CN112159518A - Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof - Google Patents

Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof Download PDF

Info

Publication number
CN112159518A
CN112159518A CN202011015968.3A CN202011015968A CN112159518A CN 112159518 A CN112159518 A CN 112159518A CN 202011015968 A CN202011015968 A CN 202011015968A CN 112159518 A CN112159518 A CN 112159518A
Authority
CN
China
Prior art keywords
poly
phthalocyanine
limiting material
amplitude limiting
conjugated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011015968.3A
Other languages
Chinese (zh)
Inventor
王挺峰
黄文博
孙涛
汤伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Optics Fine Mechanics and Physics of CAS
Original Assignee
Changchun Institute of Optics Fine Mechanics and Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Optics Fine Mechanics and Physics of CAS filed Critical Changchun Institute of Optics Fine Mechanics and Physics of CAS
Priority to CN202011015968.3A priority Critical patent/CN112159518A/en
Publication of CN112159518A publication Critical patent/CN112159518A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/11—Homopolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/18—Definition of the polymer structure conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/59—Stability
    • C08G2261/592—Stability against heat

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention belongs to the field of optical amplitude limiting materials, and particularly relates to a poly-phthalocyanine optical amplitude limiting material with a conjugated microporous structure and a preparation method thereof. The poly phthalocyanine light amplitude limiting material provided by the invention is composed of a repeating unit shown in a formula (i); adjacent repeating units share a benzene ring to form a phenylene structure; in the formula (i), M is a metal atom. The poly-phthalocyanine light amplitude limiting material provided by the invention is an organic microporous polymer with a highly delocalized pi-electron conjugated structure, has good thermal stability and processability, simultaneously shows strong third-order nonlinear optical response, can limit the intensity of nanosecond laser pulse through an excited state absorption process in a relatively wide ultraviolet and visible spectrum range, and shows strong reverse saturation absorption and light amplitude limiting response effects.

Description

Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof
Technical Field
The invention belongs to the field of optical amplitude limiting materials, and particularly relates to a poly-phthalocyanine optical amplitude limiting material with a conjugated microporous structure and a preparation method thereof.
Background
With the continuous development of laser technology in recent years, the interference, damage and damage of lasers with various pulse widths, wavelengths and energies to signals of human bodies and photoelectric components are brought, and a plurality of threats are caused to social production life and national defense safety. At present, the light amplitude limiting material reduces the intensity and transmittance of light according to the nonlinear optical performance of the material, so that the material is limited under certain power energy to achieve the laser protection effect.
Conjugated Microporous Polymers (CMPs) refer to the presence of pi conjugated structures within their macromolecules. The presence of a large number of pi bonds throughout the microporous polymer makes them an electron rich aggregate. CMPs can provide not only electrons but also pore structures when interacting with electron deficient groups. The conjugated microporous polymers have wider application value due to the characteristics of high porosity, low skeleton density, designable structure, functionalized skeleton and high stability, so that the conjugated microporous polymers are paid much attention in the field of material science.
In view of the advantages of the conjugated microporous polymer, the conjugated microporous polymer is applied to the field of optical amplitude limiting materials, and the development of a novel conjugated microporous optical amplitude limiting material with good service performance becomes a research hotspot in the fields of laser protection and material science at present.
Disclosure of Invention
In view of the above, the present invention provides a poly-phthalocyanine optical limiting material with a conjugated microporous structure and a preparation method thereof, and the poly-phthalocyanine optical limiting material provided by the present invention has good thermal stability and processability, and simultaneously exhibits strong reverse saturation absorption and optical limiting response effects.
The invention provides a poly-phthalocyanine light amplitude limiting material with a conjugated micropore structure, which is composed of a repeating unit shown in a formula (i); adjacent repeating units share a benzene ring to form a phenylene structure:
Figure BDA0002699070490000021
in the formula (i), M is a metal atom.
Preferably, M is Fe, In, Co or Ni.
The invention provides a preparation method of a poly-phthalocyanine light amplitude limiting material with a conjugated micropore structure, which comprises the following steps:
mixing 1,2,4, 5-tetracyanobenzene, metal chloride and a catalyst in a solvent, and heating and reacting in a protective gas atmosphere to obtain the poly-phthalocyanine light amplitude limiting material with a conjugated microporous structure.
Preferably, the metal chloride is ferric trichloride, indium trichloride, cobalt dichloride or nickel dichloride.
Preferably, the molar ratio of the 1,2,4, 5-tetracyanobenzene to the metal chloride is 1: (0.3-0.8).
Preferably, the catalyst is 1, 8-diazabicyclo [5,4,0] undec-7-ene; the solvent is ethylene glycol.
Preferably, the molar ratio of the 1,2,4, 5-tetracyanobenzene to the catalyst is 1: (0.5-2).
Preferably, the dosage ratio of the 1,2,4, 5-tetracyanobenzene to the solvent is (0.005-0.05) mmol: 10 mL.
Preferably, the heating mode of the heating reaction is microwave heating; the temperature of the heating reaction is 160-200 ℃; the heating reaction time is 0.5-2 h.
Preferably, the method further comprises the following steps:
and after the heating reaction is finished, washing, impurity extraction and drying are sequentially carried out on the obtained reaction product, so that the poly-phthalocyanine light amplitude limiting material with the conjugated microporous structure is obtained.
Compared with the prior art, the invention provides a poly-phthalocyanine light amplitude limiting material with a conjugated micropore structure and a preparation method thereof. The poly phthalocyanine light amplitude limiting material provided by the invention is composed of a repeating unit shown in a formula (i); adjacent repeating units share a benzene ring to form a phenylene structure; in the formula (i), M is a metal atom. The poly-phthalocyanine light amplitude limiting material provided by the invention is an organic microporous polymer with a highly delocalized pi-electron conjugated structure, has good thermal stability and processability, simultaneously shows strong third-order nonlinear optical response, can limit the intensity of nanosecond laser pulse through an excited state absorption process in a relatively wide ultraviolet and visible spectrum range, and shows strong reverse saturation absorption and light amplitude limiting response effects. Results of the experimentThe clipping threshold value of the poly phthalocyanine light clipping material with different coordination metals provided by the invention can reach 0.4J/cm2Fitting the resulting nonlinear absorption coefficient to 1.55X 10-7To 4.47X 10-7In the meantime.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a Fourier transform infrared (FT-IR) spectrum of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure according to example 1 of the present invention;
FIG. 2 is a powder diffraction (PXRD) pattern of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a poly-phthalocyanine based optical limiting material with a conjugated micropore structure provided in example 1 of the present invention;
FIG. 4 is a scanning electron microscope energy spectrum analysis diagram of a poly-phthalocyanine optical limiting material with a conjugated micropore structure provided in embodiment 1 of the present invention;
FIG. 5 shows the N-component of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure according to example 1 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 6 is a distribution diagram of pore diameters of a poly-phthalocyanine based optical limiting material having a conjugated pore structure according to example 1 of the present invention;
fig. 7 is a clipping threshold diagram of a poly-phthalocyanine based optical clipping material having a conjugated micropore structure according to example 1 of the present invention;
FIG. 8 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 100 μ J laser incident energy according to example 1 of the present invention;
FIG. 9 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 150 μ J laser incident energy according to example 1 of the present invention;
FIG. 10 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 200 μ J laser incident energy according to example 1 of the present invention;
FIG. 11 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under incident energy of a laser of 250 μ J, according to example 1 of the present invention;
FIG. 12 is a Fourier transform infrared (FT-IR) spectrum of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure according to example 2 of the present invention;
FIG. 13 is a powder diffraction (PXRD) pattern of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 2 of the present invention;
FIG. 14 is a scanning electron microscope image of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 2 of the present invention;
FIG. 15 is a scanning electron microscope energy spectrum analysis diagram of a poly-phthalocyanine optical limiting material with a conjugated micropore structure provided in embodiment 2 of the present invention;
FIG. 16 shows the N-component of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure according to example 2 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 17 is a distribution diagram of pore diameters of a poly-phthalocyanine based optical limiting material having a conjugated pore structure according to example 2 of the present invention;
fig. 18 is a slice threshold diagram of a poly-phthalocyanine based optical slice material having a conjugated micropore structure according to example 2 of the present invention;
FIG. 19 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 100 μ J laser incident energy according to example 2 of the present invention;
FIG. 20 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 150 μ J laser incident energy according to example 2 of the present invention;
FIG. 21 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 200 μ J laser incident energy according to example 2 of the present invention;
FIG. 22 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under incident energy of a laser of 250 μ J, according to example 2 of the present invention;
FIG. 23 is a Fourier transform infrared (FT-IR) spectrum of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 3 of the present invention;
FIG. 24 is a powder diffraction (PXRD) pattern of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 3 of the present invention;
FIG. 25 is a scanning electron microscope image of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 3 of the present invention;
FIG. 26 is a scanning electron microscope energy spectrum analysis diagram of a poly-phthalocyanine based optical limiting material with a conjugated micropore structure provided in example 3 of the present invention;
FIG. 27 shows N of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure according to example 3 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 28 is a distribution diagram of pore diameters of a poly-phthalocyanine based optical limiting material having a conjugated pore structure according to example 3 of the present invention;
fig. 29 is a slice threshold diagram of a poly-phthalocyanine based optical slice material having a conjugated micropore structure according to example 3 of the present invention;
FIG. 30 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 100 μ J laser incident energy according to example 3 of the present invention;
FIG. 31 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 150 μ J laser incident energy according to example 3 of the present invention;
FIG. 32 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 200 μ J laser incident energy according to example 3 of the present invention;
FIG. 33 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under incident energy of a laser of 250 μ J, as provided in example 3 of the present invention;
FIG. 34 is a Fourier transform infrared (FT-IR) spectrum of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 4 of the present invention;
FIG. 35 is a powder diffraction (PXRD) pattern of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 4 of the present invention;
FIG. 36 is a scanning electron microscope image of a poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 4 of the present invention;
FIG. 37 is a scanning electron microscope energy spectrum analysis diagram of a poly-phthalocyanine based optical limiting material with a conjugated micropore structure provided in embodiment 4 of the present invention;
FIG. 38 is a diagram showing the N-arrangement of the light confining material of the poly-phthalocyanine type having the conjugated micro-pore structure according to example 4 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 39 is a distribution diagram of pore diameters of a poly-phthalocyanine based optical limiting material having a conjugated pore structure according to example 4 of the present invention;
fig. 40 is a slice threshold diagram of a poly-phthalocyanine based optical slice material having a conjugated micropore structure according to example 4 of the present invention;
FIG. 41 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 100 μ J laser incident energy according to example 4 of the present invention;
FIG. 42 is a Z-scan of a 150 μ J laser incident energy polyphthalocyanine-based optical limiting material having a conjugated microporous structure provided in example 4 of the present invention;
FIG. 43 is a Z-scan of a poly-phthalocyanine based optical limiting material with a conjugated microporous structure under 200 μ J laser incident energy according to example 4 of the present invention;
fig. 44 is a Z-scan of the polyphthalocyanine optical limiting material having a conjugated microporous structure provided in embodiment 4 of the present invention under an incident energy of a laser of 250 μ J.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a poly-phthalocyanine light amplitude limiting material with a conjugated micropore structure, which is composed of a repeating unit shown in a formula (i); two adjacent repeating units share a benzene ring to form a phenylene structure:
Figure BDA0002699070490000061
in the formula (i), M is a metal atom, preferably Fe, In, Co or Ni.
The poly-phthalocyanine light amplitude limiting material provided by the invention is composed of repeating units shown in formula (i), wherein adjacent repeating units share a benzene ring; that is, in the chemical structure of the poly-phthalocyanine light-limiting material provided by the present invention, adjacent repeating units are connected in the form of phenylene, and the structure is represented by formula (I):
Figure BDA0002699070490000062
formula (I) shows a chemical structure consisting of 4 repeating units of formula (I), wherein the dotted line on the phenyl ring indicates that the chemical structure continues to be linked to other repeating units of formula (I).
The invention also provides a preparation method of the poly phthalocyanine light amplitude limiting material with the conjugated micropore structure, which comprises the following steps:
mixing 1,2,4, 5-tetracyanobenzene, metal chloride and a catalyst in a solvent, and heating and reacting in a protective gas atmosphere to obtain the poly-phthalocyanine light amplitude limiting material with a conjugated microporous structure.
In the preparation method provided by the invention, 1,2,4, 5-tetracyanobenzene, metal chloride and a catalyst are mixed in a solvent. Wherein, the metal chloride is preferably ferric trichloride, indium trichloride, cobalt dichloride or nickel dichloride; the catalyst is preferably 1, 8-diazabicyclo [5,4,0] undec-7-ene; the solvent is preferably ethylene glycol; the molar ratio of the 1,2,4, 5-tetracyanobenzene to the metal chloride is preferably 1: (0.3 to 0.8), more preferably 1: (0.5-0.7), specifically 1: 0.6; the molar ratio of the 1,2,4, 5-tetracyanobenzene to the catalyst is preferably 1: (0.5 to 2), more preferably 1: (0.8-1.5), specifically 1: 1; the dosage ratio of the 1,2,4, 5-tetracyanobenzene to the solvent is preferably (0.005-0.05) mmol: 10mL, more preferably (0.01 to 0.03) mmol: 10mL, specifically 0.014 mmol: 10 mL.
In the preparation method provided by the invention, 1,2,4, 5-tetracyanobenzene, metal chloride and a catalyst are mixed in a solvent and then heated to react under the atmosphere of protective gas. Wherein the protective gas is preferably nitrogen; the heating mode is preferably microwave heating; the temperature of the heating reaction is preferably 160-200 ℃, and specifically can be 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃ or 200 ℃; the heating reaction time is preferably 0.5-2 h, and specifically can be 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2 h.
In the preparation method provided by the present invention, after the heating reaction is finished, the obtained reaction product is subjected to post-treatment, and the post-treatment process preferably includes: and washing, impurity extraction and drying the obtained reaction product in sequence to obtain the poly-phthalocyanine light amplitude limiting material with the conjugated microporous structure. Wherein, the washing mode is preferably to respectively carry out ethanol washing and water washing; the impurity extraction mode is preferably that the washed product is subjected to Soxhlet extraction by respectively using methanol and acetone, and the Soxhlet extraction time is preferably 1-2 d; the drying mode is preferably vacuum drying; the drying temperature is preferably 60-100 ℃, and specifically can be 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃; the drying time is preferably 12-48 h, and specifically can be 12h, 16h, 20h, 24h, 36h or 48 h.
The poly-phthalocyanine light amplitude limiting material provided by the invention is an organic microporous polymer with a highly delocalized pi-electron conjugated structure, has good thermal stability and processability, simultaneously shows strong third-order nonlinear optical response, can limit the intensity of nanosecond laser pulse through an excited state absorption process in a relatively wide ultraviolet and visible spectrum range, and shows strong reverse saturation absorption and light amplitude limiting response effects.
Experimental results show that the amplitude limiting threshold of the poly-phthalocyanine optical amplitude limiting material with different coordination metals can reach 0.4J/cm2Fitting the resulting nonlinear absorption coefficient to 1.55X 10-7To 4.47X 10-7In the meantime.
For the sake of clarity, the following examples are given in detail.
Example 1
The method comprises the following steps: adding 0.014mmol of monomer 1,2,4, 5-tetracyanobenzene and 0.0085mmol of anhydrous ferric trichloride into a microwave reaction tube, then adding 10mL of glycol solvent, stirring uniformly, adding 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene serving as a catalyst, and reacting for 1 hour at 180 ℃ in a microwave synthesizer in a nitrogen environment to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with ethanol and hot water to remove soluble organic matters and metal chlorides so as to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two with methanol and acetone for 2 days respectively, and drying the solid dispersion in a vacuum dryer at 100 ℃ for 12 hours to obtain the poly-phthalocyanine optical limiting material with the conjugated micropore structure, wherein the chemical structure of the poly-phthalocyanine optical limiting material is shown as the formula (I-1):
Figure BDA0002699070490000081
the result of fourier transform infrared spectroscopy (FT-IR) analysis of the poly-phthalocyanine optical limiting material prepared in this example is shown in fig. 1, and fig. 1 is a fourier transform infrared spectroscopy (FT-IR) diagram of the poly-phthalocyanine optical limiting material having a conjugated microporous structure provided in example 1 of the present invention. As can be seen from fig. 1, the cyano peak in the poly-phthalocyanine based optical limiter material disappears.
The result of powder diffraction (PXRD) analysis of the poly-phthalocyanine based optical limiting material prepared in this example is shown in fig. 2, and fig. 2 is a powder diffraction (PXRD) diagram of the poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 1 of the present invention. As can be seen from fig. 2, the material has some crystallinity.
The result of scanning electron microscope observation of the poly-phthalocyanine optical limiting material prepared in this example is shown in fig. 3, and fig. 3 is a scanning electron microscope image of the poly-phthalocyanine optical limiting material with a conjugated microporous structure provided in example 1 of the present invention. As can be seen from fig. 3, the material is a large cluster structure formed by small grains aggregated.
As a result of performing scanning electron microscope energy spectrum analysis on the poly-phthalocyanine light-limiting material prepared in this example, fig. 4 is shown in fig. 4, where fig. 4 is a scanning electron microscope energy spectrum analysis diagram of the poly-phthalocyanine light-limiting material with a conjugated micropore structure provided in example 1 of the present invention, where (a) is a collective diagram of all elements and a scanning photograph, (b) is a distribution diagram of C element, (C) is a distribution diagram of N element, and (d) is a distribution diagram of Fe element. As can be seen from fig. 4, the elements in the material are uniformly and orderly distributed along the structure.
The specific surface area analysis of the poly-phthalocyanine light-limiting material prepared in this example is shown in fig. 5, and fig. 5 is the N of the poly-phthalocyanine light-limiting material with a conjugated microporous structure provided in example 1 of the present invention2And (3) an adsorption-desorption isotherm diagram, wherein the solid connecting line is an adsorption curve, and the hollow connecting line is a desorption curve. As can be seen from FIG. 5, the BET specific surface area of this material was 11.9m2/g。
The result of analyzing the pore size distribution of the poly-phthalocyanine light amplitude limiting material prepared in this example is shown in fig. 6, and fig. 6 is a pore size distribution diagram of the poly-phthalocyanine light amplitude limiting material having a conjugated pore structure provided in example 1 of the present invention. As can be seen from FIG. 6, the average pore diameter of this material is 1.5 nm.
The poly phthalocyanine optical amplitude limiting material prepared in the embodiment is subjected to amplitude limiting threshold analysis, a testing laser light source is a 532nm nanosecond pulse tunable laser light source, a Z scanning instrument is adopted to analyze the nonlinear optical property of the laser light source, and the result is shown in FIG. 7And 7 is a slice threshold diagram of the poly-phthalocyanine light slice material with the conjugated micropore structure provided in embodiment 1 of the invention. As can be seen from FIG. 7, the material can reach 0.7J/cm at a laser incident energy of 200 muJ2The clipping threshold of (1).
The result of nonlinear optical absorption coefficient analysis on the poly-phthalocyanine optical amplitude limiting material prepared in this embodiment is shown in fig. 8-11, fig. 8 is a Z-scan of the poly-phthalocyanine optical amplitude limiting material with a conjugated microporous structure provided in embodiment 1 of the present invention at 100 μ J laser incident energy, fig. 9 is a Z-scan of the poly-phthalocyanine optical amplitude limiting material with a conjugated microporous structure provided in embodiment 1 of the present invention at 150 μ J laser incident energy, fig. 10 is a Z-scan of the poly-phthalocyanine optical amplitude limiting material with a conjugated microporous structure provided in embodiment 1 of the present invention at 200 μ J laser incident energy, and fig. 11 is a Z-scan of the poly-phthalocyanine optical amplitude limiting material with a conjugated microporous structure provided in embodiment 1 of the present invention at 250 μ J laser incident energy. The nonlinear absorption coefficient of the material is 2.24 multiplied by 10 as can be obtained through the function fitting results in the graphs of 8-11-7To 3.68X 10-7In the meantime.
Example 2
The method comprises the following steps: adding 0.014mmol of monomer 1,2,4, 5-tetracyanobenzene and 0.0085mmol of anhydrous indium trichloride into a microwave reaction tube, then adding 10mL of ethylene glycol solvent, stirring uniformly, adding 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene serving as a catalyst, and reacting for 1 hour at 180 ℃ in a microwave synthesizer in a nitrogen environment to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with ethanol and hot water to remove soluble organic matters and metal chlorides so as to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two with methanol and acetone for 2 days respectively, and drying the solid dispersion in a vacuum dryer at 100 ℃ for 12 hours to obtain the poly-phthalocyanine optical limiting material with the conjugated micropore structure, wherein the chemical structure of the poly-phthalocyanine optical limiting material is shown as the formula (I-2):
Figure BDA0002699070490000101
the result of fourier transform infrared spectroscopy (FT-IR) analysis of the polyphthalocyanine optical limiting material prepared in this example is shown in fig. 12, and fig. 12 is a fourier transform infrared spectroscopy (FT-IR) diagram of the polyphthalocyanine optical limiting material having a conjugated microporous structure provided in example 2 of the present invention. As can be seen from fig. 12, the cyano peak in the poly-phthalocyanine based optical limiter material disappeared.
Powder diffraction (PXRD) analysis of the poly-phthalocyanine based optical limiting material prepared in this example was performed, and the result is shown in fig. 13, where fig. 13 is a powder diffraction (PXRD) pattern of the poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 2 of the present invention. As can be seen from fig. 13, the material has some crystallinity.
Scanning electron microscope observation is carried out on the poly-phthalocyanine light amplitude limiting material prepared in the embodiment, and the result is shown in fig. 14, and fig. 14 is a scanning electron microscope image of the poly-phthalocyanine light amplitude limiting material with the conjugated micropore structure provided in the embodiment 2 of the invention. As can be seen from fig. 14, the material is a large cluster structure formed by small grains aggregated.
As a result of performing scanning electron microscope energy spectrum analysis on the poly-phthalocyanine light-limiting material prepared In this example, fig. 15 is shown In fig. 15, where (a) is a collective diagram of all elements and a scanning photograph, (b) is a distribution diagram of C element, (C) is a distribution diagram of N element, and (d) is a distribution diagram of In element, and fig. 15 is a scanning electron microscope energy spectrum analysis diagram of the poly-phthalocyanine light-limiting material having a conjugated micropore structure provided In example 2 of the present invention. As can be seen in fig. 15, the elements in the material are uniformly and orderly distributed along the structure.
The specific surface area analysis of the poly-phthalocyanine light-limiting material prepared in this example was performed, and the result is shown in fig. 16, where fig. 16 is the N of the poly-phthalocyanine light-limiting material with a conjugated microporous structure provided in example 2 of the present invention2And (3) an adsorption-desorption isotherm diagram, wherein the solid connecting line is an adsorption curve, and the hollow connecting line is a desorption curve. As can be seen from FIG. 16, the BET specific surface area of this material can be made 41.2m2/g。
The result of analyzing the pore size distribution of the poly-phthalocyanine light amplitude limiting material prepared in this example is shown in fig. 17, and fig. 17 is a pore size distribution diagram of the poly-phthalocyanine light amplitude limiting material having a conjugated pore structure provided in example 2 of the present invention. As can be seen from FIG. 17, the average pore diameter of this material was 1.4 nm.
The poly-phthalocyanine optical amplitude limiting material prepared in this embodiment is subjected to amplitude limiting threshold analysis under the same test conditions as in example 1, and the result is shown in fig. 18, where fig. 18 is an amplitude limiting threshold diagram of the poly-phthalocyanine optical amplitude limiting material with a conjugated micropore structure provided in embodiment 2 of the present invention. As can be seen from FIG. 18, the material can reach 0.6J/cm at a laser incident energy of 200 μ J2The clipping threshold of (1).
Fig. 19 to 22 show the results of nonlinear optical absorption coefficient analysis of the poly-phthalocyanine light-amplitude limiting material prepared in this embodiment, where fig. 19 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in example 2 of the present invention at 100 μ J laser incident energy, fig. 20 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in example 2 of the present invention at 150 μ J laser incident energy, fig. 21 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in example 2 of the present invention at 200 μ J laser incident energy, and fig. 22 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in example 2 of the present invention at 250 μ J laser incident energy. The nonlinear absorption coefficient of the material is 1.54 multiplied by 10 as can be obtained through the function fitting results in the graphs of 19-22-7To 3.02X 10-7In the meantime.
Example 3
The method comprises the following steps: adding 0.014mmol of monomer 1,2,4, 5-tetracyanobenzene and 0.0085mmol of anhydrous cobalt dichloride into a microwave reaction tube, then adding 10mL of glycol solvent, uniformly stirring, adding 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene serving as a catalyst, and reacting for 1 hour at 180 ℃ in a microwave synthesizer in a nitrogen environment to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with ethanol and hot water to remove soluble organic matters and metal chlorides so as to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two with methanol and acetone for 2 days respectively, and drying the solid dispersion in a vacuum dryer at 100 ℃ for 12 hours to obtain the poly-phthalocyanine optical limiting material with the conjugated micropore structure, wherein the chemical structure of the poly-phthalocyanine optical limiting material is shown as the formula (I-3):
Figure BDA0002699070490000121
fourier transform infrared spectroscopy (FT-IR) analysis was performed on the poly-phthalocyanine optical limiting material prepared in this example, and the result is shown in FIG. 23, where FIG. 23 is a Fourier transform infrared spectroscopy (FT-IR) diagram of the poly-phthalocyanine optical limiting material with a conjugated microporous structure provided in example 3 of the present invention. As can be seen from fig. 23, the cyano peak of the polymer in the poly-phthalocyanine based optical limiter material disappeared.
Powder diffraction (PXRD) analysis of the poly-phthalocyanine based optical limiting material prepared in this example was performed, and the result is shown in fig. 24, where fig. 24 is a powder diffraction (PXRD) diagram of the poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 3 of the present invention. As can be seen from fig. 24, the material has some crystallinity.
Scanning electron microscope observation is carried out on the poly-phthalocyanine light amplitude limiting material prepared in the embodiment, and the result is shown in fig. 25, and fig. 25 is a scanning electron microscope image of the poly-phthalocyanine light amplitude limiting material with the conjugated micropore structure provided in embodiment 3 of the invention. As can be seen from fig. 25, the material is a large cluster structure formed by small grains aggregated.
As a result of performing scanning electron microscope energy spectrum analysis on the poly-phthalocyanine light-limiting material prepared in this example, fig. 26 is shown in fig. 26, where (a) is a collective drawing of all elements and a scanning photograph, (b) is a distribution drawing of C element, (C) is a distribution drawing of N element, and (d) is a distribution drawing of Co element, and fig. 26 is a scanning electron microscope energy spectrum analysis drawing of the poly-phthalocyanine light-limiting material having a conjugated micropore structure provided in example 3 of the present invention. As can be seen in fig. 26, the elements in the material are uniformly and orderly distributed along the structure.
The specific surface area analysis of the poly-phthalocyanine light-limiting material prepared in this example was performed, and the result is shown in fig. 27, where fig. 27 is the N of the poly-phthalocyanine light-limiting material having a conjugated microporous structure provided in example 3 of the present invention2And (3) an adsorption-desorption isotherm diagram, wherein the solid connecting line is an adsorption curve, and the hollow connecting line is a desorption curve. As can be seen from FIG. 27, the BET specific surface area of this material was 27.7m2/g。
The result of analyzing the pore size distribution of the poly-phthalocyanine light amplitude limiting material prepared in this example is shown in fig. 28, and fig. 28 is a pore size distribution diagram of the poly-phthalocyanine light amplitude limiting material having a conjugated pore structure provided in example 3 of the present invention. As can be seen from FIG. 28, the average pore diameter of this material was 1.5 nm.
The poly-phthalocyanine optical amplitude limiting material prepared in this example is subjected to amplitude limiting threshold analysis under the same test conditions as example 1, and the result is shown in fig. 29, where fig. 29 is an amplitude limiting threshold diagram of the poly-phthalocyanine optical amplitude limiting material with a conjugated micropore structure provided in example 3 of the present invention. As can be seen from FIG. 29, the material can reach 0.5J/cm at a laser incident energy of 200 μ J2The clipping threshold of (1).
Fig. 30 to 33 show the results of nonlinear optical absorption coefficient analysis of the poly-phthalocyanine light-amplitude limiting material prepared in this embodiment, in which fig. 30 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in embodiment 3 of the present invention at 100 μ J laser incident energy, fig. 31 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in embodiment 3 of the present invention at 150 μ J laser incident energy, fig. 32 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in embodiment 3 of the present invention at 200 μ J laser incident energy, and fig. 33 is a Z-scan of the poly-phthalocyanine light-amplitude limiting material with a conjugated microporous structure provided in embodiment 3 of the present invention at 250 μ J laser incident energy. The nonlinear absorption coefficient of the material is 2.15 multiplied by 10 as can be obtained through the function fitting results in the graphs of 30-33-7To 4.47X 10-7In the meantime.
Example 4
The method comprises the following steps: adding 0.014mmol of monomer 1,2,4, 5-tetracyanobenzene and 0.0085mmol of anhydrous nickel dichloride into a microwave reaction tube, then adding 10mL of glycol solvent, uniformly stirring, adding 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene serving as a catalyst, and reacting for 1 hour at 180 ℃ in a microwave synthesizer in a nitrogen environment to obtain a mixed solution;
step two: respectively washing the mixed solution obtained in the step one with ethanol and hot water to remove soluble organic matters and metal chlorides so as to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two with methanol and acetone for 2 days respectively, and drying the solid dispersion in a vacuum dryer at 100 ℃ for 12 hours to obtain the poly-phthalocyanine light amplitude limiting material with the conjugated micropore structure, wherein the chemical structure of the poly-phthalocyanine light amplitude limiting material is shown as the formula (I-4):
Figure BDA0002699070490000141
fourier transform infrared spectroscopy (FT-IR) analysis was performed on the poly-phthalocyanine optical limiting material prepared in this example, and the result is shown in FIG. 34, where FIG. 34 is a Fourier transform infrared spectroscopy (FT-IR) diagram of the poly-phthalocyanine optical limiting material with a conjugated microporous structure provided in example 4 of the present invention. As can be seen from fig. 3, the cyano peak in the poly-phthalocyanine based optical limiter material disappears.
Powder diffraction (PXRD) analysis of the poly-phthalocyanine based optical limiting material prepared in this example was performed, and the result is shown in fig. 35, where fig. 35 is a powder diffraction (PXRD) pattern of the poly-phthalocyanine based optical limiting material having a conjugated microporous structure provided in example 4 of the present invention. As can be seen from fig. 35, the material has some crystallinity.
Scanning electron microscope observation is carried out on the poly-phthalocyanine light amplitude limiting material prepared in the embodiment, and the result is shown in fig. 36, and fig. 36 is a scanning electron microscope image of the poly-phthalocyanine light amplitude limiting material with the conjugated micropore structure provided in embodiment 4 of the invention. As can be seen in fig. 36, the material is a large cluster structure formed by small grains aggregated.
As a result of performing scanning electron microscope energy spectrum analysis on the poly-phthalocyanine light-limiting material prepared in this example, as shown in fig. 37, fig. 37 is a scanning electron microscope energy spectrum analysis diagram of the poly-phthalocyanine light-limiting material with a conjugated micropore structure provided in example 4 of the present invention, wherein (a) is a collective diagram of all elements and a scanning photograph, (b) is a distribution diagram of C element, (C) is a distribution diagram of N element, and (d) is a distribution diagram of Ni element. As can be seen in fig. 37, the elements in this material are uniformly and orderly distributed along the structure.
The specific surface area analysis of the poly-phthalocyanine light-limiting material prepared in this example was performed, and the result is shown in fig. 38, where fig. 38 is the N of the poly-phthalocyanine light-limiting material with a conjugated microporous structure provided in example 4 of the present invention2And (3) an adsorption-desorption isotherm diagram, wherein the solid connecting line is an adsorption curve, and the hollow connecting line is a desorption curve. As can be seen from FIG. 38, the BET specific surface area of this material was 33.7m2/g。
The result of analyzing the pore size distribution of the poly-phthalocyanine light amplitude limiting material prepared in this example is shown in fig. 39, and fig. 39 is a pore size distribution diagram of the poly-phthalocyanine light amplitude limiting material having a conjugated pore structure provided in example 4 of the present invention. As can be seen from FIG. 39, the average pore diameter of this material was 1.8 nm.
The poly-phthalocyanine optical amplitude limiting material prepared in this example is subjected to amplitude limiting threshold analysis under the same test conditions as in example 1, and the result is shown in fig. 40, where fig. 40 is an amplitude limiting threshold diagram of the poly-phthalocyanine optical amplitude limiting material with a conjugated micropore structure provided in example 4 of the present invention. As can be seen from FIG. 40, the material reached 0.5J/cm at a laser incident energy of 200. mu.J2The clipping threshold of (1).
The result of nonlinear optical absorption coefficient analysis of the poly-phthalocyanine light amplitude limiting material prepared in this example is shown in fig. 41-44, where fig. 41 is a Z-scan of the poly-phthalocyanine light amplitude limiting material with the conjugated microporous structure provided in example 4 of the present invention under 100 μ J laser incident energy, and fig. 42 is a material of the poly-phthalocyanine light amplitude limiting material with the conjugated microporous structure provided in example 4 of the present invention under 150 μ J laser incident energyFig. 43 is a Z scan of the polyphthalocyanine optical limiting material having a conjugated microporous structure provided in embodiment 4 of the present invention at a laser incident energy of 200 μ J, and fig. 44 is a Z scan of the polyphthalocyanine optical limiting material having a conjugated microporous structure provided in embodiment 4 of the present invention at a laser incident energy of 250 μ J. The nonlinear absorption coefficient of the material is 1.94 multiplied by 10 as can be obtained through the function fitting results in FIGS. 41-44-7To 3.41X 10-7In the meantime.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A poly phthalocyanine light amplitude limiting material with a conjugated micropore structure is composed of a repeating unit shown in a formula (i); adjacent repeating units share a benzene ring to form a phenylene structure:
Figure FDA0002699070480000011
in the formula (i), M is a metal atom.
2. The poly-phthalocyanine-based optical limiting material according to claim 1, wherein M is Fe, In, Co, or Ni.
3. A method for preparing the light-limiting material of the poly-phthalocyanine type having a conjugated microporous structure according to claim 1, comprising the steps of:
mixing 1,2,4, 5-tetracyanobenzene, metal chloride and a catalyst in a solvent, and heating and reacting in a protective gas atmosphere to obtain the poly-phthalocyanine light amplitude limiting material with a conjugated microporous structure.
4. The method according to claim 3, wherein the metal chloride is iron trichloride, indium trichloride, cobalt dichloride or nickel dichloride.
5. The method of claim 3, wherein the molar ratio of 1,2,4, 5-tetracyanobenzene to metal chloride is 1: (0.3-0.8).
6. The method of claim 3, wherein the catalyst is 1, 8-diazabicyclo [5,4,0] undec-7-ene; the solvent is ethylene glycol.
7. The method of claim 3, wherein the molar ratio of 1,2,4, 5-tetracyanobenzene to catalyst is 1: (0.5-2).
8. The method according to claim 3, wherein the ratio of the 1,2,4, 5-tetracyanobenzene to the solvent is (0.005-0.05) mmol: 10 mL.
9. The method according to claim 3, wherein the heating means for the heating reaction is microwave heating; the temperature of the heating reaction is 160-200 ℃; the heating reaction time is 0.5-2 h.
10. The method according to any one of claims 3 to 9, further comprising:
and after the heating reaction is finished, washing, impurity extraction and drying are sequentially carried out on the obtained reaction product, so that the poly-phthalocyanine light amplitude limiting material with the conjugated microporous structure is obtained.
CN202011015968.3A 2020-09-24 2020-09-24 Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof Pending CN112159518A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011015968.3A CN112159518A (en) 2020-09-24 2020-09-24 Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011015968.3A CN112159518A (en) 2020-09-24 2020-09-24 Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112159518A true CN112159518A (en) 2021-01-01

Family

ID=73863652

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011015968.3A Pending CN112159518A (en) 2020-09-24 2020-09-24 Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112159518A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539544A (en) * 2022-01-12 2022-05-27 四川大学 Copper phthalocyanine polymer nano particle and preparation method and application thereof
CN117299212A (en) * 2023-09-04 2023-12-29 东北师范大学 Cobalt phthalocyanine covalent organic framework desulfurization catalyst and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140343334A1 (en) * 2009-06-12 2014-11-20 Aggregate Energy, Llc Catalyst with Supplement Component for Hydroprocessing of Bio-feedstock
CN105017263A (en) * 2015-06-16 2015-11-04 南方科技大学 Metal phthalocyanine nanometer crystal and preparation method thereof, and transistor cpplications
CN108409976A (en) * 2018-01-19 2018-08-17 北京化工大学 The topological organic polymer of solubility based on full conjugate rigid structure and quasi- phthalocyanine activated centre and preparation
CN108822260A (en) * 2018-04-27 2018-11-16 江西理工大学 It is a kind of without aggregation phthalocyanine MA-VA polymer optical limiting materials and preparation method thereof
CN111072983A (en) * 2019-11-22 2020-04-28 吉林大学 Rare earth metal phthalocyanine grafted anthraquinone, preparation method thereof and application thereof in optical amplitude limiting

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140343334A1 (en) * 2009-06-12 2014-11-20 Aggregate Energy, Llc Catalyst with Supplement Component for Hydroprocessing of Bio-feedstock
CN105017263A (en) * 2015-06-16 2015-11-04 南方科技大学 Metal phthalocyanine nanometer crystal and preparation method thereof, and transistor cpplications
CN108409976A (en) * 2018-01-19 2018-08-17 北京化工大学 The topological organic polymer of solubility based on full conjugate rigid structure and quasi- phthalocyanine activated centre and preparation
CN108822260A (en) * 2018-04-27 2018-11-16 江西理工大学 It is a kind of without aggregation phthalocyanine MA-VA polymer optical limiting materials and preparation method thereof
CN111072983A (en) * 2019-11-22 2020-04-28 吉林大学 Rare earth metal phthalocyanine grafted anthraquinone, preparation method thereof and application thereof in optical amplitude limiting

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TINGFENG WANG ET AL.: "Two-Dimensional Metal-Polyphthalocyanine Conjugated Porous Frameworks as Promising Optical Limiting Materials", 《APPL. MATER. INTERFACES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114539544A (en) * 2022-01-12 2022-05-27 四川大学 Copper phthalocyanine polymer nano particle and preparation method and application thereof
CN117299212A (en) * 2023-09-04 2023-12-29 东北师范大学 Cobalt phthalocyanine covalent organic framework desulfurization catalyst and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN108892759B (en) Conjugated microporous polymer and preparation method thereof
CN112159518A (en) Poly-phthalocyanine light amplitude limiting material with conjugated micropore structure and preparation method thereof
CN112592474B (en) Benzotriazole covalent organic framework material and preparation method and application thereof
CN111495426A (en) Polyaniline/perylene bisimide organic heterojunction photocatalyst, preparation method and application thereof
CN110746601A (en) Porphyrin-based polypyrrole conjugated microporous polymer and preparation method thereof
CN113751047B (en) Covalent organic framework-carbon nitride nanosheet hybridization photocatalysis hydrogen evolution material and preparation method and application thereof
CN109304204B (en) Phosphorus-doped cobaltosic oxide quantum dot modified graphite phase nitrogen carbide composite material, and preparation method and application thereof
CN114874591B (en) Conductive super-crosslinked conjugated polymer electromagnetic wave absorbing material and preparation method thereof
Wang et al. Simple synthesis of conducting poly (2-aminothiazole) with high molecular weight
CN112574019B (en) Covalent organic framework material based on twisted hexabenzocoronene and preparation method thereof
Zhong et al. Oligo (phenylenevinylene)‐Based Covalent Organic Frameworks with Kagome Lattice for Boosting Photocatalytic Hydrogen Evolution
CN115851271B (en) Preparation method of nitrogen-doped fluorescent carbon dots
CN110227533B (en) Preparation method of graphite-phase carbon nitride photocatalyst
CN110227544B (en) Honeycomb structured porphyrin COP and g-C3N4Synthesis of composite material and application of composite material in aspect of photocatalytic degradation of dye
CN111484602B (en) 1,3,6,8-tetra (p-formylphenyl) pyrene-based conjugated microporous polymer and preparation method thereof
Qin et al. Rational Design of Vinylene‐Linked Covalent Organic Frameworks for Modulating Photocatalytic H2 Evolution
CN108752583B (en) High-conductivity composite material and preparation method thereof
CN112111132B (en) Conjugated microporous poly phthalocyanine-graphene composite laser protection material and preparation method thereof
Zhang et al. Enhanced photocatalytic H 2 evolution over covalent organic frameworks through an assembled NiS cocatalyst
Wen et al. Template-free assembly of nanoporous terpolymer sheets with internal heterojunction for photocatalytic hydrogen evolution from water
CN110624610B (en) Visible light photocatalyst for synthesizing water gas and preparation and application thereof
CN109181235B (en) Thermoelectric film and preparation method thereof
Lei et al. Naphthalene-based semiconducting microporous polyimides for high-efficiency photo-catalytic dye degradation
CN112159519B (en) Porous poly-phthalocyanine laser protection material with carbon bridging and preparation method thereof
CN114150397B (en) Tetra-beta-carboxylic acid metal phthalocyanine/polypyrrole binary nanofiber and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210101