CN112111132A - Conjugated microporous poly phthalocyanine-graphene composite laser protection material and preparation method thereof - Google Patents

Conjugated microporous poly phthalocyanine-graphene composite laser protection material and preparation method thereof Download PDF

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CN112111132A
CN112111132A CN202011014524.8A CN202011014524A CN112111132A CN 112111132 A CN112111132 A CN 112111132A CN 202011014524 A CN202011014524 A CN 202011014524A CN 112111132 A CN112111132 A CN 112111132A
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phthalocyanine
conjugated microporous
graphene
microporous poly
composite laser
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CN112111132B (en
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王挺峰
黄文博
孙涛
汤伟
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Changchun Institute of Optics Fine Mechanics and Physics of CAS
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • 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
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • 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
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    • 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

Abstract

The invention belongs to the field of laser protection materials, and particularly relates to a conjugated microporous poly phthalocyanine-graphene composite laser protection material and a preparation method thereof. The composite laser protection material provided by the invention comprises graphene and conjugated microporous poly phthalocyanine adsorbed on the surface of the graphene; the conjugated microporous poly phthalocyanine is composed of a repeating unit represented by formula (i) or a repeating unit represented by formula (ii); adjacent repeating units share a benzene ring to form a phenylene structure; in the formula (ii), M is a metal atom. The conjugated microporous poly phthalocyanine-graphene composite laser protection material provided by the invention is an organic microporous polymer which takes graphene as a substrate and has a large delocalized pi electron conjugated structure, has outstanding forgeability and thermal stability, and shows strong three-order nonlinear optical response so as to show strong reverse saturation absorptionThe effect is received, and the poly phthalocyanine can be evenly attached to the graphene and can be effectively prevented from gathering.

Description

Conjugated microporous poly phthalocyanine-graphene composite laser protection material and preparation method thereof
Technical Field
The invention belongs to the field of laser protection materials, and particularly relates to a conjugated microporous poly phthalocyanine-graphene composite laser protection material and a preparation method thereof.
Background
In recent years, with the continuous progress and development of laser science and technology, the research of laser protection materials is more and more focused and valued by people. However, the development of laser protection technology is still slow compared to the rapid development of laser technology, and the gap between laser technology and laser protection technology is getting farther. Therefore, the research on laser protection materials at the present stage is just an urgent need in aspects such as industrial production, military defense, scientific and technical research, and the like. The current laser protective material reduces the light intensity and transmittance of laser due to the nonlinear optical response thereof, thereby limiting the laser protective material under certain power energy to show the protective capability.
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 polymer has the characteristics of high porosity, low skeleton density, designable structure, functionalized skeleton and high stability, so that the conjugated microporous polymer has wider application value.
In view of the advantages of the conjugated microporous polymer, the conjugated microporous polymer is applied to the field of laser protection materials, and the development of a novel conjugated microporous laser protection material with good service performance becomes a research hotspot in the field of laser protection and the field of material science at present.
Disclosure of Invention
In view of the above, the present invention provides a conjugated microporous poly phthalocyanine-graphene composite laser protection material and a preparation method thereof, and the composite laser protection material provided by the present invention has outstanding forgeability and thermal stability, and can effectively prevent aggregation of poly phthalocyanine while exhibiting a strong reverse saturation absorption effect.
The invention provides a conjugated microporous poly phthalocyanine-graphene composite laser protection material, which comprises graphene and conjugated microporous poly phthalocyanine adsorbed on the surface of the graphene;
the conjugated microporous poly phthalocyanine is composed of a repeating unit represented by formula (i) or a repeating unit represented by formula (ii); adjacent repeating units share a benzene ring to form a phenylene structure:
Figure BDA0002698604250000021
in the formula (ii), M is a metal atom.
Preferably, M is Pb or Sn.
The invention provides a preparation method of a conjugated microporous poly phthalocyanine-graphene composite laser protection material, which comprises the following steps:
ultrasonically dispersing 1,2,4, 5-tetracyanobenzene and graphene in a solvent, mixing the mixture with a catalyst, and then heating the mixture to react in a protective gas atmosphere to obtain a conjugated microporous poly-phthalocyanine-graphene composite laser protective material, wherein the conjugated microporous poly-phthalocyanine in the composite laser protective material is composed of a repeating unit shown in a formula (i);
or the like, or, alternatively,
the preparation method comprises the following steps of ultrasonically dispersing 1,2,4, 5-tetracyanobenzene and graphene in a solvent, mixing the mixture with a metal chloride and a catalyst, and heating the mixture in a protective gas atmosphere for reaction to obtain the conjugated microporous poly-phthalocyanine-graphene composite laser protective material, wherein the conjugated microporous poly-phthalocyanine in the composite laser protective material is composed of a repeating unit shown in a formula (ii).
Preferably, the mass ratio of the 1,2,4, 5-tetracyanobenzene to the graphene is (2-10): 1.
preferably, the time of ultrasonic dispersion is more than or equal to 20 min.
Preferably, the metal chloride is lead dichloride or stannous dichloride;
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 molar ratio of the catalyst to the 1,2,4, 5-tetracyanobenzene catalyst is (0.5-2): 1.
preferably, the solvent is ethylene glycol; the dosage ratio of the solvent to the 1,2,4, 5-tetracyanobenzene is 10 mL: (0.005-0.05) mmol.
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 as to obtain the conjugated microporous poly phthalocyanine-graphene composite laser protective material.
Compared with the prior art, the invention provides a conjugated microporous poly phthalocyanine-graphene composite laser protection material and a preparation method thereof. The composite laser protection material provided by the invention comprises graphene and conjugated microporous poly phthalocyanine adsorbed on the surface of the graphene; the conjugated microporous poly phthalocyanine is composed of a repeating unit represented by formula (i) or a repeating unit represented by formula (ii); adjacent repeating units share a benzene ring to form a phenylene structure; in the formula (ii), M is a metal atom. The conjugated microporous poly phthalocyanine-graphene composite laser protection material provided by the invention is an organic microporous polymer which takes graphene as a substrate and has a large delocalized pi electron conjugate structure, has outstanding forgeability and thermal stability, shows strong three-order nonlinear optical response so as to show a strong reverse saturation absorption effect, and meanwhile, poly phthalocyanine can be uniformly attached to the graphene to effectively prevent aggregation of the poly phthalocyanine. Experimental results show that the nonlinear absorption coefficient obtained by fitting the composite laser protection material provided by the invention is 1.84 multiplied by 10-7To 4.97X 10-7In between, can reach 0.4J/cm2The clipping threshold of (1).
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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 schematic structural diagram of surface conjugated microporous poly-phthalocyanine in a conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention;
FIG. 2 is a Fourier transform infrared (FT-IR) spectrum of a conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in example 1 of the present invention;
fig. 3 is a clipping threshold diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention;
fig. 4 is a Z-scan of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under 100 μ J laser incident energy;
fig. 5 is a Z-scan of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under 150 μ J laser incident energy;
fig. 6 is a Z-scan of the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 1 of the present invention under 200 μ J laser incident energy;
fig. 7 is a Z-scan of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under incident energy of 250 μ J laser;
fig. 8 is a schematic structural diagram of surface conjugated microporous poly-phthalocyanine in a conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention;
FIG. 9 is a Fourier transform infrared (FT-IR) spectrum of a laser protection material of conjugated microporous poly phthalocyanine-graphene provided in example 2 of the present invention;
fig. 10 is a clipping threshold diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention;
fig. 11 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protective material provided in embodiment 2 of the present invention under 100 μ J laser incident energy;
fig. 12 is a Z-scan of the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 2 of the present invention under 150 μ J laser incident energy;
fig. 13 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protective material provided in embodiment 2 of the present invention under 200 μ J laser incident energy;
fig. 14 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention under incident energy of 250 μ J laser;
fig. 15 is a schematic structural diagram of surface conjugated microporous poly-phthalocyanine in a conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention;
FIG. 16 is a Fourier transform infrared (FT-IR) spectrum of a conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in example 3 of the present invention;
fig. 17 is a clipping threshold diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention;
fig. 18 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protective material provided in embodiment 3 of the present invention under 100 μ J laser incident energy;
FIG. 19 is a Z-scan of the conjugated microporous poly (phthalocyanine) -graphene composite laser protection material provided in example 3 of the present invention at a laser incident energy of 150 μ J;
fig. 20 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention under 200 μ J laser incident energy;
fig. 21 is a Z scan of the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 3 of the present invention under incident energy of 250 μ J laser.
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 conjugated microporous poly phthalocyanine-graphene composite laser protection material, which comprises graphene and conjugated microporous poly phthalocyanine adsorbed on the surface of the graphene;
the conjugated microporous poly phthalocyanine is composed of a repeating unit represented by formula (i) or a repeating unit represented by formula (ii); adjacent repeating units share a benzene ring to form a phenylene structure:
Figure BDA0002698604250000051
in the formula (ii), M is a metal atom, preferably Pb or Sn.
In the composite laser protection material provided by the invention, the conjugated microporous poly phthalocyanine is composed of a repeating unit shown in a formula (i) or a repeating unit shown in a formula (ii), and 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) or formula (II):
Figure BDA0002698604250000061
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);
Figure BDA0002698604250000062
formula (II) shows a chemical structure consisting of 4 repeating units of formula (II), wherein the dotted line on the phenyl ring indicates that the chemical structure continues to be linked to other repeating units of formula (II).
The invention also provides a preparation method of the conjugated microporous poly phthalocyanine-graphene composite laser protection material, which comprises the following steps:
ultrasonically dispersing 1,2,4, 5-tetracyanobenzene and graphene in a solvent, mixing the mixture with a catalyst, and then heating the mixture to react in a protective gas atmosphere to obtain a conjugated microporous poly-phthalocyanine-graphene composite laser protective material, wherein the conjugated microporous poly-phthalocyanine in the composite laser protective material is composed of a repeating unit shown in a formula (i);
or the like, or, alternatively,
the preparation method comprises the following steps of ultrasonically dispersing 1,2,4, 5-tetracyanobenzene and graphene in a solvent, mixing the mixture with a metal chloride and a catalyst, and heating the mixture in a protective gas atmosphere for reaction to obtain the conjugated microporous poly-phthalocyanine-graphene composite laser protective material, wherein the conjugated microporous poly-phthalocyanine in the composite laser protective material is composed of a repeating unit shown in a formula (ii).
In the preparation method provided by the invention, 1,2,4, 5-tetracyanobenzene and graphene are ultrasonically dispersed in a solvent. Wherein, the graphene is preferably single-layer graphene or few-layer graphene with less than 5 layers, and the light transmittance of the graphene is preferably more than 90%; the solvent is preferably ethylene glycol; the mass ratio of the 1,2,4, 5-tetracyanobenzene to the graphene is preferably (2-10): 1, more preferably (3-7): 1, specifically 5: 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; the ultrasonic frequency of the ultrasonic dispersion is preferably 20-100 Hz, and specifically can be 50 Hz; the time of ultrasonic dispersion is preferably not less than 20min, more preferably 25-45 min, and particularly can be 30 min.
In the preparation method provided by the invention, after the ultrasonic dispersion is finished, the dispersed mixed solution is mixed with the catalyst or the catalyst and the metal chloride. Wherein, whether the metal chloride is added or not is determined whether the chemical structure of the conjugated microporous poly phthalocyanine in the final product to be prepared contains metal elements or not, and if not, the metal chloride is not added, and vice versa. In the present invention, the catalyst is preferably 1, 8-diazabicyclo [5,4,0] undec-7-ene; the molar ratio of the catalyst to the 1,2,4, 5-tetracyanobenzene catalyst is preferably (0.5-2): 1, more preferably (0.8 to 1.5): 1, specifically 1: 1; the metal chloride is preferably lead dichloride or stannous dichloride; the molar ratio of the metal chloride to the 1,2,4, 5-tetracyanobenzene is preferably (0.3-0.8): 1, more preferably (0.5 to 0.7): 1, specifically 0.6: 1.
In the preparation method provided by the invention, after the mixing is finished, the reaction is heated under the protective gas atmosphere. 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 conjugated microporous poly phthalocyanine-graphene composite laser protection material provided by the invention is an organic microporous polymer which takes graphene as a substrate and has a large delocalized pi electron conjugate structure, has outstanding forgeability and thermal stability, shows strong three-order nonlinear optical response so as to show a strong reverse saturation absorption effect, and meanwhile, poly phthalocyanine can be uniformly attached to the graphene to effectively prevent aggregation of the poly phthalocyanine.
Experimental results show that the nonlinear absorption coefficient obtained by fitting the composite laser protection material provided by the invention is 1.84 multiplied by 10-7To 4.97X 10-7In between, can reach 0.4J/cm2The clipping threshold of (1).
For the sake of clarity, the following examples are given in detail.
Example 1
The method comprises the following steps: adding 0.014mmol (2.5mg) of monomer 1,2,4, 5-tetracyanobenzene and 0.5mg of single-layer graphene (light transmittance is more than 90%) into a reaction vessel, adding 10mL of ethylene glycol solvent, dispersing in a 50Hz ultrasonic cleaner for 30 minutes, adding 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene serving as a catalyst, and reacting in a microwave synthesizer at 180 ℃ for 1 hour 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: and (3) Soxhlet extracting the product of the powder material obtained in the step two with methanol and acetone respectively for 1 day, and drying the solid dispersion in a vacuum drier at 100 ℃ for 12 hours to obtain the conjugated microporous poly phthalocyanine-graphene composite laser protective material.
The surface chemical structure of the conjugated microporous poly phthalocyanine-graphene composite prepared in this embodiment is shown in fig. 1, and fig. 1 is a schematic structural diagram of the surface conjugated microporous poly phthalocyanine in the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 1 of the present invention.
The result of fourier transform infrared spectroscopy (FT-IR) analysis of the conjugated microporous poly phthalocyanine-graphene composite laser protection material prepared in this example is shown in fig. 2, and fig. 2 is a fourier transform infrared spectroscopy (FT-IR) diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in example 1 of the present invention. As can be seen from fig. 2, the cyano peak in the conjugated microporous poly phthalocyanine-graphene composite laser protection material disappears.
The limiting threshold value of the conjugated microporous poly phthalocyanine-graphene composite laser protective material prepared in this example is analyzed, a testing laser light source is 532nm tunable nanosecond pulse laser, a Z scanning instrument is used for analyzing the nonlinear optical property of the laser, and the result is shown in fig. 3, where fig. 3 is the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in example 1 of the present inventionAnd (3) a limiting threshold map of the laser protection material. As can be seen from FIG. 3, the material can reach 0.5J/cm at a laser incident energy of 200 muJ2The clipping threshold of (1).
The results of nonlinear optical absorption coefficient analysis of the conjugated microporous poly phthalocyanine-graphene composite laser protective material prepared in this example are shown in fig. 4 to 7, FIG. 4 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under 100 μ J laser incident energy, FIG. 5 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under 150 μ J laser incident energy, FIG. 6 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under 200 μ J laser incident energy, fig. 7 is a Z scan of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 1 of the present invention under incident energy of 250 μ J laser. The nonlinear absorption coefficient of the material is 1.85 multiplied by 10 as can be obtained through the function fitting results in the graphs in FIGS. 4 to 7-7To 4.16X 10-7Third order non-linear polarizability x(3)At 2.77X 10-11To 6.24X 10-11esu.
Example 2
The method comprises the following steps: adding 0.014mmol (2.5mg) of monomer 1,2,4, 5-tetracyanobenzene and 0.5mg of single-layer graphene (light transmittance is more than 90%) into a reaction vessel, adding 10mL of ethylene glycol solvent, dispersing in a 50Hz ultrasonic cleaner for 30 minutes, then taking 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene as a catalyst and 0.0085mmol of metal chloride anhydrous lead dichloride, and reacting in a microwave synthesizer at 180 ℃ for 1 hour 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: and (3) 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 drier at the temperature of 80 ℃ for 12 hours to obtain the conjugated microporous poly phthalocyanine-graphene composite laser protective material.
Fig. 8 shows a surface chemical structure of the conjugated microporous poly phthalocyanine-graphene composite prepared in this embodiment, and fig. 8 is a schematic structural diagram of the surface conjugated microporous poly phthalocyanine in the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 2 of the present invention.
The result of fourier transform infrared spectroscopy (FT-IR) analysis of the conjugated microporous poly phthalocyanine-graphene composite laser protection material prepared in this example is shown in fig. 9, where fig. 9 is a fourier transform infrared spectroscopy (FT-IR) diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in example 2 of the present invention. As can be seen from fig. 9, the cyano peak in the conjugated microporous poly phthalocyanine-graphene composite laser protection material disappears.
The amplitude limiting threshold analysis is performed on the conjugated microporous poly phthalocyanine-graphene composite laser protection material prepared in this embodiment, the test conditions are the same as those in embodiment 1, and the result is shown in fig. 10, where fig. 10 is an amplitude limiting threshold diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention. As can be seen from FIG. 10, the material can reach 0.7J/cm at a laser incident energy of 200 μ J2The clipping threshold of (1).
The results of nonlinear optical absorption coefficient analysis of the conjugated microporous poly phthalocyanine-graphene composite laser protective material prepared in this example are shown in fig. 11-14, FIG. 11 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention under 100 μ J laser incident energy, FIG. 12 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention under 150 μ J laser incident energy, FIG. 13 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention under 200 μ J laser incident energy, fig. 14 is a Z scan of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 2 of the present invention under incident energy of 250 μ J laser. The nonlinear absorption coefficient of the material is 1.84 multiplied by 10 as can be obtained through the function fitting results in the graphs of FIGS. 11-14-7To 4.24X 10-7Third order non-linear poles corresponding toConversion rate χ(3)At 2.76X 10-11To 6.31X 10-11esu.
Example 3
The method comprises the following steps: adding 0.014mmol (2.5mg) of monomer 1,2,4, 5-tetracyanobenzene and 0.5mg of single-layer graphene (the light transmittance is more than 90%) into a reaction container, adding 10mL of glycol solvent, dispersing in a 50Hz ultrasonic cleaner for 30 minutes, then taking 0.014mmol of 1, 8-diazabicyclo [5,4,0] undec-7-ene as a catalyst and 0.0085mmol of metal chloride anhydrous stannous dichloride, and reacting in a microwave synthesizer at 180 ℃ for 1 hour 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: and (3) 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 drier at the temperature of 80 ℃ for 12 hours to obtain the conjugated microporous poly phthalocyanine-graphene composite laser protective material.
Fig. 15 shows a surface chemical structure of the conjugated microporous poly phthalocyanine-graphene composite prepared in this embodiment, where fig. 15 is a schematic structural diagram of a surface conjugated microporous poly phthalocyanine in the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 3 of the present invention.
The result of fourier transform infrared spectroscopy (FT-IR) analysis of the conjugated microporous poly phthalocyanine-graphene composite laser protection material prepared in this example is shown in fig. 16, and fig. 16 is a fourier transform infrared spectroscopy (FT-IR) diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in example 3 of the present invention. As can be seen from fig. 16, the cyano peak in the conjugated microporous poly phthalocyanine-graphene composite laser protection material disappears.
The amplitude limiting threshold analysis is performed on the conjugated microporous poly phthalocyanine-graphene composite laser protection material prepared in this embodiment, the test conditions are the same as those in embodiment 1, and the result is shown in fig. 17, where fig. 17 is an amplitude limiting threshold diagram of the conjugated microporous poly phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention. From FIG. 17As can be seen, the material can reach 0.4J/cm at the laser incidence energy of 200 muJ2The clipping threshold of (1).
The results of nonlinear optical absorption coefficient analysis of the conjugated microporous poly phthalocyanine-graphene composite laser protective material prepared in this example are shown in fig. 18-21, FIG. 18 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention under 100 μ J laser incident energy, FIG. 19 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention under 150 μ J laser incident energy, FIG. 20 is a Z-scan of the conjugated microporous poly-phthalocyanine-graphene composite laser protection material provided in embodiment 3 of the present invention under 200 μ J laser incident energy, fig. 21 is a Z scan of the conjugated microporous poly phthalocyanine-graphene composite laser protective material provided in embodiment 3 of the present invention under incident energy of 250 μ J laser. 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 18-21-7To 4.97X 10-7Third order non-linear polarizability x(3)At 3.22X 10-11To 7.45X 10-11esu.
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 conjugated microporous poly phthalocyanine-graphene composite laser protection material comprises graphene and conjugated microporous poly phthalocyanine adsorbed on the surface of the graphene;
the conjugated microporous poly phthalocyanine is composed of a repeating unit represented by formula (i) or a repeating unit represented by formula (ii); adjacent repeating units share a benzene ring to form a phenylene structure:
Figure FDA0002698604240000011
in the formula (ii), M is a metal atom.
2. The conjugated microporous poly phthalocyanine-graphene composite laser protection material of claim 1, wherein M is Pb or Sn.
3. The preparation method of the conjugated microporous poly phthalocyanine-graphene composite laser protection material of claim 1, comprising the following steps:
ultrasonically dispersing 1,2,4, 5-tetracyanobenzene and graphene in a solvent, mixing the mixture with a catalyst, and then heating the mixture to react in a protective gas atmosphere to obtain a conjugated microporous poly-phthalocyanine-graphene composite laser protective material, wherein the conjugated microporous poly-phthalocyanine in the composite laser protective material is composed of a repeating unit shown in a formula (i);
or the like, or, alternatively,
the preparation method comprises the following steps of ultrasonically dispersing 1,2,4, 5-tetracyanobenzene and graphene in a solvent, mixing the mixture with a metal chloride and a catalyst, and heating the mixture in a protective gas atmosphere for reaction to obtain the conjugated microporous poly-phthalocyanine-graphene composite laser protective material, wherein the conjugated microporous poly-phthalocyanine in the composite laser protective material is composed of a repeating unit shown in a formula (ii).
4. The preparation method according to claim 3, wherein the mass ratio of the 1,2,4, 5-tetracyanobenzene to the graphene is (2-10): 1.
5. the preparation method according to claim 3, wherein the time of ultrasonic dispersion is not less than 20 min.
6. The production method according to claim 3, wherein the metal chloride is lead dichloride or stannous dichloride;
the molar ratio of the 1,2,4, 5-tetracyanobenzene to the metal chloride is 1: (0.3-0.8).
7. The method of claim 3, wherein the catalyst is 1, 8-diazabicyclo [5,4,0] undec-7-ene; the molar ratio of the catalyst to the 1,2,4, 5-tetracyanobenzene catalyst is (0.5-2): 1.
8. the production method according to claim 3, wherein the solvent is ethylene glycol; the dosage ratio of the solvent to the 1,2,4, 5-tetracyanobenzene is 10 mL: (0.005-0.05) mmol.
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 as to obtain the conjugated microporous poly phthalocyanine-graphene composite laser protective material.
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CN105778090A (en) * 2016-05-19 2016-07-20 吉林大学 Hyperbranched metal phthalocyanine oligomer containing imide structure and preparation method thereof
CN107683305A (en) * 2015-05-26 2018-02-09 联邦科学与工业研究组织 Microporous polymer compositions
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
CN109678143A (en) * 2019-03-04 2019-04-26 吉林大学 Hyperbranched rare earth phthalocyanine modification graphene oxide and its preparation and the application in lasing safety

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107683305A (en) * 2015-05-26 2018-02-09 联邦科学与工业研究组织 Microporous polymer compositions
CN105778090A (en) * 2016-05-19 2016-07-20 吉林大学 Hyperbranched metal phthalocyanine oligomer containing imide structure and preparation method thereof
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
CN109678143A (en) * 2019-03-04 2019-04-26 吉林大学 Hyperbranched rare earth phthalocyanine modification graphene oxide and its preparation and the application in lasing safety

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