High performance tpee elastomer and method for its preparation

Abstract

This invention belongs to the field of polymer material synthesis, specifically relating to a high-performance TPEE elastomer and its preparation method. The method for preparing the high-performance TPEE elastomer provided by this invention uses chemically synthesized aminoketone as a ligand and isopropyl titanate as a titanium source to generate an aminoketone-coated titanate coordination catalyst in situ. This catalyst is then used to prepare the TPEE elastomer, achieving the synthesis of TPEE with high elasticity at a high soft segment content. The TPEE products prepared at the same hardness exhibit significantly improved heat resistance and tensile strength, and possess excellent color, thereby increasing the added value of the product and broadening its application scenarios.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis, specifically relating to a high-performance TPEE elastomer and its preparation method. Background Technology

[0002] Thermoplastic polyether ester elastomer (TPEE) is a block copolymer containing polyester hard segments and polyether soft segments, typically copolymerized from terephthalic acid (PTA), 1,4-butanediol (BDO), and polytetrahydrofuran ether (PTMG). TPEE molecules exhibit a two-phase associative structure; the crystalline hard segments act as physical cross-links, stabilizing product dimensions, while the amorphous soft segments impart high resilience to the polymer. It possesses advantages such as high mechanical strength, good elasticity, impact resistance, creep resistance, cold resistance, flexural fatigue resistance, oil resistance, and resistance to chemical and solvent corrosion. It also exhibits good processability and can be filled, reinforced, and alloyed. TPEE is widely used in automotive parts, hydraulic hoses, cables and wires, electronics, industrial products, sporting goods, and biomaterials.

[0003] With the rapid development of modern industry, the demand for elastomer materials that combine high elasticity, high modulus, high strength, and high heat resistance has increased significantly. However, to improve elasticity, the traditional method is to increase the content of soft segments, but this will significantly reduce its melting point. As the content of the soft segment PTMEG continues to increase, the hardness of TPEE continues to decrease, and the resilience continues to increase, while the melting point, tensile strength, and tear strength continue to decrease.

[0004] Therefore, traditional methods of adjusting the ratio of soft and hard segments cannot simultaneously achieve effective improvements in elasticity, heat resistance, and mechanical properties. Summary of the Invention

[0005] This invention aims to at least partially address one of the technical problems in related technologies. To this end, embodiments of this invention propose a method for preparing a high-performance TPEE elastomer.

[0006] The method for preparing high-performance TPEE elastomer according to embodiments of the present invention includes the following steps: (1) Add benzoin and 2,6-diaminopyridine to a hydrochloric acid solution of toluene to react. After the reaction is completed, filter under reduced pressure to obtain aminoketone residue. (2) Dissolve isopropyl titanate in 1,4-butanediol, ultrasonically stir, add the amino ketone residue obtained in step (1), and react under reduced pressure to obtain the catalyst; (3) Add terephthalic acid to 1,4-butanediol and the catalyst prepared in step (2). Heat and pressurize to carry out esterification reaction. Start timing after water is released. Add polytetrahydrofuran ether after esterification reaction to continue reaction. After the reaction is completed, add the auxiliary agent tributyl phosphate and antioxidant 1010 to carry out pre-condensation reaction by heating and depressurizing. After the pre-condensation reaction is completed, carry out final condensation reaction under high vacuum to obtain TPEE product.

[0007] The advantages and technical effects of the preparation method of high-performance TPEE elastomer in this invention are as follows: 1. In the method of this invention, a chemically synthesized aminoketone is used as a ligand, and isopropyl titanate is used as a titanium source to generate an aminoketone-coordinated titanate ester coordination catalyst in situ. As a multidentate complex, the nitrogen atom, amino group (-NH), and carbon group (-C=O) on the pyridine ring can coordinate with the titanium atom, thereby stabilizing the catalytic activity of titanium and reducing the generation of side reactions. As the reaction proceeds, the continuously dissociated aminoketone complex, with its rigid structure containing multiple benzene rings and pyridine rings and the presence of C=O and NH bonds, can enhance the intermolecular forces with the TPEE molecular chain through intermolecular hydrogen bonds, n-Π, and Π-Π interactions, improving the mechanical and heat resistance properties of the polymer while maintaining its toughness and elasticity. 2. In the method of this invention, the addition of phosphate ester can both react with the incompletely coordinated isopropyl titanate in the catalytic system to stabilize the highly active titanate ester in the esterification stage and act as a promoter in the transesterification stage to accelerate the reaction. The addition of antioxidants can reduce the oxidation of molecules with high content of flexible chains at high temperatures, thus maintaining the excellent color of the product; 3. The method of this invention improves the stability of the catalyst while ensuring the catalytic activity of titanium. The introduced amino ketone structure can enhance the intermolecular forces inside the material, realizing the synthesis of TPEE with high elasticity under high soft segment content. The heat resistance and tensile strength of the TPEE products prepared under the same hardness are significantly improved, and they have excellent color, which increases the added value of the product and broadens the application scenarios of the product.

[0008] In some embodiments, in step (1), the molar ratio of benzoin to 2,6-diaminopyridine is (1.5~3):1; And / or, in step (1), the concentration of benzoin and 2,6-diaminopyridine in the hydrochloric acid solution of toluene is 1~5 mol / L; And / or, in step (1), the concentration of hydrochloric acid in the hydrochloric acid solution of toluene is 0.1~0.5 mol / L.

[0009] And / or, in step (1), the reaction temperature is 50~110 ℃ and the reaction time is 6~18 h.

[0010] In some embodiments, in step (2), the concentration of isopropyl titanate in 1,4-butanediol is 0.5~5 mol / L.

[0011] In some embodiments, in step (2), the molar ratio of the aminoketone residue to isopropyl titanate is (1~2):1, wherein the molar amount of the aminoketone residue is equal to the molar amount of 2,6-diaminopyridine. And / or, the pressure of the decompression reaction is 5~20 kPa, the temperature of the reaction is 40~80 ℃, and the reaction time is 2~6 h.

[0012] In some embodiments, in step (3), the molar ratio of terephthalic acid and 1,4-butanediol is 1:(1.4~2.0). And / or, in step (3), the amount of catalyst added is 200~600 ppm, based on the titanium content in the catalyst relative to the mass of terephthalic acid; or, the catalyst is added in two parts, 150~300 ppm is added during the esterification reaction, and 50~300 ppm is added at the same time as the addition of the polytetrahydrofuran, based on the titanium content in the catalyst relative to the mass of terephthalic acid.

[0013] In some embodiments, in step (3), the temperature of the esterification reaction is 220~240℃, the pressure of the esterification reaction is 50~80kPa, and the time of the esterification reaction is 1.5~3h.

[0014] In some embodiments, in step (3), the molecular weight of the polytetrahydrofuran is 500~2000 g / mol, the theoretical mass ratio of polytetrahydrofuran to the polymer is (0.5~0.7):1, and the reaction continues for 0.5~2 h after the addition of the polytetrahydrofuran.

[0015] In some embodiments, in step (3), the amount of tributyl phosphate added is 0.02~0.2 wt%, and the amount of antioxidant 1010 added is 0.01~0.05 wt%, based on the mass of terephthalic acid.

[0016] In some embodiments, in step (3), the temperature of the pre-condensation reaction is 240~250℃, the reaction time is 60~120min, and the reaction pressure is 1~5kPa; And / or, in step (3), the temperature of the final polycondensation reaction is 240~250℃, the reaction pressure is 50~200Pa, and the reaction time is 2~5 h.

[0017] This invention also provides a high-performance TPEE elastomer, which is prepared using the above-described preparation method. Attached Figure Description

[0018] Figure 1 This is the infrared spectrum of the catalyst prepared in Example 1; Figure 2 This is the 1H NMR spectrum of the TPEE obtained in Example 1; Figure 3 This is the 1H NMR spectrum of the TPEE obtained in Example 2. Detailed Implementation

[0019] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0020] The method for preparing high-performance TPEE elastomer according to embodiments of the present invention includes the following steps: (1) Add benzoin (2-hydroxy-1,2-diphenyl ethyl ketone) and 2,6-diaminopyridine to a hydrochloric acid solution of toluene to carry out the reaction. After the reaction is completed, filter under reduced pressure to obtain amino ketone residue. (2) Dissolve isopropyl titanate in 1,4-butanediol, ultrasonically stir, add the amino ketone residue obtained in step (1), and react under reduced pressure to obtain the catalyst; (3) Add terephthalic acid (PTA) to 1,4-butanediol (BDO) and the catalyst prepared in step (2). Heat and pressurize to carry out esterification reaction. Start timing after water is discharged. After esterification reaction, add polytetrahydrofuran ether (PTMEG) to continue the reaction. After the reaction is completed, add the auxiliary agent tributyl phosphate and antioxidant 1010 and heat and pressurize to carry out pre-condensation reaction. After the pre-condensation reaction is completed, carry out the final condensation reaction under high vacuum to obtain TPEE product.

[0021] The method for preparing high-performance TPEE elastomers in this invention uses chemically synthesized aminoketone as a ligand and isopropyl titanate as a titanium source to generate an aminoketone-coordinated titanate ester coordination catalyst in situ. As a multidentate complex, the nitrogen atom, amino group (-NH), and carbon group (-C=O) on the pyridine ring can coordinate with titanium atoms, thereby stabilizing the catalytic activity of titanium and reducing the formation of side reactions. As the reaction proceeds, the continuously dissociated aminoketone complex, with its rigid structure containing multiple benzene and pyridine rings and the presence of C=O and NH bonds, can enhance intermolecular forces with the TPEE molecular chain through intermolecular hydrogen bonds, n-π, and π-π interactions, improving mechanical and heat resistance properties while maintaining the polymer's toughness and elasticity. In this invention, the addition of phosphate ester can both react with the incompletely coordinated isopropyl titanate in the catalytic system, stabilizing the highly active titanate ester during the esterification stage, and also act as a promoter in the transesterification stage, accelerating the reaction. The addition of antioxidants can reduce the oxidation of molecules with high soft segment content at high temperatures, thus maintaining the excellent color of the product. The method of this invention improves the stability of the catalyst while ensuring the catalytic activity of titanium. The introduced amino ketone structure can enhance the intermolecular forces within the material, realizing the synthesis of TPEE with high elasticity under high soft segment content. The heat resistance and tensile strength of the TPEE products prepared under the same hardness are significantly improved, and they also have excellent color, which increases the added value of the product and broadens the application scenarios of the product.

[0022] The structure of the catalyst is shown in Formula I: Formula I. It should be noted that the catalyst obtained by this invention is a mixture having the two structures described above.

[0023] In some embodiments, preferably, in step (1), the molar ratio of benzoin to 2,6-diaminopyridine is (1.5~3):1; And / or, in step (1), the concentration of benzoin and 2,6-diaminopyridine in the hydrochloric acid solution of toluene is 1~5 mol / L; And / or, in step (1), the concentration of hydrochloric acid in the hydrochloric acid solution of toluene is 0.1~0.5 mol / L.

[0024] And / or, in step (1), the reaction temperature is 50~110 ℃ and the reaction time is 6~18 h.

[0025] In the embodiments of this invention, the preferred molar ratio of benzoin to 2,6-diaminopyridine is beneficial to the formation of multidentate aminoketone complexes and subsequent coordination reactions. If the amount of benzoin is too high, there will be more benzoin remaining after the reaction, which is not conducive to the subsequent coordination of titanate. If the amount of benzoin is too low, there will be more diaminopyridine remaining after the reaction is incomplete, which is more likely to form strong amino-coordinated complexes and reduce the catalyst activity.

[0026] In some embodiments, preferably, in step (2), the concentration of isopropyl titanate in 1,4-butanediol is 0.5~5 mol / L.

[0027] In some embodiments, preferably, in step (2), the molar ratio of the amino ketone residue to isopropyl titanate is (1~2):1, wherein the molar amount of the amino ketone residue is equal to the molar amount of 2,6-diaminopyridine; And / or, the pressure of the decompression reaction is 5~20 kPa, the temperature of the reaction is 40~80 ℃, and the reaction time is 2~6 h.

[0028] In the embodiments of the present invention, the amount of amino ketone is preferred, which is beneficial to coordinate with isopropyl titanate to regulate the catalytic activity of titanium atoms; if the amount of amino ketone is too low, it cannot effectively combine with titanate to reduce the occurrence of side reactions; if the amount of amino ketone is too high, the combination with titanate is too tight, resulting in a significant decrease in catalytic activity.

[0029] In some embodiments, preferably, in step (3), the molar ratio of terephthalic acid and 1,4-butanediol is 1:(1.4~2.0). And / or, in step (3), the amount of catalyst added is 200~600 ppm, based on the titanium content in the catalyst relative to the mass of terephthalic acid; or, the catalyst is added in two parts, 150~300 ppm is added during the esterification reaction, and 50~300 ppm is added at the same time as the addition of the polytetrahydrofuran, based on the titanium content in the catalyst relative to the mass of terephthalic acid.

[0030] In some embodiments, preferably, in step (3), the temperature of the esterification reaction is 220~240℃, the pressure of the esterification reaction is 50~80kPa, and the time of the esterification reaction is 1.5~3 h.

[0031] In some embodiments, preferably, in step (3), the molecular weight of the polytetrahydrofuran is 500~2000 g / mol, the theoretical mass ratio of polytetrahydrofuran to the polymer is (0.5~0.7):1, and the reaction continues for 0.5~2 h after the addition of the polytetrahydrofuran.

[0032] In some embodiments, preferably, in step (3), the amount of tributyl phosphate added is 0.02~0.2wt%, and the amount of antioxidant 1010 added is 0.01~0.05wt%, based on the mass of terephthalic acid.

[0033] In some embodiments, preferably, in step (3), the temperature of the pre-condensation reaction is 240~250℃, the reaction time is 60~120min, and the reaction pressure is 1~5kPa; And / or, in step (3), the temperature of the final polycondensation reaction is 240~250℃, the reaction pressure is 50~200Pa, and the reaction time is 2~5 h.

[0034] This invention also provides a high-performance TPEE elastomer, which is prepared using the above-described preparation method.

[0035] The technical solution of the present invention will now be described in detail with reference to specific embodiments and accompanying drawings.

[0036] Example 1 (1) 63.7 g (0.30 mol) of benzoin (2-hydroxy-1,2-diphenyl ethyl ketone) and 16.4 g (0.15 mol) of 2,6-diaminopyridine were added to 150 mL of toluene hydrochloric acid solution (hydrochloric acid concentration was 0.20 M) and reacted at 105 °C for 12 h. After the reaction was completed, the above solution was filtered under reduced pressure to remove excess solvent and obtain amino ketone residue. (2) Dissolve 28.4 g (0.1 mol) of isopropyl titanate in 100 mL of 1,4-butanediol, disperse by ultrasonication, add to the amino ketone residue obtained in step 1 (molar ratio of amino ketone residue to isopropyl titanate is 1.5:1), and react under reduced pressure at 70 °C and 15 kPa for 4 h to obtain an alcoholic solution of the catalyst, wherein the titanium content of the catalyst is 2.1%; (3) An alcoholic solution of 1900g (11.4mol) PTA, 1650g (18.3mol) BDO and 17.1g catalyst (with a titanium content of 0.36g) was added to an esterification reactor. The mixture was heated to 230℃ at 60kPa and stirred for negative pressure esterification. After 1.5h, the mixture was transferred to a polymerization reactor and 20g of an alcoholic solution of catalyst (with a titanium content of 0.42g) and 5800g of polytetrahydrofuran (PTMEG) (Mn=1000g / mol, with a theoretical mass ratio of 0.7:1 to the polymer) were added. The reaction was continued for 30min. 1.5g of tributyl phosphate and 0.5g of antioxidant 1010 were added and the mixture was heated to 240℃ and the pressure was reduced to 2~5kPa. The reaction was continued for 90min. At the same temperature, the pressure was reduced to 50~200Pa and the reaction was continued for 4h. The mixture was then discharged, cooled with water and pelletized to obtain TPEE product.

[0037] The infrared spectrum of the catalyst prepared in this embodiment is as follows: Figure 1 As shown, the wavenumber is 3299.6 cm⁻¹. -1 The position is correlated with the stretching vibration of OH or NH, indicating the possible presence of hydroxyl or amino groups in the molecule; wavenumber 1670.2 cm⁻¹ -1 This peak may be related to the stretching vibration of C=O, with a wavenumber of 1591.7 cm⁻¹. -1 1442.1 cm -1 1377.2 cm -1 and 1050.9 cm -1 These peaks in the region are typically associated with stretching vibrations of C=C and CN bonds or skeletal vibrations of aromatic rings; the low wavenumber is 949.4 cm⁻¹. -1 817.3 cm -1 754.1 cm -1 704.2cm -1 695.91 cm -1 These peaks are typically associated with stretching vibrations of CO and CN or out-of-plane bending vibrations of aromatic rings. The proton NMR spectrum of the prepared TPEE is shown below. Figure 2 As shown, the peak with a shift of approximately 8.3 ppm represents the composition of the hard segment terephthalic acid in TPEE, and the peak with a shift of approximately 3.8 ppm represents the composition of the soft segment PTMEG in TPEE.

[0038] Example 2 The catalyst prepared in Example 1 was used.

[0039] An alcoholic solution of 1900g PTA, 1650g BDO, and 17.1g catalyst (with a titanium content of 0.36g) was added to an esterification reactor. The reactor was heated to 230℃ at 60kPa and stirred under negative pressure for esterification. After 1.5h, the solution was transferred to a polymerization reactor, where 5.3g of catalyst alcoholic solution (with a titanium content of 0.11g) and 2500g PTMEG (Mn=1000g / mol, theoretical mass ratio of polymer 0.5:1) were added, and the reaction continued for 30min. Then, 1.1g tributyl phosphate and 0.3g antioxidant 1010 were added, and the temperature was raised to 240℃, and the reaction was carried out under reduced pressure to 2-5kPa for 90min. At the same temperature, the pressure was reduced to 50-200Pa, and the reaction continued for 3h. The product was then discharged, water-cooled, and pelletized to obtain TPEE product.

[0040] The 1H NMR spectrum of the TPEE obtained in this embodiment is as follows: Figure 3 As shown.

[0041] Example 3 The catalyst prepared in Example 1 was used.

[0042] An alcoholic solution of 1900g PTA, 1650g BDO, and 17.1g catalyst (with a titanium content of 0.36g) was added to an esterification reactor. The reactor was heated to 230℃ under negative pressure and stirred at 60kPa. After 1.5h, the solution was transferred to a polymerization reactor, where an alcoholic solution of 20g catalyst (with a titanium content of 0.42g) and 5800g PTMEG (Mn=650g / mol, theoretical mass ratio of polymer 0.7:1) were added, and the reaction continued for 60min. Then, 1.1g tributyl phosphate and 0.3g antioxidant 1010 were added, and the temperature was raised to 240℃, and the reaction was carried out under reduced pressure to 2-5kPa for 90min. At the same temperature, the pressure was reduced to 50-200Pa, and the reaction continued for 4h. The product was then discharged, water-cooled, and pelletized to obtain TPEE product.

[0043] Example 4 The catalyst prepared in Example 1 was used.

[0044] An alcoholic solution of 1900g PTA, 1650g BDO, and 17.1g catalyst (with a titanium content of 0.36g) was added to an esterification reactor. The reactor was heated to 230℃ under negative pressure and stirred. After 1.5 hours, the solution was transferred to a polymerization reactor, where an alcoholic solution of catalyst (with a titanium content of 0.42g) and 5800g PTMEG (Mn=2000g / mol) were added, and the reaction continued for 60 minutes. Then, 1.5g tributyl phosphate and 0.8g antioxidant 1010 were added, and the temperature was raised to 240℃. The reaction was then carried out under reduced pressure to 2-5kPa for 90 minutes. At the same temperature, the pressure was reduced to 50-200Pa, and the reaction continued for 4 hours. The product was then discharged, water-cooled, and pelletized to obtain TPEE.

[0045] Example 5 The catalyst prepared in Example 1 was used.

[0046] An alcoholic solution containing 1900g PTA, 1650g BDO, and 37.1g catalyst (with a titanium content of 0.78g) was added to an esterification reactor. The reactor was heated to 230℃ under 60kPa and stirred for negative pressure esterification. After 1.5h of water removal, the solution was transferred to a polymerization reactor, and 5800g PTMEG (Mn=1000g / mol, theoretical mass ratio of polymer 0.7:1) was added. The reaction continued for 30min. Then, 1.5g tributyl phosphate and 0.5g antioxidant 1010 were added, and the temperature was raised to 240℃. The reaction was then carried out under reduced pressure to 2-5kPa for 90min. At the same temperature, the pressure was reduced to 50-200Pa, and the reaction continued for 4h. The product was then discharged, water-cooled, and pelletized to obtain TPEE product.

[0047] Comparative Example 1 1900g PTA, 1650g BDO, and 2.2g isopropyl titanate were added to an esterification reactor. The mixture was heated to 230℃ at 60kPa and stirred under negative pressure for esterification. After 1.5h of water removal, the mixture was transferred to a polymerization reactor, where 2.7g isopropyl titanate and 5800g PTMEG (Mn=1000g / mol, theoretical mass ratio of polymer 0.7:1) were added, and the reaction was continued for 30min. Then, 1.5g tributyl phosphate and 0.5g antioxidant 1010 were added, and the temperature was raised to 240℃. The reaction was then carried out under reduced pressure to 2-5kPa for 90min. At the same temperature, the pressure was reduced to 50-200Pa, and the reaction was continued for 4.5h. The mixture was then discharged, water-cooled, and pelletized to obtain TPEE product.

[0048] Comparative Example 2 The catalyst prepared in Example 1 was used.

[0049] An alcoholic solution of 1900g PTA, 1650g BDO, and 17.1g catalyst (with a titanium content of 0.36g) was added to an esterification reactor. The reactor was heated to 230℃ under 60kPa and stirred for negative pressure esterification. After 1.5h, the solution was transferred to a polymerization reactor, where an alcoholic solution of 20g catalyst (with a titanium content of 0.42g) and 5800g PTMEG (Mn=1000g / mol, theoretical mass ratio of polymer 0.7:1) were added, and the reaction continued for 30min. The temperature was then raised to 240℃, and the pressure was reduced to 2-5kPa, continuing the reaction for 90min. At the same temperature, the pressure was reduced to 50-200Pa, and the reaction continued for 5h. The product was then discharged, water-cooled, and pelletized to obtain TPEE product.

[0050] The products obtained in Examples 1-5 and Comparative Examples 1-2 were tested according to the following standards for relevant indicators: hardness (GB / T531.1-2008); melt index (GB / T3682.1-2018); hue, carboxyl groups and melting point (GB / T14190-2017); tensile strength and elongation at break (GB / T528-2009). The results are shown in Table 1: Table 1

[0051] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0052] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.

Claims

1. A method for preparing a high-performance TPEE elastomer, characterized in that, Includes the following steps: (1) Add benzoin and 2,6-diaminopyridine to a hydrochloric acid solution of toluene to react. After the reaction is completed, filter under reduced pressure to obtain aminoketone residue. (2) Dissolve isopropyl titanate in 1,4-butanediol, ultrasonically stir, add the amino ketone residue obtained in step (1), and react under reduced pressure to obtain the catalyst; (3) Add terephthalic acid to 1,4-butanediol and the catalyst prepared in step (2). Heat and pressurize to carry out esterification reaction. Start timing after water is released. Add polytetrahydrofuran ether after esterification reaction to continue reaction. After the reaction is completed, add the auxiliary agent tributyl phosphate and antioxidant 1010 to carry out pre-condensation reaction by heating and depressurizing. After the pre-condensation reaction is completed, carry out final condensation reaction under high vacuum to obtain TPEE product.

2. The method for preparing the high-performance TPEE elastomer according to claim 1, characterized in that, In step (1), the molar ratio of benzoin to 2,6-diaminopyridine is (1.5~3):1; And / or, in step (1), the concentration of benzoin and 2,6-diaminopyridine in the hydrochloric acid solution of toluene is 1~5 mol / L; And / or, in step (1), the concentration of hydrochloric acid in the hydrochloric acid solution of toluene is 0.1~0.5 mol / L; And / or, in step (1), the reaction temperature is 50~110 ℃ and the reaction time is 6~18 h.

3. The method for preparing the high-performance TPEE elastomer according to claim 1, characterized in that, In step (2), the concentration of isopropyl titanate in 1,4-butanediol is 0.5~5 mol / L.

4. The method for preparing the high-performance TPEE elastomer according to claim 1 or 3, characterized in that, In step (2), the molar ratio of the amino ketone residue to isopropyl titanate is (1~2):1, wherein the molar amount of the amino ketone residue is equal to the molar amount of 2,6-diaminopyridine. And / or, the pressure of the decompression reaction is 5~20 kPa, the temperature of the reaction is 40~80 ℃, and the reaction time is 2~6 h.

5. The method for preparing the high-performance TPEE elastomer according to claim 1, characterized in that, In step (3), the molar ratio of terephthalic acid and 1,4-butanediol is 1:(1.4~2.0). And / or, in step (3), the amount of catalyst added is 200~600 ppm, based on the titanium content in the catalyst relative to the mass of terephthalic acid; or, the catalyst is added in two parts, 150~300 ppm is added during the esterification reaction, and 50~300 ppm is added at the same time as the addition of the polytetrahydrofuran, based on the titanium content in the catalyst relative to the mass of terephthalic acid.

6. The method for preparing the high-performance TPEE elastomer according to claim 1 or 5, characterized in that, In step (3), the temperature of the esterification reaction is 220~240℃, the pressure of the esterification reaction is 50~80kPa, and the time of the esterification reaction is 1.5~3 h.

7. The method for preparing the high-performance TPEE elastomer according to claim 1, characterized in that, In step (3), the molecular weight of the polytetrahydrofuran is 500~2000 g / mol, and the theoretical mass ratio of polytetrahydrofuran to the polymer is (0.5~0.7):

1. After adding the polytetrahydrofuran, the reaction continues for 0.5~2 h.

8. The method for preparing the high-performance TPEE elastomer according to claim 1, characterized in that, In step (3), the amount of tributyl phosphate added is 0.02~0.2 wt%, and the amount of antioxidant 1010 added is 0.01~0.05 wt%, based on the mass of terephthalic acid.

9. The method for preparing the high-performance TPEE elastomer according to claim 1, 7, or 8, characterized in that, In step (3), the temperature of the pre-condensation reaction is 240~250℃, the reaction time is 60~120min, and the reaction pressure is 1~5kPa; And / or, in step (3), the temperature of the final polycondensation reaction is 240~250℃, the reaction pressure is 50~200Pa, and the reaction time is 2~5 h.

10. A high-performance TPEE elastomer, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 9.

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