CN110341097A - A kind of thermoplastic polymer and application based on DLP photocuring 3D printing - Google Patents
A kind of thermoplastic polymer and application based on DLP photocuring 3D printing Download PDFInfo
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- CN110341097A CN110341097A CN201910717349.XA CN201910717349A CN110341097A CN 110341097 A CN110341097 A CN 110341097A CN 201910717349 A CN201910717349 A CN 201910717349A CN 110341097 A CN110341097 A CN 110341097A
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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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
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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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/40—Plastics, e.g. foam or rubber
-
- 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
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
- B29C33/52—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles soluble or fusible
-
- 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
- B29C64/00—Additive 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
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
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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
- B33Y80/00—Products made by additive manufacturing
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The invention discloses a kind of thermoplastic polymers based on DLP photocuring 3D printing, the thermoplastic polymer is that photosensitive resin precursor liquid is prepared by the 3D printing of DLP photocuring, the photosensitive resin precursor liquid includes Monofunctional monomers, photoinitiator, light absorber and molecular weight regulator, and the Monofunctional monomers are the acrylate monomer of mono acrylic ester base or the acrylamide monomer of single acrylamido.The invention also discloses a kind of thermoplastic polymers based on DLP photocuring 3D printing in water-soluble or high temperature melting mold application.Thermoplastic polymer provided by the invention can be prepared by the way of based on DLP photocuring 3D printing, and the thermoplastic polymer prepared can be used as mold to obtain other non-photocuring models.
Description
Technical field
The present invention relates to Polymer Processing manufacturing field more particularly to a kind of thermoplasticity based on DLP photocuring 3D printing
Polymer and application.
Background technique
3D printing (increasing material manufacturing) is one kind based on digital model file, carrys out structure by layer-by-layer printing
The forming technique of body has been widely used for the direct manufacture of mold, the model manufacturing of industrial design and some products.As one
Kind straight forming technology does not need to be that can construct some three irregularly, complicated using mold and its advantage most outstanding
Tie up structure.
In the Method of printing of building complicated shape polymer, light processing DLP (Digital Light is digitized
Procession it is) a kind of 3 D-printing technique based on digitized projection technology, uses a kind of digital light of high-resolution
Processor solidifies liquid photopolymer, successively solidifies to liquid polymer.Compared to other polymers forming method packet
The point-by-point molding of melt extrusion technology FDM, Stereo Lithography technology SLA are included, face, which forms DLP technology, has shaping speed fast and essence
High advantage is spent, but there is also following disadvantages:
(1) resin material that DLP is used generally requires to be added prepolymer for reducing cure shrinkage, but viscosity is opposite
It is higher, so that print procedure levelling is difficult, significantly reduce print speed；
(2) on the other hand due to the introducing of polyfunctional prepolymer so that photocuring obtained is a kind of thermosetting material,
Later period is difficult to be processed again；
(3) in addition, resin material must be the material for capableing of light initiation polymerization since forming method depends on photocuring technology
Other common used materials such as epoxy resin, polydimethylsiloxane etc. are the structures that can not realize labyrinth by material
It builds.
Therefore, how to realize that the labyrinth rapid shaping of non-photo-curing material is a difficult point, for existing mold
Manufacture, the period is long and labyrinth demoulding is difficult.Photocuring thermoplastic polymer can provide a kind of new solution for this contradiction
Means.
Summary of the invention
The purpose of the present invention is to provide a kind of thermoplastic polymers based on DLP photocuring 3D printing, can use DLP
The method rapid build thermoplastic polymer of photocuring 3D printing is used for multiple material as water-soluble or high temperature melting mold
The moulding of system assigns its higher added value.
A kind of thermoplastic polymer based on DLP photocuring 3D printing, the thermoplastic polymer are photosensitive resin forerunner
Liquid is prepared by the 3D printing of DLP photocuring, and the photosensitive resin precursor liquid includes Monofunctional monomers, photoinitiator, light absorption
Agent and molecular weight regulator, the Monofunctional monomers are the acrylate monomer or single acrylamido of mono acrylic ester base
Acrylamide monomer.
In the present invention, the Monofunctional monomers in the photosensitive resin precursor liquid contain active function groups, can be in illumination
It penetrates down by photoinitiator initiated polymerization；And an active function groups are contained only, polymer forms the gel of physical entanglement
Network.Preferably, molecular weight needed for the polymerization speed of Monofunctional monomers must quickly reach gel, and meet its homopolymerization
The glass transition temperature of object is higher than room temperature, is used for stable gel network.
Thermoplastic polymer provided by the invention is obtained using a kind of sp act monomer material by photocuring DLP technology
One molecular weight is controllable, complex three-dimensional structure thermoplastic's polymer mold of structure-controllable.Since the viscosity of monomer is low and table
Printing speed may be implemented in layer oxygen inhibition characteristic, and the content by changing chain-transferring agent can control the molecule of material well
Amount, the heat in conjunction with monomer is melted or water-soluble property realizes fast demoulding.
Based on mass fraction, the resin includes the light absorber and 0.1- of the photoinitiator of 0.1-5%, 0.01-0.1%
2% molecular weight regulator.
The acrylate monomer is selected from one or both of isobornyl acrylate or isobornyl methacrylate
Combination；The acrylamide monomer is selected from the combination of one or both of acryloyl morpholine or dimethylacrylamide.
Preferably, the Monofunctional monomers are acryloyl morpholine.Acryloyl morpholine has good water solubility, can be by
Preparation for water-soluble mold.
The photoinitiator is selected from benzoin and derivative, benzil class, alkylbenzene ketone, acyl group neighbour oxide, hexichol
One of ketone class or thioxanthones or at least two combination.
Preferably, the photoinitiator is selected from styrax, benzoin dimethylether, diphenylethan, Dimethoxyphenyl benzene
Ethyl ketone, hydroxyalkyl phenones, aroyl phosphorous oxides, benzophenone, 2,4-DihydroxyBenzophenone or thio propoxyl group thioxanthene
One of ketone or at least two combination.
The molecular weight regulator is selected from one of aliphatic mercaptan, styrene polymer or amylene or at least two
Combination.
The molecular weight regulator (also known as chain-transferring agent) is the component with transmitting free radical ability.It can be used for adjusting
Polymer molecular weight is to improve the water-soluble energy of material.
Preferably, the aliphatic mercaptan is single functionality mercaptan, structure are as follows:
R1-SH
Wherein R1It can be aliphatic chain or aromatic rings or other cyclic structures, such as be selected from methyl, ethyl, propyl and its isomery
Group, butyl and its isomeric groups, amyl and its isomeric groups, hexyl and its isomeric groups, heptyl and its isomeric groups, octyl
And its isomeric groups, nonyl and its isomeric groups, decyl and its isomeric groups, 11 carbon-based and its isomeric groups, ten dicarbonyls
And its isomeric groups, 13 carbon-based and its isomeric groups, 14 carbon-based and its isomeric groups, pentadecane base and its isomeric groups,
16 carbon-based and its isomeric groups；Aryl and its homologue group；Furfuryl group, pyridyl group, thienyl, imidazole radicals, pyrrole radicals etc. are miscellaneous
One of cyclic group is a variety of.
Preferably, the resin further includes light absorber, and the light absorber is selected from S Ⅰ, S Ⅱ, oil red, phthalein
Cyanines are green, one of phthalocyanine blue, famille rose, lemon yellow, titanium dioxide or carbon black or at least two combination.With mass percent
Meter, light absorber additional amount account for the 0.01%-0.5% of resin.
In the present invention, by DLP photocuring 3D printing prepare thermoplastic polymer method be face form projector by
Layer illumination curing molding, cooperation platform is mobile to complete print procedure.
Specifically, the photosensitive resin precursor liquid prepares the method packet of thermoplastic polymer by DLP photocuring 3D printing
Include following steps:
(1) photosensitive resin precursor liquid is placed in and is installed in plastic holding device, corresponding exposure is designed according to the structure of printer model
Parameter, adjustment platform elemental height start to print；
(2) solidification is exposed to photosensitive resin precursor liquid by preset model slice using DLP projector, then passes through platform
Continuous moving obtains three dimensional model printing part；
(3) three dimensional model printing part is removed to be placed in solvent and washes away residual monomer, be put into later ultra-violet curing case into
Solidify after row, obtains thermoplastic polymer.
Preparation method provided by the invention is to obtain one by digitized projection technology to have 3 D complex structure, molecule
Measure adjustable thermoplastic polymer.The committed step of the method for the present invention be using DLP projector to single functionality photosensitive resin before
It drives liquid and carries out straight forming.
The processing of model slice described in step (2) can be completed using business software, and slice thickness is 10 μm -200 μm, be put down
The mobile mode of platform can be adjusted according to model, can be divided into continuous decline, and interval declines, three kinds of decline lifting.The work of projector
Mode is illumination+blank screen.Projector is in black state in platform moving process.Light application time is dense according to photoinitiator in formula
Degree, light absorber additional amount, chain transfer agent concentration are adjusted between 0.3-10s.The blank screen time can be adjusted between 0-5s.
The DLP projector of DLP projector commodity in use in the present invention.
The wave band that DLP projector light source issues is 400-700nm.The ultraviolet waves less than 400nm can also be used in DLP projector
Light source in the light source displacement DLP projector of section.
In step (3), the solvent be selected from ethyl alcohol, ethyl acetate, butyl acetate, methylene chloride, chloroform, benzene, toluene,
One of tetrahydrofuran or dimethylformamide or at least two combination.The wave-length coverage of ultra-violet curing case is 312-
700nm.Light application time can be adjusted depending on model structure between 1-1000s.
The present invention also provides a kind of, and the thermoplastic polymer based on DLP photocuring 3D printing is used as water-soluble or high temperature melting
The application of mold.
Preferably, the water-soluble or high temperature melting mold is used to prepare thermosetting polymer without the thermosetting property polymerization
Object is thermosetting epoxy resin or dimethyl silicone polymer.
Compared with prior art, the beneficial effects of the present invention are embodied in:
(1) thermoplastic polymer can not realize that the present invention is special by having selected from the author's angle from DLP Method of printing
Reaction monomers realize the printing of thermoplastic polymer, due to there was only the presence of the reactive monomer of low viscosity, the levelling speed of resin
Degree is exceedingly fast, and can help to realize DLP printing speed without other ancillary equipments.
(2) thermoplastic polymer in high temperature melting or can combine and the water-soluble feature of dimethomorph, complicated shape can be with
It is endowed other non-photocuring printed materials, such as commercial heatset epoxy resin, polydimethylsiloxane etc..
Detailed description of the invention
Fig. 1 is the digitized projection equipment and schematic device that the present invention uses；
Fig. 2 is that the illumination of photosensitive resin precursor liquid provided by the invention polymerize situation schematic diagram；
Fig. 3 is three-dimensional hollow structure pictorial diagram prepared by embodiment 1；
Fig. 4 is the schematic diagram in application examples 1 as water-soluble mold；
Fig. 5 is another schematic diagram as water-soluble mold in application examples 1.
Specific embodiment
The present invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply the range of example expression.
As shown in Figure 1, digitized projection equipment and device that the present invention uses prepare thermoplasticity solidfied material, comprising: calculate
Machine 1, DLP projector 2, print platform 3 and resin storage tank 4；Photosensitive resin precursor liquid 5 is filled in resin storage tank.Application of the invention
Range is not limited to the photocuring 3D printing method of (top-down) from top to bottom shown in Fig. 1, also includes other photocurings
(bottom-up) photocuring 3D printing method using face shadow casting technique prepares photocuring polymerization to 3D printing method such as from bottom to top
The method of object.
DLP projector 2 is connected by G code (G code) with computer 1, and the pattern of projection is by 1 Computer Aided Design of computer
CAD model be transmitted to DLP projector 2；It is repeatedly projected to 5 surface of photosensitive resin precursor liquid by 2 part of DLP projector, it
By certain blank screen time is gone through, fresh resin is supplemented to cured resin surface and is formed by platform movement in the blank screen time
One layer of new liquid layer.Projector, which continues to project next layer pattern, to the end of the blank screen time is solidified, successively stack formed it is three-dimensional
Structure.After the completion of solidification, obtained 3 D-printing part will be solidified and wash away excess monomer, curing process after carrying out after doing is wiped, until beating
Until printed document surface is no longer tacky.
Embodiment 1 prepares hydrophily acryloyl morpholine resin
Photosensitive resin precursor liquid raw material:
A) acryloyl morpholine (ACMO): Lihou (Guangdong) company；
B) oil red: Aladdin company；
C) 1- decanethiol (decylthiol): Aladdin company；
D) bis- (2,4,6- trimethylbenzoyl) phosphine oxides (Irgacure 819) of phenyl: Sigma-Aldrich company；
By monomer and other substances (mass fraction ACMO:decylthiol:Irgacure 819:Sudan by a certain percentage
III=100:1:1:0.025) be uniformly mixed, using digitized projection equipment and device figure illustrated in Figure 1 carry out circulation projection,
Expose and solidify: the wave band that DLP projector light source issues is 400-700nm, and the single projection time is 1.8s, platform decline drive
Resin flows to form new liquid layer, exposes next layer pattern again, persistently moves down to obtain threedimensional model by platform
Printout.
Fig. 2 illustrates the quick levelling ability of photosensitive resin precursor liquid.Since photosensitive resin precursor liquid only has activated monomer
In the presence of, overall viscosity is very low so that photosensitive resin precursor liquid in print procedure can levelling quickly, shorten the blank screen time.
Additionally, due to oxygen present in air, so that the oxygen concentration of photosensitive resin precursor liquid surface layer gas-liquid two-phase exists in print procedure
Difference.The presence of surface oxygen inhibition has further speeded up the infiltration of fresh photosensitive resin precursor liquid, so that printing speed can be realized.
With the cure kinetics in the illumination polymerization situation simulation print procedure of single layer photosensitive resin precursor liquid, surface layer oxygen inhibition in Fig. 2
So that curing degree is from bottom to top gradually decreased being parallel to light source direction, monomer conversion is gradually reduced, it was demonstrated that in certain light
Cured skin residual monomer is more according under the conditions of.
Fig. 3 illustrates the structure of the thermoplastic polymer based on DLP photocuring 3D printing, using photosensitive in embodiment 1
Resin precursor liquid, obtained three dimensional model printing part are hollow out, hanging and hollow structure
Application examples 1
Fig. 4,5 illustrate the three dimensional model printing part that uses embodiment 1 to prepare as water-soluble mold.
The water-soluble mold of the labyrinth moulding as thermosetting epoxy resin is illustrated in Fig. 4.Epoxy resin forerunner
Formula of liquid: (molar fraction epoxy E44: diamine D-230=1:1), 130 DEG C solidify 2 hours, and mold can be half small in 50 DEG C of water
When dissolve.
Fig. 5 is that three dimensional model printing bracket is put into PDMS precursor liquid, obtains three by dissolving bracket after being heating and curing
Tie up micro-channel structure.
Claims (8)
1. a kind of thermoplastic polymer based on DLP photocuring 3D printing, which is characterized in that the thermoplastic polymer is photosensitive
Resin precursor liquid is prepared by the 3D printing of DLP photocuring, and the photosensitive resin precursor liquid includes Monofunctional monomers, light-initiated
Agent, light absorber and molecular weight regulator, the Monofunctional monomers are the acrylate monomer or single third of mono acrylic ester base
The acrylamide monomer of acrylamide base.
2. the thermoplastic polymer according to claim 1 based on DLP photocuring 3D printing, which is characterized in that with quality
Score meter, the resin include the molecular weight tune of the photoinitiator of 0.1-5%, the light absorber of 0.01-0.1% and 0.1-2%
Save agent.
3. the thermoplastic polymer according to claim 1 based on DLP photocuring 3D printing, which is characterized in that described third
Olefin(e) acid ester monomer is selected from the combination of one or both of isobornyl acrylate or isobornyl methacrylate；The propylene
Amide monomer is selected from the combination of one or both of acryloyl morpholine or dimethylacrylamide.
4. the thermoplastic polymer according to claim 1 based on DLP photocuring 3D printing, which is characterized in that the light
Initiator is selected from benzoin and derivative, benzil class, alkylbenzene ketone, acyl group neighbour oxide, benzophenone or thioxanthene
One of ketone or at least two combination.
5. the thermoplastic polymer according to claim 1 based on DLP photocuring 3D printing, which is characterized in that described point
Son amount regulator is selected from the combination of one of aliphatic mercaptan, styrene polymer or amylene or at least two.
6. the thermoplastic polymer according to claim 1 based on DLP photocuring 3D printing, which is characterized in that the light
Quick resin precursor liquid by DLP photocuring 3D printing prepare thermoplastic polymer method the following steps are included:
(1) photosensitive resin precursor liquid is placed in and is installed in plastic holding device, corresponding exposure parameter is designed according to the structure of printer model,
Adjustment platform elemental height starts to print；
(2) it is sliced using DLP projector by preset model and solidification is exposed to photosensitive resin precursor liquid, then is continuous by platform
Movement obtains three dimensional model printing part；
(3) three dimensional model printing part is removed to be placed in solvent and washes away residual monomer, after being put into the progress of ultra-violet curing case later
Solidification, obtains thermoplastic polymer.
7. a kind of any thermoplastic polymer based on DLP photocuring 3D printing of claim 1-6 as water-soluble or
The application of high temperature melting mold.
8. the application of the thermoplastic polymer according to claim 7 based on DLP photocuring 3D printing, which is characterized in that
The water-soluble or high temperature melting mold is used to prepare thermosetting polymer, and the thermosetting polymer is thermosetting epoxy resin
Or dimethyl silicone polymer.
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Cited By (9)
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| CN110964154A (en) * | 2019-11-18 | 2020-04-07 | 华南协同创新研究院 | Photosensitive resin material for indirect 3D printing auxiliary forming and preparation method and application thereof |
| CN111976132A (en) * | 2020-08-25 | 2020-11-24 | 张超 | Rapid normal-temperature pouring equipment and method based on SLA photocuring technology |
| CN112094386A (en) * | 2020-08-25 | 2020-12-18 | 浙江新光饰品股份有限公司 | Photosensitive resin for ashless 3D printing |
| CN113150199A (en) * | 2020-01-20 | 2021-07-23 | 中国科学院化学研究所 | Recyclable photocuring 3D printing linear polymer part and preparation method and application thereof |
| RU2760736C1 (en) * | 2021-04-19 | 2021-11-30 | Федеральное государственное бюджетное учреждение науки Байкальский институт природопользования Сибирского отделения Российской академии наук (БИП СО РАН) | Curable resins for making heat-resistant 3d objects using dlp 3d printing |
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| CN114656590A (en) * | 2020-12-07 | 2022-06-24 | 中国科学院福建物质结构研究所 | Degradable thermosetting 3D printing mold and preparation method thereof |
| CN116284566A (en) * | 2022-09-09 | 2023-06-23 | 南方科技大学 | Photo-curing slurry and organic hydrogel for high-elasticity wearable strain sensor and preparation method thereof |
| WO2024126332A1 (en) * | 2022-12-12 | 2024-06-20 | Nexa3D Aps | Sacrificial additively manufactured mold with controlled moisture and liquid absorption properties |
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| CN112094386A (en) * | 2020-08-25 | 2020-12-18 | 浙江新光饰品股份有限公司 | Photosensitive resin for ashless 3D printing |
| CN114591601A (en) * | 2020-12-07 | 2022-06-07 | 中国科学院福建物质结构研究所 | Preparation method of multifunctional 4D printing material |
| CN114656590A (en) * | 2020-12-07 | 2022-06-24 | 中国科学院福建物质结构研究所 | Degradable thermosetting 3D printing mold and preparation method thereof |
| RU2760736C1 (en) * | 2021-04-19 | 2021-11-30 | Федеральное государственное бюджетное учреждение науки Байкальский институт природопользования Сибирского отделения Российской академии наук (БИП СО РАН) | Curable resins for making heat-resistant 3d objects using dlp 3d printing |
| CN116284566A (en) * | 2022-09-09 | 2023-06-23 | 南方科技大学 | Photo-curing slurry and organic hydrogel for high-elasticity wearable strain sensor and preparation method thereof |
| WO2024126332A1 (en) * | 2022-12-12 | 2024-06-20 | Nexa3D Aps | Sacrificial additively manufactured mold with controlled moisture and liquid absorption properties |
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