A high-strength polyether block polyamide blend and a method for making the same

Abstract

The application relates to the technical field of high polymer materials, in particular to a high-strength polyether block polyamide blended material and a preparation method thereof. The preparation method comprises the following steps: step 1, drying and removing water from an elastomer and a compatibilizer according to a proportioning ratio, and mechanically mixing to obtain a premix; and step 2, melt blending the premix to obtain the high-strength polyether block polyamide blended material. The application introduces a specific proportioning ratio of the compatibilizer to improve the compatibility of the material, maintain the strength and elongation at break of the material, and improve the heat resistance of the material. The polyether block polyamide blended material in the application comprises a polyetheramide elastomer, a polyurethane elastomer and a compatibilizer; the polyetheramide elastomer serves as the main body to provide the toughness of the material, the polyurethane elastomer is added to consider the strength of the material, and the three different compatibilizers are used to improve the compatibility of the material, maintain the strength and elongation at break of the material.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically a high-strength polyether block polyamide blend material and its preparation method. Background Technology

[0002] With the continuous advancement of science and technology and the accelerated pace of industrialization, thermoplastic elastomers have attracted much attention due to their unique performance advantages. Thermoplastic polyamide elastomers, with their advantages such as flexibility at low temperatures, processability, light weight, thermal stability, and excellent mechanical properties, are considered a thermoplastic elastomer material with great development potential. They have experienced rapid development in the past decade and have become a research hotspot in the field of materials science.

[0003] Polyetheramide (PEBAX) is a diblock copolymer and a thermoplastic elastomer. It consists of rigid polyamide (PA) segments and flexible polyether (PE) segments. The polyamide segments commonly use PA6 and PA12 to provide mechanical strength; the polyether segments are typically polyethylene oxide or polybutene oxide. The microstructure of Pebax consists of PA dispersed within a PE matrix.

[0004] Due to its light weight, excellent strength, and high elasticity, it is used to make foam materials for various sportswear such as shoes. Furthermore, its high tensile strength, flexural properties, and elongation at break also make it suitable for use in high-precision medical equipment. Its excellent mechanical properties and ease of processing have led to its widespread application in the automotive, transportation, and power industries.

[0005] Although polyether amide (PEBAX) can adjust the thermal properties, mechanical properties, and hardness of materials by different combinations and ratios of polyamide and polyether segments, its high material price makes it difficult to produce and use in large-scale industrial applications.

[0006] Therefore, it is of great significance to provide a PEBAX blend material that is simple to produce, can maintain excellent performance similar to PEBAX, can significantly reduce production costs, and can form a uniform dispersion system with good compatibility. Summary of the Invention

[0007] The purpose of this invention is to provide a high-strength polyether block polyamide blend material and its preparation method, so as to solve the problems mentioned in the background art.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0009] A method for preparing a high-strength polyether block polyamide blend material includes the following steps:

[0010] Step 1: Dry and dehydrate the elastomer and compatibilizer according to the specified ratio, and then mechanically mix them to obtain a premix.

[0011] Step 2: Melt-blend the premix to obtain the blended material.

[0012] In a more optimized manner, the elastomer in the raw materials of the premix includes polyetheramide elastomer and polyurethane elastomer in a mass ratio of 25wt%~75wt%:75wt%~25wt%.

[0013] In a further embodiment, the polyetheramide elastomer is PEBAX 4033; the polyurethane elastomer is a TPU elastomer.

[0014] In a more optimized manner, the compatibilizer accounts for 5 wt% to 20 wt% of the elastomer in the raw materials of the premix.

[0015] In a more optimized manner, the specific process of drying and dehydration in step 1 is as follows: drying at 80~100℃ for 6~8 hours.

[0016] In a more optimized manner, the specific parameters for melt blending in step 2 are as follows: the screw speed is set to 30~80 rpm, the temperature is set to 160~200℃, and the melt blending time is set to 10 min.

[0017] In a further embodiment, a screw extruder or a HAAKE torque rheometer is used in the melt blending process.

[0018] More preferably, the compatibilizer includes one or more of POE-g-MAH, POE-g-GMA, SEBA-g-MAH, and PEG-E51-HDI.

[0019] Ideally, the compatibilizer is POE-g-MAH.

[0020] More preferably, the compatibilizer includes POE-g-MAH, POE-g-GMA, and PEG-E51-HDI in a mass ratio of 1:0.2~0.5:2~3.

[0021] The optimized preparation process of the PEG-E51-HDI is as follows:

[0022] Step 1: Under a nitrogen atmosphere, hexamethylene diisocyanate and hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 80-90°C for 3-4 hours. After purification, intermediate A was obtained. Intermediate A, 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, and azobisisobutyronitrile were added to tetrahydrofuran and reacted under ultraviolet light at 50-60°C for 2-4 hours. After purification, pyrimidine monomer was obtained.

[0023] Step 2: Pyrimidine monomer, hexamethylene diisocyanate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, bisphenol A type E51 epoxy resin, and dibutyltin dilaurate are added to toluene and reacted at 50~80℃ for 3~4 hours. Then the mixture is dried and the solvent is removed to obtain PEG-E51-HDI.

[0024] More preferably, the pyrimidinyl monomer comprises the following components by mass: 1-2 parts hexamethylene diisocyanate, 9-11 parts hydroxyl polyethylene glycol acrylate, 3-4 parts 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, 0.2-0.5 parts azobisisobutyronitrile, and 40-50 parts tetrahydrofuran;

[0025] The PEG-E51-HDI comprises the following components by mass: 4-5 parts pyrimidinyl monomer, 2-3 parts hexamethylene diisocyanate, 2-3 parts 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-4 parts bisphenol A type E51 epoxy resin, 0.2-0.5 parts dibutyltin dilaurate, and 40-50 parts toluene.

[0026] In the proposed method, when two elastomers are blended, the surface tension between the two phases affects the dispersion and compatibility, resulting in the prepared blend material not achieving the desired effect. Therefore, a compatibilizer obtained by mixing three reactive compatibilizers with different active functional groups in a specific ratio can effectively promote the formation of a uniform dispersion system between different components, prevent phase separation, improve the compatibility of the blend material, and further improve the mechanical properties of the blend material. At the same time, heat-resistant groups such as pyrimidine, ether bonds, and siloxy groups are introduced to improve the heat resistance of the blend material.

[0027] The polyethylene glycol molecular weight of the hydroxyl-containing polyethylene glycol acrylate is 1000.

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] This invention discloses a high-strength polyether block polyamide blend and its preparation method. The polyether block polyamide blend includes a polyether amide elastomer, a polyurethane elastomer, and a compatibilizer. The polyether amide elastomer serves as the main component, providing material toughness, while the added polyurethane elastomer contributes to material strength. Three different compatibilizers are used to improve the material's compatibility and maintain its strength and elongation at break. This invention achieves simple and efficient reinforcement based on commercially available polyether amide elastomers by directly melt-blending two elastomers with similar polarities and functions. The addition of the compatibilizer improves the agglomeration of the dispersed phase, reduces particle size, and further enhances the system's compatibility, thus improving the mechanical properties of the polyether amide elastomer blend. Furthermore, by introducing a specific proportion of compatibilizer, a uniform dispersion system is formed to prevent phase separation, thereby improving the compatibility of the blend and further enhancing its mechanical properties and processing performance. Additionally, heat-resistant groups are introduced to improve the heat resistance of the blend. Detailed Implementation

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] It should be noted that the following parts are by weight. There are no special restrictions on the manufacturers of the raw materials involved in this invention. Exemplary examples include: in the following embodiments, the polyetheramide elastomer is PEBAX 4033, purchased from Arkema, France; the polyurethane elastomer is TPU elastomer, purchased from Covestro, Germany; and the hydroxyl polyethylene glycol acrylate product code is 80030202-1000, item number is 80030202, purchased from Guangzhou Carbon Water Technology Co., Ltd.

[0032] In the following examples, the polyetheramide elastomer is PEBAX 4033; the polyurethane elastomer is TPU elastomer.

[0033] Example 1: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0034] 12.50g of PEBAX elastomer and 37.50g of TPU elastomer were weighed out and dried in an oven at 80℃ for 6 hours using a melt blending method. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50rpm, and the blending time at 10min.

[0035] Example 2: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0036] 11.91g of PEBAX elastomer, 35.71g of TPU elastomer, and 2.38g of compatibilizer POE-g-MAH were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0037] Example 3: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0038] 11.36 g of PEBAX elastomer, 34.09 g of TPU elastomer, and 4.55 g of compatibilizer POE-g-MAH were weighed out by melt blending and dried in an oven at 80°C for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190°C, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0039] Example 4: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0040] 10.87g of PEBAX elastomer, 32.61g of TPU elastomer, and 6.52g of compatibilizer POE-g-MAH were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0041] Example 5: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0042] 10.42g of PEBAX elastomer, 31.25g of TPU elastomer, and 8.33g of compatibilizer POE-g-MAH were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0043] Example 6: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0044] 11.91g of PEBAX elastomer, 35.71g of TPU elastomer, and 2.38g of compatibilizer POE-g-GMA were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0045] Example 7: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0046] 11.36 g of PEBAX elastomer, 34.09 g of TPU elastomer, and 4.55 g of compatibilizer POE-g-GMA were weighed out by melt blending and dried in an oven at 80°C for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190°C, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0047] Example 8: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0048] 10.87g of PEBAX elastomer, 32.61g of TPU elastomer, and 6.52g of compatibilizer POE-g-GMA were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0049] Example 9: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0050] 10.42g of PEBAX elastomer, 31.25g of TPU elastomer, and 8.33g of compatibilizer POE-g-GMA were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0051] Example 10: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0052] 11.91g of PEBAX elastomer, 35.71g of TPU elastomer, and 2.38g of compatibilizer SEBS-g-MAH were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0053] Example 11: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0054] 11.36 g of PEBAX elastomer, 34.09 g of TPU elastomer, and 4.55 g of compatibilizer SEBS-g-MAH were weighed out by melt blending and dried in an oven at 80°C for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190°C, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0055] Example 12: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0056] 10.87g of PEBAX elastomer, 32.61g of TPU elastomer, and 6.52g of compatibilizer SEBS-g-MAH were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0057] Example 13: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0058] 10.42g of PEBAX elastomer, 31.25g of TPU elastomer, and 8.33g of compatibilizer SEBS-g-MAH were weighed out by melt blending and dried in an oven at 80℃ for 6 hours. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0059] Example 14: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0060] Step 1: Under a nitrogen atmosphere, 1.5 parts of hexamethylene diisocyanate and 10 parts of hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 85°C for 3.5 hours. After purification, intermediate A was obtained. Intermediate A, 3.5 parts of 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, and 0.3 parts of azobisisobutyronitrile were added to 45 parts of tetrahydrofuran and reacted under ultraviolet light at 55°C for 3 hours. After purification, pyrimidine monomer was obtained.

[0061] Step 2: Add 4.5 parts of pyrimidinyl monomer, 2.5 parts of hexamethylene diisocyanate, 2.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3.5 parts of bisphenol A type E51 epoxy resin, and 0.3 parts of dibutyltin dilaurate to 45 parts of toluene, react at 65°C for 3.5 hours, then dry and remove the solvent to obtain PEG-E51-HDI; mix POE-g-MAH, POE-g-GMA, and PEG-E51-HDI in a ratio of 1:0.35:2.5 to obtain a compatibilizer;

[0062] Step 3: Using a melt blending method, weigh 11.36g of PEBAX elastomer, 34.09g of TPU elastomer, and 4.55g of compatibilizer POE-g-MAH, and dry them in an oven at 80℃ for 6 hours. Using a HAAKE torque rheometer, set the temperature to 190℃, the screw speed to 50rpm, and the blending time to 10 minutes.

[0063] Example 15: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0064] Step 1: Under a nitrogen atmosphere, 1.5 parts of hexamethylene diisocyanate and 10 parts of hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 85°C for 3.5 hours. After purification, intermediate A was obtained. Intermediate A, 3.5 parts of 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, and 0.3 parts of azobisisobutyronitrile were added to 45 parts of tetrahydrofuran and reacted under ultraviolet light at 55°C for 3 hours. After purification, pyrimidine monomer was obtained.

[0065] Step 2: Add 4.5 parts of pyrimidinyl monomer, 2.5 parts of hexamethylene diisocyanate, 2.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3.5 parts of bisphenol A type E51 epoxy resin, and 0.3 parts of dibutyltin dilaurate to 45 parts of toluene, react at 65°C for 3.5 hours, then dry and remove the solvent to obtain PEG-E51-HDI; mix POE-g-MAH, POE-g-GMA, and PEG-E51-HDI in a ratio of 1:0.2:2 to obtain a compatibilizer;

[0066] Step 3: Using a melt blending method, weigh 11.36g of PEBAX elastomer, 34.09g of TPU elastomer, and 4.55g of compatibilizer POE-g-MAH, and dry them in an oven at 80℃ for 6 hours. Using a HAAKE torque rheometer, set the temperature to 190℃, the screw speed to 50rpm, and the blending time to 10 minutes.

[0067] Example 16: A method for preparing a high-strength polyether block polyamide blend material, comprising the following steps:

[0068] Step 1: Under a nitrogen atmosphere, 1.5 parts of hexamethylene diisocyanate and 10 parts of hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 85°C for 3.5 hours. After purification, intermediate A was obtained. Intermediate A, 3.5 parts of 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, and 0.3 parts of azobisisobutyronitrile were added to 45 parts of tetrahydrofuran and reacted under ultraviolet light at 55°C for 3 hours. After purification, pyrimidine monomer was obtained.

[0069] Step 2: Add 4.5 parts of pyrimidinyl monomer, 2.5 parts of hexamethylene diisocyanate, 2.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3.5 parts of bisphenol A type E51 epoxy resin, and 0.3 parts of dibutyltin dilaurate to 45 parts of toluene, react at 65°C for 3.5 hours, then dry and remove the solvent to obtain PEG-E51-HDI; mix POE-g-MAH, POE-g-GMA, and PEG-E51-HDI in a ratio of 1:0.5:3 to obtain a compatibilizer;

[0070] Step 3: Using a melt blending method, weigh 11.36g of PEBAX elastomer, 34.09g of TPU elastomer, and 4.55g of compatibilizer POE-g-MAH, and dry them in an oven at 80℃ for 6 hours. Using a HAAKE torque rheometer, set the temperature to 190℃, the screw speed to 50rpm, and the blending time to 10 minutes.

[0071] Comparative Example 1: Pure PEBAX elastomer: dried in an oven at 80°C for 6 hours, then pressed into sheets using a tablet press at 190°C and 10 MPa. The samples were then cut into standard tensile strips using a standard cutter for testing.

[0072] Comparative Example 2: Pure TPU elastomer: dried in an oven at 80°C for 6 hours, then pressed into sheets using a sheet press at 190°C and 10 MPa. The samples were then cut into standard tensile strips using a standard cutter for testing.

[0073] Comparative Example 3: Based on Example 3, without adding a compatibilizer, the ratio of PEBAX elastomer to TPU elastomer is 3:1, and the remaining processes remain unchanged. Specifically:

[0074] 37.50 g of PEBAX elastomer and 12.50 g of TPU elastomer were weighed out and dried in an oven at 80°C for 6 hours using a melt blending method. A HAAKE torque rheometer was then used, with the temperature set at 190°C, the screw speed at 50 rpm, and the blending time at 10 minutes.

[0075] Comparative Example 4: Based on Example 3, without adding a compatibilizer, the ratio of PEBAX elastomer to TPU elastomer is 1:1, and the remaining processes remain unchanged. Specifically:

[0076] 25g of PEBAX elastomer and 25g of TPU elastomer were weighed out and dried in an oven at 80℃ for 6 hours using a melt blending method. A HAAKE torque rheometer was then used, with the temperature set at 190℃, the screw speed at 50rpm, and the blending time at 10min.

[0077] Comparative Example 5: Based on Example 14, PEG-E51-HDI was directly prepared from intermediate A and bisphenol A type E51 epoxy resin, and a compatibilizer was prepared. The remaining processes remained unchanged. Specifically:

[0078] Step 1: Under a nitrogen atmosphere, 3 parts hexamethylene diisocyanate and 5 parts hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 85°C for 3.5 hours. After purification, intermediate A was obtained.

[0079] Step 2: Intermediate A, 3.5 parts of bisphenol A type E51 epoxy resin, and 0.3 parts of dibutyltin dilaurate were added to 45 parts of toluene and reacted at 65°C for 3.5 hours. The mixture was then dried to remove the solvent, yielding PEG-E51-HDI. POE-g-MAH, POE-g-GMA, and PEG-E51-HDI were mixed in a ratio of 1:0.35:2.5 to obtain a compatibilizer.

[0080] Step 3: Using a melt blending method, weigh 11.36g of PEBAX elastomer, 34.09g of TPU elastomer, and 4.55g of compatibilizer POE-g-MAH, and dry them in an oven at 80℃ for 6 hours. Using a HAAKE torque rheometer, set the temperature to 190℃, the screw speed to 50rpm, and the blending time to 10 minutes.

[0081] Comparative Example 6: Based on Example 14, PEG-E51-HDI was used instead of the compatibilizer, while the rest of the process remained unchanged. Specifically:

[0082] Step 1: Under a nitrogen atmosphere, 1.5 parts of hexamethylene diisocyanate and 10 parts of hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 85°C for 3.5 hours. After purification, intermediate A was obtained. Intermediate A, 3.5 parts of 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, and 0.3 parts of azobisisobutyronitrile were added to 45 parts of tetrahydrofuran and reacted under ultraviolet light at 55°C for 3 hours. After purification, pyrimidine monomer was obtained.

[0083] Step 2: Add 4.5 parts of pyrimidinyl monomer, 2.5 parts of hexamethylene diisocyanate, 2.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3.5 parts of bisphenol A type E51 epoxy resin, and 0.3 parts of dibutyltin dilaurate to 45 parts of toluene, react at 65°C for 3.5 hours, then dry and remove the solvent to obtain the compatibilizer;

[0084] Step 3: Using a melt blending method, weigh 11.36g of PEBAX elastomer, 34.09g of TPU elastomer, and 4.55g of compatibilizer POE-g-MAH, and dry them in an oven at 80℃ for 6 hours. Using a HAAKE torque rheometer, set the temperature to 190℃, the screw speed to 50rpm, and the blending time to 10 minutes.

[0085] Test experiment: The high-strength polyether block polyamide blend material prepared by Examples 1-16 and Comparative Examples 1-6 was tested for its performance: (1) Mechanical property test: The mechanical properties of the high-strength polyether block polyamide blend material prepared by Examples 1-16 and Comparative Examples 1-6 were tested, and the results are shown in Table 1;

[0086] index Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 1 Example 2 Example 3 Example 4 Example 5 Tensile strength (MPa) 28.30 60.72 26.95 26.37 56.38 56.22 48.89 49.22 56.11 49.87 43.74 Elongation at break (%) 1070.30 853.44 1102.28 963.49 1291.66 1291.49 1185.12 1133.34 1291.45 1223.61 1080.98 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Tensile strength (MPa) 51.13 47.92 43.68 45.01 46.89 43.25 44.03 42.93 57.86 57.29 57.42 Elongation at break (%) 1203.52 1111.86 1096.32 1153.07 1121.04 1076.56 1063.82 1071.38 1330.62 1397.12 1398.44

[0087] Table 1

[0088] Results Analysis: Table 1 shows that compared to the pure PEBAX material in Comparative Example 1 and the pure TPU material in Comparative Example 2, Comparative Examples 3 and 4, while achieving improved elongation at break after simple blending, exhibited a significant decrease in tensile strength. However, as shown in Example 1, when the PEBAX to TPU ratio reaches 1:3, the blend material simultaneously possesses high strength and high elongation at break. This is because the functional groups in the two raw materials have similar polarity, resulting in good compatibility through simple blending. However, in Comparative Examples 3 and 4, the TPU phase is more prone to agglomeration than the PEBAX phase in Example 1, significantly reducing the tensile strength of the blend material. This is because no compatibilizer was added, leading to incompatibility between the two systems and severely impacting the mechanical properties of the blend material.

[0089] In Comparative Examples 5 and 6, compared to Comparative Example 5 in Example 13, which directly prepared PEG-E51-HDI from intermediate A and then prepared a compatibilizer, eliminating the intermediate secondary operation, the tensile strength and elongation at break were lower than those in Example 13. In contrast, Comparative Example 6 replaced the compatibilizer with PEG-E51-HDI and obtained the compatibilizer without mixing, and it was found that the mechanical properties measured by the compatibilizer with a specific ratio were higher than those of a single compatibilizer.

[0090] Comparing the data from Examples 2-5, the use of POE-g-MAH to improve the compatibility of the blend system in Example 1 shows that the addition of POE-g-MAH increases both the elongation at break and the tensile strength of the blend material, reaching its maximum at an addition of 10 parts. The strength is 14.8% higher than that of Example 1 and 98.3% higher than that of pure PEBAX material. This is mainly due to the reaction between the maleic anhydride groups in the compatibilizer and the amide groups in PEBAX, as well as the similarity in polarity between the POE backbone and the blend system, leading to improved compatibility.

[0091] Comparing the data from Examples 6-9, using POE-g-GMA to improve the compatibility of the blend system in Example 1 reveals that the reinforcing effect on the blend system reaches its maximum when the addition amount of POE-g-GMA reaches 5 parts. The strength is increased by 4.6% compared to Example 1 and by 80.7% compared to pure PEBAX material. The POE backbone still plays a toughening and miscibility-enhancing role in the system, but the grafted GMA groups react less with the system compared to MAH groups, resulting in a lower overall strength compared to using POE-g-MAH as a compatibilizer.

[0092] Comparing the data from Examples 10-13, it can be seen that using SEBS-g-MAH to improve the compatibility of the blend system in Example 1 results in a lower overall strength than that of a simple blend. This is because PEBAX, which can react with MAH groups, accounts for only 25% of the total, while the SEBS main chain, due to its low polarity, is difficult to be compatible with, thus reducing the strength.

[0093] Comparing the data from Examples 14-16, the compatibilizers obtained by specific ratios have higher compatibilities than single compatibilizers, and the mechanical properties of the prepared products are generally higher than those prepared by single compatibilizers. The performance of the intermediate ratio is higher than that of the ratios at the upper and lower limits.

[0094] Compared to pure PEBAX material, blending it with TPU material after adding a compatibilizer can simultaneously combine the high toughness of PEBAX and the high strength of TPU. At the same time, the preparation process of this blend is simple, time-saving, and has a high yield, and it effectively solves the problem of the high price of pure PEBAX material.

[0095] The formulation of this invention can increase the strength of pure PEBAX material by 98.3% with little change in elongation at break. Moreover, the preparation of the blend is simple, safe, and time-saving. At the same time, adding only 25% PEBAX can effectively reduce the cost of use.

[0096] Test experiment: The high-strength polyether block polyamide blend material prepared in Example 3, Example 14-16 and Comparative Example 5-6 was tested for its performance: (1) Heat resistance test: The heat resistance of the high-strength polyether block polyamide blend material prepared in Example 3, Example 14-16 and Comparative Example 5-6 was tested, and the results are shown in Table 2;

[0097]

[0098] Table 2

[0099] Results Analysis: According to the data analysis in Table 2, it can be seen that the compatibilizer prepared by using a specific ratio and introducing heat-resistant groups such as pyrimidine, ether bonds, and siloxy groups can improve the heat resistance of the blended material.

[0100] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A method for preparing a high-strength polyether block polyamide blend, characterized in that: Includes the following steps: Step 1: Dry and dehydrate the elastomer and compatibilizer according to the specified ratio, and then mechanically mix them to obtain a premix. Step 2: Melt-blend the premix to obtain a blended material; The compatibilizers include POE-g-MAH, POE-g-GMA, and PEG-E51-HDI in a mass ratio of 1:0.2~0.5:2~3; The preparation process of the PEG-E51-HDI is as follows: Step 1: Under a nitrogen atmosphere, 1.5 parts of hexamethylene diisocyanate and 10 parts of hydroxyl polyethylene glycol acrylate were added to toluene and reacted at 85°C for 3.5 hours. After purification, intermediate A was obtained. Intermediate A, 3.5 parts of 4-hydroxy-6-mercaptopyrazole (3,4-d)pyrimidine, and 0.3 parts of azobisisobutyronitrile were added to 45 parts of tetrahydrofuran and reacted under ultraviolet light at 55°C for 3 hours. After purification, pyrimidine monomer was obtained. Step 2: Add 4.5 parts of pyrimidinyl monomer, 2.5 parts of hexamethylene diisocyanate, 2.5 parts of 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 3.5 parts of bisphenol A type E51 epoxy resin, and 0.3 parts of dibutyltin dilaurate to 45 parts of toluene, react at 65°C for 3.5 hours, then dry and remove the solvent to obtain PEG-E51-HDI; The hydroxyl-containing polyethylene glycol acrylate has a polyethylene glycol molecular weight of 1000; The elastomers in the premixed material include polyetheramide elastomers and polyurethane elastomers in a mass ratio of 25wt%~wt75%:75wt%~wt25%.

2. The method for preparing a high-strength polyether block polyamide blend material according to claim 1, characterized in that: In the raw materials of the premix, the compatibilizer accounts for 5wt% to 20wt% of the elastomer.

3. The method for preparing a high-strength polyether block polyamide blend material according to claim 1, characterized in that: In step 1, the specific process of drying and dehydration is as follows: drying at 80~100℃ for 6~8 hours.

4. The method for preparing a high-strength polyether block polyamide blend material according to claim 1, characterized in that: The specific parameters for melt blending in step 2 are as follows: screw speed is set to 30~80 rpm, temperature is set to 160~200℃, and melt blending time is set to 10 min.

5. The blend material prepared by the method for preparing a high-strength polyether block polyamide blend material according to any one of claims 1 to 4.

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