Polyether hydrazide as well as preparation method and application thereof

Abstract

The invention provides polyether hydrazide as well as a preparation method and application thereof. The preparation method comprises the following steps: firstly, taking polyether amine and anhydride as raw materials, carrying out ring-opening reaction to prepare polyether carboxylic acid, then carrying out esterification reaction on the polyether carboxylic acid and monofunctional alcohol to obtain polyether amide carboxylic acid methyl ester, and finally reacting the polyether amide carboxylic acid methyl ester with hydrazine hydrate to generate polyether hydrazide. The preparation method of the polyether hydrazide has the characteristics of wide raw material source and simple route, can effectively reduce the production cost and improve the yield and purity, and is beneficial to industrial production; the oil solubility of the polyether hydrazide can be accurately adjusted by regulating and controlling the length of a polyether chain segment in a polyether hydrazide molecule, and the potential application scene of the polyether hydrazide is further expanded. The invention further provides resin based on polyether hydrazide, the resin has good degradability and excellent mechanical strength, on one hand, the resin can be hydrolyzed to generate hydrazide groups, and the degradability is achieved; on the other hand, the resin can generate intermolecular hydrogen bond synergy through a plurality of hydrogen bond sites in the polyether hydrazide structure, so that the mechanical strength is improved.

Description

Technical Field

[0001] This invention relates to the field of polymer synthesis, specifically to a polyether hydrazide, its preparation method, and its applications. Background Technology

[0002] Acyl hydrazides, as an important class of organic nitrogen-containing compounds, play a crucial role in organic synthesis, materials science, and biochemistry. In materials science, they are widely used to develop high-performance polymers, functional coatings, and adhesives, demonstrating excellent performance in applications requiring high flexibility and chemical resistance. Currently, the main methods for preparing acyl hydrazides include the hydrazine-acyl chloride method, the hydrazine-carboxylic acid ester method, and the hydrazine-carboxylic acid method, among which the hydrazine-carboxylic acid ester method is the most commonly used and economical industrial approach.

[0003] However, the existing technologies for synthesizing acylhydrazides still have limitations. On the one hand, the raw material sources for synthesizing acylhydrazides using existing technologies are limited, the synthetic routes are complex, and the yield and purity of the products are both at a low level, making it difficult to meet the actual needs of large-scale industrial production. On the other hand, due to the easy crystallization and high polarity of acylhydrazides, their solubility in most organic solvents is poor. Therefore, when acylhydrazides synthesized using existing technologies are used to prepare polymer materials, a large amount of polar solvents are required for auxiliary dissolution during the preparation process. For example, the acylhydrazide chain extender synthesized in Chinese Patent CN 117362253 A requires 0.85g of this acylhydrazide chain extender to be dissolved in 50mL of N,N-dimethylformamide before it can be used to prepare polyurethane samples. This not only increases production costs but also imposes an environmental burden, making it difficult to meet the requirements of green chemistry and sustainable development. Therefore, the synthesis of an acylhydrazide with good solubility and structural stability is of great significance to the field of materials science.

[0004] Furthermore, when using hydrazide as a raw material to prepare polymer materials, traditional techniques also face the dual challenges of performance and environmental protection. The resulting products often fail to simultaneously achieve both biodegradability and mechanical properties, thus failing to meet the dual demands of modern materials in terms of green environmental protection and high strength performance.

[0005] In conclusion, a new technical solution is urgently needed to address the problems existing in the current technology. Summary of the Invention

[0006] Based on this, the present invention provides a novel method for preparing polyether hydrazide that is rich in raw materials, has excellent oil solubility, is simple in process, and is low in cost. The polyether segments in this polyether hydrazide improve the solubility of the hydrazide in organic solvents, reducing the amount of solvent used in the application process. Furthermore, the prepared polyether hydrazide is suitable for the synthesis of polymers containing dynamic covalent bonds or can be directly used as a crosslinking agent in the preparation of polyurethanes, polyureas, or polyacrylates.

[0007] One object of the present invention is to provide a polyether hydrazide, wherein the polyether hydrazide has the following structural formula:

[0008]

[0009] in,

[0010] R is independently selected from one or more of alkyl, alkyl derivatives, aryl or aryl derivatives with straight-chain, branched or cyclic structures;

[0011] One or more carbon atoms in the alkyl derivative are substituted with oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups.

[0012] and / or

[0013] One or more hydrogen atoms in the alkyl derivative are substituted with fluorine atoms, oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups.

[0014] The aryl derivative is selected from groups containing one or more benzene ring structures, wherein all hydrogen atoms on the benzene ring are unsubstituted.

[0015] or

[0016] One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, olefinic, alkyneic, carboxyl, ester, cyano, or nitro groups;

[0017] R1 is selected from one or more of the following structures:

[0018]

[0019] R, R2, and R3 are independently selected from one or more of alkyl, alkyl derivatives, aryl, or aryl derivatives with straight-chain, branched, or cyclic structures;

[0020] One or more carbon atoms in the alkyl derivative are substituted with oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups.

[0021] and / or

[0022] One or more hydrogen atoms in the alkyl derivative are substituted with fluorine atoms, oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups.

[0023] The aryl derivative is selected from groups containing one or more benzene ring structures, wherein all hydrogen atoms on the benzene ring are unsubstituted.

[0024] or

[0025] One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, olefinic, alkyneic, carboxyl, ester, cyano, or nitro groups;

[0026] R2 can also be selected from hydrogen atoms;

[0027] R3 may not exist;

[0028] m is independently selected from 1-100;

[0029] n is selected from 1 to 100;

[0030] x1+y1+z1 is selected from 1-100;

[0031] x² + y² + z² is selected from 1-100.

[0032] Further, the R is selected from one or more of the following groups:

[0033]

[0034] Furthermore, n is selected from one of 2.5, 6.1, 33 or 68.

[0035] Furthermore, when y1 = 9.0, x1 + z1 = 3.6; when y1 = 12.5, x1 + z1 = 6.0; or when y1 = 39, x1 + z1 = 6.0.

[0036] Furthermore, when R2 = C2H5 and R3 = CH2, x2 + y2 + z2 = 5 - 6; when R2 = H and R3 does not exist, x2 + y2 + z2 = 50; or when R2 = H and R3 does not exist, x2 + y2 + z2 = 85.

[0037] Another object of the present invention is to provide a method for preparing the above-mentioned polyether hydrazide, comprising the following steps:

[0038] S1. React polyetheramine with acid anhydride to obtain polyether carboxylic acid;

[0039] S2. The polyether carboxylic acid and monofunctional alcohol are heated and reacted in the presence of a catalyst to obtain polyether amide carboxylic acid methyl ester;

[0040] S3. Dissolve the polyether amide carboxylic acid methyl ester in a solvent, and then react it with hydrazine hydrate to obtain polyether hydrazine.

[0041] Further, in step S1, the polyetheramine is selected from one or more of polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, polyetheramine ED600, polyetheramine ED900, or polyetheramine ED2003.

[0042] Further, in step S1, the anhydride is selected from one or more of succinic anhydride, glutaric anhydride, phthalic anhydride, tetrahydrophthalic anhydride, or maleic anhydride.

[0043] Further, in step S1, the amino group of the polyetheramine reacts with the acid anhydride to generate an amide and a carboxylic acid, yielding polyether carboxylic acid; in step S2, the reaction is a reflux reaction, whereby the carboxylic acid is converted into methyl carboxylate, which is then neutralized and washed to obtain polyether amide carboxylate methyl ester; in step S3, the methyl carboxylate is converted into acyl hydrazine by reacting with hydrazine hydrate, which is then purified and distilled to obtain polyether acyl hydrazine.

[0044] Further, in step S2, the monofunctional alcohol is selected from one or more of monohydric alcohols, aromatic alcohols, or cyclic alcohols; the monohydric alcohol includes methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and tert-butanol; the aromatic alcohol includes benzyl alcohol and phenethyl alcohol; and the cyclic alcohol includes cyclohexanol.

[0045] Further, in step S2, the catalyst is selected from one or more of concentrated sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, or acidic ion exchange resin.

[0046] Further, in step S3, the solvent is an organic solvent, which is selected from one or more of alcohols or aprotic solvents; the alcohols include methanol and ethanol; the aprotic solvents include tetrahydrofuran and dichloromethane.

[0047] Further, in step S1, the molar ratio of the functional groups of the polyetheramine to the acid anhydride is 1:1 to 1:5; the reaction temperature is 0-80℃; and the reaction time is 1-24h.

[0048] Further, in step S2, the molar ratio of the polyether carboxylic acid and the catalyst is 100:1-10:1, and the reaction time is 1-24h.

[0049] Further, in step S3, the functional group molar ratio of the polyether amide methyl carboxylate and hydrazine hydrate is 1:2-1:5, the reaction temperature is 25-80℃, and the reaction time is 1-24h.

[0050] Another object of the present invention is to provide a resin synthesized from the above-mentioned polyetherhydrazide.

[0051] Compared with the prior art, the main advantages of the present invention are as follows:

[0052] (1) This invention discloses a polyether hydrazide, its preparation method, and its application. First, using various polyetheramines and acid anhydrides with different structures as raw materials, the invention prepares polyether carboxylic acid by the ring-opening reaction of the amino group of the polyetheramine with the acid anhydride to generate amide bonds and carboxylic acid groups. Then, the polyether carboxylic acid is esterified with a monofunctional alcohol under the action of a catalyst, converting the carboxylic acid groups into methyl carboxylate to obtain polyether amide carboxylate methyl ester. Finally, the polyether amide carboxylate methyl ester is dissolved in a solvent and subjected to a hydrazinolysis reaction with hydrazine hydrate, promoting the conversion of the methyl carboxylate groups into acyl hydrazine groups to obtain the target product, polyether hydrazide. The preparation method of polyether hydrazide in this invention uses widely available starting materials and a simple synthetic route, effectively reducing production costs while significantly improving the yield and purity of polyether hydrazide, laying the foundation for large-scale industrial production. Meanwhile, the polyether hydrazide prepared by this invention contains polyether, amide, and hydrazide structures, is soluble in some neutral polar solvents, can react with aldehydes / ketones to form dynamic covalent bonds of hydrazones, or can be used directly as a crosslinking agent, making it suitable for epoxy, polyurethane, polyurea, and polyacrylate systems. Furthermore, by controlling the length of the polyether segment in the polyether hydrazide molecule, its oil solubility can be precisely adjusted, further expanding the potential application scenarios of the material in the field of polymer materials.

[0053] (2) The present invention also provides a resin based on polyether hydrazide, which has good degradability and excellent mechanical strength. On the one hand, the resin can undergo hydrolysis to produce hydrazide groups, thus having good degradability; on the other hand, the polyether hydrazide structure of the resin contains multiple hydrogen bond sites, which effectively improve the mechanical strength of the resin through the synergistic effect of intermolecular hydrogen bonds. Attached Figure Description

[0054] Figure 1 The 1H NMR spectrum of the polyether hydrazide of Example 1 is shown.

[0055] Figure 2 The stress-strain curve of the resin prepared in the application example is shown.

[0056] Figure 3 The appearance of the resin prepared in the application example before and after degradation is shown;

[0057] in,

[0058] Figure 3 (a) shows the appearance of the resin prepared in the application example before degradation;

[0059] Figure 3 (b) shows the appearance of the resin prepared in the application example after degradation. Detailed Implementation

[0060] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0061] Example 1

[0062] A polyether hydrazide, the structural formula of which is shown below:

[0063]

[0064] The preparation method of the above-mentioned polyetherhydrazide includes the following steps:

[0065] S1. Mix 20.0g of polyetheramine D400, 10.0g of succinic anhydride and 20mL of anhydrous tetrahydrofuran, heat to 50℃ and react for 4h, then remove the tetrahydrofuran under vacuum to obtain polyether carboxylic acid.

[0066] S2. The polyether carboxylic acid was mixed with 50 mL of methanol, 10 drops of concentrated sulfuric acid were added, and the mixture was heated to 65 °C and refluxed for 6 h. After the reaction was completed, 50 mL of ethyl acetate was added, and the mixture was washed with saturated NaHCO3 solution and deionized water. The organic phase was dried with anhydrous magnesium sulfate, and the ethyl acetate was removed under vacuum to obtain dimethyl polyether amide carboxylic acid.

[0067] S3. The polyether amide carboxylic acid dimethyl ester was dissolved in 50 mL of ethanol, and 9.37 g of hydrazine hydrate (80 wt%) was added. The mixture was refluxed at 75 °C for 3 h. After the reaction was completed, excess ethanol and hydrazine hydrate were removed under vacuum. Tetrahydrofuran was added to precipitate the byproducts. The mixture was then filtered, and the solvent was removed under vacuum to obtain polyether amide hydrazine with a yield of 66.7%.

[0068] Structural characterization: The 1H NMR spectrum of the polyetherhydrazide prepared in Example 1 was measured using a Bruker AVANCE 500MHz nuclear magnetic resonance spectrometer. Deuterated dimethyl sulfoxide (DMSO-d6) was used as the deuteration reagent, and 1H NMR spectra were acquired.

[0069] Figure 1 The 1H NMR spectrum of the polyether hydrazide of Example 1 is shown. As can be seen from the figure, 9.0 ppm and 7.1 ppm represent hydrogen on -NH- in the hydrazide and amide, respectively, 4.12 ppm represents hydrogen on -NH2 in the hydrazide, and the multiplet at 2.25 ppm represents hydrogen on -CH2-. Therefore, it can be shown that the structure of the polyether hydrazide is consistent with the expectation.

[0070] Example 2

[0071] A polyether hydrazide, the structural formula of which is shown below:

[0072]

[0073] The preparation method of the above-mentioned polyetherhydrazide includes the following steps:

[0074] S1. Mix 100.0g of polyetheramine D2000, 10.0g of succinic anhydride and 50mL of anhydrous tetrahydrofuran, heat to 60℃ and react for 5h, then remove the tetrahydrofuran under vacuum to obtain polyether carboxylic acid.

[0075] S2. The polyether carboxylic acid was mixed with 50 mL of methanol, and 0.971 g of sodium p-toluenesulfonate was added. The mixture was heated to 65 °C and refluxed for 10 h. After the reaction was completed, 50 mL of ethyl acetate was added, and the mixture was neutralized and washed with saturated NaHCO3 solution and deionized water. The organic phase was dried with anhydrous magnesium sulfate, and the ethyl acetate was removed under vacuum to obtain dimethyl polyether amide carboxylic acid.

[0076] S3. The polyether amide carboxylic acid dimethyl ester was dissolved in 50 mL of ethanol, and 9.37 g of hydrazine hydrate (80 wt%) was added. The mixture was reacted at 50 °C for 12 h. After the reaction was completed, excess ethanol and hydrazine hydrate were removed under vacuum. Tetrahydrofuran was added to precipitate the byproducts, and the mixture was filtered. After removing the solvent under vacuum, polyether amide hydrazine was obtained with a yield of 75.0%.

[0077] Example 3

[0078] A polyether hydrazide, the structural formula of which is shown below:

[0079]

[0080] The preparation method of the above-mentioned polyetherhydrazide includes the following steps:

[0081] S1. Mix 11.5g of polyetheramine D230, 9.8g of maleic anhydride and 50mL of anhydrous tetrahydrofuran, and react at 25°C for 8h. Then remove the tetrahydrofuran under vacuum to obtain polyether carboxylic acid.

[0082] S2. The polyether carboxylic acid was mixed with 50 mL of methanol, 2 drops of concentrated sulfuric acid were added, and the mixture was heated to 65 °C and refluxed for 5 h. After the reaction was completed, 50 mL of ethyl acetate was added, and the mixture was neutralized and washed with saturated NaHCO3 solution and deionized water. The organic phase was dried with anhydrous magnesium sulfate, and the ethyl acetate was removed under vacuum to obtain dimethyl polyether amide carboxylic acid.

[0083] S3. The polyether amide carboxylic acid dimethyl ester was dissolved in 50 mL of methanol, and 12.5 g of hydrazine hydrate (80 wt%) was added. The mixture was reacted at 60 °C for 12 h. After the reaction was completed, excess methanol and hydrazine hydrate were removed under vacuum. Tetrahydrofuran was added to precipitate the byproducts. The mixture was then filtered, and the solvent was removed under vacuum to obtain polyether amide hydrazine with a yield of 76.3%.

[0084] Example 4

[0085] A polyether hydrazide, the structural formula of which is shown below:

[0086]

[0087] Where: x² + y² + z² = 5 - 6.

[0088] The preparation method of the above-mentioned polyetherhydrazide includes the following steps:

[0089] S1. Mix 14.6g of polyetheramine T403, 10.0g of succinic anhydride and 50mL of anhydrous tetrahydrofuran, heat to 50℃ and react for 5h, then remove the tetrahydrofuran under vacuum to obtain polyether carboxylic acid.

[0090] S2. The polyether carboxylic acid was mixed with 50 mL of methanol, 2 drops of concentrated sulfuric acid were added, and the mixture was heated to 65 °C and refluxed for 5 h. After the reaction was completed, 50 mL of ethyl acetate was added, and the mixture was washed with saturated NaHCO3 solution and deionized water. The organic phase was dried with anhydrous magnesium sulfate, and the ethyl acetate was removed under vacuum to obtain trimethyl polyether amide carboxylic acid.

[0091] S3. The polyether amide trimethyl carboxylate was dissolved in 50 mL of methanol, and 12.5 g of hydrazine hydrate (80 wt%) was added. The mixture was reacted at 65 °C for 8 h. After the reaction was completed, excess methanol and hydrazine hydrate were removed under vacuum. Tetrahydrofuran was added to precipitate the byproducts, and the mixture was filtered. After removing the solvent under vacuum, polyether amide was obtained with a yield of 76.3%.

[0092] Application examples

[0093] A resin synthesized from the polyether hydrazide synthesized in Example 1.

[0094] The method for preparing the resin includes the following steps:

[0095] L1. Vanillin (60.0 g), epichlorohydrin (146.4 g), and tetrabutylammonium bromide (4.13 g) were mixed and reacted at 80 °C for 2 h. The mixture was then cooled to room temperature, and 100 g of 40 wt% sodium hydroxide solution was added dropwise over 30 min, while simultaneously adding 100 g of butyl acetate for dilution. After the sodium hydroxide solution addition was complete, the reaction continued for 1 h. After the reaction was complete, the mixture was filtered to obtain a solid product, and the filtrate was precipitated with petroleum ether to obtain more solid product. All collected solid products were washed with deionized water until the filtrate was neutral, then washed twice with ethanol, and dried to obtain 64.0 g of pale yellow solid vanillin glycidyl ether, yield 77%.

[0096] L2. The vanillin glycidyl ether (1.24 g) and the polyether hydrazide (2.51 g) synthesized in Example 1 were added to N,N-dimethylformamide (3.7 g). After pre-reaction at 60°C for 30 min, the mixture was placed in a vacuum oven at 80°C for 12 h to remove the solvent, thereby obtaining the resin. This resin is a vanillin-based epoxy resin containing acylhydrazone bonds, named D400PEH-VGE1.

[0097] Test Example 1

[0098] The properties of the polyetherhydrazides obtained in Examples 1-4 were tested.

[0099] Test method:

[0100] Solubility: At room temperature, 15g of polyetherhydrazide was mixed with 100g of tetrahydrofuran, ethanol, N,N-dimethylformamide and water respectively, and the separation was observed.

[0101] The test results are shown in Table 1.

[0102] Table 1. Results of Solubility Performance Tests for Polyetherhydrazide

[0103] project Tetrahydrofuran ethanol N,N-Dimethylformamide water Example 1 Totally dissolved Totally dissolved Totally dissolved Totally dissolved Example 2 Totally dissolved Totally dissolved Totally dissolved Totally dissolved Example 3 Slight stratification Totally dissolved Totally dissolved Totally dissolved Example 4 Layering Totally dissolved Totally dissolved Totally dissolved

[0104] The test results above show that the polyether hydrazide of the present invention has good solubility in ethanol, N,N-dimethylformamide, and water. This is due to the presence of polar amide and hydrazide groups in the polyether hydrazide. In tetrahydrofuran, Examples 3 and 4 exhibited stratification. This is because the polyether hydrazides in Examples 3 and 4 have a lower proportion of polyether segments and a higher overall polarity, while Example 4 has more polar groups. Therefore, stratification with different degrees of layering occurred in the moderately polar solvent tetrahydrofuran.

[0105] Test Example 2

[0106] The performance of the resin obtained from the corresponding use cases was tested.

[0107] Test method:

[0108] The resin obtained in the application example was heated to 120°C and cured for 2 hours to obtain a resin film with a thickness of 0.5 mm. Then, the performance was tested according to the following method.

[0109] Mechanical property testing: Measured using a SANS universal testing machine at room temperature. Cured samples were cut into dumbbell-shaped strips and measured at a tensile speed of 50 mm / min and a gauge length of 1.2 mm.

[0110] Degradation performance test: 20 mg of sample was immersed in 10 mL of 1 M H2SO4 / THF (2 mL: 8 mL) at room temperature, the degradation time was recorded, and the degradation rate was calculated.

[0111] The test results are shown in Table 2 and Figure 2-3 As shown.

[0112] Table 2 Resin Performance Test Results

[0113] project Tensile strength (MPa) Elongation at break (%) <![CDATA[Degradation rate (mg·ml -1 ·h -1 )]]> Application examples 25 375 0.14

[0114] Figure 2 The stress-strain curves of the resin prepared in the application example are shown. As can be seen from the figure, the tensile strength of D400PEH-VGE1 reaches 25 MPa. This is because, although the polyether segments account for a high proportion in the crosslinking network, the polyether hydrazide D400PEH used can provide multiple hydrogen bonding sites, which, after forming hydrogen bonds, can improve the tensile strength of the resin.

[0115] Figure 3 The appearance of the resin prepared in the application example before and after degradation is shown;

[0116] in,

[0117] Figure 3 (a) shows the appearance of the resin prepared in the application example before degradation;

[0118] Figure 3 (b) shows the appearance of the resin prepared in the application example after degradation. As can be seen from the figure, the resin completely degrades after being treated under weak acid conditions at room temperature for a certain period of time, proving that the introduction of acylhydrazone bonds endows the resin with good acid degradation performance.

[0119] The test results above show that the resin prepared in the application example contains acylhydrazone bonds, which can be hydrolyzed into aldehyde groups and acylhydrazine groups under acidic conditions, giving the epoxy resin good degradability, with a degradation rate of up to 0.14 mg·ml. -1 ·h -1 Furthermore, polyetherhydrazide contains multiple hydrogen bond sites, which, through the synergistic effect of intermolecular hydrogen bonds, can effectively improve the mechanical properties of the epoxy resin, achieving a tensile strength of 25 MPa and an elongation at break of 375%.

[0120] In summary, the polyether hydrazide provided by this invention has abundant raw materials, a simple process, and a designable structure. When applied to the synthesis of polymer materials, it can effectively improve the degradability and mechanical properties of polymer materials. Its synthesis method is of great significance for the development of functional polymer materials.

[0121] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0122] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A polyetherhydrazide, characterized in that, The structural formula of the polyether hydrazide is: in, R is independently selected from one or more of alkyl, alkyl derivatives, aryl or aryl derivatives with straight-chain, branched or cyclic structures; One or more carbon atoms in the alkyl derivative are substituted with oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups. and / or One or more hydrogen atoms in the alkyl derivative are substituted with fluorine atoms, oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups. The aryl derivative is selected from groups containing one or more benzene ring structures, wherein all hydrogen atoms on the benzene ring are unsubstituted. or One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, olefinic, alkyneic, carboxyl, ester, cyano, or nitro groups; R1 is selected from one or more of the following structures: R, R2, and R3 are independently selected from one or more of alkyl, alkyl derivatives, aryl, or aryl derivatives with straight-chain, branched, or cyclic structures; One or more carbon atoms in the alkyl derivative are substituted with oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups. and / or One or more hydrogen atoms in the alkyl derivative are substituted with fluorine atoms, oxygen atoms, alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester, cyano, or nitro groups. The aryl derivative is selected from groups containing one or more benzene ring structures, wherein all hydrogen atoms on the benzene ring are unsubstituted. or One or more hydrogen atoms at any position on one or more benzene rings are substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, olefinic, alkyneic, carboxyl, ester, cyano, or nitro groups; R2 can also be selected from hydrogen atoms; R3 may not exist; m is independently selected from 1-100; n is selected from 1 to 100; x1+y1+z1 is selected from 1-100; x² + y² + z² is selected from 1-100.

2. The polyetherhydrazide according to claim 1, characterized in that, The R is selected from one or more of the following groups:

3. The polyetherhydrazide according to claim 1, characterized in that, The value of n is selected from one of 2.5, 6.1, 33 or 68.

4. The polyetherhydrazide according to claim 1, characterized in that, When y1 = 9.0, x1 + z1 = 3.6; when y1 = 12.5, x1 + z1 = 6.0; or when y1 = 39, x1 + z1 = 6.

0.

5. The polyetherhydrazide according to claim 1, characterized in that, When R2 = C2H5 and R3 = CH2, x2 + y2 + z2 = 5 - 6; when R2 = H and R3 does not exist, x2 + y2 + z2 = 50; or when R2 = H and R3 does not exist, x2 + y2 + z2 = 85.

6. The method for preparing the polyether hydrazide according to any one of claims 1-5, characterized in that, Includes the following steps: S1. React polyetheramine with acid anhydride to obtain polyether carboxylic acid; S2. The polyether carboxylic acid and monofunctional alcohol are heated and reacted in the presence of a catalyst to obtain polyether amide carboxylic acid methyl ester; S3. Dissolve the polyether amide carboxylic acid methyl ester in a solvent, and then react it with hydrazine hydrate to obtain polyether hydrazine.

7. The method for preparing polyetherhydrazide according to claim 6, characterized in that, In step S1, the polyetheramine is selected from one or more of polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, polyetheramine ED600, polyetheramine ED900, or polyetheramine ED2003.

8. The method for preparing polyetherhydrazide according to claim 6, characterized in that, In step S1, the anhydride is selected from one or more of succinic anhydride, glutaric anhydride, phthalic anhydride, tetrahydrophthalic anhydride, or maleic anhydride.

9. The method for preparing polyetherhydrazide according to claim 6, characterized in that, In step S2, the monofunctional alcohol is selected from one or more of monohydric alcohols, aromatic alcohols, or cyclic alcohols.

10. A resin synthesized from the polyether hydrazide according to any one of claims 1-5.

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