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CN-121991506-A - Benzoxazine dual-curing photosensitive resin composition and preparation method thereof

CN121991506ACN 121991506 ACN121991506 ACN 121991506ACN-121991506-A

Abstract

The invention relates to the field of 3D printing, in particular to a benzoxazine dual-curing photosensitive resin composition for additive manufacturing and a preparation method thereof. The benzoxazine dual-curing photosensitive resin composition comprises 40-70 parts of benzoxazine resin, 5-20 parts of polyurethane acrylic ester, 10-30 parts of reactive diluent, 1-5 parts of photoinitiator, 0.01-2 parts of light absorber, 0.1-4 parts of auxiliary agent and 1-10 parts of thermosetting agent. By regulating and controlling the crosslinking density of the photopolymer network, the thermosetting conversion rate of the benzoxazine resin is ensured to the greatest extent, so that a 3D printing forming product with high strength is obtained under the condition of not influencing the three-dimensional structure. The resin composition has wide application prospect in the fields of aerospace, vehicle engineering, mechanical manufacturing and the like.

Inventors

  • ZHAO DOUDOU
  • ZHAO ZHEN
  • YAN JIAWEI
  • GAO MINGYU
  • Shi Shuoqing

Assignees

  • 中航西安飞机工业集团股份有限公司

Dates

Publication Date
20260508
Application Date
20251204

Claims (10)

  1. 1. The benzoxazine dual-curing photosensitive resin composition is characterized by comprising 40-70 parts of benzoxazine resin, 5-20 parts of polyurethane acrylic ester, 10-30 parts of reactive diluent, 1-5 parts of photoinitiator, 0.01-2 parts of light absorber, 0.1-4 parts of auxiliary agent and 1-10 parts of thermosetting agent.
  2. 2. A method for preparing a benzoxazine dual-curing photosensitive resin composition, which is characterized by comprising the following steps: preparing benzoxazine resin; Stirring a reactive diluent, a photoinitiator, a light absorber and an auxiliary agent at room temperature for 0.5-1 h under the condition of light shielding to obtain a uniform mixture 3, stirring polyurethane acrylic ester and the mixture 3 at 40-60 ℃ for 0.5-1 h to form a mixture 4, and finally stirring the benzoxazine resin, a thermosetting agent and the mixture 4 at room temperature for 0.5-2 h to obtain the benzoxazine dual-curing photosensitive resin composition for additive manufacturing.
  3. 3. The preparation method according to claim 2, wherein the benzoxazine resin is prepared by: Step 1, adding phenolic and amine compounds into an organic solvent, and stirring at room temperature until the phenolic and amine compounds are completely dissolved to obtain a mixture 1; And 2, adding paraformaldehyde into the mixture 1, heating to a reaction temperature, stopping stirring after the reaction is finished to obtain a mixture 2, and carrying out vacuum distillation to remove the organic solvent, the small molecular impurities and the water after the mixture 2 is cooled to room temperature to obtain the benzoxazine resin.
  4. 4. The preparation method of claim 3, wherein the molar ratio of the phenol compound to the amine compound in the step 1 is 1-2:1, wherein the phenol compound is at least one of phenol, allylphenol, vinylphenol, nonylphenol, bisphenol A, bisphenol F and biphenol, the amine compound is at least one of aniline, toluidine, metaphenylene diamine, propargylamine, acrylamide and methacrylamide, and the organic solvent is at least one of toluene, dioxane, acetone, ethanol, N-hexanol, diethyl ether and N, N-dimethylformamide.
  5. 5. The preparation method of the high-purity formaldehyde resin according to claim 4, wherein the molar ratio of paraformaldehyde to phenols to amines in the step 2 is 2-4:1-2:1, the reaction temperature in the step 2 is 60-100 ℃, and the reaction time is 1-10 h.
  6. 6. The method according to claim 2, wherein the reactive diluent is at least one of isobornyl acrylate, ethoxyethoxy acrylate, 4-acryloylmorpholine, cyclotrimethylolpropane methylacrylate, dicyclopentadienyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylamide, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, and (2-hydroxyethyl) isocyanuric acid triacrylate.
  7. 7. The method according to claim 2, wherein the photoinitiator is at least one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, and 2-isopropylthioxanthone.
  8. 8. The method of claim 2, wherein the light absorber is at least one of UV absorber UV-329, UV absorber UV-328, UV absorber UV-327, UV absorber UV-326, fluorescent whitening agent OB-1.
  9. 9. The method according to claim 2, wherein the thermosetting agent is at least one of benzoyl peroxide, dicumyl peroxide, 2-methylimidazole, 4-diaminodiphenylmethane, and zinc acetylacetonate.
  10. 10. The preparation method according to claim 2, wherein the auxiliary agent comprises at least one of an antifoaming agent, a leveling agent, a dispersing agent, an antioxidant and a polymerization inhibitor, wherein the antifoaming agent is exemplified by but not limited to TEG0 900, 2517 and BYK-1790, the leveling agent is exemplified by but not limited to BYK-345, BYK-371 and BYK-333, the dispersing agent is exemplified by but not limited to BYK-103, BYK-111 and BYK-410, the antioxidant is exemplified by but not limited to antioxidant MIANOX, antioxidant MIANOX, antioxidant MIANOX and 770, and the polymerization inhibitor is exemplified by but not limited to MEHQ and hydroquinone.

Description

Benzoxazine dual-curing photosensitive resin composition and preparation method thereof Technical Field The invention relates to the field of 3D printing, in particular to a benzoxazine dual-curing photosensitive resin composition for additive manufacturing and a preparation method thereof. Background The 3D printing technology based on photo-curing is widely applied to the fields of aerospace, vehicle engineering, machine manufacturing and the like with extremely high printing speed, printing precision, low energy consumption and environmental friendliness. However, the 3D printed samples exhibit significant anisotropy, low mechanical strength and poor performance stability, resulting in a very limited industrial application of 3D printing in the field of high performance materials. In response to these problems, dual curing strategies have been proposed and used to improve the isotropy, mechanical properties and heat resistance of photo-cured 3D printing materials. Among the dual cure strategies, photo-thermal sequential dual cure is the most common strategy. As the thermosetting resin for dual curing, a high-performance thermosetting resin such as an epoxy resin, a cyanate resin, an isocyanate resin, a polyimide resin, and the like is generally selected. Disclosure of Invention The invention aims to provide a benzoxazine dual-curing photosensitive resin composition and a preparation method thereof, which can reduce anisotropy and increase mechanical strength. The technical scheme is as follows: a benzoxazine dual-curing photosensitive resin composition comprises 40-70 parts of benzoxazine resin, 5-20 parts of polyurethane acrylic ester, 10-30 parts of reactive diluent, 1-5 parts of photoinitiator, 0.01-2 parts of light absorber, 0.1-4 parts of auxiliary agent and 1-10 parts of thermosetting agent. A method for preparing a benzoxazine dual-curing photosensitive resin composition, comprising: preparing benzoxazine resin; Stirring a reactive diluent, a photoinitiator, a light absorber and an auxiliary agent at room temperature for 0.5-1 h under the condition of light shielding to obtain a uniform mixture 3, stirring polyurethane acrylic ester and the mixture 3 at 40-60 ℃ for 0.5-1 h to form a mixture 4, and finally stirring the benzoxazine resin, a thermosetting agent and the mixture 4 at room temperature for 0.5-2 h to obtain the benzoxazine dual-curing photosensitive resin composition for additive manufacturing. Further, a benzoxazine resin is prepared, specifically: Step 1, adding phenolic and amine compounds into an organic solvent, and stirring at room temperature until the phenolic and amine compounds are completely dissolved to obtain a mixture 1; And 2, adding paraformaldehyde into the mixture 1, heating to a reaction temperature, stopping stirring after the reaction is finished to obtain a mixture 2, and carrying out vacuum distillation to remove the organic solvent, the small molecular impurities and the water after the mixture 2 is cooled to room temperature to obtain the benzoxazine resin. Further, the molar ratio of the phenols and the amine compounds in the step 1 is 1-2:1, wherein the phenol compounds are at least one of phenol, allylphenol, vinylphenol, nonylphenol, bisphenol A, bisphenol F and biphenol, the amine compounds are at least one of aniline, toluidine, m-phenylenediamine, propargylamine, acrylamide and methacrylamide, and the organic solvent is at least one of toluene, dioxane, acetone, ethanol, N-hexanol, diethyl ether and N, N-dimethylformamide. Further, the molar ratio of the paraformaldehyde to the phenols to the amines in the step 2 is 2-4:1-2:1, the reaction temperature in the step 2 is 60-100 ℃, and the reaction time is 1-10 h. Further, the reactive diluent is at least one of isobornyl acrylate, ethoxyl acrylate, 4-acryloylmorpholine, cyclotrimethylol propane methylal acrylate, dicyclopentadienyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylamide, dipropylene glycol diacrylate, tripropylene glycol diacrylate, 1, 6-hexanediol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate and (2-hydroxyethyl) isocyanuric acid triacrylate. Further, the photoinitiator is at least one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl phenyl phosphonic acid ethyl ester, 2-hydroxy-2-methyl-1-phenyl 1-acetone, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxy cyclohexyl phenyl ketone and 2-isopropyl thioxanthone. Further, the light absorber is at least one of ultraviolet light absorber UV-329, ultraviolet light absorber UV-328, ultraviolet light absorber UV-327, ultraviolet light absorber UV-326, fluorescent whitening agent OB and fluorescent whitening agent OB-1. Further, the heat curing agent is at least one of benzoyl peroxide, dicumyl peroxide, 2-methylimidazole, 4-diaminodiphenylmethane and zinc acetylacetonate. Further, the auxiliary agent comprises at least one of an antifoaming agent, a leveling agent, a