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CN-121975111-A - Covalent organic framework material and preparation method thereof, optical limiting material and preparation method and application thereof

CN121975111ACN 121975111 ACN121975111 ACN 121975111ACN-121975111-A

Abstract

The invention discloses a covalent organic framework material and a preparation method thereof, an optical limiting material and a preparation method and application thereof, wherein the preparation method comprises the following steps: and carrying out solvothermal reaction on the metal perfluorinated phthalocyanine and the amino-containing monomer in the presence of a first solvent and a catalyst to obtain the covalent organic framework material connected by piperazine bonds. The covalent organic framework material provided by the invention has good nonlinear optical performance, and the Covalent Organic Framework (COF) @ polymethyl methacrylate (PMMA) optical limiting material is uniformly mixed, so that the covalent organic framework material can be used for preparing optical plastics and has extremely strong application potential in the practical application of the nonlinear optical field.

Inventors

  • JIANG HAICHAO
  • WU QIONG
  • QIAO SHANLIN
  • LI QING
  • ZHANG BOYING
  • WANG YUPAN
  • LIU HAINING

Assignees

  • 河北科技大学

Dates

Publication Date
20260505
Application Date
20260302

Claims (10)

  1. 1. A preparation method of a covalent organic framework material is characterized by comprising the step of carrying out solvothermal reaction on metal perfluorinated phthalocyanine and an amino-containing monomer in the presence of a first solvent and a catalyst to obtain the covalent organic framework material connected by piperazine bonds.
  2. 2. The production method according to claim 1, wherein the production method comprises: S1, uniformly mixing the metal perfluorinated phthalocyanine, an amino-containing monomer, a first solvent and a catalyst to obtain a uniformly mixed solution; s2, carrying out liquid nitrogen degassing and sealing treatment on the container containing the uniformly mixed solution in the step S1; And S3, placing the container treated in the step S2 in heating equipment, carrying out solvothermal reaction on the mixed solution in the container to obtain a precipitate, and washing and vacuum drying the precipitate to obtain the covalent organic framework material.
  3. 3. The production method according to claim 1 or 2, wherein the amine group-containing monomer is at least one of 2,3,5, 6-pyridine tetramine, 2,3,5, 6-tetra (amino) p-benzoquinone, and phenazine-2, 3,7, 8-tetramine; The molecular formula of the metal perfluorinated phthalocyanine is MPcF 16 , and the central metal M is Cu, co, ni, zn or Fe; the catalyst is at least one of triethylamine, potassium carbonate and potassium hydroxide.
  4. 4. The production method according to claim 1 or 2, wherein the first solvent is at least one selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, 1,3, 5-trimethylbenzene, 1, 4-dioxane and p-xylene; the molar ratio of the metal perfluorinated phthalocyanine to the amino-containing monomer is (0.8-1.2): 1.5-2.5; The dosage ratio of the metal perfluorinated phthalocyanine to the catalyst is (0.01-0.05) (0.05-0.2) mmol/mL; the temperature of the solvothermal reaction is 100-150 ℃ and the time is 5-10 days.
  5. 5. The process according to claim 2, wherein the washing solvent used in the step S3 is at least one of N, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, absolute ethanol and acetone; The temperature of the vacuum drying is 50-100 ℃ and the time is 10-16h.
  6. 6. A covalent organic framework material prepared by the preparation method of any one of claims 1-5.
  7. 7. An optical limiting material comprising the covalent organic framework material of claim 6 and polymethyl methacrylate.
  8. 8. The optical limiting material of claim 7, wherein the mass ratio of the covalent organic framework material to polymethyl methacrylate is (0.3-10): 250-6000.
  9. 9. The method for preparing an optical limiting material according to claim 7 or 8, wherein the covalent organic framework material according to claim 6 and polymethyl methacrylate are uniformly mixed in the presence of a second solvent, and then the second solvent is removed to obtain the optical limiting material; Preferably, the temperature of the mixing is 50-80 ℃ and the time is 5-10 h, the feed liquid ratio of the covalent organic framework material to the second solvent is (0.3-10): (3-10) g/L, and the second solvent is N, N-dimethylformamide and/or N-methylpyrrolidone.
  10. 10. Optical limiting material according to claim 7 or 8 or the optical limiting material prepared by the preparation method according to claim 9 is applied to optical limiting in third-order nonlinear optics.

Description

Covalent organic framework material and preparation method thereof, optical limiting material and preparation method and application thereof Technical Field The invention belongs to the technical field of functional polymer materials, and particularly relates to a covalent organic framework material and a preparation method thereof, an optical limiting material and a preparation method and application thereof. Background Covalent Organic Frameworks (COFs) have been a new class of porous crystalline materials, and in recent years, research into COFs in optical limiter materials has been advanced. In 2018, researchers successfully realize the controllable adjustment of the material band gap from 2.67 eV to 1.5 eV by precisely adjusting the donor-acceptor (D-A) structure of the COF, and the breakthrough obviously improves the third-order nonlinear optical response of the material band gap. Marking the first application of COF in this field. In 2019, scientists have further developed metallized phthalocyanine-based COFs that exhibit intensity-dependent nonlinear optical switching behavior under 532 nm laser excitation. These materials not only have fast response characteristics (picosecond scale) but also exhibit a broad spectral operating range. COF is a potential candidate for optical limiting materials with a broad optical limiting window, fast optical response, strong anti-saturation absorption (RSA) properties, low linear absorption and high initial transmittance, and can effectively attenuate laser beams and protect the human eye and important optoelectronic devices. Therefore, intensive research on how to effectively regulate the nonlinear optical (NLO) performance of COF has important scientific significance and practical value. Disclosure of Invention The invention aims to provide a covalent organic framework material, a preparation method thereof, an optical limiting material, a preparation method thereof and application thereof, wherein the covalent organic framework material shows good nonlinear optical performance, and the Covalent Organic Framework (COF) @ polymethyl methacrylate (PMMA) optical limiting material is uniformly mixed, so that the covalent organic framework material can be used for preparing optical plastics and has extremely strong application potential in the practical application of the nonlinear optical field. In order to achieve the above object, a first aspect of the present invention provides a method for preparing a covalent organic framework material, which comprises subjecting a metal perfluorinated phthalocyanine and an amine group-containing monomer to solvothermal reaction in the presence of a first solvent and a catalyst to obtain a covalent organic framework material (i.e., phthalocyanine group covalent organic framework material TAP-MPcF 16 -COF) connected by piperazine bonds. According to the present invention, preferably, the preparation method comprises: S1, uniformly mixing the metal perfluorinated phthalocyanine, an amino-containing monomer, a first solvent and a catalyst to obtain a uniformly mixed solution; s2, carrying out liquid nitrogen degassing and sealing treatment on the container containing the uniformly mixed solution in the step S1; And S3, placing the container treated in the step S2 in heating equipment, carrying out solvothermal reaction on the mixed solution in the container to obtain a precipitate, and washing and vacuum drying the precipitate to obtain the covalent organic framework material. In the present invention, in step S3, preferably, after the temperature of the whole container treated in step S2 reaches room temperature, the container is placed in a heating device, so that the solvent-thermal reaction is performed on the uniformly mixed solution therein. According to the present invention, preferably, the amine group-containing monomer is at least one of 2,3,5, 6-pyridine tetraamine, 2,3,5, 6-tetra (amino) p-benzoquinone and phenazine-2, 3,7, 8-tetraamine; The molecular formula of the metal perfluorinated phthalocyanine is MPcF 16, and the central metal M is Cu, co, ni, zn or Fe; the catalyst is at least one of triethylamine, potassium carbonate and potassium hydroxide. According to the present invention, preferably, the first solvent is at least one selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, 1,3, 5-trimethylbenzene, 1, 4-dioxane and para-xylene; the molar ratio of the metal perfluorinated phthalocyanine to the amino-containing monomer is (0.8-1.2): 1.5-2.5; The dosage ratio of the metal perfluorinated phthalocyanine to the catalyst is (0.01-0.05) (0.05-0.2) mmol/mL; the temperature of the solvothermal reaction is 100-150 ℃ and the time is 5-10 days. In the invention, a solvent thermal method is adopted to synthesize a total system solution, namely, the total system solution comprises metal perfluorinated phthalocyanine, an amino-containing monomer, a first solvent and a catalyst. In the invention,