Photosensitive polyimide oligomer, method of preparation and polyimide photosensitive resin composition prepared therefrom

Abstract

The present application relates to photosensitive polyimide oligomer, preparation method and polyimide photosensitive resin composition prepared by the same, the present application provides the molecular formula of photosensitive polyimide oligomer, which is prepared from 1, 4, 5, 8-naphthalene tetracarboxylic anhydride, N, N-dimethylacetamide, triethylamine, tetramethyl benzene dimethyl diisocyanate, hydroquinone methyl ether, dibutyl tin dilaurate and hydroxyethyl acrylate according to the molar ratio of 2.5:10-15:1.2-1.6:3.0:0.0035-0.0045:0.007-0.01:2-2.5.The good solubility group is introduced into the molecular structure, so that it has good solubility in active diluent, and the polyimide oligomer can be photocured reaction;The device printed by the polyimide photosensitive resin composition prepared by the same has small shrinkage, high precision, and has the excellent performance of photosensitive polyimide oligomer, and has certain toughness and excellent weather resistance.

Description

Technical Field

[0001] This invention relates to the field of 3D printing material manufacturing, specifically to photosensitive polyimide oligomers, preparation methods, and polyimide photosensitive resin compositions prepared therefrom. Background Technology

[0002] 3D printing technology is an emerging rapid prototyping technology, also known as additive manufacturing. Photopolymer 3D printing technology has been widely used due to its high precision and good surface smoothness. Currently, the material used in photopolymer 3D printing technology is photosensitive resin. Existing photosensitive resin 3D printed parts generally suffer from poor thermal stability, poor wear resistance, and low strength, thus limiting their application in aerospace and other fields requiring high heat resistance, high wear resistance, and high strength.

[0003] Photopolymer 3D printing materials, commonly known as photosensitive resins, are mainly composed of oligomers, reactive diluents (active monomers), photoinitiators, and other additives. Generally, photopolymer oligomers used in 3D printing are mostly acrylate, polyurethane, and epoxy resin oligomers. However, with the development of 3D printing technology and the continuous expansion of its application fields, special fields such as electronics and aerospace require high-precision, high-heat-resistant, and flame-retardant photosensitive resins that can be used directly after photopolymerization. Therefore, these types of photosensitive resins cannot meet the requirements.

[0004] Photosensitive polyimide resins possess many excellent properties, such as superior mechanical properties, flame retardancy, good chemical stability, and high heat resistance. However, polyimide oligomers are poorly soluble in reactive diluents when preparing 3D printing resins, increasing the system viscosity and creating numerous challenges for their application. Therefore, the development of photosensitive polyimide oligomers is of great value.

[0005] Currently, the main problems hindering the development of photosensitive resins for 3D printing are: first, how to design the molecular structure of polyimide oligomers so as to maintain good solubility in reactive diluents; and second, how to prepare polyimide photosensitive resins with certain toughness, strength, and high precision in printed devices. Summary of the Invention

[0006] This invention provides a photosensitive polyimide oligomer, a preparation method thereof, and a polyimide photosensitive resin composition prepared therefrom. The photosensitive polyimide oligomer of this invention incorporates groups with good solubility in its molecular structure, giving it good solubility in reactive diluents. Moreover, the polyimide oligomer can undergo photocuring. Devices printed using the polyimide photosensitive resin composition prepared therefrom exhibit low shrinkage, high precision, and possess the excellent properties of the photosensitive polyimide oligomer, as well as certain toughness and excellent weather resistance.

[0007] This invention is achieved through the following technical solution:

[0008] Photosensitive polyimide oligomer, with the following structural formula:

[0009]

[0010] Furthermore, the photosensitive polyimide oligomer is prepared from 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide, triethylamine, tetramethylphenyldimethyl diisocyanate, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate in a molar ratio of 2.5:10-15:1.2-1.6:3.0:0.0035-0.0045:0.007-0.01:2-2.5.

[0011] Furthermore, the method for preparing the photosensitive polyimide oligomer includes the following steps:

[0012] Under N2 protection, 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide and triethylamine were added to the reaction vessel, and then the temperature was raised to 70-75℃ and stirred for 0.5-1.5 h.

[0013] Then add tetramethylbenzyl dimethyl diisocyanate dropwise (over 3-4 hours), followed by thorough stirring at 70-75°C for 12-36 hours, and then add hydroquinone methyl ether, dibutyltin dilaurate and hydroxyethyl acrylate.

[0014] Next, stir at 70-75℃ for 4-8 hours, then cool to room temperature, and finally bake in a vacuum oven at 50-60℃ for 12-24 hours to obtain the photosensitive polyimide oligomer.

[0015] The synthetic route of the aforementioned photosensitive polyimide oligomer is as follows:

[0016]

[0017]

[0018] The 1,4,5,8-naphthalenetetracarboxylic anhydride, triethylamine, tetramethylbenzene dimethyl diisocyanate (TMDXI), hydroquinone methyl ether (MEHQ), N,N-dimethylacetamide (DMAC), dibutyltin dilaurate, and hydroxyethyl acrylate (HEA) were purchased from Myriel Chemical Reagent Co., Ltd.

[0019] The polyimide photosensitive resin composition is prepared from the following components in the following mass fraction ratio:

[0020]

[0021] The polyurethane acrylate oligomer is one or more of aromatic polyurethane acrylate oligomers, aliphatic polyurethane acrylate oligomers, and hyperbranched polyurethane acrylates, or any combination thereof.

[0022] The aliphatic polyurethane acrylate oligomers and aromatic polyurethane acrylate oligomers have 2 or fewer functional groups, while the hyperbranched oligomers have 6-12 functional groups. The aliphatic polyurethane acrylate oligomers have a viscosity of 20,000-60,000, the aromatic polyurethane acrylate oligomers have a viscosity of 2,000-10,000, and the hyperbranched oligomers have a viscosity of 100-800.

[0023] The active diluent is one or more of the following: dicyclopentenyl acrylate, N-vinylpyrrolidone, isobornyl acrylate, hydroxyethyl acrylate, butyl acrylate, lauryl acrylate, acryloylmorphin, vinylimidazole, phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, N-vinylcaprolactam, methoxy polyethylene glycol monoacrylate, polyethylene glycol diacrylate, dodecyl acrylate, isodecanyl acrylate, tetrahydrofuran acrylate, lauryl methacrylate, cyclotrimethylolpropane methyl acetal propane ester, glycidyl methacrylate, and 4-tert-butylcyclohexyl acrylate.

[0024] The functional monomers are one or more of the following: propane triacrylate, tripropylene glycol diacrylate, 1,6-hexanediol acrylate, tricyclodecane acrylate, trimethylolpropane triacrylate, bisphenol A diacrylate ethoxylate, diethylene glycol dimethacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tricyclodecanediacrylate diacrylate, bisphenol A dimethacrylate ethoxylate, 3(2-hydroxyethyl) isocyanurate triacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2-ethyleneoxy acrylate, and bis(trimethylolpropane)tetraacrylate.

[0025] The free radical photoinitiator is one or more of the following: Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropanone), Irgacure 184 (1-hydroxycyclohexylbenzophenone), TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide), 907 (2-methyl-1-(4-methylthiophenyl)-2-morphonyl-1-propanone), benzoin dimethyl ether BDK, 1105 (isopropylthioxanthone (2,4 isomer mixture)), 819 (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), DETX (2,4-diethylthiazolinone), benzophenone, TPO-L (ethyl 2,4,6-trimethylbenzoylphosphonate), EDB (ethyl 4-dimethylaminobenzoate), OMBB (methyl o-benzoylformate), and CBP (4-chlorobenzophenone).

[0026] The stabilizer is one or more of the following: 4-tert-butyl-1,2-dihydroxybenzene, 2,6-di-(tert-butyl)-4-methylphenol, 4-methoxyphenol, pyrogallol, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, and lauryl gallate.

[0027] Compared with previous technologies, the present invention has the following advantages: the obtained photosensitive polyimide oligomer has good solubility in diluent; when heated to 60°C, the photosensitive polyimide can be in a liquid state at a mass percentage of 50%, 80%, and 100% of the diluent; the obtained photosensitive polyimide oligomer has photosensitivity; different mass fractions of well-dissolved photosensitive polyimide and initiator become viscous after 30 seconds of ultraviolet light irradiation and solidify after 1 minute of irradiation; the samples made from the polyimide photosensitive resin composition have high strength, good temperature resistance, and excellent weather resistance. Experimental data refer to the flexural strength, HDT, and QUV aging data in the examples. It can be seen that the 3D printing resin using this polyimide has a high flexural strength of 158 MPa, an HDT of 210°C, and a QUV aging retention rate of 85%, and also possesses a certain degree of toughness; the dimensional deformation of the samples made from the polyimide photosensitive resin composition is very small, far smaller than that of traditional products. Attached Figure Description

[0028] Figure 1 The solubility of the photosensitive polyimide oligomer prepared in this invention in N-ethylpyrrolidone, acryloylmorphone, isobornyl methacrylate, and dodecyl acrylate is shown. Detailed Implementation

[0029] The present invention will be further described below with reference to specific embodiments. Specific Implementation

[0031] The photosensitive polyimide oligomers in the following examples were prepared from the following components in the following mass fraction ratios.

[0032]

[0033]

[0034] The preparation method of the photosensitive polyimide oligomer in the following embodiments includes the following steps:

[0035] Under N2 protection, 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide and triethylamine were added to the reaction vessel, and then the temperature was raised to 70-75℃ and stirred for 0.5-1.5 h.

[0036] Then add tetramethylbenzyl dimethyl diisocyanate dropwise (over 3-4 hours), followed by thorough stirring at 70-75°C for 12-36 hours, and then add hydroquinone methyl ether, dibutyltin dilaurate and hydroxyethyl acrylate.

[0037] Next, stir at 70-75℃ for 4-8 hours, then cool to room temperature, and finally bake in a vacuum oven at 50-60℃ for 12-24 hours to obtain the photosensitive polyimide oligomer.

[0038] The polyimide photosensitive resin composition is prepared from the following components in the following mass fraction ratio:

[0039]

[0040] The polyurethane acrylate oligomers in the following examples are selected from one or more of aromatic polyurethane acrylate oligomers, aliphatic polyurethane acrylate oligomers, and hyperbranched polyurethane acrylates, or any combination thereof.

[0041] In the following examples, the aliphatic polyurethane acrylate oligomers and aromatic polyurethane acrylate oligomers have 2 or fewer functional groups, while the hyperbranched oligomers have 6-12 functional groups. The aliphatic polyurethane acrylate oligomers have a viscosity of 20,000-60,000, the aromatic polyurethane acrylate oligomers have a viscosity of 2,000-10,000, and the hyperbranched oligomers have a viscosity of 100-800.

[0042] The reactive diluents in the following examples are selected from one or more of the following: dicyclopentenyl acrylate, N-vinylpyrrolidone, isobornyl acrylate, hydroxyethyl acrylate, butyl acrylate, lauryl acrylate, acryloylmorphin, vinylimidazole, phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, N-vinylcaprolactam, methoxy polyethylene glycol monoacrylate, polyethylene glycol diacrylate, dodecyl acrylate, isodecanyl acrylate, tetrahydrofuran acrylate, lauryl methacrylate, cyclotrimethylolpropane methyl acetal propane ester, glycidyl methacrylate, and 4-tert-butylcyclohexyl acrylate.

[0043] The functional monomers in the following embodiments are selected from one or more of the following: propane triacrylate, tripropylene glycol diacrylate, 1,6-hexanediol acrylate, tricyclodecane acrylate, trimethylolpropane triacrylate, bisphenol A diacrylate ethoxylate, diethylene glycol dimethacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tricyclodecanediacrylate diacrylate, bisphenol A dimethacrylate ethoxylate, 3(2-hydroxyethyl) isocyanurate triacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2-ethyleneoxy acrylate, and bis(trimethylolpropane)tetraacrylate.

[0044] The free radical photoinitiators used in the following examples are selected from one or more of the following: Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropanone), Irgacure 184 (1-hydroxycyclohexylbenzophenone), TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide), 907 (2-methyl-1-(4-methylthiophenyl)-2-morphonyl-1-propanone), benzoin dimethyl ether BDK, 1105 (isopropylthioxanthone (2,4 isomer mixture)), 819 (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), DETX (2,4-diethylthiazolinone), benzophenone, TPO-L (ethyl 2,4,6-trimethylbenzoylphosphonate), EDB (ethyl 4-dimethylaminobenzoate), OMBB (methyl oxobenzoate), and CBP (4-chlorobenzophenone).

[0045] The stabilizers used in the following examples are one or more of the following: 4-tert-butyl-1,2-dihydroxybenzene, 2,6-di-(tert-butyl)-4-methylphenol, 4-methoxyphenol, pyrogallol, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, and lauryl gallate.

[0046] Example 1

[0047] The photosensitive polyimide oligomer of this embodiment was prepared from 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide, triethylamine, tetramethylphenyldimethyl diisocyanate, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate in a molar ratio of 2.5:10:1.2:3.0:0.0035:0.007:2.

[0048] The preparation method is as follows: Under N2 protection, 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide and triethylamine are added to the reaction vessel, and then the temperature is raised to 70℃ and stirred for 1.5 h;

[0049] Then tetramethylbenzene dimethyl diisocyanate was added dropwise (over 3 hours), followed by thorough stirring at 70°C for 36 hours. After that, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate were added.

[0050] Next, the mixture was stirred at 70°C for 8 hours, then cooled to room temperature, and finally dried in a vacuum oven at 50°C for 24 hours to obtain the photosensitive polyimide oligomer.

[0051] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 20g of the above-mentioned photosensitive polyimide oligomer, 40g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0052] Compare with Example 1

[0053] The composition of the polyimide photosensitive material resin mixture for 3D printing is as follows: 60g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. Stir at room temperature until completely dissolved and no particles are visible to prepare a polyimide photosensitive material resin composition for 3D printing. Then, use a 3D printer to create a model of this resin composition and print a sample. After post-curing in a UV curing chamber for 30 minutes, test the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample.

[0054] The difference between Comparative Example 1 and Example 1 is that aromatic polyurethane acrylate oligomer A was used instead of the self-made photosensitive polyimide oligomer.

[0055] Example 2

[0056] The photosensitive polyimide oligomer of this embodiment was prepared from 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide, triethylamine, tetramethylphenyldimethyl diisocyanate, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate in a molar ratio of 2.5:15:1.6:3.0:0.0045:0.01:2.5.

[0057] The preparation method is as follows: Under N2 protection, 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide and triethylamine are added to the reaction vessel, and then the temperature is raised to 75℃ and stirred for 0.5 h;

[0058] Then tetramethylbenzene dimethyl diisocyanate was added dropwise (over 4 hours), followed by thorough stirring at 75°C for 12 hours. After that, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate were added.

[0059] Next, the mixture was stirred at 75°C for 4 hours, then cooled to room temperature, and finally dried in a vacuum oven at 60°C for 12 hours to obtain the photosensitive polyimide oligomer.

[0060] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 30g of the above-mentioned photosensitive polyimide oligomer, 30g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0061] Example 3

[0062] The photosensitive polyimide oligomer of this embodiment was prepared from 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide, triethylamine, tetramethylphenyldimethyl diisocyanate, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate in a molar ratio of 2.5:12:1.4:3.0:0.0040:0.008:2.2.

[0063] The preparation method is as follows: Under N2 protection, 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide and triethylamine are added to the reaction vessel, and then the temperature is raised to 72℃ and stirred for 1 hour;

[0064] Then tetramethylphenyl dimethyl diisocyanate was added dropwise (over 3.5 hours), followed by thorough stirring at 72°C for 24 hours. After that, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate were added.

[0065] Next, the mixture was stirred at 72°C for 4-8 hours, then cooled to room temperature, and finally dried in a vacuum oven at 55°C for 36 hours to obtain the photosensitive polyimide oligomer.

[0066] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 40g of the above-mentioned photosensitive polyimide oligomer, 20g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0067] Example 4

[0068] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 50g of photosensitive polyimide oligomer from Example 1, 10g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0069] Compare with Example 2

[0070] The composition of the polyimide photosensitive material resin mixture for 3D printing is as follows: 60g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemicals), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. Stir at room temperature until completely dissolved and no particles are visible to prepare a polyimide photosensitive material resin composition for 3D printing. Then, use a 3D printer to create a model of this resin composition and print a sample. After post-curing in a UV curing chamber for 30 minutes, test the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample.

[0071] Example 5

[0072] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 20g of photosensitive polyimide oligomer from Example 1, 40g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemicals), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0073] The difference between Comparative Example 2 and Example 5 is that aliphatic polyurethane acrylate oligomer B was used instead of the self-made photosensitive polyimide oligomer.

[0074] Example 6

[0075] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 30g of photosensitive polyimide oligomer from Example 1, 30g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemicals), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0076] Example 7

[0077] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 40g of photosensitive polyimide oligomer from Example 1, 20g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemicals), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0078] Example 8

[0079] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 50g of photosensitive polyimide oligomer from Example 1, 10g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemicals), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0080] Example 9

[0081] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 40g of photosensitive polyimide oligomer from Example 1, 10g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 10g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0082] Example 10

[0083] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 20g of photosensitive polyimide oligomer from Example 1, 20g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 20g of aliphatic polyurethane acrylate oligomer B (purchased from Sartoma Chemical), 30g of acrylamide, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0084] Compare with Example 3

[0085] The composition of the polyimide photosensitive material resin mixture for 3D printing is as follows: 60g of hyperbranched oligomer C (purchased from Sartoma Chemicals), 30g of acryloylmorphon, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. Stir at room temperature until completely dissolved and no particles are visible to prepare a polyimide photosensitive material resin composition for 3D printing. Then, use a 3D printer to create a model of this resin composition and print the sample. After post-curing in a UV curing chamber for 30 minutes, test the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample.

[0086] Example 11

[0087] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 50g of photosensitive polyimide oligomer from Example 1, 10g of hyperbranched oligomer C (purchased from Sartoma Chemicals), 30g of acryloylmorphone, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0088] The difference between Comparative Example 3 and Example 11 is that hyperbranched oligomer C was used instead of the self-made photosensitive polyimide oligomer.

[0089] Example 12

[0090] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 20g of photosensitive polyimide oligomer from Example 1, 40g of hyperbranched oligomer C (purchased from Sartoma Chemicals), 30g of acryloylmorphone, 8g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0091] The photosensitive polyimide oligomers prepared in this invention exhibit good solubility and flowability in functional monomers such as acryloylmorphone and N-vinylpyrrolidone. (Solubility is as follows...) Figure 1 As shown: (Solubility of the transparent liquid in N-ethylpyrrolidone, acrylmorphone, isobornyl methacrylate, and dodecyl acrylate, respectively)

[0092] Example 13

[0093] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 45g of photosensitive polyimide oligomer from Example 1, 5g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 40g of acrylamide, 5g of tricyclodecane acrylate, 5g of photoinitiator TPO, and 2g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0094] Example 14

[0095] The polyimide photosensitive resin composition for 3D printing in this embodiment consists of: 50g of photosensitive polyimide oligomer from Example 1, 13g of aromatic polyurethane acrylate oligomer A (purchased from Changxing Chemical), 20g of acrylamide, 15g of tricyclodecane acrylate, 2g of photoinitiator TPO, and 0.5g of p-tert-butylcatechol. The mixture is stirred at room temperature until completely dissolved and no particles are visible, thus preparing a polyimide photosensitive material resin composition for 3D printing. This resin composition is then used to create a model and print a sample using a 3D printer. After curing in a UV curing chamber for 30 minutes, the relevant mechanical properties, heat resistance, dimensional stability, and QUV aging performance of the sample are tested.

[0096]

[0097]

[0098] 1. Elongation at break is usually used to represent the toughness of a material; 2. Bending strength is usually used to represent the strength of a material; 3. HDT is usually used to represent the temperature resistance of a material; 4. QUV accelerated aging is usually used to represent the performance stability of a material; 5. Dimensional deformation rate test is based on a model designed according to industry experience, and the test data is obtained.

[0099] The comparative data in the table above show that, compared with Comparative Examples 1, 2, and 3, the polyimide oligomer photosensitive resin compositions prepared in other embodiments of the present invention have significant advantages in terms of strength, heat resistance, QUV aging, and dimensional stability. At the same time, the resulting products also have a certain degree of toughness.

[0100] This invention is not limited to the above embodiments. Any simple substitutions and improvements made based on the principles of this invention are within the scope of protection of this invention.

Claims

1. A photosensitive polyimide oligomer, characterized in that: The simplified structural formula is 。 2. The method for preparing the photosensitive polyimide oligomer according to claim 1, characterized in that: The photosensitive polyimide oligomer is prepared from 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide, triethylamine, tetramethylphenyl dimethyl diisocyanate, hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate in a molar ratio of 2.5: 10-15: 1.2-1.6: 3.0: 0.0035-0.0045: 0.007-0.01: 2-2.

5. The steps are as follows: Under N2 protection, 1,4,5,8-naphthalenetetracarboxylic anhydride, N,N-dimethylacetamide and triethylamine were added to the reaction vessel, and then the temperature was raised to 70-75℃ and stirred for 0.5-1.5 h. Then add tetramethylphenyl dimethyl diisocyanate dropwise over 3-4 hours, followed by stirring thoroughly at 70-75°C for 12-36 hours. After that, add hydroquinone methyl ether, dibutyltin dilaurate, and hydroxyethyl acrylate. Next, stir at 70-75℃ for 4-8 hours, then cool to room temperature, and finally bake in a vacuum oven at 50-60℃ for 12-24 hours to obtain the photosensitive polyimide oligomer.

3. A polyimide photosensitive resin composition, characterized in that: It is prepared from the following components in the following mass ratios: The photosensitive polyimide oligomer 20-50 according to claim 1 Polyurethane acrylate oligomers 5-40 Reactive diluent 20-40 Functional monomers 5-15 Free radical photoinitiator 2-5 Stabilizer 0.5-2; The active diluent is one or more of the following: dicyclopentenyl acrylate, N-vinylpyrrolidone, isobornyl acrylate, hydroxyethyl acrylate, butyl acrylate, lauryl acrylate, acryloylmorphin, vinylimidazole, phenoxyethyl acrylate, 3,3,5-trimethylcyclohexyl acrylate, N-vinylcaprolactam, methoxy polyethylene glycol monoacrylate, polyethylene glycol diacrylate, dodecyl acrylate, isodecanyl acrylate, tetrahydrofuran acrylate, lauryl methacrylate, cyclotrimethylolpropane methyl acetal propane ester, glycidyl methacrylate, and 4-tert-butylcyclohexyl acrylate. The functional monomers are one or more of the following: propane triacrylate, tripropylene glycol diacrylate, 1,6-hexanediol acrylate, tricyclodecane acrylate, trimethylolpropane triacrylate, bisphenol A diacrylate ethoxylate, diethylene glycol dimethacrylate, pentaerythritol hexaacrylate, pentaerythritol tetraacrylate, tricyclodecanediacrylate diacrylate, bisphenol A dimethacrylate ethoxylate, 3(2-hydroxyethyl) isocyanurate triacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 2-ethyleneoxy acrylate, and bis(trimethylolpropane)tetraacrylate.

4. The polyimide photosensitive resin composition according to claim 3, characterized in that: The polyurethane acrylate oligomer is one or more of aromatic polyurethane acrylate oligomers, aliphatic polyurethane acrylate oligomers, and hyperbranched polyurethane acrylates, or any combination thereof.

5. The polyimide photosensitive resin composition according to claim 4, characterized in that: The aliphatic polyurethane acrylate oligomers and aromatic polyurethane acrylate oligomers have 2 or fewer functional groups, while the hyperbranched oligomers have 6-12 functional groups; the aliphatic polyurethane acrylate oligomers have a viscosity of 20,000-60,000, the aromatic polyurethane acrylate oligomers have a viscosity of 2,000-10,000, and the hyperbranched oligomers have a viscosity of 100-800.

6. The polyimide photosensitive resin composition according to claim 3, characterized in that: The free radical photoinitiator is one or more of the following: 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylbenzophenone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morphonyl-1-propanone, benzoin dimethyl ether (BDK), isopropylthioxanthone (2,4 isomer mixture), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4-diethylthiazolinone, benzophenone, ethyl 2,4,6-trimethylbenzoylphosphonate, ethyl 4-dimethylaminobenzoate, methyl o-benzoylformate, and 4-chlorobenzophenone.

7. The polyimide photosensitive resin composition according to claim 3, characterized in that: The stabilizer is one or more of the following: 4-tert-butyl-1,2-dihydroxybenzene, 2,6-di-(tert-butyl)-4-methylphenol, 4-methoxyphenol, pyrogallol, p-tert-butylcatechol, 2,6-di-tert-butyl-p-methylphenol, and lauryl gallate.

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