ultrasonically treated 15min, will locate
The product managed is centrifuged, washes, dried, and it is dopamine modified Nano particle to obtain surface；
(3) dioxane will be added by different proportion through the modified Nano particle that step (2) obtain and thermoplastic polymer
In, nanoparticle concentration is maintained at 5mg/mL, and 24h is stirred at 37 DEG C, by the product reacted revolving, dries, is modified
Nano-particle is dispersed in the composite of polymeric matrix；
(4) will be added through the material that step (3) obtain in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：160℃；2nd area：190℃；3rd area：180℃；Head temperature：175℃；Screw speed is controlled in 125r/
min；Obtain the Bone Defect Repari modified Nano particle composite thermoplastic through traction, water cooling, air-dried, winding after melting extrusion and polymerize
Thing 3D printing material；
Material through step (4) melting extrusion by traction, water cooling, air-dry, wind to obtain by filament winding machine again and described have
Bone Defect Repari PLLA composites, the hauling speed of filament winding machine are arranged to 180r/min, so as to obtain a diameter of 1.75mm rule
Whole wire rod.
A diameter of 1.75mm regular wire rod is sent into 3D printer, parameter is arranged to nozzle temperature in print procedure
230 DEG C, floor height 0.2mm, extruded velocity 90mm/s, translational speed 150mm/s, filling rate 15%.
Comparative example 2
There is Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material in the present embodiment, by following
The component composition of mass fraction：PLLA is 70 parts；Hydroxyapatite is 30 parts；Tris buffer concentrations are 0.1mol/L；It is more
Bar amine concentration remains 7mg/mL.
The Bone Defect Repari is as follows with the preparation method of PLLA composites：
(1) the Tris cushioning liquid prepared, concentration 0.1mol/L add dopamine, and concentration remains 7 mg/mL；
(2) the solution (1) nano-particle addition step prepared, concentration are maintained at 5mg/mL, are ultrasonically treated 15min, will locate
The product managed is centrifuged, washes, dried, and it is dopamine modified Nano particle to obtain surface；
(3) dioxane will be added by different proportion through the modified Nano particle that step (2) obtain and thermoplastic polymer
In, nanoparticle concentration is maintained at 5mg/mL, and 24h is stirred at 37 DEG C, by the product reacted revolving, dries, is modified
Nano-particle is dispersed in the composite of polymeric matrix；
(4) will be added through the material that step (3) obtain in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：160℃；2nd area：190℃；3rd area：180℃；Head temperature：175℃；Screw speed is controlled in 125r/
min；Obtain the Bone Defect Repari modified Nano particle composite thermoplastic through traction, water cooling, air-dried, winding after melting extrusion and polymerize
Thing 3D printing material；
Material through step (4) melting extrusion by traction, water cooling, air-dry, wind to obtain by filament winding machine again and described there is bone
PLLA composites are used in reparation, and the hauling speed of filament winding machine is arranged to 180r/min, so as to obtain the regular of a diameter of 1.75mm
Wire rod.
A diameter of 1.75mm regular wire rod is sent into 3D printer, parameter is arranged to nozzle temperature in print procedure
230 DEG C, floor height 0.2mm, extruded velocity 90mm/s, translational speed 150mm/s, filling rate 15%.
Comparative example 3
There is Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material in the present embodiment, by following
The component composition of mass fraction：PLLA is 90 parts；Hydroxyapatite is 10 parts.
The Bone Defect Repari is as follows with the preparation method of PLLA composites：
Nano-particle and PLLA are well mixed and added in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：160℃；2nd area：190℃；3rd area：180℃；Head temperature：175℃；Screw speed is controlled in 125r/
min；Obtain the Bone Defect Repari modified Nano particle composite thermoplastic through traction, water cooling, air-dried, winding after melting extrusion and polymerize
Thing 3D printing material；
Material through single screw rod melt blending extrusion by traction, water cooling, it is air-dried, wound to obtain the tool again by filament winding machine
There are Bone Defect Repari PLLA composites, the hauling speed of filament winding machine is arranged to 180r/min, so as to obtain a diameter of 1.75mm's
Regular wire rod.
A diameter of 1.75mm regular wire rod is sent into 3D printer, parameter is arranged to nozzle temperature in print procedure
230 DEG C, floor height 0.2mm, extruded velocity 90mm/s, translational speed 150mm/s, filling rate 15%.
Comparative example 4
There is Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing material in the present embodiment, by following
The component composition of mass fraction：PLLA is 70 parts；Hydroxyapatite is 30 parts.
The Bone Defect Repari is as follows with the preparation method of PLLA composites：
Nano-particle and PLLA are well mixed and added in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature
Degree is arranged to：One area：160℃；2nd area：190℃；3rd area：180℃；Head temperature：175℃；Screw speed is controlled in 125r/
min；Obtain the Bone Defect Repari modified Nano particle composite thermoplastic through traction, water cooling, air-dried, winding after melting extrusion and polymerize
Thing 3D printing material；
Material through single screw rod melt blending extrusion by traction, water cooling, it is air-dried, wound to obtain the tool again by filament winding machine
There are Bone Defect Repari PLLA composites, the hauling speed of filament winding machine is arranged to 180r/min, so as to obtain a diameter of 1.75mm's
Regular wire rod.
A diameter of 1.75mm regular wire rod is sent into 3D printer, parameter is arranged to nozzle temperature in print procedure
230 DEG C, floor height 0.2mm, extruded velocity 90mm/s, translational speed 150mm/s, filling rate 15%.
To the product in above-described embodiment 1, embodiment 2, comparative example 1, comparative example 2, comparative example 3, comparative example 4 and commonly
PLLA carries out Mechanics Performance Testing, and method of testing uses GB/T1040.2-2006 standards, as a result as shown in following table one
Table one
| Embodiment | Tensile strength (MPa) |
| Embodiment 1 | 34.97 |
| Embodiment 2 | 40.98 |
| Comparative example 1 | 35.41 |
| Comparative example 2 | 32.73 |
| Comparative example 3 | 30.50 |
| Comparative example 4 | 27.22 |
| Common PLLA | 27.87 |
The Bone Defect Repari PLLA for fusion sediment 3D printing prepared from table one, the preparation method that the application proposes
Composite, technique is relatively easy effectively, compared to product of the prior art, uses product made from PLLA composites
Tensile strength is significantly improved, and PLLA and hydroxyl are improved while PLLA and hydroxyapatite each characteristic is maintained
The interface interaction of base apatite.
Above content is further description made for the present invention in conjunction with specific embodiments, it is impossible to assert the present invention
Specific implementation be confined to these explanations.With reference to description of the invention, some equivalent substitutes or obvious modification are made, and
Performance or purposes identical behavior, are all anticipated that for those skilled in the art, should all be considered as belonging to the present invention
Protection domain.
Claims (10)
1. a kind of high-strength bone reparation modified Nano particle composite thermoplastic polymer 3D printing material with life activity,
It is characterised in that it includes thermoplastic polymer and modified Nano particle, thermoplastic polymer is 60~95 mass parts, nano-particle
5~40 mass parts；
Above-mentioned thermoplastic polymer is the one or more in polyesters compound or poly- acid compounds；
Above-mentioned nano-particle is hydroxyapatite；
Above-mentioned modification uses dopamine and alkyl diamine compound, and modified mode is solution modification, dopamine and alkyl diamine
The mass concentration of compound is respectively 2~10mg/mL and 10~100mg/mL.
2. according to a kind of modified Nano particle composite thermoplastic polymer 3D printing material of Bone Defect Repari described in claim 1,
Characterized in that, thermoplastic polymer is selected from PLA, polycaprolactone, Poly(D,L-lactide-co-glycolide, poly-succinic fourth two
One or more in alcohol ester.
3. according to a kind of modified Nano particle composite thermoplastic polymer 3D printing material of Bone Defect Repari described in claim 1,
Characterized in that, Nanoparticle shape is needle-like, particle diameter length is 20~40nm.
4. according to a kind of modified Nano particle composite thermoplastic polymer 3D printing material of Bone Defect Repari described in claim 1,
Characterized in that, alkyl diamine compound is diamine compound of the C atom numbers of alkyl chain between 2~12.
5. according to a kind of modified Nano particle composite thermoplastic polymer 3D printing material of Bone Defect Repari described in claim 1,
Characterized in that, solution modification system is Tris cushioning liquid.
6. according to a kind of modified Nano particle composite thermoplastic polymer 3D printing material of Bone Defect Repari described in claim 5,
Characterized in that, Tris buffer concentrations are 0.1mol/L.
7. prepare the Bone Defect Repari modified Nano particle composite thermoplastic polymer 3D printing described in claim ball any one of 1-6
The method of material, it is characterised in that comprise the following steps：
(1) the Tris cushioning liquid prepared, dopamine is added, adds alkyl diamine compound；
(2) the solution (1) nano-particle addition step prepared, is ultrasonically treated 10~60min, by the product handled centrifugation, water
Wash, dry, obtain dopamine modified Nano particle of the surface containing a large amount of amino；
(3) the modified Nano particle and thermoplastic polymer that are obtained through step (2) are proportionally added into oil-based solvent, in 25-
Aminolysis reaction is carried out at 60 DEG C and stirs 12~36h, by the product reacted revolving, dries, obtains changing for surface modification polymer
Property nano-particle and its be dispersed in the composite of polymeric matrix；
(4) will be added through the material that step (3) obtain in the hopper of single screw extrusion machine, single screw extrusion machine Zhong Ge areas temperature is set
It is set to：One area：150~170 DEG C；2nd area：180~200 DEG C；3rd area：170~190 DEG C；Head temperature：160~180 DEG C；Screw rod
Rotating speed is controlled in 100~200r/min；Obtain the Bone Defect Repari through traction, water cooling, air-dried, winding after melting extrusion and received with modification
Rice corpuscles composite thermoplastic polymer 3D printing material.
8. according to the method for claim 7, it is characterised in that oil-based solvent is dioxane, chloroform, dichloromethane, four
One or more of mixed solutions in hydrogen furans.
9. according to the method for claim 7, it is characterised in that concentration of the nano-particle in (1) solution that step is prepared is maintained at
5~10mg/mL, concentration of the modified Nano particle in oil-based solvent are maintained at 5~10mg/mL.
10. according to the method for claim 7, it is characterised in that the 3D with Bone Defect Repari performance for obtaining the step (4) is beaten
Print material from single screw rod nose towing wind the step of, the automatic hauling speed of the bracing wire hauling machine is arranged to 100~300r/
Min, so as to obtain the regular wire rod of diameter.
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| CN109082091A (en) * | 2018-07-09 | 2018-12-25 | 福建师范大学 | A kind of 3D printing wire rod of Desulphurization filling degradable low temperature and preparation method thereof |
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| WO2021016288A1 (en) * | 2019-07-25 | 2021-01-28 | D2 Medical Llc | Bone-derived thermoplastic filament and method of manufacture |
| CN110682512A (en) * | 2019-10-15 | 2020-01-14 | 武义斯汀纳睿三维科技有限公司 | Preparation method of enhanced 3D printing material |
| CN110947033A (en) * | 2019-12-03 | 2020-04-03 | 中南大学 | Artificial bone scaffold material, material preparation method and preparation method of artificial bone scaffold |
| CN112545710A (en) * | 2020-12-08 | 2021-03-26 | 中国人民解放军空军军医大学 | Porous polyurethane support based on 3D prints |
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