CN112280370B - Cyanate ester ink for 3D printing and preparation method and application thereof - Google Patents
Cyanate ester ink for 3D printing and preparation method and application thereof Download PDFInfo
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- CN112280370B CN112280370B CN202011298348.5A CN202011298348A CN112280370B CN 112280370 B CN112280370 B CN 112280370B CN 202011298348 A CN202011298348 A CN 202011298348A CN 112280370 B CN112280370 B CN 112280370B
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- 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
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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
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- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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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
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides 3D printing cyanate ester ink and a preparation method and application thereof, and belongs to the technical field of 3D printing high-performance resin materials. The 3D printing cyanate ester ink provided by the invention comprises cyanate ester resin, glycidyl methacrylate, reactive diluent, photoinitiator, cross-linking agent and dye, and the 3D printing cyanate ester ink has higher printing precision by optimizing the types of the cyanate ester resin, the reactive diluent, the photoinitiator, the cross-linking agent and the dye. The 3D printed cyanate ester ink is preformed through 3D printing and then subjected to thermocuring treatment, so that the obtained formed part has high precision, excellent mechanical property and heat resistance. The embodiment shows that the tensile strength of a formed part obtained by carrying out photocuring and thermocuring treatment on the 3D printing cyanate ester ink provided by the invention reaches 95MPa, and the glass transition temperature (T) isg) Up to 191 ℃ and an initial decomposition temperature (T)5％) Up to 338 ℃.
Description
Technical Field
The invention relates to the technical field of 3D printing high-performance resin materials, in particular to 3D printing cyanate ester ink and a preparation method and application thereof.
Background
High-performance thermosetting resins are widely used in advanced fields of aerospace, automobile industry and the like due to their excellent mechanical properties and heat resistance. But it is difficult to realize 3D printing of thermosetting resin due to its severe molding conditions. In recent years, the strategy of implementing thermosetting resin 3D printing by using photocuring molding and post-treatment has achieved good effects, such as epoxy resin, polyimide resin, bismaleimide resin, and the like, but the strategies still have problems of low heat resistance, low printing precision, poor mechanical properties, and the like. Therefore, how to realize high-precision 3D printing on the premise of maintaining the original performance of the thermosetting resin becomes especially critical.
Disclosure of Invention
In view of this, the present invention provides a cyanate ester ink for 3D printing, and a preparation method and an application thereof. The 3D printing cyanate ester ink provided by the invention has the capability of forming a double-network cross-linked structure, has higher printing precision, and after the 3D printing cyanate ester ink is subjected to pre-curing and thermosetting treatment, the formed part has excellent heat resistance and mechanical properties.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides 3D printing cyanate ester ink which comprises the following components:
cyanate ester resin, glycidyl methacrylate, reactive diluent, photoinitiator, crosslinking agent and dye;
the cyanate resin is one or more of bisphenol F cyanate, bisphenol M cyanate, bisphenol E type cyanate, phenolic aldehyde type cyanate, dicyclopentadiene type cyanate and bisphenol A type cyanate;
the active diluent is one or more of N-vinyl pyrrolidone, hydroxyethyl methacrylate, tetrahydrofuran acrylate, 4-acryloyl morpholine, cyclotrimethylolpropane methylal acrylate, tetrahydrofurfuryl methacrylate and isobornyl methacrylate;
the photoinitiator is one or more of Irgacure 184, Darocur 1173, Irgacure2959, Irgacure 369, Irgacure 907, Irgacure 651, Irgacure 250, Irgacure 819 and Lucirin TPO;
the cross-linking agent is one or more of triallyl isocyanurate, tris (2-hydroxyethyl) isocyanurate triacrylate, bis-pentaerythritol hexaacrylate and pentaerythritol triacrylate;
the dye is one or more of Aorisu yellow 190, Aorisu blue 755, Aorisu orange 247 and Aorisu brown 322.
Preferably, the mass ratio of the cyanate ester resin to the glycidyl methacrylate is more than or equal to 1.
Preferably, the mass ratio of the cyanate ester resin to the reactive diluent is 60: (15-200).
Preferably, the mass ratio of the cyanate ester resin to the photoinitiator is 60: (0.2-1.0).
Preferably, the mass ratio of the cross-linking agent to the reactive diluent is 1: (0.1 to 50).
Preferably, the mass ratio of the photoinitiator to the dye is (0.1-20): (0.01-1).
The invention also provides a preparation method of the 3D printing cyanate ester ink, which comprises the following steps:
mixing a cross-linking agent and a reactive diluent to obtain a first solution;
mixing the first solution, a photoinitiator and a dye to obtain a photocuring matrix resin;
and mixing the photo-curing matrix resin, glycidyl methacrylate and cyanate ester resin to obtain the 3D printing cyanate ester ink.
The invention also provides the 3D printing cyanate ester ink in the technical scheme or the 3D printing cyanate ester ink obtained by the preparation method in the technical scheme, and the application of the 3D printing cyanate ester ink in 3D printing.
Preferably, the application comprises the steps of:
precuring the 3D printed cyanate ester ink to obtain a preformed piece;
and carrying out thermosetting treatment on the preformed piece to obtain a formed piece.
Preferably, the heat curing process includes a first heat treatment, a second heat treatment, a third heat treatment, a fourth heat treatment, and a fifth heat treatment which are sequentially performed;
the temperature of the first heat treatment is 100-140 ℃, and the heat preservation time is 2-8 h;
the temperature of the second heat treatment is 150-160 ℃, and the heat preservation time is 2-8 h;
the temperature of the third heat treatment is 170-180 ℃, and the heat preservation time is 2-8 h;
the temperature of the fourth heat treatment is 190-210 ℃, and the heat preservation time is 2-8 h;
the temperature of the fifth heat treatment is 220-280 ℃, and the heat preservation time is 2-8 h.
The invention provides 3D printing cyanate ester ink which comprises the following components: cyanate ester resin, glycidyl methacrylate, reactive diluent, photoinitiator, crosslinking agent and dye; the cyanate resin is one or more of bisphenol F cyanate, bisphenol M cyanate, bisphenol E type cyanate, phenolic aldehyde type cyanate, dicyclopentadiene type cyanate and bisphenol A type cyanate; the active diluent is one or more of N-vinyl pyrrolidone, hydroxyethyl methacrylate, tetrahydrofuran acrylate, 4-acryloyl morpholine, cyclotrimethylolpropane methylal acrylate, tetrahydrofurfuryl methacrylate and isobornyl methacrylate; the photoinitiator is one or more of Irgacure 184, Darocur 1173, Irgacure2959, Irgacure 369, Irgacure 907, Irgacure 651, Irgacure 250, Irgacure 819 and Lucirin TPO; the cross-linking agent is one or more of triallyl isocyanurate, tris (2-hydroxyethyl) isocyanurate triacrylate, bis-pentaerythritol hexaacrylate and pentaerythritol triacrylate; the dye is one or more of Aorisu yellow 190, Aorisu blue 755, Aorisu orange 247 and Aorisu brown 322.
The invention uses one or more of crosslinking agents of triallyl isocyanurate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, bis-pentaerythritol hexaacrylate and pentaerythritol triacrylate to ensure that a resin system forms a high crosslinking degree system after crosslinking; the reactive diluent N-vinyl pyrrolidone, hydroxyethyl methacrylate, tetrahydrofuran acrylate, 4-acryloyl morpholine, cyclotrimethylolpropane methylal acrylate, tetrahydrofurfuryl methacrylate and isobornyl methacrylate are used, so that the crosslinking agent and cyanate ester resin can be well dissolved, and the 3D printing cyanate ester ink has rheological property suitable for 3D printing; the invention uses one or more of photoinitiators Irgacure 184, Darocur 1173, Irgacure2959, Irgacure 369, Irgacure 907, Irgacure 651, Irgacure 250, Irgacure 819 and Lucirin TPO to promote the active diluent to form a net-shaped cross-linking structure with the cross-linking agent in the photocuring process of 3D printing; the dye added in the invention can reduce the sensitivity of 3D printing cyanate ester ink to light and prevent the edge of a printed part from being over-cured, thereby improving the printing precision of the cyanate ester ink. According to the 3D printing cyanate ester ink provided by the invention, due to the optimized formula of the reactive diluent, the cross-linking agent, the dye and the photoinitiator, the 3D printing cyanate ester ink is endowed with extremely high printing precision, so that a finally printed formed part has excellent mechanical properties and heat resistance.
The invention also provides a preparation method of the 3D printing cyanate ester ink, which is simple and easy to operate.
The invention also provides the application of the 3D printing cyanate ester ink in 3D printing, the 3D printing cyanate ester ink is pre-cured and further cured through thermal curing treatment, so that the cyanate ester resin is completely reacted, and the obtained formed part has high precision, excellent mechanical property and heat resistance.
The data of the embodiment show that the tensile strength of the formed part obtained by carrying out photocuring and thermocuring treatment on the 3D printing cyanate ester ink provided by the invention can reach 95MPa, and the glass transition temperature (T) can reachg) Up to 191 ℃ and an initial decomposition temperature (T)5％) Up to 338 ℃.
Drawings
FIG. 1 is an IR spectrum of bisphenol A cyanate ester monomer, 3D printed cyanate ester ink, photo-curable matrix resin and molded part of example 1;
FIG. 2 is a graph showing the viscosity curves of the photo-curable matrix resin, the 3D printing cyanate ester ink and the bisphenol A type cyanate ester monomer obtained in example 1;
FIG. 3 is a stress-strain curve of the molded article obtained in example 1 at normal temperature;
FIG. 4 is a graph of loss factor (Tan. delta.) vs. temperature for the shaped parts obtained in examples 1 and 2;
FIG. 5 shows the Thermogravimetry (TG) -temperature curves of the shaped parts obtained in example 1 and example 2;
FIG. 6 is an appearance of the molded article obtained in examples 1 to 6.
Detailed Description
The invention provides 3D printing cyanate ester ink which comprises the following components:
cyanate ester resin, glycidyl methacrylate, reactive diluent, photoinitiator, crosslinking agent and dye.
In the present invention, the starting materials used in the present invention are all commercially available products unless otherwise specified.
In the invention, the cyanate ester resin is one or more of bisphenol F cyanate ester, bisphenol M cyanate ester, bisphenol E cyanate ester, phenolic cyanate ester, dicyclopentadiene cyanate ester and bisphenol A cyanate ester, and preferably bisphenol F cyanate ester or bisphenol A cyanate ester. The cyanate resin added in the invention can generate triazine cyclization structure by self-polymerization in the heat treatment process of the printed matter, and simultaneously forms a network interpenetrating structure with the photocuring matrix resin, thereby improving the mechanical property and the thermal stability of the 3D printing cyanate ink.
The present invention is not particularly limited with respect to the source of the glycidyl methacrylate. According to the invention, glycidyl methacrylate is added, in the curing process, unsaturated double bonds of the glycidyl methacrylate react with the reactive diluent or the cross-linking agent, and epoxy groups of the glycidyl methacrylate react with cyanate groups, so that the occurrence of phase separation between the photocuring matrix resin and the cyanate ester resin is reduced; endows the formed part with excellent mechanical property and heat resistance.
In the invention, the reactive diluent is one or more of N-vinyl pyrrolidone, hydroxyethyl methacrylate, tetrahydrofuran acrylate, 4-acryloyl morpholine, cyclotrimethylolpropane formal acrylate, tetrahydrofurfuryl methacrylate and isobornyl methacrylate, and is preferably N-vinyl pyrrolidone or hydroxyethyl methacrylate.
In the invention, the photoinitiator is one or more of Irgacure 184, Darocur 1173, Irgacure2959, Irgacure 369, Irgacure 907, Irgacure 651, Irgacure 250, Irgacure 819 and Lucirin TPO, and preferably Irgacure 184 or Irgacure 819.
In the invention, the crosslinking agent is one or more of triallyl isocyanurate, tris (2-hydroxyethyl) isocyanurate triacrylate, bis-pentaerythritol hexaacrylate and pentaerythritol triacrylate, and is preferably triallyl isocyanurate or bis-pentaerythritol hexaacrylate.
In the invention, the dye is one or more of oridin yellow 190, oridin blue 755, oridin orange 247 and oridin brown 322, and is preferably the oridin yellow 190 or the oridin blue 755. In the invention, the addition of the dye can reduce the sensitivity of the cyanate ester ink for 3D printing to light and prevent the edge of a printed part from being excessively cured, thereby improving the printing precision of the cyanate ester ink.
In the present invention, the mass ratio of the cyanate ester resin to the glycidyl methacrylate is preferably not less than 1, and more preferably 20.
In the present invention, the mass ratio of the cyanate ester resin to the reactive diluent is preferably 60: (15-200), more preferably 60: (20-45), and particularly preferably 60: 30. 60: 36.82, 60: 45. 60: 24.23 or 60: 40.
in the present invention, the mass ratio of the cyanate ester resin to the photoinitiator is preferably 60: (0.2 to 1.0), and particularly preferably 60: 0.6, 60: 0.32 or 60: 0.4.
in the present invention, the mass ratio of the crosslinking agent to the reactive diluent is preferably 1: (0.1 to 50), and particularly preferably 1: 3. 1: 2 or 1: 1.
in the invention, the mass ratio of the photoinitiator to the dye is preferably (0.1-20): (0.01 to 1), and particularly preferably 0.6: 0.036, 0.32: 0.019 or 0.4: 0.024.
the invention also provides a preparation method of the 3D printing cyanate ester ink, which comprises the following steps:
a cross-linking agent and a reactive diluent are mixed to obtain a first solution;
mixing the first solution, a photoinitiator and a dye to obtain a photocuring matrix resin;
and mixing the light-cured matrix resin, the glycidyl methacrylate and the cyanate ester resin to obtain the 3D printing cyanate ester ink.
The present invention mixes a crosslinking agent and a reactive diluent to obtain a first solution.
The present invention is not particularly limited in the manner described, as long as the crosslinking agent and the reactive diluent can be uniformly mixed.
After the first solution is obtained, the first solution, the photoinitiator and the dye are mixed to obtain the 3D printing photocuring matrix resin.
The mixing manner is not particularly limited in the present invention, as long as the first solution, the photoinitiator and the dye can be uniformly mixed.
After the photo-curing matrix resin is obtained, the photo-curing matrix resin, the glycidyl methacrylate and the cyanate ester resin are mixed to obtain the 3D printing cyanate ester ink.
The mixing manner is not particularly limited in the present invention, as long as the photocurable matrix resin, the glycidyl methacrylate, and the cyanate ester resin can be uniformly mixed. In the present invention, after the completion of the mixing, the mixed material liquid is preferably subjected to vacuum defoaming in the present invention, and the parameters of the vacuum defoaming are not particularly limited in the present invention.
The invention also provides application of the 3D printing cyanate ester ink in the technical scheme or the 3D printing cyanate ester ink obtained by the preparation method in the technical scheme in 3D printing
In the present invention, when the 3D printing cyanate ester ink is applied to 3D printing, it preferably includes the following steps:
precuring the 3D printed cyanate ester ink to obtain a preformed piece;
and carrying out thermosetting treatment on the preformed piece to obtain a formed piece.
According to the invention, the 3D printing cyanate ester ink is pre-cured to obtain the preformed piece.
In the invention, the pre-curing mode is preferably ultraviolet curing; the time of the ultraviolet light curing is preferably 5 min. In the present invention, the apparatus for precuring is preferably a digital light processing apparatus or a stereolithography apparatus.
After the preform is obtained, the preform is subjected to thermosetting treatment to obtain a molded part.
In the present invention, the heat curing treatment preferably includes a first heat treatment, a second heat treatment, a third heat treatment, a fourth heat treatment, and a fifth heat treatment which are sequentially performed.
In the invention, the temperature of the first heat treatment is preferably 100-140 ℃, and the heat preservation time is preferably 2-8 h; the temperature of the second heat treatment is preferably 150-160 ℃, and the heat preservation time is preferably 2-8 h; the temperature of the third heat treatment is preferably 170-180 ℃, and the heat preservation time is preferably 2-8 h; the temperature of the fourth heat treatment is preferably 190-210 ℃, and the heat preservation time is preferably 2-8 h; the temperature of the fifth heat treatment is preferably 220-280 ℃, and the heat preservation time is preferably 2-8 h.
The formed part obtained by pre-curing and thermosetting treatment of the 3D printing cyanate ester ink provided by the invention has excellent mechanical property and heat resistance.
The following describes the cyanate ester ink for 3D printing, the preparation method and the application thereof in detail with reference to the following embodiments, but they should not be construed as limiting the scope of the present invention.
Example 1
Fully dissolving 15g of triallyl isocyanurate in 45g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of oridin yellow 190, and fully and uniformly stirring to obtain a photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol A cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 5min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 2
Fully dissolving 12.27g of triallyl isocyanurate in 36.82g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain the photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol A cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 3
Fully dissolving 10g of triallyl isocyanurate in 30g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.4g of photoinitiator Irgacure 819 and 0.024g of dye orlistat yellow 190, and fully and uniformly stirring to obtain a photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol A cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 4
Fully dissolving 8.07g of triallyl isocyanurate in 24.23g N-vinyl pyrrolidone monomer to form homogeneous solution, then adding 0.32g of photoinitiator Irgacure 819 and 0.019g of dye olylcine yellow 190, and fully and uniformly stirring to obtain photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol A cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 5
Fully dissolving 15g of triallyl isocyanurate in 45g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain a photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol F cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 6
Fully dissolving 20g of triallyl isocyanurate in 40g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain a photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol A cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 7
Fully dissolving 20g of triallyl isocyanurate in 40g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain a photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol F cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 8
Fully dissolving 30g of triallyl isocyanurate in 30g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain the photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol A cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 9
Fully dissolving 30g of triallyl isocyanurate in 30g of N-vinyl pyrrolidone monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain the photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol F cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Example 10
Fully dissolving 15g of triallyl isocyanurate in 45g of hydroxyethyl methacrylate monomer to form a homogeneous solution, then adding 0.6g of photoinitiator Irgacure 819 and 0.036g of dye orlistat yellow 190, and fully and uniformly stirring to obtain the photocuring matrix resin; and adding the obtained photocuring matrix resin and 3g of glycidyl methacrylate into 60g of bisphenol F cyanate, uniformly stirring, and defoaming in vacuum to obtain the final 3D printing cyanate ester ink.
Carrying out ultraviolet curing on the prepared 3D printing cyanate ester ink to obtain a preformed piece, and carrying out thermocuring treatment on the preformed piece to obtain a formed piece; wherein the ultraviolet curing time is 10min, and the thermal curing treatment comprises the following steps: 100 ℃/4h +160 ℃/6h +180 ℃/8h +200 ℃/8h, and post-treatment is carried out at 280 ℃/8 h.
Performance detection
Infrared spectrum test: performing infrared tests on the bisphenol a cyanate ester monomer, the 3D printed cyanate ester ink, the photo-curable matrix resin and the molded part in example 1, wherein the obtained infrared spectrum is shown in fig. 1; as can be seen from FIG. 1, the cyano double absorption peak (2271 cm) in the photo-cured and thermosetting molded article was observed in comparison with the bisphenol A cyanate ester and 3D printed cyanate ester inks-1And 2236cm-1) Disappearance, appearance of infrared characteristic absorption peak of triazine structure (1367 cm)-1And 1508cm-1) The cyanate ester groups of the 3D printing cyanate ester ink are all reacted after the photo-curing and the thermal curing treatment, and the triazine structure is generated; epoxy group infrared characteristic absorption peak (916 cm) of photocured and thermocured treated molded article compared to 3D printed cyanate ester ink-1) Disappearance indicates that the epoxy groups in the added glycidyl methacrylate have all reacted. These results indicate that the thermosetting resin in the 3D printed cyanate ester ink has reacted completely after photo-curing and thermal curing.
And (3) viscosity testing:
the viscosity of the photo-curable matrix resin, the 3D printing cyanate ester ink and the bisphenol a type cyanate ester monomer obtained in example 1 were measured, and the obtained viscosity curve is shown in fig. 2: as can be seen from fig. 2: the viscosity of the light-cured matrix resin is minimum and is about 0.025Pa & s; the viscosity of bisphenol A cyanate ester is maximum, about 0.11 pas; the viscosity of the 3D printed cyanate ester ink is substantially unaffected by shear rate. These results show that the 3D printing cyanate ester ink prepared in embodiment 1 of the present invention has an extremely low viscosity, is suitable for 3D printing, and is beneficial to improving the printing accuracy.
The viscosity of the 3D printed cyanate ester inks obtained in examples 2 to 10 was measured by the same method, and the results are shown in table 1.
TABLE 1 viscosity of 3D printed cyanate ester inks obtained in examples 2-10
As can be seen from table 1: the cyanate ester ink for 3D printing provided by the invention has lower viscosity and is suitable for 3D printing conditions.
And (3) testing mechanical properties:
the mechanical property test of a formed part formed by carrying out photocuring-thermocuring treatment on the 3D printed cyanate ester ink obtained in the embodiment 1 is carried out on a universal tester, and the parameter setting of the universal tester comprises the following steps: the stretching rate is 5mm/s, and fig. 3 is a stress-strain curve of a formed part formed by performing photocuring-thermocuring treatment on the 3D printed cyanate ester ink obtained in example 1 at normal temperature. As can be seen from fig. 3: after the 3D printing cyanate ester ink prepared in example 1 is subjected to photo-curing and thermosetting treatment, the tensile strength of the formed part at normal temperature is about 95MPa, and the elongation at break is about 5.2%, which shows that the 3D printing cyanate ester ink prepared in this example has outstanding mechanical properties after being subjected to photo-curing and thermosetting treatment.
The mechanical property test of the molded parts obtained in examples 2 to 10 was carried out by the above method, and the results are shown in table 2.
Table 2 test results of mechanical properties of molded articles obtained in examples 1 to 10
As can be seen from table 2: the 3D printing cyanate ester ink provided by the invention can achieve higher tensile strength, and the elongation at break is not fluctuated greatly.
And (3) testing heat resistance:
(1) the loss factor (Tan δ) -temperature curves of the molded parts formed by the photo-curing and thermo-curing treatment of the 3D printing cyanate ester inks obtained in example 1 and example 2 were tested, and the results are shown in fig. 4. As can be seen from fig. 4: glass transition temperature (T) of molded part obtained by photo-curing and thermosetting 3D printing cyanate ester ink provided in example 1 and example 2g) The temperature can reach 188 ℃ and 191 ℃ respectively, and the 3D printing cyanate ester ink prepared by the invention is proved to have outstanding heat resistance after being subjected to photo-curing and thermal curing.
(2) The thermogravimetry (Tg) -temperature curves of the molded articles formed by the photocuring-thermocuring treatment of the 3D-printed cyanate ester inks prepared in example 1 and example 2 were tested, and the results are shown in fig. 5. As can be seen from fig. 5, the 3D printing cyanate ester inks provided in examples 1 and 2 have initial decomposition temperatures (T) after photo-curing and thermal-curing processes5％) The residual rate (Y) can reach 333 ℃, 338 ℃ and 600 ℃ respectively600℃) Respectively accounting for 17.64% and 19.25%, and the 3D printing cyanate ester ink prepared by the invention is proved to have higher thermal stability after being subjected to photo-curing and thermal curing treatment.
The glass transition temperature and initial decomposition temperature (T) of the molded articles obtained in examples 3 to 10 were measured by the methods described above5％) And a residual rate (Y) at 600 ℃600℃) The test was carried out and the results are shown in Table 3.
TABLE 3 Heat resistance test results of molded articles obtained in examples 1 to 10
As can be seen from table 3: the 3D printing cyanate ester ink provided by the invention has higher glass transition temperature and initial decomposition temperature, and an ink system can be suitable for being used in a high-temperature extreme environment below 180 ℃.
FIG. 6 is an appearance of the molded articles obtained in examples 1 to 6, and it can be seen from FIG. 6 that: the 3D printing cyanate ester ink provided by the invention can be used for printing 3D printing pieces with different shapes, structures and sizes, and the 3D printing cyanate ester ink prepared by the invention is proved to have the capability of printing various high-precision complex structures.
According to the embodiment, the 3D printing cyanate ester ink provided by the invention has the viscosity suitable for 3D printing, can realize high-precision printing of precision devices, and the printed product has outstanding mechanical property and thermal stability and has a larger application value.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The cyanate ester ink for 3D printing is characterized by comprising the following components:
10g of triallyl isocyanurate, 30g of N-vinyl pyrrolidone monomer, 8190.4 g of photoinitiator Irgacure, 1900.024 g of dye orlistat yellow, 3g of glycidyl methacrylate and 60g of bisphenol A cyanate.
2. The preparation method of the 3D printing cyanate ester ink according to claim 1, characterized by comprising the following steps:
mixing a cross-linking agent and a reactive diluent to obtain a first solution; the cross-linking agent is triallyl isocyanurate, and the reactive diluent is N-vinyl pyrrolidone;
mixing the first solution, a photoinitiator and a dye to obtain a photocuring matrix resin; the photoinitiator is Irgacure 819, and the dye is Alice yellow 190;
mixing the photo-curing matrix resin, glycidyl methacrylate and cyanate ester resin to obtain the 3D printing cyanate ester ink; the cyanate resin is bisphenol A cyanate.
3. The 3D printing cyanate ester ink according to claim 1 or the 3D printing cyanate ester ink obtained by the preparation method according to claim 2 is applied to 3D printing.
4. Use according to claim 3, characterized in that it comprises the following steps:
precuring the 3D printed cyanate ester ink to obtain a preformed piece;
and carrying out thermosetting treatment on the preformed piece to obtain a formed piece.
5. The use according to claim 4, wherein the heat curing process comprises a first heat treatment, a second heat treatment, a third heat treatment, a fourth heat treatment and a fifth heat treatment, which are carried out in this order;
the temperature of the first heat treatment is 100-140 ℃, and the heat preservation time is 2-8 h;
the temperature of the second heat treatment is 150-160 ℃, and the heat preservation time is 2-8 h;
the temperature of the third heat treatment is 170-180 ℃, and the heat preservation time is 2-8 h;
the temperature of the fourth heat treatment is 190-210 ℃, and the heat preservation time is 2-8 h;
the temperature of the fifth heat treatment is 220-280 ℃, and the heat preservation time is 2-8 h.
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