CN112390948B - Hyperbranched poly (1, 4, 5-substituted triazole) and preparation method and application thereof - Google Patents

Hyperbranched poly (1, 4, 5-substituted triazole) and preparation method and application thereof Download PDF

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CN112390948B
CN112390948B CN202011161184.1A CN202011161184A CN112390948B CN 112390948 B CN112390948 B CN 112390948B CN 202011161184 A CN202011161184 A CN 202011161184A CN 112390948 B CN112390948 B CN 112390948B
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唐本忠
李白雪
秦安军
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of polymer synthesis, and discloses hyperbranched poly (1, 4, 5-substituted triazole) and a preparation method and application thereof. The hyperbranched poly (1)The 4, 5-substituted triazole has the following structural general formula,
Figure DDA0002744365840000011
wherein, A 3 、A 4 Each represents a triaryl group and a tetraaryl group, B 2 Represents a dialkyl group or an aryl group. The preparation method comprises the following steps: under the inert or air atmosphere, carrying out cycloaddition polymerization reaction on a polybasic alkyne-aldehyde compound and a binary azide compound in an organic solvent to obtain a product. The method is simple and efficient, and can synthesize polymers with higher molecular weight; the obtained product has better thermal stability and excellent processability. Moreover, the hyperbranched polymer structure contains a large number of aldehyde groups and alkyne aldehyde groups, so that the hyperbranched polymer can be applied to the fields of patterning, information encryption, storage and the like. In addition, the periphery and the interior of the obtained product can also be accurately subjected to multistage post-modification reaction, and an effective means is provided for structure regulation and diversification of the polymer.

Description

Hyperbranched poly (1, 4, 5-substituted triazole) and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to hyperbranched poly (1, 4, 5-substituted triazole) and a preparation method and application thereof.
Background
Due to the unique structure of the hyperbranched polymer, molecular chains are not entangled, and a large number of end groups are densely distributed on the surface of the hyperbranched polymer, so that the hyperbranched polymer has the properties of low viscosity, high solubility, high reactivity and the like. These advantages make it applicable in the fields of coatings, polymeric liquid crystals, drug release, supramolecular chemistry and chemical sensors, etc. Alkyne-azide cycloaddition polymerization has been applied to the preparation of hyperbranched polymers due to its high atom utilization, high efficiency and other characteristics. And a plurality of reactive groups are densely distributed on the surface of the prepared hyperbranched polymer, and modification reaction can be carried out after the periphery of the hyperbranched polymer. At present, hyperbranched polymers prepared based on alkyne-azide cycloaddition polymerization mainly use poly 1, 4-substituted triazole as a main product, and the preparation of hyperbranched poly 1,4, 5-substituted triazole is less; furthermore, no post-modification studies have been reported for hyperbranched poly-1, 4, 5-substituted triazoles. Post-modification of hyperbranched poly-1, 4-substituted triazole structures reported so far mainly modifies the periphery thereof, and the structural regulation and derivation degrees of freedom are still low (Macromolecules, 2012,45, 7692.).
Based on this, the invention designs and synthesizes multi-alkyne aldehyde monomer, uses it and binary azide compound to prepare hyperbranched poly 1,4, 5-substituted triazole, the obtained product not only has a large amount of aldehyde groups and activated internal alkyne groups on the periphery, but also has a large amount of aldehyde groups on the internal triazole ring, therefore, post-modification reaction can be carried out not only on the periphery, but also on the internal side chain, thus, multi-stage post-modification reaction can be accurately carried out. The structure and function regulation of the product is realized by introducing different functional groups, which provides an effective means for enriching the polymer structure and developing a response type sensor. In conclusion, the invention has important significance for the preparation of hyperbranched poly-1, 4, 5-substituted triazole, the structural derivation and the development of product function diversification.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide hyperbranched poly (1, 4, 5-substituted triazole).
Another object of the present invention is to provide a process for the preparation of the above hyperbranched poly-1, 4, 5-substituted triazoles.
It is a further object of the present invention to provide patterned applications of the hyperbranched poly-1, 4, 5-substituted triazoles described above.
The invention further aims to provide the application of the hyperbranched poly (1, 4, 5-triazole) in information encryption and storage.
It is a further object of the present invention to provide post-modification applications of the above hyperbranched poly-1, 4, 5-substituted triazoles.
The purpose of the invention is realized by the following technical scheme:
a hyperbranched poly (1, 4, 5-substituted triazole) having any one of the structures of the general structural formulae shown below:
Figure BDA0002744365820000021
wherein, A 3 、A 4 Each represents a triaryl group and a tetraaryl group, B 2 Represents a dialkyl group or an aryl group.
Further, said A 3 Is any one of the following chemical structural formulas (1) to (5), A 4 Is any one of the following chemical structural formulas (6) to (7), B 2 Is any one of the following chemical structural formulas (8) to (16):
Figure BDA0002744365820000031
wherein a, b, c, d and e are integers from 1 to 12; x is C, O or S element, and represents a substitution position.
The preparation method of the hyperbranched poly-1, 4, 5-substituted triazole comprises the following preparation steps: under the inert or air atmosphere, carrying out cycloaddition polymerization reaction on a polybasic alkyne-aldehyde compound and a binary azide compound in an organic solvent, and separating a product to obtain hyperbranched poly (1, 4, 5-substituted triazole); the multi-element alkyne-aldehyde compound is a ternary alkyne-aldehyde compound or a quaternary alkyne-aldehyde compound.
Further, the ternary alkynaldehyde compound is
Figure BDA0002744365820000032
The quaternary alkynaldehyde compound is
Figure BDA0002744365820000033
The binary azide is N 3 B 2 N 3 。
Further, the organic solvent is one or a mixture of more than two of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and is preferably one of dimethyl sulfoxide and N, N-dimethylformamide.
Furthermore, the temperature of the cycloaddition polymerization reaction is 90-180 ℃, and the reaction time is 0.5-3 h.
Further, the molar ratio of the polybasic alkyne aldehyde compound to the binary azide compound is 1 (1-1.5); the concentration of the multi-element alkyne-aldehyde compound in the organic solvent is 0.1-0.6 mol/L.
Further, after the reaction is finished, dissolving the product in a solvent, then adding the solvent into methanol or n-hexane for precipitation, collecting the precipitate, and drying the precipitate to constant weight to obtain the hyperbranched poly-1, 4, 5-substituted triazole.
Patterning application of the hyperbranched poly (1, 4, 5-substituted triazole).
The hyperbranched poly (1, 4, 5-triazole) is applied to anti-counterfeiting and information storage.
Post-modification application of the hyperbranched poly-1, 4, 5-substituted triazole.
Furthermore, the post-modification application refers to the preparation of functional polytriazoles with different thermal stability and optical properties by performing cycloaddition reaction or Knoevenagel reaction on hyperbranched poly (1, 4, 5-substituted triazole) and an azido or nitrile monomer.
The preparation method and the obtained product have the following advantages and beneficial effects:
(1) The electron-withdrawing effect of carbonyl in the monomer enables acetylene monomers to have high reaction activity, so that the acetylene monomers can be polymerized with azide compounds under the condition of no catalysis. The method is simple and efficient, and can synthesize the high molecular weight polytriazole.
(2) The polymerization process of the invention has no byproduct and accords with atom economy.
(3) The hyperbranched poly (1, 4, 5-triazole) prepared by the polymerization method can be applied to patterning and can also be applied to the fields of anti-counterfeiting and information storage.
(4) The hyperbranched poly (1, 4, 5-substituted triazole) obtained by the invention has better thermal stability and excellent processability, the substituent group on the triazole ring is aldehyde group with good derivation, and a series of polytriazoles with precise structures and advanced functions can be prepared by various polymer post-modification means (cycloaddition and Knoevenagel reaction).
Drawings
FIG. 1 shows hyperbranched poly-1, 4, 5-substituted triazoles P1 and their corresponding monomers in CDCl 3 Medium nuclear magnetic resonance hydrogen spectrum.
FIG. 2 is a scheme showing hyperbranched poly-1, 4, 5-substituted trisAzole P1 and its corresponding monomer in CDCl 3 Nuclear magnetic resonance carbon spectrum.
FIG. 3 is a diagram of the patterned use of hyperbranched poly-1, 4, 5-substituted triazoles P1 (hydrazine).
FIG. 4 is a diagram of the patterned use (HCl) of hyperbranched poly-1, 4, 5-substituted triazoles P1.
FIG. 5 is a diagram of the use of hyperbranched poly-1, 4, 5-substituted triazoles P1 for information encryption and storage (hydrazines).
FIG. 6 is a diagram of the use (HCl) of hyperbranched poly-1, 4, 5-substituted triazoles P1 for encryption and storage of information.
FIG. 7 is a diagram of the UV-visible absorption spectrum of hyperbranched poly-1, 4, 5-substituted triazole P1 and the post-modified product PM2 in tetrahydrofuran solution.
FIG. 8 is a fluorescence spectrum of hyperbranched poly-1, 4, 5-substituted triazole P1 and a post-modified product PM2 in tetrahydrofuran solution.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the embodiments and the scope of the present invention are not limited thereto.
Example 1
The hyperbranched poly (1, 4, 5-substituted triazole) P1 is prepared by cycloaddition polymerization of ternary alkynal M1 and binary azide M2 without metal catalysis.
Figure BDA0002744365820000051
Wherein, the monomer M1 is synthesized by referring to a synthesis method in a published literature (Green chem.,2019,21,509.; J.Am.chem.Soc.2011,133, 169901.); m2 was synthesized according to the synthesis method in the published literature (ym. Chem.,2012,3, 1075).
40.1mg (0.1 mmol) of the monomer M1 and 36.0mg (0.1 mmol) of the monomer M2 were put into a 10mL polymerization tube, evacuated to exchange nitrogen for 3 times, and injected with 0.5mL of ultra-dry dimethyl sulfoxide (DMSO) by a syringe, and after the monomers were completely dissolved, the mixture was put into an oil bath pan which was kept constant at 150 ℃ to react for 50 minutes. After the reaction is finished, adding 3mL of tetrahydrofuran, dropwise adding the obtained polymer solution into 100mL of vigorously stirred methanol, standing, filtering and drying to obtain the poly hyperbranched 1,4, 5-substituted triazole P1. The final product, polytriazole P1, was determined to have a yield of 81%, a weight average molecular weight of 26400 and a molecular weight distribution of 2.26 (molecular weight and molecular weight distribution determined by ultra high performance polymer chromatography with a diode array detector. Tetrahydrofuran was used as the mobile phase, a flow rate of 0.5mL/min, calibrated against linear monodispersed polystyrene standards). The temperature at 5% weight loss on heating was 353 ℃.
The nuclear magnetic resonance spectrum comparison graph (star represents solvent peak) of the hyperbranched poly (1, 4, 5-substituted triazole) P1 (C) and the corresponding monomer (A, B) is shown in figure 1 and figure 2. As can be seen from FIG. 1, the chemical shifts of the aldehyde hydrogens shifted from 9.42ppm to 10.07 and 10.13ppm of the acetylenic aldehyde monomer, and the peak intensities of the monomers were greatly reduced. The chemical shifts of the methylene hydrogens adjacent to the azide group shift from 3.27ppm to 4.33ppm and 4.75ppm of the azide monomer. As can be seen from FIG. 2, the characteristic peaks corresponding to the chemical shifts 94.75ppm and 89.13ppm of the monomer M1 at the carbon-carbon triple bonds are still retained in the polymer spectrum, but the intensity is greatly reduced. The characterization results of FIGS. 1 and 2 show that the monomers are polymerized to obtain the target polymer.
Example 2
The hyperbranched poly (1, 4, 5-substituted triazole) P2 is prepared by cycloaddition polymerization of alkynal M1 and azide M3 without metal catalysis.
Figure BDA0002744365820000061
Monomer M3 was synthesized according to the synthesis method disclosed in the published literature (polym. Chem.,2012,3, 1075). 40.1mg (0.1 mmol) of the monomer M1 and 47.8mg (0.1 mmol) of the monomer M3 were put into a 10mL polymerization tube, evacuated to exchange nitrogen gas for 3 times, and 0.5mL of ultra-dry DMSO was injected by a syringe, and after the monomers were completely dissolved, the mixture was put into an oil bath pan which was kept constant at 150 ℃ to react for 50 minutes. After the reaction is finished, adding 3mL of tetrahydrofuran, dropwise adding the obtained polymer solution into 100mL of vigorously stirred methanol, standing, filtering and drying to obtain the hyperbranched poly-1, 4, 5-substituted triazole P2. The final product, polytriazole P2, was determined to have a yield of 84% and a weight-average molecular weight24460 and a molecular weight distribution of 2.11. The temperature at 5% weight loss on heating was 350 ℃. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):10.16,10.08,9.40,7.72,7.53,7.37-7.08,6.74,4.75,4.34,3.88,1.94,1.77-1.36。
Example 3
The hyperbranched poly (1, 4, 5-substituted triazole) P3 is prepared by cycloaddition polymerization of alkynal M1 and azide M4 without metal catalysis.
Figure BDA0002744365820000071
Monomer M4 was synthesized according to the synthesis method disclosed in the published literature (adv. Funct. Mater, 2009,19, 1891). 40.1mg (0.1 mmol) of the monomer M1 and 44.2mg (0.1 mmol) of the monomer M4 were placed in a 10mL polymerization tube, evacuated to exchange nitrogen gas for 3 times, 0.5mL of ultra-dry DMSO was injected by a syringe, and after the monomers were completely dissolved, the mixture was placed in an oil bath constant at 150 ℃ and reacted for 50 minutes. After the reaction is finished, adding 3mL of tetrahydrofuran, dropwise adding the obtained polymer solution into 100mL of vigorously stirred methanol, standing, filtering and drying to obtain the hyperbranched poly-1, 4, 5-substituted triazole P3. The final product, polytriazole P3, was determined to have a yield of 91%, a weight average molecular weight of 13940 and a molecular weight distribution of 2.12. The temperature at 5% weight loss on heating was 338 ℃. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):10.14,10.01,9.38,7.72,7.52,7.13-6.81,5.82,5.42。
Example 4
The hyperbranched poly (1, 4, 5-substituted triazole) P4 is prepared by cycloaddition polymerization of alkynal M1 and azide M5 without metal catalysis.
Figure BDA0002744365820000081
Monomer M5 was synthesized according to the synthesis method disclosed in the published literature (ym. Chem.,2012,3, 1075). 40.1mg (0.1 mmol) of the monomer M1 and 48.6mg (0.1 mmol) of the monomer M5 are introduced into a 10mL polymerization tube, the nitrogen is exchanged 3 times by evacuation, 0.5mL of ultra-dry DMSO is injected by means of a syringe, after complete dissolution of the monomers, the tube is placed at a constant temperature of 150 DEG CWas put in an oil bath and reacted for 50 minutes. After the reaction is finished, adding 3mL of tetrahydrofuran, dropwise adding the obtained polymer solution into 100mL of vigorously stirred methanol, standing, filtering and drying to obtain the hyperbranched poly-1, 4, 5-substituted triazole P4. The final product, polytriazole P4, was determined to have a yield of 75%, a weight average molecular weight of 15350 and a molecular weight distribution of 2.70. The temperature at 5% weight loss on heating was 342 ℃. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):10.15,9.90,9.40,7.84-7.65,7.52,7.30,7.13-6.89,4.12,3.96,3.90,3.74,1.40-1.11。
Example 5
The hyperbranched poly-1, 4, 5-substituted triazole P5 is prepared by cycloaddition polymerization of alkynal M1 and azide M6 without metal catalysis.
Figure BDA0002744365820000091
Monomer M5 was synthesized according to the synthesis method disclosed in the published literature (polym. Chem.,2012,3, 1075). 40.1mg (0.1 mmol) of the monomer M1 and 48.6mg (0.1 mmol) of the monomer M6 are put into a 10mL polymerization tube, the vacuum is pumped for 3 times, nitrogen is exchanged, 0.5mL of ultra-dry DMSO is injected by a syringe, after the monomer is completely dissolved, the mixture is put into an oil bath kettle which is constant at 150 ℃ for reaction for 50 minutes. After the reaction is finished, adding 3mL of tetrahydrofuran, dropwise adding the obtained polymer solution into 100mL of vigorously stirred methanol, standing, filtering and drying to obtain the hyperbranched poly-1, 4, 5-substituted triazole P5. The final product, polytriazole P5, was determined to have a yield of 78%, a weight average molecular weight of 12490 and a molecular weight distribution of 2.29. The temperature at 5% weight loss on heating was 327 ℃. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):10.15,9.90,9.40,7.84-7.67,7.52,7.30,7.13-6.89,4.13,3.97,3.89,3.75,1.40-1.11。
Example 6
Patterning applications of hyperbranched poly-1, 4, 5-substituted triazoles.
The hyperbranched poly (1, 4, 5-triazole) contains a large number of aldehyde groups, and the D-A intensity in molecules is adjusted through the chemical reaction of the aldehyde groups and hydrazine or alkyne aldehyde and HCl, so that the luminous color and intensity of the polymer are changed, and further the pattern application is realized. As shown in fig. 3, taking P1 as an example, firstly, spraying a tetrahydrofuran solution of P1 on a filter paper by using a mold, and obtaining a yellow-green "cat" pattern under the irradiation of ultraviolet light; next, hydrazine hydrate was sprayed onto the filter paper to obtain a blue-green "cat" pattern under UV irradiation. In addition, we also use commercially available HCl as a model to realize the patterning application of polytriazole, as shown in fig. 4, and still take P1 as an example, a tetrahydrofuran solution of P1 is sprayed on the filter paper, and a yellow-green background is obtained under the irradiation of ultraviolet light; subsequently, HCl was sprayed on the filter paper using a die, and a dark red "cat" pattern was obtained under irradiation of ultraviolet light.
Example 7
The application of the hyperbranched poly-1, 4, 5-substituted triazole in information encryption and storage.
Similar to the principle in the embodiment 6, the aldehyde group is used for reacting with hydrazine or alkyne aldehyde and HCl to change the D-A effect for the polymer, thereby changing the color and the intensity of the emitted light of the polymer, and realizing the application of the polymer in the aspect of information encryption and storage. As shown in fig. 5, we take P1 as an example, firstly spray the tetrahydrofuran solution of P1 on the filter paper by using the mold "8" at the position b, spray the tetrahydrofuran solution of P6 at the position a, both polymers are yellow-green under the irradiation of the ultraviolet lamp, when hydrazine hydrate is sprayed, P1 changes from yellow-green to blue-green, P6 remains yellow-green without changing in color, and the character of blue-green 9 appears as the original yellow-green number 8.
In addition, we also use commercially available HCl as a model to realize the application of information encryption and storage of polytriazole, as shown in fig. 6, taking P1 as an example, firstly, a tetrahydrofuran solution of P1 is sprayed on a filter paper by using a mold "8" at a position b thereof, and a tetrahydrofuran solution of P6 is sprayed on a position a thereof, both polymers are yellow-green under the irradiation of an ultraviolet lamp, when HCl is sprayed, P1 changes from yellow-green to dark-red, P6 still changes from yellow-green without changing in color, and the original yellow-green number 8 changes into a character of yellow-green 9.
The structural formula of P6 is as follows, and the color of P6 does not change under the irradiation of an ultraviolet lamp after spraying hydrazine hydrate and HCl because the P6 does not contain aldehyde groups and alkyne aldehyde groups.
Figure BDA0002744365820000101
Example 8
Post-modification application of hyperbranched poly (1, 4, 5-substituted triazole).
The periphery of the hyperbranched poly-1, 4, 5-substituted triazole contains a large number of alkyne aldehyde groups which can generate cycloaddition reaction with azide groups, and PM1 is obtained by taking the cycloaddition reaction of P1 and benzyl azide as an example for illustration.
Figure BDA0002744365820000111
60.0mg of polymer P1 and 30.0mg of benzyl azide were added to a 10mL polymerization tube, vacuum-pumped and nitrogen-exchanged for 3 times, 2mL of ultra-dry DMSO was injected by a syringe, and after the reaction was completely dissolved, the mixture was put in an oil bath which was kept constant at 120 ℃ and reacted for 6 hours. After the reaction is finished, 1mL of chloroform is added, the obtained polymer solution is dripped into 80mL of vigorously stirred methanol, and the post-modification product PM1 is obtained after standing, filtering and drying. By assay analysis, 55.7mg of polytriazole PM1 is finally obtained. The thermal stability of the modified product was also changed, at a temperature of 326 ℃ at a weight fraction of 5% of the thermal weight loss. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):10.14-10.03,7.72,7.38-7.24,7.08,6.79-6.72,5.93,5.56,4.74,4.35,3.85,1.94,1.68,1.44,1.35。
Example 8
Post-modification application of hyperbranched poly (1, 4, 5-substituted triazole).
The periphery and the interior of the hyperbranched poly (1, 4, 5-substituted triazole) contain a large amount of aldehyde groups, and the aldehyde groups have rich and active chemical properties, so that a plurality of post-modification approaches can be used for carrying out structural and functional expansion on the obtained polymer. The example of PM2 obtained by Knoevenagel reaction of P1 with diethyl cyanomethylphosphonate will be described.
Figure BDA0002744365820000112
Adding 6.0mg of sodium hydride (60% dispersed in mineral oil) into a 10mL polymerization tube, vacuumizing and changing nitrogen for 3 times, injecting 0.5mL of redistilled tetrahydrofuran by using a syringe, dropwise adding 20.0mg of diethyl cyanomethylphosphonate after ice bath for half an hour, recovering the room temperature for reaction for half an hour, injecting 2mL of ultra-dry DMSO solution containing P1 (15.0 mg) by using the syringe, after the reactant is completely dissolved, placing the mixture into an oil bath kettle which is constant at 60 ℃ and reacting for 6 hours. After the reaction was complete, it was extracted 3 times with chloroform/brine, the organic phase was collected and spin-dried to give the product. The resulting product was dissolved in 1mL of tetrahydrofuran, added dropwise to 80mL of vigorously stirred methanol, allowed to stand, filtered, and dried to give 10.8mg of the post-modification product PM2. The thermal stability of the modified product was also changed, at a temperature of 269 ℃ at a weight fraction 5% of the thermal weight loss. 1 H NMR(500MHz,CDCl 3 ),δ(TMS,ppm):7.57-7.13,6.88-6.86,6.81-6.71,6.54-6.52,6.35-6.31,5.91-5.89,5.77-5.63,5.44-5.41,4.45,4.31,3.83,1.87-1.21。
In the post-modification reaction, a cyano group with strong electron withdrawing is introduced, so that PM2 with different photophysical properties from P1 is obtained. Fig. 7 and 8 are the uv-vis absorption spectrum and the fluorescence spectrum of P1 and PM2, respectively, in a tetrahydrofuran solution. Compared with P1, the maximum absorption peak of PM2 is reduced by 29nm, and the fluorescence is red-shifted by 41nm; as can be seen from the inset, the post-modification product PM2 turned brick red in the color of the solid powder, which was essentially non-luminescent in the solid state. From the insets of the two solutions, the solution of the polytriazole is changed from blue-green to yellow-green through modification, and the fluorescence quantum yield is reduced from 36.8% to 16.3%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A hyperbranched poly 1,4, 5-substituted triazole, wherein the hyperbranched poly 1,4, 5-substituted triazole has any one of the following general structures:
Figure DEST_PATH_IMAGE001
wherein A is 3 、A 4 Each represents a triaryl group and a tetraaryl group, B 2 Represents a dialkyl group or an aryl group;
the hyperbranched poly-1, 4, 5-substituted triazole is prepared by performing cycloaddition polymerization reaction on a polybasic alkyne-aldehyde compound and a binary azide compound in an organic solvent; the molar ratio of the polybasic alkynylaldehyde compound to the binary azide compound is 1.
2. Hyperbranched poly (1, 4, 5-triazole) as claimed in claim 1 wherein A is 3 Is any one of the following chemical structural formulas (1) to (5), A 4 Is any one of the following chemical structural formulas (6) to (7), B 2 Is any one of the following chemical structural formulas (8) to (16):
Figure 247799DEST_PATH_IMAGE002
wherein a, b, c, d and e are integers from 1 to 12; x is O or S element, and represents a substitution position.
3. The preparation method of the hyperbranched poly (1, 4, 5-substituted triazole) as claimed in claim 1 or 2, which comprises the following preparation steps: under the inert or air atmosphere, carrying out cycloaddition polymerization reaction on a polybasic alkyne-aldehyde compound and a binary azide compound in an organic solvent, and separating a product to obtain hyperbranched poly (1, 4, 5-substituted triazole); the multi-element alkyne-aldehyde compound is a ternary alkyne-aldehyde compound or a quaternary alkyne-aldehyde compound.
4. The method for preparing hyperbranched poly (1, 4, 5-substituted triazole) as claimed in claim 3, wherein the ternary alkyne isThe aldehyde compound is
Figure DEST_PATH_IMAGE003
(ii) a The quaternary alkynaldehyde compound is
Figure 633781DEST_PATH_IMAGE004
(ii) a The binary azide is
Figure DEST_PATH_IMAGE005
。
5. The method for preparing hyperbranched poly-1, 4, 5-substituted triazole as claimed in claim 3, wherein the organic solvent is one or a mixture of two or more of tetrahydrofuran, dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
6. The preparation method of hyperbranched poly (1, 4, 5-triazole) as claimed in claim 3, wherein the temperature of the cycloaddition polymerization reaction is 90 to 180 ℃, and the reaction time is 0.5 to 3 hours; the concentration of the polybasic alkynaldehyde compound in the organic solvent is 0.1 to 0.6mol/L.
7. The method for preparing hyperbranched poly (1, 4, 5-substituted triazole) as claimed in claim 3, wherein the product is isolated by: after the reaction is finished, dissolving the product in a solvent, then adding the solvent into methanol or n-hexane for precipitation, collecting the precipitate, and drying the precipitate to constant weight to obtain the hyperbranched poly-1, 4, 5-substituted triazole.
8. Patterned use of the hyperbranched poly-1, 4, 5-substituted triazole as claimed in claim 1 or 2.
9. Use of the hyperbranched poly-1, 4, 5-substituted triazole as claimed in claim 1 or 2 for encryption and storage of information.
10. Post-modification use of the hyperbranched poly (1, 4, 5-substituted triazole) according to claim 1 or 2.
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