CN109366983A - A kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket - Google Patents

A kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket Download PDF

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Publication number
CN109366983A
CN109366983A CN201811146510.4A CN201811146510A CN109366983A CN 109366983 A CN109366983 A CN 109366983A CN 201811146510 A CN201811146510 A CN 201811146510A CN 109366983 A CN109366983 A CN 109366983A
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CN
China
Prior art keywords
polycaprolactone
printing
electrostatic
bracket
shaggy
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Pending
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CN201811146510.4A
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Chinese (zh)
Inventor
李文超
张祥林
石磊
周奎
艾凡荣
曹传亮
刘东雷
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Nanchang University
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Nanchang University
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Priority to CN201811146510.4A priority Critical patent/CN109366983A/en
Publication of CN109366983A publication Critical patent/CN109366983A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/165Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/16Cooling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20Apparatus for additive manufacturing; Details thereof or accessories therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/205Means for applying layers
    • B29C64/209Heads; Nozzles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30Auxiliary operations or equipment
    • B29C64/379Handling of additively manufactured objects, e.g. using robots
    • 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
    • B33Y30/00Apparatus for additive manufacturing; Details thereof or accessories therefor
    • 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
    • B33Y40/00Auxiliary operations or equipment, e.g. for material handling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/16Cooling
    • B29C2035/1616Cooling using liquids

Abstract

The present invention relates to 3D technology field more particularly to a kind of electrostatic 3D printing preparation methods of shaggy polycaprolactone bracket.Include the following steps: step 1: polycaprolactone particle being mixed with glacial acetic acid, is placed in closed environment and is stirred until homogeneous clear solution, configuration concentration is greater than 25wt%;Step 2: the clear solution is placed in 3D printing plateform system, carries out the printing of polymer support, obtains polycaprolactone three-dimensional rack, and the reception substrate of the 3D printing plateform system uses made of metal cold plate, and refrigeration plate temperature is -20~-10 DEG C;Step 3: the polycaprolactone three-dimensional rack is freezed into 1-4h, then carries out vacuum freeze drying 5-12h, obtains shaggy polycaprolactone bracket.It is easy to control, the electrostatic 3D printing preparation of polycaprolactone three-dimensional rack is easily realized, while realizing the preparation of rough surface polycaprolactone three-dimensional rack by freeze drying process, does not introduce other chemical substances, convenient formation is quick, has expanded the technical solution in electrostatic 3D printing field.

Description

A kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket
Technical field
The present invention relates to 3D technology field more particularly to a kind of electrostatic 3D printing systems of shaggy polycaprolactone bracket Preparation Method.
Background technique
Polycaprolactone is that a kind of implantable degradable biological authenticated by U.S.'s food and Drug Administration (FDA) is compatible Property polymer is easily processed to the supporting structure of different-shape and extensive simultaneously because it possesses excellent rheological property Basis material as organizational project biological support.
Currently, it is three-dimensional to hundred micron order polycaprolactones that electrostatic 3D printing technique is able to achieve micron in numerous preparation processes Bracket controllably prints building, and regenerating in research to the research of stem cell microenvironment and customization defective tissue has big advantage, But the polycaprolactone stent surface smoothing prepared by it, it is unfavorable for cell adherence and proliferation.To realize that surface topology changes Property, the method that need to use chemical attack, this scheme is not only complicated cumbersome, and is readily incorporated poisonous and hazardous chemical residue, Reduce the safety of polycaprolactone biological support.Therefore, in a manner of simple and is direct in electrostatic 3D printing rack surface shape There are important research and application value at topological structure.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, adapt to reality and need, and provide a kind of shaggy poly- The electrostatic 3D printing preparation method of caprolactone bracket.
In order to achieve the object of the present invention, the technical solution adopted by the present invention are as follows:
A kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket, includes the following steps:
Step 1: polycaprolactone particle is mixed with glacial acetic acid, is placed in closed environment and is stirred until homogeneous clear solution, match Concentration is set greater than 25wt%;
Step 2: the clear solution is placed in 3D printing plateform system, is carried out the printing of polymer support, is gathered Caprolactone three-dimensional rack, the reception substrate of the 3D printing plateform system use made of metal cold plate, and refrigeration plate temperature is -20~- 10℃;
Step 3: the polycaprolactone three-dimensional rack is freezed into 1-4h, then carries out vacuum freeze drying 5-12h, obtains table The coarse polycaprolactone bracket in face.
The matter average molecular weight of the polycaprolactone is between 40000~80000, the concentration of the transparent polycaprolactone solution For 25~45wt%.
In the step 2, the 3D printing plateform system includes: including print head, print carriage, and the print head is perpendicular Straight setting is provided with stamp pad on the print carriage upper end, the print carriage;The print head can be controlled and be moved down On gantry, gantry main body is in " Π " shape for dynamic setting, and the setting that both ends can slide back and forth on the downside of described gantry is being beaten Print bracket two sides;The print carriage side is provided with electrostatic high-pressure power supply, and the electrostatic high-pressure power supply is passing through high input voltage just Polar curve is connect with print head, and the print carriage other side is provided with control system, and the print carriage is connect with control system; The stamp pad upper end is provided with made of metal cold plate, and the stamp pad side is provided with ultralow temperature control cabinet, the ultralow temperature control The sub-cooled fluid circulation that cabinet processed is minimum -20 DEG C, the ultralow temperature control cabinet pass through refrigerating fluid water inlet pipe and refrigerating fluid Outlet pipe is connected with made of metal cold plate, and the print head prints polycaprolactone bracket on made of metal cold plate.
The print carriage two sidewalls are horizontally disposed there are two groove, are provided on the downside of described gantry matching convex Block, the setting that described gantry can be slid back and forth by the cooperation of groove and convex block is in print carriage two sides.
The print head includes setting storage cavity on the horizontal guide rail and the spray head that storage cavity bottom is arranged in, described Spray head is Metallic Nozzle At The Ingot, and spray head is flat mouth, and aperture is 20~30G.
In the step 2, the printing of the polymer support includes: that dispensing is taken the lead in polycaprolactone solution loading In the syringe of syringe needle, it is packed into micro extrusion device, connects electrostatic high-pressure power supply, imports bracket path, adjustment squeezes out flow, needle The electrostatic 3D printing of polycaprolactone bracket is realized to the distance and driving voltage for receiving substrate in head lower end.
The distance of the syringe needle lower end to made of metal cold plate 4 is 3~20mm, and the extrusion flow is 0.2~5ml/ h。
In the step 2, environment temperature is set as 16~20 DEG C, and humidity set is 20~40%.
In the step 3, the polycaprolactone bracket is saved 2 hours in -20 DEG C of refrigerator, then in freeze dryer Middle vacuum drying 6 hours, obtains rough surface polycaprolactone three-dimensional rack.
The beneficial effects of the present invention are:
The present invention is by configuring a certain proportion of polycaprolactone and glacial acetic acid homogeneous transparent solution, and using this solution as quiet Electric 3D printing raw material receive substrate comprising ultralow temperature, carry out the printing of polymer support in 3D printing plateform system, Polycaprolactone three-dimensional rack is obtained, then this bracket is freezed and is dried in vacuo again, to obtain shaggy polycaprolactone Bracket.This method causes glacial acetic acid crystallization to induce the molten liquid phase separation of polycaprolactone and solidifying and setting by ultralow temperature, is easy control System, easily realizes the electrostatic 3D printing preparation of polycaprolactone three-dimensional rack, while realizing surface by freeze drying process The preparation of coarse polycaprolactone three-dimensional rack, does not introduce other chemical substances, and convenient formation is quick, has expanded electrostatic 3D printing neck The technical solution in domain.
Detailed description of the invention
The present invention is described further with case study on implementation with reference to the accompanying drawing.
Fig. 1 is ultralow temperature electrostatic 3D printer schematic diagram;
Fig. 2 is rough surface polycaprolactone bracket front view;
Fig. 3 is rough surface polycaprolactone bracket side view.
Wherein, 1. control system, 2. motion platform, 3. print head, 4. made of metal cold plate, 5. ultralow temperature control cabinet 6. is made 8. electrostatic high-pressure power supply of cold 7. refrigerating fluid outlet pipe of liquid water inlet pipe, 9. high input voltage electrode line 10. ground connection polar curve 11. gathers oneself Lactone bracket.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples:
Referring to Fig. 1-3.
The invention discloses a kind of electrostatic 3D printing preparation methods of shaggy polycaprolactone bracket, including walk as follows It is rapid:
Step 1: polycaprolactone particle is mixed with glacial acetic acid, is placed in closed environment and is stirred until homogeneous clear solution, match Concentration is set greater than 25wt%;
Step 2: the clear solution is placed in 3D printing plateform system, is carried out the printing of polymer support, is gathered Caprolactone three-dimensional rack, the reception substrate of the 3D printing plateform system use made of metal cold plate, and refrigeration plate temperature is -20~- 10℃;
Step 3: the polycaprolactone three-dimensional rack is freezed into 1-4h, then carries out vacuum freeze drying 5-12h, obtains table The coarse polycaprolactone bracket in face.
The matter average molecular weight of the polycaprolactone is between 40000~80000, the concentration of the transparent polycaprolactone solution For 25~45wt%.
In the step 2, the 3D printing plateform system includes: including print head 3, print carriage 13, the print head 3 are vertically arranged in 13 upper end of print carriage, are provided with stamp pad 14 on the print carriage 13;The print head 3 can be with The setting that left and right moves up and down is on gantry 12, and 12 main body of gantry is in " Π " shape, and the 12 downside both ends of gantry can be former The setting slided afterwards is in 13 two sides of print carriage;13 side of print carriage is provided with electrostatic high-pressure power supply 8, and the electrostatic is high Voltage source 8 is connect by high input voltage electrode line 9 with print head 3, and 13 other side of print carriage is provided with control system 1, The print carriage 13 is connect with control system 1;14 upper end of stamp pad is provided with made of metal cold plate 4, the stamp pad 14 Side is provided with ultralow temperature control cabinet 5, and the sub-cooled fluid circulation that the ultralow temperature control cabinet 5 is minimum -20 DEG C is described Ultralow temperature control cabinet 5 is connected by refrigerating fluid water inlet pipe 6 and refrigerating fluid outlet pipe 7 and made of metal cold plate 4, and the print head is in gold Belong to and prints polycaprolactone bracket 11 on cold plate 4.
13 two sidewalls of print carriage are horizontally disposed there are two groove 15, are provided on the downside of described gantry 12 matching Convex block, the setting that described gantry 12 can be slid back and forth by the cooperation of groove 15 and convex block is in 14 two sides of print carriage.
The print head includes setting storage cavity on the horizontal guide rail and the spray head that storage cavity bottom is arranged in, described Spray head is Metallic Nozzle At The Ingot, and spray head is flat mouth, and aperture is 20~30G.
In the step 2, the printing of the polymer support includes: that dispensing is taken the lead in polycaprolactone solution loading In the syringe of syringe needle, it is packed into micro extrusion device, connects electrostatic high-pressure power supply, imports bracket path, adjustment squeezes out flow, needle The electrostatic 3D printing of polycaprolactone bracket is realized to the distance and driving voltage for receiving substrate in head lower end.
The distance of the syringe needle lower end to made of metal cold plate 4 is 3~20mm, and the extrusion flow is 0.2~5ml/ h。
In the step 2, environment temperature is set as 16~20 DEG C, and humidity set is 20~40%.
In the step 3, the polycaprolactone bracket is saved 2 hours in -20 DEG C of refrigerator, then in freeze dryer Middle vacuum drying 6 hours, obtains rough surface polycaprolactone three-dimensional rack.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, are similarly included in In scope of patent protection of the invention.

Claims (9)

1. a kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket, characterized by the following steps:
Step 1: polycaprolactone particle being mixed with glacial acetic acid, is placed in closed environment and is stirred until homogeneous clear solution, is configured dense Degree is greater than 25wt%;
Step 2: the clear solution is placed in 3D printing plateform system, carries out the printing of polymer support, obtains gathering in oneself Ester three-dimensional rack, the reception substrate of the 3D printing plateform system use made of metal cold plate, and refrigeration plate temperature is -20~-10 DEG C;
Step 3: the polycaprolactone three-dimensional rack is freezed into 1-4h, then carries out vacuum freeze drying 5-12h, it is thick to obtain surface Rough polycaprolactone bracket.
2. the electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 1, feature exist In: for the matter average molecular weight of the polycaprolactone between 40000~80000, the concentration of the transparent polycaprolactone solution is 25 ~45wt%.
3. the electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 1, feature exist In: in the step 2, the 3D printing plateform system includes: including print head (3), print carriage (13), the print head (3) it is vertically arranged in the print carriage (13) upper end, is provided with stamp pad (14) on the print carriage (13);The printing Head (3) can control the setting moved up and down on gantry (12), and gantry (12) main body is in " Π " shape, the gantry (12) The setting that downside both ends can slide back and forth is in print carriage (13) two sides;Print carriage (13) side is provided with electrostatic height Voltage source (8), the electrostatic high-pressure power supply (8) are connect by high input voltage electrode line (9) with print head (3), the printing branch Frame (13) other side is provided with control system (1), and the print carriage (13) connect with control system (1);The stamp pad (14) upper end is provided with made of metal cold plate (4), and stamp pad (14) side is provided with ultralow temperature control cabinet (5), described ultralow The sub-cooled fluid circulation that warm control cabinet (5) is minimum -20 DEG C, the ultralow temperature control cabinet (5) are intake by refrigerating fluid (6) and refrigerating fluid outlet pipe (7) and made of metal cold plate (4) connection are managed, the print head prints on made of metal cold plate (4) gathers oneself Lactone bracket (11).
4. a kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 3, special Sign is: print carriage (13) two sidewalls are horizontally disposed there are two groove (15), be provided on the downside of the gantry (12) with Matched convex block, the setting that the gantry (12) can be slid back and forth by the cooperation of groove (15) and convex block is in print carriage (14) two sides.
5. a kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 3, special Sign is: the print head includes setting storage cavity on the horizontal guide rail and the spray head that storage cavity bottom is arranged in, described Spray head is Metallic Nozzle At The Ingot, and spray head is flat mouth, and aperture is 20~30G.
6. a kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 1, special Sign is: in the step 2, the printing of the polymer support includes: that a plastic pin is taken the lead in polycaprolactone solution loading In the syringe of head, it is packed into micro extrusion device, connects electrostatic high-pressure power supply, imports bracket path, adjustment squeezes out flow, syringe needle The electrostatic 3D printing of polycaprolactone bracket is realized to the distance and driving voltage for receiving substrate in lower end.
7. a kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 3, special Sign is: the distance of the syringe needle lower end to made of metal cold plate (4) is 3~20mm, and the extrusion flow is 0.2~5ml/ h。
8. the electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 1, feature exist In: in the step 2, environment temperature is set as 16~20 DEG C, and humidity set is 20~40%.
9. the electrostatic 3D printing preparation method of shaggy polycaprolactone bracket according to claim 1, feature exist In: in the step 3, the polycaprolactone bracket is saved 2 hours in -20 DEG C of refrigerator, then the vacuum in freeze dryer It is 6 hours dry, obtain rough surface polycaprolactone three-dimensional rack.
CN201811146510.4A 2018-09-29 2018-09-29 A kind of electrostatic 3D printing preparation method of shaggy polycaprolactone bracket Pending CN109366983A (en)

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CN112743850A (en) * 2020-12-23 2021-05-04 华中科技大学鄂州工业技术研究院 Preparation method of low-temperature biological 3D printing composite stent
CN114103099A (en) * 2021-11-24 2022-03-01 华中科技大学鄂州工业技术研究院 Preparation method of polyethylene lactone-hydrogel coaxial stent based on low-temperature biological 3D printing
CN115232782A (en) * 2022-07-16 2022-10-25 南昌大学 Coaxial microfluid-based double-exposure micro-wrinkle blood vessel processing platform and method

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CN108085768A (en) * 2018-02-12 2018-05-29 华中科技大学鄂州工业技术研究院 A kind of preparation method of porous polymeric fibres and porous polymeric fibres obtained
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CN114103099B (en) * 2021-11-24 2023-09-19 华中科技大学鄂州工业技术研究院 Preparation method of polycaprolactone-hydrogel coaxial scaffold based on low-temperature biological 3D printing
CN115232782A (en) * 2022-07-16 2022-10-25 南昌大学 Coaxial microfluid-based double-exposure micro-wrinkle blood vessel processing platform and method
CN115232782B (en) * 2022-07-16 2023-10-31 南昌大学 Double-exposure micro-fold vascular processing platform and method based on coaxial microfluid

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