CN107936685A - A kind of preparation method of polyimides ink available for 3D printing - Google Patents
A kind of preparation method of polyimides ink available for 3D printing Download PDFInfo
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- CN107936685A CN107936685A CN201711143567.4A CN201711143567A CN107936685A CN 107936685 A CN107936685 A CN 107936685A CN 201711143567 A CN201711143567 A CN 201711143567A CN 107936685 A CN107936685 A CN 107936685A
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- polyimides
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- preparation
- silicon dioxide
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- 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
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The present invention relates to a kind of preparation method of the polyimides ink available for 3D printing.Using collosol and gel combination 3D printing technique, diamines and dianhydride monomer are added into catalyst synthesizing polyamides acid solution, silica is added and forms polyamic acid colloidal sol, become the polyimides ink of high concentration after stirring, printed using 3D printing technique, obtain the polyimides gel of low-density.Material of the present invention, which is modified its molecular structure, makes its fusible, has processability well, high-performance polyimide colloidal sol has been obtained using 3D printing technique.Polyimide aerogels prepared by the present invention have excellent high temperature resistant, corrosion resistance and higher mechanical strength.This kind of extremely-low density polyimide aerogels have good electric conductivity and high-compressibility, lightening fire resistant material can be made in space industry, advanced low-k materials can be fabricated in wireless electron field, heat-insulating heat-preserving material etc. is made in building field, it is seen that low-density polyimide aeroge has very wide application prospect in multiple fields.
Description
Technical field
The invention belongs to aerogel material preparing technical field, and in particular to a kind of polyimides ink available for 3D printing
The preparation method of water.
Background technology
RP technique is a kind of threedimensional model that object is established with computer, and as the skill for relying on direct forming
Art, is the intersection of multiple subjects such as bioengineering, material processing and forming, microcomputer modelling.Quick forming method is divided into many kinds,
Such as laser sintered, laser fusion, fusion sediment, 3D printing, three-dimensional optical soliton interaction.The groundwork of RP technique is former
Reason is modeling, accumulation and Quick-forming, and the physical form of object is converted into three by modeling software or spatial digitizer first
Dimension word three-dimensional model, is then successively accumulated material using the above method, is cured by appropriate post processing, is needed
Molded component, RP technique are widely applied in developed country.
3D printing technique is one kind in RP technique, its operation principle is similar to inkjet printing, i.e., in computer
Control under, the CAD according to printed matter（CAD）Model obtains the model converted after data, accurate by material
3D accumulates, the digitlization forming technique of the quick 3D objects for manufacturing designated shape.3D printing technique has easy to operate, forming speed
It hurry up, the free of contamination feature of forming process.
The current species of polymeric material available for 3D printing is less, the such as acrylonitrile butadiene styrene reported
Terpolymer (ABS) and polylactic acid (PLA), wherein ABS resin intensity is not high, and as molecular weight increases, under processing performance
Drop.And PLA poor mechanical properties, brittle fracture easily occurs, limits its processing performance.So it is diligent to develop new 3D printing
The fast-developing short slab that energy fluidized polymer material restricts 3D printing field to making up is of great significance.
Aeroge, the solid most light as the world, is selected in Guiness World Records.Aeroge includes substantial amounts of air,
For typical hole dimension in l-l00 nanometer ranges, hole ratio is a kind of porous material with nanostructured more than 80%,
Its peculiar property is shown in aspects such as mechanics, acoustics, calorifics, optics.Polyimide aerogels are as a kind of mechanical property
Preferably, heat endurance is high, and the good organic aerogel of heat-proof quality gets more and more people's extensive concerning in recent years.Polyimide aerogels
Larger contraction causes the density of aeroge generally higher.We are by configuring polyimides ink come the original as 3D printing
Material, effectively by simplifying its structure, greatly reduces the density of polyimide aerogels.
The content of the invention
It is an object of the invention to provide a kind of cost is relatively low, medicament is easier to obtain, reaction process is simple, experimental implementation just
Polyimides ink for 3D printing prompt, reaction time is short, possible industry is amplified.Its basic ideas is sub- by polyamides
Amine colloidal sol is combined in 3D printing technique, obtains the material with preferable heat-proof quality of extremely-low density.It is to use dianhydride first
With diamine monomer synthesizing polyamides acid oligomer solution, then silicon dioxide aerogel powder of the particle diameter in 20-50um is added
Into polyamic acid solution, uniformly mixing, then passes through chemical imines process and forms polyimide/silicon dioxide aerogel powder
The 3D printing ink of plural gel, i.e. gained, the polyimides gel of set structure is printed through 3D printer, is most passed through afterwards
CO 2 supercritical is dried to obtain polyimide aerogels powder plural gel.Particular content is as follows：
The present invention proposes a kind of preparation method of the polyimides ink available for 3D printing, using sol-gal process, specifically
Step is as follows：
(1) by the 4,4'- of dianhydride 3,3 ' bibenzene tetracarboxylic dianhydrides i.e. and diamine monomer, that is, 2,2- couple [4- (4- phenalgins epoxide) phenyl]
Propane is dissolved in 40ml organic solvent 1-methyl-2-pyrrolidinones, wherein：The adding proportion of dianhydride and diamines is 8.35mmol:
8.35mmol；Stirred 30 minutes in room temperature and make polyamic acid solution；
(2) silicon dioxide aerogel powder 2g is added to the polyamic acid solution obtained by step (1), stirs evenly, obtain at room temperature
Obtain polyamic acid/silicon dioxide aerogel powder composite solution；
(3) add dehydrating agent in the mixed solution obtained to step (2), carry out chemical imines process, formed polyimides/
Silicon dioxide aerogel powder mixed gel；
(4) gel obtained by step (3) is printed to the structure of setting using 3D printer.
In the present invention, silicon dioxide aerogel powder particle diameter is in 20-50um described in step (2).
In the present invention, dehydrating agent described in step (2) is 6.5ml ethanedioic acids and the mixed solution of 5.6ml pyridines composition.
The beneficial effects of the present invention are：
The present invention is with cost is relatively low, medicament is easier to acquisition, reaction process is simple, experimental implementation is convenient, reaction time is short, may
The features such as industry amplification.On the one hand, double [4- (the 4- phenalgins epoxide) phenyl] third of lower-cost 2, the 2- for being easier to obtain have been used
Alkane, the product have relatively low rigidity compared to traditional diaminodiphenyl ether, and flexibility is good, when being conducive to extend the gel of ink
Between, storage time is added, on the other hand, the contraction of the introducing of inorganic silicon dioxide aerogel powder to organic polyimide rises
Inhibitory action is arrived.Polyimides colloidal sol is printed using 3D printer, obtains extremely-low density, the aeroge of structure-controllable,
The properties for asking aeroge can be greatly promoted, while reduce the density of aeroge, excellent heat-proof quality, which allows, to be obtained
Mixing aerogel material in fields such as the anti-heat insulating member of spacecraft, the anti-insulating of building and commercial insulating products
In be respectively provided with important application value.
Brief description of the drawings
Viscosity change curve of Fig. 1 tradition polyimides gel inks under different shear rate；
The polyimides gel that Fig. 2 Regenovo Bio-Architect 3D biometric print machines print；Wherein：(a) it is to beat
400 microns of needle diameter of print, 90 degree of samples for being mutually perpendicular to print,（b）For 400 microns of needle diameter, tiltedly accumulate for 45 degree and beat
The sample printed off；
The microscopic appearance of the polyimide-based carbon aerogels of Fig. 3 3D direct write types is wherein：A-1 it is) 400 microns of needle diameter, 90 degree of phases
Microscopic appearance of the sample mutually vertically printed under scanning electron microscope（100*）, a-2) and it is 400 microns of needle diameter, 90 degree are mutually
Microscopic appearance of the sample vertically printed under scanning electron microscope（1000*）, b-1）For 400 microns of needle diameter, 45 degree of oblique heaps
Microscopic appearance of the sample that product prints under scanning electron microscope（100*） ,b-2）For 400 microns of needle diameter, 45 degree of tiltedly accumulations
Microscopic appearance of the sample printed under scanning electron microscope（1000*）, c-1) and it is 300 microns of needle diameter, 90 degree are mutually perpendicular to
Microscopic appearance of the sample printed under scanning electron microscope（100*）, c-2) and it is 300 microns of needle diameter, 90 degree are mutually perpendicular to beat
Microscopic appearance of the sample printed off under scanning electron microscope（1000*）.
Embodiment
By the following examples and attached drawing is further elaborated with the present invention.（Each raw material is marketable material, and nothing is especially said
Bright purity is chemical pure or the pure grade of analysis）
Embodiment 1：Preparation for the polyimides ink of 3D printing
By diamines and dianhydride（Diaminodiphenyl ether：3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride=1.672g：2.556g）It is dissolved in 50mL
1-methyl-2-pyrrolidinone in, synthesizing polyamides acid solution, is stirred half an hour, then adds the dioxy that 1g particle diameters are 20-50um
SiClx aerogel powder, and half an hour is quickly stirred, add dehydrating agent 12.1mL（Ethanedioic acid：Pyridine=6.5mL：5.6mL）,
Refrigerator-freezer preservation is put into after rapid stirring before gel.Carry out 3D printing is taken out after a period of time, the clathrate gel printed exists
Place at room temperature.Pictorial diagram is as shown in Figure 1.
Embodiment 2：Preparation for the polyimides ink of 3D printing
By diamines and dianhydride（Diaminodiphenyl ether：3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride=1.672g：2.556g）It is dissolved in
In the 1-methyl-2-pyrrolidinone of 100mL, synthesizing polyamides acid solution, is stirred half an hour, and it is 20-50um's then to add 2g particle diameters
Silicon dioxide aerogel powder, and half an hour is quickly stirred, add dehydrating agent 12.1mL（Ethanedioic acid：Pyridine=6.5mL：
5.6mL）, refrigerator-freezer preservation is put into after rapid stirring before gel.Carry out 3D printing, the clathrate printed are taken out after a period of time
Gel is placed at room temperature.
Embodiment 3：Preparation for the polyimides ink of 3D printing
By diamines and dianhydride（Diaminodiphenyl ether：3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride=1.672g：2.556g）It is dissolved in
In the 1-methyl-2-pyrrolidinone of 150mL, synthesizing polyamides acid solution, is stirred half an hour, and it is 20-50um's then to add 4g particle diameters
Silicon dioxide aerogel powder, and half an hour is quickly stirred, add dehydrating agent 12.1mL（Ethanedioic acid：Pyridine=6.5mL：
5.6mL）, refrigerator-freezer preservation is put into after rapid stirring before gel.Carry out 3D printing, the clathrate printed are taken out after a period of time
Gel is placed at room temperature.
As shown in Fig. 2, acid imide gel ink is carried out using Regenovo Bio-Architect 3D biometric prints machines
The printing of layer upon layer.A diameter of 400um of syringe needle is printed, line width is 600 um.In print procedure, gel can be successfully
Linear gel is extruded into from nozzle, syringe needle is blocked without the addition because of silicon dioxide aerogel powder.Whole line
Bar is continuously shaped, and fracture is occurred without in print procedure.The solidification shape of lines keeps stablizing at the same time, between lines without because
" spreading out " phenomenon and be bonded to each other.In addition, gel lines are in-between without because deformation of caving in occurs in gravity
Phenomenon, illustrates that the mechanical strength of gel lines is preferable.The overall structure of gel network is high-visible, and grid space is uniformly distributed.
As shown in figure 3, under scanning electron microscope the polyimide-based carbon aerogels of 3D direct writes type microscopic appearance, three kinds of different print structures
Polyimide aerogels suffer from the orderly periodic structure of comparison.Fig. 3 a-1 are the syringe needles 90 using a diameter of 400 um
Degree is mutually perpendicular to the sample printed, its lines diameter is in 250 um or so.In Fig. 3 b-1, print procedure equally using
The tiltedly accumulation of 45 degree of the angle that the syringe needle of 400 um still prints, its a diameter of 220 um.However, using a diameter of 300 um's
90 degree of syringe needle is mutually perpendicular to the sample printed（Fig. 3 c-1）Maintain preferable cylindric strip structure, a diameter of 110 um
Left and right.In addition, there are some larger pore space structures in linear after excessive erosion, macroscopic periodically structure is realized
In microporous structure double-layer network structure.
For embodiment described above only for the technological thought and feature of the explanation present invention, its object is to make this area
Those of ordinary skill can understand present disclosure and implement according to this, and the scope of this patent is not limited merely to above-mentioned specific reality
Example is applied, i.e., all equal changes or modification made according to disclosed spirit, still cover within the scope of the present invention.
Claims (3)
1. the preparation method of a kind of polyimides ink available for 3D printing, it is characterised in that using sol-gal process, specifically
Step is as follows：
(1) by the 4,4'- of dianhydride 3,3 ' bibenzene tetracarboxylic dianhydrides i.e. and diamine monomer, that is, 2,2- couple [4- (4- phenalgins epoxide) phenyl]
Propane is dissolved in 40ml organic solvent 1-methyl-2-pyrrolidinones, wherein：The adding proportion of dianhydride and diamines is 8.35mmol:
8.35mmol；Stirred 30 minutes in room temperature and make polyamic acid solution；
(2) silicon dioxide aerogel powder 2g is added to the polyamic acid solution obtained by step (1), stirs evenly, obtain at room temperature
Obtain polyamic acid/silicon dioxide aerogel powder composite solution；
(3) add dehydrating agent in the mixed solution obtained to step (2), carry out chemical imines process, formed polyimides/
Silicon dioxide aerogel powder mixed gel；
(4) gel obtained by step (3) is printed to the structure of setting using 3D printer.
2. preparation method according to claim 1, it is characterised in that dehydrating agent described in step (2) is 6.5ml ethanedioic acids
With the mixed solution of 5.6ml pyridines composition.
3. preparation method according to claim 1, it is characterised in that silicon dioxide aerogel powder grain described in step (2)
Footpath can support 3D printing structural framework, while will not block nozzle in 20-50um.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774321A (en) * | 2018-06-28 | 2018-11-09 | 黑龙江省科学院高技术研究院 | Polyimide resin powder and preparation method thereof suitable for alternative sintering |
| CN109545951A (en) * | 2018-11-16 | 2019-03-29 | 清华大学深圳研究生院 | A kind of organic thermo-electric device template and preparation method thereof and a kind of thermo-electric device |
| CN109647331A (en) * | 2018-11-29 | 2019-04-19 | 朗缪环保科技(天津)有限公司 | A kind of preparation method and application of composite adsorbing material |
| CN109897199A (en) * | 2019-02-22 | 2019-06-18 | 黑龙江省科学院石油化学研究院 | The polyimide precursor gel and its preparation method and application for inhaling wave and heat resistant poly acid imide lightweight labyrinth can be prepared |
| CN111154336A (en) * | 2020-01-03 | 2020-05-15 | 中国科学院兰州化学物理研究所 | Porous polyimide ink, preparation method thereof and method for preparing porous polyimide through direct writing 3D printing |
| WO2020147567A1 (en) * | 2019-01-14 | 2020-07-23 | 四川大学 | Functional ink suitable for 3d printing and preparation method thereof |
| CN112707402A (en) * | 2020-12-31 | 2021-04-27 | 中国人民解放军国防科技大学 | Silica aerogel ink for 3D direct-writing printing and preparation method thereof |
| US11020895B2 (en) * | 2018-07-05 | 2021-06-01 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | Direct-writing polyimide additive manufacturing material and preparation method thereof |
| CN115028836A (en) * | 2022-07-13 | 2022-09-09 | 同济大学 | Nano multi-level structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof |
| CN115850970A (en) * | 2022-12-22 | 2023-03-28 | 中国人民解放军国防科技大学 | Preparation method of 3D printing polyimide-silicon oxide hybrid aerogel |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774321B (en) * | 2018-06-28 | 2020-09-01 | 黑龙江省科学院高技术研究院 | Polyimide resin powder suitable for selective sintering and preparation method thereof |
| CN108774321A (en) * | 2018-06-28 | 2018-11-09 | 黑龙江省科学院高技术研究院 | Polyimide resin powder and preparation method thereof suitable for alternative sintering |
| US11020895B2 (en) * | 2018-07-05 | 2021-06-01 | Lanzhou Institute Of Chemical Physics, Chinese Academy Of Sciences | Direct-writing polyimide additive manufacturing material and preparation method thereof |
| CN109545951A (en) * | 2018-11-16 | 2019-03-29 | 清华大学深圳研究生院 | A kind of organic thermo-electric device template and preparation method thereof and a kind of thermo-electric device |
| CN109545951B (en) * | 2018-11-16 | 2023-02-03 | 清华大学深圳研究生院 | Organic thermoelectric device template, preparation method thereof and thermoelectric device |
| CN109647331B (en) * | 2018-11-29 | 2021-09-03 | 朗缪环保科技(天津)有限公司 | Preparation method and application of composite adsorption material |
| CN109647331A (en) * | 2018-11-29 | 2019-04-19 | 朗缪环保科技(天津)有限公司 | A kind of preparation method and application of composite adsorbing material |
| WO2020147567A1 (en) * | 2019-01-14 | 2020-07-23 | 四川大学 | Functional ink suitable for 3d printing and preparation method thereof |
| US11530331B2 (en) | 2019-01-14 | 2022-12-20 | Sichuan University | Functional ink suitable for 3D printing and preparation method thereof |
| CN109897199A (en) * | 2019-02-22 | 2019-06-18 | 黑龙江省科学院石油化学研究院 | The polyimide precursor gel and its preparation method and application for inhaling wave and heat resistant poly acid imide lightweight labyrinth can be prepared |
| CN111154336A (en) * | 2020-01-03 | 2020-05-15 | 中国科学院兰州化学物理研究所 | Porous polyimide ink, preparation method thereof and method for preparing porous polyimide through direct writing 3D printing |
| CN112707402A (en) * | 2020-12-31 | 2021-04-27 | 中国人民解放军国防科技大学 | Silica aerogel ink for 3D direct-writing printing and preparation method thereof |
| CN115028836A (en) * | 2022-07-13 | 2022-09-09 | 同济大学 | Nano multi-level structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof |
| CN115850970A (en) * | 2022-12-22 | 2023-03-28 | 中国人民解放军国防科技大学 | Preparation method of 3D printing polyimide-silicon oxide hybrid aerogel |
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Application publication date: 20180420 |