CN109400505B - Azobenzene isonitrile monomer, polymer thereof and preparation method of polymer - Google Patents

Azobenzene isonitrile monomer, polymer thereof and preparation method of polymer Download PDF

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CN109400505B
CN109400505B CN201811260808.8A CN201811260808A CN109400505B CN 109400505 B CN109400505 B CN 109400505B CN 201811260808 A CN201811260808 A CN 201811260808A CN 109400505 B CN109400505 B CN 109400505B
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刘娜
刘文斌
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Hefei University of Technology
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Abstract

The invention discloses an azobenzene isonitrile monomer, a polymer thereof and a preparation method thereof, wherein the azobenzene isonitrile polymer has a structure shown in the following general formula:
Figure DDA0002694543740000011
in the formula (I), the compound is shown in the specification,
Figure DDA0002694543740000012
wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3. The preparation method comprises the step of polymerizing the azobenzene isonitrile monomer under the catalysis of palladium to prepare the azobenzene isonitrile polymer. The method combines azobenzene and isonitrile, has simple operation and easy synthesis, and the prepared polymer has great potential application value in the fields of fluorescent probes, biomedicine, nanotechnology, intelligent materials, photoelectric materials and the like.

Description

Azobenzene isonitrile monomer, polymer thereof and preparation method of polymer
Technical Field
The invention relates to the field of functional polymers and polymer reaction, in particular to an azobenzene isonitrile monomer, a polymer thereof and a preparation method thereof.
Background
Polyisocyanide (poly isocyanide) is one of the earliest discovered macromolecules with stable helical conformation, has stable property, easily obtained monomers and simple polymerization method, can well maintain the helical structure in solution and solid state, and is a very significant artificially synthesized polymer. The polyisonitrile is the first reported polymer with stable helical conformation, when various functional groups (such as stimuli-responsive groups, photoswitches and other structures) are grafted onto the side group of the helical polyisonitrile, new properties and functions are endowed to the material, so that a functional polymer material with new structure and new properties is generated, and the material has important research significance and application prospect in the fields of chiral molecular recognition, asymmetric catalysis, enantiomer separation, drug carriers, liquid crystal display and the like.
In recent years, azobenzene derivatives have been used not only for synthesizing smart polymers, liquid crystal materials, molecular switches, molecular machines, and the like as functional elements of optical switch response, but also are rapidly permeating into various aspects of chemical biological system research and analysis.
If the azo molecule unit is grafted to the side group of the helix polyisonitrile, a helix macromolecule with a new structure is generated and is endowed with new structure and function, such as drug tracing, fluorescent probe, biosensor and the like. Therefore, those skilled in the art have made an effort to develop an azobenzene isonitrile polymer which has stable properties, is easily synthesized, and has potential value in the fields of fluorescent probes, biomedicine, nanotechnology, smart materials, photoelectric materials, and the like.
Disclosure of Invention
The invention aims to provide an azobenzene isonitrile monomer, a polymer thereof and a preparation method thereof. The polymer combines azobenzene and isonitrile, has simple operation and easy synthesis, and has great potential value in the fields of fluorescent probes, biomedicine, nanotechnology, intelligent materials, photoelectric materials and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
an azobenzene isonitrile monomer, wherein the chemical structure general formula of the monomer is as follows:
Figure GDA0002694543720000021
in the formula
Figure GDA0002694543720000022
Wherein m is 1, 1.5, 2, 2.5 or 3.
An azobenzene isonitrile polymer, wherein the chemical structure formula of the polymer is as follows:
Figure GDA0002694543720000023
in the formula
Figure GDA0002694543720000024
Wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3.
Preferably, the preparation method of the azobenzene isonitrile monomer comprises the following steps:
(1) weighing 4- (phenyl diazanyl) phenol, a reagent B, potassium iodide and potassium carbonate in a reaction bottle, vacuumizing, and filling nitrogen; under the nitrogen atmosphere, injecting a solvent DMF, placing a reaction bottle in an oil bath pot, stirring for 24 hours at the temperature of 80 ℃, adding water to precipitate yellow solid, and performing suction filtration and drying to obtain a product a;
(2) weighing the product a in the step (1), a reagent C, EDCI and DMAP, putting the mixture into a two-neck flask, adding DCM as a solvent, reacting for 5 hours, concentrating, and purifying by using a chromatographic column to obtain a product b;
(3) weighing the product b in the step (2) and zinc powder in a two-neck flask, vacuumizing, filling nitrogen, injecting ethanol and glacial acetic acid in the nitrogen atmosphere, reacting for 24 hours, adding anhydrous sodium bicarbonate to quench the reaction, filtering, and concentrating to obtain a product c;
(4) weighing the product c obtained in the step (3), vacuumizing, filling nitrogen, injecting a solvent EA under the nitrogen atmosphere, adding formic anhydride at 0 ℃, moving to room temperature for reaction for 4 hours, adding anhydrous sodium bicarbonate to remove redundant acid, drying, performing suction filtration, and concentrating to obtain a product d;
(5) weighing the product d obtained in the step (4), vacuumizing, filling nitrogen, injecting solvents DCM and triethylamine in the nitrogen atmosphere, dropwise adding BTC dissolved in DCM at 0 ℃, reacting for 1h, concentrating, and purifying by using a chromatographic column to obtain the azobenzene isonitrile monomer.
The synthetic route of the azobenzene isonitrile monomer is as follows:
Figure GDA0002694543720000031
preferably, the reagent C is one or more of o-nitrobenzoic acid, m-nitrobenzoic acid and p-nitrobenzoic acid.
Preferably, the preparation method of the azobenzene isonitrile monomer comprises the following steps:
(1) weighing 4- (phenyl diazenyl) phenol, a reagent B, potassium iodide and potassium carbonate in a reaction bottle, vacuumizing, filling nitrogen, injecting a solvent DMF in the nitrogen atmosphere, placing the reaction bottle in an oil bath kettle, stirring at 80 ℃ for 24 hours, adding water to precipitate yellow solid, and performing suction filtration and drying to obtain a product;
(2) weighing the product in the step (1), a pentafluorophenol isonitrile monomer and DMAP (dimethyl propyl ether) in a reaction bottle, vacuumizing, filling nitrogen, injecting dry triethylamine and THF in the nitrogen atmosphere, placing the reaction bottle at room temperature, stirring for 4-5 h, filtering, concentrating, and purifying by using a chromatographic column to obtain the azobenzene isonitrile monomer.
The synthetic route of the azobenzene isonitrile monomer is as follows:
Figure GDA0002694543720000041
preferably, the reagent B is one or more of 2-chloroethanol, 2-bromoethanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1-chlorobutanol, 4-bromo-1-butanol, 5-chloro-1-pentanol, 5-bromo-1-pentanol, 6-chloro-1-hexanol and 6-bromo-1-hexanol.
Preferably, the preparation method of the azobenzene isonitrile polymer comprises the following steps:
adding a palladium catalyst and an azobenzene isonitrile monomer into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and oxygen-free conditions, adding a dry solvent A, performing reflux reaction at 50-90 ℃ for 6-24 h, adding methanol to stop the reaction, washing the obtained product with methanol, and performing vacuum drying until the quality of the product is unchanged to obtain an azobenzene isonitrile polymer P, wherein the structural general formula of the palladium catalyst is as follows:
Figure GDA0002694543720000042
in the formula (I), the compound is shown in the specification,
Figure GDA0002694543720000043
the structural general formula of P is:
Figure GDA0002694543720000051
in the formula (I), the compound is shown in the specification,
Figure GDA0002694543720000052
wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3.
Preferably, the molar ratio of the palladium catalyst to the benzilonitrile monomer is 1: (40-200), when the dosage of the azobenzene isonitrile monomer is 30-100 mg, the dosage of the solvent A is 1-3 mL.
Preferably, the preparation method of the azobenzene isonitrile polymer comprises the following steps:
adding a palladium catalyst and an azobenzene isonitrile monomer into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and oxygen-free conditions, adding a dry solvent A, carrying out reflux reaction at 55-60 ℃ for 20-24 h, adding methanol to stop the reaction, washing the obtained product with methanol, and drying in vacuum until the quality of the product is unchanged to obtain an azobenzene isonitrile polymer P, wherein the structural general formula of the P is as follows:
Figure GDA0002694543720000053
in the formula
Figure GDA0002694543720000054
Wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3.
Preferably, in the preparation method of the azobenzene isonitrile polymer, the solvent A is one or more of tetrahydrofuran, trichloromethane and toluene.
Compared with the prior art, the invention has the beneficial effects that:
(1) the azobenzene isonitrile polymer in the invention has simple synthesis, no harsh requirements on experimental conditions, simple operation and easy reaction.
(2) The synthesis steps can be simplified through the ester exchange of the pentafluorophenol isonitrile monomer, and the azobenzene isonitrile monomer can be simply and quickly obtained.
(3) The azobenzene isonitrile polymer has wide raw material sources; the variety of catalysts for catalyzing the azobenzene isonitrile monomer reaction is more.
(4) The azobenzene isonitrile polymer combines azobenzene and isonitrile, and has great application value in the fields of fluorescent probes, biomedicine, nanotechnology, intelligent materials, photoelectric materials and the like.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of an azobenzene isonitrile monomer 3 in example 3 of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of TPE-based palladium catalyst of example 5 of the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of a palladium propiolate catalyst in example 6 of the present invention.
FIG. 4 is a nuclear magnetic hydrogen spectrum of the azobenzene isonitrile polymer P1 in example 4 of the present invention.
FIG. 5 is a gel permeation chromatogram of an azobenzene isonitrile polymer P1 in example 4 of the present invention.
FIG. 6 shows the different THF/H ratios of the azobenzene isonitrile polymer P1 in example 4 of the present invention2Fluorescence spectrum in O mixed solution, in which H is2The volume ratio of O to THF is 60%, 50%, 40%, 30%, 20%, 10%, 0 from top to bottom.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely 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.
Example 1
The synthesis method of the azobenzene isonitrile monomer 1 comprises the following steps:
weighing 2g of 4- (phenyl diazanyl) phenol, 1.83g of 2-bromoethanol, 1.94g of potassium iodide and 2.05g of potassium carbonate in a reaction bottle, vacuumizing, and filling nitrogen; injecting 80mL of DMF (dimethyl formamide) in a nitrogen atmosphere, placing a reaction bottle in an oil bath kettle, stirring at 80 ℃ for 24 hours, adding a large amount of water to precipitate a yellow solid, and performing suction filtration and drying to obtain a product 1, wherein the structural formula of the product 1 is as follows:
Figure GDA0002694543720000071
the route for the synthesis of product 1 of this example is as follows:
Figure GDA0002694543720000072
weighing 500mg of product 1, 500mg of pentafluorophenol isonitrile monomer and 390mg of DMAP (dimethyl formamide) in a reaction bottle, vacuumizing, and filling nitrogen; injecting dried triethylamine and THF under the atmosphere of nitrogen; and (2) stirring the reaction at room temperature for 5 hours, filtering, concentrating, and purifying by using a chromatographic column to obtain an azobenzene isonitrile monomer 1, wherein the azobenzene isonitrile monomer 1 has a structural formula:
Figure GDA0002694543720000073
the scheme for synthesizing azobenzene isonitrile monomer 1 in this example is as follows:
Figure GDA0002694543720000074
example 2
The synthesis method of the azobenzene isonitrile monomer 2 comprises the following steps:
weighing 2g of 4- (phenyl diazanyl) phenol, 1.59g of 1-chlorobutanol, 1.95g of potassium iodide and 2.03g of potassium carbonate in a reaction bottle, vacuumizing, and filling nitrogen; injecting 80mL of DMF (dimethyl formamide) in a nitrogen atmosphere, placing a reaction bottle in an oil bath kettle, stirring at 80 ℃ for 24 hours, adding a large amount of water to precipitate a yellow solid, and performing suction filtration and drying to obtain a product 2, wherein the structural formula of the product 2 is as follows:
Figure GDA0002694543720000081
the route for the synthesis of product 2 of this example is as follows:
Figure GDA0002694543720000082
weighing 500mg of product 2, 500mg of pentafluorophenol isonitrile monomer and 390mg of DMAP in a reaction bottle, vacuumizing, and filling nitrogen; injecting dried triethylamine and THF under the atmosphere of nitrogen; and (2) stirring the reaction at room temperature for 5 hours, filtering, concentrating, and purifying by using a chromatographic column to obtain an azobenzene isonitrile monomer 2, wherein the azobenzene isonitrile monomer 2 has the structural formula:
Figure GDA0002694543720000083
the scheme for synthesizing azobenzene isonitrile monomer 2 in this example is as follows:
Figure GDA0002694543720000084
example 3
The synthesis method of the azobenzene isonitrile monomer 3 comprises the following steps:
weighing 4g of 4- (phenyl diazenyl) phenol, 4.1g of 6-chloro-1-hexanol, 3.88g of potassium iodide and 4.15g of potassium carbonate in a reaction bottle, vacuumizing and filling nitrogen; under the nitrogen atmosphere, 100mL of DMF is injected, the reaction bottle is placed in an oil bath pot, after stirring for 24 hours at 80 ℃, a large amount of water is added to precipitate a yellow solid, and the yellow solid is subjected to suction filtration and drying to obtain a product 3, wherein the structural formula of the product 3 is as follows:
Figure GDA0002694543720000091
the route for the synthesis of product 3 of this example is as follows:
Figure GDA0002694543720000092
weighing 500mg of product 3, 500mg of pentafluorophenol isonitrile monomer and 390mg of DMAP (dimethyl formamide) in a reaction bottle, vacuumizing, and filling nitrogen; injecting dried triethylamine and THF under the atmosphere of nitrogen; and (2) stirring the reaction at room temperature for 5 hours, filtering, concentrating, and purifying by using a chromatographic column to obtain the azobenzene isonitrile 3, wherein the structural formula of the azobenzene isonitrile monomer 3 is as follows:
Figure GDA0002694543720000093
the synthesis route of azobenzene isonitrile monomer 3 in this example is as follows:
Figure GDA0002694543720000094
FIG. 1 shows a nuclear magnetic hydrogen spectrum of the azobenzene isonitrile monomer 3.
Example 4
The azobenzene isonitrile polymer P1 was prepared as follows:
adding 6.75mg of methoxy palladium catalyst and 198.46mg of azobenzene isonitrile monomer 3 into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and oxygen-free conditions, adding 2mL of dried tetrahydrofuran, reacting at 55 ℃ for 12h, adding methanol to stop the reaction, washing the obtained product with methanol, and drying in vacuum until the mass is unchanged to obtain the azobenzene isonitrile polymer P1.
The route for preparing azobenzene isonitrile polymer P1 by catalyzing the polymerization of azobenzene isonitrile monomer 3 in this example is as follows:
Figure GDA0002694543720000101
FIG. 4 is a nuclear magnetic resonance spectrum of the azobenzene isonitrile polymer P1 in this example.
FIG. 5 is a gel permeation chromatogram of the azobenzene isonitrile polymer P1 in this example.
FIG. 6 shows the different THF/H ratios of the azobenzene isonitrile polymer P1 in this example2Fluorescence spectrum in O mixed solution, in the fluorescence spectrum of FIG. 6, H2The volume ratio of O to THF is 60%, 50%, 40%, 30%, 20%, 10%, 0 from top to bottom.
Example 5
The azobenzene isonitrile polymer P2 was prepared as follows:
adding 4.8mg of TPE-based palladium catalyst (the nuclear magnetic hydrogen spectrum of the TPE-based palladium catalyst is shown in figure 2) and 94mg of azobenzene isonitrile monomer 3 into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and oxygen-free conditions, adding 2mL of dry tetrahydrofuran, reacting at 55 ℃ for 12h, adding methanol to stop the reaction, washing the obtained product with methanol, and drying in vacuum until the mass of the product is unchanged to obtain the azobenzene isonitrile polymer P2.
The route for preparing azobenzene isonitrile polymer P2 by catalyzing the polymerization of azobenzene isonitrile monomer 3 in this example is as follows:
Figure GDA0002694543720000102
example 6
The azobenzene isonitrile polymer P3 was prepared as follows:
adding 3.9mg of palladium propiolate catalyst (the nuclear magnetic hydrogen spectrum of the palladium propiolate catalyst is shown in figure 3) and 134.48mg of azobenzene isonitrile monomer 3 into a polymerization bottle, vacuumizing and charging nitrogen under anhydrous and oxygen-free conditions, adding 2mL of dry chloroform, reacting at 55 ℃ for 12h, adding methanol to terminate the reaction, washing the obtained product with methanol, and drying in vacuum until the mass is unchanged to obtain the azobenzene isonitrile polymer P3.
The route for preparing azobenzene isonitrile polymer P3 by catalyzing the polymerization of azobenzene isonitrile monomer 3 in this example is as follows:
Figure GDA0002694543720000111
example 7
The synthesis method of the azobenzene isonitrile monomer 4 comprises the following steps:
(1) weighing 4g of 4- (phenyl diazenyl) phenol, 4.1g of 6-chloro-1-hexanol, 3.88g of potassium iodide and 4.15g of potassium carbonate in a reaction bottle, vacuumizing and filling nitrogen; under the nitrogen atmosphere, 100mL of DMF is injected, the reaction bottle is placed in an oil bath pot, after stirring for 24 hours at 80 ℃, a large amount of water is added to precipitate yellow solid, and the yellow solid is filtered, filtered and dried to obtain 5.5g of a product a;
(2) weighing 2.8g of p-nitrobenzoic acid, 1.64g of DMAP and 3.9g of EDCI into a two-neck flask, adding DCM for dissolution, and stirring on a magnetic stirrer for 10 min; weighing 5g of the product a in the step (1), adding the product a into the solution, continuously stirring for reaction for 5 hours, concentrating, and purifying by using a chromatographic column to obtain 7g of a product b;
(3) weighing 5g of the product b in the step (2) and 5.8g of zinc powder in a two-neck flask, vacuumizing, and filling nitrogen; under the nitrogen atmosphere, injecting a proper amount of ethanol and glacial acetic acid (the volume ratio is 3:1), reacting for 24 hours, adding anhydrous sodium bicarbonate to quench the reaction, filtering, and concentrating to obtain 4.5g of a product c;
(4) weighing 4.5g of the product c in the step (3), vacuumizing and filling nitrogen; injecting solvent EA under the nitrogen atmosphere, adding 8mL of formic anhydride at 0 ℃, then transferring to room temperature for reaction for 4h, adding anhydrous sodium bicarbonate to remove redundant acid, drying, carrying out suction filtration, and concentrating to obtain 4.5g of product d;
(5) weighing 3g of the product d obtained in the step (4), vacuumizing, and filling nitrogen; under nitrogen atmosphere, solvents DCM and triethylamine were injected, 1.76g of BTC dissolved in DCM was added dropwise at 0 ℃ to react for 1h, and after concentration, purification was performed with a chromatography column to obtain 2.5g of azobenzene isonitrile.
The synthesis route of azobenzene isonitrile monomer 4 in this example is as follows:
Figure GDA0002694543720000121
the foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.

Claims (7)

1. An azobenzene isonitrile monomer, wherein the chemical structure general formula of the monomer is as follows:
Figure FDA0002694543710000011
in the formula
Figure FDA0002694543710000012
Wherein m is 1, 1.5, 2, 2.5 or 3.
2. An azobenzene isonitrile polymer, wherein the chemical structure of the polymer is as follows:
Figure FDA0002694543710000013
in the formula
Figure FDA0002694543710000014
Wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3.
3. The method for preparing azobenzene isonitrile monomer according to claim 1, comprising the steps of:
(1) weighing 4- (phenyl diazenyl) phenol, a reagent B, potassium iodide and potassium carbonate in a reaction bottle, wherein the reagent B is one or more of 2-chloroethanol, 2-bromoethanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1-chlorobutanol, 4-bromo-1-butanol, 5-chloro-1-pentanol, 5-bromo-1-pentanol, 6-chloro-1-hexanol and 6-bromo-1-hexanol, vacuumizing and filling nitrogen; under the nitrogen atmosphere, injecting a solvent DMF, placing a reaction bottle in an oil bath pot, stirring for 24 hours at the temperature of 80 ℃, adding water to precipitate yellow solid, and performing suction filtration and drying to obtain a product a;
(2) weighing the product a, a reagent C, EDCI and DMAP in the step (1), putting the reagent C into a two-neck flask, adding DCM (DCM) as a solvent, reacting for 5 hours, concentrating, and purifying by using a chromatographic column to obtain a product b, wherein the reagent C is one or more of o-nitrobenzoic acid, m-nitrobenzoic acid and p-nitrobenzoic acid;
(3) weighing the product b in the step (2) and zinc powder in a two-neck flask, vacuumizing, filling nitrogen, injecting ethanol and glacial acetic acid in the nitrogen atmosphere, reacting for 24 hours, adding anhydrous sodium bicarbonate to quench the reaction, filtering, and concentrating to obtain a product c;
(4) weighing the product c obtained in the step (3), vacuumizing, filling nitrogen, injecting a solvent EA under the nitrogen atmosphere, adding formic anhydride at 0 ℃, moving to room temperature for reaction for 4 hours, adding anhydrous sodium bicarbonate to remove redundant acid, drying, performing suction filtration, and concentrating to obtain a product d;
(5) weighing the product d obtained in the step (4), vacuumizing, filling nitrogen, injecting solvents DCM and triethylamine in the nitrogen atmosphere, dropwise adding BTC dissolved in DCM at 0 ℃, reacting for 1h, concentrating, and purifying by using a chromatographic column to obtain the azobenzene isonitrile monomer;
the synthetic route of the azobenzene isonitrile monomer is as follows:
Figure FDA0002694543710000021
4. the method for preparing azobenzene isonitrile monomer according to claim 1, comprising the steps of:
(1) weighing 4- (phenyl diazenyl) phenol, a reagent B, potassium iodide and potassium carbonate in a reaction bottle, wherein the reagent B is one or more of 2-chloroethanol, 2-bromoethanol, 3-chloro-1-propanol, 3-bromo-1-propanol, 1-chlorobutanol, 4-bromo-1-butanol, 5-chloro-1-pentanol, 5-bromo-1-pentanol, 6-chloro-1-hexanol and 6-bromo-1-hexanol, vacuumizing, filling nitrogen, injecting a solvent DMF (dimethyl formamide) in a nitrogen atmosphere, placing the reaction bottle in an oil bath kettle, stirring for 24 hours at 80 ℃, adding water to precipitate a yellow solid, and performing suction filtration and drying to obtain a product;
(2) weighing the product obtained in the step (1), a pentafluorophenol isonitrile monomer and DMAP (dimethyl propyl ether) in a reaction bottle, vacuumizing, filling nitrogen, injecting dry triethylamine and THF in the atmosphere of nitrogen, placing the reaction bottle at room temperature, stirring for 4-5 h, filtering, concentrating, and purifying by using a chromatographic column to obtain an azobenzene isonitrile monomer;
the synthetic route of the azobenzene isonitrile monomer is as follows:
Figure FDA0002694543710000031
5. the method for preparing an azobenzene isonitrile polymer according to claim 2, comprising the steps of:
adding a palladium catalyst and an azobenzene isonitrile monomer into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and oxygen-free conditions, adding a dry solvent A, wherein the solvent A is one or more of tetrahydrofuran, trichloromethane and toluene, performing reflux reaction at 50-90 ℃ for 6-24 hours, adding methanol to terminate the reaction, washing the obtained product with methanol, and performing vacuum drying until the quality of the product is unchanged to obtain an azobenzene isonitrile polymer P, wherein the structural general formula of the palladium catalyst is as follows:
Figure FDA0002694543710000041
in the formula (I), the compound is shown in the specification,
Figure FDA0002694543710000042
the structural general formula of P is:
Figure FDA0002694543710000043
in the formula (I), the compound is shown in the specification,
Figure FDA0002694543710000044
wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3.
6. The method according to claim 5, wherein the step of preparing the azobenzene isonitrile polymer comprises: the molar ratio of the palladium catalyst to the benzene isonitrile monomer is 1: (40-200), when the dosage of the azobenzene isonitrile monomer is 30-100 mg, the dosage of the solvent A is 1-3 mL.
7. The method of claim 5, comprising the steps of:
adding a palladium catalyst and an azobenzene isonitrile monomer into a polymerization bottle, vacuumizing and filling nitrogen under the anhydrous and oxygen-free conditions, adding a dry solvent A, carrying out reflux reaction at 55-60 ℃ for 20-24 h, adding methanol to stop the reaction, washing the obtained product with methanol, and drying in vacuum until the quality of the product is unchanged to obtain an azobenzene isonitrile polymer P, wherein the structural general formula of the P is as follows:
Figure FDA0002694543710000051
in the formula
Figure FDA0002694543710000052
Wherein the polymerization degree n is 40-200, and m is 1, 1.5, 2, 2.5 or 3.
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