Polyether as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer synthesis, and discloses polyether as well as a preparation method and application thereof. The polyether has a structural general formula as shown in formula (I), n is an integer of 2-200, and R1 and R2 are the same or different organic groups. The preparation method comprises the following step: in an inert or air atmosphere, carrying out polymerization reaction on a binary alkyne aldehyde compound and a binary hydroxyl compound in an organic solvent to obtain the polyether. According to the invention, the alkyne aldehyde monomer is designed and synthesized, and the high reaction activity of the monomer enables the monomer to be polymerized with a hydroxyl compound under the condition of no metal catalysis. The method is simple and efficient, and the polymer with high molecular weight and good thermal stability can be synthesized. The obtained polyether contains an aldehyde group side chain, so that selective detection and high-sensitivity detection of hydrazine are realized; and the structure and the function of the polymer can be expanded through a post-modification way. Formula (I)

Description

Technical Field

[0001] This invention belongs to the field of polymer synthesis technology, specifically relating to a polyether, its preparation method, and its application. Background Technology

[0002] Developing novel polymerization methods is crucial for constructing polymer materials with unique structures and advanced functions. With the advancement of triple bond chemistry, hydroxyl-yne click polymerization has become an important method for preparing polyether functional materials. Given the low reactivity of common yne groups, researchers both domestically and internationally have attempted to conjugate them with electron-withdrawing groups such as carbonyl and ester groups, designing and synthesizing various single / double activated yne groups in an effort to improve their reactivity. It should be noted that current reports on hydroxyl-yne polymerization mainly focus on activated terminal yne groups. Although various polyethers with diverse structures and functions have been prepared, many problems remain. For example, the preparation conditions for carbonyl-activated terminal yne groups are relatively demanding, and some polymerizations still require metal catalysts, which limits their widespread application to some extent. Furthermore, most products obtained from activated terminal yne polymerization can only achieve post-modification of the terminal groups, resulting in low structural control and derivatization freedom. Moreover, the structures of currently reported polyether degradation products are unclear, hindering the effective and value-added recovery of materials.

[0003] In contrast, developing the polymerization of activated alkynes and hydroxylated compounds not only maintains the high reactivity of alkynes but also introduces highly reactive groups into the polymer structure, producing polyethers with high structural derivatization. This enriches polymer structures and facilitates the development of high-tech applications for the materials. Furthermore, hydroxyl monomers can be synthesized using bio-based vanillin and polyols, enabling closed-loop recycling of the resulting polyethers, which is of great significance in alleviating the resource crisis. Summary of the Invention

[0004] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a polyether.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned polyether.

[0006] Another object of the present invention is to provide the degradation application of the above-mentioned polyether under acidic conditions.

[0007] Another object of the present invention is to provide the application of the above-mentioned polyether in the detection of hydrazine.

[0008] Another object of the present invention is to provide post-modification applications of the above-mentioned polyether.

[0009] The objective of this invention is achieved through the following technical solution: a polyether having the general structural formula shown in formula (I): Formula (I); Where n is an integer from 2 to 200, R 1R 2 These are the same or different organic groups.

[0010] The 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): Where m and h are integers from 1 to 15; X is a C, O, or S element; and * indicates the substitution position.

[0011] The above-mentioned method for preparing polyether includes the following preparation steps: under an inert or air atmosphere and in the presence of a non-metallic alkaline catalyst, a diacetylaldehyde compound of formula (II) and a dihydroxy compound of formula (III) are polymerized in an organic solvent. After the reaction is complete, the mixture is extracted with chloroform / water, the organic phase is collected and dried by rotary evaporation, 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 polyether. Formula (II); Equation (III).

[0012] Furthermore, the organic solvent is one or a mixture of two or more of tetrahydrofuran, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and chloroform.

[0013] Furthermore, the polymerization reaction is carried out at a temperature of 20~120 °C for 1~6 hours.

[0014] Further, 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 base catalyst is 1:(1~2.5); and the concentration of the diacetylaldehyde compound in the organic solvent is 0.05~0.5 mol / L.

[0015] Further, the alkaline catalyst 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.

[0016] The above-mentioned application of polyether degradation under acidic conditions will reduce R 2 A polyether with chemical structure (9) or (10) is degraded with one of trifluoroacetic acid, hydrochloric acid, or p-toluenesulfonic acid to obtain vanillin.

[0017] The application of the above-mentioned polyether in the detection of hydrazine.

[0018] The above-mentioned post-modification application of polyether involves reacting the polyether with amine or nitrile monomers via Schiff base or Knoevenagel reactions to prepare polyether derivatives.

[0019] The preparation method and the product obtained by the present invention have the following advantages and beneficial effects: (1) The present invention starts from the monomer structure and designs to synthesize acetylaldehyde monomer. The synthesis conditions of this monomer are mild and do not require the use of 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.

[0020] (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.

[0021] (3) The R obtained in this invention 2 Polyethers with chemical structures of (9) or (10) can be precisely degraded under acidic conditions to obtain vanillin; the obtained vanillin is then used to synthesize the corresponding hydroxyl monomers, thereby achieving closed-loop recycling of the polymer.

[0022] (4) The polyether prepared by the present invention contains aldehyde groups, which can achieve selective detection of hydrazine.

[0023] (5) The polyether obtained by the present invention has good thermal stability and excellent processability; moreover, the polymer side chain has aldehyde groups with good derivatization, and a series of polyethers with precise structure and advanced functions can be prepared by various polymer post-modification methods. Attached Figure Description

[0024] Figure 1 This is the 1H NMR spectrum of polyether P1 and its corresponding monomer in CDCl3.

[0025] Figure 2 This is the carbon NMR spectrum of polyether P1 and its corresponding monomer in CDCl3.

[0026] Figure 3 These are fluorescence spectra of polyether P1 solutions at different hydrazine hydrate contents. Detailed Implementation

[0027] 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

[0028] Polyether P1 was prepared by metal-free polymerization of acetylene aldehyde M1 and hydroxyl compound M2.

[0029]

[0030] 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. The temperature at which 5% weight loss occurred was 243 °C.

[0031] A comparison of the NMR spectra of polyether P1(C) and its corresponding monomers (A, B) (* represents solvent peaks) is shown below. Figure 1 and Figure 2 .from Figure 1 As can be seen, the chemical shift of the aldehyde hydrogen group moves from 9.48 ppm in the acetylacetonate monomer to 10.07 and 9.56 ppm in the polymer; and the chemical shifts of newly formed double-bonded hydrogens in the polymer appear at 6.32 and 5.53 ppm. From... Figure 2 As can be seen, the characteristic peaks of M1 at chemical shifts of 95.89 ppm and 89.36 ppm corresponding to the carbon-carbon triple bond disappear in the polymer spectrum. In summary... Figure 1 and 2 The characterization results show that the monomers were almost completely polymerized, yielding the target polymer.

[0032] Example 2 Polyether P2 was prepared by metal-free polymerization of acetylene aldehyde M1 and hydroxyl compound M3.

[0033]

[0034] 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), δ (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. Example 3

[0035] Polyether P3 was prepared by metal-free polymerization of acetylacetic aldehyde M1 and hydroxyl compound M4.

[0036]

[0037] 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), δ (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. Example 4

[0038] Polyether P4 was prepared by metal-free polymerization of acetylacetic aldehyde M1 and hydroxyl compound M5.

[0039]

[0040] 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), δ (TMS, ppm):10.03, 9.52, 7.58, 7.14-6.46, 6.24, 5.34, 1.98, 1.03, 0.64. Example 5

[0041] Polyether P5 was prepared by metal-free polymerization of acetylene aldehyde M6 and hydroxyl compound M2.

[0042]

[0043] 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), δ (TMS, ppm): 10.09, 9.60, 7.91-7.55,7.07, 6.63, 6.29, 5.53, 1.66, 1.53. Example 6

[0044] Polyether P6 was prepared by metal-free polymerization of acetylene aldehyde M6 and hydroxyl compound M3.

[0045]

[0046] 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), δ (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. Example 7

[0047] Polyether P7 was prepared by metal-free polymerization of acetylene aldehyde M6 and hydroxyl compound M4.

[0048]

[0049] 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), δ (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. Example 8

[0050] Polyether P8 was prepared by metal-free polymerization of acetylene aldehyde M6 and hydroxyl compound M5.

[0051]

[0052] 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), δ (TMS, ppm):10.05, 9.52, 7.86, 7.62, 7.12-6.47, 6.26, 5.33, 1.59. Example 9

[0053] Polyether P9 was prepared by metal-free polymerization of acetylene M7 and hydroxyl group M5.

[0054]

[0055] 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, added to n-hexane for precipitation, 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), δ (TMS, ppm): 10.32, 9.34, 7.75, 7.52, 7.19, 7.00, 6.82, 6.62, 5.79, 5.65. Example 10

[0056] Degradation of polyethers. The degradation of polyether P6 under acidic conditions is illustrated using this example. 103 mg of polyether P6 was added to a 10 mL polymerization tube, followed by 1.5 mL of chloroform. After the polymer was completely dissolved, 0.3 mL of trifluoroacetic acid and 5 μL of deionized water were added, and the reaction was carried out at room temperature for 3 hours. After the reaction, the mixture was extracted three times with chloroform / salt water. The organic phase was collected and evaporated to dryness to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate as the washing solvent. NMR results of the degradation main product: 1 HNMR (500 MHz, CDCl3), δ (TMS, ppm): 9.83, 7.42, 7.05, 6.18, 3.97. Mass spectrometry results showed that the molecular ion peak of the degradation product was 151.3, indicating that it was vanillin. Example 11

[0057] Degradation of polyethers. The degradation of polyether P7 under acidic conditions is illustrated using this example. 105 mg of polyether P7 was added to a 10 mL polymerization tube, followed by 1.5 mL of chloroform. After the polymer was completely dissolved, 0.3 mL of trifluoroacetic acid and 5 μL of deionized water were added, and the reaction was carried out at room temperature for 3 hours. After the reaction, the product was extracted three times with chloroform / salt water. The organic phase was collected and evaporated to dryness to obtain the crude product. The crude product was purified by silica gel column chromatography using petroleum ether / ethyl acetate as the washing agent. NMR and mass spectrometry results of the degradation product indicated that the degradation product was vanillin. Example 12

[0058] Application of polyether in hydrazine detection. The polyether in this invention contains a large number of aldehyde groups. The aldehyde groups react chemically with hydrazine to adjust the intramolecular DA intensity, thereby changing the polymer's luminescence color and intensity, and thus achieving hydrazine detection. Taking P1 as an example, hydrated hydrazine is used as a model to verify the selective detection of hydrazine by the polyether. Figure 3 The fluorescence spectra of P1 in tetrahydrofuran solution at different hydrazine concentrations (0-250 equivalents) are shown. The fluorescence intensity of P1 decreases with increasing hydrazine hydrate content. The calculated limit of detection for hydrazine by P1 is 6.46 × 10⁻⁶. -6 M exhibits excellent sensitivity. Example 13

[0059] Post-modification applications of polyethers. Utilizing the reactive chemical properties of aldehyde groups, various post-modification pathways are employed to extend the structure and function of the resulting polymers. The Schiff base reaction of P1 with benzoylhydrazine is illustrated as an example.

[0060]

[0061] Benzoyl hydrazide was purchased from Bidex Pharmaceuticals. 30.5 mg of polymer P1 was added to a 10 mL polymerization tube, followed by 0.5 mL of redistilled tetrahydrofuran to dissolve the polymer. Then, 1.5 mL of redistilled tetrahydrofuran containing 13.6 mg of benzoyl hydrazide was added dropwise. After the reactants were completely dissolved, the tube was placed in an oil bath maintained at 60 °C and reacted for 6 hours. After the reaction was complete, the resulting polymer solution was added dropwise to 100 mL of vigorously stirred n-hexane. The mixture was allowed to stand, filtered, and dried to obtain 33.2 mg of the modified product PM1. Example 14

[0062] Post-modification applications of polyethers are illustrated using the Schiff base reaction of P1 with p-toluidine.

[0063]

[0064] p-Toluidine was purchased from Anegig. 31.6 mg of polymer P1 was added to a 10 mL polymerization tube, followed by 0.5 mL of redistilled tetrahydrofuran to dissolve the polymer. Then, 1.5 mL of redistilled tetrahydrofuran containing 23.0 mg of p-toluidine was added dropwise. After the reactants were completely dissolved, the tube was placed in an oil bath maintained at 60 °C and reacted for 6 hours. After the reaction was complete, the resulting polymer solution was added dropwise to 100 mL of vigorously stirred n-hexane. The mixture was allowed to stand, filtered, and dried to obtain 16.2 mg of the modified product PM2. Example 15

[0065] Post-modification applications of polyethers. The Knoevenagel reaction of P1 with diethyl cyanomethyl phosphate is used as an example for illustration.

[0066]

[0067] Diethyl cyanomethyl phosphate was purchased from Anegig. 5.0 mg of sodium hydride (60% dispersed in mineral oil) was added to a 10 mL polymerization tube. The tube was evacuated and purged with nitrogen three times. 1 mL of redistilled tetrahydrofuran was injected using a syringe. After a 30-minute ice bath, 26.5 mg of diethyl cyanomethyl phosphate was added dropwise. The reaction was allowed to return to room temperature for another 30 minutes. Then, 1 mL of a tetrahydrofuran solution containing P1 (30.5 mg) was injected using a syringe. After the reactants were completely dissolved, the tube was placed in an oil bath at 40 °C and reacted for 6 hours. After the reaction was complete, the tube was extracted three times with chloroform / salt water. The organic phase was collected and evaporated to dryness to obtain the product. The product was dissolved in 1.0 mL of tetrahydrofuran and added dropwise to 100 mL of vigorously stirred n-hexane. After standing, filtration, and drying, 18.3 mg of the modified product PM3 was obtained.

[0068] 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, characterized by: The polyether has a general structural formula shown in formula (I). Formula (I); wherein n is an integer from 2 to 200, R 1 , R 2 are the same or different organic groups.

2. A polyether according to claim 1, characterized in that: 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, h are integers from 1 to 15; X is a C, O or S element, and * indicates a substitution position.

3. A process for the preparation of a polyether as claimed in claim 1 or 2, characterized in that: The preparation steps include: under inert or air atmosphere, a binary acetylene aldehyde compound of structure of formula (II) and a binary hydroxyl compound of structure of formula (III) are subjected to polymerization reaction in an organic solvent under the action of a non-metallic base catalyst, after the reaction is completed, chloroform / water extraction is carried out, the organic phase is collected and spin-dried, the crude product is dissolved in an organic solvent, and then precipitated by adding into n-hexane, the precipitate is collected, dried to constant weight, and a polyether is obtained; Formula (II); Formula (III).

4. A process for the preparation of a polyether according to claim 3, characterized in that: The organic solvent is one or a mixture of two or more of tetrahydrofuran, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dimethylacetamide, and chloroform.

5. A process for the preparation of a polyether according to claim 3, characterized in that: The temperature of the polymerization reaction is 20-120 DEG C, and the reaction time is 1-6 hours.

6. A process for the preparation of a polyether according to claim 3, characterized in that: The molar ratio of the diacetylene aldehyde compound to the dihydroxy compound is 1:(1-1.1); the molar ratio of the diacetylene aldehyde compound to the base catalyst is 1:(1-2.5); and the concentration of the diacetylene aldehyde compound in the organic solvent is 0.05-0.5 mol / L.

7. A process for the preparation of a polyether according to claim 3, characterized in that: The base catalyst 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.

8. Use of the polyether according to claim 2 for the degradation under acidic conditions, characterized by: R 2 degradation reaction with one of trifluoroacetic acid, hydrochloric acid, p-toluenesulfonic acid to obtain vanillin.

9. The polyether of claim 1 or 2 for use in detecting hydrazine.

10. The post-modification of the polyether of claim 1 or 2, characterized in that: The polyether is subjected to a Schiff base or Knoevenagel reaction with an amine or nitrile monomer to prepare a polyether derivative.

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