CN117247500A - Solvent-free polyimide photosensitive resin, one-pot method rapid preparation thereof and application thereof in 3D printing - Google Patents

Solvent-free polyimide photosensitive resin, one-pot method rapid preparation thereof and application thereof in 3D printing Download PDF

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CN117247500A
CN117247500A CN202311241323.5A CN202311241323A CN117247500A CN 117247500 A CN117247500 A CN 117247500A CN 202311241323 A CN202311241323 A CN 202311241323A CN 117247500 A CN117247500 A CN 117247500A
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bis
polyimide
solvent
photosensitive resin
printing
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郭玉雄
鲁耀钟
姬忠莹
吴涛
王晓龙
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention provides a solvent-free polyimide photosensitive resin, a one-pot method for rapid preparation and application thereof in 3D printing, and relates to the technical field of polyimide photosensitive resin preparation. The invention takes active diluent with high dissolution characteristic as reaction medium, grafts aromatic diamine and reactive reagent with active double bond group into active double bond group capable of photo-curing reaction, then reacts with aromatic dianhydride in the active diluent to synthesize polyimide precursor oligomer with end-capped active double bond, and after adding active cross-linking agent and photoinitiator, solvent-free polyimide photosensitive resin capable of photo-curing 3D printing is obtained, and then photo-curing 3D printing forming and thermal imidization are carried out to obtain polyimide printing products with high printing precision forming, high dimensional stability and high comprehensive performance. The invention adopts a one-pot method to directly prepare the polyimide material with high solubility, high photosensitivity and no solvent, the preparation route is greatly shortened, no solvent and three wastes are generated, and the batch preparation is easy.

Description

Solvent-free polyimide photosensitive resin, one-pot method rapid preparation thereof and application thereof in 3D printing
Technical Field
The invention relates to the technical field of polyimide photosensitive resin preparation, in particular to solvent-free polyimide photosensitive resin, and one-pot method rapid preparation and application thereof in 3D printing.
Background
Polyimide (PI) is an aromatic heterocyclic polymer compound constructed by imide chain links, has special performances of high strength, high toughness, wear resistance, high temperature resistance, corrosion resistance and the like, is a special engineering material, and is widely applied to the fields of aviation, aerospace, electric and electronic, semiconductor engineering, microelectronics and integrated circuits, nanomaterials, liquid crystal displays, LED packaging, separation membranes, lasers, locomotives, automobiles, precision machinery, automatic office machinery and the like. However, the rigid molecular structure of polyimide results in its "poorly soluble" nature, and its further application and development as a coating and precision parts is greatly limited.
In recent years, 3D printing technology has been applied to rapidly manufacturing a variety of complex objects, and has been successfully expanded to the fields of electronic manufacturing, tissue engineering, aerospace, and the like. For research and technical development of polyimide photosensitive resin for 3D printing, researchers introduce groups with flexibility and high solubility from a main chain in view of molecular structure design of photosensitive polyimide, improve the solubility and flexibility of polyimide, introduce photosensitive groups at side chains and improve the solubility of oligomers and other design ideas, solve the problems of indissolvable and refractory polyimide, and successfully synthesize and prepare the photo-cured polyimide photosensitive material (such as CN105837760A, CN 116143974A) with 3D printing. However, the above method is required to be prepared in two steps, in which, in the first step, aromatic dianhydride and aromatic diamine are added to a high boiling point proton solvent (such as dimethyl pyrrolidone, dimethyl formamide) to synthesize polyamic acid oligomer at a low temperature, and then imidization is performed by chemical imidization or high temperature solution imidization, and then precipitation-suction filtration-drying is performed to obtain polyimide oligomer having high solubility and photosensitivity; and secondly, compounding the prepared polyimide photosensitive oligomer with a reactive diluent, a solvent, a reactive crosslinking agent, a photoinitiator and the like to form the polyimide photosensitive resin for 3D printing. The method for preparing polyimide photosensitive resin by using the solvent system has the defects of complex process (one preparation period is about 7-8 days), large batch difficulty, more industrial three wastes and the like, and the obtained photosensitive resin has the problems of poor comprehensive performance, poor molding stability, low applicability of printed products and the like.
How to develop the preparation technology of solvent-free, simple process, batch preparation and the like of the polyimide photosensitive resin with high comprehensive performance for 3D printing is critical, and also directly determines the rapid development of the polyimide photosensitive resin in the 3D printing field and meets the actual application requirements.
Disclosure of Invention
In view of the above, the present invention aims to provide a solvent-free polyimide photosensitive resin and a one-pot method for preparing the same and application thereof in 3D printing. The invention realizes the one-pot method rapid preparation of the solvent-free polyimide photosensitive resin, has simple process, no solvent and no three wastes, is easy for batch preparation, and the prepared polyimide photosensitive resin has excellent comprehensive performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a one-pot method for rapidly preparing solvent-free polyimide photosensitive resin, which comprises the following steps:
mixing aromatic diamine and a reactive diluent capable of being crosslinked by photo-curing reaction to obtain a mixed solution;
adding a reaction reagent with an active double bond group into the mixed solution for grafting reaction to obtain an intermediate solution;
adding aromatic dianhydride into the intermediate solution for polycondensation reaction to obtain a resin solution containing polyimide precursor oligomer capped by active double bonds;
and adding an active crosslinking agent and a photoinitiator into the resin solution containing the polyimide precursor oligomer with the end capped by the active double bond, and mixing to obtain the solvent-free polyimide photosensitive resin.
Preferably, the reactive diluent capable of being crosslinked by the photo-curing reaction is one or more of N-vinylformamide, dimethylacrylamide, N-vinylacetamide, caprolactone acrylate, styrene, norbornyl methacrylate, N-vinylpyrrolidone, dicyclopentenyl acrylate, divinyl siloxane-bisbenzocyclobutene, acryloylmorpholine, hydroxyethyl methacrylate, vinyl siloxane and divinyl tetramethyl disiloxane.
Preferably, the method comprises the steps of, the aromatic diamine is 4,4' -diamino-2, 2' -bistrifluoromethyl biphenyl, 9-bis (3-fluoro-4-aminophenyl) fluorene, 9-bis (4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 1, 3-bis (aminopropyl) tetramethyl disilyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 4' -diamino-2, 2' -dimethylbiphenyl, 2- (4-aminophenyl) -5-aminobenzimidazole, 2-bis (4-hydroxy-3-aminophenyl) propane, N, one or more of N ' - (2, 2' -bis (trifluoromethyl) - [1,1' -biphenyl ] -4,4' -diyl) bis (4-aminobenzamide), 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 3' -dihydroxybenzidine, 4' -diaminodiphenyl ether, and 3,4' -diaminodiphenyl ether;
the aromatic dianhydride is one or more of hexafluorodianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 3, 4-diphenyl sulfone tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, bis [ (3, 4-dianhydride) phenyl ] terephthalate, bisphenol AF diester dianhydride and p-biphenylene-bisphenol trimellitate dianhydride.
Preferably, the molar ratio of the aromatic diamine to the aromatic dianhydride is (1.2-2): 1; the ratio of the mass of the reactive diluent capable of being crosslinked by the photo-curing reaction to the total mass of the aromatic dianhydride and the aromatic diamine is 1:0.5-1:1.5.
Preferably, the reactant with the active double bond group is one or more of 2-ethyl acryloyl chloride, glycidyl methacrylate, 4-phenyl chloroacrylate, 3, 4-epoxy cyclohexyl methacrylate, acryloyl chloride, methacryloyl chloride, 2-allyloxyphenoxymethyl ethylene oxide, ethyl methacrylate, chloropropene, 4- (2-epoxy ethylmethoxy) butyl acrylate, 2-methyl chloroacrylate and isocyanate ethyl acrylate; the molar ratio of the reactive agent with active double bond group to the aromatic diamine is (0.5-1): 1.
Preferably, the grafting reaction is carried out at a temperature of 5-30 ℃ for 4-12 hours; the temperature of the polycondensation reaction is 0-5 ℃ and the time is 5-12 h.
Preferably, the active cross-linking agent is one or more of ethoxylated pentaerythritol tetraacrylate, tri (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, methacryloxypropyl cage polysilsesquioxane, acryloxypropyl cage polysilsesquioxane, pentaerythritol triacrylate and di-pentaerythritol hexaacrylate; the mass of the active crosslinking agent is 10-20% of the mass of the resin solution containing the polyimide precursor oligomer with the end capped by the active double bond.
The invention provides the solvent-free polyimide photosensitive resin prepared by the preparation method.
The invention provides an application of the solvent-free polyimide photosensitive resin in 3D printing, which comprises the following steps: and carrying out photocuring 3D printing on the solvent-free polyimide photosensitive resin, and carrying out thermal imidization treatment on the obtained molded part in a protective atmosphere to obtain a polyimide printed part.
Preferably, the thermal imidization treatment includes sequentially performing a first thermal treatment, a second thermal treatment, a third thermal treatment, a fourth thermal treatment, and a fifth thermal treatment; the temperature of the first heat treatment is 80-100 ℃, and the heat preservation time is 1-2 h; the temperature of the second heat treatment is 120-150 ℃, and the heat preservation time is 1-2 h; the temperature of the third heat treatment is 180-220 ℃, and the heat preservation time is 1-2 h; the temperature of the fourth heat treatment is 260 ℃ and the heat preservation time is 1-2 h; the temperature of the fifth heat treatment is 300 ℃, and the heat preservation time is 1-2 h.
The invention provides a one-pot method for preparing solvent-free polyimide photosensitive resin, which takes reactive diluent with high dissolution property as a reaction medium system, introduces active double bond groups capable of photo-curing reaction through grafting reaction of aromatic diamine and reactive reagent with the active double bond groups, and then polycondenses the reactive double bond groups with aromatic dianhydride in the reactive diluent to synthesize polyimide precursor oligomer containing active double bond end-capped, and then adds active cross-linking agent and photoinitiator into the reaction solution to obtain the solvent-free polyimide photosensitive resin capable of photo-curing 3D printing. The invention uses the reactive diluent as the medium of the reaction system and also as the dissolvent of polyimide oligomer precursor and the photo-curing reactant of photosensitive polyimide resin, adopts a one-pot method to directly prepare the needed high-solubility and high-photosensitivity solvent-free polyimide photosensitive material, has the advantages of greatly shortened preparation process route, simple process, no solvent and three wastes, is easy to prepare in batches, and breaks through the complicated preparation process technology of the existing photosensitive polyimide resin. And the prepared solvent-free polyimide photosensitive resin is used for 3D printing, and after the solvent-free polyimide photosensitive resin is subjected to photo-curing 3D printing, thermal imidization treatment is performed, so that the comprehensive performance of the whole 3D printing polyimide workpiece is enhanced, and meanwhile, the dimensional stability and shrinkage characteristic of the workpiece are ensured.
Drawings
FIG. 1 is a diagram of a one-pot method for directly preparing 1 kg of polyimide photosensitive resin according to the invention;
FIG. 2 is a schematic illustration of a photo-curing 3D printing process for a polyimide photosensitive resin according to the present invention;
FIG. 3 is a graph showing a comparison of the photo-cured 3D printed article of the polyimide photosensitive resin of the examples before and after thermal imidization.
Detailed Description
The invention provides a one-pot method for rapidly preparing solvent-free polyimide photosensitive resin, which comprises the following steps:
mixing aromatic diamine and a reactive diluent capable of being crosslinked by photo-curing reaction to obtain a mixed solution;
adding a reaction reagent with an active double bond group into the mixed solution for grafting reaction to obtain an intermediate solution;
adding aromatic dianhydride into the intermediate solution for polycondensation reaction to obtain a resin solution containing polyimide precursor oligomer capped by active double bonds;
and adding an active crosslinking agent and a photoinitiator into the resin solution containing the polyimide precursor oligomer with the end capped by the active double bond, and mixing to obtain the solvent-free polyimide photosensitive resin.
In the present invention, unless otherwise specified, all the materials involved are commercially available products well known to those skilled in the art.
The invention mixes aromatic diamine and reactive diluent capable of being crosslinked by photo-curing reaction to obtain mixed solution. In the present invention, the aromatic diamine is preferably 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl, 9-bis (3-fluoro-4-aminophenyl) fluorene, 9-bis (4-aminophenyl) fluorene, 2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 1, 3-bis (aminopropyl) tetramethyl disilyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 4 '-diamino-2, 2' -dimethylbiphenyl, 2- (4-aminophenyl) -5-aminobenzimidazole, 2-bis (4-hydroxy-3-aminophenyl) propane, N, N '- (2, 2' -bis (trifluoromethyl) - [1,1 '-biphenyl ] -4,4' -diyl) bis (4-aminobenzamide), 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 3 '-dihydroxybenzidine, one or more of 4,4' -diaminodiphenyl ether and 3,4 '-diaminodiphenyl ether, more preferably 4,4' -diaminodiphenyl ether, 1, 3-bis (aminopropylalkyl) tetramethyldisilyl ether, one or more of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 3,3' -dihydroxybenzidine.
In the present invention, the reactive diluent which can be crosslinked by the photo-curing reaction is preferably one or more of N-vinylformamide, dimethylacrylamide, N-vinylacetamide, caprolactone acrylate, styrene, norbornyl methacrylate, N-vinylpyrrolidone, dicyclopentenyl acrylate, divinyl siloxane-bisbenzocyclobutene, acryloylmorpholine, hydroxyethyl methacrylate, vinyl siloxane and divinyl tetramethyldisiloxane, more preferably one or more of N-vinylpyrrolidone, N-vinylformamide and acryloylmorpholine, and when the reactive diluent is a mixture of several kinds, the mixing ratio is not particularly limited and may be mixed in any ratio. In the invention, the reactive diluent not only has the photo-curing reaction characteristic, but also has good dissolution characteristic on the aromatic dianhydride and the aromatic diamine, and also has good solubility on polyimide oligomer synthesized by reaction. In the present invention, the ratio of the mass of the photocurably reactive cross-linked reactive diluent to the total mass of the aromatic dianhydride and the aromatic diamine is preferably 1:0.5 to 1:1.5, more preferably 1:0.9 to 1:1.4.
In the invention, aromatic diamine is preferably added into a reactive diluent capable of being crosslinked by photo-curing reaction for mixing; the mixing is preferably carried out in a nitrogen atmosphere, the manner of which is not particularly critical in the present invention, and the mixing means known to those skilled in the art are employed to ensure uniform mixing of the aromatic diamine and the photocurably reactive cross-linking reactive diluent to form a homogeneous solution, particularly if stirring.
After the mixed solution is obtained, the invention adds the reactant with active double bond group into the mixed solution to carry out grafting reaction, thus obtaining the intermediate solution. In the present invention, the reactive agent having an active double bond group is preferably one or more of 2-ethyl acryl chloride, glycidyl methacrylate, phenyl 4-chloroacrylate, 3, 4-epoxycyclohexyl methacrylate, acryl chloride, methacryl chloride, 2-allyloxyphenoxymethyl ethylene oxide, ethyl methacrylate, chloropropene, 4- (2-oxiranylmethoxy) butyl acrylate, methyl 2-chloroacrylate and ethyl isocyanate acrylate, more preferably ethyl methacrylate and/or acryl chloride; the molar ratio of the reactive agent having an active double bond group to the aromatic diamine is preferably (0.5 to 1): 1, more preferably (0.7 to 0.9): 1. In the present invention, the addition is preferably carried out dropwise, and the rate of addition is preferably such that the reaction reagent having an active double bond group is completely added within 0.5 hour.
In the present invention, the temperature of the grafting reaction is preferably 5 to 30 ℃, more preferably 15 to 25 ℃, and in the present embodiment, the grafting reaction is performed at normal temperature; the time for the grafting reaction is preferably 4 to 12 hours, more preferably 6 to 10 hours, calculated from the completion of the addition of the reactive agent having an active double bond group. The invention adopts an active diluent with high dissolution characteristic as a medium of a reaction system, and introduces an active double bond group capable of photo-curing reaction through the grafting reaction of aromatic diamine and a reactant with the active double bond group to obtain the intermediate solution. In the present invention, the reactive diluent is used as a reaction system and also as a solvent for the polyimide precursor.
After obtaining an intermediate solution, the invention adds aromatic dianhydride into the intermediate solution to carry out polycondensation reaction, thus obtaining a resin solution containing polyimide precursor oligomer capped by active double bonds. In the present invention, the aromatic dianhydride is preferably one or more of hexafluorodianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A-type diether dianhydride, 3, 4-diphenylsulfone tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, bis [ (3, 4-dianhydride) phenyl ] terephthalate, bisphenol AF diester dianhydride and p-biphenylene-dibenzotrimellitate dianhydride, more preferably one or more of hexafluorodianhydride, bisphenol a type diether dianhydride and 3,3', 4' -benzophenone tetracarboxylic dianhydride; the molar ratio of the aromatic diamine to the aromatic dianhydride is preferably (1.2 to 2): 1, more preferably (1.5 to 1.8): 1.
In the present invention, the temperature of the polycondensation reaction is preferably 0 to 5 ℃, preferably 0 to 2 ℃, and the time is preferably 5 to 12 hours, more preferably 10 to 12 hours. In the invention, the intermediate solution is preferably cooled to the temperature of the polycondensation reaction, and then aromatic dianhydride is added into the intermediate solution for the polycondensation reaction; the aromatic dianhydride is preferably added in several portions, and in the embodiment of the present invention, the aromatic dianhydride is specifically added in three portions; the time of the polycondensation reaction is calculated from the completion of the addition of the aromatic dianhydride. In the present invention, the molecular weight of the polyimide precursor oligomer terminated with an active double bond is 1000 to 10000.
After obtaining a resin solution containing an active double bond end capped polyimide precursor oligomer, the invention adds an active cross-linking agent and a photoinitiator into the resin solution containing the active double bond end capped polyimide precursor oligomer, and mixes the active cross-linking agent and the photoinitiator to obtain the solvent-free polyimide photosensitive resin. In the present invention, the reactive crosslinking agent is preferably one or more of ethoxylated pentaerythritol tetraacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, methacryloxypropyl cage polysilsesquioxane (CAS: 622404-27-7), acryloxypropyl cage polysilsesquioxane (CAS: 1620202-27-8), pentaerythritol triacrylate and dipentaerythritol hexaacrylate, more preferably trimethylolpropane triacrylate; the mass of the reactive crosslinking agent is preferably 7 to 20%, more preferably 7.5 to 12%, of the resin solution containing the reactive double bond-terminated polyimide precursor oligomer. In the present invention, the photoinitiator is preferably one or more of trimethylbenzoyl diphenyl phosphine oxide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-isopropylthioxanthone and phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide, more preferably trimethylbenzoyl diphenyl phosphine oxide; the mass of the photoinitiator is preferably 1 to 3%, more preferably 1.2 to 2% of the mass of the resin solution containing the reactive double bond-terminated polyimide precursor oligomer. In the invention, it is also preferable to add an auxiliary agent, preferably one or more of commercial defoamer, wetting agent, leveling agent and ultraviolet absorber, to the resin solution containing the reactive double bond terminated polyimide precursor oligomer, and the invention has no special requirement on the defoamer, wetting agent, leveling agent and ultraviolet absorber, and adopts corresponding auxiliary agents well known to those skilled in the art; the mass of the auxiliary agent is preferably 0.1 to 1% by mass, more preferably 0.5 to 1% by mass, of the resin solution containing the active double bond-terminated polyimide precursor oligomer.
The mixing mode is not particularly limited in the invention, and the components are uniformly mixed by adopting a mixing mode well known to a person skilled in the art, and in the embodiment of the invention, the mixing is preferably stirring and mixing, and the stirring and mixing time is preferably 2-5 h.
The polyimide material with high solubility, high photosensitivity and high comprehensive performance is directly prepared by adopting a one-pot method, the preparation process route is greatly shortened, the preparation process time is shortened to be completed within 24 hours, and meanwhile, the batch preparation is easy to carry out and the stability of the batch preparation is improved; and the method has the advantages of no solvent, no generation of three wastes and environmental protection. FIG. 1 is a diagram of a one-pot method for directly preparing 1 kg of polyimide photosensitive resin according to the invention. In addition, the preparation method provided by the invention has the characteristic of adjustable molecular weight.
The invention provides the solvent-free polyimide photosensitive resin prepared by the preparation method. In the present invention, the viscosity of the solvent-free polyimide photosensitive resin is preferably 2000 to 20000mpa.s. The solvent-free polyimide photosensitive resin provided by the invention has the advantages of strong photosensitivity, stable molding, high mechanical strength, good heat resistance and high temperature resistance, low shrinkage rate and the like, has excellent comprehensive performance, is directly used for photocuring 3D printing and integrated manufacturing of high-precision complex customized parts thereof, can meet the technical requirements of key materials such as solvent-free polyimide protective coatings, insulation protection and the like which are easy to mold under extreme working condition environments, and greatly expands the application and popularization of the photosensitive polyimide resin in the key technical fields such as microelectronics, aerospace, nuclear energy and the like.
The invention provides an application of the solvent-free polyimide photosensitive resin in 3D printing, which comprises the following steps: and carrying out photocuring 3D printing on the solvent-free polyimide photosensitive resin, and carrying out thermal imidization treatment on the obtained molded part in a protective atmosphere to obtain a polyimide printed part. The invention has no special requirements on the printing parameters of the photo-curing 3D printing.
The method has no special requirement on the photo-curing 3D printing mode, and can adopt the photo-curing 3D printing technology such as DLP, SLA, LED, LCD, ultraviolet-assisted direct writing and the like. Fig. 2 is a display of the photo-polyimide photosensitive resin photo-curing 3D printing process.
In the present invention, the thermal imidization treatment preferably includes sequentially performing a first thermal treatment, a second thermal treatment, a third thermal treatment, a fourth thermal treatment, and a fifth thermal treatment; the temperature of the first heat treatment is preferably 80-100 ℃, more preferably 85-90 ℃, and the heat preservation time is preferably 1-2 h, more preferably 1h; the temperature of the second heat treatment is preferably 120-150 ℃, more preferably 130-140 ℃, and the heat preservation time is preferably 1-2 h, more preferably 2h; the temperature of the third heat treatment is preferably 180-220 ℃, more preferably 180-200 ℃, and the heat preservation time is preferably 1-2 h, more preferably 2h; the temperature of the fourth heat treatment is preferably 260 ℃, and the heat preservation time is preferably 1-2 h, more preferably 1h; the temperature of the fifth heat treatment is preferably 300 ℃, and the holding time is preferably 1 to 2 hours, more preferably 2 hours. In the present invention, the thermal imidization treatment is preferably performed under vacuum or an inert atmosphere.
In order to further illustrate the present invention, the solvent-free polyimide photosensitive resin provided by the present invention and its one-pot rapid preparation and application in 3D printing are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
600g N-vinyl pyrrolidone is added into a 2000mL three-neck flask, nitrogen is introduced into the flask and the flask is stirred for 30min, then 360.1g of 4,4' -diaminodiphenyl ether is added into the flask and the flask is stirred for 1h; then 250g of ethyl methacrylate serving as a grafting reagent is added, dropwise added slowly, the addition is completed within half an hour, and then the reaction is carried out for 6 hours at normal temperature. After the reaction is finished, placing the three-neck flask into an ice water bath, and after the temperature of the reaction solution is reduced to 0 ℃, adding 444.24g of hexafluorodianhydride for three times, and reacting for 12 hours in the ice water bath; after the reaction is finished, adding 200g of active crosslinking agent trimethylolpropane triacrylate into a reaction system, and adding 20g of photoinitiator trimethylbenzoyl diphenyl phosphine oxide and 10g of Pick BYK-066N defoamer to obtain the photo-curing 3D printing polyimide photosensitive resin with the viscosity of-800 Pa.s.
Printing a complex structure on the obtained polyimide photosensitive resin on a commercial LED printer, and performing thermal imidization treatment on a workpiece after printing, wherein the imidization temperature process program is as follows in a vacuum oven: the polyimide printing product with high comprehensive performance is finally obtained after heat preservation at 85 ℃ for 1 hour, 120 ℃ for 2 hours, 180 ℃ for 2 hours, 260 ℃ for 1 hour and 300 ℃ for 2 hours. Fig. 3 is a comparison of the photo-cured 3D printed article of polyimide photosensitive resin before and after thermal imidization.
The performance data of the polyimide printed article finally obtained in example 1 are shown in table 1.
Example 2
In a 2000mL three-neck flask, 500g N-vinylpyrrolidone and 300g N-vinylformamide are added and nitrogen is introduced to stir for 30min, then 497.02g of 1, 3-bis (aminopropyl) tetramethyl disilyl ether is added and stirred for 1 hour; then adding 232.72g of grafting reagent ethyl methacrylate, slowly dripping, finishing the addition within half an hour, and then reacting for 6 hours at normal temperature. After the reaction is finished, placing the three-neck flask into an ice water bath, and after the temperature of the reaction solution is reduced to 0 ℃, adding 520.49g of bisphenol A type diether dianhydride for three times, and reacting for 12 hours in the ice water bath; after the reaction is finished, adding 210g of trimethylolpropane triacrylate serving as an active crosslinking agent into a reaction system, and adding 20g of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide serving as a photoinitiator, 10g of Pick BYK-A530 defoamer and 10g of Pick BYK-333 flatting agent to obtain the photo-curing 3D printing polyimide photosensitive resin with the viscosity of-600 mPa.s.
Printing a complex structure on the obtained polyimide photosensitive resin on a commercial LED printer, and performing thermal imidization treatment on a workpiece after printing, wherein the imidization temperature process program is as follows in a vacuum oven: the polyimide printing product with high comprehensive performance is finally obtained after heat preservation at 80 ℃ for 1 hour, 140 ℃ for 2 hours, 200 ℃ for 2 hours, 260 ℃ for 1 hour and 300 ℃ for 2 hours.
The performance data of the polyimide printed article finally obtained in example 2 are shown in table 1.
Example 3
In a 5000mL three-necked flask, 1000g N-vinylpyrrolidone, 500g N-vinylformamide and 400g acryloylmorpholine were added and stirred for 30min under nitrogen, followed by addition of 497.02g of 1, 3-bis (aminopropyl) tetramethyldisilyl ether and 668.52g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and stirring for 1 hour; then adding 271.5g of grafting reagent acryloyl chloride, slowly dripping in an ice-water bath, finishing the addition within half an hour, and then reacting for 6 hours at normal temperature. After the reaction is finished, placing the three-neck flask into an ice water bath, reducing the temperature of a reaction solution to 0 ℃, adding 444.24g of hexafluorodianhydride and 294.12g of 3,3', 4' -benzophenone tetracarboxylic dianhydride for three times, and reacting for 12 hours in the ice water bath; after the reaction is finished, 150g of active crosslinking agent trimethylolpropane triacrylate and 150g of methacryloxypropyl cage polysilsesquioxane (CAS: 622404-27-7) are added into a reaction system, and 80g of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 20g of Pick BYK-A530 defoamer and 20g of Pick BYK-333 flatting agent are added, so that the photocuring 3D printing polyimide photosensitive resin with the viscosity of 7500mPa.s can be obtained.
Printing a complex structure on the obtained polyimide photosensitive resin on a commercial LED printer, and performing thermal imidization treatment on a workpiece after printing, wherein the imidization temperature process program is as follows in a vacuum oven: the polyimide printing product with high comprehensive performance is finally obtained after heat preservation at 90 ℃ for 1 hour, 130 ℃ for 2 hours, 180 ℃ for 2 hours, 260 ℃ for 1 hour and 300 ℃ for 2 hours.
The performance data of the polyimide printed article finally obtained in example 3 are shown in table 1.
Example 4
1000g of N-vinylpyrrolidone and 1000g of N-vinylformamide are added into a 5000mL three-neck flask, the mixture is stirred for 30min by introducing nitrogen, 497.02g of 1, 3-bis (aminopropyl) tetramethyl disilyl ether and 432g of 3,3' -dihydroxybenzidine are then added, and the mixture is stirred for 1 hour; then 180g of acrylic chloride and 150g of ethyl methacrylate are added as grafting reagent, slowly added dropwise in an ice water bath, completed within half an hour, and then reacted for 6 hours at normal temperature. After the reaction is finished, placing the three-neck flask into an ice water bath, and after the temperature of the reaction solution is reduced to 0 ℃, adding 888.48g of hexafluorodianhydride for three times, and reacting for 12 hours in the ice water bath; after the reaction is finished, 200g of active crosslinking agent trimethylolpropane triacrylate and 120g of methacryloxypropyl cage polysilsesquioxane (CAS: 622404-27-7) are added, 40g of photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide and 35g of 2-isopropylthioxanthone are added, 20g of Pick BYK-012 defoamer and 20g of Pick BYK-358N flatting agent are added, and the photo-curing 3D printing photosensitive polyimide resin with the viscosity of 8500mPa.s can be obtained.
Printing a complex structure on the obtained polyimide photosensitive resin on a commercial LED printer, and performing thermal imidization treatment on a workpiece after printing, wherein the imidization temperature process program is as follows in a vacuum oven: the polyimide printing product with high comprehensive performance is finally obtained after heat preservation at 90 ℃ for 1 hour, 130 ℃ for 2 hours, 180 ℃ for 2 hours, 260 ℃ for 1 hour and 300 ℃ for 2 hours.
The performance data of the polyimide printed article finally obtained in example 4 are shown in table 1.
TABLE 1 example 3D printing of the Performance parameters of the finally obtained polyimide printed article
Test methods and criteria in table 1: the thermal decomposition temperature is GB/T27761-2011; heat distortion temperature GB/T1634.2-2019; tensile Strength and elastic modulus GB/T1040-1992; the printing accuracy is mainly tested by printing layer thickness, and the dimensional shrinkage is tested according to the standard ASTM D4974-04; the curing wavelength is tested mainly by experimental means.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.

Claims (10)

1. A one-pot method for rapidly preparing solvent-free polyimide photosensitive resin comprises the following steps:
mixing aromatic diamine and a reactive diluent capable of being crosslinked by photo-curing reaction to obtain a mixed solution;
adding a reaction reagent with an active double bond group into the mixed solution for grafting reaction to obtain an intermediate solution;
adding aromatic dianhydride into the intermediate solution for polycondensation reaction to obtain a resin solution containing polyimide precursor oligomer capped by active double bonds;
and adding an active crosslinking agent and a photoinitiator into the resin solution containing the polyimide precursor oligomer with the end capped by the active double bond, and mixing to obtain the solvent-free polyimide photosensitive resin.
2. The preparation method according to claim 1, wherein the photocurable reactive cross-linking reactive diluent is one or more of N-vinylformamide, dimethylacrylamide, N-vinylacetamide, caprolactone acrylate, styrene, norbornyl methacrylate, N-vinylpyrrolidone, dicyclopentenyl acrylate, divinyl siloxane-bisbenzocyclobutene, acryloylmorpholine, hydroxyethyl methacrylate, vinyl siloxane and divinyl tetramethyl disiloxane.
3. The method according to claim 1, wherein, the aromatic diamine is 4,4' -diamino-2, 2' -bistrifluoromethyl biphenyl, 9-bis (3-fluoro-4-aminophenyl) fluorene, 9-bis (4-aminophenyl) fluorene, 2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 1, 3-bis (aminopropyl) tetramethyl disilyl ether, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 4' -diamino-2, 2' -dimethylbiphenyl, 2- (4-aminophenyl) -5-aminobenzimidazole, 2-bis (4-hydroxy-3-aminophenyl) propane, N, one or more of N ' - (2, 2' -bis (trifluoromethyl) - [1,1' -biphenyl ] -4,4' -diyl) bis (4-aminobenzamide), 1, 4-bis (4-amino-2-trifluoromethylphenoxy) benzene, 3' -dihydroxybenzidine, 4' -diaminodiphenyl ether, and 3,4' -diaminodiphenyl ether;
the aromatic dianhydride is one or more of hexafluorodianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 3, 4-diphenyl sulfone tetracarboxylic dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, bis [ (3, 4-dianhydride) phenyl ] terephthalate, bisphenol AF diester dianhydride and p-biphenylene-bisphenol trimellitate dianhydride.
4. The process according to any one of claims 1 to 3, wherein the molar ratio of the aromatic diamine to the aromatic dianhydride is (1.2 to 2): 1; the ratio of the mass of the reactive diluent capable of being crosslinked by the photo-curing reaction to the total mass of the aromatic dianhydride and the aromatic diamine is 1:0.5-1:1.5.
5. The preparation method according to claim 1, wherein the reactive agent with an active double bond group is one or more of 2-ethyl acryloyl chloride, glycidyl methacrylate, phenyl 4-chloroacrylate, 3, 4-epoxycyclohexyl methacrylate, acryloyl chloride, methacryloyl chloride, 2-allyloxyphenoxymethyl ethylene oxide, ethyl methacrylate, chloropropene, 4- (2-oxiranylmethoxy) butyl acrylate, methyl 2-chloroacrylate and ethyl isocyanate acrylate; the molar ratio of the reactive agent with active double bond group to the aromatic diamine is (0.5-1): 1.
6. The method according to claim 1, wherein the grafting reaction is carried out at a temperature of 5 to 30 ℃ for a time of 4 to 12 hours; the temperature of the polycondensation reaction is 0-5 ℃ and the time is 5-12 h.
7. The preparation method according to claim 1, wherein the active crosslinking agent is one or more of ethoxylated pentaerythritol tetraacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, trimethylolpropane triacrylate, methacryloxypropyl cage polysilsesquioxane, acryloxypropyl cage polysilsesquioxane, pentaerythritol triacrylate and di-pentaerythritol hexaacrylate; the mass of the active crosslinking agent is 10-20% of the mass of the resin solution of polyimide precursor oligomer terminated by active double bond groups.
8. The solvent-free polyimide photosensitive resin prepared by the preparation method of any one of claims 1 to 7.
9. Use of the solvent-free polyimide photosensitive resin of claim 8 in 3D printing, the method of use being: and carrying out photocuring 3D printing on the solvent-free polyimide photosensitive resin, and carrying out thermal imidization treatment on the obtained molded part in a protective atmosphere to obtain a polyimide printed part.
10. The use according to claim 9, wherein the thermal imidization treatment comprises sequentially performing a first thermal treatment, a second thermal treatment, a third thermal treatment, a fourth thermal treatment, and a fifth thermal treatment; the temperature of the first heat treatment is 80-100 ℃, and the heat preservation time is 1-2 h; the temperature of the second heat treatment is 120-150 ℃, and the heat preservation time is 1-2 h; the temperature of the third heat treatment is 180-220 ℃, and the heat preservation time is 1-2 h; the temperature of the fourth heat treatment is 260 ℃ and the heat preservation time is 1-2 h; the temperature of the fifth heat treatment is 300 ℃, and the heat preservation time is 1-2 h.
CN202311241323.5A 2023-09-25 2023-09-25 Solvent-free polyimide photosensitive resin, one-pot method rapid preparation thereof and application thereof in 3D printing Pending CN117247500A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117886706A (en) * 2024-03-14 2024-04-16 安徽国风新材料股份有限公司 Monoamine monomer containing trifluoromethyl and alkynyl, application of monoamine monomer, photosensitive polyimide film and preparation method of photosensitive polyimide film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117886706A (en) * 2024-03-14 2024-04-16 安徽国风新材料股份有限公司 Monoamine monomer containing trifluoromethyl and alkynyl, application of monoamine monomer, photosensitive polyimide film and preparation method of photosensitive polyimide film

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