CN107814940A - A kind of preparation method of shape-memory polymer and its application in 4D printings - Google Patents
A kind of preparation method of shape-memory polymer and its application in 4D printings Download PDFInfo
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- CN107814940A CN107814940A CN201711072125.5A CN201711072125A CN107814940A CN 107814940 A CN107814940 A CN 107814940A CN 201711072125 A CN201711072125 A CN 201711072125A CN 107814940 A CN107814940 A CN 107814940A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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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
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
Abstract
A kind of preparation method of shape-memory polymer and its application in 4D printings.The present invention relates to intellectual material to print field, and in particular to a kind of preparation method and applications of shape-memory polymer.The present invention is can not to be printed as arbitrary shape according to being actually needed to solve existing method, and existing shape-memory polymer Tg is higher, it is impossible to meets that small-power drives, the problem of can not meeting bio-medical demand.The present invention is copolymerized after obtaining bipolymer according to a certain percentage by two kinds of polymer monomers with good biocompatibility, is dissolved in low boiling high volatile organic solvent, shape-memory polymer solution is obtained by supersound process.Material prepared by the present invention controls three-dimensional mobile platform in x by software, y, the direction of motion, movement velocity in z-axis and applies pressure and then applies pressure to the high pressure spot plastic pin cylinder equipped with micro needle head by air pump, you can builds required three-dimensional structure.The present invention can be used for 4D to print.
Description
Technical field
The present invention relates to intellectual material print field, and in particular to a kind of preparation method of shape-memory polymer and its should
With.
Background technology
The application field of 3D printing technique extends with advances in technology and constantly, and at the same time 4D prints concept and triggered more
More concerns.The it is proposed of 4D printing techniques is the increases material manufacturing technology based on smart material and structure, and 4D prints the entity knot of manufacture
Configuration shape can change with external environment.3D printing is static, and 4D printings are dynamic.In fact, 4D printings are just
It is a kind of technology for employing energy auto Deformation material and realizing printing.After scientist completes modeling and setting track by software,
With printing technique by a kind of preliminary printing shaping of deformable material, according to initial setting, deformable material can be at the appointed time automatic
It is deformed into required shape.At present, 4D researchs are overall also needs to widening intelligence also in laboratory exploratory stage, 4D printings
Material ranges, exploitation print software, optimization printing technology, innovation intellectual material Method of printing, solve the simultaneous of different intelligent material
Furtherd investigate, can be obtained in fields such as medical treatment, military affairs, electronics, amusement, space flight extensively should in terms of the problems such as capacitive
With.
Shape-memory polymer is an important branch of intellectual material.Shape-memory polymer is changed in its original shape
When becoming and being fixed as other shapes, by the outside stimulus such as heat, electricity, magnetic, light, actively its initial shape can be spontaneously returned back to
Shape, acted on without any external force.Shape-memory polymer has the advantages of many traditional materials are incomparable, such as deformation quantity
Greatly, prepare simply, wide in variety, selectable range is wide, and shape memory recovery temperature scope is big, light weight, transmission easy to package, relies on
Physical environment stimulates driving, drives responding fast, is acted on without external force, cheap, corrosion-resistant, electrical insulating property and heat insulation effect
OK etc..In addition with time deformation characteristic, shape-memory polymer is the key intelligence for realizing 4D printing techniques for its unique active
One of material.
Although shape-memory polymer illustrates huge application potential and practical value in 4D printings field, its
Using being still within the starting stage.One of the reason for important is the shape memory because being influenceed by traditional contour machining procedure
Polymeric material is usually processed into the simple two-dimensional shapes such as sheet material, sheet material, film, it is difficult to realizes shape memory polymer material
It is three-dimensionally shaped.This largely influences and limited the further development of 4D printing techniques.With shape memory polymers in life
Exemplified by application in thing medical science, because material glass transition temperature is higher, it is necessary to more stringent drive condition, power hungry
Height, and poor controllability, it is big to human injury's property, and the structure such as pathological tissues needs to carry out individual character according to different patient's lesion situations
Change customization and design, it is desirable to the accuracy and diversity of structure.Therefore, the shape-memory polymer material that exploitation can be three-dimensionally shaped
Material and technology, the application that more areas are printed upon to promotion shape-memory material field and 4D is very necessary.
The content of the invention
The present invention is can not to be printed as arbitrary shape according to being actually needed to solve existing method, and existing shape memory gathers
Compound Tg is higher, it is impossible to meet that small-power drives, the problem of bio-medical demand can not be met, and provide a kind of shape memory
The preparation method of polymer and its application in 4D printings.
A kind of preparation method of shape-memory polymer of the present invention is specifically carried out according to the following steps：
First, polymer monomer A and polymer monomer B are carried out in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C respectively
12h~24h dries water removal, obtains dry polymer monomer A and the polymer monomer B dried；The polymer monomer A is poly-
Lactic acid, gather vinegar in oneself, poly-succinic acid-butanediol vinegar, polyurethane, poly- third friendship vinegar one second friendship vinegar, poly-methyl methacrylate vinegar, poly- carbon
Vinegar and one kind in polypropylene vinegar or wherein several mixtures；The polymer monomer B is bioactivity glass, poly- second
One kind or wherein several mixtures in lactide, polyethyleneimine, PTMC and poly (lactic acid-glycolic acid)；
2nd, copolyreaction is carried out after the dry polymer monomer A and polymer monomer B of drying is mixed, obtains binary
Shape-memory polymer, and carry out 12h~24h in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C and dry water removal, done
Dry binary shape memory polymer；The polymer monomer A of the drying and the polymer monomer B dried mass ratio are 10:
(1~10)；
3rd, dry binary shape memory polymer is dissolved in low boiling high volatile organic solvent, prepares shape note
The concentration for recalling the material of polymer is 10%~25% solution, and the solution is then stood into 24h~48h at room temperature, waits to gather
Compound material all after dissolving, makes it be uniformly dispersed, shape-memory polymer is prepared using ultrasonic device ultrasound 3h~6h
Solution, it is stand-by；In whole solution preparation process, sealed membrane is used to prevent solvent from volatilizing, to own sealing at bottle cap simultaneously
Step is carried out under dry environment, to prevent the absorption of water point；The low boiling high volatile organic solvent is dichloromethane
Alkane, chloroform, tetrahydrochysene bark mutter, toluene, ethanol, acetone and one kind in N, N- dimethyl methyl phthalein amine or wherein several mixing
Thing.
Shape-memory polymer prepared by the above method prints for 4D, specifically carries out according to the following steps：
First, design is modeled to the three-dimensional structure to be printed by software, is manipulation high pressure by obtained model conversation
The code command of dispensing syringe motion；
2nd, shape-memory polymer solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and passes through air pump pair
High pressure spot plastic pin cylinder applies pressure；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and movement velocity in z-axis,
It is moved according to the 3 d structure model movement locus being pre-designed, obtain the three-dimensional knot with SME
Structure；It is described by air pump to high pressure spot plastic pin cylinder apply pressure be 0.2MPa~3.5MPa；The internal diameter of the syringe needle be 30 μm~
510μm；The movement velocity is 0.2mm/s~10mm/s；
3rd, the prepared three-dimensional structure with SME is heated to more than its glass transition temperature Tg,
Change shape under external force and be fixed as required temporary structure；Keeping external force to be cooled to below Tg obtains temporary structure
It is fixed；Under the stimulation of outfield, when temperature is warming up to more than Tg again, corresponding temporary structure can return to initial three
Structure is tieed up, there is the three-dimensional structure of SME to remain able to change form after being manufactured, show three-dimensional article at any time
Between dynamic change characteristic, so far complete 4D printing.
Compared with prior art, the invention has the advantages that：
1st, printing technique has designability, by copolyreaction, can realize the printing of various shapes memory polymer,
The scope of application is wide and wide.
2nd, by selecting various sizes of printing syringe needle, formed precision can select from 30 μm~510 μm, while compact dimensions
From micron order to grade.The printing of macroscopic three dimensional structure can be not only realized, while can also realize the three-dimensional knot of microscopic dimensions
The printing of structure.Machining accuracy is high, and compact dimensions scope is wide.
3rd, whole printing process can be carried out at room temperature, and no particular surroundings requirement, cost is low, suitable for technological requirement.
4th, printed material glass transition temperature is reduced by copolyreaction, as proportioning is different, Tg is within the specific limits
It is adjustable, save power so that driving is more easy, and can design and print according to being customized of user's request, is expected to make shape
Shape memory polymer plays more effects in fields such as biomedicines.
Brief description of the drawings
Fig. 1 is the dynamic thermal analysis modulus collection of illustrative plates for the shape-memory polymer that embodiment one obtains；Wherein 1 is energy storage mould
Amount, 2 be loss modulus；
Fig. 2 is the loss angle tangent collection of illustrative plates for the shape-memory polymer that embodiment one obtains.
Embodiment
Embodiment one：A kind of preparation method of shape-memory polymer of present embodiment is specifically to press following step
Suddenly carry out：
First, polymer monomer A and polymer monomer B are carried out in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C respectively
12h~24h dries water removal, obtains dry polymer monomer A and the polymer monomer B dried；The polymer monomer A is poly-
Lactic acid, gather vinegar in oneself, poly-succinic acid-butanediol vinegar, polyurethane, poly- third friendship vinegar one second friendship vinegar, poly-methyl methacrylate vinegar, poly- carbon
Vinegar and one kind in polypropylene vinegar or wherein several mixtures；The polymer monomer B is bioactivity glass, poly- second
One kind or wherein several mixtures in lactide, polyethyleneimine, PTMC and poly (lactic acid-glycolic acid)；
2nd, copolyreaction is carried out after the dry polymer monomer A and polymer monomer B of drying is mixed, obtains binary
Shape-memory polymer, and carry out 12h~24h in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C and dry water removal, done
Dry binary shape memory polymer；The polymer monomer A of the drying and the polymer monomer B dried mass ratio are 10:
(1~10)；
3rd, dry binary shape memory polymer is dissolved in low boiling high volatile organic solvent, prepares shape note
The concentration for recalling the material of polymer is 10%~25% solution, and the solution is then stood into 24h~48h at room temperature, waits to gather
Compound material all after dissolving, makes it be uniformly dispersed, shape-memory polymer is prepared using ultrasonic device ultrasound 3h~6h
Solution, it is stand-by；In whole solution preparation process, sealed membrane is used to prevent solvent from volatilizing, to own sealing at bottle cap simultaneously
Step is carried out under dry environment, to prevent the absorption of water point；The low boiling high volatile organic solvent is dichloromethane
Alkane, chloroform, tetrahydrochysene bark mutter, toluene, ethanol, acetone and one kind in N, N- dimethyl methyl phthalein amine or wherein several mixing
Thing.
Present embodiment is by adjusting polymer monomer A and polymer monomer B proportioning so that glass transition temperature exists
It is adjustable in certain limit, and it is below the glass transition temperature of the respective polymer of two kinds of monomers.
Have good biocompatibility and biology can between polymer monomer A and polymer monomer B in present embodiment
Degradability.
Embodiment two：Present embodiment is unlike embodiment one：Polymer described in step 1
Monomer A is PLA.Other steps and parameter are identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one or two：Gather described in step 1
Monomer adduct B is PTMC.Other steps and parameter are identical with embodiment one or two.
Embodiment four：Unlike one of present embodiment and embodiment one to three：Institute in step 2
The mass ratio for stating the dry polymer monomer A and polymer monomer B dried is 10:(1~2.5).Other steps and parameter with
One of embodiment one to three is identical.
Embodiment five：Unlike one of present embodiment and embodiment one to four：Made in step 3
The solution that the concentration of the material of standby shape-memory polymer is 20%.Other steps and parameter and embodiment one to four it
One is identical.
Embodiment six：Unlike one of present embodiment and embodiment one to five：Institute in step 3
It is dichloromethane to state low boiling high volatile organic solvent.One of other steps and parameter and embodiment one to five phase
Together.
Embodiment seven：The shape-memory polymer that present embodiment utilizes embodiment one to prepare is beaten for 4D
Print, is specifically carried out according to the following steps：
First, design is modeled to the three-dimensional structure to be printed by software, is manipulation high pressure by obtained model conversation
The code command of dispensing syringe motion；
2nd, shape-memory polymer solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and passes through air pump pair
High pressure spot plastic pin cylinder applies pressure；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and movement velocity in z-axis,
It is moved according to the 3 d structure model movement locus being pre-designed, obtain the three-dimensional knot with SME
Structure；It is described by air pump to high pressure spot plastic pin cylinder apply pressure be 0.2MPa~3.5MPa；The internal diameter of the syringe needle be 30 μm~
510μm；The movement velocity is 0.2mm/s~10mm/s；
3rd, the prepared three-dimensional structure with SME is heated to more than its glass transition temperature Tg,
Change shape under external force and be fixed as required temporary structure；Keeping external force to be cooled to below Tg obtains temporary structure
It is fixed；Under the stimulation of outfield, when temperature is warming up to more than Tg again, corresponding temporary structure can return to initial three
Structure is tieed up, there is the three-dimensional structure of SME to remain able to change form after being manufactured, show three-dimensional article at any time
Between dynamic change characteristic, so far complete 4D printing.
Solution in present embodiment in syringe can be internally formed capillary shearing in the presence of high pressure in micro needle head
Stream, then flows out from micro needle head and discharges internal stress, show shear thinning behavior.In this process, shape memory
Solvent in polymer solution can quickly volatilize, and cause the rigidity of material to rise, and the shape printed is changed into solid from liquid,
So as to obtain figuration fixation
Embodiment eight：Present embodiment is unlike embodiment seven：Software is described in step 1
One kind in AutoCAD, CATIA, UG, Pro/E or SOLIDWORKS.Other steps and parameter and the phase of embodiment seven
Together.
Embodiment nine：Present embodiment is unlike embodiment seven or eight：Pin described in step 2
The internal diameter of head is 400 μm~510 μm.Other steps and parameter are identical with embodiment seven or eight.
The internal diameter of present embodiment is suitable for larger three-dimensional dimension and is not extra high component to required precision, so
Printing effect, shortening forming time can be improved under conditions of same amount of solution.
Embodiment ten：Unlike one of present embodiment and embodiment seven to nine：Institute in step 3
Stating outfield stimulates as one kind in thermal excitation or solution excitation.One of other steps and parameter and embodiment seven to nine phase
Together.
Beneficial effects of the present invention are verified by following examples：
Embodiment one：What a kind of preparation method of shape-memory polymer was specifically carried out according to the following steps：
First, by PLA monomer and PTMC monomer respectively in the vacuum drying that temperature is 30 DEG C~50 DEG C
12h~24h is carried out in case and dries water removal, obtains dry PLA monomer and PTMC monomer；
2nd, copolyreaction is carried out after mixing dry PLA monomer and the PTMC monomer of drying,
Binary shape memory polymer is obtained, and carries out 12h~24h dryings in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C and removes
Water, obtain dry binary shape memory polymer；The PLA monomer of the drying and the PTMC dried
The mass ratio of monomer is 3:2；
3rd, dry binary shape memory polymer is dissolved in dichloromethane, prepares the material of shape-memory polymer
Concentration be 20% solution, the solution is then stood into 24h~48h at room temperature, thing material to be polymerized all after dissolving, is adopted
It is uniformly dispersed with ultrasonic device ultrasound 3h~6h, shape-memory polymer solution is prepared, it is stand-by；In whole solution system
During standby, sealed membrane is used to be sealed at bottle cap to prevent solvent from volatilizing, while all steps are entered under dry environment
OK, to prevent the absorption of water point.
Printed for 4D using shape-memory polymer prepared by embodiment one, specifically carried out according to the following steps：
First, design is modeled to the three-dimensional structure to be printed by software, is manipulation high pressure by obtained model conversation
The code command of dispensing syringe motion；The software is one kind in AutoCAD, CATIA, UG, Pro/E or SOLIDWORKS
2nd, shape-memory polymer solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and passes through air pump pair
High pressure spot plastic pin cylinder applies pressure；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and movement velocity in z-axis,
It is moved according to the 3 d structure model movement locus being pre-designed, obtain the three-dimensional knot with SME
Structure；It is described by air pump to high pressure spot plastic pin cylinder apply pressure be 0.2MPa；The internal diameter of the syringe needle is 200 μm；The motion
Speed is 2mm/s；Print 40mm × 3mm × 1mm sample, Mobile state thermo-mechanical analysis of going forward side by side test；
3rd, the prepared three-dimensional structure with SME is heated to more than its glass transition temperature Tg,
Change shape under external force and be fixed as required temporary structure；Keeping external force to be cooled to below Tg obtains temporary structure
It is fixed；Under the stimulation of outfield, when temperature is warming up to more than Tg again, corresponding temporary structure can return to initial three
Structure is tieed up, there is the three-dimensional structure of SME to remain able to change form after being manufactured, show three-dimensional article at any time
Between dynamic change characteristic, so far complete 4D printing.
Fig. 1 is the dynamic thermal analysis modulus collection of illustrative plates for the shape-memory polymer that embodiment one obtains；Wherein 1 is energy storage mould
Amount, 2 be loss modulus；Fig. 2 is the loss angle tangent collection of illustrative plates for the shape-memory polymer that embodiment one obtains.Can be with from Fig. 1
Find out, at 20 DEG C, the storage modulus of material is higher, and between 30 DEG C to 60 DEG C, the storage modulus of material drastically declines, temperature
Into the viscous state of modulus of elasticity very little during higher than 70 DEG C；From figure 2 it can be seen that loss angle reaches highest at 53.08 DEG C
Value, has the glass transition temperature lower than PLA shape-memory polymer, can more meet demand in biomedicine.
Claims (10)
1. a kind of preparation method of shape-memory polymer, it is characterised in that the preparation method of shape-memory polymer is specifically to press
What following steps were carried out：
First, polymer monomer A and polymer monomer B are subjected to 12h in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C respectively
~24h dries water removal, obtains dry polymer monomer A and the polymer monomer B dried；The polymer monomer A is poly- breast
Acid, gather vinegar in oneself, poly-succinic acid-butanediol vinegar, polyurethane, poly- third friendship vinegar one second friendship vinegar, poly-methyl methacrylate vinegar, poly- carbonic acid
Vinegar and one kind in polypropylene vinegar or wherein several mixtures；The polymer monomer B is bioactivity glass, poly- second third
One kind or wherein several mixtures in lactide, polyethyleneimine, PTMC and poly (lactic acid-glycolic acid)；
2nd, copolyreaction is carried out after the dry polymer monomer A and polymer monomer B of drying is mixed, obtains binary shape
Memory polymer, and carry out 12h~24h in the vacuum drying chamber that temperature is 30 DEG C~50 DEG C and dry water removal, obtain drying
Binary shape memory polymer；The polymer monomer A of the drying and the polymer monomer B dried mass ratio are 10:(1~
10)；
3rd, dry binary shape memory polymer is dissolved in low boiling high volatile organic solvent, prepares shape memory and gather
The concentration of the material of compound is 10%~25% solution, and the solution is then stood into 24h~48h, thing to be polymerized at room temperature
Material all after dissolving, makes it be uniformly dispersed, shape-memory polymer solution is prepared using ultrasonic device ultrasound 3h~6h,
It is stand-by；In whole solution preparation process, sealed membrane is used to be sealed at bottle cap to prevent solvent from volatilizing, while all steps are equal
Carried out under dry environment, to prevent the absorption of water point；The low boiling high volatile organic solvent is dichloromethane, trichlorine
Methane, tetrahydrochysene bark mutter, toluene, ethanol, acetone and one kind in N, N- dimethyl methyl phthalein amine or wherein several mixtures.
2. the preparation method of a kind of shape-memory polymer according to claim 1, it is characterised in that described in step 1
Polymer monomer A is PLA.
3. the preparation method of a kind of shape-memory polymer according to claim 1, it is characterised in that described in step 1
Polymer monomer B is PTMC.
4. the preparation method of a kind of shape-memory polymer according to claim 1, it is characterised in that described in step 2
Dry polymer monomer A and the polymer monomer B dried mass ratio are 10:(1~2.5).
5. the preparation method of a kind of shape-memory polymer according to claim 1, it is characterised in that prepared in step 3
The concentration of the material of shape-memory polymer is 20% solution.
6. the preparation method of a kind of shape-memory polymer according to claim 1, it is characterised in that described in step 3
Low boiling high volatile organic solvent is dichloromethane.
Printed 7. shape-memory polymer prepared by method as claimed in claim 1 is used for 4D, it is characterised in that specifically by with
What lower step was carried out：
First, design is modeled to the three-dimensional structure to be printed by software, is manipulation high pressure dispensing by obtained model conversation
The code command of syringe motion；
2nd, shape-memory polymer solution is loaded in the high pressure spot plastic pin cylinder equipped with micro needle head, and by air pump to high pressure
Dispensing syringe applies pressure；Three-dimensional mobile platform is controlled in x by software, y, the direction of motion and movement velocity in z-axis, makes it
3 d structure model movement locus according to being pre-designed moves, and obtains the three-dimensional structure with SME；Institute
It is 0.2MPa~3.5MPa to high pressure spot plastic pin cylinder application pressure to state by air pump；The internal diameter of the syringe needle is 30 μm~510 μm；
The movement velocity is 0.2mm/s~10mm/s；
3rd, the prepared three-dimensional structure with SME is heated to more than its glass transition temperature Tg, outside
The lower temporary structure changed required for shape is fixed as of power effect；Keeping external force to be cooled to below Tg is consolidated temporary structure
It is fixed；Under the stimulation of outfield, when temperature is warming up to more than Tg again, corresponding temporary structure can return to initial three-dimensional
Structure, there is the three-dimensional structure of SME to remain able to change form after being manufactured, show three-dimensional article with the time
The characteristic of dynamic change, so far complete 4D printings.
8. the preparation method of a kind of shape-memory polymer according to claim 7, it is characterised in that described in step 1
Software is one kind in AutoCAD, CATIA, UG, Pro/E or SOLIDWORKS.
9. the preparation method of a kind of shape-memory polymer according to claim 7, it is characterised in that described in step 2
The internal diameter of syringe needle is 400 μm~510 μm.
10. the preparation method of a kind of shape-memory polymer according to claim 7, it is characterised in that described in step 3
Outfield is stimulated as one kind in thermal excitation or solution excitation.
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| CN109624309A (en) * | 2019-01-16 | 2019-04-16 | 浙江大学 | The 4D Method of printing of net-wiggle double-layer structure based on temperature-responsive |
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| CN111907055A (en) * | 2020-06-11 | 2020-11-10 | 西安交通大学 | Multiple thermoplastic shape memory polymer 4D printing method |
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