Thermoplastic polyester elastomer raw material composition, thermoplastic polyester elastomer and method for producing the same

Abstract

The present application relates to the technical field of high polymer, in particular to a thermoplastic polyester elastomer raw material composition, a thermoplastic polyester elastomer and a preparation method thereof.The raw material composition contains aliphatic dihydric alcohol, aromatic diacid and / or esterification product of aromatic diacid, polyether dihydric alcohol and branching agent.A thermoplastic polyester elastomer (TPEE) material with higher molecular weight and lower melt index and different hardness intensity can be prepared by the raw material composition in the present application, and the molecular structure of the final thermoplastic polyester elastomer can be designed.

Description

Technical Field

[0001] This invention relates to the field of polymer technology, specifically to a thermoplastic polyester elastomer raw material composition, a thermoplastic polyester elastomer, and a method for preparing the same. Background Technology

[0002] Currently, my country is the world's largest consumer and importer of rubber. Due to the thermosetting nature of rubber, it suffers from limitations in primary processing and recyclability. Subsequently, since the 1940s, with Bayer's initial development of polyurethane (PU), thermoplastic elastomers (TPEs) have been found to be a good substitute for rubber in many applications due to their ease of reprocessing, leading to their rapid development.

[0003] Thermoplastic polyester elastomers (TPEEs) are linear block copolymers consisting of highly crystalline, high-melting-point polyester blocks as hard segments and amorphous polyethers or polyesters with lower glass transition temperatures as soft segments. They are also known as polyester thermoplastic elastomers or polyester rubber. The crystalline polyester forms an amorphous phase, while the partially crystalline polyester hard segments form crystalline microdomains, acting as physical crosslinking points. TPEEs possess the elasticity of rubber and the strength of engineering plastics. The soft segments impart elasticity, making them rubber-like; the hard segments impart processability, making them plastic-like. Compared to rubber, they have better processability and a longer service life; compared to engineering plastics, they also possess high strength, but with better flexibility and dynamic mechanical properties. TPEEs exhibit high strength, high elasticity, oil resistance, acid and alkali resistance, high temperature resistance, radiation resistance, and excellent dynamic mechanical properties. They have a wide operating temperature range of 50℃ to 180℃ and a hardness range of 25D to 80D. The initial research and development of TPEEs aimed to produce highly elastic fibers for the textile industry. However, TPEE has now become an irreplaceable high-performance new elastomer material, widely used in automobiles, electronics, railways and other fields.

[0004] Melt index (MCI) is a physical property parameter used to determine the flowability of a polymer and, to a certain extent, determines the molding and processing performance of the material. Generally speaking, molecular weight is inversely proportional to MCI. In actual production, MCI is an important physical property parameter, and the appropriate TPEE needs to be selected based on a comprehensive consideration of the product mold, product structure, equipment processing and plasticizing capabilities, and product performance requirements. The development of high molecular weight, low MCI materials has expanded the application range of TPEE materials. On the other hand, high molecular weight, low MCI materials have improved mechanical properties, anti-aging properties, and stability compared to ordinary materials. In extrusion molding and other processes, materials with low MCI are more suitable for preparing pipes, sheets, wires, and optical fibers, while also meeting the requirements of ordinary injection molding processes.

[0005] CN117089052A discloses a bio-based thermoplastic polyester elastomer material and its preparation method. Hard-segment prepolymers and soft-segment polyester prepolymers are prepared separately. The bio-based thermoplastic polyester elastomer is obtained by melt polycondensation of the hard-segment prepolymer and the polyester prepolymer. The resulting material exhibits good biodegradability and a long service life. However, the use of polyester prepolymers in the soft segments introduces transesterification side reactions during the actual reaction, which is detrimental to stable preparation control. The instability of the soft segment chain length also affects crystallinity and mechanical properties. Furthermore, the operation of this technique is relatively cumbersome.

[0006] CN107312165B discloses a thermoplastic polyester elastomer material with side chains and its preparation method. The method involves reacting an aromatic diacid, an aliphatic diacid with side chains, and an aliphatic diol to obtain an intermediate product, followed by the addition of a chain extender to obtain a crude product, which is then refined to obtain the final product. The material exhibits good elasticity and biodegradability. However, the soft segment of the material is a polyester elastomer, and its side reactions can lead to uncontrollable soft segment length. Secondly, the preparation process requires two-step feeding, and the refining process requires dissolution followed by filtration and drying, making it unsuitable for industrial production.

[0007] Existing thermoplastic polyester elastomer materials cannot achieve tunable molecular structure with high molecular weight and low melt index, have complex processing procedures, and poor mechanical properties.

[0008] Therefore, the thermoplastic polyester elastomer (TPEE) materials with higher molecular weight and lower melt index prepared by this invention have molecular structures that can be designed and preparation processes that are simple to operate, and can better adapt to market demands and expand their application fields. Summary of the Invention

[0009] The purpose of this invention is to overcome the problems of existing thermoplastic polyester elastomer materials, such as the inability to achieve high molecular weight and low melt index molecular structure, complex process flow, and poor mechanical properties, and to provide a thermoplastic polyester elastomer raw material composition, thermoplastic polyester elastomer, and preparation method thereof.

[0010] To achieve the above objectives, the first aspect of the present invention provides a thermoplastic polyester elastomer raw material composition comprising: an aliphatic diol, an aromatic diacid and / or an ester of an aromatic diacid, a polyether diol, and a branching agent.

[0011] A second aspect of the present invention provides a method for preparing a thermoplastic polyester elastomer, the method comprising: in the presence of a catalyst, the components of the raw material composition described in the first aspect of the present invention undergoing a contact reaction and a polycondensation reaction.

[0012] The third aspect of the present invention provides a thermoplastic polyester elastomer prepared by the preparation method described in the second aspect of the present invention.

[0013] Through the above technical solutions, the raw material composition of the present invention can be used to prepare thermoplastic polyester elastomer (TPEE) materials with higher molecular weight and lower melt index with different hardness and strength. The molecular structure can be designed and the preparation process is simple, which can better meet market demand and expand its application fields. Attached Figure Description

[0014] Figure 1 This is a gel permeation chromatography (GPC) curve of the final product, thermoplastic polyester elastomer, prepared in Example 1;

[0015] Figure 2 This is a differential scanning calorimetry melt curve of the final product, thermoplastic polyester elastomer, prepared in Example 1.

[0016] Figure 3 This is a differential scanning calorimetry (DSC) crystallization curve of the final product, thermoplastic polyester elastomer, prepared in Example 1.

[0017] Figure 4 This is the engineering stress-strain curve of the final product, thermoplastic polyester elastomer, prepared in Example 1. Detailed Implementation

[0018] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0019] Existing thermoplastic polyester elastomer materials cannot achieve tunable molecular structures with high molecular weight and low melt index, and their preparation processes are complex and their mechanical properties are poor.

[0020] The first aspect of the present invention provides a thermoplastic polyester elastomer raw material composition comprising: an aliphatic diol, an aromatic diacid and / or an ester of an aromatic diacid, a polyether diol and a branching agent.

[0021] The raw material composition of this invention can be used to prepare thermoplastic polyester elastomer (TPEE) materials with different hardness and strength, higher molecular weight, and lower melt index. The molecular structure of the final thermoplastic polyester elastomer can be designed, and the preparation process of thermoplastic polyester elastomer using this raw material composition is simple and can better meet market demands and expand its application fields.

[0022] According to a preferred embodiment of the present invention, the branching agent includes at least one of a polyol having 3-6 functional groups, a polyacid having 3-6 functional groups, an anhydride corresponding to a polyacid having 3-6 functional groups, an ester corresponding to a polyacid having 3-6 functional groups, and a hydroxy acid having 3-6 functional groups.

[0023] In this invention, by using the above-mentioned branching agent to react with other components in the raw material composition, the molecular weight of the polyester elastomer is increased and the melt index is reduced, thereby improving the mechanical properties, thermal stability and oxidation resistance of the polyester elastomer.

[0024] In this invention, a polyol having 3-6 functional groups refers to a polyol containing 3-6 hydroxyl groups. According to a preferred embodiment of this invention, the polyol having 3-6 functional groups includes at least one of glycerol, trimethylpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, and 1,1,4,4-tetra(hydroxymethyl)cyclohexanedipentaerythritol, preferably glycerol.

[0025] According to a preferred embodiment of the present invention, the polybasic acid having 3-6 functional groups includes at least one selected from 1,2,3-benzenetricarboxylic acid, trimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, pyromellitic acid, 1,1,2-triglyceride, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid.

[0026] According to a particularly preferred embodiment of the present invention, the anhydride corresponding to the polybasic acid having 3-6 functional groups is selected from trimellitic anhydride.

[0027] According to a particularly preferred embodiment of the present invention, the ester corresponding to the polybasic acid having 3-6 functional groups includes trimethyl trimellitate and / or trioctyl trimellitate, preferably trimethyl trimellitate.

[0028] According to a preferred embodiment of the present invention, the hydroxy acid having 3-6 functional groups includes at least one of malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid and mucoic acid, preferably citric acid.

[0029] In the raw material composition system of the present invention, different types of high molecular weight polyester elastomers can be obtained by controlling the specific type of branching agent.

[0030] According to a preferred embodiment of the present invention, the aliphatic diol is selected from C2-C18 aliphatic diols.

[0031] In this invention, the aliphatic chains in C2-C18 aliphatic diols can be straight chains or branched chains. According to a preferred embodiment of this invention, the aliphatic diols are selected from C2-C5 aliphatic diols. Examples of C2-C5 aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, neopentanediol, etc.

[0032] By selecting the specific types of aliphatic diols mentioned above, different types of polyester elastomers can be obtained in this invention.

[0033] According to a preferred embodiment of the present invention, the aromatic dicarboxylic acid and / or its esterifications include at least one of terephthalic acid, phthalic acid, isophthalic acid, biphenyl phthalic acid, and 2,6-naphthalenedicarboxylic acid and their esterifications.

[0034] In this invention, by selecting the specific types of the above-mentioned aromatic dicarboxylic acids and / or their esterifications, different types of polyester elastomers can be obtained.

[0035] According to a preferred embodiment of the present invention, the polyether diol is selected from at least one of polyethylene glycol, polypropylene glycol and polytetramethylene ether diol, preferably polytetramethylene ether diol.

[0036] According to a preferred embodiment of the present invention, the number average molecular weight of the polyether polyol is 200-2000, for example, 200, 400, 600, 800, 1000, 1200, 1500, 1800 or 2000.

[0037] According to a preferred embodiment of the present invention, the molar ratio of the aromatic dicarboxylic acid and / or the esterification of the aromatic dicarboxylic acid to the aliphatic diol is 1:(1-2), for example 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2, preferably 1:(1.2-1.9).

[0038] In this invention, the ratio of soft and hard segments of the elastomer can be adjusted by controlling the ratio of aliphatic diols to aromatic dicarboxylic acids and / or their esters, thereby controlling the preparation of polyester elastomers with higher molecular weights to meet different hardness and elasticity requirements. The polyester elastomers prepared in the end all have excellent performance.

[0039] According to a preferred embodiment of the present invention, the molar ratio of the aromatic diacid and / or the esterification of the aromatic diacid to the polyether diol and the aromatic diacid and / or its esterification is 1:(0.02-1.4), for example 1:0.02, 1:0.03, 1:0.05, 1:0.06, 1:0.08, 1:0.1, 1:0.11, 1:0.13, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3 or 1:1.4, preferably 1:(0.05-0.9).

[0040] According to a preferred embodiment of the present invention, the content of the branching agent is 0.01-1 wt% based on the total mass of the raw material composition, for example, 0.01 wt%, 0.03 wt%, 0.05 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, or 1 wt%, preferably 0.03-0.8 wt%.

[0041] In this invention, conventional additives in the art, such as stabilizers and processing aids, can be added as needed. According to a preferred embodiment of the invention, the raw material composition further contains at least one of an antioxidant, an anti-aging agent, a light stabilizer, a heat stabilizer, a branching agent, a release agent, a pigment, a lubricant, and a matting agent.

[0042] According to the present invention, the content of general additives in the raw material composition is 0.02-2 wt%, preferably 0.05-1 wt%.

[0043] According to a preferred embodiment of the present invention, the raw material composition further contains an antioxidant. Preferably, the content of the antioxidant in the raw material composition is 0.02-1.0 wt%; more preferably 0.05-0.5 wt%. The type of antioxidant can be a conventional type in the art, such as hindered phenolic antioxidants or phosphite antioxidants. In this invention, antioxidant 1098 is used as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto.

[0044] A second aspect of the present invention provides a method for preparing a thermoplastic polyester elastomer, the method comprising: in the presence of a catalyst, the components of the raw material composition described in the first aspect of the present invention undergoing a contact reaction and a polycondensation reaction.

[0045] The preparation method of this invention can obtain high molecular weight, low melt index polyester elastomers, and prepare thermoplastic polyester elastomers (TPEE) with higher molecular weight and lower melt index at different hardness and strength. The molecular structure can be designed, the preparation process is simple, and it can better meet market demands and expand its application fields.

[0046] According to the present invention, the catalyst can be selected from a wide range of sources. In one embodiment, the catalyst is selected from at least one of zinc acetate, magnesium acetate, calcium acetate, titanium dioxide, germanium dioxide, antimony trioxide, antimony acetate, antimony glycolate, titanium glycolate, polyethylene glycol antimony, triisobutylaluminum, dibutyltin oxide, stannous octoate, monobutyltriisooctanoate, dioctyltin oxide, tetrabutyl titanate, and isopropyl titanate. Preferably, the amount of the catalyst is 0.02-0.5 wt% of the total mass of the raw material composition.

[0047] According to a preferred embodiment of the present invention, the contact reaction and the polycondensation reaction are carried out under an inert atmosphere, wherein the inert atmosphere can be a conventional inert atmosphere in the art (wherein an inert atmosphere refers to an atmosphere that does not react with the raw materials), such as nitrogen.

[0048] According to the present invention, the conditions of the contact reaction are not particularly limited as long as the purpose of the present invention can be achieved, as long as the esterification reaction and / or transesterification reaction can be achieved. In a preferred embodiment, the conditions of the contact reaction include: a reaction temperature of 150-280°C, preferably 160-260°C, and the contact reaction time can be adjusted according to the reaction temperature, preferably 1-6 hours, preferably 1-5 hours.

[0049] According to the present invention, those skilled in the art will know that both the contact reaction and the polycondensation reaction are carried out under dynamic conditions, and the initial rotation speed is generally set to 100-300 r / min.

[0050] According to a preferred embodiment of the present invention, the polycondensation reaction includes a pre-polycondensation reaction and a final polycondensation reaction. The main purpose of the pre-polycondensation reaction is to promote further polycondensation of the materials from the esterification or transesterification reactions. The conditions for the pre-polycondensation reaction include a temperature of 180-260°C, preferably 180-220°C. Small molecule alcohols or water are generated during the polycondensation process. Generally, when the small molecule alcohols or water generated by the reaction are collected in the condenser and reach more than 90 wt% of the theoretical amount, the final polycondensation reaction is started, and the time is generally 0.5-1 h. The conditions for the final polycondensation reaction include a temperature of 180-280°C, preferably 220-250°C, a vacuum degree not exceeding 300 Pa, and the time is generally adjusted according to the selected temperature, generally 1-5 h.

[0051] According to the present invention, those skilled in the art will know that the pre-condensation reaction will generate pressure at a certain temperature, and the pressure is generally 3-10 kPa.

[0052] According to the present invention, the product material after the pre-condensation reaction may also contain water or small molecule alcohol, which can be dried using conventional drying methods in the art to obtain the final product.

[0053] The third aspect of the present invention provides a thermoplastic polyester elastomer prepared by the preparation method described in the second aspect of the present invention.

[0054] The thermoplastic polyester elastomer of the present invention has a high molecular weight and a low melt index.

[0055] The present invention will be described in detail below through examples. The raw materials and catalysts used in the following examples were all purchased commercially. The aromatic dicarboxylic acids and / or their esters, aliphatic diols, and polyether diols used were obtained from Maclean Biotechnology Co., Ltd., and the catalysts, branching agents, antioxidants, and other auxiliaries were purchased from Titan Technology Co., Ltd.

[0056] The intrinsic viscosity test shall be performed in accordance with GB / T 17931-2018: the solvent shall be a phenol / 1,1,2,2-tetrachloroethane mixed solution with a mass ratio of 1:1, the Ubbelohde viscometer shall be used with an inner diameter of 0.84 mm, and the test temperature shall be (25±0.05)℃.

[0057] The test reference standard for melt flow index (MFR) is ISO 1133, and the test conditions are 220℃ and 2.16kg.

[0058] Molecular weight determination method: The molecular weight of the sample was determined using a Waters 1515 gel permeation chromatograph (USA). The chromatographic column was an Agilent PLgel 5μm MIXED-C, the mobile phase was hexafluoroisopropanol, the flow rate was 1 mL / min, and the standard was polystyrene.

[0059] The melting and crystallization temperatures were tested according to ISO 11357-1 / -3: A TA Q2000 differential scanning calorimeter (DSC) was used to study the thermal properties of the copolyester. Under nitrogen atmosphere, 5–10 mg of sample was heated to 130 °C at a rate of 10 °C / min and held at that temperature for 10 min. Then, the sample was cooled to -50 °C at a rate of 10 °C / min. The exothermic crystallization curve was recorded, and the corresponding crystallization temperature (Tc) was read. Finally, the sample was heated to 130 °C at a rate of 10 °C / min, the melting curve was recorded, and the corresponding melting point (Tm) was read.

[0060] The reference standard for mechanical property testing is ISO 527-1 / -2.

[0061] Example 1

[0062] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate (total monomer content) were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, a thermoplastic polyester elastomer.

[0063] The gel permeation chromatography (GPC) curve of the final product, thermoplastic polyester elastomer, is shown below. Figure 1 As shown.

[0064] The differential scanning calorimetry (DSC) curve of the final product, thermoplastic polyester elastomer, is shown below. Figure 2 As shown, the horizontal axis represents temperature, and the vertical axis represents heat flux.

[0065] The differential scanning calorimetry crystallization curve of the final product, thermoplastic polyester elastomer, is shown below. Figure 3 As shown.

[0066] The engineering stress-strain curve of the final product, thermoplastic polyester elastomer, is as follows: Figure 4 As shown, the horizontal axis represents elongation at break, and the vertical axis represents tensile strength.

[0067] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 1, was 1.43 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.78 × 10⁻⁶. 4 The weight-average molecular weight is 5.95 × 10⁻⁶. 4 The melt index was 21 g / 10 min, the crystallization temperature was 154.0℃, the melting point was 201.8℃, the tensile strength of the sample was 32.25 MPa, the tensile modulus was 109.74 MPa, and the elongation at break was 1104.3%.

[0068] Example 2

[0069] 0.9 mol of dimethyl terephthalate, 1.53 mol of 1,4-butanediol, 0.05 mol of PTMG-1000, 0.0009 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum of less than 100 Pa for 1.5 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. When the rotation speed reached the minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0070] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 2, was 1.35 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.26 × 10⁻⁶. 4 The weight-average molecular weight is 5.50 × 10⁻⁶. 4 The melt index was 22.3 g / 10 min, the crystallization temperature was 155.3℃, the melting point was 210.6℃, the tensile strength of the sample was 27.73 MPa, the tensile modulus was 147.28 MPa, and the elongation at break was 624.5%.

[0071] Example 3

[0072] 0.9 mol of dimethyl terephthalate, 1.35 mol of 1,4-butanediol, 0.15 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. The reaction was stopped and the product discharged when the rotation speed reached its minimum. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0073] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 3, was 1.39 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.30 × 10⁻⁶. 4 The weight-average molecular weight is 3.81 × 10⁻⁶. 4The melt flow index was 21.8 g / 10 min, the crystallization temperature was 146.8℃, the melting point was 180.3℃, the tensile strength of the sample was 35.42 MPa, the tensile modulus was 96.01 MPa, and the elongation at break was 1251.3%.

[0074] Example 4

[0075] 0.9 mol of dimethyl terephthalate, 1.26 mol of 1,4-butanediol, 0.2 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08% (by total mass) of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 2 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, a thermoplastic polyester elastomer.

[0076] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 4, was 0.95 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.20 × 10⁻⁶. 4 The weight-average molecular weight is 3.35 × 10⁻⁶. 4 The melt flow index was 33.9 g / 10 min, the crystallization temperature was 133℃, the melting point was 178℃, the tensile strength of the sample was 19.24 MPa, the tensile modulus was 203.76 MPa, and the elongation at break was 300.0%.

[0077] Example 5

[0078] 0.9 mol of dimethyl terephthalate, 1.17 mol of 1,4-butanediol, 0.25 mol of PTMG-1000, 0.00042 mol of tetrabutyl titanate, and 0.08% (by total mass) of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 2 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, a thermoplastic polyester elastomer.

[0079] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 5, was 1.16 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.29 × 10⁻⁶. 4 The weight-average molecular weight is 4.37 × 10⁻⁶. 4 The melt flow index was 25.6 g / 10 min, the crystallization temperature was 110.6℃, the melting point was 165.3℃, the tensile strength of the sample was 30.12 MPa, the tensile modulus was 42.73 MPa, and the elongation at break was 2542.5%.

[0080] Example 6

[0081] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-500, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trioctyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum of less than 100 Pa for 1.5 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. When the rotation speed reached the minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0082] The intrinsic viscosity of the final thermoplastic polyester elastomer prepared in Example 6 was 1.42 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 2.10 × 10⁻⁶. 4 The weight-average molecular weight is 6.23 × 10⁻⁶. 4 The melt flow index was 21.4 g / 10 min, the crystallization temperature was 151.4℃, the melting point was 202.8℃, the tensile strength of the sample was 33.52 MPa, the tensile modulus was 110.82 MPa, and the elongation at break was 955.0%.

[0083] Example 7

[0084] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-2000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the reaction reached more than 90 wt% of the theoretical methanol content in the condensate, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum of less than 100 Pa for 1.5 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. When the rotation speed reached the minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0085] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 7, was 1.34 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.18 × 10⁻⁶. 4 The weight-average molecular weight is 3.59 × 10⁻⁶. 4 The melt flow index was 23.8 g / 10 min, the crystallization temperature was 158.4℃, the melting point was 201.6℃, the tensile strength of the sample was 32.11 MPa, the tensile modulus was 186.04 MPa, and the elongation at break was 713.8%.

[0086] Example 8

[0087] 0.9 mol of terephthalic acid, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 220°C and the rotation speed was set to 200 r / min for 1 hour, followed by another hour at 240°C. When the water generated from the reaction reached more than 90 wt% of the theoretical water content in the condensate, the polymerization temperature was raised to 260°C and polycondensation was carried out under a high vacuum below 100 Pa for 2 hours, during which the torque change was observed and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, a plastic polyester elastomer.

[0088] The intrinsic viscosity of the final product, the plastic polyester elastomer, prepared in Example 8, was 1.19 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.20 × 10⁻⁶. 4 The weight-average molecular weight is 4.78 × 10⁻⁶. 4 The melt flow index was 25.8 g / 10 min, the crystallization temperature was 160.0℃, the melting point was 201.0℃, the tensile strength of the sample was 33.04 MPa, the tensile modulus was 99.54 MPa, and the elongation at break was 1190.7%.

[0089] Example 9

[0090] 0.9 mol of terephthalic acid, 1.44 mol of ethylene glycol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 220°C and the rotation speed was set to 200 r / min for esterification reaction for 1 hour, followed by another 1 hour at 240°C. When the water generated from the reaction reached more than 90 wt% of the theoretical water content in the condensate, the polymerization temperature was raised to 260°C and polycondensation was carried out under a high vacuum of less than 100 Pa for 2 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0091] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 9, was 1.45 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.29 × 10⁻⁶. 4 The weight-average molecular weight is 4.53 × 10⁻⁶. 4 The melt flow index was 19.9 g / 10 min, the crystallization temperature was 146.7℃, the melting point was 203.4℃, the tensile strength of the sample was 36.80 MPa, the tensile modulus was 107.08 MPa, and the elongation at break was 1008.0%.

[0092] Example 10

[0093] 0.9 mol of terephthalic acid, 1.44 mol of 1,3-propylene glycol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 220°C and the rotation speed was set to 200 r / min for 1 hour, followed by another hour at 240°C. When the water generated from the reaction reached more than 90 wt% of the theoretical water content in the condensate, the polymerization temperature was raised to 260°C and polycondensation was carried out under a high vacuum below 100 Pa for 2 hours, during which the torque change was observed and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0094] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 10, was 1.27 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.35 × 10⁻⁶. 4 The weight-average molecular weight is 4.76 × 10⁻⁶. 4The melt flow index was 26.7 g / 10 min, the crystallization temperature was 130.5℃, the melting point was 180.6℃, the tensile strength of the sample was 24.03 MPa, the tensile modulus was 106.53 MPa, and the elongation at break was 737.0%.

[0095] Example 11

[0096] 0.9 mol of phthalic acid, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 220°C and the rotation speed was set to 200 r / min for 1 hour, followed by another hour at 240°C. When the water generated from the reaction reached more than 90 wt% of the theoretical water content in the condensate, the polymerization temperature was raised to 260°C and polycondensation was carried out under a high vacuum below 100 Pa for 2 hours, during which the torque change was observed and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0097] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 11, was 1.35 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.20 × 10⁻⁶. 4 The weight-average molecular weight is 4.56 × 10⁻⁶. 4 The melt flow index was 21.8 g / 10 min, the crystallization temperature was 154.0℃, the melting point was 192.5℃, the tensile strength of the sample was 29.31 MPa, the tensile modulus was 176.30 MPa, and the elongation at break was 590.1%.

[0098] Example 12

[0099] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of zinc acetate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1.5 h. The reaction was then carried out at 220°C for 1 h. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 3 h. During this period, the torque change was observed, and the rotation speed was gradually reduced. The reaction was stopped and the product discharged when the rotation speed reached its minimum. The product was then dried under vacuum at 30°C for 12 h to obtain the final product, thermoplastic polyester elastomer.

[0100] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 12, was 1.24 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.80 × 10⁻⁶. 4 The weight-average molecular weight is 3.60 × 10⁻⁶. 4 The melt flow index was 27.8 g / 10 min, the crystallization temperature was 165.3℃, the melting point was 202.5℃, the tensile strength of the sample was 32.68 MPa, the tensile modulus was 107.08 MPa, and the elongation at break was 1151.3%.

[0101] Example 13

[0102] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00042 mol of tetrabutyl zirconate, 0.00042 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate (total monomer mass) were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1.5 h. The reaction was then carried out at 220°C for 1 h. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 2 h, observing the torque change and gradually reducing the rotation speed. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 h to obtain the final product, a thermoplastic polyester elastomer.

[0103] The intrinsic viscosity of the final thermoplastic polyester elastomer prepared in Example 13 was 1.26 dL / g. Its number-average molecular weight, measured by gel permeation chromatography, was 1.66 × 10⁴, and its weight-average molecular weight was 5.69 × 10⁴. The melt index was 27.6 g / 10 min, the crystallization temperature was 149.9 °C, the melting point was 202.6 °C, the tensile strength of the sample was 32.90 MPa, the tensile modulus was 124.71 MPa, and the elongation at break was 1137.3%.

[0104] Example 14

[0105] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% trimellitic anhydride (total monomer mass) were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. Once the rotation speed reached its minimum, the reaction was stopped and the product discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, a thermoplastic polyester elastomer.

[0106] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 14, was 1.19 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 0.93 × 10⁻⁶. 4 The weight-average molecular weight is 4.53 × 10⁻⁶. 4 The melt flow index was 31.5 g / 10 min, the crystallization temperature was 150.7℃, the melting point was 202.8℃, the tensile strength of the sample was 32.42 MPa, the tensile modulus was 92.49 MPa, and the elongation at break was 1156.7%.

[0107] Example 15

[0108] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of glycerol (total monomer mass) were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for esterification reaction for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. The reaction was stopped and the product discharged when the rotation speed reached its minimum. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0109] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 15, was 1.32 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 0.75 × 10⁻⁶. 4 The weight-average molecular weight is 2.36 × 10⁻⁶. 4The melt flow index was 21.8 g / 10 min, the crystallization temperature was 160.4℃, the melting point was 203.6℃, ​​the tensile strength of the sample was 24.62 MPa, the tensile modulus was 186.20 MPa, and the elongation at break was 545.1%.

[0110] Example 16

[0111] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of citric acid (total monomer mass) were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for esterification reaction for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. The reaction was stopped and the product discharged when the rotation speed reached its minimum. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0112] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 16, was 1.20 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 0.90 × 10⁻⁶. 4 The weight-average molecular weight is 3.56 × 10⁻⁶. 4 The melt flow index was 26.4 g / 10 min, the crystallization temperature was 163.9℃, the melting point was 201.7℃, the tensile strength of the sample was 18.03 MPa, the tensile modulus was 203.67 MPa, and the elongation at break was 241.7%.

[0113] Example 17

[0114] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.12% (by total mass) of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for esterification reaction for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours. During this period, the torque change was observed, and the rotation speed was gradually reduced. The reaction was stopped and the product discharged when the rotation speed reached its minimum. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0115] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 17, was 1.47 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.93 × 10⁻⁶. 4 The weight-average molecular weight is 6.13 × 10⁻⁶. 4 The melt flow index was 20.4 g / 10 min, the crystallization temperature was 146.7℃, the melting point was 203.4℃, the tensile strength of the sample was 30.56 MPa, the tensile modulus was 122.38 MPa, and the elongation at break was 819.0%.

[0116] Example 18

[0117] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, and 0.00084 mol of trimethyl trimellitate (total monomer content 0.16 wt%) were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for esterification reaction for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0118] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 18, was 1.45 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.56 × 10⁻⁶. 4 The weight-average molecular weight is 6.34 × 10⁻⁶. 4 The melt flow index was 24.9 g / 10 min, the crystallization temperature was 160.8℃, the melting point was 201.6℃, the tensile strength of the sample was 29.97 MPa, the tensile modulus was 118.89 MPa, and the elongation at break was 904.0%.

[0119] Example 19

[0120] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, 0.08 wt% of trimethyl trimellitate, and 0.3 wt% of antioxidant 1098 were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour, followed by another 1 hour at 220°C. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. The reaction was stopped and the product discharged when the rotation speed reached its minimum. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0121] The intrinsic viscosity of the final product, the thermoplastic polyester elastomer, prepared in Example 19, was 1.45 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 1.79 × 10⁻⁶. 4 The weight-average molecular weight is 5.83 × 10⁻⁶. 4 The melt flow index was 25.6 g / 10 min, the crystallization temperature was 156.3℃, the melting point was 201.5℃, the tensile strength of the sample was 32.53 MPa, the tensile modulus was 112.87 MPa, and the elongation at break was 940.0%.

[0122] Comparative Example 1

[0123] 0.9 mol of dimethyl terephthalate, 1.44 mol of 1,4-butanediol, 0.1 mol of PTMG-1000, and 0.00084 mol of tetrabutyl titanate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour. The reaction was then carried out at 220°C for another hour. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. Once the rotation speed reached its minimum, the reaction was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0124] The intrinsic viscosity of the final product, thermoplastic polyester elastomer, prepared in Comparative Example 1, was 0.98 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 0.96 × 10⁻⁶. 4 The weight-average molecular weight is 4.13 × 10⁻⁶. 4The melt flow index was 31.8 g / 10 min, the crystallization temperature was 158.9℃, the melting point was 202.5℃, the tensile strength of the sample was 18.80 MPa, the tensile modulus was 234.68 MPa, and the elongation at break was 135.4%.

[0125] Comparative Example 2

[0126] 0.9 mol of dimethyl terephthalate, 1.54 mol of 1,4-butanediol, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour, followed by another 1 hour at 220°C. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum of less than 100 Pa for 1.5 hours, during which the torque change was observed and the rotation speed was gradually reduced. Once the rotation speed reached its minimum, the reaction was stopped and the product was discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, thermoplastic polyester elastomer.

[0127] The intrinsic viscosity of the final product, thermoplastic polyester elastomer, prepared in Comparative Example 2 was 0.71 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 0.84 × 10⁻⁶. 4 The weight-average molecular weight is 1.12 × 10⁻⁶. 4 The melt flow index was 46.3 g / 10 min, the crystallization temperature was 170.1℃, the melting point was 230.4℃, the tensile strength of the sample was 16.3 MPa, the tensile modulus was 125.6 MPa, and the elongation at break was 31.7%.

[0128] Comparative Example 3

[0129] 0.9 mol of dimethyl terephthalate, 1.26 mol of PTMG-1000, 0.00084 mol of tetrabutyl titanate, and 0.08 wt% of trimethyl trimellitate were added to a reactor. Under nitrogen protection, the temperature was raised to 190°C and the rotation speed was set to 200 r / min for 1 hour, followed by another hour at 220°C. When the methanol produced by the condensate reached more than 90 wt% of the theoretical methanol content, the polymerization temperature was raised to 250°C and polycondensation was carried out under a high vacuum below 100 Pa for 1.5 hours, observing the torque change and gradually reducing the rotation speed. Once the rotation speed reached its minimum, the reaction was stopped and the product discharged. The product was then dried under vacuum at 30°C for 12 hours to obtain the final product, a thermoplastic polyester elastomer.

[0130] The intrinsic viscosity of the final product, thermoplastic polyester elastomer, prepared in Comparative Example 3 was 0.65 dL / g, and its number-average molecular weight, as determined by gel permeation chromatography, was 0.96 × 10⁻⁶.4 The weight-average molecular weight is 1.14 × 10⁻⁶. 4 The melt flow index was 50.1 g / 10 min, the crystallization temperature was 113.4℃, the melting point was 167.5℃, the tensile strength of the sample was 15.3 MPa, the tensile modulus was 50.1 MPa, and the elongation at break was 134.1%.

[0131] The results from the examples and comparative examples show that by changing the ratio of aliphatic diols and polyethers and the type of polyether, the ratio of soft and hard segments in the elastomer can be adjusted, and polyester elastomers with higher molecular weights can be prepared to meet different hardness and elasticity requirements. Furthermore, the thermoplastic polyester elastomers prepared in the examples exhibit excellent performance. Specifically, different types of polyester elastomers can be obtained by changing the aromatic diacid or its corresponding ester and the type of aliphatic diol monomer; different molecular weight thermoplastic polyester elastomers can be obtained by changing the type of polymerization catalyst, the compound catalyst, and the amount of catalyst, thereby affecting the tensile strength, elongation at break, and thermal properties of the elastomer; and different types of high molecular weight polyester elastomers can be obtained by changing the type of branching agent.

[0132] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A thermoplastic polyester elastomer raw material composition, characterized in that, The raw material composition contains: aliphatic diols, aromatic dicarboxylic acids and / or esters of aromatic dicarboxylic acids, polyether diols and branching agents.

2. The raw material composition according to claim 1, characterized in that, The branching agent includes at least one of the following: a polyol having 3-6 functional groups, a polyacid having 3-6 functional groups, an anhydride corresponding to a polyacid having 3-6 functional groups, an ester corresponding to a polyacid having 3-6 functional groups, and a hydroxy acid having 3-6 functional groups.

3. The raw material composition according to claim 2, characterized in that, The polyol having 3-6 functional groups includes at least one selected from glycerol, trimethylpropane, pentaerythritol, 1,2,6-hexanetriol, sorbitol, and 1,1,4,4-tetra(hydroxymethyl)cyclohexanedipentaerythritol; and / or The polybasic acid having 3-6 functional groups includes at least one selected from 1,2,3-benzenetricarboxylic acid, trimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, trimellitic acid, 1,1,2-triglyceride, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetracarboxylic acid; and / or The anhydrides corresponding to the polybasic acids having 3-6 functional groups are selected from trimellitic anhydrides; and / or The esters corresponding to the polybasic acids having 3-6 functional groups include trimethyl trimellitate and / or trioctyl trimellitate; and / or The hydroxy acids having 3-6 functional groups include at least one of malic acid, citric acid, tartaric acid, 3-hydroxyglutaric acid, and mucilage.

4. The raw material composition according to claim 1, characterized in that, The aliphatic diol is selected from C2-C18 aliphatic diols; and / or The aromatic dicarboxylic acid and / or its esterified form comprises at least one of terephthalic acid, phthalic acid, isophthalic acid, biphenyl phthalic acid, and 2,6-naphthalenedicarboxylic acid and their esterified forms; and / or The polyether diol is selected from at least one of polyethylene glycol, polypropylene glycol, and polytetramethylene ether diol; and / or The number average molecular weight of the polyether polyol is 200-2000.

5. The raw material composition according to claim 4, characterized in that, The aliphatic diol is selected from C2-C5 aliphatic diols.

6. The raw material composition according to any one of claims 1-5, characterized in that, The molar ratio of the aromatic dicarboxylic acid and / or its ester to the aliphatic diol is 1:(1-2); and / or The molar ratio of the aromatic diacid and / or the esterified aromatic diacid to the polyether diol and the aromatic diacid and / or its esterified form is 1:(0.02-1.4); and / or The content of the branching agent is 0.01-1 wt%, based on the total mass of the raw material composition.

7. The raw material composition according to claim 6, characterized in that, The molar ratio of the aromatic dicarboxylic acid and / or its ester to an aliphatic diol is 1:(1.2-1.9); and / or The molar ratio of the aromatic diacid and / or the esterified aromatic diacid to the polyether diol is 1:(0.05-0.9); and / or Based on the total mass of the raw material composition, the content of the branching agent is 0.03-0.8 wt%.

8. The raw material composition according to any one of claims 1-7, characterized in that, The raw material composition also contains at least one of antioxidants, anti-aging agents, light stabilizers, heat stabilizers, branching agents, release agents, pigments, lubricants, and matting agents.

9. A method for preparing a thermoplastic polyester elastomer, characterized in that, The preparation method includes: In the presence of a catalyst, the components of the raw material composition according to any one of claims 1-8 undergo a contact reaction and a polycondensation reaction.

10. The preparation method according to claim 9, characterized in that, The catalyst is selected from at least one of zinc acetate, magnesium acetate, calcium acetate, titanium dioxide, germanium dioxide, antimony trioxide, antimony acetate, antimony glycol, titanium glycol, polyethylene glycol, triisobutylaluminum, dibutyltin oxide, stannous octoate, monobutyltriisooctanoate, dioctyltin oxide, tetrabutyl titanate, and isopropyl titanate; and / or Based on the total mass of the raw material composition, the amount of catalyst used is 0.02-0.5 wt% of the total mass of the raw material composition.

11. The preparation method according to claim 10, characterized in that, The contact reaction and polycondensation reaction are carried out under an inert atmosphere; and / or The conditions for the contact reaction include: a reaction temperature of 150-280℃ and / or a reaction time of 1-6 hours; and / or The polycondensation reaction includes a pre-polycondensation reaction and a final polycondensation reaction. The conditions for the pre-polycondensation reaction include a temperature of 180-260℃. The conditions for the final polycondensation reaction include a temperature of 180-280℃, a vacuum degree not exceeding 300Pa, and a time of 1-5h.

12. The preparation method according to claim 11, characterized in that, The conditions for the contact reaction include: a reaction temperature of 160-260℃ and / or a reaction time of 1-5 hours; and / or The conditions for the pre-condensation reaction include a temperature of 180-220℃ and / or a time of 0.5-1h; the conditions for the final condensation reaction include a temperature of 220-250℃.

13. A thermoplastic polyester elastomer, characterized in that, The thermoplastic polyester elastomer is prepared by the preparation method described in any one of claims 9-12.

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