Polyether with acid-base responsiveness as well as preparation method and application thereof

Abstract

The invention belongs to the field of functional materials, and discloses polyether with acid-base responsiveness as well as a preparation method and application thereof. The preparation method of the polyether with the acid-base responsiveness comprises the following steps: 1, in an inert or air atmosphere, under the action of a nonmetal base catalyst, carrying out polymerization reaction on an alkyne aldehyde compound and a hydroxyl compound in an organic solvent, and after the reaction is finished, carrying out post-treatment to obtain polyether as shown in a formula (II); and step 2, in an air atmosphere, reacting the polyether as shown in the formula (II) with hydrazine or a hydrazide compound in an organic solvent to obtain a solution of the polyether with acid-base responsiveness as shown in the formula (I). The polyether with acid-base responsiveness is prepared by utilizing the polymerization method disclosed by the invention, and high-tech application of the polyether in the aspects of patterning, copying materials, logic gates, information encryption and the like is realized by utilizing the excellent properties of quick acid-base response, obvious fluorescence change, good reversibility and the like of the polyether. Formula (I); formula (II)

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional materials, and particularly relates to a polyether with acid-base responsiveness, a preparation method and application. BACKGROUND

[0002] The chemical structure, biochemical property or physical property of a stimulus-responsive material changes under the action of external environment such as enzymes, light, pH, temperature, humidity, pressure, etc. Due to these unique properties, stimulus-responsive materials show great application potential in the fields of anti-counterfeiting encryption, data storage, sensors and biological imaging, and have been widely studied in the fields of physical chemistry, material science, biotechnology, etc. Among them, the acid-base balance not only relates to the stability of the ecological environment, but also is a key factor for maintaining human health. Therefore, it is crucial to develop a kind of acid-base responsive material that can sense pH changes and change the corresponding physical or chemical properties.

[0003] Most of the existing pH-responsive materials are focused on small molecules, and there are still deficiencies in structure design and performance. For example, the structure design is complex, the sensitivity is not high enough, and it cannot respond to acid-base changes in time and accurately. Compared with the above, the introduction of fluorescent groups makes the acid-base responsive polymer more advantageous, such as good processability, high sensitivity, fast response speed, signal amplification effect, etc. Therefore, it is of important practical significance and potential application value to develop acid-base responsive fluorescent polymers. SUMMARY

[0004] In view of the shortcomings and deficiencies of the prior art, the primary purpose of the present application is to provide a polyether with acid-base responsiveness.

[0005] Another purpose of the present application is to provide a preparation method of the polyether with acid-base responsiveness.

[0006] Another purpose of the present application is to provide the application of the above-mentioned polyether with acid-base responsiveness in patterning.

[0007] Still another purpose of the present application is to provide the application of the above-mentioned polyether with acid-base responsiveness in copying materials.

[0008] Yet another purpose of the present application is to provide the application of the polyether with acid-base responsiveness in logic gates.

[0009] Yet another purpose of the present application is to provide the application of the above-mentioned polyether with acid-base responsiveness in information encryption and storage.

[0010] The purpose of the present application is achieved by the following technical solution: a polyether with acid-base responsiveness, which has a structure general formula shown in formula (I): Formula (I); Equation (II) Wherein, n is an integer from 2 to 200, and R is an amino group, an amide group containing 1 to 12 carbons, or a polyether of formula (II) with an imine group; wherein R 1 The R is any one of the following chemical structural formulas (1) to (7), 2 It is any one of the following chemical structural formulas (8) to (15):

[0011] Where m and h are integers from 1 to 15; X is a C, O, or S element; and * indicates the substitution position.

[0012] A method for preparing an acid-base responsive polyether includes the following preparation steps: The first step involves polymerizing the (III) diacetylaldehyde compound and the (IV) dihydroxy compound in an organic solvent under an inert or air atmosphere and with the action of a non-metallic alkaline catalyst. After the reaction is complete, the mixture is extracted with chloroform / water, the organic phase is collected and evaporated to dryness, the crude product is dissolved in an organic solvent, added to n-hexane for precipitation, the precipitate is collected, and dried to constant weight to obtain the (II) polyether. Formula (III); Formula (IV); The second step involves reacting the polyether of formula (II) with hydrazine or acylhydrazine compound in an organic solvent under an air atmosphere to obtain a solution of the polyether of formula (I) that is acid-base responsive; or dissolving the product in an organic solvent, adding it to n-hexane for precipitation, collecting the precipitate, and drying it to constant weight to obtain the polyether of formula (I) that is acid-base responsive.

[0013] Furthermore, the organic solvent mentioned in the first and second steps is one or a mixture of two or more of tetrahydrofuran, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and chloroform.

[0014] Furthermore, the alkaline catalyst mentioned in the first step is one of cesium carbonate, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine, 1,5,7-trizabicyclo[4.4.0]dec-5-ene, and triethylamine.

[0015] Further, in the first step, the molar ratio of the diacetylaldehyde compound to the dihydroxyl compound is 1:(1~1.1); the molar ratio of the diacetylaldehyde compound to the alkaline catalyst is 1:(1~2.5); in the second step, the molar ratio of the polyether of formula (II) to the hydrazine or acylhydrazine compound is 1:(0.005~0.5); the concentration of the diacetylaldehyde compound in the organic solvent in the first step is 0.05~0.5 mol / L; the concentration of the polyether of formula (II) in the organic solvent in the second step is 0.005~0.1 mol / L.

[0016] Furthermore, the polymerization reaction in the first step is carried out at a temperature of 20~120 ℃ and for a reaction time of 1~6 hours; the reaction in the second step is carried out at a temperature of room temperature and for a reaction time of 1 minute~1 hour.

[0017] The above-mentioned acid-base responsive polyether is used in patterning.

[0018] The above-mentioned acid-base responsive polyether is used in copy materials.

[0019] The above-mentioned acid-base responsive polyether is used in logic gates.

[0020] The above-mentioned acid-base responsive polyether is used in information encryption and storage.

[0021] The preparation method and the product obtained by the present invention have the following advantages and beneficial effects: (1) The present invention designs and synthesizes acetylaldehyde monomers under mild synthesis conditions, without the need for highly active reagents (acetylenyl magnesium bromide) and heavy metal oxides (chromium trioxide, etc.). In addition, hydroxyl compounds can also be synthesized by using bio-based vanillin and polyols, avoiding the use of petroleum-based monomers.

[0022] (2) The electron-withdrawing properties of the aldehyde group give alkyne monomers high reactivity, enabling them to polymerize with hydroxyl compounds under non-metallic catalyst conditions. The polymerization conditions are mild, at 110°C. o High molecular weight polymers can be obtained by reacting at C for 1 hour or at room temperature for 4 hours.

[0023] (3) The polymerization process of the present invention produces no byproducts and is in line with atom economy.

[0024] (4) The reaction of polyether of formula (II) with hydrazine or acylhydrazine compound is highly efficient, and an acid-base responsive polyether can be obtained by reacting at room temperature for 1 minute.

[0025] (5) The polyether prepared by the polymerization method of the present invention has excellent properties such as rapid response to acid and alkali, obvious changes in appearance color and fluorescence, and good reversibility, so as to realize its high-tech applications in patterning, copying materials, logic gates, information encryption and storage. Attached Figure Description

[0026] Figure 1 This is the UV absorption spectrum of polyether P1-1, which has acid and alkali responsiveness, after acid and alkali fumigation.

[0027] Figure 2 This is the fluorescence spectrum of polyether P1-1, which has acid and alkali responsiveness, after acid and alkali fumigation.

[0028] Figure 3 It is a patterned application of polyether P9-1 with acid and alkali responsiveness.

[0029] Figure 4 It is an application of polyether P9-1 with acid and alkali responsiveness as a copy material.

[0030] Figure 5 It is a logic gate application of polyether P1-1 with acid and base responsiveness.

[0031] Figure 6 It is an information encryption and storage application of polyether P9-1 with acid and alkali responsiveness. Detailed Implementation

[0032] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto. Example 1

[0033] Preparation of acid-base responsive polyether P1-1.

[0034]

[0035] Monomer M1 was synthesized according to the method described in published literature (Green Chem., 2019, 21, 509.; J. Am. Chem. Soc. 2011, 133, 16901.); M2 was purchased from Bidex Pharmaceuticals. 38.2 mg (0.1 mmol) of monomer M1, 22.8 mg (0.1 mmol) of monomer M2, and 65.2 mg (0.2 mmol) of cesium carbonate were added to a 10 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 0.5 mL of ultra-dry N,N-dimethylformamide (DMF) was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P1. Analysis revealed that the final product P1 had a yield of 99%, a weight-average molecular weight of 12440, and a molecular weight distribution of 1.43 (molecular weight and molecular weight distribution were determined by gel permeation chromatography equipped with a refractive index detector. DMF was used as the mobile phase at a flow rate of 1.0 mL / min, and linearly distributed polystyrene was used as a standard for correction). The polymerization results after reacting at room temperature for 4 hours were: a yield of 99%, a weight-average molecular weight of 16160, and a molecular weight distribution of 1.87. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.06, 9.53, 7.62, 7.06, 6.88, 6.67, 6.31, 5.51, 1.95, 1.70, 0.58.

[0036] Add 3.05 mg (0.005 mmol) of polyether P1 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P1-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P1-1).

[0037] The photophysical properties of the acid-base responsive polyether P1-1 were subsequently investigated. A tetrahydrofuran solution of P1-1 was coated onto a quartz plate, and after the solvent evaporated, the UV-Vis absorption spectrum was measured. Figure 1The maximum absorption peak of P1-1 was around 450 nm. After fumigation with HCl vapor, the maximum absorption peak red-shifted to around 510 nm. After fumigation with ammonia, it essentially returned to its original absorption position. The acid-base fumigation process was also accompanied by a color change from light yellow to orange-red. Next, a tetrahydrofuran solution of P1-1 was applied to a quartz slide, and after the solvent evaporated, the fluorescence spectrum was measured. Figure 2 As shown, the polymer film initially emitted a yellowish-brown fluorescence with an emission peak at 540 nm. After fumigation with HCl vapor, the fluorescence color changed to magenta, and the emission peak red-shifted to 600 nm. When fumigated with ammonia vapor, the fluorescence essentially returned to its initial position. The reason for these changes in absorption and fluorescence spectra is due to the protonation and deprotonation of nitrogen atoms on the imine bonds in P1-1. Example 2

[0038] Preparation of acid-base responsive polyether P2-1.

[0039]

[0040] Monomer M3 was synthesized according to the published method (Angew. Chem. Int. Ed. 2025, 64, e202502416.). 38.2 mg (0.1 mmol) of monomer M1 and 39.0 mg (0.1 mmol) of monomer M3, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen, and 1 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P2. Analysis showed that the yield of the final product P2 was 99%, with a weight-average molecular weight of 14770 and a molecular weight distribution of 1.51. The polymerization results of this reaction in 0.5 mL DMF at room temperature for 4 hours were: 85% yield, weight-average molecular weight of 18060, and molecular weight distribution of 1.92. The temperature at which 5% weight loss occurred was 215 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.13, 9.51, 7.77-7.46, 7.16-6.75, 6.20, 5.67-5.38, 4.28, 3.90,1.89, 0.98, 0.62.

[0041] Add 3.86 mg (0.005 mmol) of polyether P2 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P2-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P2-1). Example 3

[0042] Preparation of acid-base responsive polyether P3-1.

[0043]

[0044] Monomer M4 was synthesized according to the published method (Angew. Chem. Int. Ed. 2025, 64, e202502416.). 38.2 mg (0.1 mmol) of monomer M1 and 40.4 mg (0.1 mmol) of monomer M4, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen, and 1 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P3. Analysis showed that the yield of the final product, polyether P3, was 99%, with a weight-average molecular weight of 14250 and a molecular weight distribution of 1.40. The polymerization results of this reaction in 1 mL DMF at room temperature for 4 hours were: a yield of 94%, a weight-average molecular weight of 15580, and a molecular weight distribution of 1.44. The temperature at which 5% weight loss occurred was 267 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.13, 9.49, 7.76-7.48, 7.18-6.99, 6.82, 5.41-4.67,3.99, 3.85, 1.88, 0.61.

[0045] Add 3.93 mg (0.005 mmol) of polyether P3 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P3-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P3-1). Example 4

[0046] Preparation of acid-base responsive polyether P4-1.

[0047]

[0048] Monomer M5 was synthesized according to the published method (Polym. Chem. 2020, 11, 2568.). 38.2 mg (0.1 mmol) of monomer M1 and 36.4 mg (0.1 mmol) of monomer M5, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen. 0.5 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P4. Analysis showed that the yield of the final product, polyether P4, was 86%, with a weight-average molecular weight of 12710 and a molecular weight distribution of 1.74. The polymerization results after reacting at room temperature for 4 hours were: a yield of 79%, a weight-average molecular weight of 15200, and a molecular weight distribution of 1.72. The temperature at which 5% weight loss occurred was 278 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm):10.03, 9.52, 7.58, 7.14-6.46, 6.24, 5.34, 1.98, 1.03, 0.64.

[0049] Add 3.73 mg (0.005 mmol) of polyether P4 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P4-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P4-1). Example 5

[0050] Preparation of acid-base responsive polyether P5-1.

[0051]

[0052] Monomer M6 was synthesized according to the published method (Green Chem., 2019, 21, 509.; J. Am. Chem. Soc. 2011, 133, 16901.). M2 was purchased from Bidex Pharmaceuticals. 29.8 mg (0.1 mmol) of monomer M6, 22.8 mg (0.1 mmol) of monomer M2, and 65.2 mg (0.2 mmol) of cesium carbonate were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen. 0.5 mL of ultra-dry N,N-dimethylformamide (DMF) was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P5. Analysis revealed that the final product P5 had a yield of 95%, a weight-average molecular weight of 13250, and a molecular weight distribution of 1.88. The polymerization results after reacting at room temperature for 4 hours were: a yield of 90%, a weight-average molecular weight of 13540, and a molecular weight distribution of 1.92. The temperature at which 5% weight loss occurred was 217 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.09, 9.60, 7.91-7.55,7.07, 6.63, 6.29, 5.53, 1.66, 1.53.

[0053] Add 2.63 mg (0.005 mmol) of polyether P5 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P5-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P5-1). Example 6

[0054] Preparation of acid-base responsive polyether P6-1.

[0055]

[0056] Monomer M3 was synthesized according to the published method (Angew. Chem. Int. Ed. 2025, 64, e202502416.). 29.8 mg (0.1 mmol) of monomer M6 and 39.0 mg (0.1 mmol) of monomer M3, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen, and 1 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P6. Analysis showed that the yield of the final product P6 was 92%, with a weight-average molecular weight of 14060 and a molecular weight distribution of 1.59. The polymerization results of this reaction in 0.5 mL DMF at room temperature for 4 hours were: 98% yield, weight-average molecular weight of 13570, and molecular weight distribution of 1.55. The temperature at which 5% weight loss occurred was 257 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.09, 9.53, 7.80-7.50, 7.14, 6.98, 6.89, 6.22, 5.67-5.38, 4.34,3.92, 1.46.

[0057] Add 3.44 mg (0.005 mmol) of polyether P6 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P6-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P6-1). Example 7

[0058] Preparation of acid-base responsive polyether P7-1.

[0059]

[0060] Monomer M4 was synthesized according to the method described in the published literature (Angew. Chem. Int. Ed. 2025, 64, e202502416.). 29.8 mg (0.1 mmol) of monomer M6 and 40.4 mg (0.1 mmol) of monomer M4, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen, and 1 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, added to n-hexane for precipitation, allowed to stand, filtered, and dried to obtain polyether P7. Analysis showed that the yield of the final product, polyether P7, was 95%, with a weight-average molecular weight of 16740 and a molecular weight distribution of 1.78. The polymerization results of this reaction in 0.5 mL DMF at room temperature for 4 hours were: a yield of 99%, a weight-average molecular weight of 14750, and a molecular weight distribution of 1.35. The temperature at which 5% weight loss occurred was 241 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.11, 9.57, 7.86-7.52, 7.17-6.88, 6.21, 5.39, 4.83,3.97-3.60, 1.45.

[0061] Add 3.51 mg (0.005 mmol) of polyether P7 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P7-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P7-1). Example 8

[0062] Preparation of acid-base responsive polyether P8-1.

[0063]

[0064] Monomer M5 was synthesized according to the published method (Polym. Chem. 2020, 11, 2568.). 29.8 mg (0.1 mmol) of monomer M6 and 36.4 mg (0.1 mmol) of monomer M5, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen. 0.5 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, precipitated in n-hexane, allowed to stand, filtered, and dried to obtain polyether P8. Analysis showed that the yield of the final product, polyether P8, was 99%, with a weight-average molecular weight of 13120 and a molecular weight distribution of 1.79. The polymerization results after reacting at room temperature for 4 hours were: a yield of 90%, a weight-average molecular weight of 11,840, and a molecular weight distribution of 1.64. The temperature at which 5% weight loss occurred was 243 °C. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm):10.05, 9.52, 7.86, 7.62, 7.12-6.47, 6.26, 5.33, 1.59.

[0065] Add 3.31 mg (0.005 mmol) of polyether P8 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P8-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P8-1). Example 9

[0066] Preparation of acid-base responsive polyether P9-1.

[0067]

[0068] Monomer M7 was synthesized according to the published method (Polym. Chem. 2020, 11, 2568.). 18.2 mg (0.1 mmol) of monomer M7 and 36.4 mg (0.1 mmol) of monomer M5, along with 65.2 mg (0.2 mmol) of cesium carbonate, were added to a 10 mL polymerization tube. The tube was evacuated three times with nitrogen. 0.5 mL of ultra-dry DMF was injected using a syringe. After the monomers were completely dissolved, the tube was placed in an oil bath maintained at 110 °C and reacted for 1 hour. After the reaction was complete, the tube was extracted with chloroform / water, and the organic phase was collected and evaporated to dryness. The crude product was dissolved in 1 mL of chloroform, precipitated in n-hexane, allowed to stand, filtered, and dried to obtain polyether P9. Analysis showed that the yield of the final product, polyether P9, was 79%, with a weight-average molecular weight of 13020 and a molecular weight distribution of 1.83. The polymerization results after reacting at room temperature for 4 hours were: a yield of 99%, a weight-average molecular weight of 12090, and a molecular weight distribution of 1.90. 1 H NMR (500 MHz, CDCl3), delta (TMS, ppm): 10.32, 9.34, 7.75, 7.52, 7.19, 7.00, 6.82, 6.62, 5.79, 5.65.

[0069] Add 2.73 mg (0.005 mmol) of polyether P9 to a 10 mL polymerization tube, inject 1 mL of tetrahydrofuran using a syringe, and after the polymer is completely dissolved, inject 75 μL of hydrazine hydrate (0.0015 mmol), stir for 1 minute to obtain P9-1 for later use; (or after the reaction is complete, precipitate in vigorously stirred n-hexane, let stand, filter, and dry to obtain P9-1). Example 10

[0070] Application of acid-base responsive polyethers in patterning.

[0071] The acid-base responsive polyether in this invention contains imine bonds. The protonation and deprotonation of the nitrogen atoms in these imine bonds are used to modulate the electron-donating and electron-withdrawing (DA) effect in the polymer, thereby altering the polymer's luminescence color and intensity, and ultimately enabling patterned applications. For example... Figure 3As shown, taking P9-1 as an example, firstly, a tetrahydrofuran solution of P1-1 is sprayed onto filter paper using a mold. Under fluorescent light, almost no pattern is visible, but under ultraviolet light, a yellowish-green fluorescent "pony" pattern is obtained. Next, the filter paper is fumigated with HCl vapor, resulting in a yellowish-brown "pony" pattern under fluorescent light, and a dark red fluorescent "pony" pattern under ultraviolet light. Then, after fumigation with NH3 vapor, the filter paper returns to its initial state. Furthermore, by configuring different concentrations of polymer solutions or controlling the fumigation time of HCl and NH3 vapors, patterns with different apparent and fluorescent colors can be obtained, achieving multi-color display. Example 11

[0072] Application of acid-base responsive polyethers in carbon copy materials.

[0073] Utilizing the acid-base responsiveness, reversible changes in apparent color and fluorescence of the polyether, as well as its good fatigue resistance, this invention utilizes it as a copying material. For example... Figure 4 As shown, taking P9-1 as an example, firstly, a tetrahydrofuran solution of P9-1 is sprayed onto the filter paper, resulting in filter paper that appears almost invisible but fluoresces blue-green under ultraviolet light. Then, after fumigation with a mold and HCl vapor, a "tiger" pattern appears light yellow under fluorescent light and dark red under ultraviolet light. Next, the pattern is erased after fumigation with NH3 vapor. The pattern is then "written" again using the mold and HCl vapor, resulting in a "pig" pattern; this process is repeated to achieve erasable and rewritable information. Example 12

[0074] Application of acid-base responsive polyethers in logic gates.

[0075] The AND gate constructed using P1 and P1-1 is illustrated as an example. A tetrahydrofuran solution of P1 is sprayed onto a quartz plate as the initial state, hydrazine and acid are used as input signals, and the maximum emission wavelength of the polyether is used as the output signal. Figure 5 As shown, when P1 reacts alone with hydrazine or acid, its fluorescence emission is in the range of 540-550 nm. When P1 reacts with hydrazine to obtain P1-1, and then is fumed with acid, the fluorescence emission redshifts to 590 nm, thus constructing an AND logic gate. Example 13

[0076] Applications of acid-base responsive polyethers in information encryption and storage.

[0077] By utilizing the acid-base responsiveness of polyethers to alter the color and intensity of polymer luminescence, applications of polymers in information encryption and storage can be realized. For example... Figure 6As shown, taking P9-1 as an example, firstly, using a mold called "Grow," a tetrahydrofuran solution of dye P10, which has the same fluorescent color, is sprayed onto a pre-designed template on filter paper. Under fluorescent light, both samples show almost no information; under ultraviolet light, they appear as a yellowish-green "Grow." After fumigation with HCl vapor, the area where P9-1 was sprayed turns a yellowish-brown under fluorescent light and a dark red fluorescent "row" under ultraviolet light. Then, after fumigation with NH3 vapor, the original text information is restored, greatly improving the security of information encryption and the density of information storage.

[0078] The structure of P10 is as follows. After reacting with HCl and NH3 vapors, its color does not change under fluorescent and ultraviolet light.

[0079]

[0080] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A polyether having acid-base responsiveness, characterized by: The polyether with acid-base responsiveness has a general structure shown in formula (I): Formula (I); Formula (II); wherein n is an integer from 2 to 200, and R is an amino group, an amide group containing 1-12 carbons, or a polyether of formula (II) with an imine group; The R 1 is any one of the following chemical structural formulae (1)~(7), the R 2 is any one of the following chemical structural formulae (8)~(15): wherein m and h are integers from 1 to 15, X is C, O, or S, and * represents a substitution position.

2. The method for preparing an acid-base responsive polyether according to claim 1, characterized in that: The preparation process comprises the following steps: In the first step, a binary acetylenic aldehyde compound of formula (III) and a binary hydroxyl compound of formula (IV) are subjected to a polymerization reaction in an organic solvent under the action of a non-metallic base catalyst in an inert or air atmosphere. After the reaction is completed, chloroform / water extraction is performed, and the organic phase is collected and spin-dried. The crude product is dissolved in an organic solvent and precipitated in n-hexane. The precipitate is collected and dried to constant weight to obtain a polyether of formula (II). Formula (III); Formula (IV); In the second step, the polyether of formula (II) is subjected to a reaction with a hydrazine or hydrazide compound in an organic solvent in an air atmosphere to obtain a solution of the polyether of formula (I) with acid-base responsiveness. Alternatively, the product is dissolved in an organic solvent and precipitated in n-hexane. The precipitate is collected and dried to constant weight to obtain the polyether of formula (I) with acid-base responsiveness.

3. The method of claim 2, wherein the polyether having acid-base responsiveness is prepared by the reaction of a polyol with a diisocyanate. The organic solvent in the first and second steps is one or a mixture of two or more of tetrahydrofuran, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and chloroform.

4. The method of claim 2, wherein the polyether having acid-base responsiveness is prepared by the reaction of a polyol with a diisocyanate. The base catalyst in the first step is one of cesium carbonate, 1,8-diazabicyclo[5.4.0]undec-7-ene, triethylenediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and triethylamine.

5. The method for preparing an acid-base responsive polyether according to claim 2, characterized in that: The molar ratio of the binary acetylenic aldehyde compound to the binary hydroxyl compound in the first step is 1:(1-1.1), the molar ratio of the binary acetylenic aldehyde compound to the base catalyst is 1:(1-2.5), and the molar ratio of the polyether of formula (II) to the hydrazine or hydrazide compound in the second step is 1:(0.005-0.5). The concentration of the binary acetylenic aldehyde compound in the organic solvent in the first step is 0.05-0.5 mol / L, and the concentration of the polyether of formula (II) in the organic solvent in the second step is 0.005-0.1 mol / L.

6. The method for preparing an acid-base responsive polyether according to claim 2, characterized in that: The temperature of the polymerization reaction in the first step is 20-120 ℃, and the polymerization reaction time is 1-6 hours. The temperature of the reaction in the second step is room temperature, and the reaction time is 1 minute-1 hour.

7. Use of the polyether with acid-base responsiveness of claim 1 in patterning.

8. Use of the polyether with acid-base responsiveness of claim 1 in carbonless copy materials.

9. Use of the polyether with acid-base responsiveness of claim 1 in logic gates.

10. Use of the polyether with acid-base responsiveness of claim 1 in information encryption and storage.

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