A high temperature resistant thermoplastic polyester elastomer and a method of making the same

Abstract

The application discloses a high-temperature-resistant thermoplastic polyester elastomer and a preparation method thereof, and relates to the technical field of polyester elastomers.The preparation method of the high-temperature-resistant thermoplastic polyester elastomer comprises the following steps: (1) mixing dimethyl terephthalate, 1,4-butanediol, an anti-aging reinforcing agent and polytetrahydrofuran ether glycol, introducing a protective gas, increasing temperature, adding a catalyst one, and performing a prepolymerization reaction; (2) adding a catalyst two, performing a vacuumization, increasing temperature, and continuously performing a polymerization reaction to obtain the high-temperature-resistant thermoplastic polyester elastomer.The high-temperature-resistant thermoplastic polyester elastomer prepared by the application has excellent tensile strength, elongation at break, anti-aging performance and high-temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of polyester elastomer technology, specifically to a high-temperature resistant thermoplastic polyester elastomer and its preparation method. Background Technology

[0002] Thermoplastic polyester elastomers are block copolymer materials composed of hard segments (usually aromatic polyesters) and soft segments (usually aliphatic polyethers or polyesters). They combine the elasticity of rubber with the processing properties of engineering plastics and are widely used in automotive parts, wire and cable sheaths, industrial transmission belts, and electronic and electrical fields. However, the performance of existing thermoplastic polyester elastomers at high temperatures still has certain limitations. On the one hand, the soft segments of the materials are mostly polyethers or aliphatic polyesters with low glass transition temperatures, which are prone to chain relaxation or even thermo-oxidative degradation under high-temperature conditions, leading to decreased material elasticity and increased permanent deformation. On the other hand, the crystalline structure of the hard segments is prone to rearrangement or partial melting under high-temperature or long-term thermal aging conditions, reducing the material's mechanical strength and dimensional stability.

[0003] Chinese invention patent CN116769283A discloses a thermoplastic polyester elastomer composite, its preparation method, and its application. The thermoplastic polyester elastomer composite comprises the following components by weight: 90-99 parts thermoplastic polyester elastomer; 1-5 parts silicone lubricant; 0.3-1 part montmorillonite wax lubricant; 0.05-0.5 parts titanium dioxide; and 0-30 parts functional additives. This invention obtains a thermoplastic polyester elastomer with low release force and no exudation by adding specific amounts of lubricant and titanium dioxide to the thermoplastic polyester elastomer, overcoming the problems of high release force and release agent exudation in existing thermoplastic polyester elastomers. The thermoplastic polyester elastomer composite can be used in the manufacture of parts with large aspect ratios, but its high-temperature resistance and mechanical properties need further improvement.

[0004] Therefore, developing a high-temperature resistant thermoplastic polyester elastomer material is of great significance for expanding its application in high-temperature conditions. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide a high-temperature resistant thermoplastic polyester elastomer and its preparation method.

[0006] A method for preparing a high-temperature resistant thermoplastic polyester elastomer includes the following steps:

[0007] (1) Mix dimethyl terephthalate, 1,4-butanediol, anti-aging agent and polytetrahydrofuran ether diol, introduce protective gas, heat up, add catalyst one to carry out prepolymerization reaction;

[0008] (2) Add catalyst II, evacuate, and heat up to continue the polymerization reaction to obtain a high-temperature resistant thermoplastic polyester elastomer;

[0009] Both catalyst one and catalyst two are tetrabutyl titanate.

[0010] The mass ratio of dimethyl terephthalate, 1,4-butanediol, anti-aging agent, polytetrahydrofuran ether glycol, catalyst one, and catalyst two is 100:(60-80):(4-8):(40-70):(0.02-0.1):(0.08-0.2).

[0011] The structural formula of the enhanced anti-aging agent is as follows:

[0012] ;

[0013] The enhanced anti-aging agent is prepared by the following method:

[0014] S1: The reaction of cyanuric chloride with N-phenyl-1,4-phenylenediamine yields intermediate 1, and the reaction equation is shown below:

[0015]

[0016] S2: Intermediate 1 reacts with γ-aminobutyric acid to give intermediate 2, and the reaction equation is shown below:

[0017]

[0018] S3: Intermediate 2 reacts with amino silicone oil to obtain an enhanced anti-aging agent. The reaction equation is shown below:

[0019]

[0020] It should be noted that the above reaction equations are only used to illustrate the reaction relationships between the functional groups. In the actual preparation process, by controlling the molar ratio of intermediate 2 to amino silicone oil to a slightly excess state, the amino groups at both ends of the amino silicone oil chain segment undergo a substitution reaction with the active chlorine atoms in the intermediate 2 molecule, thereby introducing a triazine-aromatic amine functional structure at both ends of the amino silicone oil molecule, resulting in a double-ended modified enhanced anti-aging agent.

[0021] In step (1), the protective gas is nitrogen.

[0022] In step (1), the temperature of the prepolymerization reaction is 190-210℃ and the time is 2-4h.

[0023] In step (2), the vacuum level of the vacuum pump is 80-100 Pa.

[0024] In step (2), the polymerization reaction is carried out at a temperature of 230-250°C for 4-6 hours.

[0025] In step S1, the molar ratio of cyanuric chloride to N-phenyl-1,4-phenylenediamine is 1:1.05; in step S2, the molar ratio of intermediate 1 to γ-aminobutyric acid is 1:1.1; in step S3, the mass ratio of intermediate 2 to amino silicone oil is 0.2:1.

[0026] A high-temperature resistant thermoplastic polyester elastomer is prepared by the above method.

[0027] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:

[0028] The high-temperature resistant thermoplastic polyester elastomer prepared by this invention has excellent tensile strength, elongation at break, aging resistance and high-temperature resistance. Attached Figure Description

[0029] Figure 1 The Fourier transform infrared spectrum of the enhanced anti-aging agent prepared in Example 1.

[0030] Figure 2 The hydrogen nuclear magnetic resonance spectrum of the enhanced anti-aging agent prepared in Example 1.

[0031] Figure 3 The Fourier transform infrared spectrum of the high-temperature resistant thermoplastic polyester elastomer prepared in Example 3 is shown. Detailed Implementation

[0032] Example 1: Preparation of Enhanced Anti-aging Agent

[0033] S1: Add 150 ml of dichloromethane, 0.1 mol of cyanuric chloride, and 0.11 mol of triethylamine to a reaction flask, stir and mix well, cool to 0℃, and add 0.105 mol of N-phenyl-1,4-phenylenediamine in 5 batches (5 min apart). React at 0℃ for 6 h. Adjust the pH of the filtrate to 7 with 1 wt% HCl solution, separate the layers, wash the organic phase with 50 ml of saturated brine, dry with 20 g of anhydrous magnesium sulfate, filter, and rotary evaporate the filtrate at 40℃ to constant weight to obtain intermediate 1; its 1H NMR data are as follows: 1 H NMR(400 MHz, DMSO-d6) δ 10.08 (s, 1H), 7.78 (s, 1H), 7.77 – 7.71 (m, 2H), 7.27 –7.17 (m, 2H), 7.11 – 7.01 (m, 4H),7.00 – 6.93(m, 1H); HRMS (m / z): 332.0394[M+H] +;

[0034] S2: Under nitrogen protection, 250 ml of 70 wt% ethanol solution, 0.1 mol of intermediate 1, and 0.11 mol of sodium carbonate were added to a reaction flask, stirred and mixed, heated to 40 °C, and 0.11 mol of γ-aminobutyric acid was added. The reaction was maintained at this temperature for 8 h, cooled to room temperature, and the filtrate was rotary evaporated at 60 °C to constant weight. 200 ml of deionized water was added, and the mixture was cooled to 0 °C. The pH was adjusted to 3 using 5 wt% hydrochloric acid solution, and the mixture was stirred to precipitate a solid. The solid was filtered, and the filter cake was washed with deionized water (2 × 80 ml) and dried under vacuum at 60 °C for 12 h to obtain intermediate 2. Its 1H NMR data are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 11.75 (s, 1H), 10.42 (s, 1H), 7.81 –7.71 (m, 3H), 7.26 – 7.19 (m, 2H), 7.12 – 7.02 (m, 5H), 6.99 – 6.93 (m, 1H),3.62 – 3.53 (m, 2H), 2.43 – 2.31 (m, 2H), 2.01 – 1.87 (m, 2H); HRMS (m / z): 399.1257[M+H] + ;

[0035] S3: Add 500ml toluene, 100ml DMF, 20g intermediate 2, 100g amino silicone oil (amine content 0.4mmol / g) and 0.15mol triethylamine to a reaction flask, stir and mix well, heat to 100℃ and react for 12h, cool to room temperature, add 200ml deionized water and stir and mix well, adjust pH to 7 with 1wt% HCl solution, separate the layers, rotary evaporate the toluene phase at 70℃ to constant weight to obtain crude product, slowly add the crude product to 500ml cold methanol, stir to precipitate, filter, wash the filter cake with 80wt% methanol solution (2×50ml), vacuum dry at 50℃ for 12h to obtain enhanced anti-aging agent.

[0036] Figure 1 To enhance the Fourier transform infrared spectrum of the anti-aging agent, as can be seen from the figure, at 3400 cm⁻¹ -1 A broad absorption peak appears nearby, which is the stretching vibration peak of NH and OH; 2920 cm⁻¹ -1 and 2850cm -1 The nearby absorption peak corresponds to the stretching vibration peak of aliphatic -CH2-; approximately 1710 cm⁻¹. -1 The strong absorption peak nearby is the stretching vibration peak of C=O in the carboxyl group; 1600 cm⁻¹ -1 The absorption peaks around 1500 cm⁻¹ are related to the C=C skeletal vibration of the aromatic ring, the C=N / C=N skeletal vibration of the triazine ring, and the NH bending vibration;-1 The nearby multiple absorption peaks are CN stretching vibration peaks, aromatic ring skeletal vibration peaks, and triazine ring characteristic vibration peaks; 1250 cm⁻¹ -1 The absorption peak appearing nearby is a Si-CH3 vibrational peak; 1100 cm⁻¹ -1 The presence of a distinct strong absorption peak nearby is a characteristic peak of the Si-O-Si stretching vibration, indicating that the amino silicone oil segment has been introduced into the enhanced anti-aging agent molecule; 800cm -1 The nearby absorption peaks are related to the out-of-plane bending vibrations of Si-C and the aromatic ring CH. The infrared spectrum simultaneously shows the characteristic absorptions of the triazine ring, aromatic amine, carboxyl group, aliphatic chain segment, and siloxane chain segment, indicating that intermediate 2 reacted with amino silicone oil to successfully prepare an enhanced anti-aging agent containing a triazine-aromatic amine-carboxyl-siloxane composite structure.

[0037] Figure 2 To enhance the anti-aging agent's proton NMR spectrum, the figure shows that the extremely sharp main peak at around 0 ppm represents the methyl structure on the siloxane, and the signal at 0.4-0.8 ppm is Si-CH2, confirming the presence of the siloxane skeleton. The complex signals in the regions of 1.8-2.1 ppm and 3.3-3.4 ppm are methylene proton overlap peaks. The multiplets at 6.6-7.8 ppm represent the aromatic hydrogen structure. The multiplets at 8.3-8.7 ppm represent NH. The broad peak at 10.5 ppm further confirms the presence of the terminal carboxyl group (-COOH), indicating that the enhanced anti-aging agent containing a triazine ring, aromatic amine, carboxyl flexible segment, and siloxane structure has been successfully prepared.

[0038] Example 2 Preparation of high-temperature resistant thermoplastic polyester elastomer

[0039] (1) Weigh out: 500g of dimethyl terephthalate, 300g of 1,4-butanediol, 20g of anti-aging agent (prepared in Example 1), 200g of polytetrahydrofuran ether diol, and 0.5g of catalyst (tetrabutyl titanate);

[0040] (2) Under nitrogen protection, dimethyl terephthalate, 1,4-butanediol, anti-aging agent and polytetrahydrofuran ether diol were added to the reactor in sequence, stirred and heated to 190°C, 0.1g tetrabutyl titanate was added, and the mixture was kept at the temperature for prepolymerization. The reaction was carried out for 4 hours, and the by-product methanol was continuously removed through a fractionating column during the reaction.

[0041] (3) Add 0.4g tetrabutyl titanate, apply vacuum to achieve a vacuum degree of 80Pa, heat to 230℃ for 6h polymerization reaction, cool and granulate to obtain high temperature resistant thermoplastic polyester elastomer.

[0042] Example 3 Preparation of high-temperature resistant thermoplastic polyester elastomer

[0043] (1) Weigh out: 500g of dimethyl terephthalate, 350g of 1,4-butanediol, 30g of anti-aging agent (prepared in Example 1), 300g of polytetrahydrofuran ether diol, and 1g of catalyst (tetrabutyl titanate);

[0044] (2) Under nitrogen protection, dimethyl terephthalate, 1,4-butanediol, anti-aging agent and polytetrahydrofuran ether diol were added to the reactor in sequence, stirred and heated to 200°C, 0.25g of tetrabutyl titanate was added, and the mixture was kept at the temperature for prepolymerization. The reaction was carried out for 3 hours, and the by-product methanol was continuously removed through a distillation column during the reaction.

[0045] (3) Add 0.75g tetrabutyl titanate, apply vacuum to achieve a vacuum degree of 90Pa, heat to 240℃ for 5h to obtain the polymer product; extrude the polymer product through a die with a diameter of 1.5mm into a long strip shape, cool and cut into pellets to obtain a high-temperature resistant thermoplastic polyester elastomer.

[0046] Figure 3 This is the Fourier transform infrared spectrum of thermoplastic polyester elastomer. As can be seen from the figure, at 3400 cm⁻¹... -1 A relatively weak, broad absorption peak appears nearby, mainly related to residual OH or the NH structure in the enhanced anti-aging agent; 2960 cm⁻¹ -1 and 2870cm -1 The nearby absorption peaks correspond to the stretching vibrations of -CH2- and -CH3 in the organic segments of 1,4-butanediol, polytetrahydrofuran ether diol, and siloxanes; 1750 cm⁻¹ -1 The strong and sharp absorption peaks appearing nearby are due to the C=O stretching vibration peaks of the ester group in the polyester structure; 1600-1500 cm⁻¹ -1 The absorption peaks are due to the vibrations of the aromatic amine structure and the triazine ring skeleton; 1260 cm⁻¹ -1 The strong absorption peaks in the vicinity are attributed to the CO stretching vibration and Si-CH3 vibration of the ester group; 1160-1100 cm⁻¹ -1 The absorption peak at 870 cm⁻¹ is attributed to the COC stretching vibration of the ether bond and the Si-O-Si stretching vibration of the siloxane; -1 and 720cm -1 The nearby absorption peaks are related to the out-of-plane bending vibration of the aromatic ring CH. The spectrum simultaneously shows the characteristic absorption of the triazine-aromatic amine-siloxane structure in the polyester hard segment, polyether soft segment, and the anti-aging reinforcing agent, indicating that a high-temperature resistant thermoplastic polyester elastomer containing the anti-aging reinforcing structure has been successfully prepared.

[0047] Example 4 Preparation of high-temperature resistant thermoplastic polyester elastomer

[0048] (1) Weigh out: 500g of dimethyl terephthalate, 400g of 1,4-butanediol, 40g of anti-aging agent (prepared in Example 1), 350g of polytetrahydrofuran ether diol, and 1.5g of catalyst (tetrabutyl titanate);

[0049] (2) Under nitrogen protection, dimethyl terephthalate, 1,4-butanediol, anti-aging agent and polytetrahydrofuran ether diol were added to the reactor in sequence, stirred and heated to 210°C, 0.5g tetrabutyl titanate was added, and the mixture was kept at the temperature for prepolymerization. The reaction was carried out for 2 hours, and the by-product methanol was continuously removed through a fractionating column during the reaction.

[0050] (3) Add 1g of tetrabutyl titanate, apply vacuum to achieve a vacuum degree of 100Pa, heat to 250℃ for 4h to polymerize and obtain the polymer product; extrude the polymer product through a die with a diameter of 1.5mm into a long strip shape, cool and cut into pellets to obtain a high-temperature resistant thermoplastic polyester elastomer.

[0051] Comparative Example 1

[0052] Preparation of thermoplastic polyester elastomers

[0053] (1) Weigh out: 500g of dimethyl terephthalate, 350g of 1,4-butanediol, 30g of anti-aging agent (prepared in Example 1), 300g of polytetrahydrofuran ether diol, and 1g of catalyst (tetrabutyl titanate);

[0054] (2) Under nitrogen protection, dimethyl terephthalate, 1,4-butanediol, anti-aging agent and polytetrahydrofuran ether glycol were added to the reactor in sequence, heated to 200°C, catalyst was added, and prepolymerization was carried out at the temperature for 3 hours. During the reaction, methanol by-product was continuously removed through a fractionating column. Vacuum was drawn to a vacuum degree of 90 Pa, and the temperature was raised to 240°C for 5 hours to obtain the polymer product. The polymer product was extruded through a die with a diameter of 1.5 mm into a long strip shape, cooled and granulated to obtain a high-temperature resistant thermoplastic polyester elastomer.

[0055] Comparative Example 2

[0056] The preparation method of the high-temperature resistant thermoplastic polyester elastomer is basically the same as that in Example 3, except that the reinforcing anti-aging agent is replaced with an equal weight of the reinforcing anti-aging agent prepared by the following method:

[0057] The preparation method of the enhanced anti-aging agent is basically the same as that in Example 1, except that N-phenyl-1,4-phenylenediamine in step S1 is replaced with an equimolar amount of 4-amino-N-methylaniline.

[0058] Comparative Example 3

[0059] The preparation method of the high-temperature resistant thermoplastic polyester elastomer is basically the same as that in Example 3, except that the reinforcing anti-aging agent is replaced with an equal weight of the reinforcing anti-aging agent prepared by the following method:

[0060] The preparation method of the enhanced anti-aging agent is basically the same as that in Example 1, except that γ-aminobutyric acid in step S2 is replaced with an equimolar amount of glycine.

[0061] Comparative Example 4

[0062] The preparation method of the high-temperature resistant thermoplastic polyester elastomer is basically the same as that in Example 3, except that the reinforcing anti-aging agent is replaced with an equal weight of the reinforcing anti-aging agent prepared by the following method:

[0063] The preparation method of the enhanced anti-aging agent is basically the same as that in Example 1, except that γ-aminobutyric acid in step S2 is replaced with an equimolar amount of 11-aminoundecanoic acid.

[0064] Comparative Example 5

[0065] The preparation method of the high-temperature resistant thermoplastic polyester elastomer is basically the same as that in Example 3, except that the reinforcing anti-aging agent is replaced with an equal weight of the reinforcing anti-aging agent prepared by the following method:

[0066] The preparation method of the enhanced anti-aging agent is basically the same as that in Example 1, except that intermediate 2 in step S3 is replaced with 10g.

[0067] Comparative Example 6

[0068] The preparation method of the high-temperature resistant thermoplastic polyester elastomer is basically the same as that in Example 3, except that the reinforcing anti-aging agent is replaced with an equal weight of the reinforcing anti-aging agent prepared by the following method:

[0069] The preparation method of the enhanced anti-aging agent is basically the same as that in Example 1, except that the amino silicone oil with an amino content of 0.4 mmol / g in step S3 is replaced with 40g of amino silicone oil with an amino content of 1 mmol / g (model Cheersil 8120, produced by Suzhou Qitian New Materials Co., Ltd.).

[0070] The polytetrahydrofuran ether diol used in the examples and comparative examples of this application has a number average molecular weight of 1000; the amino silicone oil is Cheersil 8150, with an amino content of 0.4 mmol / g, and is produced by Suzhou Qitian New Materials Co., Ltd.

[0071] The high-temperature resistant thermoplastic polyester elastomers prepared in the examples and comparative examples were tested for tensile strength, elongation at break, anti-aging properties, and melt temperature.

[0072] Melting temperature test: The melting peak temperature was tested according to GB / T 19466.3-2004 standard, with a heating rate of 10K / min.

[0073] Sample preparation: The thermoplastic polyester elastomers prepared in the examples and comparative examples were placed in a mold (170mm×110mm×4mm) and preheated at 230℃ for 5min. After venting, the mold was held under pressure of 10MPa for 5min, cooled to room temperature by circulating water at 25℃, demolded, and allowed to stand at room temperature for 24h to obtain the test sample.

[0074] Tensile strength and elongation at break tests: The specimens were cut into dumbbell shapes (total length of 115 mm, end width of 25 mm, width of the narrow parallel section of 6.0 mm, length of the narrow parallel section of 33 mm, radius of transition arc of 14 mm, and standard thickness of 2.0 mm). The tests were conducted using a CMT4104 universal tensile testing machine at 25°C and a tensile rate of 50 mm / min.

[0075] Anti-aging performance test: The sample was placed in a QUV accelerated aging test chamber for aging test, with an irradiation wavelength of 340nm and an irradiance of 0.89W / m. 2 The temperature was 60℃ and the aging time was 500h. The tensile strength of the aged sample was tested again, and the strength retention rate was calculated by dividing the tensile strength after aging by the tensile strength before aging by 100%.

[0076] Table 1 Performance Test Data

[0077] Example 2 220.5 33.4 520 94.5 Example 3 223.2 35.6 535 96.8 Example 4 221.8 34.2 527 95.3 Comparative Example 1 210.3 28.5 451 95.2 Comparative Example 2 212.4 33.8 534 82.4 Comparative Example 3 221.7 35.1 497 95.6 Comparative Example 4 214.2 30.4 548 96.1 Comparative Example 5 212.1 29.2 465 92.8 Comparative Example 6 215.6 32.5 494 90.2

[0078] As can be seen from the data in Table 1, the high-temperature resistant thermoplastic polyester elastomer prepared by the present invention has excellent tensile strength, elongation at break, aging resistance and high-temperature resistance.

[0079] This embodiment employs a staged catalyst addition method to prepare thermoplastic polyester elastomers. During the prepolymerization stage, 20-30% of the total catalyst is added, enabling dimethyl terephthalate, the reinforcing anti-aging agent, 1,4-butanediol, and polytetrahydrofuran ether glycol to undergo gradual transesterification and esterification reactions under relatively mild catalytic conditions, avoiding uneven reactions caused by excessively rapid initial reaction rates. The remaining catalyst is added during the subsequent polycondensation stage to improve the efficiency of the polycondensation reaction, promote further chain growth of oligomers, and increase the molecular weight and segmental regularity of the polyester elastomer. The hard segments in the thermoplastic polyester elastomer are obtained through transesterification of dimethyl terephthalate and 1,4-butanediol, exhibiting high segmental regularity and crystallinity. These segments form crystalline microregions within the material, serving as physical crosslinking points and a load-bearing skeleton, thereby improving the material's tensile strength, melting temperature, and heat resistance. The reinforcing anti-aging agent molecule contains carboxyl groups, triazine rings, aromatic amine structures, aliphatic spacer chains, and siloxane segments. The carboxyl groups can participate in esterification or transesterification reactions, stabilizing the anti-aging structure within the polyester system and reducing migration and precipitation. The triazine ring and aromatic structure possess high rigidity and thermal stability, synergistically improving the mechanical and heat resistance properties of thermoplastic polyester elastomers with the hard segments. The aromatic amine structure can capture free radicals generated during thermo-oxidative aging, delaying chain segment oxidative breakage. Appropriately flexible spacer chains buffer the restriction of chain segment movement by rigid groups, improving stress transmission. The siloxane segments have high Si-O bond energy and good flexibility, enhancing thermo-oxidative aging resistance and synergistically improving chain segment mobility with the flexible soft segments of polytetrahydrofuran ether glycol, thus imparting good elasticity and elongation at break to the material. Under the synergistic effect of hard segment reinforcement, soft segment toughening, and the anti-aging structure, thermoplastic polyester elastomers exhibit excellent tensile strength, high-temperature resistance, and aging resistance.

[0080] In Comparative Example 1, the addition of all catalyst in the initial stage of the reaction led to insufficient polycondensation kinetics in the later stages, resulting in a lower molecular weight, reduced thermal stability, and decreased mechanical strength of the final product. In Comparative Example 3, the aliphatic chain connecting the triazine and carboxyl groups in the reinforcing and anti-aging agent was shortened, resulting in insufficient molecular chain flexibility and spatial buffering. This reduced the compatibility between the aliphatic chain and the polyester hard and soft segments, making it prone to forming localized rigid enrichment points or stress concentration areas. This weakened the material's energy dissipation capacity during stretching, leading to a decrease in tensile strength and elongation at break. In Comparative Example 4, the aliphatic chain in the reinforcing and anti-aging agent was too long, weakening the interaction between the triazine ring, aromatic amine structure, and polyester hard segments. Simultaneously, the long-chain aliphatic structure easily formed flexible enrichment regions in the polyester elastomer, disrupting the regular stacking and crystallinity of the hard segment microregions, thus reducing the material's mechanical properties.

[0081] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A process for the preparation of a high temperature resistant thermoplastic polyester elastomer, characterized in that, Includes the following steps: (1) Mix dimethyl terephthalate, 1,4-butanediol, anti-aging agent and polytetrahydrofuran ether diol, introduce protective gas, heat up, add catalyst one to carry out prepolymerization reaction; (2) Add catalyst II, evacuate, and heat up to continue the polymerization reaction to obtain a high-temperature resistant thermoplastic polyester elastomer; Both catalyst one and catalyst two are tetrabutyl titanate. The mass ratio of dimethyl terephthalate, 1,4-butanediol, anti-aging agent, polytetrahydrofuran ether glycol, catalyst one, and catalyst two is 100:(60-80):(4-8):(40-70):(0.02-0.1):(0.08-0.2). The structural formula of the enhanced anti-aging agent is as follows: ； The enhanced anti-aging agent is prepared by the following method: S1: Cyanurium chloride reacts with N-phenyl-1,4-phenylenediamine to give intermediate 1. S2: Intermediate 1 reacts with γ-aminobutyric acid to give intermediate 2. S3: Intermediate 2 reacts with amino silicone oil to obtain an enhanced anti-aging agent.

2. The method for preparing a high-temperature resistant thermoplastic polyester elastomer according to claim 1, characterized in that, In step (1), the protective gas is nitrogen.

3. The method for preparing a high-temperature resistant thermoplastic polyester elastomer according to claim 1, characterized in that, In step (1), the temperature of the prepolymerization reaction is 190-210℃ and the time is 2-4h.

4. The method for preparing a high-temperature resistant thermoplastic polyester elastomer according to claim 1, characterized in that, In step (2), the vacuum level of the vacuum pump is 80-100 Pa.

5. The method for preparing a high-temperature resistant thermoplastic polyester elastomer according to claim 1, characterized in that, In step (2), the polymerization reaction is carried out at a temperature of 230-250°C for 4-6 hours.

6. The method for preparing a high-temperature resistant thermoplastic polyester elastomer according to claim 1, characterized in that, In step S1, the molar ratio of cyanuric chloride to N-phenyl-1,4-phenylenediamine is 1:1.05; in step S2, the molar ratio of intermediate 1 to γ-aminobutyric acid is 1:1.1; in step S3, the mass ratio of intermediate 2 to amino silicone oil is 0.2:

1.

7. A high-temperature resistant thermoplastic polyester elastomer, characterized in that, It is prepared by the method described in any one of claims 1-6.

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