CN112159519B - Porous poly-phthalocyanine laser protection material with carbon bridging and preparation method thereof - Google Patents

Porous poly-phthalocyanine laser protection material with carbon bridging and preparation method thereof Download PDF

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CN112159519B
CN112159519B CN202011016443.1A CN202011016443A CN112159519B CN 112159519 B CN112159519 B CN 112159519B CN 202011016443 A CN202011016443 A CN 202011016443A CN 112159519 B CN112159519 B CN 112159519B
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phthalocyanine
laser
porous
protective material
carbon
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CN112159519A (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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    • 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
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    • 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

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Abstract

The invention belongs to the field of laser protection materials, and particularly relates to a porous poly-phthalocyanine laser protection material with carbon bridging and a preparation method thereof. The porous poly-phthalocyanine laser protective material provided by the invention is composed of a repeating unit shown in a formula (i) or a repeating unit shown in a formula (ii), each repeating unit is provided with 4 bonding sites, and adjacent repeating units are bridged through carbon; in the formula (ii), M is a metal atom. The porous poly-phthalocyanine laser protection material provided by the invention is a porous organic polymer with a highly delocalized pi electron conjugated structure, and can limit the strength of nanosecond laser pulse through an excited state absorption process while keeping excellent characteristics of high porosity, low skeleton density, designable and processable structure and the like, thereby showing strong third-order nonlinear optical response and laser protection effect.

Description

Porous poly-phthalocyanine laser protection material with carbon bridging and preparation method thereof
Technical Field
The invention belongs to the field of laser protection materials, and particularly relates to a porous poly-phthalocyanine laser protection material with carbon bridging and a preparation method thereof.
Background
The laser has the characteristics of good monochromaticity, high collimation and brightness, good coherence and the like, so that the laser detector is rapidly developed. Laser detectors include laser rangefinders, laser radars, laser guidance, and laser counterweapons, among others. However, with the development of broadband tunable laser detectors, the laser has a larger spectral range and stronger energy, which has great threat to both our sensing devices and human body, and the most important damage of the laser to the human body is damage to the eye, which can penetrate through the cornea, crystalline lens and vitreous body and be absorbed by the retina and choroid in a large amount. Due to the focusing action of the eye on light, the energy density on the retina can be hundreds of thousands of times higher than that at the cornea, possibly causing serious permanent damage to the retina. Therefore, the laser protection technology must be researched to protect the laser.
The laser protection material based on the nonlinear optical principle has the advantages of high linear transmittance, high nonlinear coefficient, wide protection waveband and the like, has obvious advantages for protecting short-pulse variable-frequency laser, and is a known photoelectric protection material with the most development potential. Common nonlinear optical limiting materials include small organic molecules, carbene compounds, organometallic complexes, liquid crystal materials, inorganic metal cluster compounds, and the like. These materials all present potential application values, but at the same time have certain disadvantages.
The porous material has the characteristics of stability, firmness, high porosity, simple preparation method and the like, and can be greatly applied to the fields of adsorption separation, catalytic energy storage, photoluminescence and the like. Porous organic polymers are a new class of porous materials that have emerged in recent decades. Compared with inorganic porous materials (molecular sieves) and organic-inorganic hybrid porous Materials (MOFs), the porous organic polymer has the characteristics of high porosity and low skeleton density, and meanwhile, the structure can be designed and the skeleton can be functionalized. These characteristics make the porous organic polymer have wider application value and attract much attention in the field of material science.
In view of the advantages of porous organic polymers, the porous organic polymers are applied to the field of laser protection materials, and the development of novel porous organic polymer materials with good laser protection effects 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 aims to provide a porous poly-phthalocyanine laser protection material with carbon bridging and a preparation method thereof.
The invention provides a porous poly-phthalocyanine laser protective material with a carbon bridge, which is composed of a repeating unit shown as a formula (i) or a repeating unit shown as a formula (ii), wherein each repeating unit has 4 bonding sites, and adjacent repeating units are bridged by carbon:
Figure BDA0002699236850000021
in the formula (ii), M is a metal atom.
Preferably, M is Sn or Pb.
The invention provides a preparation method of a porous poly phthalocyanine laser protective material with carbon bridging, which comprises the following steps:
in a protective gas atmosphere, phthalocyanine monomers, a bridging agent and a catalyst are mixed and reacted to obtain a porous poly-phthalocyanine laser protective material with carbon bridging;
the phthalocyanine monomer is phthalocyanine or metal phthalocyanine compound.
Preferably, the bridging agent is dichloromethane; the catalyst is aluminum trichloride.
Preferably, the dosage ratio of the phthalocyanine monomer to the bridging agent is 1 mmol: (1000-5000) mL.
Preferably, the molar ratio of the phthalocyanine monomer to the catalyst is 1: (20 to 50).
Preferably, the metal phthalocyanine compound is tin dichlorophthalocyanine or lead phthalocyanine.
Preferably, the temperature of the mixing reaction is 0-90 ℃; the mixing reaction time is 30-100 h.
Preferably, the specific process of the mixing reaction comprises:
firstly, mixing and reacting for 2-6 h at 0-10 ℃, then mixing and reacting for 6-12 h at 25-35 ℃, then mixing and reacting for 8-16 h at 35-45 ℃, then mixing and reacting for 8-16 h at 55-65 ℃, and finally mixing and reacting for 18-36 h at 75-85 ℃.
Preferably, the method further comprises the following steps:
and after the mixing reaction is finished, carrying out cold soaking on the obtained reaction product in a hydrochloric acid solution, and then washing, extracting impurities and drying to obtain the porous poly-phthalocyanine laser protective material with carbon bridging.
Compared with the prior art, the invention provides a porous poly-phthalocyanine laser protective material with carbon bridging and a preparation method thereof. The porous poly-phthalocyanine laser protective material provided by the invention is composed of a repeating unit shown in a formula (i) or a repeating unit shown in a formula (ii), each repeating unit is provided with 4 bonding sites, and adjacent repeating units are bridged through carbon; in the formula (ii), M is a metal atom. The porous poly-phthalocyanine laser protection material provided by the invention is a porous organic polymer with a highly delocalized pi electron conjugated structure, and can limit the strength of nanosecond laser pulse through an excited state absorption process while keeping excellent characteristics of high porosity, low skeleton density, designable and processable structure and the like, thereby showing strong third-order nonlinear optical response and laser protection effect. Experimental results show that the amplitude limiting threshold of the porous poly-phthalocyanine laser protective material provided by the invention can reach 0.37J/cm2Fitting the resulting nonlinear absorption coefficient to 1.72X 10-7To 4.03X 10-7In the meantime.
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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 Fourier transform infrared (FT-IR) spectrum of a porous polyphthalocyanine laser protective material with carbon bridges provided in example 1 of the present invention;
FIG. 2 is a powder diffraction Pattern (PXRD) of a porous polyphthalocyanine-based laser protective material having carbon bridges provided in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of a porous poly-phthalocyanine-based laser protective material with carbon bridges provided in example 1 of the present invention;
FIG. 4 is a scanning electron microscopy spectroscopy analysis chart of the porous poly-phthalocyanine laser protective material with carbon bridging provided in example 1 of the present invention;
FIG. 5 shows N-type porous poly-phthalocyanine laser protective material with carbon bridge in example 1 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 6 is a distribution diagram of the pore diameters of micropores of a porous poly-phthalocyanine laser protective material with carbon bridges provided in example 1 of the present invention;
FIG. 7 is a graph of clipping threshold of porous polyphthalocyanine laser protective material with carbon bridges provided in example 1 of the present invention;
FIG. 8 is a Z-scan of a porous polyphthalocyanine laser protective material with carbon bridges under 100 muJ laser incident energy provided in example 1 of the present invention;
FIG. 9 is a Z-scan of a porous poly-phthalocyanine-based laser protective material with carbon bridges under 150 μ J laser incident energy provided in example 1 of the present invention;
FIG. 10 is a Z-scan of a porous polyphthalocyanine-based laser protective material with carbon bridges under 200 muJ laser incident energy provided in example 1 of the present invention;
FIG. 11 is a Z-scan of a porous poly-phthalocyanine-based laser protective material with carbon bridges under incident energy of a laser of 250 μ J, provided in example 1 of the present invention;
FIG. 12 is a Fourier transform infrared (FT-IR) spectrum of a porous polyphthalocyanine laser protective material having carbon bridges provided in example 2 of the present invention;
FIG. 13 is a powder diffraction (PXRD) pattern of a porous polyphthalocyanine-based laser protective material having carbon bridges provided in example 2 of the present invention;
FIG. 14 is a scanning electron microscope image of a porous poly-phthalocyanine-based laser protective material with carbon bridges provided in example 2 of the present invention;
FIG. 15 is a scanning electron microscopy spectroscopy analysis chart of the porous poly-phthalocyanine laser protective material with carbon bridging provided in example 2 of the present invention;
FIG. 16 shows N-type porous poly-phthalocyanine laser protective material with carbon bridge in example 2 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 17 is a distribution diagram of the pore diameters of micropores of a porous poly-phthalocyanine laser protective material with carbon bridges provided in example 2 of the present invention;
FIG. 18 is a graph of clipping thresholds for porous polyphthalocyanine-based laser protective materials having carbon bridges provided in example 2 of the present invention;
FIG. 19 is a Z-scan of a porous polyphthalocyanine laser protective material with carbon bridges under 100 muJ laser incident energy provided in example 2 of the present invention;
FIG. 20 is a Z-scan of a porous polyphthalocyanine-based laser protective material with carbon bridges under 150 μ J laser incident energy provided in example 2 of the present invention;
FIG. 21 is a Z-scan of a porous polyphthalocyanine-based laser protective material with carbon bridges under 200 muJ laser incident energy provided in example 2 of the present invention;
FIG. 22 is a Z-scan of a porous polyphthalocyanine-based laser protective material with carbon bridges under incident energy of a laser at 250 μ J, provided in example 2 of the present invention;
FIG. 23 is a Fourier transform infrared (FT-IR) spectrum of a porous polyphthalocyanine-based laser protective material having carbon bridges provided in example 3 of the present invention;
FIG. 24 is a powder diffraction (PXRD) pattern of a porous polyphthalocyanine-based laser protective material having carbon bridges provided in example 3 of the present invention;
FIG. 25 is a scanning electron microscope image of a porous poly-phthalocyanine-based laser protective material with carbon bridges provided in example 3 of the present invention;
FIG. 26 is a scanning electron microscopy spectroscopy analysis chart of a porous poly-phthalocyanine laser protective material with carbon bridges provided in example 3 of the invention;
FIG. 27 shows N of porous poly-phthalocyanine based laser protectant material with carbon bridge according to example 3 of the present invention2Adsorption-desorption isotherm diagram;
FIG. 28 is a distribution diagram of the pore size of micropores of a porous poly-phthalocyanine-based laser protective material with carbon bridges provided in example 3 of the present invention;
FIG. 29 is a graph of clipping thresholds for porous polyphthalocyanine-based laser protective materials having carbon bridges provided in example 3 of the present invention;
FIG. 30 is a Z-scan of a porous polyphthalocyanine-based laser protective material with carbon bridges under 100 μ J laser incident energy provided in example 3 of the present invention;
FIG. 31 is a Z-scan of a porous polyphthalocyanine-based laser protective material with carbon bridges under 150 μ J laser incident energy provided in example 3 of the present invention;
FIG. 32 is a Z-scan of a porous polyphthalocyanine-based laser protective material having a carbon bridge at 200 μ J laser incident energy as provided in example 3 of the present invention;
FIG. 33 is a Z-scan of a porous polyphthalocyanine laser protective material with carbon bridges under incident energy of a laser at 250 μ J, provided in example 3 of the present invention.
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 porous poly-phthalocyanine laser protective material with a carbon bridge, which is composed of a repeating unit shown as a formula (i) or a repeating unit shown as a formula (ii), wherein each repeating unit has 4 bonding sites, and adjacent repeating units are bridged by carbon:
Figure BDA0002699236850000061
in the formula (ii), M is a metal atom, preferably Sn or Pb.
The porous poly-phthalocyanine laser protection material provided by the invention is formed by bridging phthalocyanine repeating units, each repeating unit is provided with 4 bonding sites, and the bonding sites of adjacent repeating units are bridged by carbon. In the invention, the specific structure of the phthalocyanine repeating unit is shown as formula (I) and formula (ii), wherein the chemical structure of the porous poly-phthalocyanine laser protective material formed by the repeating unit shown as formula (I) is shown as formula (I):
Figure BDA0002699236850000062
in formula (I), the central body portion is a repeat unit of formula (I) having 4 bonding sites through "-CH2- "bonds are linked to other repeating units of formula (i), i.e. carbon bridges are formed; "-" is a simplified representation of the structure of the other part of the polymer linked to formula (i), the actual structure of the simplified part being a porous polymer structure consisting of a plurality of carbon bridges of the repeating unit (i).
In the invention, the chemical structure of the porous poly phthalocyanine laser protective material composed of the repeating units shown in the formula (II) is shown in the formula (II):
Figure BDA0002699236850000071
in formula (II), the central body portion is a repeat unit of formula (II) having 4 bonding sites through the "-CH2- "bonds are linked to other repeating units of formula (ii), i.e.carbon bridges are formed; "-" is a simplified representation of the structure of the other part of the polymer linked to the formula (ii), and the actual structure of the simplified part is a porous polymer structure composed of a plurality of carbon bridges of the repeating unit (ii).
The invention also provides a preparation method of the porous poly phthalocyanine laser protective material with carbon bridging in the technical scheme, which comprises the following steps:
in a protective gas atmosphere, phthalocyanine monomers, a bridging agent and a catalyst are mixed and reacted to obtain a porous poly-phthalocyanine laser protective material with carbon bridging;
the phthalocyanine monomer is phthalocyanine or metal phthalocyanine compound.
In the preparation method provided by the invention, the phthalocyanine monomer, the bridging agent and the catalyst are directly mixed and reacted in a protective gas atmosphere to obtain the porous poly-phthalocyanine laser protective material provided by the invention. Wherein the protective gas atmosphere is preferably nitrogen; the phthalocyanine monomer is phthalocyanine or metal phthalocyanine compound; the metal phthalocyanine compound is dichloro phthalocyanine tin or phthalocyanine lead; the bridging agent is preferably methylene chloride (both as bridging agent and reaction solvent); the catalyst is preferably aluminum trichloride; the dosage ratio of the phthalocyanine monomer to the bridging agent is preferably 1 mmol: (1000-5000) mL, more preferably 1 mmol: (3000-4000) mL, specifically 0.00225 mmol: 8 mL; the molar ratio of the phthalocyanine monomer to the catalyst is preferably 1: (20 to 50), more preferably 1: (30-35), specifically 1: 32; the mixing reaction temperature is preferably 0-90 deg.C, specifically 0 deg.C, 5 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 55 deg.C, 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C; the mixing reaction time is preferably 30-100 h, and specifically can be 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, 75h, 80h, 85h, 90h, 95h or 100 h.
In the preparation method provided by the invention, the specific process of the mixing reaction preferably comprises the following steps:
mixing and reacting at a first temperature for a first time, then mixing and reacting at a second temperature for a second time, then mixing and reacting at a third temperature for a third time, then mixing and reacting at a fourth temperature for a fourth time, and finally mixing and reacting at a fifth temperature for a fifth time. Wherein the first temperature is preferably 0-10 ℃, and specifically can be 0 ℃, 5 ℃ or 10 ℃; the first time is preferably 2-6 h, and specifically can be 2h, 4h or 6 h; the second temperature is preferably 25-35 ℃, and specifically can be 25 ℃, 30 ℃ or 35 ℃; the second time is preferably 6-12 h, and specifically can be 6h, 8h, 10h or 12 h; the third temperature is preferably 35-45 ℃, and specifically can be 35 ℃, 40 ℃ or 45 ℃; the third time is preferably 8-16 h, and specifically can be 8h, 10h, 12h, 14h or 16 h; the fourth temperature is preferably 55-65 ℃, and specifically can be 55 ℃, 60 ℃ or 65 ℃; the fourth time is preferably 8-16 h, and specifically can be 8h, 10h, 12h, 14h or 16 h; the fifth temperature is preferably 75-85 ℃, and specifically can be 75 ℃, 80 ℃ or 85 ℃; the fifth time is preferably 18-36 h, and specifically can be 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h or 36 h.
In the preparation method provided by the present invention, after the mixing reaction is finished, the obtained reaction product is subjected to post-treatment, and the post-treatment process preferably includes: and (3) carrying out cold soaking on the obtained reaction product in a hydrochloric acid solution, and then washing, extracting impurities and drying to obtain the porous poly-phthalocyanine laser protective material with carbon bridging. The hydrochloric acid solution is prepared by mixing concentrated hydrochloric acid and water, the concentration of the concentrated hydrochloric acid is 37 wt%, and the volume ratio of the concentrated hydrochloric acid to the water is (1-5): 1, specifically 2: 1; the temperature of the cold soaking is preferably 15-35 ℃, and specifically can be 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃; the time of the cold soaking is preferably 6-24 h, and specifically can be 6h, 9h, 12h, 15h, 18h, 21h or 24 h; the washing mode is preferably water washing and ethanol washing respectively; the impurity extraction mode is preferably Soxhlet extraction of the washed product by using ethanol, 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 porous poly-phthalocyanine laser protection material provided by the invention is a porous organic polymer with a highly delocalized pi electron conjugated structure, and can limit the strength of nanosecond laser pulse through an excited state absorption process while keeping excellent characteristics of high porosity, low skeleton density, designable and processable structure and the like, thereby showing strong third-order nonlinear optical response and laser protection effect.
Experimental results show that the amplitude limiting threshold of the porous poly-phthalocyanine laser protective material provided by the invention can reach 0.37J/cm2Fitting the resulting nonlinear absorption coefficient to 1.72X 10-7To 4.03X 10-7In the meantime.
For the sake of clarity, the following examples are given in detail.
Example 1
The method comprises the following steps: putting 0.00225mmol of monomer phthalocyanine into a reaction vessel, then adding 8mL of dichloromethane solvent and 0.072mmol of anhydrous aluminum trichloride as catalysts into the reaction vessel under a nitrogen environment, keeping the reaction system under the nitrogen environment, stirring for 4 hours at 0 ℃, stirring for 8 hours at 30 ℃, stirring for 12 hours at 40 ℃, stirring for 12 hours at 60 ℃, and stirring for 24 hours at 80 ℃ to obtain a porous polymer;
step two: firstly, the porous polymer obtained in the step one is treated with HCl-H2Cold O-leaching, in which HCl (37 wt%) and H2The volume ratio of O is 2:1, the cold soaking temperature is 25 ℃, and the cold soaking time is 12 hours; then washing with water and ethanol respectively to remove soluble inorganic salt and organic matters to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two by using ethanol for 1 day, and drying the solid dispersion in a vacuum dryer at 100 ℃ for 24 hours to obtain the porous poly phthalocyanine laser protective material with carbon bridging, wherein the chemical structure of the porous poly phthalocyanine laser protective material is shown as the formula (I):
Figure BDA0002699236850000091
fourier transform infrared spectroscopy (FT-IR) analysis was performed on the porous poly-phthalocyanine laser protective material prepared in the example, and the result is shown in FIG. 1, wherein FIG. 1 is a Fourier transform infrared spectroscopy (FT-IR) diagram of the porous poly-phthalocyanine laser protective material with carbon bridges provided in the example 1 of the present invention.
The powder diffraction (PXRD) analysis of the porous laser protective material of the polyphthalocyanine type prepared in this example is shown in fig. 2, and fig. 2 is a powder diffraction (PXRD) diagram of the porous laser protective material of the polyphthalocyanine type with carbon bridge provided in example 1 of the present invention. As can be seen from fig. 2, the material has some crystallinity.
The scanning electron microscope image observation of the porous poly-phthalocyanine laser protective material prepared in this example is performed, and the result is shown in fig. 3, and fig. 3 is the scanning electron microscope image of the porous poly-phthalocyanine laser protective material with carbon bridging provided in example 1 of the present invention. As can be seen in fig. 3, the material is formed by the aggregation of fine grains.
Scanning electron microscope energy spectrum analysis is performed on the porous poly-phthalocyanine laser protective material prepared in this example, and the result is shown in fig. 4, fig. 4 is a scanning electron microscope energy spectrum analysis graph of the porous poly-phthalocyanine laser protective material with carbon bridging provided in example 1 of the present invention, wherein (a) is an electron diffraction scan graph, (b) is a distribution graph of C element, (C) is a distribution graph of N element, and (d) is a distribution graph of Cl 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 porous poly-phthalocyanine laser protective material prepared in this example is shown in fig. 5, and fig. 5 is the N of the porous poly-phthalocyanine laser protective material with carbon bridge 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 10.6m2/g。
The pore size distribution of the porous laser protective material of poly phthalocyanine prepared in this example is analyzed, and the result is shown in fig. 6, where fig. 6 is a distribution diagram of the pore sizes of the micropores of the porous laser protective material of poly phthalocyanine with carbon bridge provided in example 1 of the present invention. As can be seen from FIG. 6, the average pore diameter of this material was 3 nm.
The amplitude limiting threshold value of the porous poly-phthalocyanine laser protective material prepared in this embodiment is analyzed, a testing laser light source is tunable nanosecond pulse laser with a wavelength of 532nm, nonlinear optical properties of the porous poly-phthalocyanine laser protective material are analyzed by a Z-scan instrument, and the result is shown in fig. 7, where fig. 7 is an amplitude limiting threshold value graph of the porous poly-phthalocyanine laser protective material with carbon bridging provided in embodiment 1 of the present invention. As can be seen from FIG. 7, the material can reach 0.5J/cm at a laser incident energy of 200 muJ2The clipping threshold of (1).
The nonlinear absorption coefficient analysis of the porous poly-phthalocyanine laser protective material prepared in this example is shown in fig. 8-11, fig. 8 is a Z-scan of the porous poly-phthalocyanine laser protective material with carbon bridge in 100 μ J laser incident energy provided in example 1 of the present invention, and fig. 9 is a Z-scan of the porous poly-phthalocyanine laser protective material with carbon bridge in example 1 of the present inventionThe Z scan of the porous poly-phthalocyanine laser protective material with the carbon bridge under the incident energy of the laser with 150 muJ is shown in FIG. 10, which is the Z scan of the porous poly-phthalocyanine laser protective material with the carbon bridge under the incident energy of the laser with 200 muJ provided in the embodiment 1 of the invention, and FIG. 11 is the Z scan of the porous poly-phthalocyanine laser protective material with the carbon bridge under the incident energy of the laser with 250 muJ provided in the embodiment 1 of the invention. 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 4.03X 10-7Third order non-linear polarizability x(3)At 3.38X 10-11To 6.04X 10-11esu.
Example 2
The method comprises the following steps: putting 0.00225mmol of monomer dichlorophthalocyanine tin into a reaction vessel, then adding 8mL of dichloromethane solvent and 0.072mmol of anhydrous aluminum trichloride as catalysts into the reaction vessel under a nitrogen environment, keeping the reaction system under the nitrogen environment to stir at 0 ℃ for 4 hours, at 30 ℃ for 8 hours, at 40 ℃ for 12 hours, at 60 ℃ for 12 hours, at 80 ℃ for 24 hours, and obtaining the porous polymer;
step two: firstly, the porous polymer obtained in the step one is treated with HCl-H2Cold O-leaching, in which HCl (37 wt%) and H2The volume ratio of O is 2:1, the cold soaking temperature is 25 ℃, and the cold soaking time is 12 hours; then washing with water and ethanol respectively to remove soluble inorganic salt and organic matters to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two with ethanol for 2 days, and drying the solid dispersion in a vacuum dryer at 80 ℃ for 24 hours to obtain the porous poly phthalocyanine laser protective material with carbon bridging, wherein the chemical structure of the porous poly phthalocyanine laser protective material is shown as a formula (II-1):
Figure BDA0002699236850000111
fourier transform infrared spectroscopy (FT-IR) analysis was performed on the porous poly-phthalocyanine laser protective material prepared in the example, and the result is shown in FIG. 12, wherein FIG. 12 is a Fourier transform infrared spectroscopy (FT-IR) diagram of the porous poly-phthalocyanine laser protective material with carbon bridges provided in example 2 of the present invention.
The powder diffraction (PXRD) analysis of the porous laser protective material of the polyphthalocyanine type prepared in this example is shown in fig. 13, and fig. 13 is a powder diffraction (PXRD) diagram of the porous laser protective material of the polyphthalocyanine type with carbon bridge provided in example 2 of the present invention. As can be seen from fig. 13, the material has some crystallinity.
The scanning electron microscope image observation of the porous poly-phthalocyanine laser protective material prepared in this example is performed, and the result is shown in fig. 14, and fig. 14 is the scanning electron microscope image of the porous poly-phthalocyanine laser protective material with carbon bridging provided in example 2 of the present invention. As can be seen in fig. 14, the material is formed by the aggregation of fine grains.
Scanning electron microscope energy spectrum analysis is performed on the porous polyphthalocyanine laser protection material prepared in this example, and as a result, as shown in fig. 15, fig. 15 is a scanning electron microscope energy spectrum analysis graph of the porous polyphthalocyanine laser protection material with carbon bridge provided in example 2 of the present invention, wherein (a) is an electron diffraction scanning graph of the material, (b) is a C element distribution graph, (C) is an N element distribution graph, (d) is a Cl element distribution graph, and (e) is an Sn element distribution graph. 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 porous poly-phthalocyanine laser protective material prepared in this example is shown in fig. 16, and fig. 16 is the N of the porous poly-phthalocyanine laser protective material with carbon bridge 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 was 22.4m2/g。
The pore size distribution of the porous laser protective material of poly phthalocyanine prepared in this example is analyzed, and the result is shown in fig. 17, where fig. 17 is a micropore size distribution diagram of the porous laser protective material of poly phthalocyanine with carbon bridge provided in example 2 of the present invention. As can be seen from FIG. 17, the average pore diameter of this material was 1.9 nm.
The porous poly phthalocyanine laser protective 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. 18, where fig. 18 is an amplitude limiting threshold diagram of the porous poly phthalocyanine laser protective material with carbon bridge provided in example 2 of the present invention. As can be seen from FIG. 18, the material can reach 0.3J/cm at a laser incident energy of 200 μ J2The clipping threshold of (1).
The nonlinear absorption coefficient analysis of the porous polyphthalocyanine laser protective material prepared in this embodiment is performed, and the result is shown in fig. 19-22, where fig. 19 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 2 of the present invention under 100 μ J laser incident energy, fig. 20 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 2 of the present invention under 150 μ J laser incident energy, fig. 21 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 2 of the present invention under 200 μ J laser incident energy, and fig. 22 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 2 of the present invention under 250 μ J laser incident energy. The nonlinear absorption coefficient of the material is 1.72 multiplied by 10 as can be obtained through the function fitting results in the graphs of 19-22-7To 3.21X 10-7Third order non-linear polarizability x(3)At 2.58X 10-11To 4.81X 10-11esu.
Example 3
The method comprises the following steps: putting 0.00225mmol of monomer lead phthalocyanine into a reaction vessel, then adding 8mL of dichloromethane solvent and 0.072mmol of anhydrous aluminum trichloride as catalysts into the reaction vessel under a nitrogen environment, keeping the reaction system under the nitrogen environment to be sequentially stirred at 0 ℃ for 4 hours, at 30 ℃ for 8 hours, at 40 ℃ for 12 hours, at 60 ℃ for 12 hours, at 80 ℃ for 24 hours, and obtaining the porous polymer;
step two: firstly, the porous polymer obtained in the step one is treated with HCl-H2Cold O-leaching, in which HCl (37 wt%) and H2Volume ratio of O2: 1, temperature of cold soakingThe temperature is 25 ℃, and the cold soaking time is 12 hours; then washing with water and ethanol respectively to remove soluble inorganic salt and organic matters to obtain a powder material;
step three: soxhlet extracting the product of the powder material obtained in the step two with ethanol for 2 days, and drying the solid dispersion in a vacuum dryer at 90 ℃ for 24 hours to obtain the porous poly phthalocyanine laser protective material with carbon bridging, wherein the chemical structure of the porous poly phthalocyanine laser protective material is shown as a formula (II-2):
Figure BDA0002699236850000131
fourier transform infrared spectroscopy (FT-IR) analysis was performed on the porous poly-phthalocyanine laser protective material prepared in the example, and the result is shown in FIG. 23, and FIG. 23 is a Fourier transform infrared spectroscopy (FT-IR) diagram of the porous poly-phthalocyanine laser protective material with carbon bridges provided in example 3 of the present invention.
The powder diffraction (PXRD) analysis of the porous laser protective material of the polyphthalocyanine type prepared in this example is shown in fig. 24, and fig. 24 is the powder diffraction (PXRD) diagram of the porous laser protective material of the polyphthalocyanine type with carbon bridge provided in example 3 of the present invention. As can be seen from fig. 24, the material has some crystallinity.
The scanning electron microscope image observation of the porous poly-phthalocyanine laser protective material prepared in this example is performed, and the result is shown in fig. 25, and fig. 25 is the scanning electron microscope image of the porous poly-phthalocyanine laser protective material with carbon bridging provided in example 3 of the present invention. As can be seen in fig. 25, the material is formed by the aggregation of fine grains.
Scanning electron microscope energy spectrum analysis is performed on the porous poly-phthalocyanine laser protective material prepared in the embodiment, and as a result, as shown in fig. 26, fig. 26 is a scanning electron microscope energy spectrum analysis graph of the porous poly-phthalocyanine laser protective material with carbon bridging provided in embodiment 3 of the present invention, wherein (a) is an electron diffraction scan graph of all elements of the material, (b) is a distribution graph of C element, (C) is a distribution graph of N element, and (d) is a distribution graph of Pb element. 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 porous poly-phthalocyanine laser protective material prepared in this example is shown in fig. 27, and fig. 27 is the N of the porous poly-phthalocyanine laser protective material with carbon bridge 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 47.6m2/g。
The pore size distribution of the porous laser protective material of poly phthalocyanine prepared in this example is analyzed, and the result is shown in fig. 28, where fig. 28 is a distribution diagram of the pore sizes of the micropores of the porous laser protective material of poly phthalocyanine with carbon bridge provided in example 3 of the present invention. As can be seen from FIG. 28, the average pore diameter of this material was 11 nm.
The porous poly phthalocyanine laser protective 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. 29, where fig. 29 is an amplitude limiting threshold graph of the porous poly phthalocyanine laser protective material with carbon bridge provided in example 3 of the present invention. As can be seen from FIG. 29, the material reached 0.5J/cm at a laser incident energy of 200. mu.J2The clipping threshold of (1).
The nonlinear absorption coefficient analysis of the porous polyphthalocyanine laser protective material prepared in this embodiment is performed, and the result is shown in fig. 30-33, where fig. 30 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 3 of the present invention under 100 μ J laser incident energy, fig. 31 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 3 of the present invention under 150 μ J laser incident energy, fig. 32 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 3 of the present invention under 200 μ J laser incident energy, and fig. 33 is a Z scan of the porous polyphthalocyanine laser protective material with carbon bridge provided in embodiment 3 of the present invention under 250 μ J laser incident energy. The nonlinear absorption coefficient of the material is 2.11 multiplied by 10 as can be obtained through the function fitting results in the graphs of 30-33-7To 3.91X 10-7Third order non-linear polarizability x(3)At 3.17X 10-11To 5.87X 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 (9)

1. A preparation method of a porous poly-phthalocyanine laser protective material with carbon bridges comprises the following steps:
in a protective gas atmosphere, phthalocyanine monomers, a bridging agent and a catalyst are mixed and reacted to obtain a porous poly-phthalocyanine laser protective material with carbon bridging;
the phthalocyanine monomer is phthalocyanine or metal phthalocyanine compound; the bridging agent is dichloromethane;
the porous poly-phthalocyanine laser protective material with the carbon bridge is composed of a repeating unit shown as a formula (i) or a repeating unit shown as a formula (ii), each repeating unit has 4 bonding sites, and adjacent repeating units are bridged through carbon:
Figure FDA0003053705070000011
in the formula (ii), M is a metal atom.
2. The method according to claim 1, wherein M is Sn or Pb.
3. The method of claim 1, wherein the catalyst is aluminum trichloride.
4. The method according to claim 1, wherein the ratio of the phthalocyanine monomer to the bridging agent is 1 mmol: (1000-5000) mL.
5. The method according to claim 1, wherein the molar ratio of the phthalocyanine-based monomer to the catalyst is 1: (20 to 50).
6. The method according to claim 1, wherein the metal phthalocyanine compound is tin dichlorophthalocyanine or lead phthalocyanine.
7. The preparation method according to claim 1, wherein the temperature of the mixing reaction is 0 to 90 ℃; the mixing reaction time is 30-100 h.
8. The preparation method according to claim 1, wherein the mixing reaction comprises the following specific processes:
firstly, mixing and reacting for 2-6 h at 0-10 ℃, then mixing and reacting for 6-12 h at 25-35 ℃, then mixing and reacting for 8-16 h at 35-45 ℃, then mixing and reacting for 8-16 h at 55-65 ℃, and finally mixing and reacting for 18-36 h at 75-85 ℃.
9. The method according to any one of claims 1 to 8, further comprising:
and after the mixing reaction is finished, carrying out cold soaking on the obtained reaction product in a hydrochloric acid solution, and then washing, extracting impurities and drying to obtain the porous poly-phthalocyanine laser protective material with carbon bridging.
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