Catalyst for preparing tetraisopropanolethylenediamine as well as preparation method and application of catalyst

Abstract

The invention belongs to the technical field of preparation of tetraisopropyl alcohol-based ethylenediamine, and particularly relates to a catalyst for preparing tetraisopropyl alcohol-based ethylenediamine as well as a preparation method and application of the catalyst. The catalyst is formed by chelating two amine nitrogen atoms with aluminum ions by taking an Al < 3 + > center as tetra-coordination and 1, 1-dimethoxytrimethylamine as a ligand, and has a structure as shown in a formula I in the specification. The two-component composite catalyst is formed on the basis of coordination and chelation of the organic metal compound and the organic amine, the organic metal compound can promote the antistatic performance of the tetraisopropyl alcohol ethylenediamine, and the organic amine can promote the compatibility of the tetraisopropyl alcohol ethylenediamine and a high polymer material, so that the antistatic property of the tetraisopropyl alcohol ethylenediamine is improved. Compared with a pure organic amine catalyst, the composite catalyst has the advantages of high reaction activity, side reaction inhibition, improvement of the conversion rate and selectivity of tetraisopropanolethylenediamine, no need of separation from the product, promotion of the product, reduction of the impurity separation problem in the subsequent process, reduction of the reaction pressure, low equipment requirement and reduction of the equipment investment.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of tetraisopropyl alcohol ethylenediamine preparation, and particularly relates to a catalyst for preparing tetraisopropyl alcohol ethylenediamine, a preparation method and application thereof. BACKGROUND

[0002] Tetraisopropyl alcohol ethylenediamine is a colorless transparent viscous liquid, which can promote the crystallinity and migration speed of saturated linear alkanes and isomeric alkanes in the rubber product when used as a crosslinking agent, so that the rubber product has better mechanical strength and low-temperature toughness, and the weather resistance and service life of the rubber product are prolonged; the mixing uniformity of the rubber product is improved, the dispersion of inorganic and organic fillers in the rubber product is improved, and the mechanical strength and processing performance of the rubber product are appropriately improved; when used as an antistatic agent, the surface resistance of a polymer material product can be significantly reduced, and static electricity can be effectively controlled and eliminated; when used as a stabilizer, the polymer interface layer plays a role in transmitting stress and slowing down stress concentration, prevents crack propagation, causes energy transfer or absorbs external energy of the polymer product under the action of an external force field, improves the toughness of the polymer, and improves the mechanical strength and processing adaptability of the polymer. Therefore, it is necessary to research and produce a new type of multifunctional polymer material tetraisopropyl alcohol ethylenediamine to increase a new variety in the domestic market and improve the performance of polymer material products.

[0003] Tetraisopropyl alcohol ethylenediamine is generated by ring-opening addition reaction of ethylenediamine and propylene oxide under the action of a catalyst. However, a small amount of amine ether generated by a polymerization reaction is also generated by a side reaction. The reaction formula is as follows:

[0004] ; .

[0005] Therefore, the catalyst for catalytically synthesizing tetraisopropyl alcohol ethylenediamine must accelerate the main reaction and inhibit the side reaction. However, the reaction selectivity is not significant by using a fatty amine compound such as an organic amine compound as a catalyst, the byproduct is increased, the yield is not ideal, an impurity separation process is added for a subsequent process, and the process is not suitable for large-scale continuous industrial production. SUMMARY

[0006] The application aims to provide a catalyst for preparing tetraisopropyl alcohol ethylenediamine, a preparation method and application thereof. The application is based on a double-component composite catalyst formed by coordination chelation of an organic metal compound and an organic amine, wherein the organic metal compound can promote the antistatic property of the tetraisopropyl alcohol ethylenediamine, the organic amine can promote the compatibility of the tetraisopropyl alcohol ethylenediamine with a polymer material, the composite catalyst has higher reactivity than a pure organic amine catalyst, can inhibit side reactions, improve the conversion rate and selectivity of the tetraisopropyl alcohol ethylenediamine, does not need to be separated from the product, has a promoting effect on the product, reduces the impurity separation problem in the subsequent process, reduces the reaction pressure, has low requirements on equipment, and reduces equipment investment.

[0007] The application solves the above technical problems through the following technical scheme.

[0008] The first object of the application is to provide a catalyst for preparing tetraisopropyl alcohol ethylenediamine, wherein the catalyst is an Al 3+ center, 1,1-dimethoxytrimethylamine is a ligand, and the catalyst is formed by chelating aluminum ions through two amine nitrogen atoms and has a structure as shown in Formula I. .

[0009] Further, the catalyst belongs to a P2 1 / n space group.

[0010] The second object of the application is to provide a preparation method of the above catalyst for preparing tetraisopropyl alcohol ethylenediamine, which comprises the following steps. S1, dimethyl sulfate is added dropwise into N,N-dimethylformamide at 65-85 DEG C to perform a formylation reaction to obtain an imine complex; sodium methoxide is dispersed in D60 solvent oil, W1-40 white oil or isomeric alkanes to form a suspension, and then the imine complex is added dropwise into the suspension at 20-30 DEG C to perform a deprotonation reaction to obtain 1,1-dimethoxytrimethylamine.

[0011] S2, AlMe3 solution and 1,1-dimethoxytrimethylamine solution are mixed at -30 DEG C to -40 DEG C and then stirred at room temperature to perform coordination chelation, and then the catalyst is washed and dried after removing the solvent, the precursor is placed in toluene overnight to obtain a metal organic compound containing asymmetric 1,1-dimethoxytrimethylamine ligand, i.e. the catalyst for preparing tetraisopropyl alcohol ethylenediamine.

[0012] Further, the volume ratio of the AlMe3 solution and the 1,1-dimethoxytrimethylamine solution is 3:10, the concentration of the AlMe3 solution is 13M-16M, and the concentration of the 1,1-dimethoxytrimethylamine solution is 0.08g / mL-0.1g / mL.

[0013] Further, the time for coordination chelation is 10-16 hours.

[0014] Further, the molar ratio of dimethyl sulfate and N,N-dimethylformamide is 1:1, the time for dropping dimethyl sulfate is 1-2 hours, the temperature for formylation reaction is 65-85 DEG C, and the reaction time is 1-3 hours.

[0015] Further, the molar ratio of sodium methoxide and dimethyl sulfate is 1-2:1, the time for dropping imine complex is 1-2 hours, the temperature for deprotonation reaction is 20-30 DEG C, and the reaction time is 1-4 hours.

[0016] The third object of the present application is to provide the application of the catalyst for preparing tetraisopropyl alcohol-based ethylenediamine in preparing tetraisopropyl alcohol-based ethylenediamine, which comprises the following steps: The tetraisopropyl alcohol-based ethylenediamine is separated after ring-opening addition reaction of ethylenediamine and propylene oxide under the action of the catalyst.

[0017] Further, the amount of the catalyst is 0.5-1.5 wt.% of the total amount of raw materials.

[0018] Further, the molar ratio of ethylenediamine and propylene oxide is 1:1-1.4, the reaction temperature is 140-180 DEG C, the reaction pressure is 0.1-0.2 Mpa, and the reaction time is 30-60 minutes.

[0019] Compared with the prior art, the present application has the following beneficial effects: The present application provides a catalyst for preparing tetraisopropyl alcohol-based ethylenediamine. 3+ The center is tetra-coordinated, 1,1-dimethoxytrimethylamine is used as a ligand, and the aluminum ion is formed by chelation through two amine nitrogen atoms, a double-component composite catalyst is formed based on organic metal compound and organic amine coordination chelation, wherein the organic metal compound can promote the antistatic property of tetraisopropyl alcohol-based ethylenediamine, the organic amine can promote the compatibility of tetraisopropyl alcohol-based ethylenediamine with high polymer materials, the composite catalyst has higher reaction activity than the pure organic amine catalyst, inhibits side reactions, improves the conversion rate and selectivity of tetraisopropyl alcohol-based ethylenediamine, does not need to be separated from the product, promotes the product, reduces the impurity separation problem in the subsequent process, reduces the reaction pressure, has low requirement for equipment, and reduces equipment investment.

[0020] The present application makes the imine complex react with sodium methoxide at normal temperature (20-30 DEG C) by D60 solvent oil, W1-40 white oil or isomeric alkane, does not need to provide the refrigeration equipment and process of temperature condition, avoids the generation of by-product, improves the yield of 1,1-dimethoxytrimethylamine, and is coordinated and chelated by AlMe3 and 1,1-dimethoxytrimethylamine, is formed by chelating aluminum ions through two amine nitrogen atoms, and the asymmetric 1,1-dimethoxytrimethylamine ligand-containing metal organic compound is obtained, and the catalytic performance of the catalyst is improved. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The ellipsoid diagram of the catalyst for preparing tetraisopropyl alcohol-based ethylenediamine according to the present application.

[0022] Figure 2 The infrared spectrum of 1,1-dimethoxytrimethylamine prepared in the embodiment of the present application. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0024] It should be noted that the professional terms used in the present application are only for the purpose of describing the specific embodiments, and are not intended to limit the protection scope of the present application. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present application can be purchased from the market or prepared by the existing method.

[0025] Tetraisopropyl alcohol-based ethylenediamine is prepared by ring-opening addition reaction of ethylenediamine and propylene oxide under the action of a catalyst. However, a small amount of amine ether, which is a polymerization product, is also generated by a side reaction. Therefore, the catalyst for catalytically synthesizing tetraisopropyl alcohol-based ethylenediamine must accelerate the main reaction and inhibit the side reaction. The reaction selectivity is not significant by using a fatty amine compound such as an organic amine compound, the by-product is increased, the yield is not ideal, an impurity separation process is added for the subsequent process, and it is not suitable for large-scale continuous industrial production.

[0026] Therefore, the present application provides a catalyst for preparing tetraisopropyl alcohol-based ethylenediamine. 3+ The center is tetra-coordinated, 1,1-dimethoxytrimethylamine is used as a ligand, aluminum ions are chelated through two amine nitrogen atoms, and has a structure as shown in formula I: .

[0027] In the present application, a dual-component complex catalyst is formed by coordination chelation of an organometallic compound and an organic amine, wherein the organometallic compound can promote the antistatic property of tetraisopropyl alcohol ethylenediamine, and the organic amine can promote the compatibility of tetraisopropyl alcohol ethylenediamine with the polymer material. The complex catalyst has higher reactivity than the pure organic amine catalyst, inhibits side reactions, improves the conversion rate and selectivity of tetraisopropyl alcohol ethylenediamine, does not need to be separated from the product, promotes the product, reduces the impurity separation problem in the subsequent process, reduces the reaction pressure, has low requirements for equipment, and reduces equipment investment.

[0028] In some embodiments, the catalyst belongs to the P2 1 / n space group. As shown in Figure 1 X-ray single crystal diffraction is used to characterize the synthesized single crystal, and single crystal X-ray diffraction analysis shows that the organic compound is monoclinic, and the space group is P21 / n. The mononuclear compound is composed of one Al 3+ ion, one 1,1-dimethoxytrimethylamine ligand, and two methyl groups. The central Al 3+ ion is tetrahedrally coordinated and has a distorted tetrahedral geometry. The ligand 1,1-dimethoxytrimethylamine chelates the aluminum ion through two amine nitrogen atoms. The Al-C(Me) bond length (1.941(6) Å and 1.950(6) Å) is shorter than that reported for aluminum complexes, indicating that the substituents on the amino nitrogen atoms affect the Al-C bond length. Through structural analysis, the metal-organic compound containing asymmetric 1,1-dimethoxytrimethylamine ligands, and part of the bond length and bond angle data are shown in Table 1.

[0029] Table 1 Partial bond length and bond angle data results A second object of the present application is to provide a preparation method of the above-mentioned catalyst for preparing tetraisopropyl alcohol ethylenediamine, comprising the following steps: S1, at 65-85°C, dimethyl sulfate is added dropwise to N,N-dimethylformamide to carry out formylation reaction to obtain imine complex; sodium methoxide is dispersed in a solvent to form a suspension, and then the imine complex is added dropwise to the suspension at 20-30°C to carry out deprotonation reaction to obtain 1,1-dimethoxytrimethylamine. The synthesis route is as follows:

[0030] .

[0031] As a preferred scheme of the present application, the solvent is D60 solvent oil, W1-40 white oil or isomeric alkane. Among them, D60 solvent oil, W1-40 white oil or isomeric alkane are all alkane compounds refined from petroleum or coal tar, but their main components and distillation ranges are different, wherein the main component of D60 solvent oil is linear alkane with a distillation range of 180-210℃, the main component of W1-40 white oil is naphthene with a distillation range of 140-200℃, and the main component of isomeric alkane is isomeric alkane with a distillation range of 140-200℃. Due to the difference in component structure, the solubility of the product DMFDMA is different, and the isomeric alkane as an organic solvent can quickly dissolve DMFDMA into the organic solvent, so that the organic solvent can dissolve and wrap the product generated by the reaction, thereby avoiding the generation of by-products and improving the yield.

[0032] As a preferred scheme of the present application, the molar ratio of dimethyl sulfate and N,N-dimethylformamide is 1:1, the dropping time of dimethyl sulfate is 1-2h, the temperature of formylation reaction is 65-85℃, and the reaction time is 1-3h. In the present application, the yield of imine complex first increases and then decreases with the temperature of formylation reaction, and the yield is the highest at a temperature of 75℃, so the optimal reaction temperature for synthesizing the imine complex in the first step is 75℃.

[0033] As a preferred scheme of the present application, the molar ratio of sodium methoxide and dimethyl sulfate is 1-2:1, the dropping time of imine complex is 1-2h, the temperature of deprotonation reaction is 20-30℃, and the reaction time is 1-4h. In the present application, since the reaction of imine complex and sodium methoxide is an exothermic reaction, the yield of product is relatively high when the dropping time of imine complex is 2h, and the reaction yield increases with the total time, but there is no obvious increase in the reaction yield after 4h. Therefore, considering the shortening of reaction time and the reduction of energy consumption, the total reaction time is 4h, the dropping time of imine complex is 2h, and the reaction time is 2h.

[0034] S2, using AlMe3 solution and 1,1-dimethoxytrimethylamine solution as raw materials, mixing at-30℃ to-40℃, then stirring at room temperature to perform coordination chelation, washing and drying after removing the solvent to obtain a precursor, and then placing the precursor in toluene overnight to obtain a metal organic compound containing asymmetric 1,1-dimethoxytrimethylamine ligand, which is a catalyst for preparing tetraisopropyl alcohol-based ethylenediamine. The synthesis route is as follows:

[0035] .

[0036] As a preferred scheme of the present application, the volume ratio of the AlMe3 solution and the 1,1-dimethoxytrimethylamine solution is 3:10, the concentration of the AlMe3 solution is 13M-16M, and the concentration of the 1,1-dimethoxytrimethylamine solution is 0.08g / mL-0.1g / mL. In the present application, after the coordination chelation is carried out at room temperature for 10h-16h, the volatile matter is removed under reduced pressure to obtain a white solid. The white solid is washed with n-hexane and vacuum dried to obtain a colorless solid, the white solid is dissolved in toluene, and the solution is left to stand overnight to obtain a colorless crystal, i.e. a catalyst for preparing tetraisopropylol ethylenediamine.

[0037] In addition, the present application further provides an application of the above-mentioned catalyst for preparing tetraisopropylol ethylenediamine in preparing tetraisopropylol ethylenediamine, which comprises the following steps: taking ethylenediamine and propylene oxide as raw materials, and carrying out a ring-opening addition reaction under the action of the catalyst to separate tetraisopropylol ethylenediamine.

[0038] As a preferred scheme of the present application, the amount of the catalyst is 0.5wt.%-1.5wt.% of the total amount of the raw materials, the molar ratio of the ethylenediamine and the propylene oxide is 1:1-1.4, the reaction temperature is 140℃-180℃, the reaction pressure is 0.1Mpa-0.2Mpa, and the reaction time is 30min-60min.

[0039] The present application forms tetraisopropylol ethylenediamine under the action of a metal organic compound and an organic amine composite catalyst, has high reactivity, does not need to be separated from the product, and has a promoting effect on the product, thereby reducing the impurity separation problem in the subsequent process.

[0040] The following is further illustrated through specific examples.

[0041] Example 1 The preparation method of the 1,1-dimethoxytrimethylamine comprises the following steps: S1, 73.10g (1mol) of dimethyl sulfate is added to a reaction bottle, heated and stirred, the temperature is controlled at 75℃, and dimethyl sulfate 126.13g (1mol) is slowly added dropwise, about 1h for dropwise addition, stirring is continued, the temperature is maintained at 75℃, and reaction is carried out for 2h to obtain a light yellow imine complex.

[0042] S2, Synthesis of 1,1-dimethoxytrimethylamine: 200 mL isoparaffin was added to a reaction flask, then 64.83 g (1.2 mol) of sodium methoxide was slowly added to the isoparaffin, stirring to disperse it, forming a uniform suspension; the imine complex was slowly added dropwise to the suspension, stirring, the temperature was maintained at 20-30 °C during the dropwise addition, about 2 h to complete the dropwise addition, maintaining 20-30 °C, stirring continued to react for 2 h, after the reaction was completed, the mixture was filtered, the filtrate was distilled at normal pressure using a 30 cm spiked fraction column, collecting the fraction at 104-108 °C, obtaining 1,1-dimethoxytrimethylamine. The synthesis route is as follows:

[0043] .

[0044] Example 2 The method for preparing 1,1-dimethoxytrimethylamine includes the following steps: S1, 73.10 g (1 mol) of dimethyl sulfate was added to a reaction flask, heated and stirred, the temperature was controlled at 75 °C, dimethyl sulfate 126.13 g (1 mol) was slowly added dropwise, about 1 h to complete the dropwise addition, continued stirring, maintaining the temperature at 75 °C, reacting for 2 h, obtaining a light yellow imine complex.

[0045] S2, Synthesis of 1,1-dimethoxytrimethylamine: 200 mL W1-40 white oil was added to a reaction flask, then 64.83 g (1.2 mol) of sodium methoxide was slowly added to the W1-40 white oil, stirring to disperse it, forming a uniform suspension; the imine complex was slowly added dropwise to the suspension, stirring, the temperature was maintained at 20-30 °C during the dropwise addition, about 2 h to complete the dropwise addition, maintaining 20-30 °C, stirring continued to react for 2 h, after the reaction was completed, the mixture was filtered, the filtrate was distilled at normal pressure using a 30 cm spiked fraction column, collecting the fraction at 104-108 °C, obtaining 1,1-dimethoxytrimethylamine. The synthesis route is as follows:

[0046] .

[0047] Example 3 The method for preparing 1,1-dimethoxytrimethylamine includes the following steps: S1, 73.10 g (1 mol) of dimethyl sulfate was added to a reaction flask, heated and stirred, the temperature was controlled at 75 °C, dimethyl sulfate 126.13 g (1 mol) was slowly added dropwise, about 1 h to complete the dropwise addition, continued stirring, maintaining the temperature at 75 °C, reacting for 2 h, obtaining a light yellow imine complex.

[0048] S2, Synthesis of 1,1-dimethoxytrimethylamine: 200 mL of D60 solvent oil was added into the reaction bottle, then 64.83 g (1.2 mol) of sodium methoxide was slowly added into the D60 solvent oil, and stirred to disperse to form a uniform suspension; the imine complex was slowly added into the suspension, and stirred, the temperature was kept at 20-30 °C during the dropping process, it was dropped for about 2 h, and the stirring was continued for 2 h at 20-30 °C, after the reaction was completed, the mixture was filtered, the filtrate was distilled under normal pressure by using a 30 cm thorn-shaped fractionating column, and the fraction of 104-108 °C was collected to obtain 1,1-dimethoxytrimethylamine. The synthesis route is as follows:

[0049] .

[0050] Comparative Example 1 The preparation method of 1,1-dimethoxytrimethylamine comprises the following steps: S1, 73.10 g (1 mol) of dimethyl sulfate was added into the reaction bottle, and heated and stirred to control the temperature at 75 °C, then 126.13 g (1 mol) of dimethyl sulfate was slowly added dropwise, it was dropped for about 1 h, the stirring was continued, the temperature was kept at 75 °C, and the reaction was continued for 2 h to obtain a light yellow imine complex.

[0051] S2, Synthesis of 1,1-dimethoxytrimethylamine: 200 mL of D60 solvent oil was added into the reaction bottle, then 64.83 g (1.2 mol) of sodium methoxide was slowly added into the D60 solvent oil, and stirred to disperse to form a uniform suspension; the imine complex was slowly added into the suspension, and stirred, the temperature was kept at 20-30 °C during the dropping process, it was dropped for about 2 h, and the stirring was continued for 2 h at 20-30 °C, after the reaction was completed, the mixture was filtered, the filtrate was distilled under normal pressure by using a 30 cm thorn-shaped fractionating column, and the fraction of 104-108 °C was collected to obtain 1,1-dimethoxytrimethylamine. The synthesis route is as follows:

[0052] The yield of 1,1-dimethoxytrimethylamine (DMFDMA) prepared in Comparative Examples 1-3 and Comparative Example 1 was tested, and the results are shown in Table 2. When the reaction organic solvent is petroleum ether, and the temperature is kept below 0 °C during the reaction, the yield of the product DMFDMA is 65.92%. When the reaction organic solvent is D60 solvent oil, W1-40 white oil or isomeric alkanes, and the temperature is kept at 20-30 °C during the reaction, the yield of the product DMFDMA is greatly improved. When isomeric alkanes are used as the organic solvent, DMFDMA can be quickly dissolved in the organic solvent, the product generated in the reaction is dissolved and wrapped by the organic solvent, the generation of by-products is avoided, the yield is improved, and the yield of DMFDMA is 85.41%.

[0053] Table 2 Yield of 1,1-dimethoxytrimethylamine (DMFDMA) The structure of 1,1-dimethoxytrimethylamine (DMFDMA) prepared in Example 1 was tested, Figure 2 The infrared spectrum of 1,1-dimethoxytrimethylamine prepared for the embodiment of the present application is shown in Figure 1. Figure 2 As shown, 2990 cm -1 ~ 2783 cm -1 is the stretching vibration peak of C—H, 1682 cm -1 is the stretching vibration peak of tertiary amine, 1445 cm -1 ~ 1381 cm -1 is the bending vibration peak of —CH3, 1346 cm -1 is the bending vibration peak of (—CH), 1298 cm -1 ~ 999 cm -1 is the stretching vibration peak of C—O, and 1057 cm -1 shows a strong absorption peak. The corresponding group characteristics given by the infrared spectrum and the molecular formula of DMFDMA are consistent.

[0054] 1 HNMR (400 MHz, CDCl3), δ: 4.359 (s, 1H,—CH), 3.329 (s, 6H,—OCH3), 2.289 (s, 6H,—CH3) are consistent with the structure of DMFDMA. The refractive index of DMFDMA is nD 20 = 1.395, indicating that the product is 1,1-dimethoxytrimethylamine.

[0055] Example 4 The preparation method of the catalyst for preparing tetraisopropyl alcohol-based ethylenediamine includes the following steps: 4.53 g of DMFDMA prepared in Example 1 above was dissolved in 50 mL of THF to obtain a DMFDMA solution; the DMFDMA solution was slowly added dropwise to 15 mL of AlMe3 n-hexane solution with a concentration of 15.0 M at -35°C to form a reaction mixture, and the reaction mixture was stirred at room temperature overnight, after which the volatile matter was removed under reduced pressure to obtain a white solid. The white solid was washed with n-hexane and dried under vacuum to obtain a colorless solid. Yield: 0.371 g (94%). The white solid was dissolved in toluene, and colorless crystals were obtained after the solution was left to stand overnight. A metal organic compound containing an asymmetric 1,1-dimethoxytrimethylamine ligand was obtained, which is a catalyst for preparing tetraisopropyl alcohol-based ethylenediamine. The synthetic route is as follows:

[0056] .

[0057] The catalyst prepared in Example 4 was used to prepare tetraisopropylol ethylenediamine, as shown below.

[0058] Application Example 1 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: The ethylenediamine and the catalyst were put into a reaction kettle, the air in the kettle was replaced with nitrogen, and then the temperature was raised to 50°C, the stirring speed was 200 r / min, propylene oxide was quantitatively added to the synthesis kettle through a metering pump, the temperature of the material in the kettle was controlled at 160°C, and the pressure was 0.15 MPa. After the quantitative addition of propylene oxide was completed, the molar ratio of ethylenediamine to propylene oxide was 1:1.2, the amount of catalyst was 0.7 wt.% of the total amount of raw materials, and the reaction was continued at 160°C for 50 min. Then the reaction material was transported to a distillation column for distillation, and the yield of tetraisopropylol ethylenediamine was detected by a FULI 9790 II type gas chromatograph.

[0059] Application Example 2 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: The ethylenediamine and the catalyst were put into a reaction kettle, the air in the kettle was replaced with nitrogen, and then the temperature was raised to 50°C, the stirring speed was 200 r / min, propylene oxide was quantitatively added to the synthesis kettle through a metering pump, the temperature of the material in the kettle was controlled at 160°C, and the pressure was 0.15 MPa. After the quantitative addition of propylene oxide was completed, the molar ratio of ethylenediamine to propylene oxide was 1:1.2, the amount of catalyst was 0.9 wt.% of the total amount of raw materials, and the reaction was continued at 160°C for 50 min. Then the reaction material was transported to a distillation column for distillation, and the yield of tetraisopropylol ethylenediamine was detected by a FULI 9790 II type gas chromatograph.

[0060] Application Example 3 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: The ethylenediamine and the catalyst were put into a reaction kettle, the air in the kettle was replaced with nitrogen, and then the temperature was raised to 50°C, the stirring speed was 200 r / min, propylene oxide was quantitatively added to the synthesis kettle through a metering pump, the temperature of the material in the kettle was controlled at 160°C, and the pressure was 0.15 MPa. After the quantitative addition of propylene oxide was completed, the molar ratio of ethylenediamine to propylene oxide was 1:1.2, the amount of catalyst was 1 wt.% of the total amount of raw materials, and the reaction was continued at 160°C for 50 min. Then the reaction material was transported to a distillation column for distillation, and the yield of tetraisopropylol ethylenediamine was detected by a FULI 9790 II type gas chromatograph.

[0061] Application Example 4 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: The ethylenediamine and catalyst are put into a reaction kettle, the air in the kettle is replaced by nitrogen, and then the temperature is raised to 50°C, the stirring speed is 200 r / min, propylene oxide is quantitatively added to the synthesis kettle through a metering pump, the temperature of the material in the kettle is controlled at 160°C, and the pressure is 0.15 MPa. After the quantitative addition of propylene oxide is completed, the molar ratio of ethylenediamine to propylene oxide is 1:1.2, and the amount of catalyst is 1.3 wt.% of the total amount of raw materials. The reaction is continued at 160°C for 50 min, and then the reaction material is transported to a distillation column for distillation. The yield of tetraisopropylol ethylenediamine is detected by a FULI 9790 II type gas chromatograph.

[0062] Application Example 5 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: The ethylenediamine and catalyst are put into a reaction kettle, the air in the kettle is replaced by nitrogen, and then the temperature is raised to 50°C, the stirring speed is 200 r / min, propylene oxide is quantitatively added to the synthesis kettle through a metering pump, the temperature of the material in the kettle is controlled at 160°C, and the pressure is 0.15 MPa. After the quantitative addition of propylene oxide is completed, the molar ratio of ethylenediamine to propylene oxide is 1:1.3, and the amount of catalyst is 1 wt.% of the total amount of raw materials. The reaction is continued at 160°C for 50 min, and then the reaction material is transported to a distillation column for distillation. The yield of tetraisopropylol ethylenediamine is detected by a FULI 9790 II type gas chromatograph.

[0063] Application Example 6 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: The ethylenediamine and catalyst are put into a reaction kettle, the air in the kettle is replaced by nitrogen, and then the temperature is raised to 50°C, the stirring speed is 200 r / min, propylene oxide is quantitatively added to the synthesis kettle through a metering pump, the temperature of the material in the kettle is controlled at 160°C, and the pressure is 0.15 MPa. After the quantitative addition of propylene oxide is completed, the molar ratio of ethylenediamine to propylene oxide is 1:1.1, and the amount of catalyst is 1 wt.% of the total amount of raw materials. The reaction is continued at 160°C for 50 min, and then the reaction material is transported to a distillation column for distillation. The yield of tetraisopropylol ethylenediamine is detected by a FULI 9790 II type gas chromatograph.

[0064] Application Example 7 The method for synthesizing tetraisopropylol ethylenediamine comprises the following steps: Put ethylenediamine and catalyst into the reaction kettle, replace the air in the kettle with nitrogen, then warm up to 50°C, stirring speed is 200r / min, add propylene oxide into the kettle by metering pump, control the temperature of the material in the kettle to be 160°C, pressure is 0.15MPa, after the quantitative propylene oxide is added, the molar ratio of ethylenediamine and propylene oxide is 1:1, the amount of catalyst is 1wt.% of the total amount of raw materials, continue to react at 160°C for 50min, then transport the reaction material to the distillation column for distillation, detect the yield of tetraisopropylol ethylenediamine by FULI9790II type gas chromatograph.

[0065] The yield of tetraisopropylol ethylenediamine in application examples 1-7 is shown in table 3.

[0066] Table 3 Yield of tetraisopropylol ethylenediamine As shown in table 3, with the increase of the amount of organometallic compound catalyst, the yield of tetraisopropylol ethylenediamine shows a rule of first increasing and then decreasing. When the amount is 1.0wt.%, with the increase of the amount of catalyst, the yield of tetraisopropylol ethylenediamine also rises. Because the amount of tetraisopropylol ethylenediamine is increased, the contact probability of tetraisopropylol ethylenediamine and reactants is improved, which promotes the main reaction. When the amount of catalyst is greater than 1.0wt.%, with the increase of the amount of catalyst, the yield of tetraisopropylol ethylenediamine decreases. However, with the increase of the amount of catalyst, the reaction rate of side reaction is improved, the byproduct increases, and the yield of product decreases. In addition, when ethylenediamine and propylene oxide are in a molar ratio of 1:1, one molecule of tetraisopropylol ethylenediamine can be generated. In practice, when the molar ratio of ethylenediamine and propylene oxide is small, the conversion of propylene oxide is not sufficient, so excess ethylenediamine is added. With the gradual increase of the amount of ethylenediamine, the yield of tetraisopropylol ethylenediamine also increases, and when the molar ratio of ethylenediamine and propylene oxide is 1.2:1, the yield reaches the maximum value of 91%. With the continuous increase of the amount of ethylenediamine, the side reaction increases, and the yield of tetraisopropylol ethylenediamine decreases. Therefore, the optimal molar ratio of raw materials ethylenediamine and propylene oxide is 1.2:1.

[0067] Tetraisopropylol ethylenediamine is a colorless transparent viscous liquid, which is mainly used as a crosslinking agent in rubber products, so that the rubber products have good mechanical strength. Compared with the same product produced by Bayer Company in Germany, as shown in table 4, the product quality fully meets the level of the same product of Bayer Company in Germany.

[0068] Table 4 Comparison of tetraisopropylol ethylenediamine It is to be understood that every range of values disclosed herein is to be understood to encompass any and every sub-range of values within the range. Although the preferred embodiments of the invention have been described above, it will be appreciated that those skilled in the art, on consideration of this disclosure, will be able to devise additional embodiments that, although not explicitly described or shown herein, nonetheless fall within the scope of the present invention. Accordingly, the appended claims are intended to include within their scope all such alternatives, modifications and variations as fall within the scope of the present invention. Various features and aspects of the present invention will become apparent from the following examples, which are intended only to exemplify the invention. It should be understood, of course, that in the various examples of the present invention, the specific phrasing of the claims will depend on the exact nature of the claims sought.

[0069] Obviously, numerous modifications and variations of the present application are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims and their equivalents, the present application can be practiced otherwise than as specifically described herein.

Claims

1. A catalyst for preparing tetraisopropanol-based ethylenediamine, characterized in that, The catalyst is Al 3+ The center is four-coordinated, with 1,1-dimethoxytrimethylamine as the ligand, and is formed by the chelation of aluminum ions by two amine nitrogen atoms, having the structure of Formula I: 。 2. The catalyst for preparing tetraisopropanol-ethylenediamine according to claim 1, characterized in that, The catalyst belongs to the monoclinic P2 crystal system 1 / n Space group.

3. A method for preparing the catalyst for preparing tetraisopropanol-ethylenediamine according to claim 1 or 2, characterized in that, Includes the following steps: Dimethyl sulfate was added dropwise to N,N-dimethylformamide at 65℃~85℃ to carry out a formylation reaction, yielding an imine complex; sodium methoxide was dispersed in D60 solvent oil, W1-40 white oil or isoalkanes to form a suspension, and then the imine complex was added dropwise to the suspension at 20℃~30℃ to carry out a deprotonation reaction, yielding 1,1-dimethoxytrimethylamine; Using AlMe3 solution and 1,1-dimethoxytrimethylamine solution as raw materials, the mixture was stirred at -30℃ to -40℃ and then subjected to coordination chelation at room temperature. After removing the solvent, the mixture was washed and dried to obtain a precursor. The precursor was then left to stand in toluene overnight to obtain an organometallic compound containing an asymmetric 1,1-dimethoxytrimethylamine ligand, which is the catalyst for the preparation of tetraisopropanol ethylenediamine.

4. The method for preparing the catalyst for preparing tetraisopropanol ethylenediamine according to claim 3, characterized in that, The volume ratio of AlMe3 solution to 1,1-dimethoxytrimethylamine solution is 3:10, the concentration of AlMe3 solution is 13M to 16M, and the concentration of 1,1-dimethoxytrimethylamine solution is 0.08g / mL to 0.1g / mL.

5. The method for preparing the catalyst for preparing tetraisopropanol-ethylenediamine according to claim 3, characterized in that, The coordination chelation time is 10h to 16h.

6. The method for preparing the catalyst for preparing tetraisopropanol ethylenediamine according to claim 3, characterized in that, The molar ratio of dimethyl sulfate to N,N-dimethylformamide is 1:

1. The dimethyl sulfate is added dropwise over a period of 1 to 2 hours. The formylation reaction is carried out at a temperature of 65°C to 85°C for a period of 1 to 3 hours.

7. The method for preparing the catalyst for preparing tetraisopropanol-ethylenediamine according to claim 3, characterized in that, The molar ratio of sodium methoxide to dimethyl sulfate is 1–2:1, the imine complex is added over a period of 1–2 hours, the deprotonation reaction is carried out at a temperature of 20–30°C for 1–4 hours.

8. The use of the catalyst for preparing tetraisopropanol ethylenediamine according to claim 1 or 2 in the preparation of tetraisopropanol ethylenediamine, characterized in that, Includes the following steps: Tetraisopropanol ethylenediamine was separated by a ring-opening addition reaction using ethylenediamine and propylene oxide as raw materials under the action of a catalyst.

9. The application according to claim 8, characterized in that, The amount of catalyst used is 0.5 wt.% to 1.5 wt.% of the total amount of raw materials.

10. The application according to claim 8, characterized in that, The molar ratio of ethylenediamine to propylene oxide is 1:1 to 1.4, the reaction temperature is 140℃ to 180℃, the reaction pressure is 0.1 MPa to 0.2 MPa, and the reaction time is 30 min to 60 min.

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