Schiff base metal complexes and methods of making and methods of making and using allyl epoxy-terminated polyethers

Abstract

The present application relates to a Schiff base metal complex and a preparation method and an allyl epoxy-terminated polyether preparation method and application, and belongs to the technical field of fine chemical industry. The Schiff base metal complex comprises a Schiff base ligand and a central metal ion, wherein the Schiff base ligand is a condensate of phenylenediamine and 3,5-di-tert-butyl salicylaldehyde, and the central metal ion is selected from any one of Ti, Mn, Ni, Cu and Co. The present application utilizes the electron cloud density difference of the two double bonds of the methyl allyl and the allyl, and in the presence of the Schiff base catalyst, the methyl allyl double bond is selectively epoxidized by using meta-chloroperoxybenzoic acid, so as to obtain an allyl epoxy-terminated polyether with high epoxy termination rate, high double bond termination rate and no chlorine. The product has high termination rate, basically no chlorine residue, and has good reactivity, and can be used as a raw material of high-end ternary block silicone oil and for post-processing of baby clothing materials.

Description

Technical Field

[0001] This invention belongs to the field of specialty polyether synthesis, specifically relating to a Schiff base metal complex and its preparation method, as well as a preparation method and application of an allyl epoxy-terminated polyether. Background Technology

[0002] Allyl epoxy-terminated polyethers contain both allyl and epoxy functional groups, exhibiting excellent reactivity. In the textile industry, they are primarily used to prepare ternary block silicone oils. The preparation process of ternary block silicone oils utilizes the properties of both functional groups: the allyl double bond undergoes a hydrosilylation reaction, while the epoxy group undergoes an amino ring-opening reaction. Ternary block silicone oils are an upgraded replacement for ordinary amino silicone oils, and their market share is continuously increasing, with an average annual growth rate approaching 10%.

[0003] Currently, there are two mainstream processes for preparing allyl epoxy-terminated polyethers: the Williamson process and the ring-opening / ring-closing process. As described in Chinese patent CN106957423A, the Williamson process uses allyl polyether and epichlorohydrin as raw materials to generate allyl epoxy-terminated polyethers in one step in the presence of a solid alkali or a solid alkali solution. The disadvantage of this process is that epichlorohydrin is prone to continuous ring-opening polymerization side reactions, resulting in a high organic chlorine content in the product. The ring-opening / ring-closing process also suffers from the same problem. Chen Dan previously published a process for preparing epoxy-terminated polyethers using tin tetrachloride as a ring-opening catalyst from allyl alcohol polyether and epichlorohydrin. Because the catalyst is acidic, this process can cause corrosion to the reactor. Furthermore, this process has poor selectivity and is prone to continuous ring-opening reactions of epichlorohydrin, leading to a high total chlorine content in the final product. Chinese patent CN113980262A uses activated carbon-supported phosphorus-vanadium-manganese heteropolyacid as a catalyst and also selects a ring-opening and ring-closing process. Although the epoxy end-capping rate reaches 98%, it still cannot avoid the continuous ring-opening products of epichlorohydrin.

[0004] In summary, none of the current mainstream epoxy-terminated polyether processes can completely suppress the continuous ring-opening side reaction of epichlorohydrin, and the resulting products all contain chlorine residues of more than 3000 ppm. Summary of the Invention

[0005] In view of this, the present invention first provides a Schiff base metal complex and a preparation method thereof, which can be used as a catalyst for preparing allyl epoxy-terminated polyether.

[0006] Secondly, this invention also provides a new method for preparing allyl epoxy-terminated polyether, the resulting product being completely free of chlorine residue and suitable for applications such as the post-processing of baby-grade clothing materials.

[0007] To achieve the objectives of this invention, the following technical solution is adopted:

[0008] On one hand, the present invention provides a Schiff base metal complex comprising a Schiff base ligand and a central metal ion, wherein,

[0009] The Schiff base ligand is a condensation of phenylenediamine and 3,5-di-tert-butylsalicylaldehyde, preferably a condensation of one molecule of phenylenediamine and two molecules of 3,5-di-tert-butylsalicylaldehyde.

[0010] The central metal ion is selected from any one of Ti, Mn, Ni, Cu, and Co, preferably any one of Mn and Ni.

[0011] Preferably, the Schiff base ligand has the structure shown in the following formula:

[0012]

[0013] Secondly, the present invention provides a method for preparing the above-mentioned Schiff base metal complex. Those skilled in the art should understand that the following preparation method is merely an exemplary description of the source of the Schiff base metal complex with the above-mentioned characteristics, but does not constitute any limitation.

[0014] Preferably, the preparation method of the Schiff alkali metal complex includes the following steps:

[0015] 1) Phenylenediamine and 3,5-di-tert-butylsalicylaldehyde were dissolved in an alcohol solvent, and the mixture was heated under stirring. The mixture was then cooled to precipitate a solid. The solid was filtered, washed with ice-cold ethanol, and dried to obtain a Schiff base ligand.

[0016] 2) Dissolve the Schiff base ligand from step 1) in an organic solvent, then add a soluble salt containing a central metal ion, and react under stirring. Then remove the organic solvent under reduced pressure to obtain the Schiff base metal complex.

[0017] In this invention, the molar ratio of phenylenediamine to 3,5-di-tert-butylsalicylaldehyde in step 1) is 1:2-2.1, for example 1:2.01, 1:2.03, 1:2.06, 1:2.09, preferably 1:2.05-2.1.

[0018] In this invention, the mass ratio of the alcohol solvent used in step 1) to the total mass of phenylenediamine and 3,5-di-tert-butylsalicylaldehyde is 20-30:1, for example, 20:1, 25:1, or 30:1. The amount of alcohol solvent should be appropriate, and it is required to completely dissolve phenylenediamine and 3,5-di-tert-butylsalicylaldehyde. For economic reasons, it is preferable to just completely dissolve phenylenediamine and 3,5-di-tert-butylsalicylaldehyde.

[0019] In this invention, the alcohol solvent in step 1) is selected from at least one of anhydrous ethanol and anhydrous methanol.

[0020] In this invention, the reaction in step 1) is carried out at a temperature of 60-80℃, for example, 60℃, 65℃, 70℃, 75℃, or 80℃; and for a reaction time of 5-8h, for example, 5h, 6h, 7h, or 8h.

[0021] In this invention, the cooling and precipitation of solids in step 1) is carried out at a temperature of 0-10℃, such as 0℃, 2℃, 4℃, 6℃, 8℃, or 10℃, for a time of 10-30 minutes, such as 10 minutes or 15 minutes.

[0022] For 20 min, 25 min, and 30 min, it is preferable to place the reaction system in an ice-water bath to cool and precipitate solids.

[0023] In this invention, the soluble salt containing a central metal ion in step 2) is selected from acetate, chloride, and trifluoroacetate containing a central metal ion, preferably acetate;

[0024] The central metal ion is selected from any one of Ti, Mn, Ni, Cu, and Co, preferably any one of Mn and Ni.

[0025] In this invention, the molar ratio of the soluble salt containing the central metal ion to the Schiff base ligand in step 2) is 1:0.9-1, for example 1:0.9, 1:0.93, 1:0.96, 1:0.99, preferably 1:0.9-0.95.

[0026] In this invention, the concentration of the Schiff base ligand dissolved in the organic solvent in step 2) is 0.1-0.5 g / mL, for example 0.1 g / mL, 0.3 g / mL, or 0.5 g / mL.

[0027] In this invention, the organic solvent in step 2) is selected from solvents with good solubility for Schiff base ligands, preferably at least one of dichloromethane and ethyl acetate.

[0028] In this invention, the reaction in step 2) is carried out at a temperature of 20-30°C, for example, 20°C, 22°C, 24°C, 26°C, 28°C, or 30°C; and for a reaction time of 3-5 hours, for example, 3 hours, 4 hours, or 5 hours.

[0029] Thirdly, the present invention also provides the application of the Schiff base metal complex, which can be used as a catalyst for the preparation of allyl epoxy-terminated polyethers.

[0030] The present invention provides an exemplary method for preparing allyl epoxy-terminated polyether, comprising the following steps:

[0031] S1: Methallyl polyether is prepared by reacting methyl allyl alcohol with ethylene oxide as a starting agent;

[0032] S2: Mix methyl allyl polyether with sodium methoxide and carry out an alkoxide reaction, then add allyl chloride to react and generate methyl allyl allyl double-terminated polyether;

[0033] S3: Allyl epoxy-terminated polyether is prepared by mixing and reacting methylallylallyl double-terminated polyether, m-chloroperoxybenzoic acid, and Schiff base metal complex.

[0034] In this invention, there are no particular limitations on the reaction conditions involved in step S1. Those skilled in the art can select the appropriate methods as needed, such as those disclosed in patent CN107266673B.

[0035] Preferably, the mass ratio of methyl allyl alcohol to ethylene oxide is 1:4-35, for example 1:4, 1:7, 1:10, 1:15:1:20, 1:25, 1:30, 1:35.

[0036] Preferably, the reaction is carried out at a temperature of 100-110°C, such as 100°C, 103°C, 106°C, or 109°C, for a time of 6-8 hours, such as 6 hours, 7 hours, or 8 hours.

[0037] More preferably, the reaction is carried out in the presence of a catalyst, which is a conventionally chosen alkali metal or alkali metal hydroxide, such as Na; even more preferably, the amount of catalyst used is 0.4-3.6% of the mass of methyl allyl alcohol, for example 0.3%, 1%, 2%, 3%, 3.6%;

[0038] More preferably, during the reaction process, the methyl allyl alcohol is fed continuously for 3-6 hours, and the feeding time is included in the reaction time; after the feeding is completed, the aging reaction continues for 2-5 hours.

[0039] Preferably, the methyl allyl alcohol polyether polyol has the structure shown in the following formula:

[0040] Where n = 0-50, for example 0, 10, 20, 30, 40, 50.

[0041] In this invention, there are no particular limitations on the reaction conditions involved in step S2, and those skilled in the art can screen them as needed using existing disclosed methods.

[0042] Preferably, the molar ratio of the methyl allyl polyether to sodium methoxide is 1:1-1.1, for example 1:1, 1:1.03, 1:1.06, or 1:1.09; wherein the sodium methoxide is a sodium methoxide solution (30% sodium methoxide methanol solution), which is a commercially available product.

[0043] Preferably, the alkoxide reaction is carried out at a temperature of 80-100°C, such as 85°C, 90°C, or 95°C, for a time of 3-6 hours, such as 3 hours, 4 hours, 5 hours, or 6 hours.

[0044] Preferably, the molar ratio of the methyl allyl polyether to allyl chloride is 1:1-1.1, for example, 1:

[0045] 1, 1:1.03, 1:1.06, 1:1.09.

[0046] Preferably, the reaction with allyl chloride is carried out at a temperature of 60-80°C, such as 65°C, 70°C, or 75°C, for a time of 7-8 hours, such as 7 hours, 7.5 hours, or 8 hours. More preferably, during the reaction, the allyl chloride is fed continuously for a time of 3-5 hours, such as 3 hours, 4 hours, or 5 hours, and the feeding time is included in the reaction time. After the reaction is completed, conventional post-processing operations such as filtering and desalting the product are also included, which are not particularly required in this invention.

[0047] Preferably, the methylallylallyl dual-terminated polyether has the structure shown in the following formula:

[0048] Where n = 0-50, for example 0, 10, 20, 30, 40, 50.

[0049] In this invention, there are no particular limitations on the reaction conditions involved in step S3, and those skilled in the art can screen them as needed using existing disclosed methods.

[0050] Preferably, the molar ratio of the methylallylallyl dual-terminated polyether to m-chloroperoxybenzoic acid is 1:1.0-1.05, for example, 1:1, 1:1.02, 1:1.04, or 1:1.05.

[0051] Preferably, the amount of the Schiff base metal complex added is 0.1-0.2 wt% of the mass of the methyl allyl allyl double-terminated polyether.

[0052] Preferably, the reaction is carried out at a temperature of 60-80℃, such as 65℃, 70℃, or 75℃, for a time of 3-6 hours, such as 3 hours, 4 hours, 5 hours, or 6 hours. After the reaction is completed, conventional post-treatment operations such as adsorption purification with an adsorbent are also included, but there are no special requirements for this invention.

[0053] In this invention, the allyl epoxy-terminated polyether prepared by the above method has the structure shown in the following formula:

[0054] Where n = 0-50, for example 0, 10, 20, 30, 40, 50.

[0055] In addition to the main products mentioned above, the product may also include the following five byproducts: (Byproduct 1) (Byproduct 2) (Byproduct 3)

[0056] (Byproduct 4) (Byproduct 5)

[0057] In byproducts 1-5, n takes values ​​from 0 to 50, such as 0, 10, 20, 30, 40, and 50, but there is no introduction of organochlorine in the entire process.

[0058] The allyl epoxy-terminated polyether prepared by the above method of the present invention can be used as a raw material in the fields of high-end ternary block silicone oil and silane coupling agent, and is especially suitable for the post-processing of baby-grade clothing materials.

[0059] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0060] This invention develops a novel method for synthesizing chlorine-free allyl epoxy-terminated polyethers. This route eliminates the need for epichlorohydrin in the reaction, yielding allyl epoxy-terminated polyether products with high epoxy end-capping rates (up to 99% or more), high double bond end-capping rates (up to 99% or more), and chlorine-free (<20 ppm). Downstream testing shows that the product retains high reactivity of both epoxy groups and double bonds, making it suitable as a raw material for high-end ternary block silicone oils and for post-processing of baby clothing materials. Detailed Implementation

[0061] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.

[0062] Main raw material information of this invention:

[0063] Unless otherwise specified, all materials involved in the examples are common commercially available raw materials, and the product purity is analytical grade unless otherwise specified.

[0064] The testing methods involved in the embodiments are as follows:

[0065] Epoxy end-capping rate: The content was determined by 13C-NMR testing at room temperature using a Bruker-400MHz MHz instrument with TMS as an internal standard.

[0066] End-double bond capping rate: The content was determined by 13C-NMR at room temperature using a Bruker-400MHz MHz instrument with TMS as an internal standard.

[0067] Internal double bond end-capping rate: The content was determined by 13C-NMR at room temperature using a Bruker-400MHz MHz spectral analyzer with TMS as an internal standard.

[0068] Hydroxyl end-capping rate: The content was determined by 13C-NMR at room temperature using a Bruker-400MHz MHz spectral analyzer with TMS as an internal standard.

[0069] Chlorine residue: Refer to GB / T 6324.9-2016 "Test Methods for Organic Chemical Products - Part 9: Determination of Chlorine".

[0070] The present invention will be further described below with reference to embodiments.

[0071] Example 1

[0072] The preparation of Schiff base metal complex 1 involves the following steps:

[0073] 108 g (1 mol) of phenylenediamine and 492 g (2.1 mol) of 3,5-di-tert-butylsalicylaldehyde were dissolved in anhydrous ethanol, with an appropriate amount of ethanol added to just completely dissolve the raw materials. The mixture was stirred at 80 °C for 8 h. The reaction system was cooled in an ice-water bath to precipitate a solid, which was then filtered. The filter cake was washed with 100 mL of ice-cold ethanol and dried under vacuum to obtain the Schiff base ligand.

[0074] Schiff base ligand characterization:

[0075] 1 H NMR (400MHz, CDCl3) δ12.75 (s, 2H), 8.87 (d, J = 25.6Hz, 2H), 7.52 (d, J = 12.1Hz, 2H) ,7.48(d,J=2.6Hz,2H),7.45(m,2H),7.33(d,J=7.8Hz,2H),1.35(d,J=17.0Hz,36H)

[0076] 5.40 g (0.01 mol) of the above Schiff base ligand was dissolved in 20 mL of dichloromethane, and 1.73 g (0.01 mol) of manganese acetate was added. The mixture was stirred at 30 °C for 5 h. The dichloromethane was then dried to obtain Schiff base metal complex 1.

[0077] Example 2

[0078] The preparation of Schiff base metal complex 2 involves the following steps:

[0079] 108 g (1 mol) of phenylenediamine and 468 g (2.0 mol) of 3,5-di-tert-butylsalicylaldehyde were dissolved in anhydrous ethanol, with an appropriate amount of ethanol added to just completely dissolve the raw materials. The mixture was stirred at 60 °C for 5 h. The reaction system was cooled in an ice-water bath to precipitate a solid. The solid was filtered, and the filter cake was washed with 100 mL of ice-cold ethanol. The filter cake was then dried under vacuum to obtain the Schiff base ligand.

[0080] 5.40 g (0.01 mol) of the above Schiff base ligand was dissolved in 20 mL of dichloromethane, and 1.77 g (0.013 mol) of nickel acetate was added. The mixture was stirred at 20 °C for 3 h. The dichloromethane was then dried to obtain Schiff base metal complex 2.

[0081] Examples 3-6

[0082] The steps for preparing methyl allyl alcohol polyether 1-4 are as follows:

[0083] In the examples, methyl allyl polyethers were prepared using conventional methods (specifically referring to the method in patent CN107266673B). The preparation of methyl allyl polyethers in Example 3 is used as an example for illustration. The methyl allyl polyethers in Examples 4-6 can all be synthesized using this method, with only the feeding ratio changing. The feeding ratio and the parameters of the prepared methyl allyl polyethers are shown in Table 1 below.

[0084] In a 10L high-pressure reactor, 580g of methyl allyl alcohol and 5g of Na were added. After complete nitrogen purging, the temperature was raised to 110℃, and 4420g of ethylene oxide was introduced for reaction. After 6 hours, the feeding was stopped, and the mixture was aged for 2 hours. After purification, methyl allyl polyether was prepared. The hydroxyl value was tested to be 112.3mgKOH / g, and the calculated average molecular weight was 500.

[0085] Table 1 Feed ratio and product parameters of Examples 3-6

[0086]

[0087] Example 7

[0088] Preparation of allyl epoxy-terminated polyether

[0089] In a 1L three-necked flask, 500g (1mol) of methyl allyl polyether (molecular weight 500 - Example 3) and 180g (1mol) of sodium methoxide methanol solution (30%) were added. The reaction temperature was raised to 100°C. With mechanical stirring, methanol was pumped out using a vacuum pump to promote the forward reaction. After 6 hours of reaction, the mass of the extracted methanol no longer changed, indicating that the reaction was complete. Then, the reaction temperature was adjusted to 60°C, and 77g (1mol) of allyl chloride was added over a 4-hour feeding period. After the feeding was completed, the reaction continued for another 3 hours. After filtration and desalting, methyl allyl allyl double-terminated polyether was obtained.

[0090] Methyl allyl allyl double-terminated polyether was mixed with m-chloroperoxybenzoic acid at a molar ratio of 1:1, and 0.1% of Schiff base metal complex (Example 1) by mass of methyl allyl allyl double-terminated polyether was added simultaneously. After stirring and reacting at 60°C for 5 h, 1% magnesium silicate adsorbent was added to the system, and the mixture was purified by adsorption at 110°C for 3 h. The allyl epoxy-terminated polyether (n=10) was obtained by filtration. The results are shown in Table 2.

[0091] Example 8

[0092] Preparation of allyl epoxy-terminated polyether

[0093] In a 1L three-necked flask, 500g (0.5mol) of methyl allyl polyether (molecular weight 1004 - Example 4) and 99g (0.55mol) of sodium methoxide methanol solution (30%) were added. The reaction temperature was raised to 80°C. With mechanical stirring, methanol was pumped out using a vacuum pump to promote the forward reaction. After 3 hours of reaction, the mass of the extracted methanol no longer changed, indicating that the reaction was complete. Then, the reaction temperature was adjusted to 80°C, and 42g (0.55mol) of allyl chloride was added over a 5-hour feeding period. After the feeding was completed, the reaction continued for another 3 hours. After filtration and desalting, methyl allyl allyl double-terminated polyether was obtained.

[0094] Methyl allyl allyl dual-terminated polyether was mixed with m-chloroperoxybenzoic acid at a molar ratio of 1:1.05, and 0.2% (by weight) of Schiff base metal complex (Example 2) of methyl allyl allyl dual-terminated polyether was added simultaneously. After stirring and reacting at 80°C for 3 h, 1% magnesium silicate adsorbent was added to the system, and the mixture was purified by adsorption at 110°C for 3 h. The allyl epoxy-terminated polyether (n=21) was obtained by filtration. The results are shown in Table 2.

[0095] Example 9

[0096] Preparation of allyl epoxy-terminated polyether

[0097] 500 g (0.34 mol) of methyl allyl polyether (molecular weight 1484 - Example 5) and 61 g (0.34 mol) of sodium methoxide methanol solution (30%) were added to a 1 L three-necked flask. The reaction temperature was raised to 90 °C. With mechanical stirring, methanol was pumped out using a vacuum pump to promote the forward reaction. After 5 hours of reaction, the mass of the extracted methanol no longer changed, indicating that the reaction was complete. Then, the reaction temperature was adjusted to 70 °C, and 26 g (0.34 mol) of allyl chloride was added over a 3-hour feeding period. After the feeding was completed, the reaction continued for another 3 hours. After filtration and desalting, methyl allyl allyl double-terminated polyether was obtained.

[0098] Methyl allyl allyl dual-terminated polyether was mixed with m-chloroperoxybenzoic acid at a molar ratio of 1:1.02, and 0.15% of Schiff base metal complex (Example 1) by mass of methyl allyl allyl dual-terminated polyether was added simultaneously. After stirring and reacting at 70°C for 5 h, 1% magnesium silicate adsorbent was added to the system, and the mixture was purified by adsorption at 110°C for 3 h. The allyl epoxy-terminated polyether (n=32) was obtained by filtration. The results are shown in Table 2.

[0099] Example 10

[0100] Preparation of allyl epoxy-terminated polyether

[0101] 500 g (0.25 mol) of methyl allyl polyether (molecular weight 2010 - Example 6) and 45 g (0.25 mol) of sodium methoxide methanol solution (30%) were added to a 1 L three-necked flask. The reaction temperature was raised to 100 °C. With mechanical stirring, methanol was pumped out using a vacuum pump to promote the forward reaction. After 6 hours of reaction, the mass of the extracted methanol no longer changed, indicating that the reaction was complete. Then, the reaction temperature was adjusted to 70 °C, and 19 g (0.25 mol) of allyl chloride was added over a 4-hour feeding period. After the feeding was completed, the reaction continued for another 3 hours. After filtration and desalting, methyl allyl allyl double-terminated polyether was obtained.

[0102] Methyl allyl allyl dual-terminated polyether was mixed with m-chloroperoxybenzoic acid at a molar ratio of 1:1.01, and 0.12% of Schiff base metal complex (Example 2) by mass of methyl allyl allyl dual-terminated polyether was added simultaneously. After stirring and reacting at 60°C for 6 hours, 1% magnesium silicate adsorbent was added to the system, and the mixture was purified by adsorption at 110°C for 3 hours. The allyl epoxy-terminated polyether (n=44) was obtained by filtration. The test results are shown in Table 2.

[0103] Comparative Example 1

[0104] Following the method of Example 1, except that phenylenediamine was replaced with ethylenediamine, while other operations and conditions remained unchanged, a complex was obtained; then, the catalyst of Example 7 was replaced with it to prepare allyl epoxy-terminated polyether, and the results are shown in Table 2.

[0105] Comparative Example 2

[0106] The method of Example 1 was followed, except that 3,5-di-tert-butylsalicylaldehyde was replaced with 5-tert-butylsalicylaldehyde, while other operations and conditions remained unchanged, to obtain the complex. Then, the catalyst of Example 7 was replaced with it to prepare allyl epoxy-terminated polyether, and the results are shown in Table 2.

[0107] Comparative Example 3

[0108] Following the method of Example 1, except that manganese acetate was replaced with ferric acetate, while other operations and conditions remained unchanged, a complex was obtained; then, the catalyst of Example 7 was replaced with it to prepare allyl epoxy-terminated polyether, and the results are shown in Table 2.

[0109] Comparative Example 4

[0110] Following the method of Example 7, except that the Schiff base metal complex was replaced with a porphyrin metal complex, while other operations and conditions remained unchanged, allyl epoxy-terminated polyethers were prepared, and the results are shown in Table 2.

[0111] Table 2. Test results of Examples 7-10 and comparative examples.

[0112]

Claims

1. The application of a Schiff alkali metal complex as a catalyst for the preparation of allyl epoxy-terminated polyethers, characterized in that, The Schiff base metal complex comprises a Schiff base ligand and a central metal ion, wherein, The Schiff base ligand is a condensation product of phenylenediamine and 3,5-di-tert-butylsalicylaldehyde. The central metal ion is selected from any one of Ti, Mn, Ni, Cu, and Co; The Schiff base metal complex is used as a catalyst for the preparation of allyl epoxy-terminated polyethers.

2. The application according to claim 1, characterized in that, The Schiff base ligand is a condensation product of one molecule of phenylenediamine and two molecules of 3,5-di-tert-butylsalicylaldehyde.

3. The application according to claim 1, characterized in that, The central metal ion is either Mn or Ni.

4. The application according to claim 1, characterized in that, The Schiff base ligand has the structure shown in the following formula: 。 5. The application according to claim 1, characterized in that, The method for preparing the Schiff base metal complex includes the following steps: 1) Phenylenediamine and 3,5-di-tert-butylsalicylaldehyde were dissolved in an alcohol solvent, and the mixture was heated under stirring. The mixture was then cooled to precipitate a solid. The solid was filtered, washed with ice-cold ethanol, and dried to obtain a Schiff base ligand. 2) Dissolve the Schiff base ligand from step 1) in an organic solvent, then add a soluble salt containing a central metal ion, and react under stirring. Then remove the organic solvent under reduced pressure to obtain the Schiff base metal complex.

6. The application according to claim 5, characterized in that, Step 1) The molar ratio of phenylenediamine to 3,5-di-tert-butylsalicylaldehyde is 1:2-2.1; and / or Step 1) The amount of alcohol solvent used is in a mass ratio of 20-30:1 to the total mass of phenylenediamine and 3,5-di-tert-butylsalicylaldehyde; and / or Step 1) The alcohol solvent is selected from at least one of anhydrous ethanol and anhydrous methanol; and / or The reaction described in step 1) is carried out at a temperature of 60-80℃ for 5-8 hours; and / or Step 1) involves cooling to precipitate solids, using a temperature of 0-10℃ and a time of 10-30 minutes.

7. The application according to claim 5, characterized in that, The molar ratio of phenylenediamine to 3,5-di-tert-butylsalicylaldehyde in step 1) is 1:2.05-2.

1.

8. The application according to claim 5, characterized in that, Step 2) The soluble salt containing the central metal ion is selected from acetate, chloride, and trifluoroacetate containing the central metal ion; The central metal ion is selected from any one of Ti, Mn, Ni, Cu, and Co; and / or Step 2) The molar ratio of the soluble salt containing the central metal ion to the Schiff base ligand is 1:0.9-1; and / or Step 2) The Schiff base ligand dissolved in the organic solvent has a concentration of 0.1-0.5 g / mL; and / or Step 2) The organic solvent is selected from at least one of dichloromethane and ethyl acetate; and / or The reaction described in step 2) is carried out at a temperature of 20-30℃ for 3-5 hours.

9. The application according to claim 8, characterized in that, The molar ratio of the soluble salt containing the central metal ion to the Schiff base ligand is 1:0.9-0.

95.

10. A method for preparing an allyl epoxy-terminated polyether, characterized in that, Includes the following steps: S1: Methallyl polyether is prepared by reacting methyl allyl alcohol with ethylene oxide as a starting agent; S2: Mix methyl allyl polyether with sodium methoxide and carry out an alkoxide reaction, then add allyl chloride to react and generate methyl allyl allyl double-terminated polyether; S3: Allyl epoxy-terminated polyether is prepared by mixing and reacting methyl allyl allyl double-terminated polyether, m-chloroperoxybenzoic acid, and Schiff base metal complex. The Schiff base metal complex mentioned in step S3 is the Schiff base metal complex according to any one of claims 1-9.

11. The preparation method according to claim 10, characterized in that, The molar ratio of the methyl allyl allyl double-terminated polyether to m-chloroperoxybenzoic acid in step S3 is 1:1.0-1.05; and / or The amount of Schiff base metal complex added in step S3 is 0.1-0.2 wt% of the mass of methyl allyl allyl double-terminated polyether; and / or The reaction described in step S3 is carried out at a temperature of 60-80℃ for 3-6 hours.

12. The preparation method according to claim 10, characterized in that, The mass ratio of methyl allyl alcohol to ethylene oxide in step S1 is 1:4-35; and / or The reaction described in step S1 is carried out at a temperature of 100-110°C for 6-8 hours; and / or The molar ratio of methyl allyl polyether to sodium methoxide in step S2 is 1:1-1.1; and / or In step S2, the molar ratio of methyl allyl polyether to allyl chloride is 1:1-1.1; and / or The alkoxide reaction described in step S2 is carried out at a temperature of 80-100℃ for 3-6 hours.

13. The preparation method according to claim 10, characterized in that, In step S2, the reaction with allyl chloride is carried out at a temperature of 60-80°C for 7-8 hours.

14. The preparation method according to claim 13, characterized in that, During the reaction, the allyl chloride is fed continuously for 3-5 hours, and the feeding time is included in the reaction time.

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